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 V.I 
 
 Wa'I's Dictionary of chemistry. 
 
 3 1924 002 980 567 
 
Cornell University 
 Library 
 
 The original of this book is in 
 the Cornell University Library. 
 
 There are no known copyright restrictions in 
 the United States on the use of the text. 
 
 http://www.archive.org/details/cu31924002980567 
 
WATTS' 
 
 DICTIONARY of CHEMISTRY 
 
 VOL. I. 
 
WATTS' 
 
 DICTIONARY of CHEMISTRY 
 
 BE VI BED AND ENTIRELY REWRITTEN 
 
 BY 
 
 M. M. PATTISON MUIR, M.A. 
 
 FEUtiOW, AND PBSIiECTOB IK CHEMISTET, OP GONVILIiE AND CAHJS COI/LEGE, CAMBEIDGE 
 
 AND 
 
 H. FOESTEE MOELEY, M.A. D.Sc. 
 
 PEIXOW OP UNIVEBSITY COLLEGE, LONDON, AND LBOTUKEB ON PHTBICS AND 
 CHEMISTBT AI OEABINQ OBOSS HOSFTrAL MEDIOAL SCHOOL 
 
 ASSISTED BY EMINENT CONTRIBUTORS 
 
 QUE vol 
 
 VOL. I. 
 
 IN FOUR VOLUMES 
 
 NEW IMPRESSION 
 
 LONGMANS, GEEBN, AND CO. 
 
 89 PATERNOSTER ROW, LONDON 
 
 FOURTH AVENUE & 30th STREET, NEW YORK 
 BOMBAY, CALCUTTA AND MADRAS 
 
 1918 
 A.II rightt reserved 
 

 (^^liao I 
 
 Made in Great Britain. 
 
PEBFAOE. 
 
 Twenty-five years have passed since the pubhcation of the first edition of Watts' 
 Dictionary of Chemistry began, and it is now seven years since the second part of 
 the last supplement was pubhshed. 
 
 Some time before his death, Me. Watts had agreed to prepare a new edition of 
 his Dictionary, which should give as complete an account of the present state of the 
 science as might be found compatible with the appearance of the book in four 
 volumes of about 750 pages each. Me. Watts had prepared Instructions to Con- 
 tributors, and had written sixty-three pages for the new edition, when his death — 
 which all chemists so deeply lamented — stopped the work. It has fallen to us to 
 take up the task dropped from worthier hands, and to endeavour to bring it to 
 a satisfactory conclusion. 
 
 Mk. Watts' MS. is printed very much as he left it, subject only to some 
 necessary condensation. In preparing a new edition we have found it necessary to 
 rewrite the whole book. Our instructions were that we should give as complete and 
 satisfactory an account of the present state of chemical science as we could, con- 
 sistently with the size to which we were required to confine the book. We have 
 been obliged, therefore, to adopt a very condensed style ; the descriptions of in- 
 dividual bodies are given in few words, abbreviations are freely used, and formula' 
 are frequently employed instead of names in order to save space. 
 
 The original edition was called ' A Dictionary of Chemistry and the Allied 
 Branches of other Sciences ; ' the new edition deals with chemistry only. Consider- 
 able space was devoted in the original work to processes of chemical technology , 
 the new edition gives no special information with regard to these matters. Tech- 
 nical chemistry will be treated in a companion volume to be published under the 
 editorship of Professor Thorpe. The great importance of the application of physical 
 methods to chemical questions has made it necessary to consider these methods and 
 the results gained by applying them. Hence in our enumeration of the properties 
 of each element and compound we have included those physical constants which are 
 of most importance to the chemist ; and we also intend to describe the leading 
 physical methods of investigation employed in chemistry, and to give a short 
 account of the chief results obtained, in an article entitled P%stcaZ Methods usedin 
 Chemistry. This article will be divided into sections, each of which will be written 
 by a specially qualified author. 
 
 After much consideration, it was decided to omit details regarding analytical 
 processes. In certain cases, e.g. Arsenic methods of detection are given rather 
 
Ti PREFACE. 
 
 fully. But the new edition is not intended for the use of the analyst in the labora- 
 tory, A sketch of the principles of analytical chemistry, and some account of the 
 chief classes of analytical methods, are given in the article Analysis. We have 
 been especially anxious to arrange the matter in a methodical manner, so as to 
 make the task of finding the chief facts about any specified body as little laborious 
 as possible. Cross-references are freely used. 
 
 As mere descriptions of individual bodies in strictly alphabetical order cannot 
 Buffice to give a fair notion of the present position of chemistry, we have supple- 
 mented these descriptions by short general articles on classes of elements and 
 compounds, e.g. Alkali Metals, Carbon Group of Elements, Oxides, Hydroxides, 
 Hydrates, and Amines. We have also devoted considerable space to articles on 
 important theories, hypotheses, and principles. Some of these articles may be found 
 to overlap, e.g., Chemical Change and Equilibrium, Chemical; but the great im- 
 portance of the subjects treated in such articles is, La our opinion, sufficient warrant 
 for devoting much space to their consideration, and for inviting different authors to 
 treat parts of the same subject from different points of view. 
 
 One of the editors is responsible for the inorganic and general, and the other 
 for the organic, chemistry in this work. This division was absolutely necessary if 
 the book was to appear in a reasonable time ; and moreover the nature and arrange- 
 ment of a Dictionary enables various writers to co-operate in its production without 
 material injury to the unity of the work. 
 
 We have been fortunate in securing the help of many contributors — English, 
 American, and Foreign — whose work and position enable them to speak with 
 authority on the subjects of which they treat. 
 
 We have had the advantage of the advice and assistance of Prof. G. Carey 
 Foster, f.e.s., and Dr. W. J. Eussell, f.e.s. To these gentlemen, and to all our 
 contributors and abstractors, we return our sincere thanks. 
 
 Each editor contributes an introduction to his special part. It is hoped that 
 the reader will not pass over these introductions, as they give the necessary 
 explanations of the plan on which the book has been written. The table of abbre- 
 viations used is also important. 
 
 H. FOBSTEB MOELBT. 
 
 M. M. Pattison Muib. 
 March, 1888. 
 
INTEODUOTION 
 
 TO THE POETION OF THE BOOK DEALING WITH INOEGANIC CHEMISTEY. 
 
 Each element is described in its alphabetical position. The account of the element is 
 followed by accomits of its binary compounds and those compounds which may be called 
 double binary, in alphabetical order ; e.g. bromides, chlorides, chloriodddes, sulphochlorides, 
 &c. ; but cyanides are placed together in one article. There are also short articles on 
 Bromides, Chlorides, Oxides, &c. ; and an article is devoted to each class of elements, e.g. 
 Alkali metals, Carbon group of elements, &c. Ammonium is treated as an element 
 so far as the description of the Ammonium compounds is concerned. Each group of salts, with 
 the exception of those mentioned above, is described under one heading ; e.g. all carbonates 
 are described under the heading Carbonates, all nitrates under the heading Nitrates, and 
 BO on. The salts of any specified metal are not as a rule enumerated in the article devoted to 
 tlie metal ; but in a section of this article is given a short account of the salts of the metal 
 considered as a class. When some salts belonging to one class are marked off from the 
 others member of the class, a short article is devoted to a description of these salts as a 
 whole, &c. ; thus there is an article on Alums, and each alum is described in the article 
 Sulphates. 
 
 The nomenclature adopted is generally that used in the Journal of the Chemical 
 Society, but it has not been thought expedient to attempt great strictness in this depart- 
 ment. Structural formulae are seldom used for inorganic compounds. 
 
 The term m.olecular weight is generally used only of those elements and compounds 
 which have been gasified, and the specific gravities of which in the gaseous state have 
 been determined. 
 
 The term valency is only appUed to atoms, and is used to denote the maximum 
 number of atoms of hydrogen, fluorine, chlorine, bromine, or iodine with which one atom 
 of a specified element is known to combine to form a gaseous molecule. 
 
 The symbol Aq is employed to denote an indefinite quantity of water ; when Aq is 
 Bdded to the symbol of an element or compound it means an aqueous solution of this body. 
 
 The following gentlemen have been so good as to prepare abstracts of the papers 
 dealing with inorganic chemistry which have appeared in the various journals since the 
 publication of the last supplement to the first edition of this Dictionary : — Messrs. Cosmo 
 I. Burton, William Burton, G-. J. Hill, H. A. Lawrance, Chas. Slater, and Alfred B, 
 Tutton. I am much indebted to these gentlemen, and also to Miss Ida Freund, Lecturer 
 in Chemistry at Newnham College, Cambridge, who prepared a translation of Pro£. 
 OslwaJd'g article on Affinity, and I beg to tender them my best thanks. 
 
 M. M. Pattison Muir. 
 
INTRODUCTION 
 TO THE AETICLES EELA.TING TO OBGANIO CHBMISTEY. 
 
 Oeganio chemistry probably includes a greater number of observed phenomena than 
 any other science ; it is, clearly, not possible to arrange the description of these in such a 
 way that any one, ignorant of the method of arrangement, could readily obtain the infor- 
 mation he required. The reader is therefore requested to look through this introduction 
 before referring to any of the organic articles. 
 
 The general idea is to devote a separate article to each compound and to arrange these 
 articles in strictly alphabetical order ; exceptions are made in the salts of acids and of bases, 
 the ethers, chlorides, amides, anilides, and anhydrides of acids, the acetyl and benzoyl deri- 
 vatives of compounds containing hydroxyl (OH), amidogen (NHj), or imidogen (NH), 
 the alkyl derivatives (ethers) of compoiinds containing hydroxyl, and the oxims and 
 hydrazides of ketones and aldehydes ; all these are described in the same article as the 
 parent substance. 
 
 The headings of separate articles are in thick BLACK CAPITALS, the salts are in spaced 
 type, the aJkyl and alkoyl derivatives are in spaced italics; derivatives of derivatives 
 are in spaced type. Subsidiary articles are in black type. In describing a compound 
 the physical constants (e.g. melting-point, boiling-point, solubility, refractive index) are 
 first given, then follow the modes of formation and preparation of the body, then such pro- 
 perties as cannot be expressed numerically, and finally a list of the chief reactions in which 
 it plays a part. Inasmuch as organic substances are chiefiy characterised by their melting 
 or boiling points, it has been thought desirable to give these immediately after the name 
 and formula of each compound, so that they may be most readily fovmd. The melting- 
 points are inclosed in square brackets, the boiling-points in roimd brackets. The modes 
 by which salts, ethers, acid chlorides, and amides are formed from the parent acid are only 
 given in particular cases or when the method used is not general ; a similar remark appUes 
 to the acetyl- and benzoyl- derivatives of compounds containing hydroxyl or amidogen, and 
 to the oxims and hydrazides of ketones and aldehydes. Information on the preparation 
 and properties of such derivatives wiU be found in general articles. 
 
 Nomenclature. 
 
 Constitutional names are usually employed, except when the constitution of a body is 
 doubtful ; cross-references will be found under the trivial names. Many trivial names that 
 have been almost universally adopted are nevertheless retained, e.g. aniline, aspartic acid, 
 cinnamic acid, pyrocatechin, hydroquinone, resorcin. 
 
 The names of hydrocarbons usually end in ene or ame, of phenols in ol, of bases in ine, 
 and of indifferent bodies in in. 
 
 In naming several substituting alJcyls, that with less carbon comes first, and when there 
 is an equal number of carbon atoms the imsaturated alkyl comes hefore the saturated : 
 e.g. methyl-ethyl-succinic acid; phenyl -naphthyl-amine ; allyl-propyl-malonic acid. Eadicles 
 containing a closed ring, however, precede fatty radicles, imless there is great danger of 
 ambiguity ; in the latter case cross-references wiU be given. 
 
 Ethers, acetyl and benzoyl derivatives of hydroxyUo compounds are placed under the 
 parent substance. Thus anisole and phenyl acetate are described under ' Phenol,' as its 
 methyl ether and acetyl derivative respectively. So also methoxy-benzaldehyde ia 
 described under ' Oxy-benzoio aldehyde ' as its methyl derivative. 
 
INTRODUCTION. « 
 
 Tetra-alkylatei ammorwwm compoimds are usually described under the tertiary amine 
 from which they are derived. Thus phenyl- tri-methyl-ammonium iodide is described under 
 ' di-methyl-aniline ' as its methylo-iodide. 
 
 Acetyl and benzoyl derivativts of amines are described under the amines to which 
 they belong ; thus aoetaniUde is described under ' Aniline ' as its acetyl derivative. Deriva- 
 tives of a nilin e, methylamine, &e., containing other alkoyls are usually described as the 
 anilide, methylamide, &c., of the acid from which they are derived ; thus CjHj.SGj.NEtH 
 is described as the ethylamide of ' Benzene sulphonic acid.' 
 
 Sulphon/io and ca/rhoxylio acids (whenever they are so named) are represented as 
 derivatives of the hydrocarbon, not of the radicle, thus 02Hj(C0jH)^ is called ethane tetra- 
 carboxylie acid, not acetylene tetra-carboxylio acid ; and OjH4(S03H)3 is called ethane 
 di-Bulphonic acid, not ethylene di-sulphonic acid. 
 
 When a compound contains several substituents they are named in the following order : 
 Chloro; BromO; lodo-, Cyano-, Nitro-, Oxy-, Amido-, Sulpho-, Carhoxy-. In choosing 
 the naming group (i.e. the group that is not to be represented as a substituent, but in the 
 termination of the name) the following is the order of preference : COjH, SO3H, OHO, SH, OH 
 and NH,. Amidogen has precedence over hydroxyl in fatty compounds, but the reverse 
 is the case with aromatic compounds ; thus we say oxy-propyl-amine, but amido-phenol. 
 
 Examples: ohloro-bromo-phenol, not bromo-chloro-phenol ; chloro-nitro-oxy-benzoio 
 acid, not nitro-chloro-oxy-benzoio acid, nor nitro-oxy-chloro-benzoio acid, nor oxy-chloro- 
 nitro-benzoic acid, nor oxy-nitro-chloro-benzoic acid, nor chloro-oxy-nitro-benzoio acid; 
 Bulpho-benzoic acid, not carboxy-benzene sulphonic acid; amido-phenyl mercaptan, 
 not Bulphydio-phenyl-amine, nor sulphydro-aniline. 
 
 Prefixes indicatiiig position. 
 
 The letters a, a, ^, y, &c., are employed to denote the position of substituents in 
 an open chain of carbon atoms. If the substituent is attached to the terminal carbon atom 
 it is preceded by m, while a, j3, y, indicate its attachment to the first, second, or third, 
 atom of carbon reckoned along the chain from the terminal atom. There are at least two 
 ends to an open chain ; the end to be reckoned terminal is determined by the nature of the 
 compound : in monobasic acids it is the carboxyl, in alcohols the group CH,OH, and in 
 general the group represented in the termination of the name. Thus CHjCl.CHI.CHBr.COjH 
 is called 7-chloro-a-bromo-/3-iodo-butyric acid. 
 
 When a, 0, y, &c., axe used in any other sense than that just explained, they are inclosed 
 between brackets ; e.g. (/3)-naphthol. 
 
 Exo- indicates substitution in an open chain. Esq- denotes substitution in a riag ; these 
 prefixes are used when the exact position of the substituent is unknown. The prefixes o-, 
 m-, p-, (ortho, meta, para) indicate isomerism of the di- derivatives of benzene (v. p. 454) ; 
 s- and u- are employed as contractions for symmetrical and unsymmetrical. Thus «-di- 
 phenyl-ethane is CgHj.CHj.CHj.CjHs while M-di-phenyl-ethane is (C6H5)jCH.CH3. 
 
 In derivatives of quinoline (B.) signifies the benzene ring and (Py.) the pyridine ring. 
 In anthracene, acridines, and azines {B.) signifies the benzene rings, (^1.) denotes the 
 eentral ring. 
 
 Alphabetical Order. 
 
 In determining the alphabetical order, the following prefixes are discarded: m,onO; 
 di; tri; tetra-, penta-, hexa-, hepta-, octo-, &c., per-, ortho-, m,eta-, para-, poly-, exo-, eso-, 
 prim-, sec-, tert-, iso-, pseudo-, alio-, a-, /3-, y-, a-, v-, n-, 0-, m-,p-, yjr-, «-, c-, u-, i-, (B.), 
 {Py.), (.4.), and all numbers. Of course when the entire name is numeral, e.g. hexadecane, 
 hexane, &c., this rule does not hold. Thus di-bromo-benzene is in the same article as 
 bromo-benzene ; paraldehyde is associated with aldehyde, isobutyrio acid with ra-butyrio 
 acid, &c. The prefixes pyro- and proto- do not belong to this class. 
 
 The presence or absence of hyphens between parts of a name in no way affects its 
 alphabeticsJ position ; thus ' Benzylidene ' precedes ' Benzyl iodide.' 
 
 Formnlse. 
 Formulae, to save space, are written as much as possible in one line. A por- 
 tion of a formula inclosed in brackets is usually supposed to represent a group 
 
K INTRODUCTION. 
 
 of atoms more intimately connected with the groups represented by the preceding 
 symbols, which are not in brackets, than with those following, e.g. CH2(C02H).CH2.C02H 
 is succinic acid. When numbers within square brackets follow a formula they refer to the sub • 
 stituents taken in the orderin which they occur in the formula : thus OcHjBr (NOj) (CO^H) [1:2:6J 
 is used as an abbreviation for C6H3Br(N02)(C0jH)[Br:N02:C02H = 1:2:6]. The system here 
 adopted differs, therefore, from that sometimes employed, according to which the above 
 symbol would mean 06HsBr(N0j)(C02H)[C0aH:Br:N03 = 1:2:C]. Constitutional formulse are 
 looked upon by the majority of chemists as nothing more than a short way of indicating 
 which atoms in a molecule are directly combined, and which are only indirectly combined 
 with one another. The followers of Van 't Hoff and "Wislicenus, however, suppose that con- 
 stitutional formulae can be constructed in the form of sohd figures which give some notion of 
 the actual relative positions of the atoms in a molectde. All agree that it is by the use of con- 
 stitutional formulae that the remarkable development of organic chenaistry has been made, 
 and that they cannot be abandoned untU something better can be found to take their place. 
 It is not possible to find space for discussing the .reasons which have led to the 
 adoption of each constitutional formula; where these reasons are not given, a careful 
 consideration of the methods of formation and the reactions of the compound will probably 
 reveal them. 
 
 Special Articles, 
 
 In a few articles a ntmiber of compounds are grouped together, in violation of the 
 foregoing rules. The longest of these are the articles on ' azo- ' compounds. Other such 
 articles are on the ammonia derivatives of ' Benzoic aldehyde,' on ' Benzil,' on the organic 
 derivatives of ' Antimony,' ' Arsenic,' and ' Bismuth,' on ' Camphor ' and on ' Cellulose.' 
 The following general articles, amongst others, will also be found in this volume : ' Acids," 
 'Alcohols,' 'Aldehydes,' 'Alkaloids,' action of 'Aluminium chloride,' 'Amides,' 'Amido- 
 Acids,' ' Amines,' ' Analysis,' ' Anhydrides,' ' Aromatic Series ' (see also ' Benzene '), ' Azo- 
 colouring matters,' 'Diazo- compounds,' and 'Bromo- compounds.' 
 
 Contracted Expressions. 
 
 Since the date to which Watts had brcnght the record of chemical discovery, the 
 number. of organic compounds known has doubled, nevertheless the space allotted to them 
 in the present dictionary is little more than a quarter of that devoted to organic chemistry 
 in the original dictionary and its suppleruents. It is evident that there must be extreme 
 compression, and this compels the free use of abbreviated expressions ; it is hoped, however, 
 that a reader who has once made himself acquainted with the nature of these abbreviations 
 will find that they are very convenient. In the first place, the symbols of a few common 
 reagents are used in the text with purely qualitative meaning, although when connected 
 in an equation they are used in the ordinary sense. The great saving of space (about 200 
 pages) has compelled the use of this convention, which would be reprehensible under any 
 other circumstances. The use of the contractions ' v. si. sol. ;' ' si. sol.,' ' m. sol.,' ' v. sol.,' 
 ' V. e. sol.,' and ' sol.,' for ' very sHghtly soluble in,' ' slightly soluble in,' ' moderately 
 soluble in,' ' very soluble in,' ' very easily soluble in,' and ' soluble in,' enables solubihties 
 to be given in the case of many himdred compounds where space would otherwise have 
 compelled their omission. Of course these terms are vague ; where numerical data have 
 been determined, they are usually given in the dictionary, preceded by the letter S. Par- 
 ticular attention should be paid to the exact meaning of these numbers ; they denote the 
 number of grammes of a liquid or solid dissolved by a hundred grammes of the solvent, but 
 the number of volumes of a gas dissolved by one volume of the solvent. Soluble, used as 
 an adjective, the menstruum not being named, means soluble in water. 
 
 Constants, 
 
 Numerical constants are not given in the form a + 6t + ct", &c., since such expressions 
 not only take up a great deal of room, but are usually worthless, because slight errors of 
 experiment produce an enormous effect upon the constants 6, c, &c. ; in such cases one or 
 two actual observations, of a kind likely to be useful in identifying the substance, have 
 usually been selected. 
 
INTRODUCTION. ri 
 
 It is unfortunate that there is a want of uniformity among authors in the method of 
 recording physical constants. Specific gravities are given by most authors without any 
 mention of the temperature of the water that is taken as standard. Some take water at 0°, 
 some at 4°, and others compare the substance with water at the same temperature as itself. 
 Taking the specific gravity of water at 4° as unity, that at 21° will be -OOS ; that is to say, 
 for a substance whose specific gravity is about 1 we may make an error of -002 by assimaing 
 that the author used water at 4° as a standard, whereas he really used water at 21°. Under 
 such circumstances it would be preposterous to give four places of decimals, and such 
 indefinite specific gravities have been out down to three decimal places, and even then the 
 last figure is somewhat doubtful. 
 
 Heats of formation are usually calculated on the assumption that the heat of formation 
 of 44 g. of carbonic acid is 96,960, and that of 18 grms. of water is 68,360 ; Stohmann, 
 Eodatz, and Herzberg, however, use 94,000 and 69,000 respectively, hence their heats of 
 formation are not directly comparable with those of other observers. 
 
 Molecular refraction is the value of the expression M.l^~^~\ where M is the mole 
 
 cular weight, y, the index of refraction, and d the specific gravity of the liquid at 20 
 compared with water at 4° (Landolt, P. 123, 595 ; Briihl, A. 200, 139). Other constants, 
 
 '-= — - )-3-, have also been used ; these are of course not comparable with those first 
 ji + i/ a 
 
 mentioned {of. Briihl, A. 235, 1). 
 
 The specific rotation is given by most observers for a tube of liquid 100 mm. long, but 
 many French chemists use a 200 mm. tube as a standard, and some even 50 mm. "When 
 the length of tube is stated it is easy to apply the correction, but when, as is often the case, 
 an author does not give the length of tube, his numbers are indefinite. 
 
 The rotation measured for the neutral tint is of course not the same as that measured 
 for the sodium line, yet authors occasionally faU. to mention the kind of light employed. 
 The angular rotation ought to be divided by the specific gravity of the liquid during the 
 experiment, in order that the effect of equal weights of material may be compared ; yet it is 
 to be feared that many authors neglect to perform this division, and also to mention that 
 they have not done it. 
 
 Authors frequently fail to state whether their melting and boiling-points have been 
 corrected for the exposure of part of the stem of the thermometer. This may make a 
 difference of 5°. The immersion of the whole of the mercury in the liquid or vapour is 
 indicated by i.V. 
 
 Beferences, 
 
 Where the same paper is referred to several times in the course of one article, the full 
 reference is given once, and in other places there will be found the first letter or the first 
 two letters of the author's name, inclosed within brackets ; thus, if (Perkin, C. J. 45, 390) 
 and (P.) are found in the same article, the (P.) is a contraction for (Perkin, C. J. 45, 390). 
 
 Short Article Expanded. 
 
 In order to make sure that the contractions employed are thoroughly understood, a 
 short specimen article wiU. be expanded by simply exchanging the contractions for their 
 equivalents : — 
 
 Bromo-di-oxy-benzoic acid CsH2Br(OH)2C02H [a;:2:6:l]. [184°, anhydrous]. From c-di-oxy- 
 benzoic acid in ether and Br (Zehenter, M. 2, 480). Prisms (containiug aq) ; v. sol. alcohol, 
 V. si. sol. water. Fefi\ gives a violet colour to its aqueous solution. — AgA' aq.— BaA'jTJaq. — 
 KA'l^aq. 
 
 May be expanded thus : — 
 
 Bromo-di-oxy-benzoio acid C„H2Br(OH)2C02H|TBr:OH:OH:CO.iH = a;:2:6:l] melts at 184° after it 
 has been deprived of its water of crystallisation. It is formed, according to Zehenter (Monatshe/te, 
 vol. 2, p. 480), by adding bromine to an ethereal solution of consecutive di-oxy-benzoic acid. It crys- 
 tallises in prisms, and the crystals contain one molecule of water of crystallisation to each molecule 
 of the acid. These crystals are very soluble in alcohol, but very slightly soluble in water. Ferric 
 chloride colours its aqueous solution violet. It forms the following salts 0sH2Br(OH)iC02Ag,HjO; 
 {CABr(0H),C0,l,Ba,7iH,0; and C,H^r(OH),CO,K, liH.O. 
 
INTRODUCTION. 
 
 Nomenclature of Bings. 
 Besides tbe hydrocarbon rings, represented by benzene, naphthalene, phenantbreue, 
 
 'CH. 
 
 CH, 
 
 anthracene, indonaphthene CjH4<^Y;h^^-^' tei-™ethylene / \ , tetra-methylene 
 
 OH,-CH, 
 
 CHo — CHo 
 
 ^OH,.CH„- 
 
 I I , penta-methylene OH„<'r!xT''"rlTT*x>> &o., there are a great many rings con- 
 
 CH,— OH, ^^CHj.CH,'' 
 
 taining other elements. Some of these are collected here for convenience of reference. It 
 will be noticed that glyoxahne and metapyrazole differ only in regard to the position of one 
 atom of hydrogen. The exact structure of rings containing five or six atoms is not known; 
 some alternative formulae will be found on p. 446. 
 
 Nitrogen ring compounds. 
 
 CH=CH, 
 
 I 
 CH=CH 
 
 \NH Pyrrole or Pyrrol. 
 
 HN— CH^ 
 
 I ^CH Pyraaole. 
 
 I ^CH Metapyrazole. 
 
 hc-n/ 
 
 CH— NH. 
 
 ■\ 
 
 II y^CH Qlyoxaline. 
 
 CH — N^ 
 
 N:CH>^ HN.CH^ 
 
 i >NHor I ^N Triazole. 
 N:CH/ N:CH/ 
 
 _ The di-oxy-derivative of the second form of 
 triazol has been named ' Urazole ' by Pinner. 
 
 N= N. 
 
 I >NH Tetrazole. 
 
 n=ch/ 
 
 CH— CH-CH 
 
 II I II Pyridine. 
 
 CH— N — CH 
 
 CH— N— CH D 
 
 II I II Pyrazine 
 
 CH— N— CH (*yP* °' ketines)' 
 
 CH— N — CH 
 
 II I II Pyrimidine 
 N — CH-CH 
 
 CHj — CH2V 
 I ^NH Pyrrolidine. 
 
 CHj- CH/ 
 
 ' Pyrroline ' has been used by some authors 
 for Pyrrole-dihydride. ' Pyrroline ' in the ab. 
 stracts in the Jownal of the Chemical Society 
 means Pyrrole. 
 
 C.Hv 
 
 
 CHv 
 
 iNH 
 
 and CeH^^^^N (pseudo) 
 
 Indazine. 
 
 CeH,<;^^CH Indole. 
 
 C„H,. 
 
 ,v I xCjH. Phenazint. 
 
 C,oH/|\c,.1 
 
 ,Hj Naphthazine. 
 
 ^NH 
 
 CjHj'^ Q ^CjH^ Phenazoxine 
 
 CHj— CH,— CH, 
 
 I I 
 
 CH^- NH— CHj 
 
 CHj— NH— CH, 
 
 I I 
 
 CHj— NH-CH, 
 
 Piperidine. 
 Piperazim. 
 
 .CH.CH 
 C.h/| II 
 ^N.CH 
 .CH-CH 
 
 c.hZ| II 
 
 \CH— N 
 N-CH 
 
 QuinoUne. 
 
 ^ii^i\ I II QuinoxaUne. 
 
 \n-ch 
 
 CH— N 
 
 CaH,^ I II 
 
 ^N — CH 
 .CH-CH 
 
 c.h/| II 
 
 ^N- N 
 
 Quinazoline. 
 CinnoUne. 
 
INTKODUOTION. 
 
 Oxygen ring compounds, 
 
 CH=CHv 
 
 I >0 Furfurane, 
 
 CH=CH^ 
 
 O^^'^ Q^CS Coumarone. 
 CH^°^>0„H2<^^>CH Bemodifurfuram. 
 
 Sulphur ring compounds. 
 CH=CHv 
 I >S Thiophene. 
 
 ch=ch/ 
 
 CH=CHv 
 
 I >s 
 
 C = C ^ Thiophthene. 
 
 '£be numbers indicating position in compounds of naphthalene are as follows :-- 
 
 1' 1 
 
 2', 
 
 4' 4 
 
 The positions 1, 4, 1', 4' are termed (a), while 2, 3, 2', 3' are called (/8). Quinoline is 
 numbered thus :— 
 
 1 1 
 
 CH CH 
 
 2 HC C CH 2 
 
 I B. \ Py. I 
 
 3 HC C CH 3 
 
 \ / \ / 
 
 CH N 
 
 i i 
 
 Thus {B. 4)-bromo-(P^- 3) -oxy- quinoline would be 
 
 CH CH 
 / \ / \ 
 
 HC 
 
 CH 
 
 Pyridine is numbered thus : 
 
 HC C C.OH 
 
 \Br/\/ 
 
 1 
 
 CH 
 
 /\ 
 
 6 HC CH 2 
 
 I I 
 
 6 HC CH 3 
 
 \/ 
 
 N 
 
 4 
 One of the assumptions made by the recent doctrine of tautomerism is that a lactam 
 CO.NH can readily change into a lactim C(OH):N, and that the group CO.CHj can change 
 into C(OH):CH. It is obviously expedient to describe two compounds which are mutually 
 interchangeable, if not identical, in the same article, hence rings containing CO.NH or 
 CO.OH2 are named as if they were hydroxylic compounds of the form C(OH):N and 
 C(OH):CH. 
 
 Lactones and. Anhydrides. 
 
 Lactones and anhydrides are usually described under the substance from which they 
 may be derived by the abstraction of water ; thus, butyro-lactone will be described under 
 oxy-butyrie acid. 
 
 Prefixes discarded. 
 
 The prefixes homO; hydro-, and mono- are not used. The hydro- compoimds of un- 
 saturated bodies are, if saturated, named in the usual way ; thus hydro-ainnamic acid ia 
 phenyl-propionic acid. The hydro- derivatives of ring compounds are described as hydrides 
 of the simpler compounds from which they are derived : e.g. di-hydro phthalic acid as 
 
siv INTRODUCTION. 
 
 pMhalic acid d/ihydride. Compounds beginning with homo- must be re-named: thus 
 homo-salicylic acid is oxy-toluic acid. 
 
 Hyphens. 
 
 H3^hens are placed between each significant part of a name ; absence of the hyphen 
 asually indicates close connection between two groups of atoms ; e.g. phenylethyl-urea is 
 CjH5.CjH4.NH.CO.NH2 while phenyl-othyl-urea is CeHjNH.CO.NHCjHs. 
 
 Ambiguous names. 
 
 A number of names have been used in several senses by different authors ; it may 
 therefore be well to mention the names chosen in some of these cases. The terms cyanide 
 and isocyanide are altogether discarded, carham/me and rdtrile being used instead. Cycmate 
 is used for ordinary potassium cyanate and the ethers that may be derived therefrom ; the 
 •corresponding sulphtu; compounds are described as sulphocyanides and thio-earhmndea 
 (mustard oils). Cinnamyl is CgHj.CHiCH.CHj, the acid radicle CgHj.CHrCH.CO being 
 nirmamoyl and C6H5.CH:CH is termed siyryl. 
 
 Tolyl is used only for CHj-CgH^. and not for benzyl CeHj.CHj. nor for CHj.CjH^.CHj. 
 
 Cresyl is not used as a name. Xylyl is only used for (CH3)2CeH3., not for 
 CHj.CgH^.CH,. nor for (CH3)2CaH3.CHj. Bv/rene is used as synonymous with tetra- 
 methyl-benzene. 
 
 Discarded names. 
 
 As it commonly happens that several names have been given to the same compound, 
 it may be well to give a list of the names that have been chosen in a few cases. 
 
 Carbamio ether is used instead of XJrethane 
 
 Urea 
 
 Thio-carbimide 
 
 Tolylene 
 
 Methyl-pyridine 
 
 Di-methyl-pyridine 
 
 Tri-methyl-pyridiue 
 
 Methyl-thiophene 
 
 Di-methyl-tMophene 
 
 Oxy-pyridine 
 
 Methyl-quinolina 
 
 Diquinoline 
 
 — hydiazide 
 
 (B. 1). 
 
 Carbamide 
 
 Mustard oil 
 
 Tdluylene 
 
 PicoKne 
 
 Lutidine 
 
 Colliding 
 
 ThiotoUne 
 
 Thioxene 
 
 Pyridone 
 
 Quinaldine 
 
 Diguinolyl 
 
 — isine 
 
 ana- 
 
 Acknowledgments. 
 
 I have been fortunate in seciu-ing the assistance of Messrs. A. G. Green, V. H, Veley, 
 G. N. Himtly, E. E. Graves, Cecil H. Cribb and Cosmo I. Burton, and of Drs. Samuel 
 Eideal and T. A. Lawson. I am also greatly indebted to Mr. A. G. Green for assistance in 
 revising the proof-sheets. "Without the assistance of these gentlemen, it would have been 
 impossible to have done anything like justice to the multitudes of original researches that 
 appear every month, and I have therefore great pleasure in publicly thanking them for 
 the zeal they have shown in endeavouring to render the portion of the Dictionary dealing 
 with Organic Chemistry as far as possible complete. 
 
 H. FORSIGR MORLET. 
 
INITIALS' OF SPECIAL 00NTBIBUT0B8. 
 
 c. P. c. . 
 
 W.D, . 
 
 A. G.G.. 
 
 J. J. H. . 
 W. D. H 
 
 F. E. J. . 
 
 E. E. L. . 
 
 L. M. . 
 
 E. M. . 
 
 W. O. . 
 
 E. T. P. . 
 
 W.E. . 
 
 C. O'S. . 
 
 T. S. . 
 
 J.J. T. . 
 
 T. E. T. . 
 
 E. W. . 
 C. J. W. . 
 H. W. . 
 
 C. p. CEOSS, Esq., Consulting Chemist. Contributes Cellulose. 
 
 WILLUM DITTMAE, Ph.D., F.E.S., Professor of Chemistry at Anderson's College, 
 Olasgow. Contributes Analysis. 
 
 AETHUE G. GEEEN, Esq., P.l.C, Research Chemist to the Atlas Works, Hackney 
 Wick. Contributes Diazo- compounds. 
 
 J. J. HOOD, Esq., D.Sc. Contributes Chemical Change. 
 
 W. D. HALLIBUETON, M.D., B.So. Assistant Professor of Physiology at University 
 College, London. Contributes Blood. 
 
 FEANCIS E. JAPP, M.A., Ph.D., F.E.S., Assistant Professor of Chemistry at the 
 Normal School of Science, South Kensington. Contributes Benzil, Ammonia 
 
 DBKIVATIVES OE BeNZIL, AmMONU DEKIVATIVES OE BENZOIC ALDEHYDE, BENZOIN. 
 
 E. EAT LANKESTEE, M.A., F.E.S., Professor of Zoology at University College, 
 London. Contributes Bacteeia. 
 
 LOTHAE MEYEE, Ph.D., Professor of Chemistry in the University of Tubingen. 
 Contributes Allotkopy. 
 
 EAPHAEL MELDOLA, P.E.S., Professor of Chemistry at the Finsbury Technical 
 College. Contributes Azo- oolodeiko matteks. 
 
 WILHELM OSTWALD, Ph.D., Professor of Physical Chemistry in the Landwirth- 
 schaftliches Institut, Leipzig. Contributes Afeinitt. 
 
 EICHAED T. PLIMPTON, Ph.D., Assistant Professor of Chemistry at University 
 College, London. Contributes Amylamines. 
 
 WILLIAM EAMSAY, Ph.D., Professor of Chemistry at University College, London 
 Contributes Acids and Allots. 
 
 C. O'SULLIVAN, F.I.C., Burton-on-Trent. Contributes Aeabic acid, Bassokin, and 
 Cekasin. 
 
 THOMAS STEVENSON, M.D., LscHrer on Forensic Medicine at Guy's Hospital. 
 Contributes Detection and Estimation oe Poisonous Alkaloids. 
 
 J. J. THOMSON, M.A., F.E.S., Professor of Experimental Physics in the University 
 of Cambridge. Contributes Aggbegation, states of. 
 
 T. E. THOEPE, Ph.D., P.E.S., Professor of Cliemistry at the Boyal School of Mines. 
 Contributes Atmosphebe. 
 
 E. WAEINGTON, Esq., F.E.S. Contributes Ash or okganic bodies. 
 
 CHAELES J. WILSON, Esq., F.I.C. Contributes Caoutchouc. 
 
 HENEY watts, B.A., F.E.S. (the late). Contributes many special articles, and the 
 first half of Alcohols. 
 
 Articles by Mr. MUIE are initialed M. M. P. M. 
 Umsigned Articles are by Dr. MOELEY. 
 
ABBEBVIATIONS 
 
 Liebig's Annalen der Chemie. 
 
 Annates de la Sociedad Cientifica Argentina. 
 
 Annales de Chimie et de Physique. 
 
 Proceedings of the American Academy ot Arts and Scienoee 
 
 American Chemical Journal. 
 
 Annales des Mines. 
 
 American Journal of Science. 
 
 Journal of the American Chemical Society, 
 
 American Chemist. 
 
 I. JOUBKALS AND BoOES. 
 
 When an author has oeen mentioned in an article, he is tisually refirred to ihtrettfur 
 in that article by his initial only. 
 
 A. . . 
 A. A.. . 
 A.Ch. . 
 P. Am. A. 
 Am. . . 
 Ann. M, . 
 Am. 8. . 
 A.O.J.. 
 Am. Ch. 
 Am. J. 
 Pliarvi. 
 An. . . 
 
 A. Ph. S. 
 Ar. N. . 
 Acad. 
 Ar. Ph. . 
 Ar. Sc. . 
 B.. . . 
 B.A. . 
 
 m. . . 
 
 B.D. . 
 B.C. . 
 B.J.. . 
 
 B. M. . 
 C.S.Mem. 
 C.J.. . 
 C.J.Proc. 
 C.N. . 
 C.B. . 
 
 CO.. . 
 D. P. J. 
 
 Fr. . . 
 
 a.. . . 
 
 O.A.. . 
 
 H. . . 
 
 T. . . . 
 
 /. . . . 
 
 J. C. T. . 
 J.M. . 
 J. de Ph. 
 J. Ph. . 
 J.pr. 
 J. Th. . 
 J.B.. . 
 J.Z.. . 
 
 L.r. . 
 
 M. . . 
 M.S. 
 Mem. 
 d'A. 
 Mim. B. 
 
 8. 
 
 American Journal of Pharmacy. 
 
 The Analyst. 
 
 Proceedings of the American Philosophical Society. 
 
 Archives n^erlandaises — The Hague. 
 
 MSmoires de I'Acad^mie des Sciences. 
 
 Archiv der Pharmacie. 
 
 Archives des Sciences phys. et nat. 
 
 Berichte der deutschen chemischen Gesellschaft. 
 
 Beports of the British Association. 
 
 Bulletin de la Soci£t£ chimique de Paris. 
 
 Berliner Akademie-Bcrichte. 
 
 Biedermann's Centralblatt fur Agricultur -Chemie. 
 
 Bcrzelius' Jahresbcrichte. 
 
 Berliner Monatsberichte. 
 
 Memoirs of the Chemical Society of London. 
 
 Journal of the Chemical Society of London. 
 
 Proceedings of the Chemical Society of London. 
 
 Chemical News. 
 
 Cumptcs-rendus hebdomadaircs des Stances de I'Acadimie des Scienoes- 
 
 Paris. 
 Chemisches Central-Blatt. 
 Dingler's polytechnisches Journal. 
 Frcsenius' Zeitschrift fiir analytische Chemie 
 Qazzetta chimica italiana. 
 Gilbert's Annalen der Physik und Chemie. 
 Hoppe-Seyler's Zeitschrift fiir physiologische Chemie. 
 Proceedings of the Boyal Irish Academy. 
 Jahresbericht iiber die Fortscbritte der Chemie and verwandter Theiln 
 
 anderer Wissenschaften. 
 Jahresbericht fiir Chemischo Tcchnologie. 
 Jahrbuch fiir Mineralogie. 
 Journal de Physique et des Sciences accessoires. 
 Journal de Pharmacie et de Chimie. 
 Journal fiir praktische Chemie. 
 Jahresbericht iiber Thierchemie. 
 Journal of the Bussian Chemical Society. 
 Jenaische Zeitschrift fiir Medicin und Naturwissenschaft. 
 Landwirthschaftliche Yersuchs-Stationen. 
 
 Monatshefte fiir Chemie und verwandte Theile anderer Wissenschaften. 
 Le Moniteur Scientifique. 
 M^moires de la Soci£t6 d'Arcueil. 
 
 M^moires couronn£s par I'AcadSmie de Braxelles. 
 
XVUl 
 
 ABBREVIATIONS. 
 
 N. - . . 
 N.Ed.P.J, 
 N.J. P. 
 N. B. P. 
 N.J.T.. 
 N. Z. B. 
 P.M. . 
 P.. . . 
 P.B.. . 
 Pf. . . 
 Pr.E. . 
 Ph. . . 
 Ph.G. . 
 Pr. . . 
 P. B. I. . 
 P.Z. . 
 B.T.O.. 
 B.P. . 
 Q.J.S.. 
 S.. . . 
 Scher. J. 
 S. C. I. . 
 SiU.W. . 
 T. or Tr. 
 T.E.. . 
 W. . . 
 W.J. . 
 z. . . 
 Zeitang. 
 
 Ch. 
 Z.B. . 
 Z.f.d.g. 
 
 Natwr- 
 
 tuiss. 
 Z.K.. . 
 Z. P. c. 
 z. v.. . 
 
 Bn. . . 
 
 E.P. . 
 
 G.P. . 
 
 Om. . . 
 
 Gm.-K. . 
 
 Oerh. . 
 
 K.. . . 
 
 O.O. . 
 Stas, 
 
 Bech. 
 Stas, 
 Nouv. B. 
 
 Th. . . 
 
 Nature. 
 
 New Edinburgh Philosophical Journal. 
 
 Neuer Jahresberioht der Pharmacie. 
 
 Neues Bepertorium fiir die Pharmacie. 
 
 Nenes Journal von Trommsdorff. 
 
 Neue Zeitschrift fiir Eiibenzuckerindustrie. 
 
 Philosophical Magazine. 
 
 Poggendorff's Annalen der Physik und Chemie. 
 
 Beiblatter zu den Annalen der Physik und Chemie. 
 
 Pfliiger's Archiv fiir Physiologie. 
 
 Proceedings of the Eoyal Society of Edinburgh. 
 
 Phaimaceutical Journal and Transactions. 
 
 Pharmaceutisches Central-Blatt. 
 
 Proceedings of the Eoyal Society. 
 
 Proceedings of the Eoyal Institution of Great Britain. 
 
 Pharmaceutisohe Zeitschrift fur Eussland. 
 
 Eecueil des travaux chimiques des Pays-Baa. 
 
 Bepertorium fiir die Pharmacie. 
 
 Quarterly Journal of Science. 
 
 Sohweigger's Journal der Physik. 
 
 Soherer's Journal der Chemio. 
 
 Journal of the Society of Chemical Industry. 
 
 Sitzungsberiohte der K. Akademie zu Wien. 
 
 Transactions of the Eoyal Society. 
 
 Transactions of the Eoyal Society of Edinburgh. 
 
 Wiedemann's Annalen der Physik und Chemie. 
 
 Wagner's Jahresberioht. 
 
 Zeitschrift fiir Chemie. 
 
 Zeitschrift fiir angewandte Chemie. 
 
 Zeitschrift fiir Biologic. 
 
 Zeitschrift fur die gesammten Naturwissenschaften. 
 
 Zeitschrift fiir Krystallographie und Mineralogie. 
 
 Zeitschrift fiir physikalische Chemie. 
 
 Zeitschrift des Yereins fiir die Biibenzuckerindustrie des deutsohen 
 
 Eeiches. 
 Handbuch der organischen Chemie : von F. Beilstein, 2te Auflago. 
 English Patent. 
 German Patent. 
 
 Gmelin's Handbook of Chemistry — English Edition. 
 Gmelin-Kraut: Handbuch der anorganischen Chemie. 
 Traits de Chimie organique : par Charles Gerhardt. 
 Lehrbuch der organischen Chemie : von Aug. Kekul^. 
 Graham-Otto : Lehrbuch der anorganischen Chemie [5th Ed.] 
 Stas' Becherches, &e. ~| 
 
 [. Aronstein's German translation is re- 
 Stas' Nouvelles Eecherehes, &o.J f erred to as Chem. Proport, 
 
 Thomsen's Thermochemische Untersuchungen. 
 
 Aq . 
 
 aq . 
 A' . 
 A" . 
 A'" 
 B'B"*( 
 
 cone, 
 dil. . 
 
 g- • • 
 mgm. 
 mm. . 
 mol. . 
 
 } 
 
 II. Tebms and Qhantities, &o., pbequentlt useb. 
 
 Water ; e.g. NaOHAq means an aqueous solution of caustic soda. 
 
 18 parts by weight of water. 
 
 Besidues of mono-, di-, and tri-basic acids. ThuB, in describing the salts 
 
 of a monobasic acid NaA', CaA'j, AlA'a may be written, HA' standing 
 
 for the acid. For a dibasic acid we should write NajA", CaA", AljA"3 &o. 
 Stand for bases of the ammonia type, in describing their salts. Thus the 
 
 hydrochloride would be B'HCl or B"2HC1, according as the base is 
 
 monacid or diacid, &o. 
 Concentrated. 
 Dilute, 
 gram, 
 milligram, 
 millimetre, 
 molecule 
 
oU. . . 
 pp. . . 
 to ppt. . 
 
 ppg- • • 
 
 ppd. . . 
 sol. . . 
 iusol. . . 
 V. e. sol. . 
 V. sol. . 
 m. sol. . 
 si. sol. . 
 V. si. sol. 
 
 V. . . . 
 c/.. . . 
 0. . . . 
 
 [°] ■ • 
 
 k:! : : 
 
 A.t. w. . 
 Mol.w.or 
 
 M. w. 
 D. . . . 
 cor. . . 
 uncor. . 
 i.V. . . 
 V.D. . . 
 S.G. . . 
 S.G. ig" . 
 S.G. w 
 S.G.ii . 
 
 S.H. . . 
 
 S.H.v. . 
 
 S.H.p. . 
 
 H.C. . . 
 
 H.C.V. 
 
 H.C.p. 
 
 H.P. 
 
 H.F.V. 
 
 H.F.p. 
 H.V. . 
 
 T.C. 
 S.V. 
 
 S.V.S. 
 
 E.G. . . 
 
 C.E. (10° 
 
 to 20°) 
 
 a. . . 
 
 S. (alco- 
 hol) 
 
 /iB,&C. . 
 
 ABBREVIATIONS. xix 
 
 liquid, nearly, or quite, insoluble in water. 
 
 precipitate. 
 
 to precipitate. 
 
 precipitating. 
 
 precipitated. 
 
 soluble in. 
 
 insoluble in. 
 
 very easily \ 
 
 very 
 
 moderately V soluble in.. 
 
 slightly 
 
 very sUghtly J 
 
 see. 
 
 compare. 
 
 about. 
 
 a melting-point. 
 
 a boiling-point. 
 
 Hardness (of minerals). 
 
 Atomic weight. 
 
 Molecular weight. 
 
 Density. 
 
 corrected. 
 
 uncorrected. 
 
 in vapour. 
 
 vapour-density, i.e. density of a gas compared with hydrogen or air. 
 
 Specific gravity compared with water. 
 
 „ „ at 10' compared with water at 0°- 
 
 l.'5° 4° 
 
 t> i» II ■'■*' II II II II * • 
 
 „ „ „ 12° ; compared with water of which the temperature ia 
 
 not given. 
 Specific heat. 
 
 „ „ of a gas at constant volume. 
 „ „ „ „ „ pressure. 
 
 Quantity of heat, in gram-units, produced during the complete com- 
 bustion of the mass of a BoUd or liquid body represented by its 
 
 formula, taken in grams. 
 Heat of combustion in gram-units of a gram-molecule of an element or 
 
 compound, when gaseous, under constant volume. 
 The same, under constant pressure. 
 Quantity of heat, in gram-units, produced during the formation of the 
 
 mass of a solid or liquid body represented by its formula, taken in 
 
 grams, from the masses of its constituent elements expressed by 
 
 their formulas, taken in grams. 
 Heat of formation of a gram-molecule of a gaseous compound from the 
 
 gram-molecules of its elements under constant volume. 
 The same, under constant pressure. 
 Heat of vaporisation of a liquid, i.e. gram-units of heat required to change 
 
 a gram-molecule of the liquid compound at B.P. into gas at same 
 
 temperature and pressure. 
 Thermal conductivity (unit to be stated). 
 Specific volume ; or the molecular weight of a gaseous compound divided 
 
 by the S.G. of the liquid compound at its boiling-point compared with 
 
 water at 4°. 
 Specific volume of a solid ; or the mass of the solid expressed by its 
 
 formula, taken in grams, divided by its S.G. 
 Electrical conductivity (the unit is stated in each case). 
 Coefficient of expansion (between 10° and 20°). 
 
 {of a gas = volume dissolved by 1 volume of water, 
 of a liquid or solid = number of grms. dissolved by 
 100 grms. of water. In both cases the temperature 
 is stated. 
 Index of refraction for hydrogen line 0. 
 
 „ „ „ sodium „ D, &o. 
 
 Molecular refraction for sodium light, i.e. index of refraction for lino D 
 minus one, multiplied by molecular weight, and divided by S.G. at 15" 
 compared with water at 0°. 
 The same ; S.G. being determined at 15°-20° and referred to water at 4°. 
 The same for line of infinite wave-longth, index being determined by 
 Oauchy's formula (Briihl's EJ. 
 
ABBREVIATIONS. 
 
 Mi 
 
 I. M 
 
 Bz . . 
 
 Cy . . 
 
 Et . • 
 
 Me . . 
 
 Ph . . 
 
 Pr . . 
 
 Pr . . 
 E, E' &c. 
 
 prim . . 
 
 sec . . 
 
 tert . . 
 
 n . , , 
 
 m,o,p . 
 
 c . . . 
 
 > . . . 
 
 s . . , 
 
 u . , , 
 
 ^ . . . 
 
 a,P,y,&e. 
 1,2,3, &o. 
 
 W. (-8). 
 &0. 
 
 (B.) . . 
 
 {A.) . . 
 
 eso- , . 
 exo- . . 
 alio- . • 
 
 thio- . , 
 sulpho- . 
 gulphydrO' 
 
 Specific rotation for sodium light. 
 „ „ „ neutral tint. 
 
 [«] 
 
 100 
 
 X -. a - obberved rotation (or 
 a 
 
 100 mm. of liquid. d = S.G. of liquid. 2) = no- of grammes of active 
 substance in 100 grammes of liquid. 
 
 Molecular magnetic rotatory power = j-j^ 
 
 - where m = molecular 
 ■ » 
 
 weight of the body of S.Gr. = d, o = angle of rotation under magnetio 
 
 influence, o' = angle of rotation of water under same influence, and 
 
 m' - molecular weight of water (18). 
 Acetyl C,,HjO. 
 Benzoyl C,HjO. 
 Cyanogen ON. 
 Ethyl Cfi,. 
 Methyl CH,. 
 
 Phenyl CjHs. 1-in formols. 
 
 Normal Propyl CH.,. CH^. CH,. 
 Isopropyl CH(CH3),. 
 Alcohol radicles or alkyla, 
 primary, 
 secondary, 
 tertiary, 
 normal. 
 
 meta — ortho — para, 
 consecutive, 
 irregular, 
 symmetrical, 
 nnsymmetrical. 
 pseudo. 
 
 attached to nitrogen. 
 Employed to denote that the substituent is attached to a carbon atom 
 
 which is next, next but one, or next but two, respectively, to the 
 
 terminal carbon atom. The end to be reckoned from is determined 
 
 by the nature of the compound. Thus CHs.CHBr.COjH is a-bromo- 
 
 propionic acid, 
 denotes that the element or radicle which follows it is attached to a ter- 
 minal carbon atom, 
 indicate position in an open chain, only, 
 indicate position in a ring only. 
 Used when o, ;8, &c. are employed in a sense different from the above, 
 
 e^. (a)-di-bromo-camphor. 
 Baeyer's Nomenclature : 
 
 benzene ring. 
 
 pyridine ring. 
 
 Thus {B. 1:3) dichloroquinoline, means a meta-dichloroquinoline in 
 
 which the chlorine atoms are both in the benzene ring. 
 
 While (Py. 1:3) dichloroquinoline, means a similar body, only the 
 
 chlorine atoms are in the pyridine ring. The numbers are counted 
 
 from two carbon atoms which are in different rings, but both united 
 
 to the same carbon atom, 
 denotes the central ring in the molecule of anthracene, aoridines, and 
 
 azinea. 
 means that the element or radicle it precedes is in a closed ring. 
 
 ,, „ ,, „ ,, not in a benzene ring. 
 
 denotes isomerism that is not indicated by ordinary formulse ; thug maltic 
 
 acid may be called aZto-fumaric acid, 
 denotes displacement of oxygen by sulphur. 
 
 „ the group SO3H, except in the word sulphocyanide. 
 „ the group SH. 
 Tribromonitrobenzene sulphonic acid [1:2:3:4:5] means that the three 
 
 bromines occupy positions 1, 2, and 3; the nitro- group the position 4, 
 
 and the sulpho- group the position 5. 
 
 ■< Denotes that the formula to which it is affixed has not been determined by 
 analysis. But it by no means follows that formula; without this mark are those of 
 analysed compounds. 
 
 All temperatures are given in degrees Centigrade unless when specially stated 
 otherwise. 
 
 Wave-lengths are given in 10 ' mm. 
 
 Formula, when used instead of names of substances, have a qualitative mesning 
 only. 
 
 Thomsen'B notation is used in thermochemical data. 
 
DICTIONARY OF CHEMISTRY. 
 
 ASIES, — The needles of A.pectinata contain 
 a sugar called Abietite, CuHjOa, very much like 
 raannite, but differing therefrom in composition 
 and in solubility. The same plant contains a 
 tannin identical with the soluble tannin of the 
 horse-chestnut, CjjHijOj, and convertible by hy- 
 drochloric acid into an anhydride O^^^^sO^st in- 
 soluble in cold water, but soluble in boiling 
 potash-iye, slightly in water and alcohol (Eoch- 
 leder, J.pr. 105, 63, 123).— The fruits of Abies 
 RegincB Amalim, indigenous in Arcadia, yield, 
 by distillation with water, about 18 p.o. of a 
 colourless volatile oil CuH,,,, smelling like lemons, 
 S.G. -868 (156-159°) ; slightly Isevorotatory. Ee- 
 sinifies quickly in the air, exerting an ozonising 
 influence stronger than that of turpentine-oil. 
 Dissolves iodine, and absorbs hydrogen chloride, 
 forming a liquid compound C,„Hi5.HCl (Buchner 
 a. Thiel, J. pr. 92, 109). H. W. 
 
 ABIETEIIE 0,H,5.— The heptane of Pinus 
 sabiniana (v. HEPiisEs). 
 
 ABIETIC ACID C^^H^Os [139°] or [165°].— 
 Caillot, J. Ph. 16, 436 ; Maly, A. 129, 94 ; Em- 
 merling, B. 12, 1441 ; Kelbe, B. 13, 888.— Oc- 
 currence. The clear liquid turpentine of various 
 species of pine contains abietio anhydride 
 OjjHjjO,, which, on exposure to the air, absorbs 
 moisture and is converted into abiotic acid, the 
 liquid then coagulating to an opaque granular 
 pulp. The anhydride is the chief constituent 
 of common resin or colophony. 
 
 Preparation. — 1. Coarsely pounded colophony 
 is digested for two days with weak spirit ; the 
 liquid is decanted from the white crystalline pulp, 
 and squeezed in a press; the press-cake dis- 
 solved in hot strong alcohol, and the solution 
 left to itself at ordinary temperatures ; a white 
 crystalline crust is thus obtained ; the mother- 
 liquor, when cooled by ice, usually solidifies to 
 a loose mass of white lamina, which constitutes 
 the greater part of the product. The crystalline 
 crust consists of sylvic acid C^jHjdOz, the laminse 
 of abietic acid (M.). — 2. Colophony is digested 
 for two days with spirit of 70 p.c, and the undis- 
 solved portion, after washing with weak spirit, 
 is dissolved in the smallest possible quantity of 
 glacial acetic acid. From this solution the acid 
 separates in crusts, and on adding a little water 
 to its solution in hot alcohol and stirring, it 
 is obtained in crystalline scales (E.). — 3. Soda- 
 lye which has been used for purifying crude 
 resin-oil is mixed with common salt, and the 
 soap which separates is dried at 70°-80°, and 
 purified by exhaustion with ether. The residue 
 dissolves in alcohol, and the solution, on evapo- 
 ration, deposits needle-shaped crystals of sodium 
 abietate, the aqueous solution of which yields. 
 Vol. I. 
 
 on_ addition of hydrochloric acid, a white pp. of 
 abietic acid, which melts to a resinous mass if 
 the mixture is boiled (K.). 
 
 Properties.— Separatea from hot alcoholic- 
 solution in irregular transparent pointed tri- 
 clinic crystals melting at 165° (M., K.) ; 139° 
 (E.) ; 135° (Fliickiger). Sol. alcohol, ether, ben- 
 zene, glacial HOAo, CHCl, and CS^. 
 
 Reactions. — 1. Abietic acid distilled with zinc 
 chloride yields a heavy oil (70°-250°) containing 
 heptylene (E.). — 2. Strong hydrochloric and hy- 
 driodic acids at 145° abstract the elements of 
 water from it, leaving the anhydride (E.) ; but 
 when treated in alcoholic solution with gaseous 
 HCl, it yields sylvic and sylvinolic acids : 
 
 p< A,0, + H,0 = C,,-B,fi, + G„n,fi, (?) 
 Sylvic acid is also formed when a hot alcoholic 
 solution of abietio acid is mixed with sulphuric 
 acid (M.). — 3. Triturated with PCI5 it yields on 
 distillation a volatile oil C^Hj,,, called by Maly 
 abietone, together with HCl and POCI3. — 4. By 
 oxidation with KMnO,, abietic acid yields car- 
 bonic, acetic and formic acids. — 5. Boiled with 
 chromic mixture, it yields large quantities of 
 acetic and formic acids, and, after removal of 
 these by distillation, ether extracts from the 
 liquid a small quantity of trimellitio acid 
 CsH3(COj,H)3 (E.).— 6. The anhydride (colophony), 
 oxidised with nitric acid, yields isophthalic acid, 
 together with trimellitic acid (Schroder, B. 6, 
 413). — 7. Abietic acid fused with potash yields 
 propionic, but no protocatechuio, acid (M.). — 8. 
 Sodium-amalgam added to a warm alcoholic 
 solution of abietio acid converts it into hydra- 
 bietio acid OjjHjsOj, a dibasic acid which 
 forms white unctuous laminse melting at 160° 
 (M.). — 9. Abietio acid with acetic chloride or an- 
 hydride at 160° yields an oily acetyl-compound 
 (E.). — 10. Bromine added to a solution of abietio 
 acid in CSj forms a bromo-derivative, probably 
 Cj^HsjBr.Ps, which separates from alcohol as a 
 red powder melting at 134° (E.).— 11. Distilled 
 with zinc dust it yields toluene, w-ethyltoluene, 
 naphthalene, methyl-naphthalene, and methyl, 
 anthracene (Ciamician, G. 9, 305, B. 11, 269). 
 
 Salts. — Abietic acid is dibasic, mostly form- 
 ing normal, rarely acid, salts. The alkaline salts 
 are difficultly crystallisable. The normal able, 
 tates of the other metals C^jHsjiT'Os are sparingly 
 soluble in water, and are obtained by precipita- 
 tion. Na^A", needles (from alcohol). — MgA", 
 flocculent, v. sol. alcohol. — MgHjA/. — CaA". — 
 BaA".— ZnA", si. sol. alcohol.— CuA", v. sol. CS, 
 or ether ; pale green. 
 
 Ethyl Abietate Et^A", obtained by decom- 
 posing silver abietate with ethyl iodide diluted 
 with ether, forms a yellowish mass, having aa 
 
 B 
 
ABIETIO ACID. 
 
 ■ethsric odour j insoluble in water, slightly so- 
 luble in alcohol, easily in ether and CSj. 
 
 Abietin G^;3.,fi^i.e.C^;^.^^[CB.Ue■.CB.)fia 
 is deposited from a mixture of glycerin and a 
 ■concentrated alcoholic solution of abietic acid, 
 lifter exposure to a low temperature for several 
 ■days, in small white crystals melting at 125°, 
 soluble in ether and alcohol (M.). H. W. 
 
 ABIETIC ANHYDRIDE C„He,Oi is not 
 formed by direct dehydration of the acid, but 
 ■exists, as already observed, in the clear fresh 
 ■turpentine of certain conifers, and forms the 
 essential part of colophony. H. W. 
 
 ABIETIN. V. supra. 
 
 ABIETITE CjHsOa.— ^iiefoZ. The sugar of 
 Aiies pectinata. 
 
 ABEOTINE CjiHjjN.O.— An alkaloid from 
 Artemisia ahrotanum (P. Giacosa, /. 1883, 1356). 
 White crystalline powder -or white needles. SI. 
 sol. hot water. Its solutions fluoresce blue. 
 Salts: B"H.,PtCle.-B/'H.,S046aq. Needles. 
 
 ABSINTHIN or AbsyntUin O^HjsO, [120°- 
 125°].— (Mein, A. 8, 61 ; Luck, A. 78, 87 ; Kro- 
 mayer, Ar. Ph. [2] 108, 129).— The bitter prin- 
 ciple of wormwood (Artemisia absynlhium). 
 Prepared by exhausting the dry herb with cold 
 water ; absorbing the bitter principle from the 
 concentrated extract with boneblack ; extracting 
 with alcohol ; purifying by treatment with basic 
 lead acetate, precipitating the lead with H^S, 
 »nd evaporating the filtrate. 
 
 Properties. — Yellow powder, composed of 
 minute crystals. V. si. sol. cold water, si. sol. 
 hot water, v. sol. alcohol or ether. Very bitter. 
 Neutral to litmus. Smells like wormwood. 
 
 Reactions. — 1. Cone. H^SOj forms a brown 
 solution, turning greenish-blue. A little water 
 turns the colour to a splendid blue, destroyed by 
 more water. — 2. Boiling dilute HjSO, acquires 
 a yellowish-green fluorescence, and deposits a 
 hrown resin. — 3. Does not reduce Fehling's solu- 
 tion. — 4. Gives a mirror with warm ammoniacal 
 AgNOj. — 5. An alcoholic solution gives a sticky 
 pp. with tannin. — 6. Gives no pps. with metallic 
 salts. H. W. 
 
 ABSINTHOl.— C,„H,.0 (195°) or (204°).— 
 (Beilstein a. Kupffer, B. 6, 1183, A. 170, 290 ; 
 Wright, C. /. 27, 1 and 319).— Isomeric with 
 common camphor. Forms the essential principle 
 of wormwood-oil, in which it is associated with 
 aterpene (b.p. below 160°) and a deep-blue oil 
 (270°-300°) identical with the blue chamomile 
 oil examined by Kachler {B. 4, 36). Absinthol 
 boils at 195° (B. and K.), at 200°-205° (W.), 
 217° (Gladstone). Differs essentially from cam- 
 phor in chemical reactions, not being converted 
 into camphoric acid by oxidation with nitric 
 acid, nor into eampho-oarboxylic acid, C„H,j03 = 
 C,|,Hn(0H).C02H, by sodium and CO^, and yield- 
 ing with melting potash a large quantity of resin 
 but no acid. Heated with P^Sj it yields cymene 
 C„Hn, and cymyl hydrosulphide CuHisSH, boil- 
 ing at 2B0°-240° (W.). Cymene is also formed, 
 though in smaller quantity, by treating absinthol 
 with zinc chloride (W.). H. W. 
 
 ABSORPTION or GASES BY LIQUIDS AND 
 rSOXIDS V. Gases. 
 
 ABSORPTION-SPECTRA v. Physicai, Me- 
 iTHODS : sect. Optioai,. 
 
 ACACIN or Acacia gum v. Akabin. 
 
 iACAJOTJ. — The pericarp of the nuts of the 
 
 Acajou or Cashew-nut tree, Anacardium occu 
 dentate, growing in the West Indies and South 
 America, contains a large quantity of a red-brown 
 resinous vesicating substance, which may be ex- 
 tracted by ether, the solution when evaporated 
 leaving a network of small crystals of anacardic 
 acid soaked in an oily liquid called ca/rdol, to 
 which the resin owes its acrid properties (StS- 
 deler, A. 63, 137). A catechin C^jHjjO.s [165°] 
 may be got from acajou-wood (Gautier, Bl. 30, 
 568). H. W. 
 
 ACAROID RESIN Eesin of Xanthorrhea 
 
 feisiiKs, a liliaceous tree of Australia : also called 
 resin of Botany Bay. Yellow, fragrant, soluble 
 in alcohol, ether and caustic potash. The potash- 
 solution treated with HCl deposits benzoic and 
 cinnamic acids. Nitric acid readily oxidises it 
 to picric acid. Yields on distillation phenol and 
 small quantities of benzene and styrene (Sten- 
 house, A. 57, 84). By potash-fusion it gives 
 ^-oxy-benzoic scid, resoroin, and pyrocatechin 
 (Hlasiwetz a. Earth, A. 139, 78). H. W. 
 
 ACECHLOBIDE OE PLATINUM v. Acetone. 
 
 ACECONITIC ACID 0,H„Oe.— The ethyl ether 
 is formed, together with the (probably isomeric) 
 citracetio ether, by the action of sodium on 
 ethyl bromo-acetate : 
 
 SEtCjHjBrO^ H- 3Na = EtjC^HjOs -(- 3NaBr -f- H3 
 (Baeyer, A. 135, 306). The product is distilled 
 in vacuo, and the ethers saponified by baryta. 
 Baric aceconitate crystallises, leaving the 
 gummy baric citracetate in solution. 
 
 Properties. — Nodular groups of needles. V. 
 sol. ether. Gives no crystalline sublimate. 
 
 Salts. — Barium salt forms small, sparingly 
 soluble crystals. A solution of the calcium salt 
 becomes turbid when heated. — AgjA^aq. Ethyl 
 ether. — EtjA'". Lighter than water. H. W. 
 
 ACEDIAMINE C^H^Nj i.e. NH^.CMe : NH 
 
 V. ACET-AMIDINE. 
 
 ACENAPHTHENE Gi^H,, i.e. C,„Hs : CjH„ 
 CH CH 
 
 CH 
 
 CH 
 
 
 
 1 I 
 Clig — CHg 
 
 M.w. 154. [95°] (Behr a. Dorp, A, 172, 265), [103^ 
 (Schifl), (278° i. v.). V.D. 5-35 (for 5-33). S.V.S. 
 149-16 (Schiff, A. 223, 263). 
 
 Occurrence. — In coal-tar oil (Berthelot, Bl. 
 [2] 8, 226). 
 
 Formation. — 1. By passing a mixture of 
 ethylene and benzene or naphthalene through 
 a red-hot tube (Berthelot). — 2. By passing 
 (a) -ethyl-naphthalene through a red-hot tube. — 
 3. By treating (o) -ethyl-naphthalene with Br at 
 183° and decomposing the product, C,|,H,.C2H,Bri 
 with alcoholic KOH at 100° (Berthelot a. Bardy, 
 C. R. 74, 1463). 
 
 Preparation.— Bea,vj coal-tar oil (260°-290'') 
 is carefully fraotioned, and the fraction 260°- 
 270° cooled strongly till it solidifies. Eecrystal- 
 lised from alcohol (Terrisse, A. 227, 134). 
 
 Properties. — Long needles (from alcohol). V. 
 sol. hot alcohol, v. si. sol. col4 alcohol. 
 
ACETAL. 
 
 3 
 
 Reactions. — 1. A mixture of alcoholic solu- 
 tions of aoenaplitliene and picric acid de- 
 posits orange-yellow needles of the picrate, 
 C,ja,o.O,H2(NOj)30H [162°].— 2. Cone. E^SO^ 
 forms a sulphonate whose salts are very soluble. 
 A little HNOj turns the solution in HjSOj green. 
 3. Cold HNOj forms di-nitro-acenaphthene. 
 Yellow needles (from beuzoline) ; insol. in alco- 
 hol. — 4. CrOj and H2SO4 give naphthalio acid, 
 0,oHs(C02H)2 (B.a.D.).— 5. Bromine added to an 
 ethereal solution forms bromo-acenaphthene, 
 CioHsBrCjHj [53'] ; tables (from alcohol) ; oxi- 
 dises to bromo-naphthalio acid (Blumenthal, 
 B. 7, 1095). — 6. A further quantity of bromine 
 added to a solution in CSj forms C^HgErj ; 
 white needles (from alcohol). — 7. Iodine at 100' 
 polymerises it. — 8. Cone. HI at 100° forms a 
 hydrocarbon (? C|2H,2) (c. 270°).— 9. Cone. HI 
 (20 pts.) at 280° produces naphthalene di-hydride 
 and ethane. — 11. Potassium gives off hydrogen, 
 forming Ci^HiK (Berthelot). 
 
 ACEKAPHTHYIENE C.^He i.e. 0,^,:G^M^; 
 probably 
 
 CH CH 
 
 CH = CH 
 [93°] (265°-275°). 
 
 Freparaticm. — Aoenaphthene (6g.) is put into 
 a combustion tube, and the rest of the tube filled 
 with litharge. The aoenaphthene is heated 
 strongly, and the vapours pass over the litharge, 
 which must not be red hot (Blumenthal, B. 7, 
 1092 ; Behr a. Doi-p, B. 6, 758). 
 
 Properties. — Large golden plates (from alco- 
 hol). Ispartly decomposed by boiling. V. e. sol. 
 alcohol, ether or benzene. 
 
 Reactions. — 1. Sodium amalgam reduces it, 
 in alcoholic solution, to aoenaphthene. — 2. Chro- 
 mic mixture oxidises it to naphthalic acid. — 
 3. Combines, in ethereal solution, with bromine, 
 forming 
 
 ,CHBr 
 C,.H. < I 
 
 \CHBr 
 [121°-123°]. This forms white needles (from 
 benzene mixed with alcohol). Chromic mixture 
 oxidises it to naphthalic acid. Alcoholic KOH 
 converts it into bromo-acenaphthylene, 
 
 yCBX 
 
 \CH 
 
 This is a liquid, but its picrate forms yeUow 
 needles. Bromo-aoenaphthylene is converted by 
 bromine into orange-red plates of di-bromo-ace- 
 naphthylene, 
 
 ^OBr 
 
 C,oH,Br 
 
 /; 
 
 P&rafe.-C,AC<,Hj,(NO2),OH[202°]. Yellow 
 needles. V. si. sol. cold alcohol. 
 
 ACETACETIC ACID v. Aoeto-aoetic Acid. 
 
 ACETAI C^HnOj i.B. 0H3.CH(0Et)j.— Di- 
 ethyl-acetal, di-ethyl aldehydate (v. Aldehyde). 
 M.w. 118. (104°) (Stas) ; (103-2°) at 752 mm. 
 
 (E. Sohiff, A. 220, 104) ; (21°) at 22 mm., (SO-S") 
 at 121 mm., (102-2°) at 760 mm. (Kahlbaum). 
 S.G. 'i -8314 (Briihl) ; ^| -8319, || -8233 (Perkin) ; 
 "f? -7364(80.). V.D. 4-141. Critical temperature 
 254-4° (Pawlewski, B. 16, 2633). S. 4-6 at 25°. 
 S.V. 159-88 (So.), lig 1-886. E™ 52-52 (B.). 
 M.M. 6-968 at 16-1° (P.). 
 
 Occurrence. — In crude spirit, after filtering 
 through charcoal (Geuther, A. 126, 63). 
 
 Formation. — 1. By the imperfect oxidation 
 of alcohol (Doebereiner ; Liebig, A. 5, 25 ; 14, 
 156 ; Stas, A. Ch. [3] 19, 146 ; Wurtz, A. Ch. 
 [3] 48, 370 ; A. 108, 84). Hence its occurrence 
 in raw spirit and in old wines. — 2. By action ot 
 chlorine on alcohol : 
 
 8C AO + 01^= CeH, A + 2HC1 + HjO. 
 
 3. One of the products of action of alcohol on 
 ethyl di-bromo-acetate (Kessel, B. 11, 1917). 
 
 4. By passing non-inflammable PH3 into a mix- 
 ture of equal volumes of aldehyde and alcohol 
 at -21° (R. Engel a. De Girard, C. R. 91, 692 ; 
 C. J. 38, 458). 
 
 Preparation. — I. Prom Alcohol. — 1. By im- 
 perfect oxidation under the influence of plati- 
 num-black. Fragments of pumice are moistened 
 with nearly absolute alcohol in a wide-mouthed 
 flask, the upper part of which is filled with 
 shallow glass capsules containing platinum- 
 black, and the fiask, covered with a glass plate, 
 is left in a room at 20° till nearly aU the alcohol 
 is converted into acetic acid. Alcohol of 60 p.o. 
 is then poured in, and the flask, again covered 
 with the glass plate, is exposed to the same tem- 
 perature for a fortnight or three weeks, by which 
 time the liquid above the pumice will have be- 
 come viscid. This liquid is then poured off, more 
 alcohol is added, and this course of proceeding 
 is repeated till a few litres of very acid liquid 
 have been obtained. This product is saturated 
 with potassium carbonate, dried with calcium 
 chloride, and about a fourth of it is distilled off ; 
 the distillate is treated with calcium chloride ; 
 the lower layer of liquid — consisting of aldehyde, 
 ethyl acetate, and alcohol— is again mixed with 
 calcium chloride, and distilled till the distillate 
 no longer reduces silver nitrate ; and the residue 
 is treated with potash-lye, washed, dried with 
 calcium chloride and rectified (Stas). — 2. By 
 distilling alcohol (2 pts.) with manganese dioxide 
 (3 pts.), sulphuric acid (3 pts.), and water (2 pts.), 
 and rectifying the product, which consists of 
 acetal mixed with aldehyde, ethyl acetate, &o., as 
 above. — 3. By passing chlorine through alcohol 
 of 80 p.c. cooled to between 10° and 15° tUl a 
 portion becomes turbid on addition of water, in- 
 dicating the formation of substitution-products. 
 One fourth of the acid liquid is then distilled 
 off; the distillate is neutralised with chalk; a 
 fourth part again distilled off ; and the distillate, 
 consisting of alcohol, ethyl acetate, aldehyde, 
 and acetal, is treated as above to separate the 
 acetal (Stas). According to Lieben {A. Ch. [3] 
 52, 813), the chief products of the action of 
 chlorine on 80 p.c. alcohol are mono- and di- 
 chloracetal. 
 
 II. From Aldehyde. — 1. By passing gaseous 
 hydrogen chloride into a mixture of 1 vol. alde- 
 hyde and 2 vol. absolute alcohol, cooled by a freez- 
 ing mixture, whereby the compound C^HjClO 
 is obtained, as an ethereal liquid floating on the 
 
 B 2 
 
ACETAL. 
 
 aqueous hydrochloric acid, and treating this 
 compound with sodium ethylate: 
 
 C„H,0 + aH„0 + HCl = H,0 + C^HsClO ; 
 
 and OjHjCib + CjHjONa = NaCl + CsHnO^ 
 
 (Wurtz a. FrapoUi, O. B. 47, 418 ; A. 108, 223). 
 
 2. By treating aldehyde with PBrj, whereby it is 
 converted into ethylidene bromide, and acting on 
 this compound with sodium ethylate : 
 
 CHMeBr2+ 2NaOEt = 2NaBr + CHM:e{0Et)2 
 (W. a. P.). 
 
 Properties. — Colourless liquid, less mobile 
 than ether, having a peculiar agreeable odour 
 and refreshing taste, with an after-taste like that 
 of hazel-nuts. Separated from aqueous solution 
 by calcium chloride and other soluble salts. 
 Misoible with ether or alcohol. 
 
 Reactions. — 1. Not altered by mere exposure 
 to air, but quickly oxidised in contact with j>la- 
 tinum-black to aldehyde and acetic acid. Oxi- 
 dised also by nitric and by chromic acid. — 2. Not 
 decomposed by caustic alkalis if air is excluded. 
 
 3. Forms substitution-products with chlorine. 
 
 4. Strong sulphuric and hydrochloric acids dis- 
 solve and decompose it, the mixture turning 
 black. — 5. Dilute acids, even in the cold, split up 
 acetal into alcohol and aldehyde. — 6. A solution 
 of acetal does not give the iodoform reaction, 
 unless it be first acidified (Grodzki, B. 16, 512). 
 7. PCI5 forms CH,.CHC1.0Et, EtCl and POCl, 
 (Buchanan, A. 218, 38). — 8. Heated with glacial 
 HOAc it forms acetic ether, thus : 
 
 CH3.CH(0Et)2 + 2AcOH = 
 CH5CHO + HjO -I- 2AcOEt. 
 9. Does not reduce AgNOjAq. — 10. Chromic 
 mixture forms acetic acid. — 11. Heated with 
 MeOH it is almost completely converted into 
 EtOH and CHsCH(0Me)2.— 12. Heated with 
 PrOH it is mostly unchanged, but some 
 CH3.CH(0Et)(0Pr) and some CH3CH(OPr)2 are 
 formed. — 13. Heated with iso-amyl alcohol it 
 behaves as in 12. 
 
 Beferences. — Homologues of acetal are de- 
 scribed under the aldehydes, to which they cor- 
 respond. Bromo- and chloro-aoetals are described 
 under bromo- and chloro-acetic aldehyde. For 
 oiy-acetal v. glycoUic aldehyde. 
 
 ACETALDEHYDS v. AiEEHYDE. 
 
 ACETAMIDE C2H5NO i.e. NH^Ao or 
 CH3.CO.NH2 — ^Amide of acetic acid. M.w. 59. 
 [83°] (Hofmann, B. 14, 2729) (222° cor.). S.G. 
 , 1-159 (Schroder, B. 12, 562). Eoo 24-35 in a 
 34-p.c. aqueous solution (Kauonnikoff, J. pr. [2] 
 31, 347). Discovered by Dumas, Malaguti, and 
 Leblano in 1847 (O. B. 25, 657). 
 
 Formation. — 1. By heating ethyl acetate with 
 strong aqueous ammonia at 120° 
 
 AoOEt -h NH3 == AcNHj + HOEt. 
 
 2. By action of ammonia on acetic anhydride : 
 
 Ac^O + 2NH3 = NH^Ac + AcONH,. 
 
 3. By distillation of ammonio acetate : 
 AcONH, = AcNHj-(-H20 (Kundig, A. 105, 277). 
 
 4. When dry NaOAo (580 g.) is distilled with 
 NHjCl (225 g.) very little acetamide (70 g.) is 
 got : the distillate is chiefly NH, and acid am- 
 monic acetate, which boils at 145°. 
 
 Preparation. — 1. Acetic ether and aqueous 
 ammonia are left in a closed vessel until the ether 
 has disappeared. The product is distilled. — 
 2. Glacial acetic acid (1 kilo.) is saturated with 
 dry NHj and the product distilled in a current 
 of dry NH,. Above 190° acetamide (460 g.) comes 
 
 over ; the first distillate (below 190°) is treated 
 in the same way : it gives more acetamide (170 g.). 
 A third repetition of this operation gives more 
 acetamide (110 g.). Total yield : 740 g. (EeUer, 
 J. pr. [2] 31, 364). — 3. Ammonio chloride and 
 Bodio acetate are heated in an enamelled iron 
 digester for six hours at 230^. The product is 
 distilled (Hofmann, B. 15, 981).— 4. A mixture 
 of ammonio acetate (20 g.) and acetic anhydride 
 (26 g.) yields on distillation 96 p.c. (12 g.) of 
 acetamide (Schulze, J.pr. [2] 27, 512).— 5. Am- 
 monio sulphocyanide (1 mol.) is boiled for four 
 days with glacial acetic acid (2| mols.) : 
 NH4CNS + 2AcOH = 2ACNH2 -^ COS + H^O (S.). 
 
 Purification. — Acetamide can be freed from 
 ammonic acetate by drying over lime (Mensohut- 
 kin, J. B. 17, 259). 
 
 Properties. — White hexagonal scales, smell- 
 ing like excrement of mice. Deliquescent. V. 
 e. sol. water. Conducts electricity and is easily 
 electrolysed. 
 
 Beactions. — 1. Eesolved by distillation with 
 P2O5 into water and acetonitrUe, CjHjN. — 2. With 
 P2S5 it also yields aeetonitrile, giving off H^S, and 
 leaving a blackish tumefied residue. — 3. Heated 
 in dry HCl-gas it yields : a. A liquid distillate 
 consisting of acetic acid with a small quantity 
 of acetyl chloride ; b. A- crystalline distillate of 
 (C2H5N0)2HC1, and a compound of acetamide 
 and diacetamide OjHjNO.CjHiNOj, the latter of 
 which may be dissolved out by ether ; c. A non- 
 volatile residue of acetamidine hydrochloride 
 mixed with sal-ammoniac : 
 
 2C2H5NO + HCl = C2HeNj,.HCl + CjH.Oj 
 (Streeker, A. 103, 328).— 4. Acetamide heated 
 in sealed tubes with saturated hydriodic acid 
 yields ammonia, acetic acid, and ethane : 
 
 2O2H5NO + 3H2 = CjH.Oj + 2NH3 + CjH, 
 (Berthelot, Bl. [2] 9, 183).— 5. With CSj at 
 about 210° it gives off H^S, COS, CO, and pro- 
 bably ethane, leaving ammonium sulphocyanide 
 mixed with undecomposed acetamide : 
 
 2CJH5NO + CSj = NHj.SCN + COS + CO + C^ 
 (Ladenburg, Z. [2] 4, 651). V. Aldehtdes. — 
 6. Nascent hydrogen (copper-zinc couple or 
 sodium-amalgam) forms some alcohol^nd alde- 
 hyde (Essner, Bl. [2] 42, 98).— 7. Heated with 
 NaOEt at 180° it forms ethylamine (Seifert, B. 
 18, 1357).— 8. With ethyl orthofcyrmate at 180° 
 acetamide yields ethyl alcohol and diacetyl- 
 formamidine : 
 
 2NH2AC + CH(OEt), = 3EtOH + N2(CH) Ao,,H. 
 Another reaction, however, takes place at the 
 same time, producing alcohol, ethyl acetate, and 
 formamidine : 
 
 2NH2Ao + CH(OEt)3 = 
 
 EtOH -I- 2EtOAc + Nj(CH)H, 
 
 (WicheUiaus, B. 3, 2). — 9. Acetamide heated in 
 
 sealed tubes with hensaldehyde is converted into 
 
 benzylidene-diaeetamide : 
 
 2NH2A0 -I- PhCOH = HjO + PhCH(NHAc);. 
 With aldehyde in like manner, it yields 
 MeCH(NHAc)2 in large prisms [169°], partly de- 
 composed by distillation, and giving off aldehyde 
 when treated with acids (TawUdarow, B. 5, 477). 
 With anisaldehyde the compound Ci^HijNjO, is 
 formed in nodular groups of needles [180°], sol- 
 uble in water, insoluble in alcohol and ether, 
 decomposed by HCl, not altered by boiling with 
 potash (Schuster, Z. [2] 6, 681). With salicylic 
 aldehyde a yellow lieutral body is formed (Cred- 
 
AUJiTAMIDINE. 
 
 ner, ib. 80). With chloral aoetamide unites 
 directly, forming the crystalline compound 
 OjHjNO.CjHCljO. («.Ohlokal).— 10. Heated with 
 mesityl oxide it forms a basic substance, OgHuNO, 
 ' oxy-hydro-collidine.' A yellowish liquid 
 (175°-180°) (Canzoneri a. Spica, G. 14, 349). 
 
 Combinations. — Aoetamide unites directly 
 with the stronger acids. The hydrochloride 
 (NH2Ao)2HCl is formed by passing gaseous HGl 
 into its solution in ether-alcohol. Long needles 
 (from alcohol) ; insol. in ether. — NH2ACHOI 
 (Pinner a. Klein, S. 10, 1P96).— The nitrate, 
 NHjAcHNOs [98°], separates from a solution 
 of aoetamide in strong HNO3. It is very acid, 
 and is deliquescent. SI. sol. ether. Gives off 
 COj, NjO and HNO3 when heated. 
 
 SaZis.— AcNHAg. Scales.— (AcNH)2Hg. Six- 
 sided prisms [195°]. Both formed by dissolving 
 the oxides in aoetamide. — (AoNH)2Zn. From 
 ZnEtj and aoetamide. Amorphous. (Frankland.) 
 
 Chloro-acetamides. — The amides of the chloro- 
 acetic acids are described under those acids. 
 Aceto-chloro-amide NAoClH [110°]. is formed 
 by passing chlorine into fused aoetamide, or by 
 pouring aqueous HCl upon aoeto-bromo-amide ■ 
 
 2NAoBrH + HCl = NAcClH + NAcH^ + Br,, 
 (Hofmann, B. 15, 410). Sol. ether. Split up 
 by HCl into chlorine and aoetamide. 
 
 Bromo-aoetamideB v. Bbomo-acetio acids. 
 
 Aceto-bromo-amide 
 NHBrAo [108°]. NHBrAc aq. [70°-80°]. 
 Formed by adding aqueous KOH to a solution of 
 Br (1 mol.) in aoetamide (1 mol.). Striated 
 rectangular plates (from ether). 
 
 Reactions. — 1. Boiled with water it forms 
 aoetamide, Br, HBrO, methyl-acetyl-urea, and 
 methylamine. — 2. Heated with AgjCOj it forms 
 methyl cyanate : 
 
 2CH3.CO.NHBr -I- Ag,C03 = 
 2CH3NCO + 2AgBr + CO2 + H^O. 
 3. Boiled with KOHAq it forms HBr, CO^, and 
 methylamine, the methyl cyanate formed ac- 
 cording to the last reaction being decomposed 
 in the usual way. — 4. Aoetamide and NaOHAq 
 form methyl-acetyl-urea. — 5. Ammonia reacts 
 violently, thus : 
 
 SNAcHBr + 5NH3 = SNAoH^ + 3NH,Br + N^. 
 6. Aniline forms acetanilide and tri-bromo- 
 aniline. — 7. Phenol gives tri-bromo-phenol and 
 aoetamide (Hofmann, B. 15, 407). 
 
 Salts. — NAcBrNa. Hair-like needles, ppd. 
 bycono.NaOH. NAcBrNaBr^aq. Made by adding 
 cono. NaOH to a mixture of aoetamide (1 mol.) 
 and bromine (1 mol.). Eectangular plates. De- 
 composed by water into NaBr and aceto-di- 
 bromo-amide. 
 
 Aceto-di-bromo-amide NAcBr^ [100°]. 
 Madeby adding aqueous KOH to a dUute solution 
 of bromine (Imol.)andbromo-acetamide (Imol.) 
 (Hofmann, B. 15, 413). Golden needles or plates ; 
 sol. warm water, alcohol, or ether. Boiled with 
 water, it gives HBrO, NAoBrH, and NAcHj. 
 Potash decomposes it into nitrogen, acetic acid 
 and potassio hypobromite. H. W. 
 
 Bromo-chloro-acetamide v. Chlobo-bbomo- 
 
 AOBIIC ACID. 
 
 lodo-acetamide v. Iodo-aoeiic acid. 
 
 Di-aoetamide NAc^H. M.w. 180 [82°] (210°- 
 215°). 
 
 Preparaticm, — 1. The ethereal solution of 
 the crystalline compound of aoetamide and di- 
 
 aoetamide got by heating aoetamide in a current 
 of HCl {v. Reaction 3), deposits, when gaseous 
 HCl is passed through it, spicular crystals of 
 aoetamide hydrochloride, and the filtrate yields, 
 by evaporation over HjSOj, crystals of diaceta- 
 mide. — 2. By heating acetonitrile with glacial 
 HOAo, or aoetamide with AcO at 250° (Gautier, 
 Z. 1869, 127).— 3. By boiling' methyl-acetyl-urea 
 with AOjO (Hofmann, B. 14, 2731). 
 
 Properties. — Long needles (from ether). 
 Neutral. V. e. sol. water, v. sol. alcohol or ether. 
 Does not combine with acids, so that HCl gives 
 no pp. in an ethereal solution. 
 
 Reactions. — 1. By boiling with acids or by 
 heating with ZnClj it is resolved into acetic acid 
 and aoetonitril. — 2. Fuming HNO3 reacts, giving 
 off NjO. H. W. 
 
 Tri-aoetamide NA03 [79°]. — Formed in small 
 quantity when a mixture of acetic anhydride and 
 acetonitrile is heated to 200°, and may be dis- 
 solved out by ether after the excess of AcjO has 
 been distilled off. White flexible needles [78°- 
 79°]. Neutral. Gently warmed with silver oxide 
 it yields silver acetate ; so likewise do aoeta- 
 mide and diacetamide (Wichelhaus, B. 3, 847). 
 
 H. W. 
 
 Tri-acet-di-amide NjAcsH, [212°-217°]. — 
 This is the compound of aoetamide and di-aoet- 
 amide mentioned under aoetamide {Reaction 3) 
 and di-acetamide (Preparation 1). 
 
 Di-azo-acetamide v. Azo compounds. 
 
 Ethyl-aoetamide v. Ethyl-amine. 
 
 Methyl-acetamide v. Methyl-amine. 
 
 Phenyl-acetamide v. Aniline. 
 
 ACET-. — If compounds whose names begin 
 with acet or aceto are not here described, remove 
 this prefix and look for the remaining word, 
 changing the termination ide, if present, into ine. 
 
 ACETAMIDINE C^H^N^ i.e. CH3.C(NH).NH2 
 Acediamine, Ethenyl-amidine, Acet-imid-amide 
 (Streoker, A. 103,828; Hofmann, B. 17, 1924).— 
 The hydrochloride of this base is left as a residue 
 when aoetamide is distilled in a current of HCl 
 {v. Aoetamide, Reaction 3) . The mass is extracted 
 with alcohol, which leaves NH,C1 behind. 
 
 Properties. — When liberated from solutions 
 of its salts, it splits up into ammonia and am- 
 monic acetate. 
 
 Salts. -'B'B.Cl: prisms (from alcohol), [165°]. 
 — (B'HClJzPtCl, : yellowish-red prisms. 
 — B'2H,S04 : pearly lamina. 
 
 Reactions. — 1. The hydrochloride boiled with 
 AO2O and NaOAo for Ig hours forms anhydro- 
 di-aoetyl-acet-amidine and anhydro-di-acetyl- 
 acet-amidil (Pinner, B. 17, 173).— 2. V. Aceio- 
 ACETic ETHEK, Reaction 25. 
 
 Anhydro - di - acetyl - aoetamidine O^HgNjO 
 [253°]. — Prepared as just stated, the product 
 being treated with aqueous NaOH and the pp. 
 boiled with water, which dissolves the ' amidil,' 
 but not the amidine. 
 
 Silky needles (from alcohol). Insol. water, 
 si. sol. cold alcohol, v. sol. hot alcohol, v. e. soL 
 dilute acids. Forms a platino-chloride. 
 
 Anhydro-di-acetyl-aoet-amidil OsH, ,N302aq. 
 //N . C . CH3 
 CH3.Cf 
 Possibly ^N 
 
 CH3.cf 
 
 \nh.co.ch 
 
 [185°]. Obtained as above. Nodules of small 
 
6 
 
 ACETAMIDINE. 
 
 prisms. Loses 2aq over H^SO^. SI. sol. cold 
 ■water, v. sol. hot water, v. e. sol. alcohol and in 
 dilute acids. Forms a platinum salt. 
 
 ACETAHIDOXIII V. Ethentl-amieoxim. 
 
 ACETANILISE v. AaiLisE Acetyl deiiva- 
 tive. 
 
 ACETIC ACID OjHjOj i.e. CH3.CO.OH or 
 XoOB..^Methane earboxylic acid, PyroUgneous 
 acid.— M.W. 60 [16-5°] (Zander), [17-5°] (Sonstadt, 
 C. N. 37, 199). (118-29°) (Z.), (117-5°) (SohifE.). 
 Critical tenvperature 321-5° (Pawlewsky, B. 16, 
 2634). S.G. Solid, g 1-0701 (Z.) ; V 1"0607 
 (MendeUefE, J. 1860, 7). S.G. Lictwid. i^ 1-0576, 
 ¥ 1-0543, W 1-0503 (Pettersson, J. pr. [2] 24, 
 301) ; =5° 1-0495 (Briihl) ; at boiling-point -9325 
 (Ramsay, C. J. 35, 463). V.D. 29-7 at 250° and 
 upwards. C.B. (0°-10°) -00106 (Z.). H.F.p. 
 105,290. H.F.V. 104,130. S.H. (between 0° and 
 100°) -497. Latent heat of fusion for 1 mol. (at 
 1-5° to 4-2°) 2619. fi-fi 1-3765. Bo, 20-69 (B.). 
 M.M. 2-525 (Perkin). S.V. 64-3 (E^. 
 
 Occurrence. — In the j uices of plants, especially 
 of trees, and in certain animal secretions. 
 
 Synthesis. — 1. From acetylene (i.e. from C 
 and H) by converting that hydrocarbon into 
 ethylene by direct addition of hydrogen, then 
 the ethylene into alcohol, and oxidising the 
 alcohol ; or more simply by heating acetylene 
 dichloride with aqueous potash at 230° or with 
 alcoholic potash at 100° for ten hours: 
 
 CjH^Clj + 3KH0 = CjHsO^E + 2KC1 + H^O 
 (Berthelot,. Z. [2] 5, 683).— 2. When a mixture, 
 1 vol. acetylene and 2 vols, air, is exposed to 
 daylight over dilute potash-lye, the acetylene is 
 slowly oxidised to acetic acid, which is absorbed 
 by the alkali : C^H^ + + KOH = C2H3O2K (Ber- 
 thelot, A. Ch. [4] 23, 212).— 8. From sodium- 
 methyl and carbonic acid : 
 
 CHaNa + CO2 = CH3.C0jNa 
 
 (Wanklyn, A. Ill, 234). — 4. By boiling aceto- 
 nitrile (methyl cyanide) with potash : 
 
 CH3CN + KOH + R.fl = CH3CO2K + NH3 
 (Frankland a. Kolbe, A. 65, 298). — 5. By passing 
 CO over sodium methylate at 160° : 
 
 CH30Na + CO = CHjCOjNa 
 
 (Frohlich, A. 202, 294). 
 
 Formation. — 1. By dry distillation of organic 
 bodies, especially wood.— 2. By the action of 
 atmospheric oxygen, chromic acid, nitric acid, 
 hypochlorous acid, and other oxidisers, on al- 
 cohols and other organic bodies, especially under 
 the influence of ferments which act as carriers 
 of oxygen. — 3. By the action of EOH or NaOH 
 at a high temperature on various organic bodies, 
 e.g. tartaric, citric, and malic acids, sugar, alco- 
 hol, &c. — 4. In various processes of fermentation 
 and putrefaction {J. 1878, 1017, 1019, 1023). 
 
 Preparation. — 1. By oxidation of ethyl al- 
 cohol, the alcohol being first converted into 
 aldehyde: C^H^O + = H^O -H C^HjO, and the 
 aldehyde then oxidised to acetic acid. The oxi- 
 dation may be effected : 
 
 a. By the influence of spongy platinum. If 
 a tray containing this substance be placed over 
 a dish containing a little alcohol, the whole 
 being covered with a bell-glass open below as 
 weU as at the top, on gently warming the dish 
 the alcohol will be rapidly oxidised, acetic >>,cid 
 sondensiug in abundance on the inside of the 
 
 jar. Much of the alcohol is, however, converted 
 into aldehyde and lost by volatilisation. 
 
 6. Under the influence of ferments. This is 
 the ordinary process of making vinegar from 
 alcohoUo liquids, vrine being generaUy used for 
 the purpose in France and Germany, and malt in 
 England. The most favourable temperature is 
 25°-30°. The experiments of Pasteur have 
 shown that the oxidation of alcohol in the ordi- 
 nary process of vinegar-making depends essen- 
 tially on the presence of a fungoid plant called 
 Mycoderma mm, Mycoderma aceti, or ' mother- 
 of-vinegar,' and is invariably preceded by its 
 development on the surface of the liquid. It 
 appears to act like platinum-black, as a carrier 
 of oxygen. The plant may be sown on the sur- 
 face of the liquid by introducing a small portion 
 of it from another vinous liquid already in the 
 fermenting state, or by simply exposing the 
 liquid to the air in which the germs of this 
 fungus, as of many others, are always floating. 
 Like all other plants, it requires food for its de- 
 velopment, and this it finds in the albuminous 
 matter and mineral salts contained in ordinary 
 vinous liquors. If these are absent the plant 
 cannot grow, and acetification cannot take place. 
 Thus, pure aqueous alcohol may be exposed to 
 the air for any length of time vrithout turning 
 acid, because the germs of the mycoderma which 
 fall into it from the air remain barren for want 
 of nutriment. Moreover, pure aqueous alcohol 
 may be acetified without the aid of any albu- 
 minous matter, provided the mycoderma have 
 access to it, and be supplied with the nitrogen 
 and saline matters necessary for its growth. 
 Pasteur has in fact shown that this nutriment 
 may be supplied in the form of alkaline and 
 earthy phosphates and aumionium phosphate, 
 the latter furnishing the nitrogen. Under these 
 circumstances the mycoderm grows, though less 
 quickly than in ordinary vinous liquids, and the 
 alcohol is slowly converted into acetic acid. If 
 the mycoderma be allowed to remain in the liquid 
 after the acetification is complete, the whole of 
 the acetic acid may be destroyed and the liquid 
 rendered perfectly neutral. (Pasteur, Etudes sur 
 le Vimaigre, Paris, 1868 ; also Annates ScienO- 
 flques de I'&ole normale supiriewre, tome i. 
 1864 ; Bl. 1861, p. 94 ; J. 1861, 726.) 
 
 Malt Vinegar is prepared from a fer- 
 mented wort obtained by mashing malt, or a 
 mixture of malt and raw barley, vrith water, as 
 in brewing. 
 
 Quick Vinegar Process. — The oxidation of the 
 alcoholic liquor may be greatly accelerated by 
 allowing it to trickle down in a fine shower over 
 chips of wood covered by the mycoderma, and 
 exposed to an upward current of air. 
 
 Wood Vinegar — Pyroligneoxis Acid. — The 
 greater part of the acetic acid now used in arts 
 and manufactures is obtained by the destructive 
 distillation of wood. The wood is heated in large 
 iron cylinders connected with a series of con- 
 densers. The watery liquid which condenses in 
 the receivers, consisting of water, tar, methyl 
 alcohol or wood-spirit, methyl acetate and aoetio 
 acid, is redistilled after separation of the tar, 
 the wood-spirit passing over among the first 
 portions of the distillate and the acetic or pyro- 
 ligneous acid afterwards. The acid thus ob- 
 tained is coloured and has a strong tarry flavour, 
 
ACETIC ACID. 
 
 not removable by distillation. To purify it, 
 the crude liquor is saturated with lime, which 
 removes part of the tarry matter, the rest re- 
 maining in solution with the calcium acetate. 
 The liquid, clarified by repose or by filtration, is 
 evaporated in an iron pot to half its bulk, and 
 mijted with enough hydrochloric acid to give a 
 slight acid reaction, whereupon the greater part 
 of the tarry matter separates, andmay b&skimmed 
 off the surface. The hydrochloric acid also de- 
 composes certain compounds of lime with creo- 
 sote and other volatile substances, which may 
 then be expelled by heat. The calcium acetate 
 thus purified is completely dried and distilled 
 with hydrochloric acid. The density of the 
 acetic acid thus obtained is about 1-06. If it 
 contains hydrochloric acid it may be purified by 
 redistillation with addition of a small quantity 
 of sodium carbonate, or, better, 2 or 3-p.o. potas- 
 sium dichromate, this latter at the same time 
 destroying certain organic impurities which give 
 the acid a peculiar odour (Volckel, A. 82, 49). 
 Crude wood vinegar contains small quantities of 
 propionic, ji.-butyrio, Ji-valeric, and two orotonic 
 acids (Grodzki a. Kramer, B. 11, 1356). 
 
 Crystallisable or Qlacial Acetic Acid 
 — the pure acid, C^HjOj, so-called because it 
 crystallises at ordinary temperatures — is ob- 
 tained : 1. From the ordinary aqueous acid by 
 fractional distillation, repeated tiU. the residue 
 solidifies on cooling. 2. By distilling certain 
 dry metallic acetates with strong sulphuric acid 
 or with hydrogen potassium sulphate, 
 
 2C2H3KO2 + H,SO, = K^SO, + 20,H,0j ; 
 and OjHaKOj + HKSO^ = K,SO, + C^H A- 
 3. Together with acetone and other products, 
 by dry distUlation of cupric acetate (SpiriUis 
 ^ruginis or Sp. Veneris). 
 
 Physical Properties. — The solid acid forms 
 prismatic or tabular crystals. The liquid acid 
 is transparent, colourless, and mobile. Vapour- 
 density at 250° and upwards is 2-08 (air = 1) or 
 29-7 (H = l), which is nearly half the molecular 
 weight of the acid, showing that at these high 
 temperatures the vapour exhibits the normal 
 condensation. But at temperatures nearer to 
 the boiling-point the density of the vapour is 
 much greater, showing a condensation to | vol. 
 or even less (Cahours, 0. B. 19, 771 ; 20, 51). 
 The pressure of the vapour of solid acetic acid 
 is 1-3 mm. at— 5-7°, 2-0 mm. at 0°, and 9-5 mrn. 
 at 16-4° ; the vapour-pressure of liquid acetic 
 acid being 3-2 mm. at 0°, 6-3 mm. at 10°, 11-8 
 mm. at 20°, 19-9 mm. at 30° (Eamsay a. Young, 
 C. J. 47, 45). 
 
 Glacial acetic acid has a pungent sour taste 
 and odour and blisters the skin. It does not 
 redden litmus paper per se, but reddens it 
 strongly when mixed with water. It does not 
 attack CaCOa until water is added. It is hygro- 
 scopic. 
 
 Aqueous Acid. — Acetic acid mixes with 
 water in all proportions. The density of the 
 aqueous acid does not vary in proportion to the 
 amount of real acid present ; and consequently 
 the strength of any sample cannot be inferred 
 from its density, but must be determined by 
 titration with standard alkali. The following 
 table has been constructed in this manner by 
 Oudemans (Fr. 5, 452) for the temperatures 0°, 
 15°, and 40°. 
 
 Density of Aqueous Acetic Acid (Oudemans). 
 
 C.HA 
 
 Density 
 
 p. 0. 
 
 atO° 
 
 at 16° 
 
 at40» 
 
 
 
 0-9999 
 
 0-9992 
 
 0-9924 
 
 1 
 
 1-0016 
 
 1-0007 
 
 0-9936. 
 
 2 
 
 1-0033 
 
 1-0022 
 
 0-994» 
 
 3 
 
 1-0051 
 
 1-0037 
 
 0-996O. 
 
 4 
 
 1-0069 
 
 1-0052 
 
 0-997a 
 
 5 
 
 1-0088 
 
 1-0067 
 
 0-9984 
 
 6 
 
 1.0106 
 
 1-0083 
 
 0-9996. 
 
 7 
 
 1-0124 
 
 1-0098 
 
 1-0008 
 
 8 
 
 1-0142 
 
 1-0113 
 
 1-0020 
 
 9 
 
 1-0159 
 
 1-0127 
 
 1-0032 
 
 10 
 
 1-0176 
 
 10142 
 
 1-0044 
 
 11 
 
 1-0194 
 
 1-0157 
 
 1-0056 
 
 12 
 
 1-0211 
 
 1-0171 
 
 1-0067 
 
 13 
 
 1-0228 
 
 1-0185 
 
 10079 
 
 14 
 
 1-0245 
 
 1-0200 
 
 1-0090 
 
 15 
 
 1-0262 
 
 1-0214 
 
 1-0101 
 
 16 
 
 1-0279 
 
 1-0228 
 
 1-0112 
 
 17 
 
 1-0295 
 
 1-0242 
 
 1-0123 
 
 18 
 
 1-0311 
 
 1-0256 
 
 1-0134 
 
 19 
 
 1-0327 
 
 1-0270 
 
 1-0144 
 
 20 
 
 1-0343 
 
 1-0284 
 
 1-0155 
 
 21 
 
 1-0359 
 
 1-0298 
 
 1-0166 
 
 22 
 
 1-0374 
 
 1-0311 
 
 1-0176 
 
 23 
 
 1-0390 
 
 1-0324 
 
 1-0187 
 
 24 
 
 1-0405 
 
 1-0337 
 
 1-019T 
 
 25 
 
 1-0420 
 
 1-0350 
 
 1-0207 
 
 26 
 
 1-0435 
 
 1-0B63 
 
 1-021T 
 
 27 
 
 1-0450 
 
 1-0375 
 
 1-022T 
 
 28 
 
 1-0465 
 
 1-0388 
 
 1-0236 
 
 29 
 
 1-0479 
 
 1-0400 
 
 1-0246. 
 
 30 
 
 1-0493 
 
 1-0412 
 
 1-0255. 
 
 31 
 
 1-0507 
 
 1-0424 
 
 1-0264. 
 
 82 
 
 1-0520 
 
 1-0436 
 
 1-0274 
 
 33 
 
 1-0534 
 
 1-0447 
 
 1-0283 
 
 34 
 
 1-0547 
 
 1-0459 
 
 1-0291 
 
 35 
 
 1-0560 
 
 1-0470 
 
 l-030» 
 
 36 
 
 1-0573 
 
 1-0481 
 
 l-030a 
 
 37 
 
 1-0585 
 
 1-0492 
 
 1-0316 
 
 38 
 
 1-0598 
 
 1-0502 
 
 1-0324 
 
 39 
 
 1-0610 
 
 1-0513 
 
 1-0332 
 
 40 
 
 1-0622 
 
 1-0523 
 
 1-0340 
 
 41 
 
 1-0634 
 
 1-0533 
 
 1-0348 
 
 42 
 
 1-0646 
 
 1-0543 
 
 1-0355 
 
 43 
 
 1-0657 
 
 1-0552 
 
 1-0363 
 
 44 
 
 1-0668 
 
 1-0562 
 
 1-0370 
 
 45 
 
 1-0679 
 
 1-0571 
 
 1-0377 
 
 46 
 
 1-0690 
 
 1-0580 
 
 1-0384 
 
 47 
 
 1-0700 
 
 1-0589 
 
 1-0391 
 
 48 
 
 1-0710 
 
 1-0598 
 
 1-039T 
 
 49 
 
 1-0720 
 
 1-0607 
 
 1-0404 
 
 50 
 
 1-0730 
 
 1-0615 
 
 1-0410 
 
 51 
 
 1-0740 
 
 1-0623 
 
 1-0416 
 
 52 
 
 1-0749 
 
 1-0631 
 
 1-0423 
 
 53 
 
 1-0758 
 
 1-0638 
 
 1-0429- 
 
 54 
 
 1-0767 
 
 1-0646 
 
 1-0434 
 
 55 
 
 1-0775 
 
 1-0653 
 
 1-044O 
 
 56 
 
 1-0783 
 
 1-0660 
 
 1-0445 
 
 57 
 
 1-0791 
 
 1-0666 
 
 1-0450 
 
 58 
 
 1-0798 
 
 1-0673 
 
 1-0455 
 
 59 
 
 1-0806 
 
 1-0679 
 
 1-046O 
 
 60 
 
 1-0813 
 
 1-0685 
 
 1-0464 
 
 61 
 
 10820 
 
 1-0691 
 
 1-0468 
 
 62 
 
 1-0826 
 
 1-0697 
 
 1-0472 
 
 63 
 
 1-0832 
 
 1-0702 
 
 1-0475 
 
ACETIC ACID. 
 
 CJt.0. 
 
 Density 
 
 p. u. 
 
 atO" 
 
 at 15° 
 
 at 40° 
 
 64 
 
 1-0838 
 
 1-0707 
 
 1-0479 
 
 S5 
 
 1-0845 
 
 1-0712 
 
 1-0482 
 
 86 
 
 1-0851 
 
 1-0717 
 
 1-0485 
 
 67 
 
 1-0856 
 
 1-0721 
 
 1-0488 
 
 68 
 
 1-0861 
 
 1-0725 
 
 1-0491 
 
 69 
 
 1-0866 
 
 1-0729 
 
 1-0493 
 
 70 
 
 1-0871 
 
 1-0733 
 
 1-0495 
 
 71 
 
 1-0875 
 
 1-0737 
 
 1-0497 
 
 72 
 
 1-0879 
 
 1-0740 
 
 1-0498 
 
 73 
 
 1-0883 
 
 1-0742 
 
 1-0499 
 
 74 
 
 1-0886 
 
 1-0744 
 
 1-0500 
 
 75 
 
 1-0888 
 
 1-0746 
 
 1-0501 
 
 76 
 
 1-0891 
 
 1-0747 
 
 1-0501 
 
 77 
 
 1-0893 
 
 1-0748 
 
 1-0501 
 
 78 
 
 1-0894 
 
 1-0748 
 
 1-0500 
 
 79 
 
 1-0896 
 
 1-0748 
 
 1-0499 
 
 80 
 
 1-0897 
 
 1-0748 
 
 1-0497 
 
 81 
 
 1-0897 
 
 1-0747 
 
 1-0495 
 
 82 
 
 1-0897 
 
 1-0746 
 
 1.0492 
 
 83 
 
 1-0896 
 
 1-0744 
 
 1-0469 
 
 84 
 
 1-0894 
 
 1-0742 
 
 1-0485 
 
 85 
 
 1.0892 
 
 1-0739 
 
 1-0481 
 
 86 
 
 1-0889 
 
 1-0736 
 
 1-0475 
 
 87 
 
 1-0885 
 
 1-0731 
 
 1-0469 
 
 88 
 
 1-0881 
 
 1-0726 
 
 1-0462 
 
 89 
 
 1-0876 
 
 1-0720 
 
 1-0455 
 
 90 
 
 1-0871 
 
 1-0713 
 
 1-0447 
 
 91 
 
 — 
 
 1-0705 
 
 1-0438 
 
 92 
 
 — 
 
 1-0696 
 
 1-0428 
 
 93 
 
 — 
 
 1-0686 
 
 1-0416 
 
 94 
 
 — 
 
 1-0674 
 
 1-0403 
 
 95 
 
 — 
 
 1-0660 
 
 1-0388 
 
 96 
 
 — 
 
 1-0644 
 
 1-0370 
 
 97 
 
 
 
 1-0625 
 
 1-0350 
 
 98 
 
 — 
 
 1-0604 
 
 1-0327 
 
 99 
 
 . — 
 
 1-0580 
 
 1-0301 
 
 100 
 
 — 
 
 1-0553 
 
 1-0273 
 
 The maximum density corresponds at 0° to 
 about 81 P.O., and at 40° to about 76 p.c. Ortho- 
 acetic acid, CH3C(OH)3, would contain 77 p.c. of 
 HOAc. 
 
 BeacUons. — 1. Vapour inflammable, burning 
 with blue flame to water and COj. — 2. Partly 
 decomposed by passing through a red-hot tube 
 yielding carbon and combustible gases, together 
 with acetone, benzene, phenol, and naphthalene 
 (Berthelot, A.Ch. [3] 33, 295).— 3. Dropped upon 
 hot ZnCl, it gives CO, CO.^, C^B.,, CsHj, isobu- 
 tylene, and a little CHj (Lebel a. Greene, Am. 2, 
 26).— 4. Passed over zinc dust at 300°-350° it 
 gives hydrogen, acetone, CO, and some propylene 
 (Jahn, M. 1, 683). — 5. Mixes with strong sul- 
 phuric acid without evolution of gas, but the 
 mixture becomes hot, and if further heated 
 gives off CO2 mixed with SOj. Dissolves SO3 
 without giving oB gas, forming sulpho-acetio 
 acid. Not sensibly altered by nitric acid. — 6. 
 Periodic acid converts it into carbonic or formic 
 acid, with formation of iodic acid and separation 
 of iodine. — 7. With chlorine in sunshine it forms 
 mono- and tri-chloro-aoetio acids (3. v.), the 
 one or the other predominating according as 
 the acetic acid 01 the chlorine is in excess. — 8. 
 Eeated with bromine in a sealed tube it forms 
 mono- and di-bromo-acetic acide. Hot acted upon 
 
 by iodine, even in sunshine. — 9. With PCI, it 
 forms AcCl, HOI, and POCI3. With PCI3 it reacts 
 thus : 3AcOH + 2PCI3 = 3AcCl -I- PA + 3H01.— 
 
 10. With P2S5 theproducts arethio-acetic acid and 
 phosphoric oxide: 5AcOH -I- P2S5 = PA + SAoSH. 
 
 11. With chromyl dichloride CrOaCl^ it forma 
 the compound Cr,0,(C2H302)i„8H20 (Etard, A. 
 Ch. [5] 22, 286). 
 
 Detection. — The solution supposed to contain 
 acetic acid or an acetate is acidified with 
 H2SO4 and distilled. The distillate, if acid, is 
 neutralised with KOH and should then give the 
 following tests : (1) FeCl, a brown-red colour, 
 and a pp. on boiling. (2) AgNO, a white floccu- 
 lent pp., sol. hot water, separating in spangles 
 when the solution cools. (3) Evaporate to dry. 
 ness, mix with AsA ^^^ heat; a disgusting 
 odour of caoodyl is perceived. 
 
 Acetic Acid Dibromide G^B.fli.Bi^ [37°] ia 
 formed on treating acetic acid with bromine in 
 presence of a small quantity of carbon bisulphide. 
 Orange-red needles or thick roseate prisma, very 
 deliquescent ; dissolving in water with great fall 
 of temperature and separation of bromine, in 
 alcohol, benzene, and glacial acetic acid with 
 partial formation of substitution-products. At 
 100° dissociation first takes place, but finally 
 HBr and CjHjBrOj are formed. 
 
 Compounds of acetic acid with Br and HBr. 
 On adding bromine to well-cooled glacial acetic 
 acid saturated with HBr, the whole solidifies to 
 a mass of thick, rather large, tabular, crystals, 
 which when dried have the composition 
 {02ll.fi^)fii^HBi; they fume in the air, melt 
 and decompose at + 8°, and are decomposed by 
 water and by potash-lye, yielding {02H,02)2.Br, 
 and KBrO,. Heated in a sealed tube, they 
 yield bromaoetic acid (Steiner, B. 1874, 184). 
 The compound (CjHjO.liBrj.HBr has also 
 been prepared by Hell a. Miihlhauser (B. 1878, 
 241), who by using larger quantities of bromine 
 have further obtained (C2H402)4Brj(BrH)2 in 
 radiate groups of hard roseate crystals, which 
 may be dried in the lime exsiccator. 
 
 Acetates. — Acetic acid is monobasic, the 
 general formula of its normal salts being : 
 
 EW(CH3.C00)n = KWA'„ 
 the symbol K<"> denoting an w-valent radicle 
 metallic or alkylic, and A' standing for C^B^O^. 
 METALLIC ACETATES.- The nor- 
 mal acetates all dissolve in water, and most 
 of them readily. The least soluble are the silver 
 and mercury salts, so that solutions of other 
 acetates added to mercurous nitrate or silver 
 nitrate throw down white shining scales of mer- 
 curous or silver acetate. But for the most part 
 acetates are formed not by precipitation, but by 
 the action of acetic acid on metaUio oxides or 
 carbonates ; many carbonates, however, those of 
 barium and calcium for example, are not decom- 
 posed by acetic acid in its most concentrated 
 state. All acetates are decomposed by heat, most 
 of them yielding carbon dioxide, acetone and an 
 empyreumatic oil. Those which are easily de- 
 composed, and likewise contain bases forming 
 stable carbonates, are almost wholly resolved into 
 acetone and carbonate, e.g. : 
 
 Ba(0 . CO . Me)2 = COMcj H- BaCO,. 
 Those which, like the potassium and sodium 
 salts, require a higher temperature to decompose 
 them, yield more complex products, but always a 
 
ACETIO AOID. 
 
 9 
 
 certain quantity of acetone. Among the products 
 are found methyl ethyl ketone and methyl propyl 
 ketone, together with dumasin CjH,„0 (Fittig, 
 A. 110, 17). Acetatesoontainingweaker bases give 
 off part of the acetic acid undecomposed,the re- 
 maining portion being resolved into acetone and 
 carbonic anhydride, or if the heat be strong, yield- 
 ing empyreumatio oil and charcoal : the residue 
 consists sometimes of oxide, sometimes, as in the 
 case of copper and silver, of reduced metal ; in this 
 case part of the acetic acid is burnt by the oxygen 
 abstracted from the metal. The decomposition 
 of silver acetate may be expressed by the equa- 
 tion: 
 
 4CH3.C02Ag = 3CH,.C0.,H + CO^ + C + 4Ag 
 (Iwig a. Hecht, J3. 19, 238). Acetates heated 
 with a large excess of fixed caustic alkali, are 
 resolved at a temperature below redness into 
 marsh gas and alkaline carbonate, e.g. : 
 KC2H3O2 + KOH = K1CO3 + CH^. 
 Acetates distilled with sulphuric acid and alco- 
 hol yield ethyl acetate. The acetates of the 
 alkali-metals, and probably others also, treated 
 with phosphorus oxychloride, yield acetyl chlo- 
 ride, together with a tribasic phosphate : 
 3NaOAo -I- POCI3 = 3AcCl + NajPO,. 
 Many acetates may be decomposed by water 
 into acetic acid and metallic oxide. This de- 
 composition in the case of aluminio and ferric 
 acetates occurs at 100°, while at 175° the acetates 
 of Mn, Co, Ni, Zn, Ur, Cu, and Ag, as well as 
 ferrous and mercuric acetates, are slowly de- 
 composed (Eiban, O. B. 93, 1140). 
 
 Alumininm Acetates. — The normal salt AIA'3 
 exists only in solution, being decomposed on 
 evaporation. The solution, which is much used 
 as a mordant in dyeing and calico-printing, and 
 is called ' red liquor ' because it yields madder 
 reds and pinks, may be formed by dissolving 
 freshly precipitated aluminium hydroxide in 
 strong acetic acid, or by precipitating a solution 
 of normal aluminium sulphate with lead acetate : 
 
 Al2(S0 J3 -h SPbA'j = 3PbS0^ + AI3A',. 
 When quickly evaporated at a low temperature, 
 by spreading it out in thin layers on glass or 
 porcelain, it leaves a soluble basic acetate : 
 
 AlA-SCiHA-^HjO or Mfi{AoO),Anfi, 
 forming a gummy mass perfectly soluble in 
 water ; but, if heated, or left to evaporate at ord. 
 temp., it deposits insoluble basic salts, containing 
 in the first case two, and in the second five mo- 
 lecules of water, instead of four. The soluble 
 acetate exposed in dilute solution to the tempera- 
 ture of boiling water for several days, undergoes 
 a remarkable change, the whole or nearly the 
 whole of the acid being expelled and a peculiar 
 modification of alumina remaining dissolved (u. 
 AiUMiNinM) (Walter Crum, 0. J. 6, 216). A 
 dilute solution of aluminio acetate, free from 
 alkali, may be boiled without a pp. being formed 
 (Beinitzer, If. 3, 259). ,.„„., 
 
 Ammonium Acetates.— Thenormal saltNHiA' 
 [89°], obtained by saturating glacial acetic acid 
 with dry ammonia-gas, is white, odourless, ex- 
 tremely soluble, and difficult to crystaUise, its 
 aqueous solution when evaporated giving off 
 ammonia and leaving the acid salt (Berthelot, 
 Bl. 22, 440 ; Smit, Bl. 24, 539 ; Bahrmann, J.pr. 
 [2] 27, 29G). When distOled with phosphoric 
 anhydride it loses 2 mol. water, and gives oft 
 »cetonitrile CAN = NH,C3H302 - 2H,0, '^^"' 
 
 aqueous solution known in the Pharmacopoeia as 
 Spiritus Mindereri is prepared by saturating 
 aqueous acetic acjd with ammonia or ammonium 
 carbonate. The acid salt NH4HA'2 (145°) is ob- 
 tained as a crystaUine sublimate with evolution of 
 ammonia by heating powdered ammonium chlo- 
 ride with potassium or calcium acetate {v. Acei- 
 amide). When commercial ammonium acetate 
 is dissolved in its own weight of glacial acetic 
 acid, an acid salt is obtained in long needles, 
 having the composition 2NH4A'3HA' (Berthelot, 
 Bl. 24, 107). 
 
 Barium Acetate BaA'^aq, prepared by de- 
 composing the carbonate or sulphide with acetic 
 acid, is obtained, on evaporating the solution at 
 a gentle heat, in fiattened prisms ; and on cool- 
 ing to 0°, in monoclinic prisms, BaA'33aq. The 
 crystals dried at 100° yield the anhydrous salt 
 as a white powder, resolved at a high temperature 
 into barium carbonate and acetone. S.G. (of 
 BaA'^aq) 2-02; (of BaAy 2-47 (Schroder). V. e. 
 sol. water, insol. alcohol. 
 
 Acid SaZis.— BaA'2 HA'2aq.— BaA'22HA'2aq. 
 (Villiers, BZ. 30, 177; G. B. 85, 1234). 
 
 Double SaZZ.— BaA'(N03)4aq (Lucius, A. 103, 
 113). 
 
 Sismuth Acetate separates in micaceous 
 laminae from a warm mixture of bismuth nitrate 
 and potassium acetate. Acetic acid mixed with 
 a solution of bismuth nitrate prevents the pre- 
 cipitation of that salt by water. 
 
 Cadmium Acetate CdA'jSaq. — Monoclinic 
 prisms. V. e. sol. water, deliquescent and diffi- 
 cult to crystallise (Hauer, Sitz. B. 16, 131). S.G. 
 2-01 (dry, 2-34, Schroder). 
 
 Calcium Acetate CaA'^aq. Small effiorescent 
 needles. V. sol. water, si. sol. alcohol. S.G. of 
 aqueous solutions of CaA'2 at 17-5° (Franz, J.pr. 
 [2] 5, 298) : 
 
 P.O. 
 
 s.a. 
 
 P.O. 
 
 S.G. 
 
 P.O. 
 
 s.a. 
 
 1 
 
 1-0066 
 
 11 
 
 1-0527 
 
 21 
 
 1-0925 
 
 3 
 
 1-0198 
 
 13 
 
 1-0597 
 
 1 23 
 
 1-1027 
 
 5 
 
 1-0330 
 
 15 
 
 1-0666 
 
 1 25 
 
 1-1180 
 
 7 
 
 1-0394 
 
 17 
 
 1-0750 
 
 ( 27 
 
 1-1248 
 
 9 
 
 1-0458 
 
 19 
 
 1-0834 
 
 29 
 
 1-1366 
 
 The 
 
 Calcic acetate splits up on distillation into 
 CaCOa and acetone. 
 
 Acid salt CaA'^HAlfaq. Hygroscopic, 
 
 Double salt CaA'jCaCljlOaq. Monoclinic 
 prisms, permanent in air. 
 
 Cerous Acetate CcjA'sSaq forms radiate 
 groups of small needles, which become anhydrous 
 in dry air without losing their crystalline form ; 
 after drying at 115° they carbonise at a higher 
 temperature without fusing, and when strongly 
 heated leave a residue of cerous oxide (Large, 
 J.pr. 82, 129). 
 
 Chromium Acetates. — The chromous salt, 
 CrA'jaq, obtained from the chloride by decom- 
 position with potassium or sodium acetate, forms 
 red transparent crystals which when moist ab- 
 sorb oxygen very rapidly from the air, sometimes 
 taking fire (Peligot, A. Ch. [3] 12, 5il).— Nor- 
 mal Chromic Acetate Cr2A'„2aq is obtained by 
 evaporating a solution of chromic hydroxide in 
 acetic acid, as a green crystalline mass, insoluble 
 in alcohol. Its aqueous solution, green by e*- 
 
10 
 
 ACETIO ACID. 
 
 fleeted, red by transmitted light, is not decom- 
 posed either by boiling or by addition of lime- 
 water; but ammonia throws down from it a 
 green precipitate of chromic hydroxide, soluble 
 in excess (H. SchifE,^. Gh. [3] 71, 140; Schiitz- 
 enberger, Bl. [2] 4, 86). The solution of the nor- 
 mal acetate heated for several days with excess 
 of chromic hydroxide loses its acid reaction, and 
 yields by evaporation a green powder soluble in 
 water, consisting ofabasicaoetate Cr2A'i(OH)2 
 Sohiff, A. 124, 168). 
 
 Chromic Diacetotetrachloride, CrjA'jCl, is 
 obtained by dissolving CrjOCl, in strong 
 acetic acid. It is an unstable salt, which gives 
 ofi acetic acid when heated above 100°. The 
 chlorine is but very slowly precipitated from it 
 by silver nitrate at ordinary temperatures, but, 
 on the other hand, the salt easily yields acetic 
 ether when heated with sulphuric acid and 
 alcohol (Sohiff). — Chromic Diaceto-sulphate 
 CT^k'2(^0^^ obtained by dissolving chromic 
 disulphate in acetic acid, is a crystalline salt 
 which becomes anhydrous at 100°, and gives off 
 acetic acid at a higher temperature (Schiff). — 
 Chromic Pentaceio-nitrate GrJiJ^NO^iaq is ob- 
 tained by mixing a solution of chromic hydroxide 
 in a slight excess of acetic acid with a solution 
 of the same quantity of chromic hydroxide in 
 the exact quantity of nitric acid required to 
 dissolve it. The concentrated solution, when 
 left to itself, deposits an abundant crystallisation 
 of a dark green salt, which may be purified by 
 recrystallisation from water or from glacial acetic 
 acid. It forms dark green bulky laminie, which 
 give off nitrous fumes at 100°, the chromium 
 being at the same time converted into trioxide. 
 (Schiitzenberger). 
 
 Cobalt Acetate CoA'24aq. — Bed needles. 
 
 Copper Acetates. — The cuprous salt Cu^A'j 
 sublimes towards the end of the distillation of 
 normal cupric acetate. According to Berzelius, 
 it is contained in green verdigris and sublimes 
 on distillation. Soft loose white flakes which 
 redden Utmus and have a caustic astringent 
 taste. Decomposed by water, yielding normal 
 cupric acetate and cuprous oxide. 
 
 The normal cupric salt CuA'^aq is prepared 
 by dissolving cupric oxide or common verdigris 
 in hot acetic acid, or by decomposing normal lead 
 acetate with cupric sulphate. Dark-green mo- 
 noolinic crystals (S.G. 1'9), efflorescent, soluble 
 in 14 pts. cold and 6 pts. boiling water, sparingly 
 also in alcohol, insoluble in ether. The solution 
 boiled with grape-sugar yields a red precipitate 
 of cuprous oxide. Cupric acetate crystallised at 
 a temperature near 8° yields crystals contain- 
 ing CuA'jSHjO. A solution of cupric acetate 
 heated in a sealed tube at 200° forms crystallised 
 cuprous oxide and cupric glycoUate (Caseneuve, 
 C. B. 89, 525). 
 
 Acid Cupric Acetate CuA'jHA'aq (Vil- 
 liers, O. R. 85, 1234). 
 
 Basio Cupric Acetates. — These salts 
 may be regarded as compounds of the normal salt 
 with CuO, as compounds of Ac^O with CuO, or, 
 by taking account of water of crystallisation, as 
 ftoeto-hydrates, e.g. : 
 
 Sesquibasic : Cu0.2CuA'2.6aq = 
 
 3CuO.2A02O.6Aq = 2CuA'(OH).CuA'j.5aq. 
 
 Dibasic : CuO.CuA'j6Aq=2CuO.A0aO.6aq = 
 2(HO.CuA')5aq. 
 
 Tribasic : 2CuO.CuA'22aq = 8CuO.AO2O.2aq 
 = 2(HO.CuA')Cu(OH)2. 
 
 They are contained in common verdigris 
 (vert-de-gris), a substance obtained by exposing 
 plates of copper to the air in contact with acetic 
 acid, and much used as a pigment and as a 
 mordant in dyeing wool black. There are two 
 varieties of this substance, the blue and the 
 green, the former consisting almost wholly of 
 dibasic cupric acetate, the latter of the sesqui- 
 basic salt mixed with smaller quantities of the 
 dibasic and tribasic acetates. The dibasic salt 
 or blv£ verdigris is prepared at MontpeDier and 
 in other parts of the south of France, by ex- 
 posing copper to the air in contact with fer- 
 menting wine-lees. The same compound is ob- 
 tained by exposing copper plates to damp air 
 in contact with normal cupric acetate made into 
 a paste with water. It forms deUcate, silky, blue 
 crystalline needles and scales, which yield a 
 beautiful blue powder. They contain 6 mol. 
 water, which they give off at 60°, and are then 
 converted into a green mixture of the monobasic 
 and tribasic salt. 
 
 Green Verdigris is manufactured at Grenoble 
 by frequently sprinkling copper plates with vine- 
 gar in a warm room; and in Sweden by dis- 
 posing copperplates in alternate layers with flan- 
 nels soaked in vinegar. 
 
 Calcio-cuprio Acetate CaA'jCuA'jSaq, obtained 
 by heating a mixture of 1 mol. CuA', and 1 mol. 
 Ca(0H)2 with 8 pts. water and sufficient acetic 
 acid to dissolve the precipitated CuO, and evapo- 
 rating the filtrate at 25°-27°, crystalUses in large 
 blue square prisms, slightly efflorescent, giving 
 off acetic acid and faUing to powder at 75°; 
 readily soluble in water. Another calcio-oupric 
 acetate often exists in crystallised verdigris. 
 
 Cupric Aceto-arsenite CuA'28Cu(As02)2. — 
 Schweinfurt green, Imperial green, Mitis green, 
 and when mixed with gypsum or heavy spar, 
 Neuweider green. Mountain green. Used as a 
 pigment, and prepared on the large scale by 
 mixing arsenious acid with cupric acetate and 
 water; 5 pts. of verdigris are made up to a thin 
 paste, and added to a boiling solution of 4 pts. 
 or rather more of arsenious acid in 50 pts. 
 of water. The boiling must be well kept up, 
 otherwise the precipitate assumes a yellow-green 
 colour, from formation of copper arsenite; in 
 that case acetic acid must be added, and the 
 boiling continued a, few minutes longer. The 
 precipitate then becomes crystalline, and ac- 
 quires the fine green colour peculiar to the aeeto- 
 arsenite. The salt is insoluble in water, and 
 when boiled with water for a considerable time, 
 becomes brownish and gives up acetic acid. 
 Acids abstract the whole of the copper, and 
 aqueous alkalis first separate blue cupric hy- 
 droxide, which when boiled with the liquid is 
 converted into cuprous oxide, an alkaline arsenate 
 being formed at the same time. 
 
 Didymium Acetate DiA'3 4aq. S.G. 1-882. 
 S.V.S. 207-8.— DiA'saq. Bed needles. S.G. 
 2-237. S.V.S. 150-6 (CMve, Bl. [2] 43, 365). 
 
 Erbium Acetate EbA'34aq. — Isomorphous 
 with didymium acetate (Thomsen, B. 6, 712). 
 
 Iron Kc6ta,teB.— Ferrous acetate FeA'2 4aq, 
 obtained by dissolving iron or ferrous sulphide 
 in strong acetic acid, separates on concentration 
 in small colourless silky needles, which dissolve 
 
ACETIC ACID. 
 
 11 
 
 readily in water and quickly absorb oxygen from 
 the air. 
 
 Ferric Acetate is not known in the solid state 
 its a salt of constant composition. The dark 
 red solution of ferric hydroxide in acetic acid 
 (Liquor ferri acetici) contains a basic salt. The 
 following basic ferric acetates have been dis- 
 tinguished : Fe2A',(OH)2, obtained by dissolving 
 at 50° the ferric hydroxide from 1 pt. Fe in 10 
 pts. acetic acid of 30 p.o. and evaporating at 
 70°. Amorphous, soluble in alcohol and water 
 (Oudemans, y. 1858, p. 282).— FejA,'3(OH)3, pro- 
 bably contained in the red solution formed on 
 treating FejA'3(0H)Cl2 (infra) with silver oxide. 
 Becomes syrupy in a vacuum but does not 
 crystallise ; decomposes quickly at ord. temp., 
 forming an oohreous jelly (Scheurer-Kestuer).— 
 Fe2A'2(OH),2Fe2 03 is the ochreous deposit 
 formed in a solution of ferrous acetate exposed 
 to the air. Other basic salts appear to be formed 
 in the decomposition of the normal salt by heat 
 or otherwise. A solution of ferric acetate, quite 
 free from other salts, is not ppd. by boiling 
 (Beinitzer, M. 3, 257). 
 
 Acetonitrates (Kestner, A. Ch. [3] 63, 422 ; 
 68, 472 ; J. 1861, 307).— Formed by mixing so- 
 lutions of ferric nitrate and acetate in various 
 proportions, or by dissolving ferric hydroxide in 
 various mixtures of acetic and nitric acids. 
 Mostly very unstable, decomposed by boiUng 
 with water. — FeA'3(OH)2N03 forms deep red flat- 
 tened prisms, very soluble in water and in alco- 
 hol,insol.in ether.— FeA'4(OH)N034aq forms red- 
 brown rhombic prisms, sol. in water and alcohol, 
 decomposing on flight rise in temperature. The 
 diformi-diaceto-nitrate Fe.^ (COH) j (OAc) j (NOs)^ 
 is very soluble in water and alcohol, insol. in 
 ether, very unstable. 
 
 Acetochlorides. — Fe2A'sClj(OH)3aq is ob- 
 tained on cautiously adding nitric acid to a 
 solution of FeClj in acetic acid at 86°; also when 
 ferric hydroxide (1 mol.), acetic acid (1 mol.), 
 and hydrochloric acid (1 mol.) are digested 
 together at 40° for two or three days. Very hard 
 crystals, black by reflected, red by transmitted 
 light, very soluble in water. With silver oxide 
 they yield ferric triacetate (K. ; Schiff, A. Ch. 
 [3] 66, 136).— Fe^A'iClj, obtained by dissolving 
 1 mol. ferric hydroxide in a mixture of HCl (2 
 mol.) and CjHjOj (4 mols.), or by oxidising ferrous 
 chloride dissolved in very strong acetic acid 
 with nitric acid. Tellowish-red crystals, sol. in 
 water and in alcohol, easily resolved into acetic 
 acid and Fe2A'j(OH)Cl2. Heated at 50° for 
 twelve hours with silver nitrate, it is converted 
 into ferric tetraceto-dirUtrate : 
 
 Fe^A'^Cl^ + 2AgN03 = 2AgCl + ¥e^&.\CSO,)^. 
 
 Lanthanum Acetate LaA'sl^aq. — Small 
 needles (Cl^ve, Bl. [2] 21, 196). 
 
 Lead Acetates, or Plumbic Acetates. — The 
 normal salt PbA'2 3aq, Sugar of lead, Sel sac- 
 eharum Saturni, [75°] S.G. 2-5. — Prepared by 
 dissolving lead oxide or carbonate in acetic acid 
 (Wichmann, J. 1853, 738). 
 
 Properties. — Monochnic efflorescent crystals, 
 easily "oluble in water and in spirit of ordinary 
 strength, insoluble in cold absolute alcohol, com- 
 pletely dehydrated by prolonged boiling with ab- 
 solute alcohol. An aqueous solution saturated at 
 15°oontains387-623g.saltina litre, andhasaden- 
 Bity of 1-2367 (Michel a. Kraft, J. 1854, p. 296). 
 
 Density of the Agueous Solution at 14°. 
 (Oudemans, Fr. 7, 419 ; J. 1868, 29.) 
 
 Oryst.Saltp.o. 
 
 Density 
 
 Cryat.Saltp.o. 
 
 Density 
 
 1 
 
 5 
 
 10 
 
 15 
 
 1-0057 
 1-0317 
 1-0659 
 1-1018 
 
 20 
 25 
 30 
 33 
 
 1-1399 
 1-1808 
 1-2248 
 1-2525 
 
 Normal lead acetate melts at 75°, begins to 
 give off water with a portion of its acid a little 
 above 100°, and is completely dehydrated at 280°. 
 Above that temperature it decomposes, giving 
 ofE acetic acid, carbonic anhydride, and acetone, 
 and leaving metallic lead very finely divided and 
 highly combustible. The aqueous solution isi 
 partially decomposed by the carbonic acid of 
 the air, carbonate of lead being precipitated, and 
 a portion of acetic acid set free, which prevents 
 further decomposition. The solution is not pre- 
 cipitated by ammonia in the cold, but yields 
 crystals of lead oxide when heated with a large 
 excess of ammonia. Normal lead acetate forms 
 crystalline compounds with chloride and peroxide 
 of lead (Gm. 8, 310). Bromine added to a solu- 
 tion of the normal salt throws down a brown 
 precipitate of PbOj, which, if the liquid be 
 warmed, continues to form till 2 at. Br have 
 been added to 2 mol. PbA'j. The solution then 
 contains lead bromide and acetic acid: 
 
 2PbA'2 + 2H2O + Br^ = PbOj + PbBr^ + 4HA' 
 (Chapman a. Smith, O. J. 22, 185). 
 
 Basic Lead Acetates. — Pb2A'3(0H), 
 formed by repeatedly drenching the normal salt 
 with absolute alcohol; the residue crystallises 
 from hot absolute alcohol in nacreous six-sided 
 plates, easily soluble in water, sparingly in cold 
 alcohol (Plochl. B. 13, 1647).— PbA'i,Pb02aq. 
 Lead-vinegar, Acetum Saturni. Prepared by 
 dissolving litharge in the aqueous normal salt, 
 and evaporating at a gentle heat, whereupon it 
 crystallises in needles. According to Wittstein- 
 (A. 52, 253) the crystals contain only 1 mol. H^O. 
 Easily soluble in water and in alcohol of 90 p.c. 
 Eeacts alkaline. Decomposed by COj. A so- 
 lution of this salt mixed with alcohol forms 
 Goulard's lotion. — PbA'22PbOaq, obtained by dis- 
 solving PbO in normal lead acetate, or by mixing 
 a solution of the normal salt with ammonia. 
 Crystallises in silky needles, soluble in 5-55 pts. 
 water at 100°, insoluble in absolute alcohol 
 (Payen, A. 25, 124 ; A. Ch. [4] 8, 6 ; Lowe, /. 
 pr. 98, 385 ; J. 1866, 235). 
 
 An Aceto-ohloride ClPbA' is formed by heat- 
 ing recently precipitated lead chloride with nor- 
 mal lead acetate and acetic acid at 180°, and 
 crystallises in monocUnic prisms. Decomposed 
 by water into lead chloride and the more soluble 
 salt PbA'jClPbA'. The analogous compounds, 
 BrPbA' and IPbA' obtained in like manner, form 
 small monoclinic crystals (Carius, A. 125, 87). 
 
 Sodio- and Potassio-plumbic Acetates. — 
 PbA'jNaA'faq. Monoclinic crystals (Eammels- 
 berg, /. 1855, 503) .— PbA'22Pb04KA' is formed on 
 adding potash-lye (S.G. 1-06) with agitation to 
 a boiling solution of normal lead acetate (S.G. 
 1-25 to 1-30). Crystalline pulp, moderately so- 
 luble in water (Taddei, J. 1847-8, 548). 
 
 Aceto-formate (CH02)Pbj(C2H,02)32aq. 
 
12 
 
 ACETIC ACID. 
 
 Needles, easily soluble in water, sparingly in 
 alcohol (Ploohl. B. 13, 1645). 
 
 Lithium Acetates. — LiA'2aq. Bbombio 
 prisms [o. 70°]. Dissolves in less than ^ pt. 
 water at 15° ; in 4'64 pts. alcohol of density 0"81 
 at 14° (Pleisch. Zeitschr.f. Physih, 4, 108). Ao- 
 Bording to Eammelsberg [A. 56, 221), the crystals 
 Bontain only 1 mol. HjO. — LiA'HA', obtained by 
 spontaneous evaporation of a solution of the 
 normal salt in glacial acetic acid [99°]. Ro- 
 tates on -water. Under somewhat different cir- 
 cumstances it crystallises in small four-sided 
 plates, containing Aq and melting at 85° (Les- 
 cceur, Bl. 24, 516). 
 
 Magnesium Acetate MgA'2 4aq. — S.G. 1-45 
 (Schroder). Monoclinic, slightly deliquescent, 
 very soluble in water and in alcohol (v. Hauer, 
 J. 1855, 501 ; Patrouillard, O. B. 84, 553). 
 
 Manganous Acetate MnA'2 4aq. — -Pale red 
 transparent monoclinic plates, permanent in the 
 - air, soluble in 3-3-5 pts. water, also in alcohol. 
 S.G. 1-6 (Schroder). 
 
 Acid SaUMTiA;jl.k'2B.q (ViUiers, Bl. 30, 177). 
 
 Manganic Acetate MnA'32aq. — Browncrystals 
 (Otto, A. 93, 372 ; Christensen, J.pr. [2] 28, 14). 
 
 Mercury Acetates. — 1. HgjA'j. Obtained by 
 precipitation. Micaceous scales. S. '75 at 13°. 
 — HgA'j. Brilliant micaceous laminas. S. 25 at 
 10°, 36 at 19°, 100 at 100°. Dissolves with par- 
 tial decomposition in 17'7 pts. alcohol (S.G. 
 •811) at 19° (Gm. 8, 332).— An aceto-sulphide, 
 HgA'jHgS, is precipitated, on passing H^S into 
 a solution of mercuric acetate, as a white crys- 
 talline powder. — Mercuro-diamTnonium Acetate 
 NjHijHgA'jHjO. Eectangular plates ; easily so- 
 luble in water, nearly insoluble in alcohol ; 
 smells of acetic acid, and decomposes gradually 
 on exposure to the air (Hirzel, J. 1851, 437). 
 
 Nickel Acetate. — ^Apple-green prisms, soluble 
 in 6 pts. cold water, insoluble in alcohol (Tup- 
 puti, A. Ch. 78, 164). 
 
 Potassium Acetates. — Normal salt KA'. 
 Terra foliata tartari.—S. 188 at 2" ; 229 at 
 13-9° ; 492 at 62° (Osann). A boiling saturated 
 solution contains 8 pts. salt to 1 pt. water, and 
 boils at 169° (Berzelius). Soluble in 3 pts. cold 
 and 2 pts. hot alcohol. Exists in many plant- 
 juices. White, difficult to crystallise, extremely 
 deliquescent, insoluble in ether. Chlorine passed 
 into its aqueous solution liberates CO^ and forms 
 a bleaching liquid. On passing an electric 
 current through a concentrated aqueous solu- 
 tion of the salt, hydrogen is evolved at the 
 negative pole, and at the positive a mixture of 
 ethane and COj. The principal decomposition is : 
 2(CH3.C02H) = G2H5 -I- 2CO2 -I- H2, methyl oxide 
 and acetate being secondary products (Kolbe, A. 
 69, 257). On passing COj-gas into a solution of 
 the salt in alcohol of 97-100 p.c, a large quan- 
 tity of potassium carbonate is thrown down, and 
 ethyl acetate is formed (Pelouze, A. 5, 265). 
 
 Acid Potassium Acetate KA'HA' is formed 
 when the normal acetate is evaporated with an 
 excess of strong acetic acid, and separates in 
 needles or laminie, or in long flattened prisms. 
 Very deliquescent; melts at 148°, and de- 
 composes at 200°, giving off pure AcOH. This 
 affords an easy method of obtaining glacial 
 acetic acid. Acid potassium acetate is also 
 formed when the normal salt is distiUed with 
 butyric or valeric acid; but neither of these 
 
 acids decomposes the salt thus produced. Hence, 
 when butyric or valeric acid is mixed with acetic 
 acid, a separation more or less complete may be 
 effected by half neutralising the liquid with 
 potash and distilling. If the acetic acid is in 
 excess, acid potassium acetate alone remains be- 
 hind, the whole of the butyric or valeric acid 
 passing over, together with the remainder of the 
 acetic acid. If, on the contrary, the other acid 
 is in excess, it passes over unmixed with acetic 
 acid, and the residue consists of potassium 
 acetate mixed with butyrate or valerate. By re- 
 peating the process a certain number of times, 
 either on the acid distillate or on the acid sepa- 
 rated from the residue by distillation with sul- 
 phuric acid, complete separation may be effected. 
 Acetic acid, therefore, is an exception to the rule 
 that when a mixture of fatty acids and their po- 
 tassium salts is boiled the most volatile acids distfl 
 over (Liebig, A. 71, 355).— KA'2HA' [112°]. S.G. 
 1-4. Deliquescent plates (Lesooeur, Bl. 22, 156). 
 Anhydrous Potassium, Diacetate or Potas- 
 sium Pyroacetatt KjCgHj^O, = 2KOAC.AC2O, pre- 
 pared by dissolving melted KOAo in boiling 
 acetic anhydride, forms colourless needles very 
 soluble in water, less deliquescent than normal 
 potassium acetate. Decomposed by heat, giving 
 off Ac^O (Gerhardt, A. Ch. [3] 37, 317). 
 
 Rhodium Acetate BhA'32^aq (Glaus, J. 1860, 
 213). 
 
 Bubidium Acetate EbA'. — Plates (Grandeau, 
 J. 1863, 184). 
 
 Samarium Acetate SmA'3 4aq. — S.G. 1'94. 
 S.V.S. 205-6. YeUow crystals (Cl^ve, Bl. [2] 43, 
 171). 
 
 Silver Acetate AgA' (S. 1-02 at 14°) sepa- 
 rates on mixing the concentrated solutions of 
 AgNOj and NaOAc. Dissolves in hot water, and 
 on cooling separates as nacreous flexible laminse. 
 Heated with iodAne it is resolved into silver 
 iodide, methyl acetate, hydrogen acetate, COj, 
 acetylene, and hydrogen (Birnbaum, A. 152, 111). 
 When dry, it combines with NHj, forming 
 AgA'2NH3 (Eeychler, B. 17, 47). 
 
 Sodium Acetates. — NaA'Saq. [58°] (123°). 
 S.G. 1-4. S. 26 at 6°, 42 at 37°, 69 at 48° 
 (Osann). S. (alcohol of S.G. -8322) 2-1 at 18°. 
 Crystallises with SE-fi in monoclinic prisms, 
 melting below 100°. According to Eeischauer 
 {J. 1860, 50), the crystals give off the whole of 
 their water in a vacuum at ord. temp. The 
 fused salt in damp air quickly takes up about 
 7H2O, forming a supersaturated solution, whereas 
 the unf used salt takes up from the air only the 
 original 3H2O. When the aqueous solution of 
 NaA' turns mouldy, oxygen is absorbed, and small 
 quantities of alcohol and formic acid are pro- 
 duced (B^champ, Z. 6, 438). 
 
 The S.G. of solutions containing the follow- 
 ing percentages of NaA' is given by Franz (J.;gr. 
 [2] 5, 297) as follows : 
 
 P.O. 
 
 S.G. 
 
 P.O. 
 
 S.G. 
 
 P.O. 
 
 S.G. 
 
 1 
 
 1-0058 
 
 11 
 
 1-0591 
 
 21 
 
 1-1134 
 
 3 
 
 1-0174 
 
 13 
 
 1-0697 
 
 23 
 
 1'1254 
 
 5 
 
 1-0292 
 
 15 
 
 1-0802 
 
 25 
 
 1-1374 
 
 7 
 
 1-0390 
 
 17 
 
 1-0910 
 
 27 
 
 1-1506 
 
 9 
 
 1-0488 
 
 19 
 
 1-1018 
 
 29 
 
 1-1638 
 
 The S.G. of a saturated solution being 1*1842. 
 
AUJiTlO ACID, 
 
 13 
 
 Acid Sodium Acetates CVillieis, Bl. 29, 153 ; 
 80, 175 ; C. R. 85, 1234 ; LesooDur, Bl. 22, 156). 
 — NaA'HA'act. Cubic (FeMing).— NaA'2HA' or 
 NaA'2HA'aq. Long needles. [127°]— 
 5NaA'4HA'6aq.— 4NaA'HA'llan.— 
 5NaA'2HA'13aq. 
 The three last are, perhaps, mixtures. 
 
 Strontium Acetates SrA'2 Jaq. — Below 15° 
 it crystallises with 4Aq in monochnio prisms. 
 
 An aceto-nitrate NOsSrA'fHjO forms triclinio 
 crystals (Hauer, J. 1858, 281 ; Zepharovioh, J. 
 1860, 309). Villiers {Bl. 30, 176) describes the 
 following acid acetates : 
 SrA'jHA'2aq. 3SrA'j4HA'6aq. 2SrA'.3HA'lJaq. 
 
 Thallium Acetates.— T^mZZous acetate TIA'. 
 White silky needles, easily soluble in water and 
 in alcohol, and deliquescent (Crookes, 0. J. 27, 
 149). 
 
 Acid Salt TIA'HA' [64°] (Lesooeur, Bl. 24, 
 616). 
 
 Basic Thallic Acetate TIA', 2T1 (OH), IJaq. 
 Colourless plates, readily resolved into acetic 
 acid and thallic oxide. 
 
 Tin Acetates. — Tin dissolves slowly in boiling 
 acetic acid, with evolution of hydrogen, and stan- 
 nous hydroxide dissolves readily in the boiling 
 acid, the solution when evaporated to a syrup 
 and covered with alcohol yielding small colour- 
 less crystals. Stannic hydroxide also dissolves 
 in the acid, the solution when evaporated leaving 
 a gummy mass. Stannic chloride forms a crys- 
 talline compound with glacial acetic acid. 
 
 Uranium Acetates — Uranous acetate. Warty 
 groups of green needles.— Dramc acetate or 
 TJranyl acetate UOjA'^, obtained by heating 
 nranic nitrate till it begins to give off oxygen, 
 dissolving the yellowish-red mass, which still 
 contains NOjH, in warm concentrated acetic 
 acid, and evaporating to the crystallising point. 
 Crystalhses from strongly acid solutions in 
 yellow transparent monoclinic prisms, containing 
 U02A'j2aq, which dissolve in boiling water with 
 separation of UO3, but are reproduced on evapo- 
 rating the solution. A weaker solution cooled 
 below 10° deposits quadratic octahedrons of 
 U02A'23aq, which give off 1 mol. H^O at 200°, the 
 rest at 275°. Double SaZfc.— NH,A'U0aA'j3aq, 
 NaA'TJOjA'2 (regular tetrahedrons), and 
 KA'TJOjA'^aq (quadratic prisms), are obtained 
 by adding the respective alkaline carbonates to 
 a solution of uranic acetate tm a precipitate is 
 formed consisting of alkali-metal uranate, redis- 
 solving this in a slight excess of acetic acid, and 
 cooling to crystallisation. The other double 
 salts of the group are formed by boiling the 
 carbonates with uranic acetate till all the UO3 
 is precipitated, redissolving in acetic acid and 
 evaporating.— BaA'22UOjA'26aq. Small yellow 
 crystalline spangles, easily soluble in water ; 
 give off their crystal-water at 275° (Wertheim, 
 /. pr. 29, 227).— CaA'j2U02A'j8aq. Sulphur- 
 yellow rhombic crystals, easUy soluble in water, 
 permanent in the air, becoming anhydrous at 
 200° (Weselsky, J.pr, 76, 65).— CdA'j2UOjA'j5aq. 
 Diohroic crystals.— PbA'jUOjA'j 6aq. Tufts of 
 pale yellow needles. —MgA'22U02A'2 8aq. Eeot- 
 angular prisms. — NiA'22U0jA'j 7aq. Emerald- 
 green rhombic crystals. — SrA'jUOjA'j 6aq. Sul- 
 phur-yellow crystals.— Zn A' J2UO2A', 3aq. Sul- 
 phur-yellow crystals, isomorphous with the 
 nickvl salt. 
 
 MnA'jUOjA'j 6aq. FeA'^UOjA'^ 7aq. 
 TlA'2U02A'j 2aq. LiA'UO^A'^ 3aq. 
 BeA'jUOjA'2 2aq. AgA'UOjA'2 aq. 
 
 Zinc Acetate.— ZnA'2 3aq. [235°-257°] S.G. 
 1-72.- ZnA'2 [242°] S.G. 1-84.- Monoclinic la- 
 minsB. Very soluble in water. May be sublimed 
 as ZnA'2, especially in vacuo (Franehimont, B. 
 12, 11). ZnA's may be crystallised, in anhy- 
 drous state, from HOAc (Peter a. Eoohefontaine, 
 Bl. [2] 42, 573). 
 
 _ Yttrium Acetate TA's8aq(?). — Isomorphous 
 with the acetates of didymium and erbium 
 (ClSve). 
 
 ALKYL ACETATES. Acetic Ethers. 
 
 Methyl Acetate C^Rfi^ or MeA'. M.w. 74. 
 (55=) at 754-4mm. (E.Schiff) ; (56-8°) at 760 mm. 
 (Kopp) ; (57-3°) (Gartenmeister) ; (57-5°) at 
 760 mm. (Elsasser, Perkin). S.G. % -9643 (G.) ; 
 s -9577 (E.) ; if -9398 (P.) ; f -9039 (Briihl) ; 
 If -9286 (P.) ; f -8825 (S.). V.D. 2-563 (for 
 2-564). C.E. (0°-10°) -00133 (G.) ; -00136 (E.). 
 S. 33 at 22° (J. Traube). S.V. 83-66 (S.) ; 83-2 
 (G.) ; 83-77 (B.). a«^ 1-3654. Ea, 28-78 (B.). 
 H.F.p. 96,720. H.F.V. 94,980. M.M. 3-362 at 
 22° (P.). 
 
 Occurrence. — In crude wood-vinegar (Weid- 
 mann a. Sohweizer, P. 43, 593). 
 
 Preparation. — 1. By distilling 2 pts. wood- 
 spirits with Ipt. very strong acetic acid and 1 pt. 
 strong sulphuric acid, removing the excess of 
 wood-spirit by means of fused calcium chloride, 
 and rectifying over sodium carbonate (Dumas a. 
 Peligot [1885], A. Oh. [2] 58, 46). 2. By heating 
 H2SO4 (50 CO.) and MeOH (50 c.c.) to 140° and 
 running in slowly a mixture of equal parts of 
 MeOH and HOAc (Pabst, Bl. [2] 33, 350). 3. By 
 distilling 3 pts. wood-spirit with 14-5 pts. dried 
 lead acetate and 5 pts. strong sulphuric acid, 
 agitating the distUlate with milk of Hme, treating 
 the supernatant oil with calcium chloride, and 
 rectifying (Kopp, A. 55, 181). 
 
 Properties. — Colourless fragrant liquid. 
 Soluble in water ; mixes in all proportions with 
 alcohol and ether. 
 
 Beacticms. — 1. Aqueous solution only slightly 
 decomposed by boiling. — 2. Eesolved by caustic 
 alkalis into methyl alcohol and acetic acid. — 3. 
 When poured on pulverised soda-lime it is 
 violently decomposed, with formation of sodium 
 acetate and formate, and evolution of hydro- 
 gen. — 4. With sodium it reacts like ethyl acet- 
 ate {q. v.), yielding as chief products sodium 
 methylate, NaOCHs and methyl sodio-aceto- 
 aoetate, COMe.CHNa.COOMe.— 6. Decomposed 
 by strong sulphuric acid, becoming hot, giving off 
 acjtio acid, and forming methyl sulphuric acid. 
 
 Ohloro-methyl Acetate CH2CIOAC (115° 
 i.V.). S.G. !i? 1-195. V.D. 3-70 (for 3-74).—Made 
 by passing chlorine into methyl acetate at 10°- 
 An oil. Slowly decomposed by water, quickly by 
 alkalis, giving HCl, HOAc, and formic aldehyde : 
 CH2Cl(0Ac) + 2K0H = 
 CH,0 + H^O + KCl + KOAc. 
 With alcoholic KOAc it gives methylene acetate, 
 CH2(0Ac)2 V. formic aldehyde (L. Henry, B. 6, 
 740). 
 
 Bi-chloro-methyl Acetate CHClj.OAo 
 (145°-148°), S.G. 1-25, is formed by passmg dry 
 chlorine through methyl acetate at a gentle heat. 
 Colourless, pungent-smelling liquid. Decomposed 
 slowly by water, quickly by aqueous potash. 
 
14 
 
 A.OETIO ACID. 
 
 violently by alooliolio potash, yielding formic, 
 acetic, and hydrochloric acids, 
 
 CHCl2(OAc) + 3KOH = 
 CH2(0K)0 + HjO + 2KC1 + EOAo 
 <Malaguti, A. 32, 47). 
 
 Tri-chlorinated Methyl Acetate 
 C3H3CI3O2 (145°). Laurent, A. Oh. [2] 73, 25. 
 
 Per-chlorinated Methyl Acetate 
 CClj.O.CO.CClj. Formed by prolonged action of 
 CI on methyl acetate v. iri-OHLOKO-AOETio acid. 
 
 Ethyl Acetate C^HjOj or Bt A.'. — Acetic 
 tther. M.w. 88. (75-5°-76-5°) at 745-5 mm. (B. 
 Schifi) ; (77-1°) at 760 mm. (Elsasser) ; (77-5°) 
 (Gartenmeister). S.G. g -9253 (G.) ; a -9239 (E.) ; 
 ^o -9007 (Briihl) ; if -9072, |f -8971 (Perkin) ; 
 'f -8306 (S.) V.D. 3-087 (for 3-079). S.H. -48. 
 C.E. (0°-10°) -001263 (E.). S. 6 at 17-5°. S.V. 
 105-7 (S.) ; 106-1 (G.) ; 106-15 (E.). m^ 1-8771. 
 R„ 8-5-46 (B.). H.F.p. 114,710. H. F. v. 112, 290. 
 SWmation. — (Lauragais, /. d. S^avans, 1759, 
 324 ; Thenard, Mim. d'Arcueil, 1, 153 ; Dumas 
 a. BouUay, /. Ph. 14, 113 ; Liebig, A. 5, 34 ; 30, 
 144; Malaguti, A. Gh. [2] 20,367 ; [3] 162, 58). 
 
 1. By heating alcohol with acetic acid or with 
 an acetate and strong sulphuric acid. 2. By dis- 
 tilling calcium or potassium ethyl-sulphate with 
 glacial acetic acid (Liebig). 
 
 Preparation. — 1. By distilling a mixture 
 of 3 pts. potassium acetate, 3 pts. absolute 
 alcohol, and 2 pts. sulphuric acid ; or 10 pts. 
 sodium acetate, 6 pts. alcohol, and 15 pts. sul- 
 phuric acid ; or 16 pts. dry lead acetate, 4^ pts. 
 alcohol, and 6 pts. sulphuric acid. The acid' is 
 first mixed with the alcohol, and the liquid is 
 jpoured upon the pulverised salt; the mixture 
 is then distilled to dryness, and the product is 
 purified by digestion with calcium chloride and 
 rectification. — 2. Frankland a. Duppa prepare 
 ethyl acetate by gradually pouring a mixture of 
 3-6 kilo, of 97-p.o. alcohol, and 9 kilo, strong 
 sulphuric acid, on 6 kUo. sodium acetate pre- 
 viously fused and dried, leaving the mixture at 
 rest for 12 hours, then distilling and rectifying 
 the distUlate (which is free from alcohol and 
 amounts to 6 kilo.) over fused and pulverised 
 calcium chloride. The best mode of mixing the 
 alcohol and sulphuric acid is to pour the alcohol 
 through a narrow glass tube to the bottom of 
 the vessel containing the acid, stirring the liquid 
 continually by means of the tube. It is best to 
 leave the ethyl-sulphuric acid thus formed for 
 24 hours before pouring it on the sodium acetate. 
 3. A mixture of alcohol and acetic acid in 
 molecular proportions is allowed to run into sul- 
 phuric acid at 130°, whereby ethyl-sulphuric acid 
 is first formed, and this with the acetic acid 
 forms ethyl acetate, which distils over, leaving 
 the sulphuric acid to be further acted on by the 
 alcohol. By this process 10 g. sulphuric acid 
 yield 232 g. ethyl acetate (Eghis, B. 6, 1177 ; 
 Pabst, Bl. [2] 33, 350). 
 
 Properties. — Colourless fragrant liquid. So- 
 luble in 17 pts. water at ord. temp. ; dissolves 
 •036 pts. of water ; freely misoible with alcohol 
 and ether. 
 
 Eeactions. — 1. B'wms with yellowish flame. 
 2. By dilute chromic acid it is oxidised to 
 acetic acid CiUfi„+02 = 2C.Sfi2 (Chapman a. 
 Thorp, C. J". 19, 484).— 3. Permanent in the air 
 when dry, but gradually decomposing when moist 
 into alcohol and acetic acid ; more quickly in 
 
 contact with alkalis. — 4. Converted by heating 
 with sulphuric acid into ethyl oxide and acetic 
 acid ; with hydrochloric acid into acetic acid and 
 ethyl chloride. — 5. The vapour passed over zinc- 
 dust at 300°-350° gives acetone, CO. hydrogen 
 and ethylene (Jahn, B. 13, 2107).— 6. With lime 
 in sealed tubes at 250°-280° it yields butyric 
 acid as chief product, calcium acetate and ethy- 
 late as intermediate products : 
 
 2CaO + 2EtOAc = Ca(0Ac)2 -I- Ca(OEt) j - 
 Ca(OH)2-l-Ca(C^H,Oj2 
 (Lubavin, Bl. [2] 34, 679).— 7. With alkalint 
 hydroxides it yields acetic acid and ethyl alco- 
 hol ; with the anhydrous oxides, acetic acid and 
 a metallic ethylate : 
 2EtOAc -I- Ba(OH)j = Ba(0Ac)2 + 2EtOH ; and 
 2EtOAc -I- 2BaO = Ba(0Ac)2 -I- Ba(0Et)2 
 (Berthelot a. Fleurieu, A. Ch. [3] 17, 80).— 
 8. With a mixture of lirne-water and chloride of 
 lime (bleaching powder)', it yields chloroform 
 (Schlagdenhauffen, /. Ph. [3] 36,190).— 9. With 
 aloohoUo KHS it forms, on heating, KOAc and 
 HjS, but no mercaptan (C. Gottig, J. pr. [2] 33, 
 90). — 10. With sodium-ethylate, forms, at 180°, 
 sodio-aceto-acetio ether. — 11. Ethyl acetate 
 heated with sodium dissolves the metal, and the 
 whole solidifies to a crystalline mass of sodium 
 ethylate and ethyl sodio-aoeto-acetate CjHjNaOj. 
 The reaction is either 
 
 2 (C2H5.O.AC) -I- Na^ = NaOO^H, + CsHsNaO, + H, ; 
 or 3(CjH5.0.Ac) + Na4= 3NaOC2H5 + C ANaO,. 
 The quantity of hydrogen evolved varies con- 
 siderably according to the temperature and pres- 
 sure at which the reaction takes place, and the 
 proportions of the materials used; sometimes 
 no gas is evolved (equ. 2), and under no circum- 
 stances yet observed is the quantity of hydro- 
 gen evolved exactly equivalent to the sodium 
 dissolved, as required by the first equation. 
 Probably, therefore, the two reactions generally 
 take place together (see, further, Aoeto-aoetio 
 Acm). — 12. With iodine and aluminium foil ethyl 
 acetate yields ethyl iodide and aluminium ace- 
 tate, 6EtOAc-l-Al2-f3l2=6EtI-H Al2(OAc)8, and 
 a similar reaction takes place with all the alkyl 
 acetates of the series C„H2„+iOAc (Gladstone a. 
 Tribe, C. J. 30, 357). — 13. Ethyl acetate com- 
 bines with titanic chloride in various propor- 
 tions (Demarpay, BZ. [2] 20, 127 ; O.B. 70, 1414)_. 
 ChiiOeinated Ethyl Acetates. — Chlorine is 
 abundantly absorbed by ethyl acetate, and acts 
 strongly upon it, even at ordinary temperatures, 
 replacing two or more atoms of hydrogen ; the 
 action is accelerated by heat and by direct sun- 
 shine. Seven compounds have been described 
 as thus formed, containing 2 to 8 at. chlorine in 
 place of hydrogen, but only three of them have 
 been obtained of constant composition, viz., 
 those containing 2, 3, and 5 at. chlorine. 
 
 Dichlorethyl Acetate C^HjCljOj i.e, 
 C2H3CI2.C2H3O2 is the product formed when ethyl 
 acetate is kept cool and in the shade during the 
 action of the chlorine. Transparent oil. S.G. 
 3-01 at 12° (Malaguti, A. Ch. [2] 70, 367). 
 
 Trichloro-ethyl-acetate CHCl,.CHC1.0Ao, 
 metamerio with ethyl W-chIiOko-acetatb (q. v.) 
 is formed by the action of chlorine at 120°, in 
 presence of iodine, on ethylidene aceto-chloride, 
 CH3CHCI.OA0 (Kessel, B. 10, 1999). 
 — CCI3.CH2OA0 (72°) at 18mm., (167°) at 736mm. 
 S.G. ?5:3 1.391. V.D. 6-89 (for 6-63). From tri- 
 chloro-ethyl alcohol andAcCl at 130°. Bectified 
 
ACETIC ACID. 
 
 IS 
 
 in mciw (GarzaroUi-Thurnlaokh, A. 210, C3). 
 > uming HNOj converts it, at 15°, into tri-cliloro- 
 aeetic acid. KOH forms tri-chloro-ethyl-glyool- 
 lio acid, CCls.CHj.O.CH^GOjH. 
 
 Octo- chlorinated Ethyl Acetate 
 CjCljOj i.e. C2GI5.C2CI3O2 is slowly formed on 
 exposing the diehlorinated ether, together with 
 chlorine, at 100° to bright summer sunshine. 
 The product, after distillation in a stream of 
 carbon dioxide to remove excess of chlorine, 
 forms a colourless pungent oil which remains 
 liquid below 0°. S.G.1-79 at 25°. Boils, with 
 partial decomposition, at 245°. Its vapour 
 passed over fragments of glass heated to 400° 
 is converted into the isomeric compound ohlor- 
 aldehyde C.fi\fi = CCls-COCl. It is decomposed 
 by water and moist air, and more completely by 
 KOH, into hydrochloric and trichloracetic acids : 
 
 C^Cls.CjCljOj + 2HjO = 2HC1 + 2(CCls.C02H) 
 (Leblano,4.C?s.C3]10, 197; Malaguti,46.15,268). 
 
 The following chlorinated acetic ethers are 
 also known : the compound of aldehyde with 
 AcGl, QLYCOL chloro-acetin, and the ethyl salts 
 of the three chloro-aceiic acids. 
 
 Brominated Ethyl Acetates 04HBBr20j = 
 CHjBr.CO.OCHBr.GH, (bromethyl bromaoetate), 
 formed on heating ethylidene acetate-chloride 
 CHMeCl(OAc) with bromine at 100°-103°, boils 
 under reduced pressure atl30-135°, and dissolves 
 in boiling water, with formation of aldehyde, 
 acetic acid, crotonaldehyde, aoetal, ethyl bro- 
 mide, and HBr. The crotonaldehyde and aoetal 
 are secondary products fprmed from aoetalde- 
 hyde, produced in the first instance as shown 
 by the equations : 
 
 GH^Br.GO.GCHBr.GH, + G,HjOH = 
 
 CH^r.GOOG .Hj + CH3.CHBr{0H) 
 
 and CH3.CHBr(bH) = HBr + CH3.CHO. 
 
 Tri- and Tetra-hrominated Ethyl Acetates 
 CjHiBrjO.^ and CJlfirfi^, formed by the action 
 of lor 2 mol. bromine at 120° and 160°, respec- 
 tively, on C2H5Br202, and freed from absorbed 
 HBr by heating in a stream of carbon dioxide, 
 are oily strongly fuming liquids, partly decom- 
 posing on distillation ; decomposed also by water 
 and alcohol, the products containing substances 
 which reduce ammoniacal silver solution, whence 
 it appears that both these ethers produce 
 aldehydes. The pentabrominated compound 
 CjH3Br502, probably CHjBr.CO.OGBr^.CHBri,, 
 formed by heating 04H^Brj02 with 1 mol. bro- 
 mine at 170°, is a liquid which scarcely fumes 
 in the air (176°), Its product of decomposition 
 by water does not reduce ammoniacal silver so- 
 lution. Heated with excess of bromine, it forms 
 C^H^BreO, (195°-198°) (Kessel, B. 10, 1994; 11, 
 1917). Other brominated acetic ethers are 
 CH^CHBr.OAo v. Aldehyde, OH^Br.GHj.OAc v. 
 Glycol, and the ethylic Beomo-acetates. 
 
 Ethyl Ortho-acetate CH3.C(OEt)3.— Triethylic 
 acetate ; (142°), S.G. 21 -94, formed, together 
 with CH201.C(0Et)3, by heating CH3.GCI3 with 
 NaOEt in a sealed tube at 110°. Fragrant 
 liquid. Decomposed by water into alcohol and 
 acetic acid (Geuther, J. 1870, 636). 
 
 The acetates of the higher alkyls, G„H2„+r. 
 are analogous in their properties and reactions 
 to ethyl acetate, and are obtained, in like man- 
 ner, either by heating the corresponding alcohols 
 with acetic and sulphuric acid, or by the action 
 of silver acetate on the corresponding alkyl 
 
 iodides. The following table shows their boiling 
 points and their S.G. in the liquid state. 
 
 utyl- \ 
 :e.OAo J 
 
 Propyl Acetates CaH,OAc : 
 
 Normal Propyl acetate 1 
 
 Me(On,XOAo or PrOAo J 
 
 Isopropyl acetate . t 
 
 MejCH.OAo or SrOAc . f 
 
 Butyl Acetates O.H,OAo : 
 
 Normal Primary : ) 
 
 MetCHJ.OAoor [ 
 
 CH^PrOAo . . . ) 
 
 Isoprimary : MeaCHOHj.OAo 1 
 
 orOH^BrOAo . . f 
 Secondary : Methyl ethyl ] 
 
 carbyl acetate [ 
 
 MeBtOH.OAo . . J 
 
 Tertiary : Trimethyl-oarbyl 1 
 
 acetate OMe,.OAo . , ) 
 
 Amyl Acetates CaHi,OAc : 
 
 Normal Primary : 1 
 
 Me(CHa)..OAo . . f 
 
 Isoprimary : 1^ 
 
 Me^CH(CH,),OAo . . f 
 
 Secondary : Diethyl - carbyl 1 
 
 acetate BtjCH.OAo ) 
 
 Methyl-isopropyl-caxbyl 1 
 
 acetate MeBrOHOAo j 
 
 Methyl-propyl-carbyl 1 
 
 acetate MePrOHOAo f 
 
 Tertiary : Dimethyl - ethyl- j 
 
 carbyl acetate MeaBtO.OAo J 
 
 ffexyl Acetates OsH„OAo ; 
 
 Normal Primary : ) 
 
 Me{OH,),OAc 
 
 Secondary : Methyl-butyl- 
 
 carbyl acetate 
 
 Me(OH,),CHMe, 
 
 Methyl-tert-butyl-carbyl \ 
 
 orPinacolyl acetate [ 
 
 Me.CHOAo.CMe, . ) 
 
 Ethyl-propyl-carbyl i 
 
 acetate BtPrCHOAo J 
 
 Septyl Acetates: 
 
 Normal from n- heptane 
 Do. from CEnanthol 
 Methyl-amyl-carbyl acetate ) 
 
 Me(C.H„)0H.OAo . f 
 Methyl-iso-amyl-carbyl ace- 1 
 
 tate Me(0,H„)OH.OAc J 
 Ethyl-iso-butyl-carbyl ace- ) 
 
 tate EtcC.fl,)CHOAo . j 
 
 Octyl Acetates; 
 
 Normal (from oil of ) 
 
 Heracleum) . . . f 
 
 Methyl-hexyl-carbyl acetate j 
 Me(O.H„)OH.OAo . / 
 
 Ennyl Acetates; 
 
 From Ennane in petroleum . 
 "Hthyl-hexyl-carbyl i ' 
 Bt(O.H„)OHOAc 
 
 Deajl Acetate ; 
 
 Normal 0,„H„OAc. Crystal-) 
 line. (125°) at 15 mm. f 
 
 Dodecyl Acetate ; 
 
 Normal O.aH^OAc. Solid. 1 
 (151°) at 15 mm. . ] 
 
 Cetyl Acetate ; 
 
 C„H„OAo. Needles. [18-6°] i 
 (200°) at 16 mm. . ; 
 
 Octadecyl Aeetats: 
 
 0„H„OAo. [31°] (223°) at 1 
 15 mm. . . . / 
 
 Iso-ceryl Acetate; 
 C„H„OAo [57°] . 
 
 Bthyl-hexyl-carbyl acetate 1 
 
 B.P. 
 
 102'^ 
 
 90°-93° 
 
 124° 
 116'6° 
 111° 
 
 148'4° 
 137° 
 132° 
 125° 
 133° 
 125° 
 
 169'5° 
 155°-167° 
 
 U0°-143° 
 150° 
 
 180° 
 192° 
 
 170° 
 167° 
 163° 
 
 207° 
 192° 
 
 210° 
 211° 
 
 s.a. 
 
 0-913 BtO° 
 
 0-9016 , 
 0-8596 , 
 0-892 , 
 
 0-8963 , 
 0-8837 „ 
 0-9090 „ 
 
 0-9222 „ 
 0-8909 „ 
 
 0-8890 at 17" 
 0-8778 at 0° 
 
 0-874 at 16° 
 0-860 at 23° 
 
 0-872 at 16° 
 
 0-878 at 0" 
 
16 
 
 ACETIC ACID. 
 
 AUyl Acetate «. Alltl aoetatb. 
 
 Phenyl Acetate v. Phenol. 
 
 Benzyl Acetate v. Benzyl acetate. 
 
 Uethylene Si-acetate v. FoitMic aldehyde. 
 
 Ethylene Acetates v. Glycol. 
 
 Folyethylenic Acetates v. Glycol. 
 
 Ethylene Aceto-butyrate v. Glycol. 
 
 Ethylene Aceto-chloride v. Glycol. 
 
 Propylene Acetate v. Propylene-glycol. 
 
 Butylene Acetate v. OxY-BniANES. 
 
 Amylene Acetate v. Oxy-pentahes. 
 
 Glyceryl Acetates v. Glycerin. 
 
 Substitution products of Acetic Acid v. 
 Bjjomo-aceiio AOioa, Chloro-aoetic acids, Iodo- 
 aoeho acids, Cyano-aoetio acid, Sulpho-cyano- 
 aoetio acids, sulpho-acetic acid. 
 
 Other deri/oaUves of Acetic Acid v. Acetyl 
 
 BROMIDE, BrOMO-AOETYL BROMIDE, ChLOBO-AOETYL 
 BROMIDE, CyANO-ACETYL BROMIDE, ACETYL CYANIDE, 
 
 Acetyl chloride. Acetyl iodide, Di-azo-acetio 
 ACID. H. W. 
 
 ACETIC BROMIDE v. Acetyl bromide. 
 
 ACETIC GHLOBIDE v. Acetyl ohi^okide. 
 
 ACETIC CYANIDE v. Acetyl cyanide. 
 
 ACETIC IODIDE v. Acetyl iodide. 
 
 ACETIC OXIDE or ANHYDRIDE C^Kfl, or 
 ACjO. — Acetyl oxide, Acetic cu:id, Anhydrous 
 acetic acid. — M.w. 102. (137-8°) at 755 mm. 
 (Kopp.) ; (44'6) at 15 mm., (136-4°) at 760 mm. 
 (Kahlbaum). S.G. 2 1-097, 'i^ 1-790 (K.) ; f 
 1-0816 (Bruhl). V.D. 3-47 (for 3-51). /i^ 1-3953. 
 Boo 35'82 (B.). H.F.p. 132,850. H.F.V. 180,820. 
 
 Formation. — 1. By the action of phos- 
 phorus trichloride or oxychloride on potassium 
 acetate, 3K0Ac -^ POCI3 = KjPO, -H 3AcCl, and 
 AoCl + KOAo = KCl + ACjO (Gerhardt, 1858, 0. E. 
 34, 755, 902 ; A. Oh. [3] 37, 285).— 2. From po- 
 tassium acetate and benzoyl chloride, the first 
 product of the reaction being aoetobenzoic 
 oxide, -which, if the potassium acetate is some- 
 what in excess, and the mixture is heated to a 
 temperature somewhat above that required for 
 its formation, is resolved into acetic and ben- 
 zoic oxides : KOAc -1- BzCl = KCl -1- AcOBz ; and 
 2AoOBz = Ao20-l-Bz20. Similarly from potas- 
 sium benzoate and acetyl chloride (Gerhardt). — 
 8. By digesting glacial acetic acid and acetyl 
 chloride in molecular proportions (Kanonuikofi 
 a. Saytzefi, A. 185, 192). — 4. From lead or silver 
 acetate and carbon bisulphide 
 
 2Pb(OAc)2 -I- CS2= 2PbS + ikofi + COj 
 (Broughton, Z. 1865, 306).— 6. From acetal chlo- 
 ride and barium oxide at 100° (Gal). — 6. In small 
 quantity by the action of phosphoric anhydride 
 on glacial acetic acid (Gal ; Etard, B. 9, 444).— 
 7. By the action of lead nitrate on acetyl chloride 
 (Laohowicz, B. 17, 1281). 
 
 Pre;paration. — 1. Acetyl chloride (1 pt.) is run 
 into sodium acetate (1 pt.) or potassium acetate 
 (Ij pt.), and the product is distilled. As, how- 
 ever, acetyl chloride is formed by the action of 
 the chlorine compounds of phosphorus on acet- 
 ates, it is clear that, for the preparation of the 
 anhydride, this chloride need not be quite free 
 from phosphorus oxychloride. It is sufficient, 
 indeed, to add POCl, (3 pts.) directly to an excess 
 of NaOAo (10 pts.) or EOAo (12 pts.) and 
 distil; or to prepare a mixture of POCl, and 
 AcCI, by the action of PCI5 (7 pts.) on glacial 
 acetic acid (2 pts.), and distil this mixture vrith 
 KaOAo (20 pts.) or KOAo (24 pts.). In all these 
 
 modes of preparation it is necessary to heat the 
 mixture strongly towards the end of the distilla- 
 tion, because a portion of the acetic oxide unites 
 with the excess of metallic acetate present, form- 
 ing a compound which requires a high temperature 
 to decompose it. The acetic oxide thus obtained 
 must be subjected to fractional distillation to free 
 it from residual chlorides and acetic acid (EekuW, 
 Lehrh. 1, 570).— 2. Hentschel (B. 17, 1285) pre- 
 pares acetic anhydride by passing a stream 0/ 
 carbonyl chloride, COClj, into fused dry sodio 
 acetate. 
 
 Properties. — Colourless, very mobile, strongly 
 refracting liquid, having an odour like that of 
 glacial acetic acid, but stronger. 
 
 Reactions. — 1. With HCl-gas acetic oxide 
 acts strongly at 100°, forming acetic acid and 
 chloride: Ao^O + HCl = AcOH H- AcCl (Gal, A. 
 Oh. [8] 66, 187).— 2. "With chlorine at 100° the 
 products are acetyl chloride and ohloracetic acid : 
 
 (C2H30)20 + Clj = CjHjOCl + CsHjClOj 
 (Gal). Similarly with Br. Withioi^iMe no action 
 at 200°, but at higher temperatures HI is 
 given off (Gal).— 3. With PCI5, it yields acetyl 
 chloride : Ac^O + PCI5 = POCI3 + 2AoCl.— 4. 
 Heated with solid aluminium chloride it forms 
 acetyl chloride and aluminium acetate : 
 SAcjO + AICI3 = 3AcCl + Al(0Ac)3 
 (Andrianowsky, /. iJ. 11,116). — 5. With pulverised 
 zinc chloride at 100° it yields acetic acid, acetio 
 oxide, and a dark brown residue having the 
 composition C^HjO (Bauer, J. 1861, 438).— 6. By 
 heating with zinc-dust it yields acetone (Jahn, 
 M. 1, 696). — 7. Eeduced by sodium amalgam it 
 forms aldehyde, and afterwards alcohol : 
 (CH3CO)20 + 2H3= 2CH3CHO + HjO ; 
 2CH3CHO + 2H3= 2CH3CH2OH 
 (Linnemann, A. 148, 249).— 8. Heated in COj- 
 gas at 60° with Cl.SOj.GH, it forms an acid, 
 C^H^SO, (Gal).— 9. With urea, at the boiling- 
 point, it forms acetyl carbamide, NHAoCO.NHj. 
 No reaction with oxamide (Scheitz ; Marsh a. 
 Geuther, Bl. [2] 10, 460).— 10. With nascent 
 zinc-ethyl (2 mol. EtI and 1 mol. Ac^O added to 
 zinc-sodium) it yields methyl-ethyl ketone : 
 (COMe)jO + ZnEt^ = ZnO -1- 2(Me.C0.Et). 
 With zinc-methyl in like manner : acetone, 
 Me.CO.Me (Saytzefi, Z. [2J 6, 104).— 11. Forms 
 crystalline compounds with NaHSOj and -with 
 NH3. The latter is formed by passing NH3 into 
 an ethereal solution of Ac^O at — 26° (Loir, 0. B. 
 88, 812). — 12. Gives a mirror with ammoniacal 
 AgNOj (Loir). — 13. Decolorises aqueous KMnO, 
 (Loir).— 14. Converted by H^SO, at 130° into 
 Bulpho-acetio acid (Franchimont, O. B. 92, 1054). 
 
 Oompounds. — A. With potassic acetate 
 AO2O2KOA0, obtained by dissolving dry potas- 
 sium acetate in AOjO at 100°, crystallises in 
 needles, and is resolved into its constituents by 
 heat (Gerhardt). B. With aldehydes.— (1.) 
 With acetaldehyde acetic oxide forms the com- 
 pounds G^B-fiAefl and C2H,02Ao20. The 
 first is obtained by heating its constituents 
 together in molecular proportion at 180° in a 
 sealed tube, and purified by fractional distUlation, 
 washing the portion which distils above 140° 
 ■with hot water, and drying over CaClj. It is a 
 liquid which boils at 168°, has an alliaceous 
 odour, and is resolved by heating with KOH 
 into acetic acid and aldehyde — distinction 
 from the isomeric compound, ethylene acetate 
 
AC'EiO-ACETIO ACID. 
 
 17 
 
 CjHj(OAo)2, which, when similarly treated, yields 
 glycol, CjHj(OH)j (Geuther, A. 106, 249). The 
 second compound, CjH40.2Ae20, formed by 
 heating paraldehyde with Ac^O at 160°, is a 
 liquid having a density of 1-07 at 10° (Geuther, 
 J. 1864, 329). (2.) With acrolein.— The com- 
 pound CjHjOAOjO is obtained by heating its 
 components in molecular proportion at 100° for 
 Biz hours, or 1 mol. acrolein chloride with 2 mols. 
 silver acetate at about 160°. Liquid immiscible 
 with water, having a fishy odour and very sharp 
 taste. S.G. 1-076 at 22° ; (180°). C3H,02Ao.,0, 
 formed by heating metacrolein with Ao^O at 
 150°, is an oily liquid boiling at 180^ (Hubner a. 
 Geuther, A. 114, 35 ; J. 1860, 306). (8.) With 
 henzaldehyde. — C,H50Ac20 is formed on heating 
 bitter-almond oil with excess of Ac^O at 150°, 
 and sepairotes on washing the product with water 
 and potash as an oily Uquid, which solidifies to 
 a crystalline mass melting at 44°-45° (Hubner, 
 Z. [2] 3, 277). These compounds may be 
 looked upon as derived from oriho-aldehydes, 
 XCH(0H)2. Similar compounds will be described 
 in articles on the several aldehydes. C. With 
 other oxides. — Vapour of SO3 is absorbed by 
 cooled AC2O, forming a gummy mass soluble in 
 water. Boric oxide dissolves slowly in AO2O, 
 forming a vitreous hygroscopic mass. Insoluble 
 tartaric oxide or anhydride, CjH^Oj, dissolves at 
 100° in acetic oxide, forming a syrup. The 
 same syrupy product is formed, together with 
 PbClj, by the action of AcCl on lead tartrate. 
 
 Aceto-arsenious Oxide C4H5O3AS2O3 or 
 Ac.O.OAs is formed by dissolving ASjOj in acetic 
 oxide at boiling heat, as a syrupy liquid, which 
 on cooling forms a vitreous hygroscopic mass. 
 
 Aceto-hypochlorous Oxide AoOCl and 
 Aceto-hyjaoiodous Oxide AoOI have been 
 described as unstable compounds by Schiitzen- 
 berger (0. B. 52, 359 ; 54, 1026 ; J. 1862, 240), 
 but their existence has been called in question 
 by Aronheim {B. 12, 26). 
 
 Aceto-silicic Oxide Si(OAc)j [110'] (148°) 
 at 6mm. From Ac^O and SiO^ (Friedel a. Laden- 
 burg, A. 145, 174). Decomposed by water, heat, 
 alcohol, or NH3, into siHca and HOAoAcuO, 
 EtOAc, and NHjAc, respectively. A compound, 
 Si(OBt)3(OAo) (c. 195°), is formed from Si(OEt)j 
 and Ac^O. 
 
 Aceto-benzoic Oxide CjHjOj i.e. AcOBz, 
 from acetyl chloride and sodium benzoate, is a 
 heavy oil. Begins to boil at 150°, and is resolved 
 at the same time into AOjO and Bz^O. By boil- 
 ing with water, and more quickly with alkalis, 
 it is converted into acetic and benzoic acids 
 (Gerh. 3, 209). HCl converts it at low tempe- 
 ratures into AoCl and HOBz ; at 150° BzCl and 
 HOAo are also formed. Chlorine forms AoCl and 
 o-ohloro-benzoic acid (Greene, C. N. 50, 61). 
 
 Aceto-cinnamio Oxide Ac.O.CgH,0. Ob- 
 tained hke the preceding, which it resembles. 
 on, heavier than water, very unstable (Gerhardt, 
 ib. 387). 
 
 Aceto-cuminic Oaiie Ao.O.C,|,H„0. Like 
 the preceding (Gerhardt, ib. 509). 
 
 Aceto-salicylic Oxide Ao.O.Cj'H.fi^. Solid; 
 dissolves in aqueous sodium carbonate, with 
 formation of sodium acetate and salicylate (Ger- 
 hardt, ib. 319). 
 
 Acetic Peroxide C4H|,04 or Ac^O^. — Prepared 
 by adding BaOj to a solution of acetic anhy- 
 V01-. L 
 
 dride in ether. The mixture Is effected gra- 
 dually, being attended with evolution of heat. 
 The ether is distilled off at a low temperature, 
 and the fluid which remains is washed with 
 water. It is a viscid liquid with pungent taste. 
 It decolorises indigo, oxidises manganous hy- 
 drate to peroxide, and potassic ferro- to ferri- 
 cyanide. It acts generally as an oxidising 
 agent. It does not reduce Cr03 or KMnO,. 
 Baryta-water is converted by it into barium 
 peroxide and acetate. It explodes when heated 
 (Brodie, Pr. 9, 363). H. W. 
 
 ACET-IMISAMIDE v. Acetamidine. 
 
 AC£I-IMIDO-£THYL-ETH£B 
 
 CHs.Cf 
 
 \OEt 
 (97°). Liquid. The hydrochloride is obtained 
 by passing dry HCl-gas into a mixture of aoeto- 
 nitrile and ethyl alcohol (equal mols.) diluted 
 with ^ their volume of ether, cooled to 0° C. 
 B'HCl, long trimetrio plates, decomposes at 
 about 100° into ethyl chloride and aoetamide 
 (Pinner, B. 16, 1654). 
 
 ACETIMIDO-NAPHTHYL-AMIDE v. Naph- 
 thyl-aoetamidine. 
 
 ACETIMIDO-TOLYL-AMIDE v. Tolyl-aoeta- 
 
 CHo.CO.CHo.COjH 
 
 MIDINE. 
 
 ACETO-ACETIC ACID 
 orCH,.C(OH):CH.C02H. 
 
 Occurrence. —In urine of diabetic patients 
 (Geuther a. Eupstein, Fr. 14, 419 ; DeichmuUer, 
 A. 209, 30 ; ToUens, A. 209, 36 ; Jaksch, H. 7, 
 487). 
 
 Preparation. — The ethyl ether (4-5 g.) is mixed 
 with water (80 g.) containing KOH (2'1 g.), and 
 after 24 hours the liquid is acidified and shaken 
 with ether (Ceresole, B. 15, 1327, 1872). 
 
 Properties. — A thick acid Uquid, miscible with 
 water. At 100° it splits up into CO2 and ace- 
 tone. Nitrous acid gas forms COj and iso-nitroso- 
 aoetone. 
 
 Salts. — BaA'jaq. Amorphous. V.e. sol. water. 
 Violet colour with FeClj. — CuA'2 2aq. Amorphous. 
 
 Ethyl Aceto-acetate or Aceto-acetic Ether 
 CHj.CO.CHj.COjEt or CH3.C(0H) : CH.CO^Et. 
 Bi-acetic ether (Geuther, J. 1863, 323), ethyl-di- 
 acetic acid (Geuther, J. 1865, 302), acetone-car- 
 boxylic acid (Frankland a. Duppa, A. 138, 211) 
 (180°) (E. Schiff, B. 19, 561); (180-8° cor.) 
 (Geuther) ; (180-6°-181-2°) at 754 mm. (Briihl) ; 
 (152-S°-153°) at 330 mm. (Perkin). S.G. "f 1-0256 
 B.); § 1-046 (S.); if 1-0317 (P.); f 1-0235 (P.). 
 in^ 1-4253. Boo 51-62 (B.). S.V. 153-34 (S.). 
 M.M. 6-501 at 16-25 (P.). 
 
 Formation. — The formation of aceto-acetic 
 ether by the saponification of cyano-acetone by 
 alcoholic HCl (Matthews a. Hodgkinson, B. 
 15, 2679) is denied by James (A. 231, 245). 
 
 Preparation. — Ethyl acetate (Ikilo.), that has 
 been carefully dried, is treated with sodium (100 
 g.) in small pieces. As soon as the first reaction 
 abates it is heated with inverted condenser over 
 a water bath for 2^ hours until the sodium ia 
 dissolved. Dilute (50 p. c.) acetic acid (550 g.) 
 is then added, and when the liquid is cool, it is 
 mixed with water (500 c.c). The light oily layer 
 is washed with a little water and fractioned. 
 The yield (175 g.) is small, but much ethyl ace- 
 tate (400 g.) is recovered (Conrad, A. 186, 214). 
 Aceto-acetic ether may be still further purified 
 
 C 
 
18 
 
 ACETO-AOETIC ACID, 
 
 by shaking with cone, aqueous NaHSOj, with 
 which it combines. Impurities may then be ex- 
 tracted by ether, and the compound of aoeto- 
 aoetic ether with NaHSOj afterwards decomposed 
 by K2CO3 (Elion, B. 3, 246). 
 
 The formation of aceto-aoetio ether may be 
 expressed by the equation : 
 
 2CH3.C02Et + Na2= 
 CH,.C0.CHNa.C02Et + NaOEt + H^, 
 the Bodio-aceto-acetic ether being afterwards de- 
 composed by the added acetic acid : 
 
 CH^.CO.CHNa.CO^Et + HO Ac = 
 OH3.CO.CH2.C02Et + NaOAo. 
 See also p. 21. 
 
 Properties. — A liquid with an agreeable sweet 
 odour. Slightly soluble in water, the liquid giving 
 a violet colour with FeClj. Unlike its ethyl and 
 acetyl derivatives, it forms a crystalline compound 
 with NaHSOj (indicating presence of the ketonie 
 carbonyl group, CO). 
 
 Salts. — Aoeto-acetic ether behaves as a mono- 
 basic acid. This may either be ascribed to the 
 situation of the group CHj between two CO 
 groups, or else by having recourse to the formula 
 CHs.C(OH) : CH.COaEt, which represents a com- 
 pound that might be expected, as a tertiary al- 
 •oohol, to possess a phenolic character. Like 
 phenol, it gives a violet colour with FeClj. 
 
 Sodio-aceto-acetic Ether 
 'CH3.C0.CHNa.C0,Et or CH3.C(0Na):CH.C02Et. 
 JSeedles. Eroduced by the action of sodium or 
 sodic ethylate upon aoeto-acetic ether in the cold. 
 
 Preparation. — Sodium (10 g.) is dissolved in 
 absolute alcohol (100 g.) ; when cold, dry ether 
 (90 g.), followed by aceto-acetio ether (56-5 g.) di- 
 luted with ether (60 c.c), is added. If the liquid 
 is well stirred with a little water (2 c.c.) solid 
 sodium acetaoetio ether separates (Harrow, G. J. 
 33, 426). The pp. is a hydrate, which becomes 
 Aty in an exsiccator (Elion, B. 3, 240). 
 
 Beactiori.s. — (a) With iodine in ethereal so- 
 lution it gives di-aceto-succinic ether (c[.v.). — (6) 
 -Heated alone or with NaOEt it gives acetone, 
 -aceto-aoetic ether, NaOAo, and sodic dehydrace- 
 tate. — (c) With alTcyl iodides it forms alkyl-aceto- 
 acetic ethers (q. v.) : 
 
 CH3.C0.CHNa.C0,Et + E'l = 
 Nal -^ CH3.CO CHE'.CO,Et. 
 Other iodo- bromo- and chloro- compounds act 
 similarly. — (d) But with tri-PHENTL-MEiHYL bro- 
 mide PhsCBr it forms CH3CO.C(OPh3).,CO,Et 
 <Allena. KoUiker, ^.227, 110).— (e) Chloroform, 
 in presence of NaOEt forms oxy-nviiio ethee : 
 CeH,Me(OH)(CO.,H)„ [1:3:4:6], the first 
 stage probably being : 
 
 2CH3.CO.CHNa.C0,Et + NaOKt + CHCI3 = 
 
 C0„Et.CHAc.0H:C(C0^Et).C0.0H, + 3NaCl-(-H0Bt 
 
 <Oppenheim a. Pfaff, B. 7, 929 ; 8, 884 ; 9, 321; 
 Conrad a. Guthzeit, A. 222, 249). 
 
 Other SaJis.— Al(CsH„0,,)3. Needles [7G°]. 
 Insol. water, v. e. sol. ether, benzene or CSj- 
 May be sublimed.— Co(C|,Hj03)2. Bed pp. Sol. 
 hot benzene or ether. — Cu("CbHj03)2 [182°]. 
 Green needles (from alcohol). Insol. water, v. 
 sol. benzene, ether or CS.^. Got by adding 
 Cu(OAc).^ to a solution of aceto-aoetic ether in 
 alcohol, the calculated quantity of ammonia 
 being also added (Conrad a. Guthzeit, B. 19, 19).— 
 jrg(C„H,,03), [240^. From aoeto-acetic ether 
 p.nd 'magnesia-mixture.' Plates (from ether- 
 Scnzenp).— Hg(C„H503)3 Amorphous. Formed 
 
 by shaking aceto-aeetic ether with HgO. — 
 Ni(C„H,03),. 
 
 Beactions. — 1. Boiled for a long time, or 
 passed through a red-hot tube, it forms dehy- 
 dracetic acid, CgHsOj, and alcohol. 
 
 2. Boiled with alkalis it gives CO2, acetone, 
 acetic acid and alcohol, according to the reac- 
 tions : CH3.CO.CH2.C02Et -I- 2K0H = 
 
 CH3.CO.CH3 + K,C03 + HOEt ; 
 
 CH3.CO.CH2.CO.,Et + 2K0H = 
 
 2CH3.CO.OK + HOEt. 
 
 3. Decomposed by water at 150', or by strong 
 acids, into CO2 acetone and alcohol. 
 
 4. Action of sodium alcoholates. — (a) Heated 
 with dry NaOEt, or with alcoholic NaOEt, ethyl 
 acetate is got in small quantity (12 p.o. of 
 the theoretical) (Wislicenus, A. 186, 193 ; Isbert, 
 A. 234, 160).— (6) 50 g. heated with NaOEt 
 (from 8-9 g. Na) and MeOH (75 g.) at 130° gives 
 methyl acetate (7 g.) and ethyl acetate (1 g.). 
 Similar results are obtained by using PrOH in- 
 stead of MeOH (Isbert).— (c) At 180° with NaOPr 
 and excess of MeOH gives methyl acetate and a 
 little propyl acetate. — (d) Heated with alcohol 
 at 180° it is not affected, but if a very little 
 NaOEt be present it is completely decomposed, 
 yielding EtOAc. Similar results are got by 
 using PrOH and NaOPr. Besacetic Acid 
 CjjHo^Os is found in all these cases as a resinous 
 body, not volatile with steam. It forms brown 
 amorphous salts, NaA', KA', and NHjA', sol. 
 wator (Isbert, A. 234, 167). 
 
 5. Sodium-amalgamiorms ;3-oxy-butyric acid: 
 
 CH3.C0.CH,.C0,Et + H2 = 
 CH3.CH(OH).CH2.C02Et. 
 
 6. Phenyl-hydrazine in the cold forms, as 
 with all ketones, a phenyl-hydrazide : 
 
 Ph.N. 
 
 I \CMe.CH2.CO2Et (?), 
 HN^ 
 but at 100° this loses EtOH and becomes methyl- 
 oxy-QUiNiziNE (g. ■!).) (Knorr, B. 17,2032). Pseudo- 
 oumyl-hydrazine produces the homologous hy- 
 drazide CH3.C(NjHC„H2Me3).CH2.C02Et [78°]. 
 Longyellow needles (from alcohol), orthickprisma 
 (from ether). V. sol. hot alcohol or ether, si. sol. 
 cold alcohol or benzoline. Very unstable, and at 
 130°-140° changes to oxy-tetra-methyl-quiniziner 
 CO . CH, 
 
 MejCjHi 
 
 \n — CMe 
 
 \/ 
 
 NH 
 
 (Haller, B. 18, 706). 
 
 7. Hydroxylamine forms, as with other 
 ketones, the oxim : CH3.C(NOH).CH„.C02Et, 
 /3-Oximido-butyric acid, CH3.C(NOH).CH2.C02H; 
 colourless crystals, [140°], si. sol. water, alcohol 
 or ether (Westenberger, B. 16, 2996). 
 
 8. Fuming nitric acid yields oxalic acid and 
 oxiMiDO-ACETO-ACETio ETHEK (o. ■!;.) (Propper, A. 
 222, 48). 
 
 9. Sulphuryl Chloride forms mono- or di- 
 chloro-aceto-aoetic ether, according to the pro- 
 portions used (AUihn, B. 11, 567) : 
 
 CH3.CO.CH2.CO.,Et + SO.,CL = 
 CH3.C0.CHCl.C0.;Et + SO2 + HCl ; 
 
 CH3.CO.CH2.C02Et + 2SO2CI3 = 
 CH3.CO.CCl2.C02Et + 2SO2 + 2HC1. 
 
 10. Bromine gives mono-, di-, tri-, and per' 
 
 BBOMO-ACETO-ACETIC ETHEBS (Wedcl, A. 219, 95), 
 
AOETO-AOETIO AOID. 
 
 10 
 
 11. Chlorine forms only di-onLOKo-AOEio- 
 
 AOTTIO BTHEIt (j. v.). 
 
 12. Phosphorus pentachloride forms the ohlo- 
 lides of two Chlobo-okotonio Aotos (q. v.). 
 
 13. Dry prussic acid heated with aoeto-aoetie 
 ether for 3 days at 100' forms a oyanhydrin, 
 CH3.C(OH)(CN).CH2.C02Et, which is converted 
 by boiling dilute HCl into oxy-pyrotartaric acid 
 (G. H. Morris, O. /. 37, 7). 
 
 14. Cyanogen chloride passed into sodio- 
 aceto-acetic ether forms Cyano-aceto-aoetio 
 EIHER {q. V.) CH3.C0.CH(CN).C02Et (Haller a. 
 Held, C. B. 95, 235). 
 
 15. Ammonia, whether dry (Precht, B. 11, 
 1193), aqueous or alcoholic (Duisberg, A, 212, 
 171), produces the imide of aoeto-acetic ether. 
 
 Aceto-acetic ether imide C^H^NOa [84°]. 
 (213° uncor.) at 760 mm., (154°) at 154 mm. 
 S.G. S2 1-014. s. (cone. NHjAq) 1-25. Dry NH, 
 is greedily absorbed by aoeto-acetic ether, the 
 compound CH3.C(OH)(NH2).CH2.C02Et being 
 doubtless at first formed. The liquid soon se- 
 parates into two layers, water and the imide of 
 aceto-acetic ether. The latter is purified by 
 distillation (Collie, A. 226, 297). Properties.— 
 Colourless monocliuic prisms. V. si. sol. water, 
 V. sol. alcohol, ether, benzene, CSj and CHGI3. 
 Moisture greatly lowers its melting-point. It is 
 CH3.C(NH).CH,.CO,EtorCH3.C(NH,):CH.C02Et. 
 Beactions. — (a) Aqueous HCl splits it up into 
 NH3 and aoeto-acetic ether (Duisberg). — (6) Cold 
 dilute NaOH has no action, but on warming it 
 gives NH3,H0Et, acetone and CO;.— (c) Pb(0Ae)2, 
 HgClj, ZnSOj, or FeCl3 also splits it into aceto- 
 acetic ether and NH3, the latter throwing down 
 the metallic hydrate. AgNO, does not give any 
 pp. — (d) Glacial acetic acid also regenerates 
 aceto-acetic ether on boiling.— (e) Sodium amal- 
 gam gives i3-oxy-butyric acid. — (/) Nitrous 
 fumes passed into aloohoho solution forms nitro- 
 80-aceto-aoetio ether. A by-product CgHiiN^Oj, 
 forms plates [170°].— (g') Ao^O at 160° forms an 
 acetyl derivative, CeH.jAcNO^ [63°] (232°),which 
 combines with bromine, forming CgHuAcBr^NOj 
 [140°]. — (h) Paraldehyde gives di-hydro-tri-me- 
 thyl-pyridine di-carboxylic acid, which is also 
 formed from aceto-acetic ether, NH3, and alde- 
 hyde. — (i) EtI at 100° forms ethyl-aceto-acetie 
 ether and a base (c. 290°), possibly ethoxy- 
 di- methyl -pyridine. Condensation -products : 
 C,|,H,3N03 [160°]. Present in the brown resin 
 got when CjHuNOj is distilled under atmo- 
 spheric pressure. Insoluble in alcohol and ether. 
 Boiled with KOHAq it forms oxy-di-methyl- 
 pyridine carboxylic acid. 
 
 16. Aceto-acetic ether methyl-imide, 
 
 CH3.C(NMe):CH2.C02Et or 
 CH3.C(NHMe) : CH.COjEt, 
 (133°) at 50 mm., (215') at 760 mm., is formed in 
 like manner from aceto-acetic ether and methyl- 
 amine (Kuohert, B. 18, 618). With paraldehyde 
 and H2SO4 it gives a condensation-product, 
 C|3H2,04N, which forms trimetrio crystals with 
 blue fluorescence [86°]. 
 
 17. DiethylamineioTmsP-di -ethyl -amido- 
 crotonic ether, CH3.C(NEt2) : CH.COjEt, a 
 liquid (160°-168°) at 20 mm. 
 
 18. Heated with amiUne (1 mol.) at 120° it 
 yields a crystalline body, C,„H,,N02, which melts 
 at 81° and is probably the anilide of acet-aoetic 
 aeid CB^.C(NFh). 03.^.00 fi. By dissolving this 
 
 substance in cold H^SO,, H^O is eliminated 
 with formation of (Py. l)-oxy-(Py. 3;-methyl. 
 QUiNOLiNE (Knorr, B. 16, 2593). 
 
 19. o-Phenylene-diamine forms : 
 
 C„H.,(N : CMe-CH^-CO^Et),. 
 
 20. o-Tolylene-diamine gvwes : 
 
 CH3.C„H3<^]|>CMe.CH,.CO,Et. 
 
 (Ladenburg, B. 12, 951 ; Witt, B. 19, 2977). 
 
 21. With aldehydes (Claisen, B. 12, 345) : 
 
 CHjGO.CH^.COjEt + ECOH = 
 HjO + CH3.CO.C(CH.E).C02Et. 
 The bodies are mixed in molecular proportions, 
 and HCl is passed in at 0'. Or the bodies may 
 be heated with Ao^O. Examples (Matthews, O. J. 
 43, 200) : — (a) Isobutyric aldehyde gives CuHuOj 
 (219°-222°). Oil. Smells like peppermint. Com- 
 bines with bromine. (6) Valeric aldehyde gives 
 C.iHisOs (237°-241°). S.G. if -9612. Oil. 
 Smells of strawberries. (c) Chloral gives 
 O3H3CI3O3 (154°_158°) at 25 mm. S.G. if 1-3420. 
 From chloral, acet-acetic ether, and AC2O at 
 150°. (d) Furfural gives CnHi^O^ [62°], (188°- 
 189°) at 30 mm. From furfural, acet-acetic ether, 
 and AcjO. Easily soluble in chloroform, acetic 
 acid, alcohol, and benzene. Large doubly-refract- 
 ing crystals (from light petroleum and ether). 
 
 22. Aoeto-acetic ether (2 mols.) condenses 
 with aldehyde-ammonia, forming di-hydro-tri- 
 
 METHTL-PTKEDINE-DI-OAKBOXTLIC ETHEB {q. V.) : 
 
 2CH3.CO.CH2.CO.,Et -1- CH3.CH(OH)NH2 = 
 
 3H,0 + C3H2NMe3(C02Et)3. 
 
 Since the product contains three methyls and 
 
 two COjEt groups, we may assume these to be 
 
 identical with the same groups in the reacting 
 
 bodies. And inasmuch as the product is not 
 
 acted upon by nitrous acid gas and forms an 
 
 ammonium iodide with Mel, it would seem to 
 
 be a tertiary base. Nevertheless, inasmuch as 
 
 methylamine and aldehyde give a similar body, 
 
 the reaction may probably be represented thus ; 
 
 CHMe 
 
 COjEt.CH HC.CO^Et 
 
 Me.COH H2 HOC.Me 
 NH 
 
 Me 
 
 8H2O + COjEt-O C.COjEt 
 
 II II 
 MeC CMe 
 
 \/ 
 
 NH 
 (Hantsoh, A. 215, 74 ; B. 18, 2579). Other aide- 
 hydes in presence of NH, form similar derivatives 
 of the pyridine series {v. Methtl-pieidine) . Thus 
 cinnamic aldehyde and ammonia forms di- 
 methyl - styryl - di -hydro - pyridine di-carboxylio 
 ether, H2C3NMe2(0H:CHPh)(CO2Et)2, [148'] 
 (Epstein, A. 231, 3). 
 
 23. Ylith. formamide and ZnClj aceto-acetio 
 ether gives di-methyl-pyridine carboxylic ether 
 (Canzeroni a. Spica, O. 14, 449). 
 
 24. With acetamide and AICI3 it forms 
 CH3.C(NAc).CH3.C02Et [65°]. Needles. Converted 
 by KOH into the amide of aoeto-acetic ether. 
 
 25. Mixing with acetamidine hydrochloride 
 and dilute NaOH, and, after standing for some 
 days, evaporating to dryness and extracting 
 with alcohol, yields a di-methyl-oxy-pyrimidine, 
 
 2 
 
20 
 
 AOETO-ACETIO ACID. 
 
 CANjO [190°]. Needles. V. sol. water or alco- 
 hol, si. sol. ether or benzene. It is probably 
 «N . CMe^ 
 CH3.Cf ^OH. 
 
 \N:C(0H)/ 
 PropUmamidine forms a homologue, methyl- 
 ethyl-oxy-pyrimidine [160°]. Its hydrochloride 
 forms thick prisms, CjHioN^OHCl [c.243°]. V. e. 
 sol. water, v. sol. alcohol— (CiHioNjOHCljjPtCl, 
 [236°]. Prisms. (Pinner, JB. 17, 2520 ; 18,2847). 
 26. With urea in alcoholic solution it forms 
 fl-nramido-crotonio ether (Behrend, A. 229, 5) : 
 MeC(OH) : CH.CO^Et + NH^.CO.NHj = 
 NH2.CO.NH.CMe : CH.C02Et + HjO. 
 The free iS-uKAMtDO-CROTONic agio, when liberated 
 from its salts, changes at once into its anhydride, 
 methyl-uracil : 
 
 NH.CO.NH.CMe:CH.CO 
 
 27. Thio-urea (40g.), heated with aceto-acetio 
 ether (40 g.) slowly to 150°, gives a compound 
 CjHjNjOS (5 g.), which may be thio-methyl- 
 uracil. It may be crystallised from water. 
 It dissolves in alkalis and is reppd. by acids. 
 Its melting-point lies above 300°. Its aqueous 
 solution gives with AgNOa an amorphous pp. of 
 CjH^AgjNjSO (Neneki a. Sieber, /. pr. [2] 25, 
 72). If a little HCl be added to an alcoholic 
 solution of thio-urea and aceto-acetio ether, un- 
 stable needles are formed. These are converted 
 by alcoholic potash into potassium thio-methyl- 
 nracil, CjHsKN.SO (List, B. 19, 219). 
 
 28. Aceto-acetic ether (20 g.), phenyl-urea 
 (10 g.), and ether (6 g.) at 150° react thus : 
 
 CeH,„0, -I- CHsN.O = C.aH.jNA + H,0. 
 The product is an oil which is decomposed by 
 alcohoUo potash with formation of ammonia 
 and aniline, and by boiling cone. HCl with form- 
 ation of CO2, alcohol, acetone, and phenyl- 
 carbamio ether, PhNH.COjEt. The reactions 
 indicate that the body CijHigNjOj has the consti- 
 tution NPhH.CO.N : CMe.CH^COjEt, or perhaps 
 
 00^ \cMe.CH2.C02Et 
 \NPh/ 
 (Behrend, A. 233, 1). 
 
 29. Combines directly with di-phenyl-urea, 
 in presence of a little ether at 150°, forming an 
 oil, OigHjjNjO,. This body is converted by al- 
 coholic KOH into aniline and KjCOj, and by 
 acids into phenyl-carbamio ether and aniline. 
 The body must be 
 
 PhNH.CO.NPh.C(OH)Me.CH2.C02Et. 
 Similar addition products are probably first 
 formed in the case of other ureas, but H^O 
 BpUts oS : 
 
 PhNH.CO.NH.C(OH)Me.CH2.C02Et = 
 HjO + PhNH.CO.N : CMe.CHj.CO^Et. 
 80. p-Di-aso-toluene Chloride, acting on an 
 alcoholic solution of aceto-acetic ether, forms 
 yellow needles of ^J-toluene-azo-aoeto-aoetic ether 
 [188°] C,H,Me.N2.CH(C0.CH3).C02Et (Bichtera. 
 Miinzer, B. 17, 1929 ; v. Azo compounds). 
 
 31. Hydrazo-benzene at 100°-150° forms 
 HOEt and a orystaUine base, CuHnNjO (A. 
 Mviller, B. 19, 1771). 
 
 32. Copper aceto-acetic ether is converted by 
 COCI2 into an anhydride of di-aoetyl-aoetone 
 di-carboxylio ether, CO(CHAo.COjEt)jp The 
 anhydride may be : 
 
 CH3.C - - O.CHj 
 
 II II 
 
 COjEiC-CO-CCOjEt. 
 
 [80°]. Sol. glacial HOAc, H^SOi, cone. HCl, ben- 
 
 zene, alcohol, or ether. NHj converts this body 
 
 into oxy-di-methyl-pyridine-di-carboxylio ether : 
 
 CHs.C-NH-C.CH3 
 
 II II 
 
 COjEt.C-CO-C.COjEt 
 (Conrad a. Guthzeit, B. 19, 22). 
 
 33. Aceto-acetic ether, heated with CSj and 
 PbO at 100°, forms ' thio-carbonyl-aceto-aoetio 
 ether • OH3.CO.C(CS).C02Et [156°-162°]. Yellow 
 needles (from alcohol) (Norton a. Oppenheim, 
 B. 10, 703). 
 
 34. S2CI2 converts sodium aceto-acetic ether 
 suspended in benzene into sulphido-aceto-acetio 
 ether S(CHAc.C02Et)2 [81°] (Buohka, B. 18, 
 2092). 
 
 35. With succinic acid it reacts thus : 
 C,H,„03 H- C,H,0, = C,„H,205 + 2H2O. 
 
 The product is a crystalline acid [76°], which is 
 the acid ether of a dibasic acid CgHjOs [200°] 
 (Fittig, B. 18, 2526). 
 
 Condensation products from aceto-acetic ether. 
 — 1. By heat: Passed through a red-hot tube 
 it forms dehydko-aoeiio acid (j. v.) and other 
 products (Perkins, jun. O. J. 47, 240).— 2. By 
 hydrochloric acid : Dry HCl at 8° forms, in four 
 weeks, acetic ether and ' carb-aoeto-acetio ether ' 
 CaH,„03(290°-295°unoor.). S.G.ai 1-136. This 
 liquid is slightly decomposed on distillation. It 
 gives no colour with aqueous Fe^Clj (Duisberg, A. 
 213, 179). Carb-aeeto-acetic ether is also formed 
 when aceto-acetio ether is heated with acetyl 
 chloride at 120° (Wedel, A. 219, 116).— 3. By 
 sulphuric acid : 
 
 CeH,(OH)(C02H).CO.O.C„H,(C02H)(C02Et) 
 [62°]. Got by leaving a mixture of aceto-acetio 
 ether (1 pt.) and cold cone. H^SO, (2^ pts.) for 
 fourteen days and then pouring into water 
 (Hantzsch, A. 222, 4). Needles resembling as- 
 bestos. SI. sol. cold water, m. sol. hot water and 
 ether, v. sol. alcohol, v. e. sol. chloroform. De- 
 composed by heat. It is acid to litmus and, 
 when hot, has a spicy odour. Its formation 
 may be represented thus : 
 
 4C„H,„03 = OiaHj^Og + SCAOH. 
 Beactio7is. — (a) Boiling alkalis form carbonate 
 and acetate, acetone, and mesityl oxide. (6) On 
 neutralising with alcoholic potash it decomposes 
 thus: 
 
 C.H,(0H)(0OaH).OO.0.O.H,(CO,H)CO,Et-HK;OH= 
 
 C.H,(CO,K)(^ \-(-C.H,(CO,Bt)<' y+2^0, 
 
 the potassium salt of mesitene-laotone carb- 
 oxylio acid being ppd. while its ether remains 
 in solution. 
 
 Mesitene-lactone Carboxylic Acid 
 CH3.C:C(C02H).CMe : CH.CO.O 
 
 [155°] (iso-dehydracetic acid). Fluffy crystals 
 (from water). SI. sol. cold water, v. sol. hot 
 water. Monoclinic prisms (from alcohol). May 
 be sublimed. 
 
 BeacUons. — Distilled with lime it gives mesi- 
 tyl oxide. 
 
 Salts.— Kk'laq,. — NaA'.— NH^A'— BaA'j.-- 
 MgA'j.— CuA'22aq.— AgjHsA',.— Ag,HA',. Strang 
 
AUJiTU-ACETIC ACID. 
 
 21 
 
 bases conveit iso-dehydracetio acid into oxy- 
 mesitene dicarboxylio acid, 
 
 CHs.C(0H)C:C(C02H).0Me:CH.C0,H, 
 which forms a stable copper salt Cu^B.Jl'\, but 
 its alkaline salts readily split off CO^ : 
 05H,(0H)(002Na)j f NaOH = 
 C8H8(0H)(C02Na) H-NajCOa, 
 forming oxy-mesitene oarboxylates. These 
 readily undergo a similar decomposition: 
 0,H8(0H) (COjNa) + NaOH = NajCOj + CsH„OH, 
 probably forming ' mesitenyl ' alcohol, which at 
 once changes to mesityl oxide. Baryta is the 
 best aiksiii to use in these decompositions. 
 Mesitene Lactone 
 
 CH3.C : CH.CMe :CH.C0.0 
 I I 
 
 [51"5°] (245° cor.). From iso-dehydracetic acid 
 by distiliation, or by heating with H^SO, at 170°. 
 Glittering tables. Very soluble in alcohol, ether, 
 or water, sparingly so in CSj. Tastes bitter and 
 spicy. Neutral to litmus. Separated by K2CO3 
 from aqueous solution. Gives with Br in CSj a 
 bromo-derivative, OjHjBrCOa [105°]. Converted 
 even by water into oxy-mesitene carboxylic acid. 
 Hence it is a 5-Iactone. 
 
 Oxy-mesitene Carboxylic Acid 
 
 C,H3(OH)(C02H) i.e. 
 CH3.C(OH):CH.CMe:CH.C02H. 
 From its lactone (mesitene-lactone) by boiling 
 with water or, better, with baryta. A thick 
 liquid, soluble in water. Its salts are amor- 
 phous, e.g. BaA'2, CaA'2. These salts on boiling 
 form carbonate and mesityl oxide. 
 
 Mesitene-lactone Carboxylate of Ethyl 
 
 CsH,{C0jEt)C02 i.e. 
 CH,.C: C(C02Et).CMe:CH.C0.0. 
 
 Formed, together with its potassium salt, by the 
 action of alcoholic KOH on the product of con- 
 densation of aceto-acetic ether, as described 
 above. Also from its potassium salt by EtI. Also 
 got when aceto-acetic ether, saturated with HCl, 
 is left at 0° for a month (Polonowska, B. 19, 
 2402). OU. Reactions. — (a) Br in CSj forms 
 CiHJBr(C02Et)C02 [87°]. Needles (from alcohol). 
 — (6) NH3 passed into an alcoholic solution forms 
 satiny plates of C8H,(CO,Et)(C02NH4)(ONHJ 
 melting at [104°], giving ofE 2NH3 + H2O, and 
 changing to the lactone. Warm water or cold 
 alcohol also change it to the lactone. Cold HClAq 
 Uberates CsH,(C02Et)(C02H)(0H), which maybe 
 extracted by ether. Small plates [76°]. Boiled 
 with water, two-thirds are changed to lactone, 
 and when the lactone is boiled with water, one- 
 third becomes oxy-acid. It forms salts of the form 
 C5H,(0H)(C02Et)(C02H), viz. CuA'^aq, PbA'^aq. 
 When the acid is boiled with alkali there is 
 formed dehydracetic acid and its decomposition 
 products, mesityl oxide, acetone, and COj, and 
 the following decomposition also occurs : 
 CH,.C:0(CO^Et).C!M;e:CH.CO.0+3HaO= 
 
 CH,.00,H+HOEt+OH,(COaH).OMe;CH.OO,H, 
 resulting in homomesaconio acid. 
 Homomesaconio Acid 
 
 CH2(C02H).CMe : CH.COjH 
 [147°]. Small prisms (from water). V. sol. cold 
 water, and alcohol, si. sol. ether. Not volatile 
 with steam, but sublimes about 120°. 
 
 SaZfc.— BaA"4iaq.— CaA"aq.— CuA"2aq.— 
 AgjA".— KHA".— NHjHA". 
 
 Ethyl ether Bt^A". (240°-242°). 
 
 Theory of the Condensation. — As acetone gives 
 mesityl oxide C^HioO or CH3.CO.CH:C(CH3)j, 
 BO aceto-acetic ether, if it is CE^.CO.GRfiO^t, 
 should give the dicarboxylio ether of mesityl 
 oxide, 03H30(COi,Et)2, or the acid,03H30(C02H)j. 
 Instead of this, it gives an isomeride of the latter, 
 C3H,(OH)(C02H)2, so that the group CO.CH 
 must have changed to C(OH):C. Assuming 
 that this group pre-exists in aceto-acetic ether, 
 the condensation would be as follows : 
 
 CH^.C(OH):C(CO,Et)H-l-H0.CMe:OH.CO,Et= 
 CH3.0(OH):0(CO,Bt).CMe:CH.CO,Bt+H,0= 
 CH,.0:0(CO,Bt).OMe:CH.OO.O+HOBt-l-H,0. 
 I 1 
 
 Aeetyl-aoeto-aoetio Ether 
 CH3.CO.CHAc.C02Et or CH3.C(0Ac):CH.C0jEt, 
 di-aceto-aeetic ether. (200°-205°). S.G. is. i-064 
 (James) ; 1^ 1-101 (Elion). Prom aceto-acetic 
 ether (65 g.), ether (50 g.) and sodium (9 g.), by 
 adding a solution of AcCl (30 g.) in ether (50 g.) 
 in the cold (J. W. James, A. 226, 210 ; 0. J. 47, 1). 
 
 Properties. — Pleasant smelling liquid, slightly 
 decomposed on distillation. Miscible with alco- 
 hol, ether, and benzene, hardly soluble in water, 
 but slowly decomposed by it into acetic acid and 
 aceto-acetic ether. Fe^Clj gives a raspberry-red 
 colour, removed by SOj. 
 
 Salts. — Acetyl-aceto-acetio acid is a strong 
 acid, and can expel acetic acid from its salts. 
 — CuA'22aq: insoluble in water; [148°]. — NaA' 
 (Elion, B. 3, 255).— NiA'22aq. 
 
 Reactions. — 1. NaOEt decomposes it into 
 EtOAc and sodium aceto-acetic ether. 
 
 Benzoyl-aceto-acetic Ether 
 
 OH3.CO.CBzH.C02Et 
 From sodium aceto-acetic ether and benzoyl 
 chloride alone (Bonn6, A. 187, 1), or dissolved in 
 ether (James, A. 226, 220 ; O. J. 47, 10). 
 
 Properties. — A fairly strong acid, capable of 
 displacing acetic acid. 
 
 SaiZ<.— CuA'2 (from benzene) [180°-190°]. 
 Formed by shaking the ether with aqueous 
 cupric acetate. SI. sol. alcohol or benzene, m. soL 
 ether. 
 
 o-Nitro -benzoyl- aceto-acetic Ether. — Pre- 
 pared as above, using nitro-benzoyl chloride. 
 It is an oil. Boiled with dilute H2SO4 it forma 
 o-nitro-phenyl methyl ketone and also o-nitro- 
 benzoyl-acetone in smaller quantity. Cono. 
 KOH forms a salt CH3CO.C (OsH4N02)K.C02Et 
 (Gevekoht, A. 221, 323). 
 
 Constitution of Aceto-aceHo Ether. 
 
 Some chemists adopt Frankland's formula 
 for aceto-acetic ether, CH3C0.CH2.C02Et ; others 
 prefer Geuther's formula, 0H3.C(0H):CH.C02Et ; 
 while a third party, relying upon the results of 
 Baeyer's researches into the constitution of the 
 derivatives of indigo, consider that both formula 
 are equally correct, or rather that at the moment 
 of reaction the first may change into the second. 
 Against Frankland's formula it is argued 
 
 (1) That the copper salt is blue or green, 
 whereas compounds in which copper is united 
 to carbon {e.g. copper acetylide) are red or yeUow. 
 
 (2) That it does not account for the existence 
 of acetyl and benzoyl derivatives. 
 
 (3) The formation of hydro-quinone di- 
 carboxylio ether, a body containing two hydroxyls, 
 by the action of sodium on di-bromo-aceto-acetid 
 
22 
 
 ACETO-ACETIO ACID, 
 
 ether. This indioatea the presence of hydroxyl 
 in di-bromo-aoeto-aeetio ether. 
 
 (4) The action of ammonia, and especially of 
 di-ethylamine. 
 
 In favour of Frantland's formula may be noted 
 the compounds with NaHSOa, phenyl-hydrazine, 
 and hydroxylamine. 
 
 The action of sodium upon aeeto-acetic ether 
 would be represented by Pranklaud'a formula, 
 thus : 
 
 CH,.C0.CH.C0aKt+Na=CH3.C0.0NaH.00,Et+n. 
 Ethyl iodide converts the product into ethyl- 
 aoeto-acetic ether : 
 
 OH3.00.0NaH.CO,Et+BtI=OH3.CO.OBtH.CO.Et+NaI 
 These two reactions may be repeated upon the 
 ethyl-aceto-aoetic ether : 
 
 CH,.C0.CEtH.C0,Bt+Na=CH3.C0.CEtNa.CO3Et+H 
 CH,.C0.CEtNa.C03Bt+BtI=0H,.C0.CEV003Et+NaI. 
 Adopting Geuther's formula, the four equations 
 become : 
 
 CH,.C( OH) :CH.CO^Et +Na= 0H,.O(0Na) rCH.OO^Et +H 
 CH,.C( ONa) iCH.CO^Et +BtI= 0H3.C(0Et) :01£.003Bt + Nal 
 
 0H3.0(0Bt):CH.C0,Et+Na=CH,.C(0Et):CNa.C0,Et+H 
 CHj.C(0B:):CNa.C03Bt+BtI=OH3.C(0Et):0Et.COaBt+NaI 
 It v?ill be seen that the third and fourth equa- 
 tions are similar to the first and second on 
 Frankland's hypothesis, but different in kind 
 to the first and second if Geuther's hypothesis 
 be accepted. Such a difference is not borne out 
 by experiment. Thus if it be held that the 
 action of sodium upon aceto-aoetic ether depends 
 upon its affinity for oxygen, the third equation 
 presents a difficulty. And if we suppose that, 
 owing to some intra-molocular change, the third 
 equation ought to be written thus : 
 
 CH,.0(OEt):CH.C03Et-HNa=OH,.0(ONa):CEt.CO,Et+H 
 then by the action of acetic acid on the product 
 we ought to get an ether 0Hs.C(0H):CEt.C02Et 
 isomeric, not identical, with ethyl-aceto-acetio 
 ether, CH3.C(OEt):CH.C02Et; but the two ethers 
 are found to be identical (James, 0. J. 47, 1). In- 
 asmuch as the change of CH3.C(0H):CEt.C0j,Et 
 into CH3.C(OEt):CH.C02Et would be contrary 
 to all analogy, it is necessary, if we adopt 
 Geuther's formula, to assume that the mode 
 of formation of di-ethyl-aoeto-acetic ether is 
 something very different from that of ethyl- 
 aceto-acetic ether. Again Geuther's formula 
 would make methyl-ethyl-aceto-acetic ether, 
 CH,.C{0Et):CMe.C02Et and ethyl-methyl-aoeto- 
 acetic ether, CH3.C(OMe):CEt.C02Et isomeric, 
 yet this does not appear to be the case (James). 
 It may be said that there is some improba- 
 bility in the assumption required by Frankland's 
 formula, of direct union between sodium and 
 carbon, but such a union is known to occur in 
 sodium acetylide and sodium ethide, and it is 
 very probable in many cases, such as sodio- 
 malonio ether, sodium nitro-ethane, and sodic 
 barbiturate. In order that hydrogen attached 
 to carbon may be displaeeable by metals, it is 
 necessary that very powerful chlorous groups 
 should also be attached to the carbon, such as 
 the nitroxyl in nitro-ethane. One carbonyl, CO, 
 is not sufficient to produce an acid, but two are. 
 Thus the hydrogen in the group CO.CH2.CO is 
 displaeeable by metals, as in barbituric acid, 
 >.NH.COv 
 C0<; NOHj. 
 
 \nh.co''^ 
 
 These considerations account for the acidity of 
 aoeto-aoetio ether, if we assume Frankland's 
 formula CH3.CO.CHj.CO.OH. 
 
 Although the existence of acetyl-aceto-acetia 
 ether favours Geuther's hypothesis, yet the fact 
 that this body is a strong acid is wholly opposed 
 to that view, and is very much better explained 
 by the formula CH3.C0.CH(C0.CH3).C0.0Et, 
 since if two carbonyls can make the group CHj 
 acid, a fortiori three carbonyls can have a simi- 
 lar effect. 
 
 The formation of ethyl and di-ethyl-aoetone 
 from ethyl-aoeto-aoetic ether and di-ethyl-aceto- 
 acetio ether respectively cannot be explained 
 on Geuther's hypothesis. 
 
 If, therefore, we have to choose between one 
 formula and the other, the balance of evidence 
 would indicate CH3.C0.CH,.C0.^Et. 
 
 Methyl aceto-acetate CsHgOj i.e. CH2Ae.C02Me 
 (170° cor.) S.G. a 1-037 (Braudes, J.Z. 3, 25). 
 From sodium and methyl acetate. Gives a cherry- 
 red colour with FejCl^. Boiled with acids or strong 
 bases it gives COj, acetone, and MeOH. 
 
 Salts.— GH,.GO.CB.^a..GOMe. SI. sol. ether. 
 — Cu(C5H,03)22aq. Separates on adding cuprie 
 acetate and baryta water to the ether as pale 
 green crystals, insoluble in alcohol. 
 
 Iso- butyl aceto-acetate CjH^Oa i.e. 
 CH^AcCO^C^H, (202°-206°) S.G. s -979; 2a -932. 
 From iso-butyl acetate and sodium. 
 
 Iso - amyl aceto - acetate Cg H,s O3 i. e. 
 CH2AC.CO2C5H,, (223°) S.G. 12.5 -954. From 
 iso-amyl acetate and Na (Conrad, A. 186, 228). 
 Converted by CI into an oHy di-chloro-derivative 
 (Conrad, A. 186, 243) and by NH3 into the imide 
 of aceto-acetate of iso-amyl [190'-195°] (Collie, 
 A. 226, 319). 
 
 ALKYLATED ACETO-ACETIC ETHEES. 
 Sodium aceto-acetio ether is converted by alkyl 
 iodides into mono-alkyl aoeto-acetic ethers, 
 CH3.CO.CXH.C02Et. The sodium derivatives 
 of these are in like manner converted by 
 alkyl iodides into di-alkyl-aceto-acetio ethers, 
 CH3.CO.CXY.C02Et. Such ethers are of great 
 service in organic syntheses, for they are split up 
 by weak alkalis into carbonic acid and mono- or 
 di-alkyl acetones : CHj.CO.CXY.CO^Et + 2K;0H = 
 CH3.C0.pXYH + H0Et + K2C03, and by strong 
 potash into mono- or di-alkyl-aoetic acid and 
 acetic acid : CH3.C0.CXY.C02Et + 2K0H = 
 CH3.CO2K -t- HCXY.CO2E + HOEt. 
 
 In practice the ketonic and acetic decompo- 
 sitions both occur, at the same time, but the 
 acetic decomposition increases with the con- 
 centration of the alkali (Wislioenus,j4.206, 308). 
 
 Preparation.— The alkyl-aceto-acetic ethers 
 are prepared by dissolving the calculated quan- 
 tity of sodium in 10 times its weight of absolute 
 alcohol, cooling, adding the aceto-acetio ether 
 and then the alkyl iodide until the liquid, which 
 may be warmed, if necessary, is neutral to 
 litmus. The greater part of the alcohol is then 
 distilled off and water is added. This dissolves 
 the Nal and the new ether rises as an oil and is 
 fractionated (Conrad a. Limpach, A. 192, 154). 
 
 A. With one monovalent eadicle.- 
 
 Methyl - aceto - acetic Acid CsHjO, i.e. 
 CH3.CO.CHMe.CO2H. A thick liquid which 
 splits up on warming into CO2 and methyl 
 ethyl ketone (Ceresole, B. 15, 1874). Its barium 
 salt is soluble and gives a violet colour with 
 Fe2Cl8. Nitrous acid forms iso-nitroso-methyl- 
 ethyl-ketone. 
 
 Methyl Ether CHi.CO.CHMe.CO^Me 
 
ACISTO-ACETIO ACID. 
 
 2» 
 
 [m-i" oor.) S.a. 2 1-020 (Brandes, Z. 1866, 
 468). From sodium aceto-aeetate of methyl 
 and Mel. Smells like mint. Gives a violet-red 
 colour with FejClg. 
 
 Ethyl Ether CHa.CO.CHMe.CO^Et (186-8° 
 cor.) (Geuther, Z. 1866, 5). S. G. s 1-009. Gives 
 a deep blue colour with FojClg. 
 
 Reactions. — 1. Sodium amalgam gives an 
 oxy-valerio acid CH3CH(0H).CHMe.C0,H.— 2. 
 Potash forms methyl-ethyl ketone, alcohol and 
 K.,COa. — 3. PCI5 gives ohloro-methyl-crotonio 
 acid [69-5°] (206°) (Kucker),chloro-methyl-aceto- 
 aoetio ether, 0,H„C103 (180°) S.G. la i-093, 
 smelling of peppermint, and di-ohloro-methyl- 
 aceto-aoetio ether (210°-220°) S.G. U 1-225 
 (Isbert, A. 234, 188). — i. Sodium and cyanogen 
 chloride form oyano-methyl-aceto-acetic 
 ether CAoMeCy.COjEt (c. 93°) at 20 mm. S. G. 
 35.-996. It is a colourless liquid insol. water and 
 alkaUs (Held, O. B. 95, 522; Bl. [2] 41, 330). 
 
 Acetyl derivative CgHuO^ i.e. CMeACjCO^Et. 
 Methyl-diacetyl-acetic ether (205°-220°). From 
 methyl-aceto-aoetic ether in ethereal solution 
 and AcCl (James, A. 226, 219, 0. J. 47, 1). SI. 
 sol. water. Coloured raspberry red by FejClj. 
 Does not pp. oupric acetate, even on addition of 
 dilute NaOH. 
 
 Ethyl-aceto-acetic acid. 
 
 Methyl ether CHj.CO.CEtH.CO^Me (189-7° 
 cor.) S. G. l*;995 (Brandes, Z. 1866, 457), Fe^Ci, 
 gives deep violet colour. Cone. NH, forms an 
 oil CjHjsNOj, the imide of ethyl-aceto-acetate of 
 methyl insoluble in water, and also silky needles 
 [83^] of a soluble amide (probably C5H,,N02 see 
 below) (Brandes, Z. 1866, 457). 
 
 Ethyl ether OsH^Oj i.e. CAoEtH.COjEt 
 (198° oor.) S.G. la -998 (G.) ; i# -983 (F. D.) 
 (Geuther, Ar. Ph. [2] 116, 97 ; Frankland a. 
 Duppa, C. J. [2] 4, 396; WisKoenus, A. 186, 187). 
 
 Preparation. — Aceto-acetic ether is dissolved 
 in benzene and four-fifths of the calculated quan- 
 tity of sodium added, then EtI, and the product 
 rectified. The aceto-acetic ether recovered is 
 treated with the remaining fifth of the sodium. 
 Yield 70 per cent. (Wedel, A. 219, 100). 
 
 Properties. — An oil. Coloured blue by FejClj. 
 
 Beactions. — 1. Eeduced by sodium, amalgam 
 to an oxy-hexoic acid,CH3.CH(0H).CHEt.C0jH. 
 2. Boiled with baryta or weak alcoholic KOH, it 
 gives methyl propyl ketone. — 3. Boiled with cone, 
 alcoholic KOH, or heated with dry NaOEt, it gives 
 re-butyric acid and acetic acid, or their ethers. — 
 4. Treated with NaOEt and cyanogen chloride 
 it forms cyano-ethyl-aceto-acetic ether, 
 CH3.C0.CEtCy.C02Et (c. 105°) at 20 mm. S.G. 
 — -976. A colourless liquid with agreeable odour. 
 Insol. in water or alkaline solutions, miscible 
 with alcohol or ether (Held, O. B. 98, 522, Bl. 
 [2] 41, 330). — 5. Bromine acting on an ethereal 
 solution forms mono- di- and tri- beomo-eihyl- 
 ACETO-AOETic ETHER (g. «.).— 6. PCI5 gives mono- 
 and di- chlobo-bthyl-aoeto-aoetio ethee, and 
 only one ohloeo-ethyl-ceotonio acid (g. v.) 
 (Isbert, A. 234, 183). — 7. Benzoic aldehyde 
 and HCl form some benzylidene-ethyl-aceto- 
 acetic ether or cinnamoyl-ethyl-acetic ether, 
 Ph.CH:CH.C0.CHEt.C02Et (210°) at 22 mm. 
 Converted by NaOEt and EtI into cinnamoyl-di- 
 ethyl-acetio ether. — 8. Gone, aqueous ammonia 
 forms two amides, one soluble in water, CbH„N02, 
 the other insoluble, CjHijNO.^. They are formed 
 
 in equi-molecular quantities ; the oily insoluble 
 amide crystallises when cooled. On distilling 
 the soluble amide does not pass over with steam. 
 
 Insoluble amide CgH,,N02 imide of etbyl- 
 aceto-aoetic ether CH3.C(NH).CHEt.C0.,Et or 
 CH,.C(NH.):CEt.C02Et [59-5'']. Monocliuio 
 tablets (from alcohol), smelling of peppermint. 
 Decomposed by water, or dilute acids, into NH, 
 and ethyl-aceto-acetic ether (Geuther, Z. 1871, 
 247). 
 
 Soluble amide CoH„N02i.e.CAcHEt.CONH4 
 [90°]. Needles (from water, alcohol, or ether).. 
 May be sublimed. May be obtained from the- 
 preceding body by heating with water at 135°., 
 On dry distillation it gives NH3, 00^ and methyl 
 propyl ketone. The latter body is also formed 
 by heating it with water at 200°, with boiling 
 aqueous HCl, with CaCl.,, ZnClj, P^Oj, or PCl^ 
 (Isbert takes it to be di-ethyl ketone). Heated 
 with dry KOH at 100° it forms butyric and aoetio 
 acids (Isbert, A. 234, 170). 
 
 SaZis.-CHj.CO.CNaEt.OOjEt. Formed by 
 adding sodium to a solution of ethyl-aceto-acetio 
 ether in dry ether or benzene (3 or 4 vols.) (J. W. 
 James, C. J. 47, 1). Also by shaking an ethereal 
 solution of the ether with perfectly dry NaOH 
 (Elion, B. 3, 234). It is amorphous. V. sol. 
 ether. A little water added to its ethereal solu- 
 tion forms a pp. of CH3.CO.CNaEt.C02Et aq, 
 insol. ether or benzene, but sol. water or alcohol. 
 Acetic acid re-eonverts the sodium salt into 
 ethyl-aceto-acetic ether (v. constitution of Aceto- 
 acetic ethek). 
 
 Ethyl aceto-acetic ether forms no copper 
 compound. This is thought to favour the fot-^ 
 mula CH3.C(OEt):CH.C02Et. 
 
 Iso-amyl ether CHj.CO.CHEt.CO^CjH.j 
 (233°-236°) S.G. |f .5 -937 gives no colour with 
 Fe^Clj (Conrad, A. 186, 228). 
 
 Acetyl derivative CHj.CO.CAcEt.CO^Et.. 
 Ethyl-di-acetyl-acetic ether (0. 230°) ; (144°- 
 150°) at 50 mm. S.G. l^ 1-034. From 
 CHj.CO.CNaEt.COjEt and AoCl (Elion, B. 3, 
 265). Liquid. Insol. KOHAq. Gives no colour- 
 with FejClj. Alcoholic NH3 converts it into- 
 acetamide and CHj.CO.CHEt.COjEt. 
 
 AUyl- aceto-acetic Ether CjH,j03 i.e., 
 CH3.CO.CH(03Hs).C02Et (206°) (Zeidler, A. 187,, 
 33) (214° cor.) at 720 mm. (Perkin, O. J. 45,. 
 540). S.G. f?.5 -982 (Z.) ; if -993 ; H -985 (P.).. 
 From sodium aceto-acetic ether and allyl iodide- 
 (Z.; Wolff, A. 201, 46). From aoeto-acetic: 
 ether, allyl iodide, and zinc, di-allyl-aceto-acetie 
 ether being also formed (0. Hofmann, A. 201, 77). 
 
 Beactions. — 1. Fe^Clj gives a crimson colour. 
 2. Boiling alcoholic KOH forms CO^ and allyl- 
 acetone.— 3. Dry NaOEt at 150°-160° gives ethyl 
 acetate and' allyl-acetate. — 4. Sodium amalgam 
 forms an oxy-heptenoio acid, 
 
 CH3.C(0H)H.CH(C3H5)C0,H. 
 
 Propyl -aceto-acetic Ether OgHuOj i.e. 
 CHj.CO.CHPr.COjEt (209*) S.G. 2 -981. From 
 aceto-acetic ether (153g.) by adding first a solu- 
 tion of sodium (27g.) in dry alcohol (270g.) and 
 then PrI (206g.) (Burton, Am. 3, 385). DecomI 
 posed by aqueous KOH into COj, alcohol, and 
 methyl butyl ketone. 
 
 Iso-propyl-aeeto-acetlc Ether CgHijOj i.e. 
 CHj.CO.CPrH.COjEt (201°) at 758 mm. S.G. « 
 •880. From sodium aceto-acetic ether and iso 
 propyl iodide (Frankland a. Duppa, A. 145, 78^ 
 
24 
 
 ACETO-ACETIC ACID. 
 
 Coloured pale reddish-violet by FejCl^ (Demar- 
 9ay, Bl. 27, 224). 
 
 iBO-butyl-aoeto-acetic Ether 0,„H,g03 i.e. 
 Pr.CHjCHAo.COjEt (218°) S.G. Hls .931. From 
 sodium aceto-aoetio ether and iso-butyl iodide 
 (Eohn, A. 190, 306). Decomposed by baryta 
 giving methyl iso-amyl ketone and iso-butyl- 
 aoetio (hexoio) acid. 
 
 Heptyl-aceto-acetic Ether C^sH^jOj i.e. 
 CH3.C0.CH(C,H,5)-C02Et (272°) S.G. '^^ -9324. 
 From sodium aceto-acetic ether and heptyl 
 iodide (Jourdan, A. 200, 105). Colourless oil. 
 Decomposed by dilute alkalis into methyl octyl 
 ketone and COj ; and by cone, alkalis into 
 acetic and n-ennoic acids. 
 
 Secondary Heptyl-aceto-acetic Ether (250°- 
 260°). Prepared similarly from secondary heptyl 
 iodide (Venable, B. 13, 1651). 
 
 Octyl-aceto-acetic Ether CuHjeOj i. e. 
 CH3.CO.C(C8H„)H.CO,Et (281°) S.G. 1|| -9354. 
 From octyl iodide and sodium aceto-acetic ether 
 (Guthzeit, A. 204, 1). Decomposed by alcoholic 
 KOH into methyl ennyl ketone and decoio 
 acid. 
 
 Benzyl -aceto-acetic Ether OuHisOj i.e. 
 0H3.00.CH(CHjPh)C02Et (276°) S.G. JIf 1-036. 
 From sodium aceto-acetic ether and benzyl chlo- 
 ride (EhrUch, B. 7, 690 ; A. 187, 12 ; Conrad, B. 
 11, 1056). Sodiumamalgamgivesexo-oxy-phenyl- 
 valerio acid CH3.CH(OH).CH(CH2Ph).C02Et. 
 Alcoholic KOH forms phenyl-ethyl methyl 
 ketone. 
 
 B. With two Di-valbni Eadioles : 
 
 Ethylene-aceto-acetic Acid. 
 CH3.CO.C(C2H4).C02H. From the ether by 
 saponification. Liquid. Decomposed by heat 
 or by dilute acids into tri-methylene methyl 
 ketone 
 
 OHj-CCCh/ I ' and CO,,. 
 \CH2 
 
 Salt.— AgA.'. 
 
 Ethyl ether.— 'EtA' (193°-195°). From aceto- 
 acetic ether (26g.) by adding a solution of sodium 
 !5g.) in alcohol followed by ethylene bromide 
 38g.) The liquid is boiled for eight hours, 
 filtered, and distilled. The residue is boiled for 
 twelve hours longer with a solution of sodium 
 (5g.) in alcohol, evaporated, and treated with 
 water. The ether is extracted by ether and 
 dried over K.COs (W. H. Perkin, jun., O.J. 47, 834 ; 
 B. 16, 2136; 19, 1247). It reacts with phenyl- 
 hydrazine, forming an oil. 
 
 Ethylidene-aceto-acetic Ether. 
 CHj.CHtCAcCOjEt (210°-212°) S.G. i5 1-023 
 By passing HCl into aldehyde (1 pt.) mixed with 
 aceto-acetic ether (3 pts.) (L. Claisen a. P. H. 
 Matthews, A. 218, 172 ; Claisen, B. 14, 345). 
 
 Pungent ethereal oil. Miscible with HjSOj. 
 
 Reactions. — 1. Hot potash decomposes it, 
 forming aldehyde. — 2. Combines with bromine. 
 
 Tri-chloro-ethylidene-aceto-acetic Ether. 
 CCI3.CH : CAc.COjBt. S.G. is. 1-342 
 
 From chloral, aceto-acetic ether and AcjO at 
 160°. (Claisen a. Matthews, A. 218, 175). 
 
 Thick oil. Decomposed by heat. 
 
 Fropylene-aceto-acetic Acid, 
 
 CH3.CH V 
 
 I >CAc.COjH 
 CH3/ 
 
 From the ether by saponification. Oil 
 Forms an amorphous silver salt, AgA'. 
 
 Ethyl ether (210°-215°) at 720 mm. Aoeto- 
 acetic ether (26g.) is heated with sodium (4-6g.), 
 dissolved in dry alcohol and propylene bromide 
 (40g.) at 100°. After two days the tubes are 
 opened and a fresh quantity of alcoholic NaOEt 
 (from 4'6g. sodium) is added, and the tubes 
 heated again at 100° (Perkin, jun., B. 17, 1443). 
 
 Tri-methylene Bromide acts on aceto- 
 acetio ether in presence of NaOEt, but the 
 product C,H„03 (V.D. 6-21) is not tri-methylene- 
 aceto-acetic ether, for its boiling point (223°) and 
 molecular magnetic rotation, 10'195, are both 
 too high, and it does not react vdth phenyl- 
 hydrazine. It is, however, the ether of a crys- 
 talline acid which splits up on distillation into 
 COj and CjH,„0, and on boiling with water into 
 CO, and acetyl-butyl alcohol. The acid is probably 
 ,C(COjH):CMe 
 
 ch/ I 
 
 \CH3.CHj.O 
 (Perkin, jun., B. 16, 208, 1789; 19, 1247, 2557). 
 
 Iso-butylidene-aceto-aoetic Ether 
 (CH3)jCH.CH:CAc.CO^t(219°-222°). 
 From isobutyrio aldehyde, aceto-acetic ether 
 and HCl (Claisen a. Matthews, A. 218, 174). 
 
 Liquid smelling of peppermint. 
 
 Iso-amylidene-aceto-acetic Ether. 
 (CH3)i,CH.CH2.CH:CAc.C02Et 
 (237°-241°) S-G. 1^ -961. From valeric aldehyde, 
 aceto-acetic ether and HCl (Claisen a. Matthews, 
 A. 218, 174). 
 
 Benzylidene-aoeto-acetic Ether 
 Ph.CH : CAc.CCEt (a-aoeto-cinnamio ether), 
 [60°] (180°-182°)' at 17 mm. (295°-297°) at 760 
 mm. From aceto-acetic ether, benzoic aldehyde 
 and gaseous HCl at 0". (Claisen a. Matthews, 
 A. 218, 177) 4 or 6 sided tables (from alcohol) ; 
 trimetric, a : b : = '447 : 1 : "962. Colourless oil, 
 solidifying very slowly. V. sol. ohjoroform, m. 
 sol. cold alcohol, ether, glacial acetic acid or 
 CS2, v. si. sol. benzoline. Insoluble in aqueous 
 KOH. HjSO, forms a bright yellow solution 
 which, on warming, becomes very dark red. On 
 pouring this solution into water a white pp. 
 is formed, and on adding NaOH this dissolves, 
 forming a violet solution. 
 
 Reactions. — Bromine in ether forms a di- 
 bromide [97°]. This forms short needles (from 
 benzoline). 
 
 Theory of the Process. — ^Benzoic aldehyde 
 probably first combines with HCl forming 
 Ph.CH(OH)Cl, and this reacts with aceto-acetic 
 ether thus : 
 
 Ph.CHCl(OH) + CHjAo-COjEt = 
 H,0 + Ph.CHCl.CHAc.CO^Et. 
 Two compounds of this formula may be isolated 
 before distillation, one forms prisms [41°], the 
 other small rhombohedra or triclinio tables 
 [72°] (both from benzoline). They are both 
 unstable, giving ofl HCl. One of them has pro- 
 bably the formula Ph.CHCl.CHAo.COjEt and 
 decomposes into HCl and Ph.CHiCAc.CO^Et, 
 which recombines with HCl forming the other 
 Ph.CHj.CClAc.C02Et. On distillation both pro- 
 bably give HCl and benzylidene-aceto-acetic ether. 
 Benzylidene-ethyl-aceto-acetic Ether 
 Ph.CH:CH.C0.CHEt.C02Et 
 (205°-220°) at 22 mm. (Cinnamoyl-ethyl-aoetic 
 ether). From benzoic aldehyde, ethyl-aoeto- 
 
ACETO-AOETIO ACID. 
 
 26 
 
 twiotio etlier, and HCl. Yield small (Claisen a. 
 Matthews, A. 218, 184). 
 
 Benzylidene-di-etliyl-aceto-acetic Ethez 
 Ph.CH:CH.C0.CEt2.C0^t 
 (101°-102°]. Formation.— (1) From the above, 
 NaOEt, and EtI. — (2) From benzoic aldehyde, 
 di-ethyl-aoeto-acetio ether, and HCl (CM.). Tri- 
 clinio prisms (from benzoline). V. sol. ether 
 or chloroform, m. sol. cold alcohol or benzoline. 
 Dibromide [55°]. 
 
 Furfural-aceto-acetic Ether 
 
 (C5H,0)"OAo.C02Et 
 [62-5°]. (189°) at 30 mm. From furfur-aldehyde, 
 aeeto-acetic ether, and AcjO at 160°. (Claisen 
 a. Matthews, A. 218, 176.) Trimetrio crystals, 
 a : b : = -489 : 1 : ■465. V. sol. alcohol, glacial 
 acetic acid, chloroform, and benzene. M. sol. 
 ether, si. sol. benzoline. 
 
 C. With two Monovalent Eadioleb. 
 Si-methyl-aceto-acetic Acid 
 
 CjHioOa i.e. CH3.CO.CMe2.CO2H. 
 From the ether by dissolving in cold dilute 
 (2^ per cent.) aqueous KOH, setting aside for a 
 day or two, then acidifying with HjSOj, ex- 
 tracting with ether, evaporating the ether, and 
 triturating with BaCO,. The crystalline barium 
 salt.BaAj', is decomposed by dilute HjSO, (Cere- 
 sole, B. 15, 1871). Very hygroscopic crystals, 
 which slowly split up into CO2 and methyl iso- 
 propyl ketone. The barium salt gives a brown 
 colour or pp. with Fefilg. It reduces boiling 
 silver nitrate. 
 Ethyl Ether 
 
 CjHuOs i.e. CH3.C0.CMe2.C02Et 
 (184°) S.G.iS-991. From sodium methyl-aceto- 
 acetic ether and Mel (Frankland a. Duppa, A. 
 138, 328). Potash or baryta splits it up into 
 alcohol, COj, and methyl iso-propyl ketone. 
 Uethyl-ethyl-aceto-acetic Ether 
 CH,.C0.CMeEt.C02Et 
 (196° uncor.) (J.) (201° i. V.) (Wislicenus, A. 
 219, 308). S.G-. 11.5 -947. From sodium ethyl- 
 aceto-acetic ether and Mel (Saur, A. 188, 257) ; 
 or sodium methyl-aceto-acetio ether and EtI 
 (J. W. James, A. 226, 209 ; C. J. 47, 1). Oil. 
 FCjCIb gives a violet colour. Distilled with dry 
 NaOEt it gives ethyl acetate and ethyl methyl- 
 ethyl-acetate (or valerate). 
 
 Hethyl-allyl-aceto-acetic Ether 
 C,„H,e03 i.e. CH3.C0.CMe(C3H5)C02Et 
 (0. 209°-211°). From allyl-aceto-acetic ether, 
 Mel, and NaOEt (James, 0. J. 47, 3). Pleasant- 
 smelling oil, miscible with alcohol, ether, or ben- 
 zene. FCjCl, gives no colour. The same body 
 may be got from methyl-aoeto-aoetio ether, allyl 
 iodide, and NaOEt. 
 
 Jlethyl-propyl-aceto-acetic Ether 
 0,„H„03 i.e. CH3.C0.CMePr.C02Et 
 (214°) (L.E.); (216°) (J.). S.G. i5 -959 (L.K.) ; 
 Y "9575 (J.). From methyl-aceto-acetic ether, 
 NaOEt, and PrI (Liebermann a. Kleemann, B. 
 17, 918) or from propyl-aceto-aoetic ether, NaOEt, 
 and Mel (E. J. Jones, A. 226, 287). 
 Si-ethyl-aceto-acetic acid 
 
 CH3.CO.C(C2H5)2.C02H. 
 Thick colourless liquid. SI. sol. water. 
 
 Preparation. — Di-ethyl-aoet-aoetio ether is 
 left in the cold for several weeks with 10 p.o. 
 aqueous KOH. After removing the unaltered 
 ether, the product is acidified and extracted with 
 ethor, and the acid purified by conversion into 
 
 the barium salt, acidifying the latter, and again 
 extracting with ether. 
 
 Reactions. — It decomposes very slowly in the 
 cold, but on heating to 60° it rapidly evolves 
 CO2, forming di-ethyl-aoetone. The latter body 
 is also formed by distilling the barium salt. 
 
 Salts. — A'Na; easily soluble white micro- 
 scopic crystals. — A'jBa 2aq; transparent prisms, 
 rotates on water (Ceresole, B. 16, 830). 
 
 Ethyl ether C,„H,803 i.e. CHj.CO.CEtj.COjEt 
 (218°). S.G. 22 -974. From sodium ethyl-aceto- 
 aoetio ether and EtI (Frankland a. Duppa, A. 
 138, 211 ; James, A. 226, 205). From CLCO^Et, 
 Na, and EtI (Geuther a. Matthey, J.pr. [2] 6, 
 160). 
 
 Reactions. — 1. With hot aqueous baryta it 
 gives di-ethyl-acetone. — 2. Distilled with dry 
 NaOEt it gives di-ethyl-acetio (hexoic) ether, 
 acetic acid, and sodic di-ethyl-acetate.— 3. PClj 
 gives mono- and di-chloro-di-ethyl-aeeto-acetio 
 ether and chloro-ethyl-crotonio ether (James, 
 A. 231, 235).— 4. With benzoic aldehyde and HCl 
 gas it forms some CsH5.CH:CH.C0.CEt2.C02Et, 
 cinnamoyl-di-ethyl-aoetic ether. Crystals, 
 [102°], (200°-205°) at 3 mm. Easily soluble in 
 ether and chloroform, slightly in cold alcohol 
 and in light petroleum (Matthews, 0. J. 43, 205). 
 Bromine in chloroform forms a di-bromide, 
 [55°]. Prisms v. sol. alcohol and light petroleum. 
 
 Si-allyl-aceto-acetic Ether 
 
 CijH.sOj i.e. CH3.CO.C(CaH3)2C02Et 
 (240°). S.G. ff .5 -948. From sodium allyl-aceto- 
 acetic ether and allyl bromide (Wolff, A. 201, 45). 
 From aceto-acetic ether, allyl iodide, and zinc 
 (0. Hofmann, A. 201, 77). Colourless oil, with 
 faint peculiar odour. Insol. water, sol. alcohol, 
 ether, or benzene. Boiling cone. KOHAq forms 
 di-allyl-acetone, or methyl heptinyl ketone, and 
 di-aUyl-acetic acid. 
 
 Si-propyl-aceto-acetic Ether C,2H2203 i.e. 
 CHs.C0.CPr2.C02Bt (236°). S.G. % -9585. From 
 sodium propyl-aceto-aoetic ether and PrI (Burton, 
 Am. 3, 386). Alkalis split it up, giving di- 
 propyl-aceto-acetio ether and di-propyl-acetone 
 or methyl heptyl ketone. 
 
 Di-isobutyl-aceto-acetic Ether C^^fi, i.e. 
 (S'rCH2)2CAo.C02Et (250°-253°). S.G. i2 -947. 
 From sodium isobutyl-aceto-acetic ether and iso- 
 butyl iodide (Mixter, B. 7, 500). 
 
 Si-n-heptyl-aceto-acetic Ether 
 
 CjoHsaO, i.e. CH3C0.C(0,H,,)2C02Et 
 (332°) S.G. Jpf -891. Formed together with di- 
 heptyl-acetio ether and methyl octyl ketone by 
 heating sodium heptyl-aceto- acetic ether with 
 heptyl iodide and dry alcohol for a long time 
 (Jourdan, A. 200, 112). Decomposed by dilute 
 alkalis into COj and methyl pentadecyl ketone, 
 and by concentrated alkalis into acetic and di- 
 heptyl-acetic (hexadeooic) acids. 
 
 Di-octyl-aceto-acetic Ether 
 C22H„03 i.e. CH3.CO.C(CsH„)2.C02Et 
 (264°) at 90 mm. (340°-342°) at 760 mm. From 
 octyl-aceto-acetic ether, NaOEt, and octyl iodide 
 (Guthzeit, A. 204, 9). Decomposed by alkalis 
 into di-octyl-acetone (methyl heptadecyl ketone) 
 and di-octyl-acetic (heptadecoio) acid. 
 Benzyl-methyl-aceto-acetic Acid 
 CiiHuOa i.e. 0H3.CO.CMe(CH2Ph).CO2H 
 [34°] (275°). From the ether by saponification 
 SI. sol. cold water. Salt : AgA'. 
 
26 
 
 ACETO-ACETIC ACID. 
 
 Ethyl ether-'EW (287°). S.G. ff 1-046. 
 Prepared by action of Mel on a mixture of 
 benzyl-aoeto-aoetio acid and sodium ethylate 
 (Conrad, B. 11, 1055). 
 
 Benzyl eftej-— PliCH^A' (53°?). Methyl hy- 
 dro-oinnamein. Liquid. 
 
 Benzyl-ethyl-aceto-aeetic Ether 
 
 CH3.CO.CEt(CH,Ph).C02Et 
 (296°). Colourless liquid. 
 
 Di-henzyl-aceto-acetio Ether 
 
 CH3.CO.C(CH2Ph)2.CO,,Et. 
 From sodium benzyl-aoeto-acetio ether and 
 benzyl chloride (Ehrlich, A. 187, 24). Thick 
 non-volatile liquid. 
 
 OTHER DERIVATIVES of aceto-acetic acid 
 will be described as acetyl derivatives, e.gr. Aoetyl- 
 
 GLUTAKIC ETHEE, AcETYL-SUCCINIO ETHEE, &C. See 
 also OXY-ACETO-ACETIO ETHEE, OxY-DI-ETHYL- 
 ACETO-ACETIC ETHEE, OXY-DI-METHYL-ACETO-ACETIO 
 ETHEE. 
 
 For analogous acids see Peopionyl-pkopionio 
 ACID, Valekyl-valeeio acid. 
 
 ACETO-BENZOYL-BENZOIC ANHYDBIDE v. 
 Benzoyl-benzoic acetic anhydp.ide. 
 
 ACETO-BEOMO-ACETIC ETHER v. Beomo- 
 
 aceto-acetic ETHEE. 
 
 ACETO-BEOMO-AMIDE v. Acetamide. 
 
 ACETO-BUTYEIC ACID v. Aoetyl-butyeio 
 acid. 
 
 ACETO-CHLOEO-AMIDE v. Acetamide. 
 
 ACETO-CHLOEHYDEIN v. Glyoekin. 
 
 ACETO-CHLOEHYDEOSE: CuHisClO, i.e. 
 CjHjAe^OsCl. Formed by treating 1 mol. an- 
 hydrous glucose with 5 mol. AoCl, and purified 
 by solution in chloroform, agitation with sodium 
 carbonate, and evaporation. — Semifluid ; some- 
 times crystalline. Dextro-gyrate. Bitter. In- 
 Bol. in water, slightly sol. in CSj, easily in alco- 
 hol, ether and chloroform. Distils in a vacuum, 
 partly undecomposed. Gives up all its chlorine 
 to alcoholic silver nitrate. Reduces Fehling's 
 solution. Reconverted into glucose by heating 
 with water (Colley, C. B., 70, 401). H. W. 
 
 ACETO-CmNAMONE v. Benzylidene-aoe- 
 
 lONE. 
 
 ACETO-COTTMAEIC ACID v. Coumaeic acid. 
 
 ACETO-CUECTJMIN v. CnEOCMiN. 
 
 ACETO-ETHYL NITRATE C^H.O, 2C2H5NO3 
 (84°-86°) S.G. la 1-045. Formed by dry distil- 
 lation of potassium ethyl-sulphate with potas- 
 sium nitrate. Liquid, having a sweet taste and 
 aromatic odour. Explodes violently when heated 
 above its boiling point. Not miscible with water. 
 Resolved by heatingwith potash-lye into aldehyde 
 and nitric acid (Nadler, A. 116, 173). H. W. 
 
 ACETO-ETHYL-SUCCINIC ACID v. Acetyl- 
 ETHYL-sncciNic acid. 
 
 ACETO-ETHYL-THIENONE v. Bthyl-thi- 
 
 ENYL METHYL KETONE. 
 
 ACETO-GLYCEEOLS v. Glyoeein. 
 ACETO-GUANAMINE v. Guanidine. 
 ACETO-TETEA-METHYLENE v. Tetkame- 
 
 rilYLENE METHYL KETONE. 
 
 ACETO-METHYl-THIENONE v. Methyl- 
 
 rUIENYL METHYL KETONE. 
 
 ACETONAMINES. 
 Di-Acetonamine 
 
 C„H,,,NO i.e. CH3.C0.CH,.CMe,.NHj. 
 Preparation. — 1. Dry ammonia-gas is passed 
 into a flask containing boiling acetone, the con- 
 
 ducting tube terminating just above the liquid ; 
 the resulting mixture of acetone- vapour and am- 
 monia is passed through a tube heated to 100°, 
 and then through a condensing tube ; the distil- 
 late is neutralised with sulphuric acid diluted 
 with an equal volume of water, and, after re- 
 moving the ammonium sulphate which crystal- 
 lises out, and distilling off unaltered acetone, the 
 liquid is evaporated to dryness and the residue 
 exhausted with boiling alcohol. Diacetonamine 
 sulphate then crystallises out on cooling, and 
 may be purified by recrystallisation from alcohol 
 (Heintz, A. 174, 154).— 2. Acetone saturated With 
 ammonia is left to itself for three or four weeks, 
 finely pounded oxalic acid is then added in quan- 
 tity sufficient to form an acid salt, and a quantity 
 of water equal to that of the acetone. The re- 
 sulting crystalline precipitate is easily separated 
 by boiling alcohol into insoluble ammonium ox- 
 alate and soluble diacetonamine oxalate. A fur- 
 ther quantity of this last salt remains in the 
 mother-liquor, together with salts of other bases 
 (Sokoloff a. Latschinoff, B. 7, 1384). 
 
 Properties. — Free diacetonamine, separated 
 from either of its salts by adding strong soda-lye 
 and agitating with ether, is a colourless liquid" 
 lighter than water, having an ammoniacal odour 
 and strong alkaline reaction ; more soluble in 
 cold than in hot water, mixes in all proportions 
 with alcohol and ether ; oxidises and turns brown 
 on exposure to the air ; forms crystalline salts 
 with hydrochloric, sulphuric, and oxalic acids. By 
 distillation it is for the most part resolved into 
 NHs and mesityl oxide C„H,„0, and on the other 
 hand is easily formed by direct combination of 
 these bodies : C„H,„0 + NH3 = CbH,3N0. 
 
 Salts. — CjHijNOHCl crystallises from alco- 
 hol in rhombic prisms, v. sol. alcohol, resolved 
 by dry distillation into NH^Cl and C^HmO 
 (Heintz,4.175,252)— (CeH,3NO,HCl)jPtClj,2H20 
 crystallises from water, in which it is easily so- 
 luble (according to Sokoloff a,. Latschinofi ; also 
 in dilute alcohol), in orange-yellow monochnic 
 prisms containing 2H„0, which they give off 
 in a vacuum (H.) ; under ordinary pressure (S. 
 and L.). The normal oxalate (C„E[,3N0)2C.^H20, 
 forms monoclinio tablets, very soluble in cold 
 water, less soluble in alcohol than the acid salt. 
 This latter CbH:,3NO,C2H204,H20, forms mono- 
 clinic prisms ; very soluble in hot, less in cold, 
 water ; easily in boiling alcohol, from which it 
 separates out almost completely on cooling. The 
 picrate C,H,3NO,C,H3(NO„)30,H20, forms gold- 
 yellow needles, somewhat sparingly soluble in 
 cold water. Ihesulphate (C|;H,3NO)2H2SOj forms 
 monoclinic crystals (from alcohol). 
 
 Reactions. — 1. HNOj decomposes the salts 
 forming di-acetone alcohol and mesityl oxide : 
 2C„H,3NO-f2HN02 = 
 C^H.^O., + C„H,„0 + 2Nj + 3HjO. 
 2. Chromic acid mixture converts it into para- 
 formaldehyde together with formic, acetic, and 
 amido-iso-valeric acids NH2.CMe2.CH2.CO2H, 
 and a small quantity of amido-iso-butyrio acid 
 NH.,.CMe2.C0.,H (Heintz, A. 198, 45).— 3. Solid 
 KOH forms an anhydride, C.jHjjNjO [83°]. 
 This is V. sol. alcohol, chloroform, or benzene, 
 m. sol. ether or light petroleum. Hot water 
 decomposes it (Antrick, A. 227, 381). It forms 
 a salt, (C,2H24N20HCl),PtClj, when dry. Small 
 prisms. — 4. An aqueous solution of diaceto- 
 
ACETONAMINES. 
 
 27- 
 
 namine hydrochloride heated for ten hours at 
 120' with aqueous hydrocyanic acid forms the 
 hydrochlorides of diacetonamine cyanhydrin 
 and of nitrUo-diaoetonamine, together with a 
 little amido-iso-butyrio acid (Heintz, A. 189, 
 231 ; 192, 340). — 5. Diacetonamine oxalate boiled 
 with alcoholio solutions of aldehydes forms 
 condensation products. — 6. Sodium amalgam 
 reduces di-acetonamine to a secondary amido- 
 iao-hexyl alcohol CH3.CH(0H).CH„.CMe2NH,. 
 
 OYANHYDEINS. 
 
 Di-Acetonamine cyar.hydrin 
 C,H,.,N,0 or Me.C(OH)(CN).CH2.CMe2.NH2. 
 
 Carbylo-di-acetonamine. — Prepared as de- 
 scribed above (Beaction 4). — Trimetrio prisms. 
 V. sol. water. Decomposed by boiling alcohol 
 into HON and diacetonamine. Boiling HCl 
 saponifies it, forming Oxy-amido-heptoic acid 
 (2. i;.), Me.C(OH)(COjH).CHj.CMe2NH2, the 
 greater part of which changes to its anhydride, 
 di-oxy-tri-methyl-pyrroline. 
 
 MeC{OH) 
 
 /' 
 
 .CO— NH 
 
 I 
 
 ^CHj— CMe. 
 (Heintz, A. 102, 329 ; Weil, A. 232, 208 v. Pykko- 
 line). 
 
 Nitrilo-di-Acetonamine CiHuN^O. The hy- 
 drochloride is obtained, as above stated, to- 
 gether with its isomeride. The free base is orys- 
 talHne, easily soluble in water, sparingly in ether, 
 and absorbs COj from the air. Distinguished 
 from oarbylodiaoetonamine by remaining un- 
 altered when heated to 100°-110° with fuming 
 hydrochloric acid. Resolved by boiling with 
 baryta water into NH., and amido-trimethyl- 
 oxybutyric acid CjHijNOj or its anhydride. 
 The platinochloride (C,U„N20,HCl)2PtCl, forms 
 yellow rhombic prisms slightly soluble in water. 
 The oxalate CjHijN^OjCjHjOj forms small crys- 
 tals m. sol. water, insol. alcohol (Heintz, A. 192, 
 342). 
 
 PRODUCTS FEOM ALDEHYDES. 
 
 Kthylidene-di-acetcnamine CjH,5N0 or 
 
 CH3.CH( 
 
 / 
 
 CH, . CO. 
 
 \ 
 
 .CH, 
 
 \NH.CMe/ 
 [27°] (200°) vinyl-di-acetonamine ; oxy-tri-methyl- 
 ietra-hydro-pyridine. 
 
 Formation. — Together with tri-acetonamine 
 by action of aldehyde and ammonia on acetone. 
 In larger quantity as oxalate, by boihng the acid 
 oxalate of diacetonamine (10 g.) for sixty hours 
 in a reflux apparatus with aldehyde (10 g.) and 
 alcohol (120 g.). The oxalate is washed with 
 hot alcohol, and the free bases separated by 
 potash (Heintz, 4. 178, 326 ; 189, 214 ; 191, 122). 
 
 Preparation. — ^By boihng an alcoholio solu- 
 tion of di-acetonamine oxalate with paralde- 
 hyde (E. Fischer, B. 17, 1793). 
 
 Properties. — Solidifies at -15° to rectangular 
 or six-sided plates or long prisms. Is deli- 
 quescent. Has a burning taste, smells like tri- 
 methylamine, but when warmed, like camphor. 
 
 Reduced by sodium amalgam to its dihydride 
 or ethenyl-di-acetone-alcamine. 
 
 SaZfe.— (B'HCy^PtCljSaq. Flat prisms.— 
 B'jH.^SO ,. Minute needles, v. sol. water, si. sol. al- 
 johol.— ij'aHjCjO,. SI. sol. alcohol.— B', SH.C^O,. 
 
 A platino-chloride of vinyl-di-acetonamine 
 and tri-acetonamine 
 
 (CsH,jNO.HCl + C8H„N0.HCl)PtClj + 2HjO 
 
 is formed by direct combination of its constituents. 
 100 pts. water at 14° dissolve 8-e5 pts. of the 
 anhydrous salt (Heintz, /. 1877, 442). 
 
 Pentylideae-di-aoetonamine CnHjiNO or 
 .CH, . CO. 
 CHMe2.CH2.CH< >CHj, 
 
 ^NH.CMe/ 
 Valeral-di-acetonamine; oxy-di-methyl-iso-butyl- 
 tetra-hydro-pyridine [15°-22°]. From valeric 
 aldehyde and alcoholic di-aoetonamine oxalate 
 (Antrick, A. 227, 367). Needles in stars (from 
 ether). Insol. water, sol. alcohol, ether, benzene, 
 and petroleum. 
 
 Salts.—B'.;R.fifi^. Needles [190°]. V. si. 
 
 sol. cold water or alcohol.— (B'HC^^PtCl, [205°]. 
 
 Heptylidene-di-acetonamine CjjH^sNO or 
 
 CH, . COv 
 
 C„H,3.CH< 
 
 / 
 
 "\ 
 
 CH, 
 
 ^NH.CMe/"^ 
 
 Oxy-di-methyl-hexyl-tetra-hydro-pyridine 
 [29'5°]. From cenanth-aldehyde and alcoholic 
 di-acetonamine oxalate (Antrick, A. 227, 370). 
 Needles (from ether). Oxalate B', B.fifii [c. 150°]. 
 
 Seuzylidene-di-acetouamine C„H,,NO or 
 >CH, . CO. 
 Ph.CH< >CH2 
 
 \NH.CMe/ 
 Oxy-phenyl-di-methyl-tetra-hydro-pyridine [61°J 
 (230°). Obtained as oxalate, by boiling 1 pt. 
 benzaldehyde, 1 pt. acid diacetonamine oxalate, 
 and 12 pts. alcohol, gradually separating as a 
 powder which may be purified by crystallisation 
 from water. Colourless needles or monoclinio- 
 prisms (from ether). V. sol. alcohol and ether ; 
 si. sol. water. Tasteless, has a faint aro- 
 matic odour. Forms normal and acid salts. — 
 C,3H,,N0HC1. Crusts or druses of crystals. — 
 (C,3H„N0.HCl),PtCl^. Warty groups of crys- 
 tals, or when separated from alcohol on ad- 
 dition of ether, elongated six-sided tablets. 
 Slightly soluble in hot, insol. in cold aleohoL 
 The aurocMoride forms pale-yellow crystals. — 
 CijHjjNOHNOj + 2H.,0 (?). Small crystals, mode- 
 rately soluble in cold water. — (C,3H„N0)2H2S04. 
 Small crystals, easily soluble in water, very 
 slightly inabsolute alcohol. — (C,3H„NO)2,C2H20.,. 
 Microscopic crystals, nearly insoluble in alcohol, 
 V. si. sol. water (E. Schiff, A. 193, 62). 
 
 m-Amido-benzylidene-di-acetouamlue 
 /CH, . CO. 
 NHj.C^H^.CH/ >CHj 
 
 \NH.CMe/ 
 From the nitro-derivative by reduction witil 
 SnCl,. Oil. Salts.— B"E.fijO, [113°]. 
 
 ^-Amido-benzylidene-di-acetonamine, — Ftom 
 the nitro-derivative by SnCl,. SaW.— B"HjCjOj» 
 
 o-IiTitro-beuzylideue-di-acetonamine 
 .CH, . CO. 
 N0,.C„H4.CH< >CHj. 
 
 \NH.CMe/ 
 From o-nitrobenzoio aldehyde and alcoholio di. 
 acetonamine oxalate. 
 
 Salts.— -B'^ H,G.,04.— B'HCl.- (B' HClj^PtCl^. 
 
 m-Nitro-benzylidene-di-acetonamiiie. 
 
 SoZis.-B'HCl [208°].-(B'HCl)2PtCl4 [203°]. 
 
 2>-^^t>^o-^Bi^27l^d6iiB-di-acetoiiaiuine [142-5°], 
 Needles (from ether). Nearly insol. light petro. 
 leum. 
 
 Salts.— B'-RCl aq. [c. 206°].— (B'HCl)^tCI„ 
 
28 
 
 ACETONAMINES. 
 
 j)-Oz7-beiiz7lidene-di-acetonamme 
 .CHj . COv 
 HO.C^,.CH< \CH,. 
 
 From di-aoetonamine oxalate (5 pts.), p-oxy- 
 benzoio aldehyde {i pts.), and alooliol (20 pts.) 
 
 Acid oxalate E'EjOjOj. 
 
 Methyl derivative 
 
 /m, . CO. 
 MeO.C5Hj.CH/ >CH2. 
 
 \KH.OMe/ 
 From anisaldeliyde and di-acetonamine oxalate. 
 
 Oxalate B'2HA04 [210°]. 
 
 Cmnamylidene-di-acetonamiiie 
 .CH, . COv 
 PI1.CH : CH.CH< >CH2 4 aa. [49']. 
 
 \NH.CMe/ 
 From cinnamio aldehyde, diacetonamine, and 
 boiling alcohol. YeUow needles (from alcohol). 
 Easily soluble in ether, light petroleum, chloro- 
 form and benzene, sparingly in water. 
 
 Vanillo-dl-aoetonamiae CnHigNOj i.e. 
 .CHj . COv 
 C,H3(0Me)(0H)CH< NcH^ 
 
 \NH.CMe/ 
 is obtained by boiling equal parts of vanillin 
 and acid diacetonamine oxalate in 10 pts. al- 
 cohol, whereby normal vaniUo-diacetonamine 
 oxalate is thrown down. This salt forms either 
 a white powder or yellowish crystalline crusts ; 
 si. sol. water, insol. alcohol and ether. The 
 free base is an alkaline oil, slightly soluble in 
 water. — OnHigNOaHCl is easily soluble in al- 
 cohol, and precipitated therefrom by ether. — 
 (C„H„NO,HCl),PtCl,.-C„H,9N03HNO,. Very 
 small crystals, m. sol. water, and cold alcohol, 
 (0„H,sN03)2H,S0,: lamina. (C„H,gN03)2C,H,0,: 
 crystalline, v. si. sol. water, insol. alcohol 
 (Heintz, A. 194, 53). 
 
 ALKYL-DI-ACETONAMINES. 
 
 Methyl di-acetonamine 
 CjH.sNO i.e. C0Me.CH,.CMe2.NHMe, 
 is formed, together with other bases, when 
 acetone saturated with methylamiue is left to 
 itself for several weeks. The base is ppd. as acid 
 oxalate, and purified by conversion into platino- 
 chloride. — Free methyldiacetonamine is very un- 
 stable, quickly splitting up into methylamine and 
 mesityl oxide. The hydrochloride is deliquescent. 
 The platinochloride (0,H,5N0HCl)3PtCl4 crys- 
 tallises ia large light-red rhombic prisms, easily 
 soluble in water, nearly insoluble in alcohol. 
 The platinosochloride (CiHisNOHCljjPtClj, pro- 
 duced simultaneously with the platinochloride, 
 forms dark red crystals. The aurochloride 
 CjH|5NO,HCl,AuCl3, forms short prisms, m. sol. 
 cold, V. sol. hot, water, alcohol, and ether. The 
 normal oxalate (C,H,5NO)202H204 forms indis- 
 tinct very deliquescent crystals, very soluble in 
 absolute alcohol; theacidoffiaZafeCjHjsKOOjHjOj 
 crystallises in small prisms, m. sol. absolute 
 alcohol. The picrate forms yellow needles 
 (Gotsohmann, A. 197, 38). 
 
 Simethyldiacetouamiue 
 CbH^NO i.e. COMe.CH2.CMe2.NMej,, 
 is formed on heating a solution of dimethyla- 
 mine in acetone at 100°-105° in a sealed tube. 
 Free dimethyldiaoetonamine has not been ob- 
 tained as it very easily splits up into dimethyl- 
 amine and mesityl oxide. The platino-chloride 
 (C8H„NOHCl)jPtCl4 crystalUses in smaU tablets ; 
 
 the awo-chloride in golden needles, si. soL 
 water ; the rdtrale and sulphate in long colour- 
 less deliquescent needles v. sol. alcohol. The 
 acid oxalate, CsH^NOCjHjO^, is crystalline, v. 
 sol. water and alcohol, nearly insoluble in ether 
 (Gotsohmann, A. 197, 27). 
 
 Ethyldiacetonamine 
 CgH„NO i.e. MeCO.CHj.CMe2.NHEt, 
 is obtained by heating a solution of ethylamine 
 in acetone at 80° for six hours. OisHgjNjOjPtClg, 
 light red hexagonal plates, insol. ether and 
 alcohol, soluble in alcohol containing HCl. S. 
 1-16 at 16°. Platinosochloride : C.jHasNjOjPtClj; 
 dark red prisms. S. 6-62 at 21°, insoluble in 
 ether and in alcohol.— CsH„NOHCl forms hy- 
 groscopic microcrystals decomposing at 150°. — 
 CsHijNOAuClj crystallises in large lemon-yellow 
 rhombic plates. S. 2-48 at 22° ; easily soluble 
 in alcohol and ether; melts under water at 
 about 70°. — The nitrate forms small needles. — 
 (CgH^NO^jHaSO, forms tufts of needles.— 
 (CsH^NOjjCjHjOj, concentric groups of hygro- 
 scopic needles. — CsHijN0C2H20,; needles. — The 
 picrate CsH„NO,C3H2(N02)30H forms short 
 needle-shaped prisms v. sol. water, insol. alcohol 
 and ether. Free ethyldiacetonamine splits up 
 even in the cold into ethylamine and mesityl 
 oxide (Eppinger, A. 204, 50). The prolonged 
 heating of ethylamine with acetone gives rise 
 only to ethyl-diacetonamine, not to any base 
 analogous to triaoetonamine. Diethylamine does 
 not appear to form any compound with acetone 
 (Eppinger). 
 
 Sehydrodiacetonamine 0sH„N(?) contained 
 in the mother-liquors of the preparation of acid 
 diacetonamine oxalate, and passes over on dis- 
 tilling them with an alkali. The platinochloride 
 forms slightly sol. laminse (Heintz, A. 183, 276). 
 
 Xriacetonamine GgH,,N0 i.e, 
 XMej.CHjv 
 NH< >G0 
 
 \CMei,.CH/ 
 Oxy - tetra -methyl - tetra - hydro -pyridine [58°] 
 (hydrated) ; [39-6°] (dry). Formation.— X. To- 
 gether with diacetonamine, by the action of 
 ammonia on acetone, especially at high tempera- 
 tures (Heintz, A. 174, 133). — 2. By prolonged 
 boiling of acetone with a solution of diaceto- 
 namine : CeH,sN0H-C3H30 = CsH„N0 + H20 
 (Heintz, A. 178, 305). This, according to Heintz, 
 is the best mode of preparing triaoetonamine. 
 It is purified by crystallisation of the oxalate. 
 Triaoetonamine separates from a solution of the 
 normal oxalate mixed with KOH, as a hydrate 
 C9H„N0,H20, which crystallises from anhydrous 
 ether in large square tablets, and the mother- 
 liquor on further evaporation and cooling to a 
 very low temperature yields long needle-shaped 
 crystals of anhydrous triaoetonamine. Hydrated 
 crystals rhombic a:h:o = 0-9586 : 0-9768 : 1. 
 Triaoetonamine sublimes slowly, even at ord. 
 temp. Distils without alteration. Decomposed 
 at 150°-200° by HjSOi or PA. b"* does not 
 yield definite products. Heated at 100° for 16 
 hours with fuming hydrochloric acid it yields 
 diacetonamine, dehydropentacetonamine and 
 other products. With chromic acid mixture it 
 gives isopropyl-butyl-amine di-carboxylio acid: 
 CsH.jNO, i.e. CO2H.CMe2.NH.CMe2.CH2.COjH 
 (Heintz, 4. 198, 69). With ethyl iodide it yields 
 NHjEt, NHEtj, NEt„ NEt^I, dehydrotriaoetona- 
 
ACETONE. 
 
 29 
 
 mine, and other products, but no ethylated 
 triaoetonamines (Heintz, A. 201, 100). 
 
 Salts. — B'HCl is easily soluble in alcohol, 
 and separates therefrom on addition of ether, 
 in prisms — (B'HC^jPtCljSHjO crystallises from 
 hot water in long, dark, gold-coloured needles, 
 V. si. sol. alcohol, insol. ether. By exposing the 
 alcoholic solution to sunlight, or heating the 
 aijueous solution for several hours, it is reduced 
 to (B'HCl) jPtCl22H20, which is much less soluble 
 in water than the platino-ehloride, and crys- 
 tallises in dark red needles or rhombic prisms. — 
 (C,H„K0)2H2S04 : delicate needles or prisms 
 v. sol. in water, insol. alcohol and ether. — 
 C,H„NO,HNOs : rhombic crystals— a : 6 : c = 
 1-2738 : 1 : 1-0251.— (C,H„N0)2HjCr0i. SmaU 
 light yellow crystals converted into the acid 
 salt by reorystaUisation from hot water. — 
 (C9H„N0)2H2Cr20,. Orange-red prisms (Heintz, 
 A. 198, 87).— (CsH„NO)2C2Hj04 forms long 
 needles, v. sol. water, v. si. sol. alcohol. — ■ 
 C5H,,N0,02H20,. Triclinio crystals, v. sol. 
 water; resolved by boiling with alcohol or 
 ether into the normal salt and oxalic acid 
 (Heintz, A. 178, 326). 
 
 Iriacetonamine Nitrosamine C9E,e(N0)N0 
 [73°], S.G. 1-14, is formed by heating aqueous 
 triaoetonamine hydrochloride with KNO, at 85°. 
 Long needles (from alcohol). V. sol. alcohol 
 and ether. Resolved by KOH into nitrogen, 
 water, and phorone, also by prolonged boiling 
 in aqueous solution. By heating with HCl or 
 HjSO,, it is for the most part reconverted into 
 triacetonamine (Heintz, A. 185, 1 ; 187, 238). 
 
 Iri-acetone-diamine 
 
 CsHj„N;,0 i.e. (NH2.CMe,.CH2),CO. 
 Found in small quantity amongst the products 
 of the action of ammonia on acetone ; produced 
 more abundantly when a mixture of 1 pt. ace- 
 tone, 2 pts. NHjAq, and 1 pt. CSj, is left at rest 
 for a month ; 3C3H5O + 2NH3 = C^B^j:) + 2H,0. 
 Oily liquid soluble in water, somewhat sparingly 
 in ether. B"2HC1 forms prismatic crystals, de- 
 composing at 200°.— B"2HCl,PtCl4 is slightly 
 soluble in cold, easily in hot water, insoluble in 
 ether. — 'B"(J^^O^•, flat needles, nearly inso- 
 luble in alcohol, much more soluble in water, 
 than the acid salt. — B"2H2C204 aq ; monochuic 
 prisms (Heintz, A. 203, 336). 
 
 Dehydro-tri-acetonamine C|,H,5N (Tetra- 
 methyl-di-hydro-pyridine?) (158°) (H.) ; (163°) 
 (O.S.). 
 
 Occurs as oxalate, together vrith tri-acetona- 
 mine, in the mother liquor got in preparing di- 
 acetonamine oxalate (g. v.), and may be separated 
 therefrom by distillation with"potash (Heintz, A. 
 174, 166 ; 183, 276). 
 
 Preparation. — Acetone (20g.),acetamide (8g.), 
 and ZnClj (30g.), are heated for 6 hours at 140° 
 (Canzeroni a. Spioa, G. 14, 341). Another base 
 (240°) is a by-product in this reaction. It ap- 
 pears to be C,5H2,N. Its platino-ohloride forms 
 dodecahedra. 
 
 Propei'iies. — Oily liquid which readily oxi- 
 dises, becoming brown. 
 
 Salts.— {B'SG^^tClt. Ehombohedra (from 
 water). V. si. sol. cold water, insol. alcohol. — 
 BHAuCl^ [127°]. Long yellow prisms (from 
 diluts alcohol). Insol. water. 
 
 It ehydro-penta-acetonamine 
 
 CijHjaN = 5C,H,0 + NH3 - SHjO. 
 
 Is formed together with ammonia and di-aceto- 
 namine by heating tri-acetonamine with fuming 
 HCl at 130°, the hydrochloride then separating 
 as a crystalline powder, sparingly soluble in 
 water. The base separated therefrom by potash 
 is an oily liquid (Heintz, A. 181, 70). H. W. 
 ACETO-NAPHTHYL-THIAMIDE v. o-Naph- 
 
 THYLAMINE. 
 
 ACETONE C3H.O i.e. CH3.CO.CH3. 
 
 Di-methyl Ketone. 
 
 M. w. 58 (55-6°-55-9° cor.) (Perkin, C. J. 45, 
 478); (56°) (Dumas; E. Schiff); (56-3°) at 760 
 mm. (Kopp, Eegnault, Zander) ; (56-53° cor.) 
 (Thorpe, C. J. 37, 212). S.G. 2 -814 ; 13:2 -799 
 (Kopp, A. 64, 214); f -8186 (T.) ; l| -7965; |f 
 -7867 (P.) ; g -8125 (Z.) ; f -7920 (Bruhl) ; ^ 
 •7506 (E. Sohiff, A. 220, 103). V.D. 2-00 
 (Dumas). C.E. (0°-10°) -00138 (T.). S.V. 77-08 
 (S.) ; 77-3 (Z.) ; 76-78 (T.). H. F. p. 65,000 
 (Berthelot) ; 58,710 (Thomsen). H. F. v. 57,260 
 (Th.). ft^ 1-3639. Eoo 25-55 (Briihl). M. M. 
 3-514 at 15-2° (P.).— Occurs in the urine, blood, 
 and brain of diabetics (Markownikoff, B. 8, 1683 ; 
 Peters, Kauhch, Betz, /. 1861, 805). 
 
 Formation. — 1. By the dry distillation of 
 acetates: e.g. (MeCO.O)j5Ba = Me2CO + BaC03.— 
 2. From zinc-methyl and acetyl chloride ; 
 
 (a) MeCOCl + ZnMe^ = MeCClMe.OZnMe, 
 
 (b) MeCClMe.OZnMe + H20 = 
 Me,.CO -I- HCl + ZnO + CH, 
 
 (Freund, A. 118, 1).— 3. By treating bromo- or 
 chloro-propylene with aqueous hypochlorous 
 acid and mercuric oxide, whereby chloracetone 
 is formed : 
 
 2C3H5CI + 2H0C1 + HgO = 
 HgCl^ + H^O -I- 2(CHjCl.CO.CH3), 
 and reducing this compoimd to acetone with 
 zinc and HCl (Linnemann, Bl. [2] 6, 216). — 
 4. By treating the isomeric compound, propylene 
 oxide, with sodium-amalgam, and dehydrogenis- 
 ing the resulting isopropyl alcohol with chromic 
 mixture, C3H,0 + H2=(CH3)2CH.0H, and 
 (CH3)2CH.0H -1- = HjO -I- (CH3)2C0 
 (Linnemann, A. 140, 178). Berthelot (O. B. 68, 
 334), effects the oxidation with aqueous chromic 
 acid. — 5. By the action of an aqueous solution 
 of mercuric bromide (Kutscheroff, B. 14, 1541), 
 or chloride {B. 17, 15), on allylene.— 6. By pass- 
 ing aldehyde vapour over red-hot lime (Schloe- 
 miloh, Z. 5, 336). — 7. Together with propionic 
 aldehyde, by heating a dilute aqueous solution of 
 propylene glycol at 180°-190° (Eltekoff, /. 11, 
 409). — 8. By heating propylene bromide with 
 water at 170°-180° : 
 
 CjHjBra + B.fi = 2HBr + CjHjO 
 (Linnemann, A. 161, 58). — 9. By heating a-a-di- 
 chloro-propane CMe^Clj with silver acetate and 
 alcohol in sealed tubes at 100° : 
 CMe^Clj + 2AgC02Me = 2AgCl -I- 2C0Mej + CO^.— 
 10. Together with a bromine compound (proba- 
 bly CHMe^Br) by the action of zinc and dilute 
 sulphuric acid on the product C3'H..filfiy:2'^> 
 formed by the action of bromine on dichlorhy- 
 drin (Lange, B. 6, 98).— 11. By distilling with 
 water the product formed, with evolution of HCl, 
 on dissolving chloro-propylene Me.CChCHj in 
 sulphuric acid (Oppenheim, A. Suppl. 6, 365). — 
 12. Together with mesitylene, on distilling with 
 water a solution of allylene in sulphuric acid 
 (Schrohe, B. 8, 367).— 13. Together with othei 
 
30 
 
 ACETONE. 
 
 products, by the action of lime on glycerin 
 ^Tawilderow, B. 12, 1487).— 14. Together with 
 isobutyric aldehyde, by oxidation of iso-butyl 
 ■alcohol. — 15. By oxidising with chromic acid the 
 hexylene obtained by the action of alcoholic 
 potash on di-methyl-isopropyl-oarbinyl iodide 
 ■(Pawlow, Bl. [2] 29, 375).— 16. By the action of 
 nascent zinc-methyl on acetic oxide (Saytzefi, Z. 
 [2] 7, 104): (COMe).,0 + ZnMe2 = ZnO+2COMe2. 
 — 17. Together with other products, by the action 
 -of zinc-sodium on a mixture of methyl iodide 
 ■and. acetic oxide (S.). — 18. By the dry distillation 
 ■of wood : occurs therefore in crude wood-spirit ; 
 also of sugar, gum, or starch, with 8 pts. lime 
 (Fremy, A. Ch. 59, 7}.— 19. By dry distillation 
 ■of citric acid, and in the oxidation of that acid 
 by potassium permanganate, or by MnOj and 
 ■dilute sulphuric acid (P^an de St. Gilles, A. 
 Ch. [3] 55, 374). 
 
 Preparation. — l.By dry distillation of barium 
 ■or calcium acetate. The barium salt decomposes 
 at a moderate heat, and when dry and pure 
 jields pure colourless acetone. The calcium 
 salt requires a higher temperature and yields a 
 distillate contaminated with an empyreumatio 
 oil (dumasin) and other products. — 2. By dis- 
 tilling in an iron retort or quicksilver bottle, a 
 mixture of lead acetate (2 pts.) and quick lime 
 {1 pt.), rectifying over calcium chloride, and 
 finally distilling over the water-bath. The pro- 
 duct may be purified from wood-spirit by distil- 
 lation over calcium chloride, or better by com- 
 bining the acetone with sodium hydrogen 
 sulphite, and decomposing the resulting com- 
 pound by an aoid or alkali ; also by converting the 
 methyl alcohol into an ether (oxalic or benzoic). 
 ■Crude acetone may also be purified by treating 
 "it with potassium permanganate, which does not 
 attack pure acetone at ordinary temperatures. 
 
 Properties. — Limpid, very mobile liquid 
 having a spirituous and slightly empyreumatio 
 •odour and biting taste. Very inflammable ; 
 burns with a white smokeless flame, mixes in 
 all proportions with water, alcohol, and ether. 
 -Dissolves camphor, fats, and resins. Separated 
 •from aqueous solution by CaClj and by KOH 
 -(difference from alcohol). Even if boiling be- 
 ■tween 56° and 58° it is liable to contain methyl- 
 acetal, CH3.CH(OCH3)j; this can be detected 
 ■by heating with cone. HCl, for it then gives ofi 
 -MeCl. Acetone reacts with hydroxylamine and 
 with phenyl-hydrazine (v. Aoetoxim, Acetone 
 .phenyl-hydbazide). It does not restore the 
 •colour of a solution of a rosaniline salt that 
 has been bleached by SOj (Schiii). 
 
 Detection.. — 1. An alcoholic liquid supposed 
 ■to contain acetone is mixed with an equal volume 
 ■of water, and a drop of benzoic aldehyde and 
 another of aqueous NaOH are added. After some 
 •hours yellow needles of di-benzylidene-acetone 
 ■separate [112°]. They dissolve in BC^SO^ giving 
 ■an orange solution (Claisen a. Ponder, A. 223, 
 143). 2. Acetone boiled with aqueous KOH and 
 iodine gives a pp. of iodoform. 3. A solution 
 of I in NHjI is added to the liquid, previously 
 made strongly alkaline with ammonia. A black 
 lip. of iodide of nitrogen at first appears, but 
 quickly disappears on shaking. As soon as this 
 pp. tends to become permanent it will change to 
 iodoform if acetone is present, but will not be 
 affected by alcohol (Gunning, Fr. 24, 147). 
 
 Beaciiores.—l.Aoetone-vapourpassed through 
 a red-hot tube deposits carbon and yields so- 
 called dumasin, also naphthalene, 00^, CH4, and 
 H (Barbieri a. Eoux, C.B. 102, 1559).— 2. By 
 nascent hydrogen (sodium-amalgam and water) 
 acetone is converted into isopropyl alcohol : 
 Me.C0.Me + H2 = Me.CH0H.Me (Friedel, C.B. 
 55, 53). — 3. Chlorine-gas passed into acetone 
 displaces 1 or 2 ats. H, forming O3H5CIO and 
 CsHjCljO, but does not remove the wholeof the 
 hydrogen, even in sunshine. Grabowski (JB. 8, 
 1438), by passing chlorine into pure acetone, as- 
 sisting the action by heat towards the end, ob- 
 tained in addition to dichloracetoue, two bodies 
 CsHjClsO and CsHjClaO. The former is a liquid 
 insoluble in water (186°). S.G. 1-330 at 29°. 
 V.D. 6-60 (calc. 6-56). Decomposed by strong 
 potash-lye, vfith separation of chloroform. The 
 second body, C,H,ClsO, is also liquid (206°- 
 208°). S.G. 1-326 at 26°. V.D. 7-55 (calc. 7-0). 
 Completely decomposed by strong potash-lye or 
 sulphuric acid. Perhapstrichlorotrimesityloxide. 
 When acetone is treated ■with excess of chlorine, 
 and the product first •with KOH and then with 
 HOI, isapoglucio acid C„H,„05 is produced. 
 With alcoholic potash, on the other hand, a body 
 CjHjdOs (?) is formed, together with an acid 
 whose lead-salt has the composition Pb(C,H903)2 
 (Mulder, J. 1868, 494). — 4. Chlorine, in presence 
 of alkalis, converts acetone into chloroform : 
 
 C3H5O + 6CI2 + B..fl = 2CHCI3 + CO2 + 6HC1. 
 Bromine acts in like manner, producing bromo- 
 form, and iodine forms iodoform. — 5. When 
 acetone saturated with HCl-gas is mixed, after 
 8-14 days, with water, a heavy brownish oil 
 separates, consisting mainly of compounds of 
 HOI with mesityl oxide, 0„H,„0 ( = 2C3H3O - H,0) 
 and phorone, CgH,,O( = 303H3O-2H2O). The 
 mesityl compound CjHijOClj, heated with KCN 
 and then with KOH, yields the K-salt of a mo- 
 nobasic acid CgH,3N03 (v. Mesitonio acid), thus : 
 C,H,jOClj + 2K0N = 2KC1 -t- C„H,j0(CN)3 ; and 
 C,H,jO(CN)2-f KOH + HjO = NH3-1- KCjHijNO,. 
 The phorone compound, similarly treated, yields 
 a neutral azotised body crystallising in shining 
 plates and subliming at about 300° (Maxwell 
 Simpson, Pr. 16, 364). According to Pinner 
 (B. 14, 1070) the neutral body is a nitrile 
 CiiHjsOjNj, formed according to the equation 
 3C3H„0-f2HCN = H20-l-C„H,802N2; it crystal- 
 lises in plates melting above 320°. Heated with 
 aqueous hydrochloric acid it gives phoronio 
 acid C„H,s02 [q.v.]: CoH,802(CN)2 -1- 4H20 = 
 2NH3 -I- H2O -H C3H,30(C02H)2.— 6. By distillation 
 ■with strong sulphuric acid, acetone yields mesi- 
 tylene, CjHij = SCjH^O — 3H20 ; but when mixed 
 with HjSOj in a cooled vessel it forms mesityl- 
 Bulphonio acid C3H5.SO3H, which, when heated 
 ■with potash, yields mesityl oxide (Hlasiwetz, 
 J. 1856, 487).— 7. With PClj acetone yields 
 chloropropylene CjHjCl and di-chloro-propane 
 CjHjCl^ (Friedel,^. 112,236).— 8. With bromine 
 acetone unites directly, forming CsH^OBrj, a 
 viscid, very unstable liquid, heavier than water 
 (Linnemann, A. 125, 307). According to E. J. 
 Mulder, however (J.pr. 91, 47), it gives rise to 
 substitution -products. — 9. With HI acetone 
 yields iodopropylene, CsHjI ; with PI, a solid 
 and two liquid iodides (Harnitz-Harnitzky, Z, 
 1863, 416). According to Berthelot (Bl. [2] 7, 
 69), acetone treated with HI yields propane. — 
 
ACETONE. 
 
 31 
 
 10. With iodine chloride aoetono yields O3HJ2O 
 (Maxwell Simpson, Laboratory, p. 79). — 11. 
 Electrolysis of a mixture of acetone and dilute 
 sulphurio acid produces acetic, formic, and car- 
 bonic acids (Friedel, /. 1859, 338).— 12. By 
 chromic acid mixture it is oxidised to acetic 
 and carbonic acids. — 13. Acetone heated with 
 ammonia yields a mixture of three bases, the 
 composition and mode of formation of which 
 are indicated by the following formula : — 
 
 Diaoetonamine .... C,'H:„X0=203H„0+NH:,— H,0 
 Triacetonamine .... C„H„NO=3C,H„0+NH,-2HjO 
 Deliyarotriacetonamine . C,H„N = 0,H„NO - HjO. 
 
 With methylamine, in like manner, Acetone 
 yields methyldiacetonamine CjHijNO and other 
 bases. With dimethylamine only dimethyldi- 
 acetonamine CjHijNO.— 14. With hydroxyla- 
 mine, acetone forms acetoxim [g.i).] MejC-.NOH, 
 which crystallises in prisms [60''], (135°). — 15. 
 Sodium strongly attacks acetone, with forma- 
 tion of crystallisedpinacone hydrate CjHijO TB.fi 
 and liquid phorone CjHuO thus : 2C3H5O + Naj = 
 Na,0 + CsH,20, and ZC^fi - IBfi = Gfi.,,0 
 (Stadeler, A. Ill, 277). — 16. Heated with ani- 
 line hydrochloride at 180° it forms di-methyl- 
 quinohne (Engler a. Eiehm, B. 18, 2245, 3296). 
 — 17. Caustic alkalis, e.g. EOH and CaO, exert a 
 dehydrating action on acetone and form con- 
 densation-products varying in composition, ac- 
 cording to the proportion of water abstracted, viz. : 
 
 B. P. 
 
 XyUte-naphthaO„H,,0,=4C,H.O— H^O .. 110°-120° 
 Mesityl oxide C.H,„0=2C,H.O— H^O .... 131° 
 Mesitylenc .. C„H„=3C,H,0-3H,0.. ISS^-ieO" 
 Phorone.... C,H,.0=3C,H,0— 2H,0.. 216<'-220'> 
 Xylite-oU .. C,,,'K„0=iC,B.,0—3B.^Oabore 250° 
 
 Vapour of acetone passed over strongly heated 
 KOH or potash -lime is resolved into methane and 
 carbonic acid, C^HoO + 2K0H = EjCOj + 2CHj. 
 At a lower temperature the chief products 
 are acetic acid, formic acid, and hydrogen, 
 C,H,0 + 2K0H + H^O = KC^H^O^ -t- KCHO^ + 3H2 
 (Dumas a. Stas, A. Ch. [2] 78, 149 ; Persoz, Bev. 
 Scient. 1, 51). — 18. Acetone heated with ZnClj 
 yields hexa-methyl-benzene CjMe^ (W. H. Greene, 
 C. B. 87, 931).— 19. Gently heated with AICI3, 
 it yields mesityl oxide, phorone, and other 
 products (Louise, G. B. 95, 602).— 20. Dry 
 PtCl^ dissolves in acetone, and the solution 
 when evaporated leaves a brown resinous mass 
 containing a yellow crystalline substance, 
 CuH,„OPtCL (?), called Aeechlcn-ide of Plati- 
 num, or Chloroplatinite of Mesityl (Zeise, A. 
 33, 29).— 21. On adding HCl to a mixture of 
 acetone, with potassium cyanide and snlpho- 
 cyanide, the compound CsH^C^NS is obtained. 
 This compound heated with HGl is resolved 
 into CO2, NH„ and o-oxy-iso-butyric acid. With 
 silver nitrate it yields CsH^AgO.^NS (Ureoh, 
 B. 6, 1113).— 22. By action of alkaUs or of HCl- 
 gas on a mixture of 1 mol. acetone and 2 mol. 
 benzaldehyde, dieenzylidene- acetone {g,-v.) 
 PhCH:CH.CO.CH:CHPh is obtained (Claison a. 
 Claparede, B. 14, 349). By the action of 
 alkalis on a solution of o-nitro-benzaldehyde 
 in acetone, methyl o-nitro-;8-oxy-5-phenyl-ethyl 
 ketone [68°] is formed according to the equation 
 NO,.C„H^.CHO -I- C0(CH,)2=- 
 N0,.C„Hj.CH(0H).CH2.C0CH, 
 (Baeyer a. Drewsen, B. 15, 2856). — The corre- 
 sponding paja-compound [58°] is obtained in 
 
 like manner from acetone ana ^-nftro-benzalde- 
 hyde (Baeyer a. Becker, B. 16, 1968).— 23. With 
 furfuraldehyde, acetone forms a compound 
 crystallising in long white needles [87°] (J. G. 
 Schmidt, B. 14, 574) — u.Fdkpuktlidene-acetone. 
 24. With pyrrol in presence of HCl it forma 
 OuH,„N2, [291°] (Baeyer, B. 19, 2184). 
 
 Combinations. —1. With Bisulphites. 
 Formed by direct combination. C3Hs(0H) SOjNHj 
 crystallises in laminas (Stadeler, A. Ill, 307)— 
 CsH5(OH)S03TSfa. — Laminse, moderately soluble 
 in water, less in alcohol. Gives off acetone 
 when boiled with aqueous sodium carbonate 
 (Limpiicht, A. 93, 238)- C3H,(OH)S03K (L.). 
 2. With Mercuric Oxide 2C3H„0 3HgO. 
 Formed by mixing acetone with mercuric chloride 
 and weak potash-lye, dialysing the filtered liquid, 
 and precipitating the liquid remaining in the 
 dialyser with acetic acid. — Gelatinous precipitate 
 which becomes resinous on drying. Its solu- 
 tion gelatinises when heated or when merely 
 left at rest (Emerson Eeynolds, Pr. 19, 431). 
 Formed also by dissolving HgO in acetone 
 (Eutscheroff, B. 17, 20). 
 
 Acetone-boric Acid, C3HjO(BHO)2 [50°]. 
 Formed together with (a) and (/3) acetone-fluo- 
 boric acid, and hydrocarbons, on saturating 
 acetone with boron fluoride and distilling the pro- 
 duct, (o) Acetonejluoboric acid, C^Rfi 3JiFBfl^ 
 (120°-123°) ; the isomeric (;3) modification [36°] 
 (90°-92°) forms shining white laminse. All 
 three compounds fume in the air, burn with 
 green flame, and are quickly decomposed by 
 water, yielding boric acid and acetone hydro- 
 fluoric acid (Landolf, C. B. 89, 173). 
 
 Acetone-hydrofluoric Acid CaHoOHF (55°) 
 obtained by fractional distillation from the pro- 
 duct of the action of water on acetone-fluoboric 
 acid. An inflammable liquid with pleasant 
 ethereal odour (LandoLf, C. B. 96, 580). Another 
 compound, CjHjO 2HF (-12°) is gaseous at ordi- 
 nary temperatures. 
 
 Acetone-sulphomc Acid CH3.CO.GH2.SO3H. 
 Formed as E-salt by treating dichloracetone 
 (118°) with a strong solution of potassium sul- 
 phite : C3H,Cl20 -^ E^SOg -f H^O = 
 
 K,S0^4-HC'1 + C3H,C10, and 
 C3H3CIO -t- E2SO3 = ECl -H C3H5O.SO3E. 
 The E-salt may be extracted from the product 
 by boiling alcohol, and separates therefrom in 
 white lamin£B. Very soluble in water, not de- 
 composed by boiling with dilute acids. Boiled 
 with strong potash-lye, it yields sulphite and 
 perhaps an acetone-alcohol (Bender, Z. 1870, 
 162 ; B. 4, 517). SaZ«s.—EA' Plates (from alcohol 
 V. e. sol. water — BaA'^ aq. Plates. — PbA'2 aq. 
 [140°]— CuA'2 l^aq. Greenish plates. 
 
 Acetone-phosphoTous Acid CjHgO.PO^H. 
 Remains on distUling acetone with I and P. 
 (C3HBO.P0.2).2Ba is amorphous, soluble in water, 
 insoluble in alcohol (Mulder, /., 1864, 329). 
 
 Acetone - cyanhydrin CH3. C (ON) (OH) . CH, 
 (Oxyisobutyronitrile). Formed by the action of 
 aqueous HCN (20 p.e.) on acetone, or by the action 
 of nascent HCN on acetone diluted with ether. 
 
 It is very unstable, for even OB evaporation 
 of its solution it changes into di-au!etone-cyan- 
 hydrin with evolution of HCN (Tiemann a. 
 Friedlander, B. 14, 1970). Alcoholic NH, 
 at 60° converts it into o-amido-iso-butyronitrile 
 CH3.C(CN)(NH2).CH3whenceHCl forms o-amido- 
 
33 
 
 ACETONE. 
 
 iao-butyiic acid. Alcoholic HCl forms the 
 imido-ether Me,C{OH)C(OEt):NH (Pinner, B. 
 17, 2009). 
 
 Diacetone cyanhydrin CMe2(CN).0.CMej(0H), 
 is prepared by adding 1 mol. HCl (gaseous or 
 aqueous) to 1 mol. KCN immersed in acetone, 
 dissolving the product in ether, and evaporating 
 (Urech, A. 164, 259). Thick shining anhydrous 
 prisms, easily soluble in water, alcohol, and 
 Ether. Melts at 135°-152° and sublimes below 
 its melting point in long needles. Decomposed 
 at ord. temp, by HCl into NHjCl, acetone, and 
 o-oxy-iso-butyric acid. 
 
 Substitution Products v. Bromo-aobtone, 
 
 CHLOHO-iOETONE, ChLOEO-BBOMO-ACETONE, IoDO- 
 ACETONE, CtAKO-ACETONE, ThIO-ACETONE. 
 
 Meta-acetone. — This name was given by 
 Fremy (A. Ch. [2] 59, 6) to an oil occurring 
 among the products of the distillation of sugar, 
 starch, or gum, with quicklime. He ascribed to 
 it the formula CjH,|,0 and boiling-point 84°. 
 Gottlieb {A. 52, 128) converted it by chromic 
 mixture into propionic acid (called therefore 
 Metacetonic acid). Benedikt {A. 162, 303) 
 found V.D. 8-53 instead of 3-59, and stated that 
 it did not combine with NaHSOj. Meta-acetone 
 has also been examined by Favre {A. Ch. [3] 11, 
 80), Cahours (0. B. 30, 319), who describes it 
 as present in crude wood spirit, Lies-Bodart (iT. 
 1856, 455), and Schwartz {J. 1850, 533). Never- 
 theless Pmner {B. 15, 586 ; 16, 1729) considers 
 metacetone to be a very complicated mixture. 
 
 H.W. 
 
 Para-acetone v. Pinacone. 
 
 ACETONE-ALCAMINES.— These are pro- 
 ducts derived from the acetouamines by reduc- 
 tion, their CO being converted into CH(OH). 
 
 Diacetone - aloamine CjHij.NO i.e. 
 
 NH2.CMej,.CH2.CH(0H).Me (175°). Formed by 
 reduction of diacetonamine by gradually adding 
 sodium-amalgam to its solution in alcohol 
 diluted with aqueous ammonia. Liquid, having 
 a faint ammoniacal odour, misoible in all pro- 
 portions with water. Absorbs CO2 from the 
 air ; fumes with HCl. (CsHisNOHC^jPtCl^ 
 forms orange-red triolinio crystals, easily soluble 
 in hot water. 
 
 Ethylidene-diacetone-alcamine 
 
 H2C-CH(0H)-CH2 
 C,H„NO i.e. I I 
 
 MeHC — NH — CMe^ 
 Oxy - tri ■ methyl - hexa - hydro -pyridine [128°]. 
 Colourless crystalline soUd. Easily soluble in 
 water and alcohol, sparingly in ether, and ben- 
 zoline. Formed by reduction of ethylidene- 
 diacetonamine with sodium-amalgam in slightly 
 acid aqueous solution. The hydro-chloride 
 forms slender needles, the sulphate large flat 
 prisms (Fischer, B. 17, 1794). 
 
 Triaoetone-alcamine CjH,jNO 
 HjC— CH(OH)— CHj 
 i.e. I 1 [128-5°] 
 
 McjC— NH — CMe, 
 Oxy-tetra-methyl-hexa-hydro-pyridine. Formed 
 together with pseudotriacetonamine by reduc- 
 tion of triaoetonamine with sodium-amalgam in 
 slightly acid aqueous solution (Fischer, B. 17, 
 1788). 
 
 Pseudotriacetonalcamine [180°]. SI. 
 sol. water and ether, crystallises from hot alcohol. 
 Its platino-chloride (Ci,H„NO,HCl)jPtCl„5HjO 
 
 forms rhombic crystals (Heintz, A. 183, 290, 
 817). 
 
 Uethyl-tri-acetone-alcamine C,|,H2,N0 [74°] 
 or, when hydrated, [60°]. Formed from tri- 
 acetone-aloamine by Mel and MeOH at 100° (B. 
 Fischer, B. 16, 1605). Slender plates (from 
 water). Strongly alkaline. H. W. 
 
 ACETONE ALCOHOL v. Aoetyl-cabeinol. 
 
 ACETONE-AMMONIA v. Aceionahznes. 
 
 ACETONE-BENZIL C.jH.eOj i.e. 
 Ph.C0.CPh(0H).CH2.C0.CH, [78°]. 
 
 Preparation. — BenzU is shaken with excess 
 of pure acetone and a little cono. KOH, and the 
 crystals obtained are dissolved in ether (free 
 from alcohol), which is allowed to evaporate. 
 C,.H,A + C,HeO = C„H,eO, (Japp a. Miller, C. 
 J. 47, 21). 
 
 Properties. — Colourless square prisms. Sol. 
 ether or alcohol. Eesolved by heat into its con- 
 stituents. 
 
 Reactions. — 1. Chromic mixture gives ben- 
 zoic and acetic acids. — 2. Dry NH, gives ace- 
 tone-bemilimide {q. v.). — 3. Alcoholic hydroxy- 
 lamine gives C„H,s02(N0H), [146°] ; m. sol. 
 benzene, si. sol. ether. This body is not affected 
 by further treatment with hydroxy! amine. 
 
 Dehydro-acetone-benzll CjiHj^Oj i.e. 
 CH 
 Ph.CO.CPh/ '\C0 [149°]. 
 \CH/ 
 
 Preparation. — Benzil is shaken with excess 
 of pure acetone and excess of cone. KOH (J. a. 
 M.) C„H,„0, + C,H«0 = C„H,A + H20. 
 
 Properties. — Colourless prisms. 
 
 EeacHons.—l. Converted by brominein chlo- 
 roform to a bromo derivative, C^HijErO^ [172°]; 
 slender needles (from glacial HO Ac). — 2. Chromic 
 acid in glacial HOAc forms an acid, C,jHnOj, 
 [152°]; needles. Salts, AgA'—BaA'^ 2aq. 
 
 Dehydro-acetone-di-benzil CjiHj^O, [195°]. 
 
 Formation. — 1. From acetone-benzil and di- 
 lute alcoholic KOH. — 2. From acetone, excess 
 of benzil, and a little cono. KOH. 
 
 2C„H,„02 -I- CsHsO = C,,-R,fit + HoO. 
 
 Properties. — Colourless crystals (from ben- 
 zene) ; si. sol. boiling alcohol. Crystallises from 
 alcohol with one molecule BtOH. 
 
 ACETONE-BENZILIMIDE C„H„N02 [176°]. 
 From acetone-benzil and dry NH,. Flat plates 
 (from alcohol). Heated with HCl and oxalic 
 acid, gives a red gum (J. a. M.). 
 
 ACETONE-BOBIC ACID v. Acetone. 
 
 ACETONE - BBOMIDE = di - Bbomo ■ fBOPANE 
 (2- v.). 
 
 ACETONE -BEOMOFOKM C^H^OBr, i.e. 
 Me2C(OH).CBr3 [175°], or, when hydrated [167°]. 
 From bromoform (5g.), acetone (30g.), and soda- 
 lime (8g.) (WiUgerodt a. A. Miiller, C. C. 1884, 
 808). 
 
 ACETONE CARBOXYLIC ACID = Aceio- 
 
 AOETIO ACID (g. v.). 
 
 Acetone di-carbozylic acid CgHgO; i.e. 
 C0jH.CH2.C0.CHjC0jH [0. 130°]. Formed by 
 heating citric acid with H^SOj. Colourless 
 needles. Split up into CO^ and acetone by 
 heat, by boiling water, or by warm acids or al- 
 kalis. It contains methylenic hydrogen dis- 
 placeable by Na. FejCl, gives a violet colour. 
 It reacts with phenyl-hydrazine (Pechmann, B. 
 17, 2542). It forms a compound with HON, 
 which on saponification produces citric acid. 
 
AOETOJSIE-PHENANTHEAQUINONE. 
 
 sa 
 
 NaNO, oonyerts it into di-ozimido-acetone (Fech- 
 raann a. Wehsarg, B. 19, 2465). 
 
 The ethyl ether is an oil which can give 
 rise to salts by exchanging its methylenio hy- 
 drogen for sodium or copper. Reactions. — 1. 
 By successive treatment with sodium and an 
 alkyl iodide (EI) the following ethers may be 
 got: C02Et.CH2.CO.CHE.C02Et, 
 
 C02Et.CHB.C0.CHE.C02Et, 
 C02Et.CHB.C0,0E,.C0.^t, 
 and finally C02Et.CB2.C0.CE2.C0,Et. 
 The acids obtained by saponifying these bodies 
 are split up by heat into CO^ and alkyl-acetones 
 (Diinsohmann a. v. Pechmann, B. 18, 2289). — 
 2. Acetone di-carboxylic ether (100 g.) is con- 
 verted by heating with Na (21 g.) into di-oxy- 
 phenyl-aoetic di-carboxylic ether 
 
 C„H(0H)2(CO2Et)i,.0H,.0O,Et 
 (Cornelius a. Pechmann, B. 19, 1446). — 3. Am- 
 monia produces 5-oxy-fl-amido-glutaramic ether, 
 C0.,Et.CH2.C(0H) (NHi,).CH2.CO.NH2 [86°] 
 (v. Pechmann a. Stokes, B. 18, 2290 ; 19, 2694). 
 
 ACETONE CHLORIDE v. dj-CKLono-PKOPANE. 
 
 ACETONE CHLOKOrOKM C^HjOClj i.e. 
 Me2C(OH).COl3. Oxy-iso - butyro - tri - chloride. 
 [96°] or when hydrated, + Jaq, [81°] (167° uncor.). 
 
 Prepared by adding solid KOH to a cold mix- 
 ture of acetone and chloroform. It is a crystal- 
 line solid, resembling camphor in appearance and 
 smell. Rotates on water. V. sol. alcohol, ether, 
 chloroform, acetone, or glacial HOAc, insol. 
 water. Volatile with steam. Converted by water 
 at 180° into o-oxy-iso-butyric acid (WiUgerodt, 
 B. 14, 2451; 15,2305; 16,1585). 
 
 ACETONE CTANHYDKIN v. Acetone. 
 
 ACEIONE-HYLEOQTJINONE CbH, A- I"rom 
 acetone and hydroquinone (Habermann, M. 5, 
 329). 
 
 ACETONE HYDEOXTIAMIDE v. Aoeioxim. 
 
 ACETONE-FHENANIHBAQTTINONE 
 C„H,A [90»]. 
 
 FormOfticm. — ^From phenanthraquinone by 
 heating with a large excess of acetone at 200°. 
 The product is washed with NaHSOj and extracted 
 with ether (Japp a. Streatfeild, G. J. 41, 274). 
 
 Preparation. — Phenanthraquinone (50 g.) is 
 shaken in a glass with acetone (60 g.) and cone. 
 NH3Aq(40c.o.). Acetone-phenanthraquinonimide 
 is formed and filtered off ; after washing with ether, 
 it is made into a cream with water and stirred 
 into a solution of oxalic acid (90 g.) in water 
 (800 CO.) at 25°. The substance dissolves, but 
 minute needles of aoetone-phenanthraquinone 
 soon separate (Japp a. Miller, C. J. 47, 18). 
 
 Properties. — Large thin blades (from ether). 
 Insol. water, v. sol. ether, acetone or alcohol. 
 
 Beactions. — 1. By heat, by hailing water, or 
 by hoiUng alcohol, it is resolved into acetone and 
 phenanthraquinone: C„H„0, = CnHjOj + C,HjO. 
 2. Zino dust and glacial HOAc form C„H,20, 
 [121°]. This is extracted by ether and crystal- 
 lised from alcohol. It forms long slender needles, 
 V. e. sol. ether or chloroform, v. sol. boiling 
 alcohol, V. si. sol. cold alcohol. Sublimes in 
 feathery crystals. It decolorises bromine. — 3. 
 A few drops of dilute aqueous KOH added to 
 an alcoholic solution forms minute crystals of 
 aoetone-di-phenanthraquinone (g. v.). — 4. Cone. 
 KOH (S.G. 1-27) added to a solution of acetone- 
 phenanthraquinone in acetone forms a crystal- 
 line mass of di-acetone-phenanthraquinone. — 
 
 VOL.L 
 
 6. Ammonia passed into an ethereal solution of 
 aoetone-phenanthraquinone forms crystals of 
 acetone-phenanthraquinonimide. 
 
 Acetone - di - phenanthraquinone CjiH^jOj 
 [190°]. Formed by adding a little dilute KOH 
 to an alcoholic solution of acetone-phenanthra- 
 quinone (J. a. M.) : 2C„H, A = CjiH^A + CaH.O. 
 Colourless crystals (from benzene). 
 
 Di - acetone - phenanthraquinone CJJ3.Jd. 
 [187°]. 
 
 Preparation. — Pure acetone (43 g.) is shaken 
 with finely powdered phenanthraquinone (50 g.) 
 and a little (2 c.c.) cone. KOHAq (S.G. 1-27). 
 After 12 hrs. the resulting solid cake is washed 
 with ether and crystallised from acetone (J. a. M.). 
 
 Properties. — Short oblique prisms. Sparingly 
 soluble in the usual menstrua. Sol. acetone or 
 benzene. Decomposed by boiling glacial HOAo 
 or amyl alcohol. Decomposed on melting into 
 acetone and phenanthraquinone. 
 
 Beactions. — Boiling Ac^O converts it into de- 
 hydro-di-acetone-phenanthraquinone. 
 
 Dehydro-di-acetone-phenanthraquinone 
 CjjH.sOj [179°-181°]. Colourless pointed prisma 
 (from benzene). Formed as above. Its constit* 
 tion is perhaps : 
 
 C,Hj.C-CH,COMe 
 
 l> 
 
 CjH^.C-CH^COMe 
 
 Dehydro-acetoue-phenanthraqninone 
 CijHijOj [195°]. Formed in small quantity, 
 together with di-acetone-phenanthraquinone 
 when excess of KOHAq (S.G. 1"27) acts upon 
 a mixture of acetone and phenanthraquinone. 
 It is present in the ethereal washings of the di- 
 acetone-phenanthraquinone (J. a. M.). 
 
 Groups of minute needles (from benzene) I 
 m. sol. hot benzene, hot alcohol, or ether. 
 
 Acetone-phenanthraquinonimide C^HuNO, 
 [130°]. Formation. — By passing NHj into an 
 ethereal solution of acetone-phenanthraquinone. 
 
 Preparation. — Phenanthraquinone (50 g.), 
 acetone (60 g.), and cone. NHjAq (40 c.c), shaken 
 together form a white crystalline powder which 
 is washed with ether and crystallised from ace- 
 tone containing a little NHjAq : 
 
 CnHsOj + CsH^O + NHa = C^Hi^NOj + H^O 
 (J. a. S.). Colourless rhomboidal laminse. 
 
 Beactions. — 1. AcjO decomposes it, forming 
 phenanthraquinone. — 2. Cold cone. HCl dis- 
 solves it, but the solution soon deposits a dark 
 blue substance. The diluted filtrate deposits co- 
 lourless needles of acetone-phenanthraquinone : 
 
 OijH.sNOj + HjO = C,,H, A + NH, 
 By using cone, aqueous oxalic acid as a solvent 
 the formation of the blue compound may be 
 avoided, and after dilution, the needles separate 
 as before. 
 
 The following constitutional formula are 
 suggested by Japp and Miller to explain the 
 properties of the preceding bodies : 
 C„H4.C(0H).CHj.C0.Me 
 
 O^H^.CO 
 
 C,H^.C(0H).CH2.C0.Me 
 
 6„H^.C:NH 
 
 for C„H, A 
 
 for 0„H,5N0, 
 
 C„H,.C(0H).CH2.C0.Me 
 C!,Hi.C(OH).CHj.CO.Mq 
 
 for CJl^O, 
 
34 
 
 AOETONE-PHENYL-HYDEAZIDE. 
 
 ACETOITE-PHEinn-HYBRAZIDE : 
 (CH3)jC:N.NHPh (165°) at 91 mm. Oil. Pre- 
 pared by mixing acetone with phenyl-hydrazine. 
 It dissolves in cold aqueous acids and on warm- 
 ing the solution it is resolved into its constituents 
 (Eeisenegger, B. 16, 662). 
 
 DI-ACETONE-PHOSPHINIC ACID 
 CeH.sPO.aq, i.e. (CH3)jCH.CHAo.PO(OH)i,aq, 
 or, less probably {0H3.C0.CH2)2PH(0H)2aq. Di- 
 acetonyl-phosphinia acid, iso-propyl-acetonyl- 
 phosphonic acid, a-acetyl-iso-butane a-phospho- 
 nic acid [64°]. Formed by the action of water 
 upon di-acetone-phosphorous chloride {infra). 
 (Michaelis, B. 17, 1273 ; 18, 902) : 
 
 CeHuO^PCl -1- 2H2O = C,H„PO< + HCl. 
 Slender needles. V. e. sol. water or alcohol, v. 
 sol. ether. Strong dibasic acid. 
 
 Salts. — NH4HA". V. sol. water, si. sol. alco- 
 hol. Crystals. — (NHJjHA"^ 2aq. Insol. alcohol. 
 — BaH2A."2 2aq. Needles ; v. sol. water, si. sol. 
 alcohol. — BaA" 6aq ; m. sol. hot water ; tri- 
 metric tables, a : h : = -785 : 1 : 2-525. — 
 PbA".-PbA" i PbO.-MgA" 6aq; ppd. by al- 
 cohol from aqueous solution in glittering plates. 
 — KHA"; deliquescent gum: v. sol. alcohol. — 
 KH3A"; ; slender needles, v. sol. water, si. sol. 
 alcohol. — AgjA". 
 
 Reactions 1. HNO3 forms a tribasic crys- 
 talline acid C4H5PO5, possibly /8-carboxy-propane- 
 phosphonio acid : CH3.CH(COjH).CH2.PO(OH)2. 
 The salts kg^K'", and BajA'"^, are crystalline. 
 
 Osim.— C5H,3(NOH)PO, [170°]. Colourless 
 crystals ; v. sol. water or alcohol ; dibasic acid. 
 
 Si-Acetoue-pheuyl-phosphinic Acid 
 CbH,2(CjH5)P03, probably 
 (CH3)jCH.CH(CO.CH3).PO{C„H,)OH. [86°]. 
 Prepared by adding P2O5 to a mixture of acetone 
 and phosphenyl chloride, and treating the pro- 
 duct with water : 
 
 (1) 2C3H,0 + C,H,PC1,-H,0 = 0,H,„(CeH,)POCl, 
 2)C„H,.(C„H,)P0C1, + 2H,0 = 
 
 C,H„(C,H,)P03 + 2HC1. 
 Long colourless plates ( H- HjO). Sol. hot water, 
 si. sol. cold water and ether, v. b. sol. alcohol. 
 The anhydrous acid forms a glassy mass, v. sol. 
 ether. A'Ag ; crystals, v. sol. water. (Michaelis, 
 B. 19, 1009.) 
 
 I)l-Acetone-;p-tolyl-pIiospliiuic Acid 
 0,H„(C,H,)P03, probably 
 (CH3)2CH.CH(CO.CH3).PO(C,H,)OH. [103°]. 
 Obtained by adding PjO, to a mixture of acetone 
 and ^-tolyl-phosphorous chloride, and treating 
 the product with water. Glistening plates ; sol. 
 hot water, v. sol. alcohol and ether. A'Ag ; 
 slender glistening soluble needles. (Michaelis, B. 
 19, 1012.) 
 
 SI-ACEIONE-PHOSPHOBIC-TBI-CHLOBIDE 
 
 (CHs),:C - 
 C,H,„OjPCl. *.e. ^ »'^ , I (?) 
 
 ' " ^ ' CH3.CO.CH-PCI3 ^ ' 
 
 [115°]. Formed by passing chlorine into a solu- 
 tion of di-acetone-phosphorous chloride in pe- 
 troleum-ether (Michaelis, B. 18, 901). Colour- 
 less crystals ; si. sol. petroleum-ether. 
 DI-ACETONEPHOSPHOBIC-CHLOEO-BEOMIDE 
 (CH3),0 - 
 
 CHj.CO.CH-PClBrj ^' 
 [142°]. Formed by addition of bromine to a so- 
 lution of di-acetone-phosphorous chloride in light 
 petroleum (Michaelis, B. 18, 900). Colourless 
 crystals. SI. sol. light petroleum. It is decom- 
 
 CgHioOoPClBr- i.e. 
 
 posed by water into mesityl oxide, phosphor!* 
 acid, HOI, and HBr. 
 
 ACETONE-PHOSPHOEOTJS ACID v. Aoetoot. 
 
 DI-ACETONE-PHOSPHOROUS CHLOBIDE 
 (CH3)jO-0 
 
 C3H.APCli.e. ,^^.,o^H.^Cl (^> 
 [36°]. (184°) at 100 mm. ; (235°) at 745 mm. 
 S.G. (liquid) ^ 1-209. Prepared by slowly add- 
 ing Al^Clj (8 pts.) to a cooled mixture of PCI, 
 (50 pts.) and 2^ times its volume of acetone ; 
 yield: 5 pts. It is decomposed by water into 
 di-acetone-phosphinic acid CjHijPOi and HCl. 
 It readily combines with 1 mol. of chlorine or 
 bromine (Michaelis, B. 17, 1273 ; 18, 898). 
 
 ACETONE STJLPHONIC ACID v. Acetone. 
 
 ACETONIC ACID v. o-Oxt-iso-buiybio Aero. 
 
 DI-ACETONIC ALCOHOL v. AoETYi-Buxni 
 
 ALCOHOL. 
 
 ACETONINE CsH.sNj. This base described 
 by Stadeler (A. Ill, 277),Hlasiwetz (4.76, 294), 
 and Mulder (A. 168, 228), was found by Heinta 
 (A. 201, 102) to be a mixture of di-acetonaminSi 
 tri-aoetonamine, and tri-acetone-di-amine. 
 
 ACETONINES. Bases obtained by Askf- 
 drating acetone-alcamines by cone. HjSO^. 
 
 £thylidene-di-acetonine CsH,jN i.e. 
 CH:CH.CHj CH2CH:CH 
 
 MeCH.NH.CMe2 " MeCH.NH.CMe2 
 Tri-methyl-tetra-hydro-pyridine. (132°-i37°.) 
 Formed from ethylidene-di-acetone-alcamiue 
 (1 pt.) and cone. HjSOj (8 pts.) by heating for 
 1^ hours at 100°. 
 
 Colourless oil with alkaline reaction. Volatile 
 with steam. SI. sol. water, more soluble in cold 
 than in hot water. Miscible with alcohol, ether, 
 or chloroform. Heated with HI, it yields iodo- 
 tri-methyl-piperidine, CjHjMealN [60°]. 
 
 Salts. — B'HI ; slender, sparingly soluble 
 needles. — B'HBr; small soluble trimetrio pyra- 
 mids (Fischer, B. 17, 1795). 
 
 Benzylidene-di-acetonine C,3H,,N i.e. 
 H2C-CH = CH HC = CH-CHj 
 
 PhHO - NH - CMoj "^ PhHC - NH - CMe^. 
 Phenyl-di-methyl-tetra-hydro-pyridine. Formed 
 by the action of strong H2SO4 on benzyKdeue- 
 di-acetoue-alcamine. 
 
 Distils undecomposed. Volatile with steam. 
 V. sol. alcohol or ether, v. si. sol. water. 
 
 Salts. — "B'HBr : colourless tables or needles, 
 si. sol. cold water. — B'HI ; sparingly soluble 
 needles.— "B'HAuCl,. (Fischer, B. 17, 1797.) 
 Tri-acetonine 
 
 HjC.CH:CH 
 CjH.jN i.e. „ "1. ^^^ I ,, (146°) at 740 mm. 
 MejCNH-CMe^ 
 
 Tetra-methyl-tetra-hydro-pyridine. 
 
 Prepared by heating tri-aoetone-aloamine 
 (1 pt.) with strong H.^SO, (3 pts.) on a water- 
 bath for an hour, pouring into water, neutraUsing 
 the acid, and distilling the base over with steam 
 (Fischer, B. 16, 1604). 
 
 Properties. — Mobile fluid, smelling like pipe- 
 ridine. It combines with water forming a hydrate 
 crystallising in long white needles, which give 
 off their water at a moderate temperature. Vo- 
 latile with steam. Poisonous. By heating with 
 HI it gives iodo-tetra-methyl-piperidine. 
 
 Salts. — B'HBr; large white prisms, si. soL 
 cold water. — B'HCl ; v. sol. water or alcohol.— 
 B'EAuCl^ ; yellow needles. 
 
AOETONYL-THIO-OAilBAMATE. 
 
 33 
 
 Nitrosamine C^^^I^O) : yellowisli tables ; 
 V. sol. alcohol, ether, and benzene, nearly in- 
 Boluble in water ; volatile with steam ; strong 
 camphor-like smell. 
 
 Methyl derivative OjHijNMe : colourless oil 
 very volatile with steam, sparingly soluble in 
 water (Fischer, B. 17, 1789). 
 
 ACETO-NITRANILIDE v. Nitbo-aniline. 
 
 ACETONITEILE C2H3N i.e. CH^.CiN. 
 Methyl cyanide, methyl isocyanide. M.w. 41. 
 (81-6°) at 760 mm. (Vincent a. Delaohanal, 
 BZ. 33, 405) ; (81-3°) (R. Schifl, B. 19, 5C7). 
 
 5. G. 2 -805 ; is. -789 (V. a. D.). S.V. 57-23 (S.). 
 H.F. p. -15,680. H.F.v.-lG,260 (Thomsen). 
 /tt„ 1-3458 (V. a. D.). Ra, 18-00 (Kanonnikoff, 
 J. pr. [2] 31, 361). V.D. 1-45 (for 1-42). 
 
 Occurrence. — In crude benzene (V. a. D.). 
 
 Formation. — 1. Dry KMeSO, is distilled with 
 dry KCN and the distillate rectified over CaCl2 
 (Frankland a. Kolbe, C. S. Mem. 3, 386; A. 65, 
 288).— 2. From Me.SO,, and KCN, the product 
 being distilled over HgO and then over P^O^ 
 (Dumas, Malaguti a. Leblanc, C. U. 25,474). — 3. 
 By distilling NH^OAc with P.^O., (Dumas, G. B. 
 35, 383).— 4. By distilling acetamide with P.;0., 
 (Buokton a. Hofmann, C. J. 9, 242).— 5. By dis- 
 tilling acetamide (5 mols.) with PjSj (1 mol.), 
 washing the product with NaOHAq and digesting 
 with PbO (Henry, A. 152, 149).— G. From aceta- 
 mide by action of PCI, (Wallach, A. 184, 21). 
 
 Preparation. — 1. By boiling acetamide (500 
 g.) for a week with a little glacial acetic acid, 
 the water produced being constantly allowed to 
 distil off. The theoretical yield is got (De- 
 margay, Bl. [2] 38, 456). 
 
 Properties. — Colourless liquid with a pleasant 
 ethereal odour ; burns with a reddish-bordered 
 flame. Miscible with water, but separated by 
 salts from the solution. Mixes with alcohol. 
 The presence of a little alcohol lowers its boiling- 
 point several degrees (D.). 
 
 Beactions. — 1. Hot aqueous KOH acts thus : 
 
 CH3.CN + H,0 + KOH = CHjGO.K -1- NH3. 
 
 2. Chromic and nitric acids have no action. — 
 
 3. Heated with Na, it forms Cyanmetiiike {q. v.) 
 and NaCN.— 4. Glacial HOAc at 200° forms di- 
 acetamide: CH,CN -1- CH3.CO.OH = (CH3.C0).,NH 
 (Gautier, A. 150, 189).— 5. Ac.,0, forms tri- 
 acetamide : CH3.CN -t- (CH,.CO),0 = (CH3.CO)3N. 
 
 6. Combines with dry HBr, HI, and (with 
 difficulty) with HCl (Gautier, A. 142, 291).— 7. 
 Brcnnine forms the hydrobromide of the nitrile 
 of Broho-aceiicaoid (q.v.). CH^Br.CHiNBr [65°]. 
 
 Combinations.— G.fi.s^'ill'By:, or CH3.CH2.NBr2 
 r47°-50°] crystals; maybe subUmed.— C2H3NPCI3 
 (72°) : dissociated above its boiling point (Hencke, 
 A. 100, 281).— CJ-IaNSbCls, formed with great 
 rise of temperature ; white crystals which may be 
 sublimed (H.). — C2H3NAUCI3 : brownish-yellow 
 powder (H.).— (C2H3N)2TiClj : white crystalline 
 crusts ; may be sublimed (H.). — (C2H3N)2SnCl4 : 
 sublimes in arborescent formations (H.).— 
 C2H3N2Hg(CN)2 : white vitreous mass ; decom- 
 poses even over H-^SOj (Hesse, A. 110, 202), 
 CH.,.C(NHJ:NOH, formed by the union of aoeto- 
 ni trile with hydroxylamine v. Bthenyl-amid-oxiji. 
 
 ACETONUKAMIC ACID C,H,„Nj03 i.e. 
 NH2.CO.NH.CMe2.COOH. a- Uramido-iso-butyric 
 acid, di-melhyl-hydantoic acid. Obtained, as 
 barium salt (C3HaN202).jBa(0H)2, by prolonged 
 boiling of a solution of di-methyl-hydantoin with 
 
 baryta-water. The acid itself appears to be very 
 unstable (TJreoh, A. 164, 255). A more stable 
 acid of the same composition is obtained by 
 evaporating the mixed solutions of the sulphate 
 of amido-isobutyric acid and potassium cyanate. 
 It forms crystals, melting, with loss of water, at 
 160°, moderately soluble in hot water and alco- 
 hol. Decomposed by prolonged heating at 
 130°-140° into water and di-methyl-hydantoin. 
 05HgAgN205 crystallises in needles (Ureoh, A. 
 164, 274). H. W. 
 
 ACETONYL-ACETO-ACETIC ETHEE C„H„04, 
 i.e. CH3.CO.CH2.CHAo.C02Et, a-^-di-aceiyl pro- 
 pionic ether. 
 
 From aceto-acetio ether and ohloro-acetona 
 (Weltner, B. 17, 67). Liquid. Warm cone. 
 HCl changes it to pyrotritaric ether CjHjOjEt. 
 Water at 160° produces some aoetonyl-aoetone, 
 
 ACETONYI-ACETONE G,B.,fi, i.e. 
 CH3.C0.CH,,.CH2.C0.CH3. Di-methylethyleiK <K- 
 ketone. (188° uncor.) 
 
 Formation.— (X) By heating pyrotritaric acid' 
 (di-methyl-f urfurane-carboxylio acid) with water 
 at 150°-160° ; yield nearly theoretical. (2) By 
 heating acetonyl-aoeto-aoetio ether with water 
 at about 160° ; small yield. 
 
 Properties. — Mobile liquid of peculiar smell. 
 Miscible with water, alcohol, and ether, insol. 
 cone. KOHAq, or KjCOjAq. 
 
 Beactions. — P2Sij, when heated with it, forms 
 thioxene C^H^S. — Heating with alcoholic NH3 
 gives di-methyl-pyrrol (Paal, B. 18, 2231) ; amines 
 behave similarly (Paal a. Schneider, B. 19, 8156). 
 
 Di-osim CH3.C(N0H).CH2.CH2.C(N0H).CH, 
 [185°]. White glistening plates, v. sol. hot water, 
 alcohol, or ether, v. si. sol. benzene. 
 Di-phenyl-di-hydrazide C2H^(CMe:N2HPh)2 
 [120°] : plates, v. sol. alcohol, ether, or benzene, 
 nearly insol. light petroleum (Paal, B. 18, 58). 
 
 ACETOKYL-CARBAMATE C,H,N03 [76°]. 
 Formed by boiling acetonyl thiocarbamate 
 (infra) with lead acetate or silver oxide. 
 Crystallises from water in prisms, may be dis- 
 tilled ; dissolves in water, alcohol, and ether, 
 Decomposed by heating with strong hydrochloric 
 acid or baryta-water, yielding COj, NH3, and 
 a-oxy-iso-butyric acid. The salts CjHjAgNOa, 
 and AgN03.2C5H,N03 are crystalline (Urech, B. 
 11, 467 ; 13, 485). H. W. 
 
 ACETONYL-PHOSPHINIC ACID 03H,P03 i.e. 
 CH3.CO.CH2.P(OH)2. Residue left after distilling 
 acetone with I and P {v. Acetone-phosphorous 
 acid under Acetone). Salt. — Ba(03HBPO3)2. 
 
 Di-acetonyl phosphinic Acid v. Di-acetonb- 
 
 PHOSPHINIC ACID. 
 
 Di-aoetonyl-phosphorous Chloride v. Di-acb« 
 
 TONE-PHOSPHOBOUS CHLOEIDE. 
 
 ACETONYL -QUINOLINE C,2Hi,N0 i.e. 
 ,CH:CH 
 
 C,H,^ 
 
 /^ 
 
 I 
 
 \n :C— CH2.CO.CH, 
 
 Quinolyl-acetone. [76°]. Prepared by reducing 
 o-nitro-oinnamoyl-acetone in alcoholic solution 
 with SnClj. Long yellow needles. Distils with- 
 out decomposition. Sparingly volatile with 
 steam. Insol. cold water, si. sol. hot water. 
 Dyes wool and silk yeliov^. Heated with strong 
 HCl at 170° it gives (Py. 3)-methyl-quinoliue 
 (Fischer a. Kuzel, B. 16, 163). 
 
 ACETONYL -THIO- CARBAMATE (so called) 
 CjHjNSOa. Thiacetoivwramio acid, [152°]. 
 
 D 2 
 
AOETONYL-THIO-OAEBAMATE. 
 
 Formed by treating acetone with a mixture of 
 potassium cyanide and sulphooyanide, and HCl : 
 C,nfi + CNH + CNSH f Kfi = NH3 + CjHjNSO^. 
 Long needles ; easily sublimable ; very soluble 
 in ether ; less easily in cold water. Besolved 
 by heating with HCl in a sealed tube at 120° 
 into CO2, HjS, NH.J, and a-oxy-iso-butyrio acid. 
 The sUver salt CjHjAgNSOj is very sparingly 
 soluble (Urech, B. 6, 1117). H. W. 
 
 ACETONYl-UREA v. di-Meihyl hmamioin. 
 
 ACETO-PHENINE v. Aceiophenone, Be- 
 action 6. 
 
 ACETO-PHENONE C^Sfi i.e. CjH5.CO.CH3. 
 Phem/l methyl ketone, Acetyl-bemene. M. w. 
 120. [20-5°]. (202° cor.). S. G. iS 1-032. 
 
 Formation. — 1. By distilling calcium ben- 
 zoate with calcium acetate (Friedel, A. 108 
 122).— 2. From BzCl and ZnMe, (Popoff, A. 
 161, 296).— 3. By action of KOHAq on ben- 
 zoyl-aceto-acetic ether. — 4. From phenyl- 
 acetylene by shaking with diluted (75 p.c.) 
 HjSOj (Friedel a. Balsohn, Bl. [2] 35, 64): 
 Ph.C:CH + H,0 = Ph.C0.CH3.— 5. From bromo- 
 styrene and H2SO4 : small yield. — 6. Bromo- 
 Btyrene heated with a large excess of water for 
 12 hours at 180° yields 66 per cent. (Friedel 
 a. Balsohn, Bl. [2] 32, 618).— 7. From ethyl- 
 benzene and chromic acid in acetic acid (F. a. 
 B.). — 8. From di-bromo-phenyl-propionic acid, 
 CHjBr.CBrPh.COjH by boiling water (Fittig a. 
 Wurster, A. 195, 160). 
 
 Preparation. — From benzene (10 pts.), acetyl 
 chloride (1 pt.), and AICI3 (2 pts.) (Eichter). 
 
 Properties. — ^Lavge plates. Does not combine 
 with NaHSOj but, like other ketones, itreactswith 
 hydroxylamine, phenyl-hydrazine, and HON. 
 
 Reactions. — 1. Chromic-mixture oxidises it to 
 benzoic and carbonic acids (Popoff). — 2. Sodium- 
 amalgam reduces it to phenyl methyl carbinol, 
 CH3.CHPh.OH, and aoetophenone-pinacone. — 
 3. With HI and P at 140° it gives di-phenyl-di- 
 methyl-ethane, CuH,,, and a compound CuHuO 
 (Graebe, B. 7, 1626 ; v. Acetophenone-pinaco- 
 LiNE).^4.C/iZonncprodueeschloro-acetophenone 
 Ph.CO.CH2.Cl [59°] (245°) and di-chloro-aceto- 
 phenone Ph.CO.CHCl^ (250°-255°) v. Ohloeo- 
 ACETOPHENONE. — 5. Bromine in CSj produces 
 bromo-aoetophenone, Ph.CO.CHjBr [50°] v. Bbo- 
 Mo-ACETOPHENONE. — 0. Avimonia in presence of 
 PjOj forms ' acetophenine ' C.^jHi^N together 
 with methane. Acetophenine crystallises from 
 alcohol in slender needles, which may be sublimed. 
 It is a weak base ; its hydrochloride crystallises 
 in plates, decomposed by water into HCl and the 
 base. Fuming HNO3 forms tri-nitro-aoetophenine 
 C„3H,,(N02)3N ; slender needles (from ether). 
 Acetophenine is probably tri-phenyl-pyridine ; 
 .CPh:GH. 
 N< >CPh 
 "^CPh.CH'^ 
 (Engler a. Eiehm, B. 19, 40).— 7. When taken 
 internally it reappears in the urine as hip- 
 purio acid, having, doubtless, been previously 
 oxidised as in Reaction 1 (M. Nencki, ■7'. pr. 
 125, 288). 
 
 Besides the derivatives described below, see 
 b1so:Amido-acetophenone, Bromo-aoeiophenone. 
 Bkomo-nitbo-acetophenone, Iodd-acetophenone, 
 j)l - methyl - amido -acetophenone, nitko - aceto- 
 
 JHENONB, ThIO-ACEIOPHENONE, AcETOPHEN-OXIU. 
 
 ACETOPHENONE -ACETO- ACETIC ACID 
 CijH.A i.e. CH3.C0.CH(C0jH).0H,C0.C,H, 
 
 Acetop'herume-acetone-carboxylicacid\X^h°-lW''\. 
 Small colourless crystals. Obtained by saponifica- 
 tion of the ether which is prepared by the action 
 of w-bromo-acetophenone on sodio-aceto-acetic 
 ether. It is very unstable. On warming with 
 absolute alcohol it evolves CO.; and yields aeeto- 
 phenone - acetone CH3. CO. CH.^. CH^. CO. C^B.^ 
 (Paal, B. 16, 2865). Acetophenone-aceto-acetie 
 ether is reduced by sodium amalgam to a oily 
 lactone, CH3.CH.CH2.CH(CHMeOH).CO.O, sol. 
 
 aqueous EOH or Ba(0H)2 but insol. aqueous 
 K2CO3 (Weltner, B. 17, 09). Amines convert aee- 
 tophenone aceto-acetic ether into derivatives of 
 pyrrol (Paal a. Schneider, B. 19, 3156). 
 
 Dehydro - acetophenone - aceto - acetic acid 
 C,oH,„03 [114°]. From acetophenone-aoeto-acetio 
 ether C„H3.CO.CH2.CH(CO.,Et).CO.CH3 by heat- 
 ing with alcoholic KOH. Large crystals (from 
 benzene mixed with benzoline). From dilute 
 alcohol it separates in hydrated needles [115°- 
 120°]. By boiling with HCl it is converted into 
 phenyl -methyl-furfurane-carboxylio acid 
 HC-C(C02H) 
 
 // % 
 
 PhC— 0— CMe. 
 
 Salts. — KA'. Long sUky needles (from al- 
 cohol).-NH,A'. 
 
 Oxim C,2H,2Nj03 : [172°] ; glistening white 
 plates ; sparingly soluble in water, easily in 
 alcohol, ether, benzene, aqueous acids, and alkalis. 
 
 Phenyl-hydrazide CigHisN^Qj : small needles 
 (Paal, B. 17, 916, 2761). 
 
 ACETOPHENONE -ACETONE C„H,20j i.e. 
 CH3.CO.CH2.GH2.CO.C3H5 (acetyl-benzoyl-etJiane 
 or ethylene methyl phenyl di-ketone). Prepared 
 by heating acetophenone-aceto-acetic acid (q.v.) 
 with absolute alcohol. Yellowish heavy oil. SU 
 sol. water, quite insol. alkalis. Cannot be dis- 
 tilled (Paal, B. 16, 2868). 
 
 Reactions. — 1. P^Oj removes HjO forming 
 
 phenyl-methyl-furfuraue, n n 
 
 MeC.O.CPh. 
 
 2. Heated with P2S, it gives, similarly,phenyl- 
 
 methyl-thiophene, n n 
 
 MeC.S.CPh. 
 
 3. Heated with alcoholic NH, it gives, simi- 
 
 larly, phenyl-methyl-pyrrol, n n 
 
 MeC.NH.CPh 
 (Paal, B. 18, 367). 
 
 Oxim C„H,3N02. [123°]. Formed by action 
 of hydroxylamine. Long white needles, soluble 
 in acids or alkalis. 
 
 Phenyl-hydrazide C„H|sN.p [c. 105°]. 
 White prisms, got by adding phenyl-hydrazine 
 slowly to asolution of theketone in ether (3 vols.). 
 V. sol. ether or benzene, nearly insoluble in light 
 petroleum (Paal, B. 17, 2763). 
 
 CijHijNj [155°]. Formed by mixing the ke- 
 tone with phenyl-hydrazine (ef . Knorr.B. 18, 305). 
 
 Behydro-acetophenoue-acetoue 0, ,H,uO. 
 
 [83°]. This body is formed together with the 
 isomeric phenyl-methyl-ruRFnr.ANE by the action 
 of Ac,0 and other dehydrating agents upon aoe- 
 tophenone-acetone. Cannot be distilled, oven 
 with steam. It combines with bromine, and 
 gives with phenyl-hydrazine the same compound, 
 
AOETOPHENONE CARBOXYLIC ACIDS. 
 
 PjtHisNj 1.155°], that the aoetophenone-acetone 
 itself gives. Henoe its constitution must be some- 
 tliing like CHj.CO.CHj.ClC.OeH.. 
 
 AOETOPHENONE AICOHOL C^Ufi^ i.e. 
 C^Hj.CO.CH.,OH V. Benzoyl-oabbingl. An iso- 
 meric body, C8H,(0H).C0.CH3, is described as 
 
 OXY-ACEIOPHENONE. 
 
 AOETOPHENONE- ANIIIDE t>. Phenyl- 
 
 AMIDO-ACETOPHENONE. 
 
 AOETOPHENONE-BENZIL C^^H^O, [102°]. 
 Acetophenone and powdered benzil in equiva- 
 lent proportions are shaken with an excess of 
 cone. KOH (S. G. 1-27). After a few days a 
 solid cake is formed, which is washed with water 
 and then treated with ether. This leaves dehydro- 
 aoetophenone-benzil undissolved, and on evapo- 
 ration deposits oblique prisms of acetophenone- 
 benzil, which should be recrystallised from 
 alcohol. It is v. sol. ether or hot alcohol, si. sol. 
 cold alcohol. Above its melting-point it gives 
 off acetophenone. Its constitution is probably 
 Ph.C0.CPh(0U).CH2.C0.Ph (Japp a. MiUer, C. 
 J.i7,3i). 
 
 Dehydro-acetophenone benzil CjjH^Oj [129°]. 
 
 Formation. — See above. 
 
 Preparation. — Equivalent quantities of aceto- 
 phenone are shaken with excess of cono. KOH 
 (S.G. 1-27) and kept liquid for some hours by the 
 appUcation of sufficient heat. The product is 
 treated as described above, but ether extracts 
 hardly anything. The residue insoluble in ether 
 is crystallised from alcohol (J. a. M.). 
 
 C„H,„02 + C,H,0 = C22H, A + H,0. 
 
 Properties. — Tufts of flat needles (from alco- 
 hol). V. si. sol. ether or cold alcohol, v. sol. 
 boiling alcohol. 
 
 Bcactions. — Bromine added to its solution in 
 chloroform unites forming large reddish crys- 
 tals which are apparently the tetrabromide 
 C,2H,50jBr, [:H0°-X15°]. Becomes dark at 70°, 
 and pale again at 80°. The bromine is given off 
 in a few weeks over lime. 
 
 Constitution. — Dehydro-aoetophenone-benzil 
 differs from dehydro-acetone-benzil not only in 
 forming a bromide but also in having a very 
 much lower melting-point than would be expected 
 if they were of analogous structure. Japp a. 
 Miller assign to dehydro-acetone-benzil the for- 
 mula Ph.CO.CPh^^g'=>CO, and the unsatu- 
 rated formula Ph.CO.CPh:CH.CO.Ph to dehydro- 
 aeetophenone-benzil. The latter formula can, 
 however, account only for a di- and not for a 
 tetra-bromide (0. J. 47, 37). 
 
 ACETOPHENONE CAEBOXYIIC AOIDS. 
 
 Acetophenone (o-Oarboxylic Acid CjHjOa 
 C|,H5.C0.CH2.C02H V. Benzoyl-aoetic acid. 
 
 Acetophenone o-Carbozylic Acid [1 : 2] 
 CO.,H.CaHj.CO.CHj. o-Acetyl-benzoia acid. 
 [115°]. 
 
 Formation. — 1. Together with COj, from 
 
 acetophenone di-carboxylic acid by heating, long 
 
 boiling with water, or by potash-fusion. — 2. By 
 
 heating phthalyl-acetio acid with water at 200°: 
 
 .C. = CH.CO^ 
 
 C.h/ \ +H,0 = 
 
 \00.0 
 
 COjH.CsH^.CO.CHa + COj 
 (Gabriel a. Michael, B. 10, 1554).— 3. From 
 methylene-phthalide by warming with aqueous 
 £0H (Gabriel, B. 17, 2524) : 
 
 C.H / \ 
 
 + H,0 = C02H.CeH,.CO.CH3. 
 
 '\co.o 
 
 Properties. — Broad crystals, with sweet taste. 
 
 _ Reactions. — 1. Bromine and glacial acetic 
 
 acid at 100° convert it into bromo-methylene- 
 
 .0 = CHBr 
 phthaUde CsHj<; \ 
 
 \co.o 
 
 2. Cono. H2SO4 forms, in the cold, two bodies, 
 C„H„04 [216°] and C,sH,A [c- 134°]. The 
 latter body is a monobasic acid, di-acetophe- 
 none carboxylio acid, and splits up into 
 CO2 and the former body when it is heated above 
 its melting-point (W.Eoser, 5.17,2620; Gabriel, 
 B. 17, 2665) .—3. Alcoholic NH3 for fourteen hours 
 at 100° forms a base, OigHuNjO^ [204°-210°] 
 It crystallises in long needles, insol. water or 
 alcohol and gives a nitroso-derivative [246°] 
 (Gabriel, B. 18, 1258).— 4. Ac.,0 and NaOAcform 
 Ao.CsHj.CO^Ao [71°] ; needles, insol. alkalis 
 (Gabriel, B. 14, 921). 
 Phenyl-hydraside 
 
 [102°]. Small prisms or large tables, v. e. sol, 
 alcohol (Eoser, B. 18, 804). 
 
 Oxim. — The anhydride of this body, 
 ^ „ .CMe:N 
 
 [159°] is formed by the action of hydroxylamine 
 (base) on acetophenone-o-earboxyhc ether, or of 
 hydroxylamine hydrochloride upon acetophenone 
 di-carboxylic ether. It is also got, together with 
 COj, when the oxim of acetophenone di-car- 
 boxylic acid is heated. It crystallises in colour- 
 less needles (Gabriel, B. 16, 1993). 
 
 Acetophenone ^-Oarboxylic Acid OjHgO, 
 [1 : 4] C0.,H.C,H,.C0.CH3. [200°]. Formed, to- 
 gether with terephthaUc acid, by warming exo- 
 oxy-isopropyl-benzoic acid Me2C(0H).CjH,.C02H 
 with chromic mixture (R. Meyer, B. 12, 1071 ■ 
 A. 219, 259). The process is similar to that 
 by which tri-methyl-carbinol is converted into 
 acetone. Needles (from water). May be sublimed. 
 V. si. sol. cold water, si. sol. hot water, alcohol 
 or ether. 
 
 SaWs.— BaA'jJaq. — CuA^'aq. — PbA'^l^aq. — 
 AgA'. 
 
 Methyl ether.— Mek', [92°]. Small needles. 
 
 Acetophenone o-io-di-carboxylic acid 
 C|„H„05aq i.e. COjH.CbHj.CO.CHj.COjH aq, 
 Bemoyl-acet-carioxylic acid. [90°]. Formed 
 by dissolving phthalyl-acetio acid (g. v.) in cold 
 aqueous NaOH and ppg. by HCl (Gabriel a. 
 Michael, B. 10, 1553). It behaves, therefore, 
 as if phthalyl-acetio acid were its anhydride. 
 Broad needles (from water). On melting, it splits 
 up into HjjO, COj and acetophenone o-carboxylio 
 acid (g. v.). 
 
 Salt : AgA' : granular pp. 
 
 Phenyl-hydrazine, in alcoholic solution 
 in presence of HOAc, forms the anhydride of the 
 
 C— CHj-CO^H 
 phenyl-hydrazide : CsHi<^ ^NJh 
 
 It is soluble in NaOHAq and is reppd. by HCL 
 [160°] giving off CO^. It forms salts, e.g. : 
 (C,aH„N203)2Ca3aq (W. Eoser, B. 18, 803). 
 
 Hydroxylamine forms, in like manner, not 
 the omim but its anhydride : 
 
ACETOPHENONE OARBOXYLIO AOIDS. 
 
 yC — CH,COjH 
 
 \co.o.^^ 
 
 [e. 150°]. This is a mono-basic acid, and splits 
 up, when heated, into CO^ and the anhydride of 
 the oxim of aoetophenone-o-oarboxylio acid 
 {above). 
 
 AC£TOFHENOir£ CHLOBIDE v. di-Chlobo- 
 
 ETHYL-BENZENE. 
 
 ACETOPHENONE CYANHYDKIN CgHsNO, 
 i.e. Ph.C(OH)(CN).Me a-oxy-a-phenyl-propio- 
 nitrile, a-oxy-hydro-atropo-nitrile. Formed by 
 mixing aoetophenone with KCN, and adding 
 fuming HCl (Spiegel, B. 14, 235). A brown oil. 
 
 Beactions. — 1. KOHAq gives atrolaetic acid, 
 Ph.CMe(0H).C02H.— 2. HCl at 130° gives 
 chloro-hydro-atropio acid : Ph.CH(CH2Cl).C02H 
 (Spiegel, B. 14, 1352). — 3. Ammonia forms 
 Ph.C(NHJ(CN).Me (Tiemann a. Kohler, B. 
 U, 1980). 
 
 ACETOPHENONE-DI-METHYL-ANILIHE v. 
 di-Methtl-amido-benztl phenyl ketone. 
 
 ACETOPHENONE DI - METHYL - HYDSA- 
 ZIDE C,„H,,N2, i.e. PhCMe:N,Me2(165°) at 190 
 mm. Formed from aoetophenone and di-methyl- 
 hydrazine at 100° (Riesenegger, B. 16, 663). 
 
 ACETOPHENONE NITEANIIIDE v. Nitbo- 
 phenyl-amido-acetophenone. 
 
 ACETOPHENONE PHENYL-HYDEAZIDE 
 ChHjjNj i.e. CPhMeiNjPhH [105°]. Formed by 
 shaking acetophenone suspended in water with 
 a solution of phenyl-hydrazine hydrochloride 
 and sodium acetate (Fischer, B. 17, 576). Also 
 by allowing a cone, alcoholic solution of phenyl- 
 hydrazine and acetophenone to stand for a day 
 (Riesenegger, B. 16, 661), or by heating the 
 oxim with phenyl-hydrazine (Just, B. 19, 1206). 
 Slender white needles or plates. V. sol. ether, 
 b1. Bol. water or cold alcohol. 
 
 ACET0PHEN0NE-(;8).PINAC0LINEC,jH,eO, 
 i.e. Ph,CMe.CO.CHs (?). [41°]. (310° unoorr.). 
 Prepared by the action of zinc and HCl on an 
 alcoholic solution of acetophenone. Rhombic 
 prisms or short pillars. Soluble in CsH„ ether, 
 acetic acid, hot alcohol, &c. By heating with 
 Boda-lime it gives HOAo and di-phenyl-methyl- 
 methane, Ph^CH.CHj. On reduction with HI 
 and P, it gives a hydrocarbon 0,|jH,j, [128°], 
 which is apparently identical with the hydrocar- 
 bon formed by the action of Na on bromo-ethyl- 
 benzene: PhCHMe.CHMePh. CrOj oxidises it 
 to di-phenyl-propionic acid, CHjCPhjCO^H. 
 
 An isomeric acetophenone-pinacoliue [70°] 
 (c. 343° i. V.) is formed when acetophenone is 
 heated \vith HI and P at 140° (Graebe, B. 7, 
 1625). It forms plates or tables (from alcohol). 
 It is not attacked by AcCl ; HI reduces it to the 
 hydrocarbon C,„H|j (Thorner a. Zincke, B. 11. 
 1988 ; 13, 642). 
 
 ACETOPHENONE-PINACONE 
 
 OA-C(OH)-CH, 
 C,.H„02 I.e. I 
 
 '" " " C,H5-C(0H)-CH3 
 
 [120°]. Prepared by the action of sodium 
 amalgam on a solution of acetophenone in 
 dilute alcohol. Needles or prisms. V. sol. 
 alcohol or ether, insol. water. It is split up on 
 heating into acetophenone and pheuyl-methyl- 
 carbinol. Aqueous acids at 150° convert it into 
 acetophenone-(0)-pinaooline, PhjCMe.CO.CH, 
 (ThSrner a. Zincke, B. X3, 641). 
 
 ACET0PHEN-0XIMC,HjNO,i.e.PhCMe:NOH 
 
 [59°]. Phenyl methyl hetoxim. Formed by 
 mixing alcoholic solutions of acetophenone and 
 hydroxylamine ; after 24 hours, the alcohol is 
 distilled off, and the product crystallised from 
 water. It forms colourless silky needles. Vola- 
 tile with steam ; soluble in hot water, alcohol, 
 ether, benzene, chloroform, or benzoline. Soluble 
 in acids and in alkalis. 
 
 ACETO-PEOPIONIC ACID v. Aoetyl-pbo- 
 
 PIONIO ACID. 
 
 ACETO-SINAPIC ACID v. Sinapio aobd. 
 ACETO-STJCCINIC ACID v. Aoetyl-sucoinio 
 
 ACID. 
 
 ACETO-THIENONE 
 
 13. ThIENYL MEIHYl 
 
 KETONE. 
 
 ACETO-THIO-TOLTJIDIDE v. Thio-aoetyl- 
 
 TOLTJIDINE. 
 
 ACETO-VAIEEIC ACID v. Aoettl-valeric 
 
 ACID. 
 
 ACETOXIM CaHjNO, i.e. Me.,C:NOH Di- 
 
 methyl-ketoxim, acetone hydroxylamide [60°] 
 (135° i. V.) at 730 mm. Prepared by leaving an 
 aqueous solution of acetone mixed with 
 hydroxylamine hydrochloride, neutralised with 
 NaOH, to stand for 24 hours ; and extracting 
 with ether (V. Meyer a. Janny, B. 15, 1324). 
 
 Properties. — Colourless prisms ; extremely 
 volatile and smelling like chloral. Very soluble 
 in water, alcohol, ether, or benzoline. Neutral 
 to litmus. Ether extracts it from a neutral, but 
 not from an acid or alkaline, solution. It ie 
 readily decomposed by boiling acids (even acetic) 
 into acetone and hydroxylamine. Acid reducing 
 agents have a like effect, but zinc dust and 
 NaOH does not affect it. 
 
 B'HCl, white powder [c. 100°], very un- 
 stable, formed by passing HCl gas into a dry 
 ethereal solution of aoetoxim. — CjHjNONaOEt, 
 crystalline scales, got by adding NaOEt to an 
 ethereal solution. 
 
 Benzoyl derivative Me2C:N(0Bz), [42°], 
 small colourless tables, very soluble in alcohol 
 and ether, slightly in water ; formed by the 
 action of benzoyl chloride on acetoxim. 
 
 Benzyl ether ^ Me,C;N(OC,H;), (c. 190°), 
 oily fluid, soluble in alcohol and ether, insoluble 
 in water; formed by the action of benzyl 
 chloride and sodium ethylate on acetoxim ; on - 
 warming with aqueous HCl, it is split up into 
 benzyl-hydroxylamine (Hi,N.OC-H;) and acetone 
 (Janny, B. 16, 170). 
 
 ACETOXIMIC ACID CsH.N.Oj, i.e. 
 CH3.C(N0H).CH(N0H). Nitroso-acetoxim, Di- 
 nitroso-jyropane [i5B°]. Formation. — (1) By the 
 action of hydroxylamine on M-di-ohlor-acetone 
 (CH3.CO.CHCI,).— (2) By the action of hydroxy- 
 lamine on nitroso-acetone (CI-Ij.CO.CH(NOH) ) 
 (Meyer a. Janny, B. 15, 1165). Small prisms. 
 Soluble in alcohol, ether, and hot water. Its 
 alkaline solutions are colourless. 
 
 ACETOXYL. Kolbe's name for aoeitl. 
 Now used to denote C^HjOj. 
 
 ACET-TOLTTIDE v. ^ccJi/Z-toltjidine. 
 ACET-TOLYL-IMID-TOLYL- AMIDE v. Tolyl- 
 acetamidine. 
 
 ACETUKIC ACID C^H,NOs i.e. 
 
 CH2(NHAo).CO^H (acetxjl-glycocoll, acetyl- 
 glycine, or acetamido-acetic acid). [206°]. S. (at 
 15°) 2-7. 
 
 ForvMtion : 1. By heating glyoocoll with 
 
ACETYL-BUTYL ALCOHOL. 
 
 kofi. 3. By beating glycoooU-silver with acetyl- 
 ohloride (Kraut a. Hartmann, A. 133, 99). 
 
 Long colourless crystals, readily soluble in 
 liot water and in alcohol, insoluble in ether, 
 chloroform and benzene. 
 
 BeacUons. — Gives a red coloration with Fe^Cl j. 
 Beadilysaponifiedby boiling with acids or alkalis. 
 
 Salts. — ^A'NH, aq : soluble needles or large 
 tables. — ^A'Ag: soluble plates. — A'jJBaSaq: easily 
 soluble needles. — A'2Ca4|aq : blue trimetrio 
 prisms, easily soluble in water and in alcohol. — 
 ATHHCl" : needles, decomposed by water. 
 
 Methyl ether.— A'Me, [59°], (254°) at 712 mm., 
 long colourless tables, easily soluble in water, 
 alcohol, and benzene, sparingly in ether. 
 
 _ Ethyl ether.— A':Et, [48°], (260°) at 712 mm., 
 trimetric plates. 
 
 Amide CH2(NHAc).CO.NH2— [137°], large 
 colourless tables, soluble in water and alcohol, 
 insoluble in ether (Curtius, B. 17, 1663). 
 
 ACETUKEIDE v. Acetyl-VmzA. 
 
 ACET-XYLIDE v. Acetyl-XYi^mmE. 
 
 ACETYL C^sO, CO.CH,,, COMe or Ac. The 
 radicle of acetic acid, &o. The name Acetyl was 
 formerly applied to the radicle C2H3. The prefix 
 acet- often indicates the radicle CH3.C: as in acet- 
 amidine ; sometimes it is merely a contraction for 
 acetyl, as in aoet-xylide. The acetyl derivatives 
 obtained by displacing H in OH or in NH^ or 
 in NH are described under the compounds from 
 which they are derived by this displacement. 
 
 DI-ACETYL C,H,02 i.e. CHj.CO.CO.CHj. 
 The oxim, CH3.C(NOH).C(NOH).CH3, of this 
 hypothetical body, called also di-methyl-glyoxim 
 or methyl-eihyl-acetoximic acid, is formed by 
 adding hydroxylamine hydrochloride to an 
 aqueous solution of methyl oximido-ethyl ke- 
 tone, CH3.C0.C(N0H).CH3. Glittering needles 
 (Schramm, B. 16, 180). 
 
 DI-ACETYL-ACETONE DI-CAKBOXYLIC 
 ACID V. AcBTO-ACETic ETHER, BeactioK 32. 
 
 ACEXYL-ACETOPHENONE v. Benzoyi-ace- 
 
 TONE. 
 
 ACETYI-ACEYIIC ACID v. Tetrio acid. 
 
 DI-a,-a2-ACETYL-ADIPIC ACID C,„H„0„ i.e. 
 C0jH.CHAc.CHj.CH2.CHAc.C0,H. 
 
 Di-ethyl-ether. — 'EAJJ'. Formed as aby- 
 product (20p.c.) of the action of ethylene bromide 
 upon sodio-aceto-acetic ether, and found in the 
 residue after distilling with steam. It is a thick 
 colourless oil ; its alcoholic solution gives a dark 
 reddish-violet coloration with Fe^Clj. 
 
 Reactions. — 1. It gives a tolerably stable di- 
 sodio-derivative which, on treatment with iodine, 
 yields the di-ethylic ether of di-acetyl-tetra- 
 methylene-di-carboxy lie -acid, 
 
 CH^CAc.COjH ., , . , , „. , .,,. 
 
 II ; an acid which crystaUisea (with 
 
 CH^CAcCOjH ' •' ^ 
 
 2aq) in pearly scales [210°].— 2. By cone. NH3 
 di-acetyl-adipic ether is converted into theketone- 
 imide, O^^^fit [177°].— 3. Phenyl-hydrazine 
 forms the phenyl-hydrazide [145°], which readily 
 splits ofE alcohol giving ethylene-di-methyl-di- 
 oxy-di-quinizine, 
 
 lirjH:CMe Me.C:HNj 
 
 4. By distillation, or on solution in cone. H^SO,, 
 it loses HjO, giving an ether OnHjoOj which pro- 
 bably has the constitution 
 
 p„^CMe.CH(C02Et).CH,v. 
 
 ^^"^vCO . CH(CO,Et).CH.,-> 
 The corresponding acid, [189°], forms a phenyl, 
 hydrazide, C,„H,20,(N2PhH) [192°] (Perkm a. 
 Obrembsky, B. 19, 2051). 
 
 ACETVL-AMIDO COMPOUNDS v. Amido 
 
 COMPOUNDS. 
 
 ACETYL-BENZOIC ACID v. Aoetophenonis 
 
 CAEBOXYLIO ACID. 
 
 ACETYl-BENZOYL-ETHANE v. Acetophe- 
 
 NONE-ACETONE. 
 
 ACETYL-BENZOYL-ETHANE CAEBOXYLIC 
 
 ACID V. ACETOPHENONE-ACETO-ACETIO ACID. 
 
 ACETYL-BENZYL-STJCCINIC ETHER 
 C„H„A«-e-CO.^t.CAc(CH,Ph).CH2.CO,Et(310'?) 
 S. G. jj 1"088. Prepared by the action of benzyl 
 chloride on a mixture of sodium ethylate and 
 acetyl-succinic ether (Conrad, B. 11, 1058). 
 
 ACETYL BKOMIDE C^HjOBr i.e. CH3.CO.Br. 
 Acetic bromide (81°). Formed by treating 
 acetic acid with PBrj (Bitter, A. 95, i09). Pre- 
 pared by gradually adding 240 g. bromine to a 
 mixture of 90 g. glacial acetic acid and 33 g. 
 amorphous phosphorus, and distilling when the 
 action is complete (Gal, A. 129, 537). Hanriot 
 (A. Ch. [5] 17, 83) uses 1 pt. phosphorus, 
 15 acetic acid and 40 bromine. Colourless 
 fuming liquid. Heated with bromine at 100° in 
 a sealed tube, it yields bromacetyl-bromida 
 C^HjBrO.Br, together with more highly bromi- 
 nated compounds, which may be separated by 
 fractional distillation (Gal). On the action of 
 bromine on CjHjOBr, see alsoUrech (B.IS, 1720; 
 J. 1880, 386). H. W. 
 
 ACETYL-BUTANE-PHOSPHONIC ACID 
 
 V. DI-ACETONE-PHOSPHINIC ACID. 
 
 ACETYL-BUTYL ALCOHOL CjH.^Oj. 
 
 Di-acetonic alcohol CH3.CO.CH2.CMe2.OH. 
 (164°). S.G.2S-931. 
 
 Preparation. — Acid oxalate of di-acetona- 
 mine (1 pt.) is dissolved in water (3 pts.) and 
 cooled to 5°, when it deposits some of the salt ; 
 solid KNO2 (2 pts.) is slowly added, and the mix- 
 ture kept cool for some days and then heated to 
 50° or 60° ; the oily layer (mesityl oxide) is re- 
 moved partly by distillation, partly by a tap- 
 funnel ; and the aqueous solution, neutralised 
 with EjCOj, is shaken with ether (Heintz, A. 
 169, 114 ; 178, 342). 
 
 Properties.— Syrup, misoible with water, al- 
 cohol, or ether, gives oS hydrogen when treated 
 with Na. 
 
 7-Acetyl-re-butyl Alcohol C^'H.^fi^ i.e. 
 CH3.CO.CH2.CH2.CH2.CH2OH. Methyl S-oxy-n- 
 butyl ketone. (155°) at 718 mm. S.G. 2 1-0143. 
 
 Formation. — 1. From bromo-propyl-aceto- 
 acetic ether (50 g.) by boiling for an hour with 
 water (50 g.) and HCl (20 g. of S.G. 1-18) (Lipp, 
 B. 18,3280).— 2. From so-called tetra-methylene 
 methyl ketone carboxylic acid by boiling with 
 water (Perkin, jun., B. 19, 2557). 
 
 Properties. — Liquid with camphor-like smell, 
 V. sol. water, alcohol, and ether ; scarcely volatile 
 with steam. It does not reduce Fehling's solu- 
 tion or ammoniacal AgN03. Chromic mixture 
 oxidises it to S-acetyl-Ji-butyric acid. Soditmt 
 amalgam reduces it to ai-S-di-oxy-hexane. 
 
 Anhydride C,H,„0 i.e. 0^<^^^^^0. 
 
 Oil. Formed by distilling the alcohol or the 
 fallowing acid. 
 
«0 
 
 ACETYL-BUTYL ALCOHOL. 
 
 Tetra-methylene methyl ketone carboxylie 
 acid, CjHioOa, appears to be a oarboxylio acid 
 formed from the anhydride of acetyl-butyl 
 alcohol: OH,<^gO^H):CMes,0 
 
 Its ethyl ether CpH„63,"(223°)! M.M. 10-195, is 
 formed by the action of trimethylene bromide on 
 aoeto-acetio ether {v. p. 24). 
 
 ACETYL-BUTYL BROMIDE CjH.iBrO i.e. 
 CH3.CO.CH2.CH,.CH2.CH3,Br. (215°) at 718 mm. 
 From the preceding acid, C,H,„Os, or from acetyl- 
 butyl alcohol by the action of HBr. Also formed 
 by heating bromo-propyl-aeeto-aeetio ether with 
 dilute acids. It is a colourless oil, v. sol. alcohol 
 or ether, v. si. sol. water ; boiling water converts 
 it into the alcohol (Lipp, B. 18, 3281 ; Perkin, 
 B. 19, 2557). 
 
 ACETYL-BITTYEIC ACIDS CsH,„03. 
 a-Aoetyl-«-butyric acid CH3.CH2.CHAc.CO2H 
 ti.EifeyZ-aceio-aceiicdoiiiunder AcETO-AOETicAcn). 
 
 ;8-Acetyl-»-butyric acid CH3.CHAc.CH2.CO2H. 
 [c.-12°]. (242°). Formed, together with its ether, 
 by boiling a-acetyl-o-methyl-sucoinic ether, 
 C02Et.CMeAo.CH2.C02Et, with HCl (Bischoff, 
 A. 206, 331). 
 
 Very hygroscopic liquid. V. sol. water, alco- 
 hol, or ether. Oxidises in air. , Hot dilute 
 HNO3 forma pyrotartario acid. 
 
 Salts. — ZnA'2 (at 100°) : nodules (from 
 alcohol). The salts of the alkalis and alkaline 
 earths are syrupy, the lead salt may be got as a 
 vitreous mass. 
 
 Ether.— ■EW (204°-205°). Oil. 
 
 7-Acetyl-71-butyricacidCH2Ac.CH2.CH2.CO2H 
 [13°]. (c. 275° i. v.). From sodium aceto-aoetio 
 ether and j8-iodopropionio ether (Fittig a. Wolff, 
 A. 216, 127). Thick liquid. V. sol. water, alco- 
 hol, or ether. Solutions are acid and deoom- 
 poseNajCOj. Forms a crystalline compound with 
 water, CH3.C(0H)2.CH2.CH2.CH2.C02H [35°-36°] 
 which forms monoclinic prisms, 
 
 a:b: c = -769 : 1 : -885 ;8 = 75° 20'. 
 Over H2S04 it loses H2O, becoming liquid. 
 
 SaZfe.— Ca(C5H803)2aq.— Pb(0sH803)2aq. — 
 ZnAV— AgA'. 
 
 Beactions. — Sodium amalgam reduces it to 
 
 S-OXT-HEXOIO AOLD (g. V.). 
 
 o-Acetyl-iso-butyrio acid (CH3)2CAo.C02H 
 V. di-methyl-aceto-acetic acid under Aoeto-aoeiio 
 Acn). 
 
 j3-Acetyl-iso-butyrio acid CHjAc.CMeH.COjH 
 (248°). Formed, together with its ether and 
 CO2, by boiling ct-acetyl-j3-methyl-sucoinic ether, 
 C02Et.CHAc.CHMe.C02Et, with HCl (Bischoff, 
 A. 206, 319). It is a liquid. V. sol. water, alco- 
 hol, or ether. Turns brown in air. Dilute HNO3 
 forms pyrotartaric acid. The salts are amor- 
 phous. The silver salt deposits silver on warm- 
 ing its solution. 
 
 Ether.— -EtA' (206°-208°). Oil. 
 
 ACETYL-TRI-CARBALLYLIC ETHEE 
 0„H220„ i.e. C02Et.CH2.CAc(C02Et).CH2.C02Et. 
 From chloro-aoetio ether and sodium acetyl-suc- 
 cinic ether, C02Et.CH2.CAcNa.C02Et (Miehle, 
 A. 190, 323). It boils with much decomposition 
 at 280°-300°. Boiling baryta water or oonc. alco- 
 holic KOH split it up completely into alcohol, 
 acetic, and tri-carballylic, acids. 
 
 ACEXYL-CARBINOL C.Ufi^ i.e. 
 CHj.CO.CHjOH. Pyruvyi alcohol, Oxij -acetone, 
 Acatok 
 
 Formation. — Cone. H2SO. dissolves ;3-ohloro- 
 allyl alcohol, CH2:CC1.CH20H, giving off HCl ; 
 the solution is diluted and distilled (Henry, 
 Bl. 39, 526). 
 
 Ethyl ei^ier.— CH3.CO.CH2.OEt. (128°). 
 S.G. is .92. Formed by heating propargyl ethtr, 
 CHiCCHjOEt, with water and HgBr^ (Henry, 
 C. B. 93, 421). Colourless liquid with peculiar 
 odour and burning taste. 
 
 Acetyl derivative C3H50(OAc). Colourless 
 fluid. (172°) S.G. ii 1-058. Soluble in water. Pre- 
 pared by heating potassium acetate with chlor- 
 acetone. Also from propargyl acetate, water, 
 and HgBrj. The alcohol has not been got by 
 its saponification. Eeadily reduces ammoniacal 
 silver nitrate or Fehling's solution, the chief 
 product of the oxidation being lactic acid. 
 
 Benzoyl derivative C3H50(OBz). Long 
 needles. [24°]. Soluble in hot water, easily in 
 alcohol and ether. Prepared by heating potas- 
 sium benzoate with chloraoetone. (Breuer a. 
 Zincke, B. 13, 637.) 
 
 ACETYL CHLORIDE CjHjO.Cl, i.e. Ac.Ol. 
 Acetic chloride. M.w. 78-5. (50-9° cor.) (Thorpe, 
 C. J. 37, 188); (51°-52°) at 720 mm. (Briihl, 
 A. 203, 14). S. G. 2 1-1377 (T.) ; '£ 1-1051. 
 C. E. (0°-10°) -001391; (0°-50°) -001504 
 S. V. 74-05 (T.). fi^ 1-3954. Ea, 26-82 (B.). 
 H.F.p. 63,300 (Berthelot). 
 
 Formation. — 1. From POCI3 and potassic ace- 
 tate: SKOAc-fPOOIs^KsPO^ + SAcCI (Gerhardt, 
 A. Gh. [3] 87, 294).— 2. Contained in the more 
 volatile portions of the product of the action of 
 chlorine on aldehyde (Wurtz, A. Ch. [3] 49, 58). 
 8. By distilling glacial acetic acid with PCI,: 
 HOAc + PCl5=AoOUClH-i-POCl3 (Bitter, A. 
 95, 209). 
 
 Preparation, — By distilling glacial acetic acid 
 (61g.) with phosphorus trichloride (93g.) (B6- 
 champ, J. 1856, 427). The reaction is as 
 follows (Thorpe, O. J. 37, 186) : 
 
 SHOAo + 2POI3 = 3AcCl + 3HC1 + P2O3. 
 If more HOAc be used AC2O is also formed. 
 The action of PCI3 is therefore precisely like 
 that of PCI5, amounting to a displacement of 
 by CI2 ; the molecule HCljAo, which might be 
 expected to be formed, cannot hold together on 
 account of the monovalent character of chlorine, 
 and so splits up at once into HCl and ClAo. 
 Under precisely similar conditions, alcohol, 
 HOEt, gives HCl and ClEt. 
 
 Properties. — Colourless, fuming, mobile, and 
 strongly refracting, liquid. Its vapour strongly 
 attacks the eyes and respiratory organs. 
 
 Beactions. — 1. Violently acted on by water, 
 with formation of HCl and acetic acid. — 2. 
 With ammonia it yields acetamide AcCl + NHj = 
 HCl + AcNH, and with aniline in like manner, 
 acetanilide, AcNHPh. — 3. Distilled with potas- 
 sium acetate or henzoate, it forms acetic or 
 aoeto-benzoic oxide : KOAc -t- AcCl = KCl + ACjO ; 
 and KOBz + AcCl = KCl + AoOBz. Similarly with 
 salts of other acids. — 4. With potassium hydro- 
 sulphide it yields acetic hydrosulphide or thio- 
 acetic acid, and with potassium monosulphMe it 
 forms acetic sulphide or thioacetic anhydride, 
 AcC1-i-KSH = KC1-hAcSH; and 2AoCl + K;2S = 
 2KCI + AC2S (Jacquemin a. Vosselmann, C. B. 
 49, 371). — 5. With potassium, nitrite it gives ofl 
 nitrosyl-chloride, and towards the end of the re- 
 action NO,, and on heating the residue to 150°, 
 
ACETYLENE. 
 
 41 
 
 Bcetio anhydride distils over: AcCl4-KN02 = 
 bfOCUKOAo, and AcCl + KOAo = KCl + Ao^O 
 (Armstrong, C. J. 26, 683). — 6. Silver nitrate 
 acts : 2AoCl + AgNOs = AgCl + N02 + CUAc,0. 
 Similarly with other nitrates : Hg(N03)2, 
 Pb(N0s)2, ^^^ KNOj are attacked immediately ; 
 Ba(NO,), is not affected; Ca(N03)2 readily. With 
 KNO3, chlorine is first evolved, NO^ only towards 
 the end (Armstrong). — 7. With succinic acid it 
 yields acetic acid and succinic anhydride, 
 C,H^(COOH)j + CH3.CO.CI = 
 HCl + CH3.COOH + C,H^(C0)20 ; 
 and it reacts in like manner with other dibasic 
 dihj dric acids ; viz., isodibromosuccinic, phtha- 
 lic, diphonic, and camphoric acids ; isosucoiuic, 
 ordinary dibroraosuocinic, fumaric, and tere- 
 phthalio acids aro not attacked ; sublimed an- 
 hydrous oxalic acid is resolved into H20,C0, 
 and CO2; benzoic acid yields benzoic chloride 
 and acetic acid (Anschiitz, B. 10, 325, 1881). — 
 8. With titanic chloride, acetyl chloride forms the 
 compound TiCl^AcCl (Bertrand, Bl. [2] 33, 403). 
 Large transparent octahedral crystals [25°-30°] 
 sol. in CS.J. — 9. Aluminium chloride reacts ac- 
 cording to the equation Al2Cl|, + 4(CH3.CO)Cl = 
 4HC1 + 2(CH3.C0.CH:C0),Al2Cl3 (Winogradoff, 
 Bl. [2] 34, 325). The product is a solid, de- 
 composed by water into COj and acetone. — 
 10. PCI5 at 190° forms chloro-acetyl chloride 
 CHjCl.CO.Cl (Samosadsky, Z. 1870, 105), and tri- 
 chloro-acetyl chloride, CClj.CO.Cl (Hubner, A. 
 120, 330). — 11. Zinc produces a brown mass 
 whence alcohol extracts ' acetylide,' CijHigOi, 
 which may be ppd. by water. Eed plates (from 
 chloroform). Sol. ether, alcohol, HClAq, fuming 
 HNO3, or AOjO. Combines with bromine ; does 
 not reduce FeUing's solution (Tommasi a. 
 Quesneville, C. B. 76, 496). — 12. Acts upon 
 benzene, in presence of AICI3, with formation 
 of acetophenone (g. v.). — 13. Acts similarly upon 
 thiophene, or its mono-haloid derivatives, dis- 
 placing, in presence of AICI3, H by Ac. But 
 in di-bromo- or di-iodo-thiophene it displaces, in 
 presence of AICI3, Br or I by Ac, e.g. : 
 
 CH^SBr^ + CLAc = O^H^SBrAo + CLBr 
 
 (Gattermann a. Eomer, B. 19, 688). H. W. 
 
 Use in Organic Investigations. — Acetyl chlo- 
 ride evolves HCl when it is heated with any sub- 
 stance containing the radicles hydroxyl, amido- 
 gen, or imidogen. Hence, if a substance does 
 not evolve HOI when so treated, it may be as- 
 sumed to be free from these radicles. If the 
 hydroxyl be alcoholic, i.e. attached to an atom 
 of carbon that is not attached to any more oxy- 
 gen, it will be converted into aoetoxyl (AoO) ; 
 and, if the substance contains no nitrogen, the 
 number of aoetoxyls it contains after this treat- 
 ment gives the number of alcoholic hydroxyls 
 the body contains. Before making the experi- 
 ment, all carboxyls should be etherified, since the 
 group COjH is attacked by AcCl (v. Reaction 7), 
 while the group COjEt is not attacked. The 
 number of acetyl groups that have entered may 
 in many oases be determined by boiling with 
 standard alkali and subsequent titration (Sohiff). 
 Acetyl chloride converts NHj into NHAc, but 
 hardly ever into NAc^. It converts NH into NAc. 
 It has no action upon tertiary amines, hence it 
 can be used in the diagnosis of bases. Acetyl 
 chloride does not act upon hydrogen directly 
 
 united to carbon, except in presence of AIOI3 or 
 some similar agent. 
 
 ACETYL CYANIDE C3H3ON or AoON 
 Pyruvo-nitrile. M. w. 69. (93°). V.D. 2'4. 
 
 Preparation. — When acetyl chloride and sil- 
 ver cyanide are heated together in a sealed tube 
 at 100°, and the product is distilled, a colourless 
 liquid passes over at 80°-90°, and afterwards a 
 compound having a much higher boiling-point. 
 The first yields acetyl cyanide on rectification. 
 
 Properties. — Oil, lighter than water, which 
 gradually dissolves it, forming HON and HOAc, 
 converted by HCl first into CH3.CO.CONH2, and 
 subsequently into pyruvic acid (Hubner, A. 120, 
 230; 123, 271; see also Kleti, G. 5, 391; /. 
 1875, 510). 
 
 Di-acetyl-di-eyanide C^H^OjNj [69°] (210° 
 cor.). V.D. 4-57 (for 4-77). Formed from acetyl 
 cyanide by heating it with KOH, or even by 
 keeping it for some time in a closed vessel. 
 
 Preparation. — Powdered KCN (32 pts.) is 
 boiled with acetic anhydride (50 pts.), diluted 
 with benzene (200 pts.) : yield is 25 p.c. of the 
 theoretical (Kleeman, B. 18, 256). Glistening 
 tables, si. sol. hot water, v. sol. alcohol, ether, or 
 benzene. Di-aeetyl-di-cyanide, like acetyl cya- 
 nide, is converted by boiling with water, H2SO4, 
 or KOH, into HON and AoOH. Heated with 
 AgNO, it yields AgCN. 
 
 ACETYLENE C^Hj or CH.CH Ethine, 
 Ethinene. M.w. 26. Physical Properties oj 
 liquid acetylene : S.G. 2 -451 ; is .420 ; m -381. 
 C.E. (-7° to 36°) -00489. Vapour-pressure: 
 16,340 mm. at 0° ; 24,900 mm. at 13-5°. Criti- 
 cal Point 37° (G. Ansdell, Pr. 29, 209). Proper- 
 ties of gaseous acetylene : V.D. -91. S. 1 at 18° ; 
 S. (CSj or isopentane) 1 ; S. (CClj or turpentine 
 oil) 2 ; S. (amyl alcohol) 3^ ; S. (benzene) 4 ; S. 
 (glacial acetic acid or abs. alcohol) (Berthelot, 
 A. Ch. [4] 9, 425). H.F.p. -47,770. H.F.V. 
 -47,770 (Th.) ;- 64,000 (Berthelot). 
 
 Occurrence. — In coal-gas (Boettger, A. 109, 
 351). 
 
 Formation. — 1. Synthetically by passing 
 hydrogen gas over charcoal heated to whiteness 
 in the electric arc (Berthelot, G. B. 54, 640) ; 
 the hydrogen may be passed through holes 
 drilled through the centre of carbon points 
 discharging powerful sparks (Dewar, Pr. 29, 
 188). — 2. By exposing marsh-gas or coal-gas to 
 a strong heat, or to the spark of a powerful 
 induction-coil : 2GB.^ = C^H.^ -I- 3H2 (Berthelot, 
 G. B. 54, 515). Part of the C^Hj is, however, 
 polymerised during the process, being converted 
 partly into benzene C^Hj, partly into black tarry 
 hydrocarbons (Berthelot, Bl. [2] 11, 142). The 
 vapours of many other organic compounds, as 
 ethylene, alcohol, ether, acetone, amyl alcohol, 
 and benzene, likewise yield acetylene when 
 induction sparks are passed through them (De 
 Wilde, Bl. [2] 6, 2C7).— 3. By the incomplete 
 combustion of hydrocarbons and other organic 
 bodies— abundantly, for example, in a Bunsen 
 lamp, when the flame strikes down and burns 
 within the chimney — also in the incomplete 
 oxidation of organic compounds at ordinary 
 temperatures, as in the voltaic circuit, e.g. in 
 the electrolysis of a solution of potassium aooni- 
 tate or succinate (Berthelot, Bl. [2] 9, 103).— 
 4. By the incomplete combustion of mixtures of 
 hydrogen and gaseous or vaporous carbou-com- 
 
42 
 
 ACETYLENE. 
 
 pounds not containing hydrogen, e.g. CO, CSj, 
 CN. — 5. By passing a mixture of methane and 
 carhon monoxide through a red-hot tube : 
 CH, + CO = H20 + C2H2.— 6. Together with H, 
 CH|, and free carbon, by passing the vapour of 
 methyl chloride (Berthelot), or of ethylene 
 chloride (De Wilde), or of pentane from Ameri- 
 can petroleum (Vohl, Bl. 4, 302), through a red- 
 hot tube. — 7. Together with benzene, by pass- 
 ing styrene vapour through a red-hot tube : 
 CaH8 = CjH,-fCeH5 (Berthelot, J. 1806,544).— 
 8. By passing chloroform vajjour over red-hot 
 copper: iGRC\-\rCu^ = ZGa.fi\^ + G.^^ (Berthe- 
 lot), or by treating chloroform with potassium- 
 amalgam (Kletzinsky, Z. 1866, 127), or with 
 sodium (]?ittig, ibid.). — 9. From iodoform 
 by the action of finely divided silver either 
 alone or mixed with finely divided copper : 
 2CHI3 + 3Ag, = 6AgI + C,H2. Aho by the action 
 of finely divided zinc or of the zinc-copper 
 couple on iodoform in presence of water (P. Caze- 
 neuve, 0. B. 97, 1371 ; Bl. [2] 41, 156).- 10. By 
 passing a mixture of CO and HCl over red-hot 
 magnesium silicide (Berthelot). — 11. By the 
 action of alcoholic potash on bromethylene : 
 CjHjBr + KOII = KBr 4- H^O + CjH^ (Sawitsch, 0. 
 B. 52, 157). — 12. By the action of water on 
 calcium carbide (produced by strongly heat- 
 ing an alloy of Zn and Ca with charcoal): 
 CaC2 + H20 = CaO-C.,H., (Wohler, 4.124,220). 
 13. Formed, together with succinic acid, by the 
 electrolysis of sodium fumarate or maleate : 
 C^H^Na^Oj + HjO = C^H^ + 200^ -1- Na.p -I- H., (Ke- 
 l£uU, J. 1864, 389).— 14. By heating isethi- 
 onic acid with potash: CjH^O.SOjK -^ KOII = 
 CjHj -F K2SO3 -h 2H2O. — 15. Formed in small quan- 
 tity by heating cupric acetate (1 pt.) with water 
 (200 pts.) in a closed flask at 100° (Tommasi, 
 Bl. [2j 38, 257). 
 
 Preparation. — 1. Air is burned in a cylinder 
 full of coal-gas, and a portion of the products 
 of combustion are sucked (by an air-pump) first 
 through a metallic condenser to cool them, and 
 then through several bottles containing an am- 
 moniacal solution of cuprous chloride. A red 
 pp., CjCujaq, is formed ; this is collected, washed 
 by decantation, and warmed with aqueous HCl, 
 when it is decomposed with evolution of acety- 
 lene gas : C.CUjHjO -1- 2HC1 = C^H., + 2CuCl + H,0 
 (Jungfleisch, C. B. 90, 264 ; J. Ph. [5] 1, 307).— 
 2. Ethylene bromide is slowly dropped into a 
 strong alcoholic solution of potash at boiling heat, 
 and the evolved gas is passed through a second 
 similar boiling solution to remove bromethylene 
 (Miasnikoff, 4. 118, 330; Sawitsch, A. 119, 184 ; 
 Sabanejeff, J.. 178, 111). To remove the last 
 traces of bromethylene, Zeisel {A. 191, 372) 
 recommends passing the gas over moderately 
 heated soda-lime. The gas may also be purified, 
 as in the first method, by passing it through an 
 ammoniacal solution of cuprous chloride. 
 
 Properties. — Colourless gas, having a dis- 
 agreeable odour. According to Zeisel, when pre- 
 pared from the copper compound as described 
 above, it is contaminated with vinyl chloride. 
 Acetylene is liquefied by a pressure of 83 atmo- 
 spncres at 18°, forming a mobile, highly refrac- 
 tive liquid, lighter than water. Liquid acetylene 
 dissolves paraffins and many fats (Cailletet, C. B. 
 85, 851). 
 
 Ueaciioii^. — 1. Decomposed by ihe induction- 
 
 sparJc with separation of carbon, and partly con- 
 verted into a liquid and a solid polyacetyleno, 
 the latter insoluble in the ordinary solvents. — 
 2. Slowly passed through a porcelain tube heated 
 to bright redness it is almost wholly resolved 
 into C and H, together with small quantities 
 of ethylene and of tar containing naphthalene. 
 Acetylene is also resolved into C and H by ex- 
 ploding a percussion-cap in it (Berthelot, O. B. 
 93, 613). Heated to dull redness in a bent glass 
 tuiie standing over mercury it is gradually poly- 
 merised, forming : a very volatile liquid probably 
 CjHj, benzene C„H„, styrene CeHj (135°-100°), a 
 liquid mixture (210°-250°) of naphthalene C,„H, 
 and probably naphthalene hydride C|„H,|„ a 
 mixture of strongly fluorescent oils distilling at 
 250°-340°, retene distilling at 360° (Berthelot, 
 C. B. 62, 905).— 3. Mixed with excess of hy- 
 drogen over mercury, and in contact with plati- 
 num-black, acetylene is converted into ethane : 
 CjHj + 2H2 = C^Hs ; by alkaline reducing agents, 
 into ethylene, C.^Hj, e.g. by the action of zinc and 
 aqueous ammonia on its copper compound (Ber- 
 thelot). — 4. With, oxidising agents. Converted by 
 KMnO, into oxalic acid, C^H^Oj, with formic and 
 carbonic acids as secondary products (Berthelot, 
 C.B.74:,Sb).- 5. Slowlyabsorbed by an ammonia- 
 cal cupric solution, and for the most part oxidised, 
 a carbonaceous substance being at the same time 
 deposited, together with a small quantity of the 
 compound CjCujH^O (Berthelot, A. Ch. [4] 9, 
 422). — 6. Passed with phosgeiie, COCI2, through a 
 red-hot tube, it is polymerised to benzene (Ber- 
 thelot, Bl. [2] 18, 9).— 7. With chlorine, either 
 pure or mixed with other gases, acetylene some- 
 times detonates, yielding HCl and free carbon. 
 Frequently, however, C^HjClj is formed with ex- 
 plosion ; or this compound is formed at first, and 
 then the mixture suddenly explodes (Berthelot, 
 Bl. [2] 5, 191).— 8. Acetylene passed into bro- 
 mine under water forms C.^H^Br^ [v. tetra-Bnouo- 
 ethane) and a non- volatile solid, a polymeride of 
 CjHBrj. — 9. Acetylene passed over iodine mois- 
 tened with alcohol forms C^HJ-^ (Sabanejeff, A. 
 178, 109, V. (ii-IoDO-ETHYLENE). — 10. Acetylene 
 passed into a solution of ICl in HCl forms 
 CjH JCl (Plimpton, O. /. 41, 392, v. Chloeo-iodo- 
 ethylene). — 11. With nitrogen. When a series 
 of strong induction-sparks is passed through a 
 mixture of acetylene and nitrogen, hydrocyanic 
 acid is formed, C^H^ -H N2 = 2HCN. Carbon and 
 hydrogen are at the same time separated, but 
 this may be prevented by diluting the gaseous 
 mixture with 10 vol. H (Berthelot, 0. B. 77, 
 1041). — 12. Passed with vapour of hydrocyanic 
 acid through a, red-hot tube acetylene yields a 
 small quantity of piooline C„H,N, and probably 
 homologues thereof (Ramsay, Ph. M. [5] 4, 241). 
 13. Strongly heated with butylene and amylene 
 it forms C,H(C,H5) and C2H(C5H„) (Prunier, A. 
 Ch. [5], 17, 5).— 14. Successive treatment with 
 H2SO4 and water forms some stable sulphonio 
 acid (Zeisel, A. 191, 366).— 15. Converted into 
 aldehyde by an aqueous solution of mercuric bro- 
 mide, even in the cold (Kutscheroft, jB. 14, 1540) : 
 
 CHsCH + HjO = CHj:CH.OH = CH3.CHO. 
 
 16. SbClj absorbs acetylene forming CjHjSbCi, 
 which, on heating, splits up into SbClj ana 
 OjHjClj.— 17. Cone. HBrAq at 100° forms a little 
 bromo-ethylene (vinyl bromide). — 18. Conc.HIAq 
 
ACETYLENE CARBOXYLIO ACIDS. 
 
 43 
 
 forms some iodo-ethylene and ethylidene iodide. 
 19. Passed through boiling sulphur, it forms 
 some thiophcne (V. Meyer, B. 16, 2176). 
 
 Metai,lio Deeivatives. — Sodium acety- 
 lene C^HNa, is formed, with evolution of hydro- 
 gen and small quantities of ethylene and ethane, 
 when sodium is gently heated in acetylene. At 
 a dull red heat disodium-acetylene C.^Na^ is 
 formed. — Potassium decomposes acetylene in 
 like manner, but with greater violence ; when 
 melted in the gas it takes fire and is converted 
 into CjKj, which is also formed when K is heated 
 to dull redness on ethylene-gas. All these com- 
 pounds are decomposed by water with explosive 
 violence and reproduction of acetylene (Berthe- 
 lot, A. 139, 150). 
 
 Calcium-acetylene G.fis. is formed by 
 strongly heating an alloy of zinc and calcium 
 with charcoal. Decomposed by water into 
 Ca(OH), and acetylene (Wohler, A. 121, 220). 
 
 Copper-acetylene G.finjlfi. It may be 
 looked upon as CaCu.^aq or as HCiC.Cu.Cu.OH; 
 in the latter case it may be called cuproso-vinyl 
 hydroxide. Berthelot (A. 138, 345) considers it 
 to be cuproso-vinyl oxide (CMCu..^)./). It con- 
 stitutes the red precipitate formed on passing 
 acetylene or coal-gas into an ammoniacal solu- 
 tion of cuprous chloride. In the dry state it ex- 
 plodes when struck or when heated to 100''-120°, 
 leaving a velvety black powder containing copper 
 and charcoal. Takes fire in contact with chlorine, 
 bromine, or finely divided iodine. Its formation 
 affords a very delicate test for acetylene, the pre- 
 sence of 0-005 mg. of that compound being thus 
 recognisable. The formula above given for it is 
 due to Blochmann [A. 173, 174). According to 
 Berthelot {Bl. [2] 5, 191) when acetylene is passed 
 into a cone, solution of cuprous chloride in KCl 
 a yellow crystalline pp. of cuprcso-vinyl chloride 
 CjHCUjCl is formed, corresponding bromides and 
 iodides being formed in a similar way. 
 
 Silver acetylene OjAg^HaO, is formed 
 on passing acetylene into an ammoniacal solu- 
 tion of silver nitrate, as a white or yellowish 
 precipitate which, when dry, explodes even more 
 easily than the copper-compound. The above 
 formula, due to Blochmann, is that ofargento- 
 vinyl hydroxide, CH:C.Ag.Ag.OH: ; Berthelot 
 on the other hand regards the compound as the 
 corresponding oxide (C^HAg2)0. The formulaj 
 of Blochmann and Berthelot require 83-7 and 
 86-7 p.c. Ag respectively; Miasnikoff (A. 118, 
 332) finds 88 p.c. Ag in the pp., a result that 
 has been confirmed by Plimpton, and agrees with 
 the formula C^fikefl. Acetylene completely 
 pps. the sUver even from a neutral solution of 
 AgNOj ; the pp. contains variable quantities of 
 AgNOj (Plimpton) . The chloride CHiC.Ag. Ag.Cl, 
 is prepared by passing acetylene into an ammo- 
 niacal solution of silver chloride (Berthelot). By 
 agitating silver acetylene with a, solution of 
 iodine in ether, till the colour of the liquid 
 disappears and then evaporating, yellow offen- 
 sive-smelling crystals are formed, the vapour of 
 which strongly attacks the eyes (Berend, A. 135, 
 257) ; Baeyer (B. 18, 2275) has shown that they 
 are di-iodo-acetylene : CMi + 2I2 = Cjlj + 2AgI. 
 
 Oold and Mercury Compoimds. — In an am- 
 moniacal solution of aurous thiosulphate, ace- 
 tylene forms a yellow highly explosive precipi- 
 tate, and in an alkaline solution of potassio- 
 
 mercuric iodide a yeUow pp.: 02HHgI,H2O, 
 which explodes slightly when heated and yields 
 acetylene when treated with acids (Bassett, C. N., 
 19, 28). H. W. 
 
 Theoretical considerations. — The explosive 
 character of acetylene is undoubtedly connected 
 with the fact that its formation from C and H is 
 attended with disappearance of heat (Berthelot). 
 It has been suggested by Baeyer {B. 18, 2277) 
 that this disappearance of heat may be due to the 
 production of a strained condition owing to the 
 alteration in the direction of the attraction be- 
 tween the two carbon atoms. 
 
 To represent his views in a mechanical model, 
 he supposes four steel wires fixed to a ball and 
 radiating from it in the direction of the angles 
 of an inscribed tetrahedron. Such a ball repre- 
 sents a free atom of carbon ; union of such 
 atoms is represented by a wire of one ball being 
 attached to, and in a straight line with, a wire 
 of another ball. If two such balls be taken and 
 three of the wires from one ball be fastened to 
 three of the wires from another ball and then 
 bent in such a way that all six wires are parallel, 
 then the arrangement is in a strained condition, 
 for the wires will readily fly apart, representing 
 the explosion of acetylene. The angle between 
 two adjacent wires in one of the balls just de- 
 scribed is 109° 28', which is very near the angle 
 of a pentagon (108°) ; hence if five balls be 
 placed at the angles of a pentagon, very little 
 bending will be required to make a wire from 
 each ball in a straight line with a wire from the 
 next. The angles of a hexagon, of a square, and 
 of an equilateral triangle, differ by 10J°, 19.j°, 
 and 49 j° respectively from 109^°; these numbers 
 ought therefore to indicate the relative stability 
 of rings containing 6, 4, and 3 carbon atoms. 
 As a matter of fact, closed rings of carbon atoms 
 usually contain five or six atoms, while rings 
 containing three, four, or seven atoms are almost 
 unknown. 
 
 Haloid derivatives of acetylene v. Bkomo-, 
 Chlobo-, and I0D0-, aceiylene, -ethylene, and 
 
 -ETHANE. 
 
 DIACETYIENE HCiC.CICH. Gas of pe- 
 culiar smell resembling dipropargyl. Formed 
 by heating diacetylene-di-carboxylic acid with 
 ammoniacal Cu^Clj solution. With ammoniacal 
 Cu.jClj it gives a violet-red pp., with ammoniacal 
 Agist O3 a very explosive yellow pp. By the action 
 of a solution of iodine upon the silver-compound 
 di-iodo-di-acetylene is formed. (Baeyer, B. 18, 
 2272.) 
 
 ACETYLENE DI-BEOMIDE v. Di-bromo- 
 
 ETHYLENE. 
 
 ACETYLENE TETEA-BEOMIDE v. Teiba- 
 
 BBOMO-ETHANE. 
 
 ACETYLENE DI-BEOMIDE DI-CAEBOXY. 
 
 Lie ACID V. Dl-BEOMO-FUMAKrC ACID. 
 
 ACETYLENE BEOMO-IODIDE v. Bromo- 
 
 IODO-ETHYLENE . 
 
 ACETYLENE CAEBOXYLIC ACIDS 
 
 CH:C.CO„H. 
 Acetylene mouo-carboxylic acid v. Fbopiolio 
 
 ACID. 
 
 Acetylene-di-carboxylic acid : 
 
 CiH^Oj. i.e. C02H.C;G.C0,H. 
 Formed by treating di-bromo- or iso-di-brotJMV 
 succinic acid with alcohoUo KOH (4 mols.) at 
 
44 
 
 ACETYLENE CAEBOXYLIO ACID3. 
 
 100" (Bandrowski, B. 10, 838). The yield is 75 
 per cent, of the theoretical (Baeyer, B. 18, 677). 
 
 Separates from water in efflorescent crystals, 
 these contain aq., which they lose over HjSO^, 
 and then crystallise from ether in thick four- 
 sided tables. The hydrated acid is v. e. sol. 
 water, alcohol or ether, but the dry acid is less 
 soluble. The acid decomposes when melted. 
 
 Salts. — Na^CjO, Sjaq. : slender needles. — 
 KHC^O^: small crystals, si. sol. water. — 
 ZnC.Ojliaq. — PbC^Ojaq. — CuCjO,3aq. : blue 
 plates, b1. sol. cold water (Bandrowski, B. 12, 
 2212). 
 
 Beaetions. — 1. The acid and its acid salts 
 are converted, by heating with water, into pro- 
 pioUc acid : C0,H.C:C.C02H = CO^H-C^CH + CO^. 
 — 2. Sodium-amalgam, reduces it to succinic 
 acid. — 3. Bromine combines forming di-bromo- 
 f umaric acid.— 4. HCl, HBr, or HI combine readily 
 forming chloro-, bromo-, or iodo-, fumario acids. 
 
 Methyl ether Ueji.". (197°). Colourless 
 liquid (Bandrowski, B. 15, 2694). 
 
 Acetylene tetra-carboxylic acid, so called, v. 
 Ethane tetra-oaeboxtlic acid. 
 
 Si-acetylene di-carboxylic acid CsHjOjaq. 
 i.e. C02H.C:C.CiC.C02H aq. Prepared by the 
 action of a concentrated aqueous solution of 
 potassio ferricyanide upon a cooled magma of 
 the cuprous compound of sodium propiolate : 
 2CuC:0.C02Na + 0^ = 2CuO + (C-C.CO^Najj. 
 Colourless needles or tables, v. sol. water, alcohol, 
 or ether, v. si. sol. benzene or benzoline. Turns 
 brown at 100° and explodes very violently at 
 c. 177°. Explodes also on percussion. Turned 
 purple by light. Gives a brownish-red pp. with 
 ammoniacal cuprous chloride. 
 
 Beaetions. — 1. Sodium-amalgamxedincesit to 
 hydro-muconic acid, 
 
 C0jH.CH:CH.CHi,.CH2.C02H, 
 
 and adipic acid, C03H.CH2.CIJ-,.CH2.CH2.C02H ; 
 some propionic is formed at the same time. — 
 2. Zinc dust and HCl also reduce it to adipic acid. 
 
 Ether.— Et^A." (184°) at 200 mm. An oil. 
 Eeduced by zinc dust and HCl to ethyl pro- 
 piolate (Baeyer, B. 18, 678, 2269). 
 
 Tetra-acetylene di-carboxylic acid 
 CjoH^O, i.e. C02H.C:C.C;C.CiC.C;C.C0jH. 
 
 Preparation. — ^An aqueous solution of the 
 acid sodium salt of di-acetylene di-carboxylio acid 
 is heated on the water-bath. Sodium di-acety- 
 lene mono-carboxylate, H.CiC.CiC.COjNa, is then 
 formed, with evolution of COj ; the cuprous com- 
 pound of this salt, Cu.C!C.C:C.C02Na (?), is then 
 prepared and this is oxidised by potassio ferri- 
 cyanide : 
 
 2CuC:C.C:O.CO^a+0,=2CuO+(C:O.C:C.CO,lira), 
 (Baeyer, B. 18, 2271). Tetra-acetylene di-car- 
 boxyho acid may be reduced to sebacic acid, 
 
 CO,H.CH,.CH,.eH;,.Ctt,.CHa.0Hj.CHa.OH..C0aH, 
 by sodium-amalgam. 
 
 lodo-acetylene carboxylic acid v. Iodo-fbo- 
 
 PIOLIC ACID. 
 
 ACETYLENE DI-CHLORIDE v. Di-chlobo- 
 
 ETHYLENE. 
 
 ACETYLENE TETRA-CHLORIDE v. Tetka- 
 
 CHIiOBO-ETHANE. 
 
 ACETYLENE CHLOEO-BEOMIDE jj. Chlobo- 
 
 BBOMO- EIHY IiENE. 
 
 ACETYLENE CHLOBO-IODIDE v. CmoBo- 
 
 lODO-BIHlLEtlB. 
 
 ACETYLENE HYDEOCHLORIDE v. CatoBO- 
 
 ETHYLENE 
 
 ACETYLENE DI-HYDROCHLOEIDE v. di- 
 
 Chlobo-ethane. 
 
 ACETYLENE IODIDE ii. ii-IoDO-EiHYiiENB. 
 ACETYLENE NAPHTHALENE v. 
 
 ACENAPHTHYLENE. 
 
 ACETYLENE-TJEEA C^HjN^Oj i.e. 
 .NH.CH.NH. 
 C0< I >C0. Glycoluril. 
 
 \nh.ch.nh/ 
 
 S. -094 at 17°. Formed as white needles when 
 cone. HCl is added to a solution of glyoxal (1 pt.) 
 and urea (2 pts.) and water (3 pts.). If the fil- 
 trate is evaporated, it deposits a yellow modifi- 
 cation or impure form (Schiff, A. 189, 157; 
 Bbttinger, B. 11, 1787). Also formed by heating 
 a mixture of tri-chloro-lactic acid, urea, and a 
 little water at 100° (Pinner, B. 17, 1997). Formed 
 when allantoiin is reduced with (1 p. c.) sodium- 
 amalgam (Eeineck, A. 131,119; Widman, B. 19, 
 2477). 
 
 Properties. — White glistening prisms, sol. hot 
 water. Gives a white flocculent pp. withHg (NOj)^. 
 SpHt up by boiling baryta water into urea and 
 hydantoic acid— C^HjAg^NjO^. 
 
 ACETYL-ETHYL-PEOPIONIC ACID v. AcB- 
 
 TYL-VALEBIO ACID. 
 
 a-ACETYL - i8 - ETHYL - SUCCINIC ETHER 
 C,2H,„05 i.e. COjEt.CHAc.CHEt.COjEt (263°) 
 S. G. jf.5 1-064. From aoeto-acetio ether (68 g.), 
 alcohol (120 g.), sodium (12 g.) and o-bromo- 
 butyric ether (102 g.) (L. T. Thorne, C. J. 39, 
 336 ; S. Young, C. J. 43, 172). 
 
 Beaetions. — 1. Decomposed by jpoias?i (2 pts.) 
 and water (1 pt.) into acetic and ethyl-succinic 
 acid. — 2. Decomposed by potash (1 pt.) and 
 water (20 pts.) into salts of COj and /3-acetyl-o- 
 ethyl-propionic acid {v. Acetyl-vaiebio acid). — 
 3. With NaOEtandMelitgivesn-acetyl-a-methyl- 
 j8-ethyl-succiuio ether (g.u.) — 4. The ether (3 pts.) 
 boiled with cone. HCl (2 pts.) and water (4 pts.) 
 for 2 days forms j8-aoetyl-n-ethyl-propionio acid, 
 which may be extracted by ether, and a crystal- 
 line acid, Ketolactonic acid (q. v.) which re- 
 mains in the water. Ethyl-succinic acid is also 
 formed. — 5. When heated, it partly splits up 
 into alcohol and ketolactonic acid. 
 
 o -ACETYL - o - ETHYL . SUCCINIC ETHER 
 CijHjjOs i.e. CO^Et.CAcEt.CHyCO^t (264°). 
 From sodium acetyl-succinic ether and EtI 
 (Huggenberg, A. 192, 146). Cone, alcoholic KOH 
 converts it into ethyl-succinic acid. 
 
 DI-ACETYL-FTJMARIC ETHER C.jHiA 
 i.e. C02Et.CAc:CAc.C02Et [96°]. Formed by 
 the action of iodine (1 mol.) upon di-sodio-di- 
 acetyl-snccinio ether (1 mol.) suspended in ether: 
 CCEt.CNaAc.CNaAc.CO^Et + 1,, = 
 CbaEt.CAciCAc.COjEt + 2NaL 
 Long silky needles (Just, B. 18, 2636). 
 
 a-ACETYL-GLUTARIC ETHER C.iH.sOs i.e. 
 C02Et.CHAc.CHj.CHjC02Et (272°) S.G. jf! 
 1'0505. From aceto-acetic ether, j8-iodo-propionio 
 ether, benzene, and sodium (Wislioenus a. Lim- 
 pach, A. 192, 130). Cone, alcoholic KOH splits 
 it into acetic and glutario acids. Boiling HCl 
 forms CO, and 7-acetyl-butyrio acid. 
 
 /3-Acetyl-glutaric acid CHAc(CH2.C0jH)j. 
 [109°]. Formed by heating o-carboxy-jS-acetyl- 
 glutaric aoid (from chloro-acetyl-propionio ether 
 
DI-AOETYL-n-IOSPHORIO ACID. 
 
 45 
 
 and Bodio-malonio ether) (Conrad a. Guthzeit, B. 
 19, 44).— AgA'. 
 
 Di-acetyl-glutaric ether CisHjjO, i.e. 
 COjEt.CHAo.CHAo.CH,.CO,Et or 
 C02Et.CHAo.CH2.CO.CHi.CH,C02Et. 
 (o. 245) at 140 mm. From bromo-aoetyl-pro- 
 j/ionio ether, CHs.CO.CHBr.CHj.COjEt and sodio- 
 aceto-acetio ether (Enorr, B. 19, 47). Ammonia 
 in HOAo converts it into di-methyl-pyrryl-acetio 
 carboxylic ether 
 
 .CMe:C.CHj.CO.Et 
 
 hn/ I 
 
 \CMe:C.C02Et 
 
 ACEXYL-GLYCOCOLL v. AcEinKio acid. 
 
 ACETYLIDE ■«. Acettl chlokide, Reaction 11. 
 
 ACETYL IODIDE C^HjOI or Acl (108°) 
 (G.) ; (105°) (C). S. G. ii 1-98 (0.). Prepared 
 by the action of P and I upon acetic anhydride 
 (Guthrie, P. M. [4] (1857) 14, 183) or on KOAo 
 (Cahours (1857) C. B,. 44, 1253). Also by heating 
 acetyl chloride with Cal^SJaq at 75°. The water 
 of crystallisation has little saponifying effect 
 (Spiudler, A. 231, 272). 
 
 Properties. — Liquid. Fumes in air ; pungent 
 smell ; sour taste. Water quickly forms HI and 
 HOAo ; alcohol forms EtOAc. Decomposed by 
 zinc or sodium at 15°, and by mercury in sun- 
 shine, forming Hgl (G.). H. W. 
 
 ACEryi-MALONIC ETHEE C<,H,,05 i.e. 
 CH3.CO.CH(CO,Et)2 (289°-245°) S.G. ^ 1-080. 
 From aoeto-acetio ether, alcoholic NaOEt and 
 ClCO.,Et. (Ehrlich, B. 7, 892 ; Conrad, A. 214, 35). 
 Aqueous NaOH decomposes it into acetone, COj, 
 alcohol, and acetic acid. 
 
 ACETYL-METHYL-ACETO-ACETIC ETHEE 
 
 V. AOETO-ACETIC ACID. 
 
 ACETYL-TETEA-METHYLENE v. Tetka- 
 
 METKYLENE METHYL KETONE. 
 
 ACETYI-TETEA-METHYLENE CAEBOXY- 
 
 LIC ACID, SO called, v. Acetyl-Butyl Alcohol. 
 
 ACETYL-TEI-METHYLENE v. <ri-METHYL- 
 
 ENE METHYL KETONE. 
 
 o-ACETYL-a-METHYL-)3-ETHYL - SUCCINIC 
 ETHEE 
 
 C,3H,A »■«• CH3.CO.CMe(CO,Et).CHEt.C02Et. 
 From a-acetyl-/3-ethyl-siiccinic ether, NaOEt and 
 Mel (S. Young, C. J. 43, 178). Boiled with dilute 
 HCl it forms a 7-oxy-octoio acid (j. v.) and 
 methyl-ethyl-succinic acid. 
 
 ACETYL-METHYL-TEI-METHYLENE CAE- 
 BOXYLIC ACID v. p-opjlcne-aceto-acetic acid 
 under Aoeto-acetio acid. 
 
 o-ACETYI-a-METHYL-GLUTAEIC ACID 
 C,2Hj„05i.e.CO.^t.CMeAc.CH„.CH2.CO.,Et.(281°); 
 S.G. It.s 1"043. From j8-iodo-propionio ether 
 and sodium methyl-aceto-acetic ether(Wislicenus 
 a. Limpaoh, A. 192, 133). With cone, alcoholic 
 KOH it gives acetic and o-methyl-glutaric acids. 
 
 ACETYL-METHYL-FYEOTAETAEIC ETHEE 
 
 V. ACETYL-DI-METHYL-SUCCINIO ETHEB. 
 
 a-ACETYL-a-METHYL-STICCINIC ETHEE 
 C„H,sO, i.e. CO,Et.CMeAo.CH,.CO,Et (c. 263°) 
 S.G. 1-067. From sodium acetyl-succinic ether 
 and Mel (Kressner, A. 192, 135). Decomposed 
 by cone, alcoholic KOH with formation of acetic 
 and pyro-tartaric acids. Baryta- water or HCl 
 produce COj and ;8-acetyl-butyric acid (3. v.). 
 
 a-Acetyl-;3-methyl-suocinic ether 
 CO,J:t.CMeH.CAoH.CO,Et (c. 258°) (C); (c. 263°) 
 (Gottstein, A. 216, 31) ; (c. 227°) at 165 mm. 
 (Bisohoff, 4. 206, 320). S.G. ff.j 1-061. Formed 
 
 by action of o-bromo-propionio ether on sodium 
 aeeto-acetio ether (Conrad, A. 188, 226). De- 
 composed by cone. KOH into alcohol, pyro- 
 tartaric acid, acetic acid, CO,, and ;3-acetyl-iso- 
 butyrio acid ; baryta-water (8 p.c), or HCl, 
 produce only COj and ;8-acetyl-iso-butyric acid. 
 
 a-Acetyl-a-;3-di-methyl-8ucclnic Ether 
 C.^H^O, i.e. C02Et.CMeAc.CHMe.C0.^t (270°- 
 272°) S.G. f|.5 1-057. Formed from n-acetyl-jS- 
 methyl-succinic ether, sodium, and Mel (Hardt^ 
 muth, A. 192, 142). Boiling cone, alcoholic 
 KOH converts it into acetic and o-j8-di-methyl- 
 succinic acids. 
 
 ACETYL OXIDE and Peroxide v. Acetio 
 
 OXIDE. 
 
 ACETYL-OXY-COMPOTJNDS 
 
 «. OXY-COM- 
 
 POnNDS. 
 
 ACETYL-PHENYLENE-DUMINE v. Phent- 
 
 LENE-DI-AMINE. 
 
 (8-ACETYL-a-PHENYL-PEOPIONIC ACID 
 
 Ci.HijOa i.e. COaH.CHPh.CH.^c. Benzyl-ace- 
 tone-y-carboxylic acid. [126°]. Prepared by 
 boiling the ethers of acetyl-phenyl-succinic acid 
 with baryta-water or dilute HCl. Plates. V. sol. 
 alcohol or ether. On reduction with sodium- 
 amalgam it gives the lactone of 7-oxy-a-phenyl- 
 valeric acid, CH,.CH(0H).CH2.CHPh.C0jH. 
 
 Salts. — "A'jZn: long white needles. — "AgA": 
 white pp. — "CuA'^: green; insol. water, sol. 
 alcohol. — "CuA'j and "BaA', are easily soluble 
 (Weltner, B. 17, 72). 
 
 ACETYL-PHENYL-SUCCINIC ACID C,,H„0, 
 i.e. CO,H.CHPh.CHAc.CO.^. [121°]. Formed 
 by saponification of the di-ethyl-ether, which is 
 prepared by the action of phenyl-bromo-acetio 
 ether on sodio-acet-acetic ether. Large plates. 
 (Weltner, B. 17, 71.) When boiled with dilute 
 hydrochloric acid or baryta water, it splits 
 off CO2, giving acetyl-phenyl-propionio acid, 
 
 Cj,H5.CH(C0jH).CH2.C0.CH,. 
 — A"K2 easily soluble glistening needles. 
 
 {a)-Mono-e.thyl-ether 0^11,^0^ i.e. 
 C02Et.CHPh.CHAc.C0.,H. [133°]. Formed to- 
 gether with the di-ethyl ether by the action of 
 phenyl-brom-acetic ether upon sodio-aceto-acetio 
 ether. On heating, it evolves CO.,, giving phenyl- 
 levulio ether (Weltner, B. 18, 790). 
 
 {P)-Mono-ethyl-ether CnHijOs i.e, 
 CO.,H.CHPh.CHAc.CO.,Et. [128°]. White pearly 
 plates ; easily soluble in alcohol and ether. 
 Formed by the action of sodium phenyl-bromo- 
 acetate upon sodio-aceto-acetic ether. By heat- 
 ing to 200° CO2 is not split off. Boiled with 
 baryta, it yields phenyl-levulic acid. It is re- 
 duced by sodium amalgam to B-phenyl-valero- 
 7-lactone-i8-carboxylic acid : 
 CHPh.CO.O 
 
 CH(C02H).CH.CH3. 
 With alcoholic NH, it yields CisHi^NjOj. 
 
 Phenyl-hydraside CjHjjN.Pj [149°], plates. 
 
 Di-ethyl-ether A"Et., [76°], plates. 
 
 DI-ACETYL-PHOSPHOEIC ACID CjH„PO, 
 i.e. HjAc^POs. A viscid liquid, formed by the 
 action of AcCl on AgjPOj (Carius a. Kammerer, 
 A. 131, 170). Boiling water decomposes it into 
 acetic and ortho-phcsphorio acids. It forms 
 a calcium salt, CaHAc2P0j2aq, crystallising in 
 needles. 
 
 ACETYL-PIPEE - PEOPYL - ALCEINK 0. 
 
 OzXFBOPyL-FIPEBIDIKE. 
 
id 
 
 AOETYL-PROPIONTO AOIDS. 
 
 ACETYI-PROPIONIC ACIDS G,Ilfi,. 
 
 a-Acetyl-propionic Acid CH3.CHA0.CO2H, v. 
 Uethyl-aceto-acetic acid under Acexo-acetic acid. 
 
 ;3-Aoetyl-propionic Acid 
 CH3.C0.CH,.CH.,.C0,H. Levtdic acid. [33-5°]. 
 (239°). S.G. 15 1-135. fio 1-443 at 15°. E„ 45-3. 
 
 Formation. — 1. By boiling acetyl-succinic 
 ether with dilute HCl (Conrad, B. 11, 2177). 
 2. By boiling the following substances with very 
 dilute HjSOj : Levulose, inulin, cane sugar 
 (Grote a. Tollens, A. 175, 181), gura arabic, or 
 caragheen moss (Bente, B. 9, 1157). Filter 
 paper and deal shavings give a small quantity. 
 Small quantities may also be got from glucose, 
 milk-sugar, and galactose, by heating with 
 aqueous HCl. 
 
 Preparation. — Cane-sugar (1500 g.) is heated 
 for 20 hours with water (1500 g.) and H^SOj 
 (150 g.), with occasional shaking. A large quan- 
 tity of humic substance separates. The thick 
 liquid is filtered under pressure, mixed with 
 CaCOs (150g.), and the whole evaporated (till it 
 weighs 1500 g.). The liquid is again filtered, 
 mixed with H2SO4 (50 g.) and shaken with ether. 
 After evaporating the ether, the levulic acid 
 (100 g.) is rectified (Grote, Kehrer a. Tollens, A. 
 206, 210). If glucose be used, the yield is not 
 so good, and it is then better to use HCl {v. 
 Conrad a. Guthzeit, B. 18, 442). Formic acid 
 is also formed in these reactions : 
 
 C,H,20„ = C^HjOs + CH,0, + H,0. 
 
 Properties. — Deliquescent trimetric plates. 
 V. sol. water, alcohol or ether. On distillation 
 it produces (a)- and (j3)-angelico-lactone, and also 
 acetic acid, and another acid possibly CuHijOj 
 [208°] (Wolff, A. 229, 2C0). Not attacked by 
 bromine in the cold. 
 
 Reactions. — 1. Chromic inixture produces 
 CO2 and acetic acid. — 2. Dilute HNO3 gives 
 succinic, oxalic, acetic, and hydrocyanic acids 
 (Tollens, B. 12,334; A. 20G, 257).— 3. Eeduced, 
 by P and HIAq at 150'-200°, or by sodium- 
 amalgam in acid solution, to ra-valerio acid. — 
 4. In alkaline solution sodium amalgam pro- 
 duces 7-oxy-valeric; acid (5. v.). — 5, Gives the 
 iodoform reaction with NaOH and I. — C. lieacts 
 with hydroxylamine, forming an oxim. 
 
 Salts. — CaA'j2aq : minute needles. — AgA': 
 six-sided tables. — NaA'; minute needles.— CuA'j 
 (at 160°) : bluish-green flat needles or prisms, 
 fearium, magnesium, and cadmium salts are 
 gummy. 
 
 Ethers.— UeA'. (191-5°). S.G. 210884. Md 
 1-4216 ai 15°. Ro5 52-2. - EtA'. (200-5°) (G. K. a.T.) 
 (204°) (W.). S.G. g 1-03-25. /i„ 1-421. E„ CO-2. 
 — PrA'. (215-5°). S.G. § 1-0103. Md 1-4246. 
 Boo 69-5. 
 
 Amide.— G.^,O.J>in.,. [108°J. From ethyl 
 levulate and alcoholic NH3 or from (a)-angelioo- 
 lactone (g. v.) and aqueous or alcoholic ammo- 
 nia. Six-sided tables (from alcohol-chloroform, 
 Wolif, A. 229, 260). 
 
 Beferejices. — See also Bbomo- and Chloko- 
 
 ACElyL-PKOPiONIO ACIDS. 
 
 ACETYL-PROPYL ALCOHOL C,H,„0., i.e. 
 CH3.C0.CH.,.CH,.CH.,0H. Methyl -y-oxy-propyl 
 ketone. A colourless liquid, soluble in water, 
 formed by boiling bromo-eliiyl-aceto-acetic ether 
 BrCH.CH,.CHAc.CO,,Et with dilute HCl. It 
 readily reduces ammoniacal AgNOjAq but not 
 Feliling's solution. It is converted by heat into 
 
 an anhydride. Soiium-amdlgwmr6S.nc6imoa.y. 
 di-oxy-n-pentane,CH..CH(OH).CH2.CHj.CH,OH 
 (Perkin jun. a. Freer, B. 19, 2566). 
 
 ACETYL-PYEO-PHOSPHOBIC ACID. 
 
 The barium salt, BaHAcP20,2aq, is got as a 
 crystalline pp., si. sol. dilute acids, by adding 
 aqueous hydrogen peroxide to a solution of 
 barium acetyl-pyrophosphite (Menschutkin, A. 
 136, 254). 
 
 ACETYL - PYKO - PHOSPHOROUS ACID, 
 AGH3P.,0,,2aq, is got by heating AcCl with HjPOj 
 at 50° (Menschutkin, A. 133, 317). CrystaUina 
 mass. 
 
 Salts.— 'K.^IikcP.p^2\a,(i : slightly sol. water. 
 BaHAcPaOj: insol. water.— PbHAcPjOj : insol. 
 water. 
 
 ACETYL-PYRO-TARTAEIC ACID v. AcsTrL- 
 
 MEIHTL-SUCCINIO ACID. 
 
 ACETYL-PYRROL v. Pykkol. 
 Pseudo-acetyl-pyrrol v. PynEYL metuyl 
 
 KETONE. 
 
 ACETYL-SUCCINIC ETHER C,„H„05 i.e. 
 C0.,Et.CHAc.CH3.C03Et. (c. 255°) ; (240° i. V.) 
 at 330 mm. S.G. fi.^ 1-079 ; if 1-088 ; p 1-080. 
 M.M. 10-343 (Perkin, C. J. 45, 517). Formed 
 by action of chloro-aoetio ether upon sodium 
 aceto-acetio ether (Courad, A. 188, 218). Oil. 
 Sol. alcohol or ether. Gives no colour with 
 Fe^Clj. Cone, alcoholic KOH splits it into acetic 
 and succinic acids ; boiling baryta-water forma 
 ;8-acetyl-propionic ether and COj. 
 
 Phenyl-hydrazideCt,J.i.,.M.flt. [80°]. At 
 150° it splits off EtOH and gives methyl-oxy-qui- 
 nizyl-acetio ether (Knorr a. Blank, B. 17, 2051). 
 
 Di-aceto-succinic Ether Ci^HmOj i.e. 
 C02Et.CHAc.CHAo.CO.,Et. [79°]. 
 
 Sodium acetaoetic ether is treated in ethereal 
 solution with iodine (Eiigheimer, B. 7, 892) : 
 
 2CO,Et.CHNa.CO.CH, + I,=(CO,Et.CIIAo),H-2NiiI. 
 
 The ethylic di-aceto-succinate crystallises from 
 the ether (Harrow, C. J. 33, 427). It forms tri- 
 metric tables, V. e. sol. alcohol, ether, or benzene. 
 Beaction. — 1. Boiled with dilute H^SO, 
 (1 : 10) it gives off CO2 and forms pyro-tritario 
 or uvic ether CgHi^Oj and carbo-pyro-tritario 
 ether CsHjO^Et.— 2. Hydroxylamine forms a di- 
 oxim (needles; Miinchmeyer, B. 19, 1849), and 
 a neutral ether C,,H„N03 (Knorr, B. 18, 1568).— 
 3. Ammonia forms di-methyl-pyrrol di-carboxy- 
 lie ether CjHMe3N(CO.,Et)2 or 
 
 .CMeiC.COjEt 
 NH< I 
 
 NCMeiC.CG^Et. 
 Primary bases act in a similar manner, thus 
 methylamine forms 
 
 -CMerC.COjEt 
 NMe < I 
 
 \CMe:C.CO„Et 
 (Knorr, B. 18, 299). 4. Pheyiyl-hydraeine 
 acts in a similar way: C,jH,gO|j-(-N2H3C|jH5 = 
 C,8H2.,NjO., H- 2H..0. The new compound, which 
 
 NPh.CMe:C.C02Et 
 may be I I 
 
 NH .CMe:C.C02Et 
 is called phenyl-di-methyl-pyridazine di-carboxy- 
 lic ether. It contains HjO less than the mono- 
 phenyl-hydrazide of di-acetyl-suocinic ether, 
 C02Et.CH(ClMe:N2PhH).CHAc.C02Et (Knorr, B. 
 17, 2058 ; 18, 305). It crystallises in prisms, 
 [127°] (from benzoline). See also Puenyl-uY' 
 
 DBAZINE. 
 
ACIDS. 
 
 47 
 
 ACETYL SULPHIDE OjH,0,S or Ao,S. 
 Iri-acetyl sulphide, Thio-acetic anhydride (120°). 
 
 Preparation. — 1. From AojO and P^S^ (Ee- 
 
 kul6, A. 90, 312). Yield 10 p.o 2. From AoCl 
 
 and KjS.— 3. By distilling PbSAo. 
 
 Properties. — An oil, slowly decomposed by 
 water into HOAo and HSAo. 
 
 Di-aoetyl Di-Bulphide CjH„0,S., or Ac,B, [21°]. 
 
 Formation.— 1. From KSAc and I {Kekul6 
 a. Linnemann, A. 123, 279).- 2. From BaO^ and 
 AcS in ethereal solution (Beokmann, J.pr. 125, 
 465) : 2AojS + BaOj = Ac^Sj + Ba(OAo)2.— 3. By 
 electrolysis of thio-acetic acid (Bunge, B. 3, 297). 
 
 Properties. — Crystalline. Insol. water, v. sol. 
 alcohol or CSj. Decomposed by warm water or 
 by alkalis forming thio-acetic acid and sulphur. 
 Decomposed by distillation. 
 
 ACETYL STJLPHOCYANIDE C3H3NSO or 
 CHa.CO.S.Cy. (133°). S.G. is 1-151. From 
 AcCl and lead sulphooyanide (Miquel, A.Ch. [5] 
 11, 295). Pungent liquid. Decomposed by water 
 into HOAc and HSCN.- Forms with NHj in 
 ethereal solution a non-volatile liquid which dis- 
 Bilves in water and gives a red colour with FOjClj. 
 
 ACETYL-THIO-TJREA v. Thio-ukea. 
 
 ACETYL-TOLYLENE-DI-AMINE v. Tolt- 
 
 LENE-DI-AMINE. 
 
 ACETYL-TJEEA v. Ueea. 
 
 ACETYL-VALERIC ACID CjH.jOa. 
 
 a-Aoetyl-ra-valeric Acid v. n-propyl-aceto- 
 acetic acid under Aceio-acetio acid. 
 
 o-Acetyl-s-tso-valerio Acid ■;;. iso-propyl-aceto- 
 acetic acid under Aceto-acetio acid. 
 
 a-Acetyl-tt-iso-valeric Acid v. methyl-ethyl- 
 aceto-acetic acid under Aceto-aoetio acid. 
 
 j8-Acetyl-M-iso-valeric Acid 
 
 CH2Ac.CHEt.CO2H. 
 (250°-252°). Got by boiling a-acetyl-3-ethyl- 
 snocinic ether (j. v.) with dilute KOH (Thome, 
 C.J. 39, 340). Liquid, miscible with water, al- 
 cohol, and ether. Turns brown in air. It is 
 gradually decomposed by heat into H^O and an 
 oil C,H,„02 (219°). S.G. |3 1-0224. 
 
 Reaction.— HNO3 oxidises it to ethyl-succinio 
 acid. 
 
 Salts. — Gummy, soluble in water. 
 
 St/!er.—EtA'(224°-226°). Lighter than water. 
 
 ACHILLEA The Iva plant {A. Moschata) 
 
 has been chemically examined by v. Planta- 
 Reichenau (A. 165, 145), who has extracted from 
 it the following substances : 1. Ivain C24H42O5, 
 obtained by distilling the dried herb (freed from 
 the roots) with water to remove volatile oil, ex- 
 hausting the dried residue with absolute alco- 
 hol, precipitating with lead acetate, removing 
 excess of lead with H^S, and exhausting the 
 evaporated residue with acetic acid to remove 
 achillein and moschatin. Ivain then remains 
 as a dark yellow resinous mass, insoluble in 
 water, easily soluble in alcohol, yielding an 
 intensely bitter solution. — 2. Achillein 
 C^oHjgNjOjs and Moschatin C^jH^jNO, are ob- 
 tained by distilling the herb, gathered before 
 flowering, with water, exhausting the concentrated 
 filtrate with absolute alcohol, evaporating off the 
 alcohol and adding water, which throws down 
 moschatin; and on treating the liquid filtered 
 therefrom with Pb(0H)2, again filtering, remov- 
 ing lead with H^S, and evaporating, Achillein 
 remains as a brown-red mass, very soluble in 
 water, less readily in alcohol, insoluble in ether ; 
 
 very bitter ; not precipitated by lead salts. Ee- 
 solved by prolonged boiling with dilute sulphurio 
 acid into sugar and aohilletin C||H|,NO„ a 
 dark-brown powder, insoluble in water, very 
 slightly soluble in alcohol; not bitter. Mos- 
 chatin CjiH^jNOj is pulverulent, nearly in- 
 soluble in water, somewhat soluble in absolute 
 alcohol ; tastes bitter. 
 
 A. Ageratum, growing in Italy and Provence, 
 yields an essential oil boiling at 165°-182°; 
 sp. gr. 0-849 at 14° (De Luoa, J. Ph. [4] 18, 105). 
 
 H. W. 
 
 ACHROO-DEXTKIN v. Dextedj and Staech. 
 
 ACIDIMETRY. The estimation of acids by 
 volumetric methods. V. Analysis. 
 
 ACID-FORMING OXIDES. Same as Anhy- 
 deides {q. v.). 
 
 ACIDS, — Salts of hydrogen. The word acid 
 (ac, sharp ; acere, to be sour ; compare acetimi, 
 vinegar, ojiis, o|os) was originally loosely applied 
 to all sour liquids. The term cannot now be ac- 
 curately defined ; but it may be stated generally 
 that an acid is a compound of hydrogen, which, 
 when mixed with, or dissolved in, water, is capable 
 of exchanging the whole, or a portion, of the hy- 
 drogen it contains for a metal, with simultaneous 
 formation of water, by the action on the aqueous 
 solution of the acid of a metallic oxide or hy- 
 droxide. 
 
 History. — The corrosive action of acids, and 
 their power of dissolving metals and other sub- 
 stances have been known from early times. 
 Thus Geber, who lived during the eighth cen- 
 tury, was acquainted with impure nitric and 
 sulphurio acids, and described them under the 
 name aguce dissolutivw. Paracelsus (16th cen- 
 tury), from whom the school of latro-ohemists 
 sprang, held that the human body in health 
 consisted of certain acid and alkaline principles 
 which balanced each other, and that disease was 
 due to a preponderance of one or other of these 
 principles. He was the first to propound a theory 
 to account for the properties common to all 
 acids ; he supposed that they all contained an 
 acid principle, which conferred taste and solu- 
 bility on all substances into which it entered. 
 This theory was ^.ccepted by Beoher (17th cen- 
 tury), who named the acid principle acidum 
 primogenium ; and he added that it consisted of 
 a compound of earth and water, both of which 
 he believed to be elements. The distinctive pro- 
 perties of acids : — their solvent power, their 
 power of changing the colour of certain vege- 
 table tinctures, and the fact that they form 
 neutral bodies with alkalis; — were catalogued 
 by Boyle (17th century). Stahl, in 1723, adopted 
 Becher's theory, and endeavoured to prove that 
 while acids were thebases of all saline bodies, the 
 principle of all acids was sulphurio acid. Stahl's 
 view continued to find supporters for a long 
 time, but its defects were at length, perceived. 
 Many of the supporters of the phlogistic theory 
 held that inorganic acids, such as sulphurio 
 and phosphoric acids, were simple substances ; 
 and that by their combinations with phlogiston 
 they gave rise to bodies such as sulphur and 
 phosphorus, which were then regarded as com- 
 pounds, but which we now know to be elements. 
 After the discovery of oxygen by Priestley and 
 Soheele, Lavoisier, in naming that element from 
 ojus (acid) and yevviu (I produce), generalised 
 
48 
 
 ACIDS. 
 
 the facts discovered by him, that many acid 
 bodies are produced by the union of ' combus- 
 tibles' with oxygen ; and although it was pointed 
 out by Berthollet in 1789 that salphydrio and 
 prussic acids contain no oxygen, the view of 
 Lavoisier generally prevailed until the researches 
 of Davy, and of Gay-Lussac and Thenard, on 
 muriatic and oxymuriatic acids (hydrochloric 
 acid and chlorine) in 1810, and the discovery 
 and examination of hydriodic acid, and the in- 
 vestigation of prussic acid by Gay-Lussao in 
 1814 and 1815, compelled chemists to recognise 
 the existence of true acids containing no oxy- 
 gen, and led to a distinction being drawn between 
 acids which contained oxygen, and those which 
 did not. 
 
 Lavoisier also regarded acids as binary oxy- 
 genated compounds; and he supposed that the 
 water which must be present in order that an 
 acid shall react on other bodies merely played 
 the part of a solvent. This view was supported 
 and extended by Berzelius, who taught that 
 certain oxides are capable of uniting with each 
 other to form ' ternary ' compounds or salts, and 
 that these salts are decomposed by electrolysis 
 into their ' binary ' constituents, which are an 
 acid and a base. Berzelius therefore applied 
 the term electronegative to that oxide which ap- 
 peared at the positive electrode on electrolysis of 
 a salt, and the term electropositive to that oxide 
 which separated at the negative electrode. The 
 negative oxides he classed as acids, and the 
 positive oxides as bases. This theory ignored 
 the fact that water is associated with these 
 oxides in their various reactions ; and, more- 
 over, it overlooked the evident analogy between 
 acids containing oxygen and acids containing 
 no oxygen, but formed by the union of the 
 halogens, or haloid groups, with hydrogen. To 
 restore this analogy, Davy proposed to abandon 
 the old view that acids were compounds of 
 certain elements with oxygen, and suggested 
 that all acids, whether they contained oxygen or 
 not, should be considered as compounds of 
 hydrogen. Dulong supported Davy's view, and 
 extended it ; he regarded acids as compounds of 
 hydrogen with elements such as CI, I, S ; or 
 with radicles such as CN, NO3, SOj. As it was 
 at that time supposed that such radicles were 
 capable of separate existence, and as Dulong's 
 hypothesis involved the creation of a large num- 
 ber of hypothetical substances, this hypothesis 
 did not meet with general support. It was re- 
 served for Gerhardt, led by a study of organic 
 substances, to prove that most acids, when 
 vaporised, do not separate into an oxide and 
 water, but pass into the state of vapour as a 
 whole. From this it followed that hydrogen, 
 replaceable by metals, must be a constituent of 
 all true acids. 
 
 Chabactekistic featukes of acids.— Bodies 
 possessing properties corresponding with the 
 definition of an acid given at the beginning of 
 this article always contain hydrogen in intimate 
 combination with one or more of the following 
 elements ; fluorine, chlorine, bromine, iodine, 
 oxygen, sulphur, selenion, tellurium, or certain 
 groups of elements {e.g. cyanogen) of which 
 carbon is one (comp. Acids, Okganic, p. 53). 
 It is true that water is not accounted an acid, 
 nor is if usual to include hydrogen dioxide 
 
 among the acids; yet it the definition of acid 
 were strictly applied hydrogen dioxide would 
 find a place in this class, for it has an acid 
 reaction with test paper, and on addition, for 
 example, of barium hydroxide to a solution of 
 it in water, the reaction characteristic of acida 
 takes place ; — 
 
 Ba(OH)2.8H,0 + H^Oj = BaO^.SHjO + 2H2O. 
 Again, the reactions of hydrogen sulphide, selen- 
 ide, and telluride, with alkalis, would lead to 
 their inclusion among acids. The name acid 
 must also be applied to most compounds of hy- 
 drogen and one of the elements above mentioned 
 with a third element. The following examples 
 will illustrate the definition given : — 
 
 Simple. 
 HP. 
 HOI. 
 HON. 
 (H,0.) 
 H^S. 
 &o. 
 
 Compound. 
 
 HBF, = HF.BFs. 
 H2PtCl, = 2HCl.PtCIj. 
 H,Fe(CN), = 4HCN.Fe(0N), 
 H,S0j = H20.S0,. 
 H2CS3 = HjS.GSj* 
 
 Such bodies as HjZnOj (Zn(0H)2), and 
 H3AIO3 (A1(0H)3), may be classed either among 
 acids or basic hydroxides, inasmuch as they 
 possess the characteristics of both classes. 
 
 Among the compounds of carbon the acids 
 form an important class. The formula of these 
 compounds may be supposed to be derived from 
 the formula either of formic acid, or of carbonic 
 acid. If formic acid be taken as the type, then 
 most acids containing carbon may be viewed aa 
 substituted formic acid ; thus : — 
 
 HCOOH. CH3COOH. C,H4C00H)j. 
 Formic acid. Acetic acid. Succinic acid. 
 CsH,(0H)(C00H)3. 
 Citric acid. 
 It is to be noticed that in two cases more 
 than one molecule of formic acid is employed ; 
 and that succinic acid, by this view, is to be 
 regarded as two molecules of formic acid, in 
 which two atoms of hydrogen are replaced by the 
 group C^Hj ; while citric acid is derived from three 
 molecules of formic acid by replacement of three 
 atoms of hydrogen by the group C3Hj(0H). The 
 carboxylic acids may be similarly derived from 
 carbonic acid (C0(0H)2), if one hydroxyl group 
 be regarded as replaced by an alkyl or similar 
 group. But it is clear that unless this view of 
 the composition of carbon acids helps to render 
 prominent the actual relations existing between 
 these compounds, it can be of no value. In this 
 view of the constitution of carbon acids these 
 compounds are all represented as containing the 
 characteristic group CO.OH ; this group has been 
 named ' carboxyl,' a word derived from ' car- 
 bonyl,' CO, and ' hydroxyl,' OH, and implying 
 the presence of these two groups. That most of 
 the acids of carbon contain the group CO.OH is 
 rendered probable by the following considera- 
 tions : when one of these acids is distilled with 
 phosphorous chloride, PCI3, the hydroxyl group 
 is replaced by chlorine, thus ; 
 3CH3.CO.OH + 2PCI3 = 3CH3CO.CI -I- PjO, + 3EC1. 
 And on warming such a chloride with water the 
 acid is re-formed ; 
 
 CH3.CO.CI + H,0 = CH3CO.OH + HCl. 
 It is thus proved that oxygen and hydrogen can 
 be removed together from the acid molecule. 
 Moreover, on treatment of the acid chloride with 
 
ACIDS. 
 
 4g 
 
 nascent hydrogen, the chlorine is replaced by 
 hydrogen, and an aldehyde is produced, thus ; 
 
 CHjCOCl + 2H = CH3CHO + HCl. 
 This aldehyde, when treated with phosphoric 
 chloride, POI5, exchanges its oxygen for two 
 atoms of chlorine, thus ; 
 
 CH3CHO + POI5 = CH3.CHCI2 + POCI3. 
 It is therefore inferred that the atom of oxygen 
 replaced by chlorine in the last reaction is 
 differently related to the other atoms in the 
 molecule from that atom of oxygen which is 
 replaceable by chlorine only when hydrogen ac- 
 companies it. The formula of the characteristic 
 group, CO.OH, thus appears reasonable. 
 
 But there are many compounds of carbon ex- 
 hibiting the property of exchanging hydrogen 
 for a metal by the action of an oxide or hydroxide, 
 which do not contain the carboxyl group. Among 
 these compounds may be mentioned bodies such 
 as ethane sulphonio acid, C.^Hj.HSOj, and ethane 
 phosphonic acid, C2H5.H2PO3, &c. ; many of these 
 bodies may be regarded as acid ethereal salts of 
 inorganic acids. There are, however, others which, 
 in spite of their acid properties, it is not usual to 
 name acids, although many of them might be 
 legitimately included in this class. For instance 
 the meroaptans, of which ethyl hydrosulphide 
 may be chosen as an example, react with oxides 
 or hydroxides in a similar manner to sulphydric 
 acid, HjS, thus, C^Hj-SH + KOH = C2H5SK + Kfi: 
 and the corresponding selenion and tellurium 
 compounds exhibit a like behaviour. Again, 
 many of the nitro-compounds of the alkyl 
 radicles have the power of exchanging hydrogen 
 for a metal, under the usual limitations, as for 
 example : 
 
 CH3NO, + KOH = CH2ENO2. + HjO :— 
 C(N02)jH yields C(N03)3K, etc. Hydroxyqui- 
 nones, such as alizarin G^tSgO.^iO'E.)^, act as 
 dibasic acids, forming compounds such as 
 Gj^'B.fi.^{0K)2 ; phenols, and their substitution 
 derivatives, also yield metallic derivatives, e.g. 
 sodium phenate CjHsONa, sodium picrate 
 CjHjINOJ, ONa. On comparing such compounds 
 with each other, and with other acids, the fol- 
 lowing deductions may be drawn : — (1.) That a 
 powerfully electro-negative element such as 
 fluorine, chlorine, bromine, or iodine, confers 
 acid properties on its compound with hydrogen. 
 (2.) That in compounds of elements exhibiting 
 less markedly electronegative properties than the 
 halogens, the presence of an electronegative ele- 
 ment is necessary to the development of acid 
 character. This may be seen from the follow- 
 ing considerations. Hydrocarbons, such as me- 
 thane, CH4, exhibit no acid properties; if an 
 atom of an electronegative element such as 
 oxygen or sulphur is introduced into the mole- 
 cule in place of one or more atoms of hydrogen, 
 the compound so formed, although not generally 
 a true acid, yet exhibits a more or less acidic 
 character. Thus, methyUc alcohol, OH3OH, 
 forms metaUio derivatives (CHjONa, &o.) by the 
 action on it of strongly positive metals ; but as 
 such compounds are decomposed by water, they 
 cannot be formed in presence of that substance. 
 Here, however, we may note that phenol,08H50H, 
 and similar compounds, reacts with the hydroxides 
 of strongly positive metals to form metallic 
 derivatives which, although comparatively un- 
 stable, are nevertheless capable of existence in 
 Vol* J. 
 
 presence of an excess of alkaline hydroxide. But 
 if a derivative of a hydrocarbon contain two or 
 more electronegative atoms or groups of atoms 
 in the molecule, then, as a rule, this compound 
 forms metallic derivatives of considerable sta- 
 bility. Thus, the replacement of two atoms of 
 hydrogen in the molecule of an alcohol by an 
 atom of oxygen (converting the group character- 
 istic of primary alcohols, CH^OH, into the car- 
 boxyl group, CO.OH) is attended by a marked 
 increase of acid properties. Similarly the ex- 
 istence of oxygen combined with carbon in 
 hydroxyquinones (as carbonyl, CO) confers on 
 hydroxyl groups present the power of exchanging 
 their hydrogen for metals by reactions common 
 to acids. And in presence of a large amount of 
 an electronegative element the exchangeable 
 hydrogen need not even be present as hydroxyl ; 
 for as shown above, such bodies as nitromethane, 
 CH3NO2, form metallic derivatives, like CHjKNOj. 
 Comp. AcETO-AOETic ACID, p. 17. Bcgarding the 
 relations between the nature of different elements 
 and the acidic character of their compounds v. 
 further Classieioation. 
 
 Basicity oe aoids. — Some acids, on treatment 
 with the oxide or hydroxide of an alkali metal, may 
 exchange all their hydrogen for metal, thus pro- 
 ducing a salt ; and it may not be possible to obtain 
 from them a body intermediate between the salt 
 and the acid ; such an intermediate derivative is 
 usually termed an acid salt. From other aoida 
 such intermediate derivatives are obtainable. 
 The acids of the former class are termed ' mo- 
 nobasic ' ; those of the latter class are termed 
 ' polybasic,' including the terms ' di- ' ' tri- ' 
 ' tetra- ' basic. The conception of the basicity 
 of acids was introduced by Graham. Before his 
 researches in 1833, it was supposed that an 
 ' acid salt ' contained, as its name imphes, both 
 acid and salt, and on the binary theory it was 
 considered to be a compound of the two. But 
 Graham showed that in neutral potassium phos- 
 phate there are, as he expressed it, three equiva- 
 lents of potash for one equivalent of phosphoric 
 acid, or in modern language, three atoms of 
 potassium for one atomic group PO4 ; and that 
 the acid phosphates differ from the neutral 
 phosphate in containing water instead of potash, 
 or as we should say, hydrogen in place of potas- 
 sium. The composition of hydrated phosphoria 
 acid being expressed by the symbol (old notation) 
 PO5.8HO, the composition of its different salt/ 
 might be expressed by the symbols : 
 
 PO5.2HO.KO; PO5.HO.2KO; PO5.3EO. 
 Phosphoric acid was therefore termed by Gra- 
 ham a ' tribasio acid.' In 1838, Liebig pointed 
 out the necessity of considering the following 
 acids as polybasic, because of the fact that they 
 form acid as well as neutral salts ; — cyanurio, 
 malonic, comenio, citric, aconitic, aconio, tartaric, 
 malic, and fumaric. In consequence of this 
 change of view, Liebig argued that it was 
 better to give up the binary theory of aoids 
 held by BerzeUus, and to go back to the older 
 theory of Davy, viz. that aoids are to be regarded 
 as formed by the oombiuation of hydrogen with 
 a simple or a compound radicle, the nature of 
 this radicle having no part in determining the 
 number of stages in which the replacement of 
 hydrogen by metal takes place. Thus by ad- 
 dition of oxygeu ox sulphur (0 sulphuretted 
 
60 
 
 ACIDS. 
 
 hydrogen (sulphydrio aoid) the following dibasic 
 acids are obtainable : — 
 
 Sulphydrio aoid . . H^S 
 Hyposulphurous acid . H.,SO, 
 Sulphurous aoid . . H.^SO, 
 Sulphuric acid . . . H.,SO, 
 Thiosulphuric acid . . H.S.Ps 
 Dithionic acid . . . HaSjOj 
 It was, however, known that many acids, 
 having a claim to be considered monobasic, 
 Btteh as hydrofluoric, acetic, benzoic, and stearic, 
 gave rise to double salts by addition of a mole- 
 cule of aoid to a molecule of salt. Laurent and 
 Gerhardt pointed out that the relative densities, 
 in the gaseous state, of many acids belonging to 
 this class imply that a molecule of each acid 
 contains only one atom of hydrogen ; further, 
 that an aoid of this class forms only one alkyl 
 (or ethereal) salt, and one amide ; that while 
 polybasio acids generally yield anhydrides by 
 some direct process, often by the action of heat 
 alone, the anhydrides of monobasic acids are 
 usually obtained indirectly, and that anhydro- 
 salts such as dichromate of potassium, are ob- 
 tainable only from polybasio acids. 
 
 The number of atoms of hydrogen contained 
 in a molecule of an aoid is no criterion of its 
 basicity ; this fact was noticed by Gerhardt, but 
 its bearings were more fully elucidated by Wurtz 
 and by KekuM. The basicity of an aoid is de- 
 termined, not by the number of atoms of hydro- 
 gen which it contains, but by the number of 
 stages in which the hydrogen can be replaced, or 
 in other words, by the number of salts which it 
 is capable of forming with a specified monovalent 
 metal. Thus a study of the salts of the follow- 
 ing acids has led to their classification as shown 
 below. 
 Monobasic— HT, HCl, HNO„ H(H,PO,), 
 
 H(HC02), HBFi, HAuCl,. 
 Dibasic— H^SO^, H„(HP03), HAO4, 
 
 H^PtCls, C2Hi(C00H)2. 
 Tribasic— HjPO,, H,Fe(CN)„, H,As04, 
 
 C3H,(OH)(COOH)3, 0,,H,N(C00H)3 
 Tetrabasio.-HjP,0„ H,Fe(CN)„ CsHatCOOH),. 
 Hexabasio. - C„{COOH)„. 
 
 The number of salts of a monovalent metal 
 which an acid is capable of forming corresponds, 
 as a rule, with its basicity. Thus tribasic ortho- 
 phosphoric acid forms three salts with potassium, 
 viz. H^KPOj, HK2PO4, and KjPO^; and similarly 
 with other acids. 
 
 This classification, as already stated, is 
 founded on a, study of the salts of acids con- 
 taining monovalent metals, practically of the 
 salts formed by the action of potash or soda on 
 the acids. The researches of Thomsen on the 
 quantities of heat produced when acids and 
 bases mutually react in equivalent quantities 
 have confirmed the conclusions drawn from a 
 study of the composition of salts. The principle 
 of the thermal method may be thus stated : — If 
 a dilute aqueous solution of a monobasic acid is 
 mixed with an equivalent quantity of an alkali 
 also in dilute aqueous solution, a definite quantity 
 of heat is produced ; if more than one equivalent 
 of acid is used for one equivalent of base, the 
 same quantity of heat is produced. This is 
 shown by the examples which follow : ' 
 ' Pigures represent gram-units of beat. 
 
 Add. 
 
 Number of equivalents of acid to one 
 
 equivalent of base (NaOHAq) 
 
 HCl.HBr.HI 
 
 13,700 
 
 1 
 13,700 
 
 i 
 6,850 
 
 HP. . 
 
 16,000 
 
 16,300 
 
 8,200 
 
 HSH . 
 
 7,700 
 
 7,700 
 
 3,900 
 
 HNC . 
 
 2,800 
 
 2,800 
 
 1,400 
 
 HNO,. . 
 
 13,600 
 
 13,700 
 
 6,800 
 
 HPH,0, . 
 
 15,400 
 
 15,200 
 
 7,000 
 
 HPO, . 
 
 14,200 
 
 14,400 
 
 — 
 
 H.C,H30, . 
 
 13,200 
 
 13,200 
 
 8,600 
 
 In most of these instances, the acid forms no 
 acid salt ; its hydrogen is replaceable in only one 
 stage. But although aoid salts of acetic aoid 
 {e.g., C2H:j02.C2H3Na02), and of hydrofluoric 
 acid (HF.ItP), are known, the formation of these 
 salts by the action of the neutral salt and the 
 aoid is accompanied by » very small thermal 
 change. This fact forms a reason, in addition 
 to those adduced by Gerhardt, ;for classing hy- 
 drofluoric and acetic acids with the monobasic 
 acids. 
 
 The thermal value of the action of a base on 
 a polybasio- aoid, unlike that of the action of a 
 base on a monobasic aoid, is dependent on the 
 proportion between the number of equivalents of 
 base and acid used. This is shown by the 
 following examples : 
 
 Acid. 
 
 Number of equivalents of acid to one 
 
 equivalent of base (NaOHAq). 
 
 
 2 
 
 1 
 
 i 
 
 k 
 
 i 
 
 i 
 
 H.SO. . 
 
 14,200 
 
 14,600 
 
 15,600 
 
 
 7,800 
 
 
 F„SO, . 
 
 — 
 
 15,900 
 
 14,500 
 
 — 
 
 7,300 
 
 
 
 HjPHO,. 
 
 14,900 
 
 14,800 
 
 14,200 
 
 9,600 
 
 — 
 
 — 
 
 H,C03 . 
 
 — 
 
 11,000 
 
 10,100 
 
 — 
 
 — 
 
 
 
 H3PO. . 
 
 14,700 
 
 14,800 
 
 13,500 
 
 11,300 1 — 
 
 5,900 
 
 H.P,0, . 
 
 — 
 
 14,400 
 
 14,300 
 
 — |13,200 
 
 9,100 
 
 Again, a small thermal change is noticed when 
 solutions of a monobasic acid and of the potas- 
 sium or sodium salt of this aoid mutually react ; 
 but if a solution of a polybasio aoid is allowed 
 to react with a solution of a neutral salt of the 
 same acid, a marked thermal change occurs. 
 Thus the formation of KHSO^ from K^SO^ and 
 HjSOj at 23° is accompanied by the disappearance 
 of about 8,000 gram-units of heat. 
 
 OETHO-Acms Asn Anhydko-acids.— The acids 
 containing oxygen have been most completely 
 investigated, owing to the fact that most of 
 them are stable at ordinary temperatures, and in 
 presence of air and water. It is inferred that in 
 these acids oxygen and hydrogen are in intimate 
 union, forming a hydroxyl group; the chief 
 reason for this view, vis., that when these acids 
 are treated with phosphorous, or phosphoric, 
 chloride they yield the chloride of the acid 
 radicle, has already been stated. Thus sul- 
 phuric aoid, 80.2(011)2, yields sulphuryl chloride, 
 SOjClj; and phosphoric acid, P0(0H)3, yields 
 phosphoryl chloride, POCI3. Such groups as 
 SO2, sulphuryl, or PC, phosphoryl, are termed 
 aoid radicles, and their compounds with hy- 
 droxyl are acids. The term ortho-acid is em- 
 ployed especially in the nomenclature of carbon 
 acids. 
 
 An ortho-acid, strictly speaking, is one in 
 which the element to which the hydroxyls are 
 
ACIDS, BASICITY OF. 
 
 61 
 
 united is not combined with any other oxygen, 
 Suoh compounds are in most oases unknown, 
 but their existence is inferred from that of their 
 metallic or ethereal salts, e.g. Si(ONa), ; C(OCH,) . : 
 CH,C(OC A)3, &c. 
 
 Many of the commonly occurring acids may 
 be regarded as derived from such ortho-acids by 
 removal of water ; thus looked at, these acids 
 are partial anhydrides. Their formation is 
 illustrated by the following examples : 
 
 S(OH), SO(OH). SO,(OH), SO, 
 
 unkuown. XTuknown. Sulphuric Sulphuric 
 
 acid. anhydi'ide. 
 
 I(OH), lO(OH), I0,(0H)3 I03(0H) 1,0, 
 
 Unkuown. Periodic Salts known. Salts Periodic 
 
 acid. known, anhydride 
 
 (? known) 
 
 P(OH), P0(0H)3 PO,(OH) P,,0, 
 
 Unknown. Orthophosphorio Metaphos- Phosphoric 
 acid. phoric acid. anhydride. 
 
 Partial anhydrides are sometimes also formed 
 by the condensation-products of two or more 
 molecules of an acid, with removal of water, 
 thus : 
 
 S(OH), S0(0H)3 SO,(OH) 
 
 >0 >0 >0 
 
 S(0H)3 S0(0H)3 SO,(OH). 
 
 Unknown. Unknown. Pyrosulphuric acid. 
 In most cases the composition of such acids is 
 inferred from that of their salts ; the very 
 numerous natural silicates may be conveniently 
 classified as salts of such condensed acids 
 (t) SniicAiEs). 
 
 Affinity (or avidity) of Acids. — By measur- 
 ing the thermal changes which occur when one 
 equivalent of an acid, in dilute aqueous solution, 
 reacts on one equivalent of the neutral salt of 
 another acid, also in dilute aqueous solution, it 
 is possible to determine the proportion in which 
 the base divides itself between the two acids. 
 Measurements have been made by Thomsen, 
 and he has named the proportion in which the 
 base combines with either acid, the relative 
 avidity of the acid. Thus when hydrochloric 
 acid (36-4 parts) is added to potassium nitrate 
 (101 parts), both in dilute aqueous solution, the 
 thermal changes which occur point to an equal 
 partition of the base between the two acids ; i.e. 
 half the potassium exists in the solution as 
 chloride, and half as nitrate. On mixing nitric 
 acid (63 parts) with potassium chloride (74-4 
 parts), the heat-change points to the same equal 
 partition of the base. Hence it is concluded 
 that the relative avidity, or affinity, of hydro- 
 chloric and nitric acids for potash is equal, and 
 is expressed by the number 0-5. The relative 
 avidity seems to be independent of the nature 
 of the base within certain limits ; it is also modi- 
 fied only to a small extent by the concentration 
 of the reacting liquids, or by small changes of 
 temperature. This conclusion of Thomsen has 
 received thorough confirmation by the researches 
 of Ostwald; and this is the more valuable in- 
 asmuch as Ostwald measured the partition of 
 acids between bases by a method depending on 
 the alteration of volume attending the mixture 
 of an acid with the salt of another acid. The 
 following table gives the relative affinities of 
 some acids towards the base soda ; the affinity 
 p f hydroghlorio ^cid being taken as unity : — 
 
 HP 
 
 0-ilS 
 
 CC1,.C00H 
 
 Avidity 1 0-24 very small 0-36 
 
 Acid '«"-". 
 
 Avidity 
 
 For more details v. Affinity, p. 67 ; Acids, 
 Basicity of, p. 51. Eegarding acids v. also 
 Classification. An acid with a large avidity 
 or affinity is frequently now spoken of as a 
 strong acid, the term weak being applied to 
 those acids the affinities of which are expressed 
 by small numbers. 
 
 Befereivces. — Lavoisier, Traiti iUmentaire da 
 CMmie, ed. 1789, i. 69 et passim ; Kopp, Oe- 
 schichte der Chamie, i. 308 ; iii. 17 ; Davy, 
 Journal of Science and the Arts, i. 285 ; also 
 (?. A. 54, 377; T. 1815, 212; Berzelius, /. 6. 
 184 ; Graliam, T. 1833, 253 ; P. M. 3. 451 and 
 469 ; Liebig, A. 26. 138, 170 ; A. Ch. 68. 5, 70 ; 
 Laurent, A. Ch. [3] 24, 163 ; MAthode de Chimie 
 (1854), 62, Translation of Cavendish Soc, 39- 
 45 ; Gerhardt, Gerh. (1856), 4. 641 ; Wurtz, A. Ch. 
 [3] 55. 466 ; 56, 342 ; 61. 161 ; KekuU, A. Ch. 
 60, 127; Odling, P. M., 18. 368; Thomsen. 
 Thermochemische TJntersiichungen, i. ; P. 138. 
 65, 208, 498 ; 189. 193 ; 140. 88, 530 ; Berthe- 
 lot, O. R. 75. 264, 435, 480, 538, 583 ; 87. 671. 
 
 W. E. 
 ACIDS, BASICITY OF.- It has been shown 
 in the art. Acids (g. v.) that some acids react 
 with the hydroxide (or oxide) of potassium or 
 sodium to form only one salt, whereas other 
 acids by a similar reaction produce more than a 
 single salt. The former acids are called mono- 
 basic, the latter polybasio. It was also shown 
 in the art. Acids that the basicity of an acid 
 may be determined by an examination of the 
 heat of neutralisation of the acid. The thermal 
 value of the reaction of a monobasic acid with 
 a base, in dilute aqueous solutions, is indepen- 
 dent of the ratio between the numbers of equi- 
 valents of acid and base used, provided not less 
 than one equivalent of base is mixed with a 
 single equivalent of acid ; but the thermal value 
 of the reaction of a polybasio acid with a base 
 varies according as 1, 2, 3, &o. equivalents of 
 base react with one equivalent of acid. If the 
 thermal reactions which occur when acids and 
 bases react in equivalent quantities, and in di- 
 lute aqueous solutions, are more closely exa- 
 mined it is found that the dibasic and tribasio 
 acids fall into certain classes. Thomsen has 
 especially examined this subject (Th. 1). The 
 quantity of heat produced during the neutralisa- 
 tion of a dibasic acid is sometimes divisible into 
 two exactly equal parts, according as one or two 
 formula-weights of soda are allowed to react 
 with one formula-weight of the acid. In other 
 cases the thermal value of each stage of the 
 total operation is different. Thus consider the 
 following data : 
 
 [H»SiJ"Aq, NaOHAq]= 13,300 [H-'SO'Aq, NaOHAq] = 
 
 14,750. 
 [H'SiF'Aq, 2NaOHAq] = 2 x 13,300 [H'SO'Aq, SNaOHAq] 
 
 = (2xl4,760)+l,900. 
 [H'SO'Aq, NaOHAq] = 15,850 
 [ffSO'Aq, 2NaOHAq] = (2 x 15,850) -2,750. 
 Each of these three acids represents a group. 
 
S3 
 
 ACIDS, BASICITY OF. 
 
 Thomsen divideg the dibasic acids examined by 
 him into three groups according as the thermal 
 value of the action of the second formula- weight 
 of soda is (1) equal to, (2) greater than, or (3) 
 smaller than, the value of the action of the first 
 formula-weight. 
 
 The data are presented in the following 
 table : — 
 
 Geotjp I. 
 Beat produced in action of 
 ' KaOH Acid 
 
 H.SiF, H,PtCl. 
 
 1st formula-weight 13,300 13,600 
 
 2nd „ „ 13,300 13,600 
 
 Group II. 
 
 H.SO. H^SeO. H^CA HAH.O. 
 
 1st 
 
 2nd 
 
 1* 
 
 II 
 If 
 
 14,750 14,750 13,850 12,450 
 16,650 15,650 14,450 12,850 
 
 Gkoup III. 
 
 1st 
 2nd 
 
 
 II 
 II 
 
 H,SO, H,SeO, H,CO. H,B,0. 
 15,850 14,750 11,000 11,100 
 13,100 12,250 9,150 8,900 
 
 1st 
 2nd 
 
 If 
 
 II 
 
 11 
 
 H.CrO. H,PHO, C,H.(CO,H), 
 13,150 14,850 12,400 
 11,550 13,600 11,750 
 
 The tribasio acids examined by Thomsen 
 may also be classified according as the thermal 
 value of the action of the second formula-weight 
 of soda is greater or smaller than that of the 
 first, and the value of the action of the third 
 formula-weight is greater or smaller than that 
 of the second. The data are as follows : — 
 
 Gkoup I. 
 
 Acid 
 Heat produced in action HgCoHaOj, HgCeHgO, 
 
 of NaOH (Aconitic Acid) (Citric Acid) 
 1st formula-weight 12,850 12,650 
 
 2nd „ „ 12,950 12,800 
 
 3rd „ „ 13,350 13,550 
 
 Gkoup II. 
 
 Acid 
 Heat produced in action of 
 
 NaOH H3ASO. H,PO. 
 
 Ist formula-weight 15,000 14,850 
 
 2nd „ „ 12,600 12,250 
 
 3rd „ „ 8,350 6,950 
 
 Group I. of the tribasic acids corresponds to 
 Group II. of the dibasic, and Group II. of the 
 tribasic, to Group III. of the dibasic, acids. 
 
 Thomsen suggests that this classification of 
 dibasic and tribasio acids may be summarised 
 in the following typical formulie : — 
 
 Dibasic Acids. 
 
 toup"*. } Typical formula I BH, ^.y.SiP..H.; 
 
 ■*'°'^II. } " {h(OH), e.?.SO,(OH).; 
 
 Group 
 Acid 
 Group III, 
 
 ■*-"'^°' } „ |r(0H)Hc.(7.S0,(0H)H. 
 
 Tkibasio Acids. 
 
 g'I^upI. }1SL{^^°^>- -^C.H.O.(OH).; 
 
 G^ot n. } forTuTa { ™(OH)H e.,. HPO.(OH)H. 
 
 As regards dibasic acids ; in the case of every 
 acid examined by Thomsen, except two, the 
 thermal value of the action of the first quantity 
 of soda added is different from that of the 
 second, equal, quantity of soda. The first of 
 the typical formula suggested by Thomsen for 
 the three classes of dibasic acids is probably to 
 
 be assigned to HjPtCl, and HjSiPb only. Why 
 should the formula B(OH)j rather than E(OH)H 
 be assigned to the acids of Group II. ? The 
 formula E(OH)H would indicate the easy separa- 
 tion of the acids into anhydride (E) and water 
 (OHH). But the acids placed in Group III. are, 
 as a class, more easily separable into anhydride 
 and water than those placed in Group II. If 
 the differences between the thermal values of 
 the first and second quantities of soda acting on 
 the acids of Group III. are tabulated we have 
 this result: H2S03 = 2,750; H^SeOa = 2,500 ; 
 HjOO, = 1,850 ; HjB^O, = 2,200 ; H^CrO, = 1,600 ; 
 HjPHOa = 1,250 ; CjH4(C02H) j = 650. These differ- 
 ences vary from 9-5 (H^SO,) to 2-7 (C2H,(C02H)2) 
 per cent, of the total heat of neutralisation. 
 We have good evidence in support of the state- 
 ment that succinic acid is a dihydroxyl com- 
 pound ; therefore, although it occurs in Thom- 
 sen's third group, we must place it with those 
 acids the typical formula of which is E(0H)2, i.e. 
 with the acids of Group II. The other acids of 
 Group III. are fairly easily separable into an- 
 hydride and water. The formula C02(0H)H 
 for carbonic acid is to some extent confirmed by 
 the fact that the higher homologues of this acid 
 although dihydric are distinctly monobasic. If 
 the differences between the thermal values of the 
 first and second quantities of soda acting on the 
 acids of Group II. are tabulated we have this 
 result: 112804 = 1,900; HoSeO^ = 900 ; HjC^O, = 
 600; B.JIfifi, = iOO. These differences vary 
 from 6 (HjSOj) to 1-5 (H^HjC^Oj) per cent, of 
 the total heat of neutralisation. The differences 
 in the case of acids of Group III. are consider- 
 ably larger than these. When the difference 
 between the thermal values under consideration 
 is small, and, as a rule, the value of the second 
 quantity of soda is greater than that of the first, 
 Thomsen regards the acid as, generally speaking, 
 belonging to the type B(0H)2 ; when the differ- 
 ence in question is large and the value of the 
 second quantity of soda is, as a rule, smaller than 
 that of the first, the acid is regarded as belong- 
 ing to the type E(OH)H. 
 
 These thermal investigations made by Thom- 
 sen point to the performance of definite functions 
 by the different hydrogen atoms in the chemi- 
 cally reacting unit, or group of atoms, of many 
 polybasio acids. Although the reacting unit of 
 a tribasic acid contains three atoms of hydrogen 
 all replaceable by metal under similar conditions, 
 nevertheless the energy-change which accom- 
 panies any one of these replacements is often 
 different from the energy-change which accom- 
 panies the other replacements ; hence we seem 
 justified in concluding that each of the replace- 
 able atoms of hydrogen in these acids is related 
 to the rest of the atoms, which with the specified 
 atom make up the chemically reacting unit of 
 the acid, in a way different from that wherein 
 the other replaceable atoms of hydrogen are 
 related to the rest of the atomic complex in 
 question. 
 
 In such acids as HjSOj, HjPOj, &o., it is 
 necessary to exhibit the differences of function 
 of the different replaceable atoms of hydrogen 
 by formulae which represent some of these acids 
 as containing one OH group, others ag contain- 
 ing two OH groups, and others three OH groups ; 
 but acids are known the reactiona of which 
 
ACIDS, ORGANIC. 
 
 03 
 
 otilige us to say that they contain more than one 
 OH group, and at the same time to assert that 
 each of these groups plays a different part in 
 the reactions of the acid. Thus, glyoollio acid 
 CE2OH.COOH is a monohasio acid ; the heat of 
 neutralisation of this acid is 
 
 [Off OH.COOHAq, NaOHAq] = 13,600 
 (De Fororand, 0. B. 96, 582) ; but the addition 
 of a second equivalent of soda to the neutral 
 salt is attended with the production of a small 
 quantity of heat 
 
 [CffOH.COONaAq, NaOHAq] = 4,200 
 (ib., Bl. [2] 40, 104). The disodium glycollate 
 thus formed is, however, an easily decomposed 
 compound. Another monobasic acid, glyoxylic, is 
 known, having the composition CH(0H)2.C00H ; 
 this acid forms a definite sodium salt, an aqueous 
 solution of which reacts with soda with the 
 production of nearly one-sixth the quantity of 
 heat produced by the reaction of the first equiva- 
 lent of soda on the acid. The data are these 
 (De Forcrand, C. B. 101, 1495) :— 
 
 [CH(OH)=.COOHAq, NaOHAq] = 13,230 ; 
 
 [CH(OH)^COONaAq, NaOHAq] = 2,000. 
 Here we have a very distinct illustration of the 
 connections between thermal changes and the 
 modification in the nature of the reaction of a 
 specified group of atoms produced by the rela- 
 tions of that group to the other atoms, or group 
 of atoms, in the chemically reacting unit of an 
 acid (v. further Affiniiy ; especially pp. 74, 75). 
 
 M. M. P. M. 
 
 ACIDS, OEGANIC. The empirical formula of 
 acetic acid CjHjOj has been expanded into the 
 structural formula CH3CO.O.H by reason of 
 the following considerations. One fourth of 
 the hydrogen of acetic acid is displaceable by 
 metals : hence we write C2H3O2.H. By the 
 action of PCI3, acetic acid may be made to 
 exchange the same quantity of hydrogen toge- 
 ther with half its oxygen for chlorine, producing 
 acetyl chloride, O^sOCl: hence we write 
 CjHsO.OH. In the electrolysis of potassium 
 acetate, ethane and carbonic acid are produced 
 at the positive pole, potassium being formed at 
 the negative pole. This decomposition may be 
 represented thus ; CjHjOjiK = K -I- COj -f CH3 ; but 
 methyl, CH3, is immediately polymerised, be- 
 coming ethane, CjHj. This experiment shows 
 that half of the carbon in acetic acid is inti- 
 mately connected with oxygen, the other half 
 being connected especially with hydrogen : hence 
 we write, finally, CHa.GO.O.H. 
 
 Analogous reasoning applied to other organic 
 acids, very frequently leads to a similar formula, 
 e,g. in the case of succinic acid to the formula 
 C2H4(CO.O.H)2. The acid character of these 
 bodies is undoubtedly connected with the group 
 CO.O.H or COjH, called carboxyl, and it is easy 
 to generalise and say that all organic acids that 
 are free from sulphur, phosphorus, arsenic or 
 silicon, contain carboxyl. Kekul6, therefore, 
 considers that the basicity of an organic acid is 
 determined solely by the number of oarboxyls 
 it contains. Such a conclusion can, however, 
 only be maintained, by defining an organic acid 
 as a substance containing carboxyl. If this 
 definition be accepted, it follows of course that 
 all organic acids do contain carboxyl. But if 
 we wish to let experiment guide us, we must 
 adopi some other definition, such as that an 
 
 acid is a substance that contains hydrogen 
 which can be displaced by metals with the 
 formation of a metallic compound not decom- 
 posable by water. According to this defi- 
 nition, phenol, pyrogallic acid, nitro-ethane, and 
 even the propargyl derivatives and perhaps 
 acetylene, are acids. Compounds like sugar- 
 lime are not necessarily salts, for the calcium 
 need not have displaced any hydrogen in the 
 sugar, but may have added itself in some way. 
 
 Sodic carbonate gives off COj when mixed 
 with solutions of strong acids; if we adopt 
 effervescence with sodic carbonate as a test of 
 acidity, we shall consider the compounds just 
 mentioned to be neutral bodies, but the nitro- 
 phenols and barbituric acid will still be acids. 
 In testing with sodic carbonate we assume that 
 carbonic acid is the weakest of all acids ; this is 
 a mere convention, the fact being that there is 
 no definite line of demarcation between acids 
 and neutral bodies, the two series shading off 
 imperceptibly into one another. 
 
 It will be noticed that the acidity of phenol 
 is greatly increased by the introduction of 
 nitroxyl. In general, the displaceable hydrogen 
 in an acid must be directly and indirectly 
 attached to strong chlorous (or electro-negative) 
 elements or radicles, for it is the balance of 
 affinities between these elements or radicles 
 and the metal that produces the stability of the 
 salt. In carboxylio salts one directly, and 
 CO indirectly, neutralise or balance the metal, 
 say sodium, forming the stable group CO.O.Na. 
 
 In sodium nitro-phenol, NOj.CjH^.O.Na, the 
 sodium is balanced by directly and by NO, 
 indirectly. In sodium nitrate, N02.0.Na, the 
 condition of the molecule is similar {v. also 
 AcETo-ACEiic ACID, p. 22). Too many or too few 
 chlorous groups weaken an acid, for the equili- 
 brium of its salts is thereby destroyed. Thus 
 aldehyde, CH3.CO.H is a neutral body, while 
 hydric hypochlorite, Cl.O.H, is a weaker acid 
 than C1.H. 
 
 For purposes of classification, it is most con- 
 venient to arrange acids according to their 
 structural formulae. Compounds whose structu- 
 ral formulae exhibit closed rings, each containing 
 more than two atoms, are classed as aromatic, 
 a term that is more particularly applied to the 
 derivatives of benzene ; all other organic com- 
 pounds belong to the fatty series. 
 
 Carboxylio acids of each series may be ar- 
 ranged according to their formulas and general 
 characters as follows : 
 
 A. Fatty Series. 
 
 (a.) Monocarboxylic acids: o. Mono-hydrio! 
 Series I, C^HjnOj or Acetic Series; Series II, 
 C„H2„_202 or Acrylic Series ; Series III, 
 C„H2„.402 or Propiolic Series; Series IV, 
 C„H2„_802, e.g. tri-ethenyl-butyric. — j8. Di-hy- 
 dric: Series I, C„H2„03 or Lactic Series; 
 Series II, C^H^j-jOa, e.g. Oxy-acrylic ; Series III, 
 CjHjo-iOj, e.g. oxypentinoic. — 7. Tri -hydric: 
 C„H2„0, or Glyceric Series. — S. Ee tonic: 
 Series I, C„H2„..203, e.g. aceto-acetic acid ; Series 
 
 II, C„H2„.403, e.g. allyl-aceto-acetic acid ; Series 
 
 III, C„H2„.„0s, e.g. di-allyl-aoeto- acetic acid. — 
 «. Di-ketonic: OoHj^.jOjje.j'. acetyl-aoeto-aoetio 
 acid. 
 
 (6.) Di-carboxylie acids: a. Di-hy. 
 drio : Series I, C.H2S.2O4 ox Oxalic SerieBt 
 
04 
 
 ACIDS, ORGANIC. 
 
 Series IT, O^Hj^,,©,, e.g. fumario acid; SerieB 
 III, C^H^n.jO,, e.g. acetylene di-carboxylio 
 acid; Series IV, G^i^-tfi„ e.g. di-acetylene 
 di-oarboxylio acid. — j8. Tri-hydrio: Series I, 
 '^nHa-jOs, malic series ; Series II, C^Hj^.jOs, 
 e.g. oxy-itaconio acid. — 7. Tetra-hydrio, 
 C„H2„.20e, e.(/. tartaric acid. — S. Penta-hydric, 
 C^Hjj.jO,, e.g. tri-oxy-adipio acid. — e. Hexa- 
 hydric, C„Hj„_20g, e.g. saccharic acid. — f. 
 Ketonic, C^Hj^-A, «■(/. acetyl-succinic acid. — 
 I). Di-ketonic, C^^^.fi^, e.g. di-acetyl-suc- 
 cinic acid. 
 
 (c) Tri-carhoxyUc acids : u. Tri-hydric: 
 Series I, C^^„,fi^, e.g. tricarballylie acid ; 
 Series II, O^L^^^fi^, e.g. aoonitic acid.— J3. 
 Tetra-hydrio: C„H2„_40„ e.g. citric acid. — 
 7. Penta-hydric : CI„H2„_jOb, e.g. desoxalic 
 acid. — 8. Ketonic: C^Hj^-jO,, e.g. aoetyl-tri- 
 carballylic acid. 
 
 (d) Tetra-carhoxylic acids : a. Tetra-hydrio 
 0„H2_50g, e.g. ethane tetra-carboxylic acid. 
 
 B. Aromatic Series. It is obvious that 
 when rings of atoms are introduced into the 
 structural formulie, the empirical formulae be- 
 come very complicated. We shall therefore not 
 attempt fully to classify the aromatic acids. 
 The most important series are as follows : 
 
 (a.) Mono-carboxylic acids, a. Mono-hydrio: 
 C„H2„_502, e.g. benzoic acid; C^U^^.^fi.^, e.g. 
 cinnamic acid ; C^H^^.jjOj, e.g. phenyl-pro- 
 piolio acid ; C^H^n-uOj, e.g. naphthoic acid ; 
 C„H2„_,j02, e.g. di-phenic acid; C„H2„.,s02, e.gr. 
 phenyl-cinnamio acid ; C„Hj„_2o02, e.g. anthra- 
 cene carboxyhc acid; CjH^j.jiOz. e.g. tri-phenyl- 
 acetic acid. — fi. Di-hydric: CoHj^.jO,, e.g. 
 salicylic acid; C„H2„_,„03, e.g. coumaric acid. — 
 y. Tri-hydric: C^Hj^.gO,, e.g. protooatechuic 
 acid, C„H2„_,„04, e.g. oxy-coumario acid. — S. 
 Tetra-hydrio, C^Hj^.sOs, e.g. gallic acid. — 
 e. Ketonic: C^Hj^.,,,©,, e.gr. oxy-acetophenone 
 oarboxylic acid. 
 
 (6.) Di-carhoxylic acids: o. Di-hydric: 
 CjHj^.jOj, e.g. hydro - terephthalic acid ; 
 C„Hj„.,„04, e.g. phtbalic aoid. — ^8. tri-hydrio: 
 C„H2„.,„05, e.g. oxy-phthalic acid. 
 
 The more complicated aromatic acids may 
 be classified in a similar way. It will be seen 
 that they are all poorer in hydrogen than the 
 corresponding fatty acids. 
 
 Organic Acids in general. — Occurrence : In 
 the vegetable kingdom, e.g. oxalic, malic, tartaric, 
 benzoic, salicylic, cinnamic, veratric, gallic, 
 and tannic acids. In animal juices and secre- 
 tions, e.g. lactic, sarcolaotic, uric, hippurio, 
 glycocholic, and taurocholic acids. In decaying 
 organised matter, e.g. acetic, butyric, valeric, 
 amido-propionio, amido-hexoic, and glutamic 
 acids. 
 
 Formation. — 1. By decomposing products of 
 the animal or vegetable kingdom by boiling 
 with dilute acids, e.g. amido-acetic, aspartio 
 and glutamic acids. — 2. From fats and fatty 
 oils by boiling with alkalis, e.g. stearic, palmitic, 
 and oleic acids. — 3. From resins by potash- 
 fusion, e.g. p-oxy-benzoic and protooatechuic 
 acids. — 4. By boiling a variety of substances 
 with dilute nitric acid (S.G. 1'2), e.g. oxalic and 
 tartaric acids from sugar and other carbo- 
 hydrates. — 6. By oxidising aromatic hydro- 
 earbons and other bodies with chromic mixture 
 (2pt8. of E,CrgO„ SptB. of H^SO^ and 3 to 5 
 
 parts of water), e.g. benzoic and terephthalic 
 acids. — 6. By oxidation with KMnO,, e.g. vanillio 
 acid from coniferin, pyridine carboxylio acids 
 from methyl-pyridines. — 7. From nitriles by 
 boiling with KOH, e.g. acetic and suooinio acids. 
 Unstable nitriles must be first converted into 
 amides by cold cone. HCl, and the amides may 
 then be turned into acids by boiling dilute HOI, 
 e.g. pyruvic acid (Claisen). The nitriles may be 
 prepared from alkyl chlorides or potassic alkyl 
 sulphates by distilling with KCy or digesting 
 with HgCy^. No nitrUes of the form XYO(ON), 
 are known (Glaus), hence derivatives of malonio 
 acid cannot be prepared in this way. — 8. By tha 
 oxidation of primary alcohols : X.CHj.OH 4-02 = 
 X.CO.OH -I- HjO. Secondary and tertiary alco- 
 hols can only produce acids with a less number 
 of carbon atoms, e.g. CH3.CH(OH).CH3 + 50 = 
 CH3CO2H + CO3H2-1-H2O. 
 
 Preparation. — The acids may be separated 
 from insoluble neutral and alkaline substances 
 by solution in aqueous potash ; they may then 
 be liberated by HaSO, and purified by one of tha 
 following methods : 
 
 (a.) If they are volatile, they are distilled 
 alone or with steam. 
 
 (6.) By conversion into a lead, barium, or 
 silver salt and, if possible, purifying the salt by 
 crystallisation. The lead salt is then decom- 
 posed by HjS, the barium salt by the calculated 
 quantity of H^SO.,, and the silver salt either by 
 HjS or by the calculated quantity of HCl. 
 
 (c.) By acidifying and extracting with ether. 
 A large number of acids are soluble in ether. 
 
 Reactions. — 1. Organic acids may be con- 
 verted into ethers in two principal ways : (a.) By 
 distilling with an alcohol and dilute H^SOj. Tha 
 reaction may be supposed to take place in two 
 stages ; the preparation of acetic ether may ba 
 thus represented : 
 
 EtOH + HjSO, = EtHSOj + H^O 
 EtHSOj + HO Ac = EtOAc + H2S0,. 
 (6.) If an acid is non-volatile, it is dissolved in 
 the alcohol and the liquid is saturated with 
 HCl. After some hours the solution is poured 
 into water and the ppd. ether distilled, if pos- 
 sible, in vacuo ; the reactions may be thus 
 represented : 
 
 EtOH + HCl = EtCl -I- H2O 
 EtCl * HOAc = EtOAc -I- HCl. 
 It is not necessary that HCl or HjSO^ should be 
 present in order that etherificatiou may take 
 place, for if equivalent quantities of an acid 
 and an alcohol be left in contact or heated 
 together for a sufficiently long time, from 64 to 
 74 p.c. will react upon each other, forming 
 an ether. The rate at which the reaction takes 
 place is greatest for acids of the formula 
 X.CH2.CO2H, slower for so-called secondary 
 acids, XYCH.CO2H, and slowest for tertiary 
 acids of the type XYZ.C.COjH, where X, Y and Z 
 are alkyls (Menschutkin, v. Chemical Change). — 
 2. Chlorides of phosphorus convert acids or their 
 salts into acid chlorides of the form X.CO.Cl. 
 These are usually soluble in ether, and are 
 decomposed by water, more or less rapidly, into 
 HCl and the acid X.CO.OH. Oxy-acids ex- 
 change not only their carboxylio hydroxyl for 
 CI, but also their other hydroxy Is ; but the 
 chlorides so produced are not reconverted by 
 water into the original acid but only into chloro- 
 
AUiLts, ORGANIC. 
 
 66 
 
 acids; thus lactic acid, CH3.CH(OH).C02H, 
 is converted by PCI5 into laotyl chloride, 
 Cn3.OHCl.COOl, whence water reproduces ohloro- 
 propionio acid, CHj.CHCl.COjH. The chlorides 
 act upon dry nitrates of the heavy metals (Ag, 
 Pb, Cu, Zn, and Hg) producing anhydrides, 8.17. : 
 2Ph.C0.01 + Pb(N03)2 = 
 (Ph.CO).,0 + PbOlj + N,0 , + 
 (Lachowicz, B. 18, 2990). — 3. Amides are formed 
 by the action of NH3 either upon the chlorides : 
 X.COCl + 2NH, = X.CO.NH2 + NHjCl, or ethers: 
 X.CO.OEt - NH3 = X.CO.NH2 + HOEt. The am- 
 ides are usually crystalline substances, and their 
 melting-points form important means of recog- 
 nising the various acids. — 4. Acetyl chloride 
 converts acids into anhydrides (v. Acetyl 
 chioeide). — 5. COCI2 converts salts into anhy- 
 drides. — 6. By heating with CaO or BaO, or 
 sometimes by heating alone, CO2 can be elimi- 
 nated from the carboxyls. — 7. Dry distillation of 
 calcium or barium salts usually produces ketones 
 (7. «.). — 8. Distillation of calcium salts with cal- 
 cium formate usually produces aldehydes {q. v.). 
 
 Salts. — Salts are formed by neutralising the 
 acids with metallic oxides or carbonates. They 
 can be conveniently obtained by the addition of 
 metallic sulphates or soluble carbonates to a 
 solution of the barium salt of the acid, or of 
 soluble chlorides to the solution of the silver 
 salt. Sodium, added to ethereal or alcoholic 
 solutions of oxy-acids, displaces not only carbo- 
 xylio but also hydroxylio hydrogen. The 
 compounds so produced are, in many cases, 
 partly decomposed by water, the sodium that has 
 displaced alcoholic hydroxyl being turned out 
 again, e.g. CH3.CH(0Na).C02Na-i-H20 = 
 
 0H3.CH(0H).C02Na -1- NaOH. 
 The silver salt is usually the least soluble, and is 
 frequently used in determining the molecular 
 weight of an acid ; for when the basicity of an 
 acid is known the molecular weight can be de- 
 duced from the percentage of silver left after 
 strongly heating the salt. Silver salts seldom 
 contain water of crystallisation. 
 
 Acetic Series CoHotOj. Nomenclature. — 
 The following names are employed in this dic- 
 tionary, the numbers denoting the value of n : 
 1. formic acid, 2. acetic acid, 3. propionic 
 acid, 4. butyric acid, 5. valeric acid, 6. hexoic 
 acid = caproic acid, 7. heptoic acid = oenanthio 
 acid, 8. octoic acid = oaprilio acid, 9. ennoio 
 acid = nonylic acid = pelargonic acid, 10. deooic 
 acid^capric acid, 11. heudecoio acid = undecy lie 
 acid, 12. dodecoic acid = lauric acid, 13. tridecoic 
 acid, 14. tetradecoio = myristic acid, 15. pentade- 
 coic acid, 16. palmitic acid = hexadecoio acid, 
 17. heptadecoic acid, 18. stearic acid = octodecoic, 
 19. enendecoic acid = arachio acid, 20. behenic 
 acid = icosoic acid. 
 
 Formation. — Besides the general methods 
 described above, the following may be noticed : — 
 1. The action of 00^ upon sodium alkyls, e.g. 
 NaC.,Hi-i-C02=C.,H5.002Na. This gives one 
 method for preparing fatty acids from com- 
 pounds containing a fewer number of atoms of 
 carbon in the molecule ; another method depends 
 upon the saponification of alkyl cyanides (v. 
 supra). — 2. The action of strong KOH upon al- 
 kylated aceto-acetio ethers {q. v.). — 3. The dis- 
 tillation of alkyl-malonic acids: XY0(C0aH)2 = 
 XYCH.C0jH + C0j, where X and Y may be 
 
 alkyls or hydrogen. Other di-basio acids are 
 decomposed in a similar way when their solu- 
 tions are mixed with uranium nitrate solution and 
 exposed to sunlight. — 5. By heating sodium alco- 
 holates with CO gas: NaOEt -t- CO = EtCO^Na.— 
 
 6. By reducing oxy-acids by heating with HI.^ 
 
 7. By reducing unsaturated acids by HI or so- 
 dium-amalgam. 
 
 Reactions. — 1. Dry distillation of salts of the 
 alkaline earths or alkalis produces ketones : e.g. 
 Ca(0.C0.Me)2= CaCOj -I- COMe,. 
 
 2. Distillation of a mixture of such salts of two 
 acids produces mixed ketones : 
 
 KO.CO.Me 4 KO.CO.Et =^ K^COj + Me.CO.Et. 
 If one of the salts be a formate the product is an 
 aldehyde : 
 
 KO.CO.Me -1- EO.CO.H = K^CO, + Me.CO.H. 
 
 3. Distillation of a salt of a fatty acid with an 
 alkaline hydrate produces a hydrocarbon : 
 
 KO.CO.Me + EO.H = K^CO, + MeH. 
 
 4. Distillation of the alkaline saltsw ith ASjO, 
 gives organic compounds containing Aesenic {g.v.) 
 
 5. Electrolysis gives saturated hydrocarbons : 
 
 2C„H,„+,.C0,K = K, + 2C0, + C,„H,,„,,. 
 
 6. Chlorine and bromine act by substitution, 
 not by addition. — 7. Distillation in a current of 
 steam of the mixture of stearic, palmitic, and 
 oleic acids got from fat slightly decomposes 
 them, forming all acids of the series from formic 
 to octoic (Cahours a. Demarijay, 0. B. 90, 156). 
 
 Synthesis. — The acids of the acetic series 
 may be built up in the following way: — (a) 
 NaMe is converted into NaCO-^RIe, or sodio 
 acetate, by CO2 (Wanklyn). — (6) Sodic acetate is 
 converted into ethyl alcohol in one of three ways : 
 a. It is converted by POCI3 into ACjO, and this is 
 reduced by sodium-amalgam (Linnemann).— 
 p. Ammonic acetate is prepared, and is con- 
 verted by P2O5 into aoetonitrile : N34C02Me = 
 2H2O -l-NCMe ; the nitrile is then reduced by Zn 
 and HjSOj (Mendius) to an amine : NCMe + 2H2 = 
 H.^N.CHjlWe, which is converted by nitrous 
 acid into an alcohol : H.,N.CH2Me + HNO^ = 
 HO.CH,Me + Nj -f H^O. This last reaction is, 
 however, accompanied by an jntra-molecular 
 change in the case of all the amines except 
 ethylamine and methylamine ; as a result of 
 this change 9i-propylamine gives rise to secon- 
 dary as well as w-propyl alcohol. — 7. The sodio 
 acetate is mixed with sodic formate and distilled; 
 the aldehyde thus got is reduced to alcohol by 
 sodium-amalgam (Lieben a. Eossi), or the oxim 
 of the aldehyde is reduced to an amine which is 
 then treated with nitrous acid. — (c) Ethyl alcohol 
 so prepared can now be turned into ethyl iodide, 
 zinc ethide, and sodium ethide, successively. 
 
 A repetition of processes (a), (b) and (c) upon 
 NaEt will produce sodio propionate, propyl 
 alcohol, and sodic propide successively, and ao 
 we can build up the series of fatty acids. 
 
 Instead of using the sodium alkyls, it is 
 more convenient to use alkyl cyanides; the 
 process is then : (a) convert methyl alcohol into 
 methyl cyanide, and this, by saponification, into 
 acetic acid ; (6) convert acetic acid into ethyl 
 alcohol by one of the three processes, u, ;8, or 7, 
 just mentioned ; (c) convert ethyl alcohol into 
 ethyl cyanide, and proceed as before to prepare 
 propionic acid, propyl alcohol &c. The acid? of 
 the acetic series may also be prepared syntheti- 
 cally with the aid of aceto-aoetio ether (p. 22) or 
 
66 
 
 ACIDS, ORGANIC. 
 
 of malonio ether {q. v.). In this way any acid ol 
 the form CHXY.CO2H, where X and Y are alkyls, 
 can be prepared. 
 
 The descent of the acetic series may be 
 effected by distilling each acid with soda-Ume, 
 whereby a hydrocarbon containing one atom of 
 carbon less is got ; this hydrocarbon is con- 
 verted by chlorine into an alkyl chloride, whence 
 by successive treatment with AgOAo and KOH 
 an alcohol may be formed. 
 
 The descent may also be effected by convert- 
 ing the acid into an amide, mixing this with 
 bromine and pouring the mixture into a 10 per 
 cent, solution of NaOH. An amine, a nitrile, 
 and a derivative of urea are then formed, the 
 amine and the nitrile contain one atom of 
 carbon less than the amide. The amine may 
 be turned into an alcohol by nitrous acid, and 
 then oxidised to an acid ; while the nitrile gives 
 the acid on mere saponification. The amides 
 containing at least 8 carbon atoms yield large 
 quantities of nitrile, while the lower amides 
 produce chiefly amine (Hofmann, B. 17, 1408). 
 The descent through nitrile from ennoic to 
 ootoic acid may be thus represented : 
 
 CaH.jCONHj + 3Brj + 8NaOH = 
 C-H.sCN -t- 6NaBr + Na^CO, + 6H,0. 
 
 CjH.sCN + KOH + H^O - C,H, jCO^K + NH,. 
 
 Melting Points. — While the boiling points of 
 the acetic series of acids gradually rise with 
 each increment of CH2, the melting-points of 
 those acids that contain an odd number of 
 atoms of carbon appear to be lower than those 
 of the acids that contain one atom of carbon 
 
 caprilio [16-5°] pelargonio [12-5°] 
 caprio [30°] hendecoic [28-5°] 
 
 laurio [43°] trideeoic [40-5°] 
 
 myristic [53-8°] pentadecoic [51°] 
 palmitic [62°] margario [59-9°] 
 
 stearic [69°] euendecoic [59-9°] 
 
 arachio [75°] meduUic (?) _[72-5°]_ 
 
 Isomerism among the fatty acids will be dis- 
 cussed under CiiAssiJPioATioN (v. also Isomebism). 
 Separation of two volatile acids. — Divide the 
 acid into two equal parts, neutralise one with 
 potash, add the other and distil. The most 
 volatile acid will pass over in preference to the 
 other ; and if it constitutes more than half the 
 entire mixture, the distillate will consist solely 
 of this acid. If, however, the less volatile acid 
 be in excess, the residue will consist of its 
 potassium salt in a pure state. The operation 
 is repeated upon whichever portion is still a 
 mixture. Acetic acid is an exception to the 
 rule, for although it be the more volatile acid, 
 it will remain behind as acid potassium acetate 
 (Liebig, A. 71, 355). If the distillation be 
 performed in aqueous solution in a current of 
 steam, the acid of highest molecular weight 
 goes over first (Heeht, A. 209, 319). 
 
 Separation of fixed acids. — An alcoholic solu- 
 tion of the mixture of acids is fractionally preci- 
 pitated by a cone, aqueous solution of magnesium 
 or barium acetate or by an alcoholic solution of 
 lead acetate. In the series of pps. so got, the 
 first contains the acid of highest molecular 
 weight and the last the acid of lowest molecular 
 weight. Each fraction is decomposed by boiling 
 dilute HCl and the melting-point taken. It a 
 series of consecutive fractious coulains acids of 
 
 identical melting-point that acid may be eoa 
 sidered pure, otherwise the process must be ro 
 peated upon each fraction (Heintz, J. pr. 66, 1 j 
 A. 92, 295). 
 
 Acrylic Series C^U^^^fi^. Nomenclature.— 
 n = 3, acrylic ; 4, orotonio ; 5, angelic ; 6, hexen- 
 oio ; 7, heptenoio ; 8, ootenoic = suberonic ; 
 9, ennenoio; 10, decenoic = campholio ; 11, hen- 
 decenoic = undeoylenic ; 12, dodecenoic ;_ 14, te- 
 tradecenoio; 15, pentadccenoio = cimioic ; 16, 
 hexadecenoic --^ hypogseic ; 18, oleic ---^ octodecen- 
 oic ; 19, doeglio = enendecenoio ; 22, erucio and 
 brassic acids. 
 
 Occurrence. — As compound ethers in fats and 
 oils, e.g. oleic acid. 
 
 Formation.— 1. From /3-, and sometimes 
 from a-, bromo- or iodo- derivatives of the acetic 
 series by boiling with alkalis or Ag-^O : 
 CHjI.CH2.COjK + KOH = 
 GB.^:Gn.COJS. + Kl + B..fi. 
 
 2. From ;8-oxy-acids, by distillation : 
 
 CHjOH.CH^-COjH = H,,0 + CHjtCH.COjH. 
 
 3. From certain )3-oxy-ethers by PCI3 : 
 
 3CMe,0H.C0„Et + 2PCI3 = 
 3CMe,Ci.C02Et + F^O, + 3HC1 
 CMe^Cl.COjEt = CH2:CMe.C02Et + HCl 
 (Frankland a. Duppa, G. J. [2] 3, 133). Similarly 
 Me2C(0H).CHj.C0jEt gives MejCiCH.COjEt.— 
 
 4. From derivatives of aoeto-aoetio or malonio 
 ethers containing allyl, ethylene, &c. — 5. By 
 Perkin's reaction, by heating aldehydes, C„H2„0, 
 with sodic acetate and AOjO {v. Aldehyhes). 
 
 Properties. — As in the acetic series, the lower 
 members of the acrylic series are volatile liquids 
 miscible with water. Solubility and specific 
 gravity diminish as molecular weight and boiling 
 point increase. The higher members are non- 
 volatile and insoluble in water. 
 
 Beactions.—l. The acids of this series con- 
 tain the group C:C and consequently combine 
 directly with bromine and chlorine, usually with 
 HBr or HI in cone, solution, and frequently with 
 H2, the latter combination is effected either by 
 action of sodium amalgam on a solution in water 
 or alcohol or by heating with cone. HI. — 2. 
 Fusion with potash produces two acids, one of 
 which is almost always acetic acid. The mole- 
 cular formula is split up in the middle of the 
 group C:C, e.g. : 
 
 CH^.CHiCH.COjH H- 2K0H = 
 CH3CO2K + HjCH.COjK + Hj. 
 
 3. Boiled dilute with K^SOj, they often change 
 into the lactone of saturated oxy-acids: thus 
 hydro-sorbic acid, CHj.CHiCH.CHj.CHj.COjH, 
 changes into oxy-hexo-lactone, 
 
 CH3.CH2.CH.CH2.CHj,.CO.O 
 I I 
 
 4. Many of the higher members are poly- 
 merised by nitrous acid. 
 
 Series C„H2„ .^0^. Nomenclature. — n = 3. Pro- 
 piolic; 4, tetrolic; 5, pentinoic; 6, hexinoio = sorbioj 
 7, heptinoic = benzoleic ; 8, octinoio = di-allyl- 
 acetic ; 9, lauronolio = enninoic ; 10, camphio" 
 decinoic ; 11, hendecinoio = undeoolic ; 14, 
 myristolic = tetradecinoio ; 15, pentadecinoio j 
 IG, palmitolio = hexadeoinoic ; 17, eloeomar- 
 garic = heptadecinoio ; 18, stearolio = octodeoi- 
 noic ; 22, bebenolio. 
 
 Formation.— Fromdi-brominated (ordi-chlor- 
 inated) acids of the acetic series, or mono- 
 
ACONIC ACID. 
 
 57 
 
 brominated acida of the acrylic series by treat- 
 ment with alcoholic EOH. 
 
 Reactions. — Combine with Br^ or with Br„ 
 also with HBr or 2HBr, and with Hj and some- 
 times with H,. 
 
 Lactic Series 0„H2„03. Nomenclature. — n = 
 2, Glyco'llic ; 3, lactic and hydracrylic ; 4, 
 oxybutyric ; 5, oxy- valeric ; 6, oxy-hexoio &o. — 
 oxy being prefixed to the names used in the 
 acetic series. 
 
 Formation.— 1. By the general methods: 
 thus (7) by saponification of oxy-nitriles, (8) by 
 oxidation of glycols. — 2. From bromo-, chloro- 
 or iodo- derivatives of the acetic series by dis- 
 placing the halogen by hydroxyl: (a) by boiling 
 with much water, (6) by moist Ag^O, or (c) by 
 EOHAq. — 3. From amido-aoids by nitrous acid. 
 i. From aldehydes or ketones by addition of 
 HON followed by saponification of the resulting 
 cyanhydrin by HCl : 
 
 CHs.CHO + HON = CH3.CH(0H).CN 
 
 CHs.CH(OH).CN + HCl + 2H2O = 
 
 CH,.CH(OH).COjH + NHjCl. 
 
 5. By oxidation of acids containing methenyl : 
 
 (CH3) jCH-CO^H + = (CH3)2C(0H).C02H. 
 
 6. By action of zinc alkyls on oxaUc ethers : 
 
 COjEt.COjEt + 2ZnEt2 = 
 
 C0^t.CEt2.0ZnEt + EtZnOEt, 
 
 C02Et.CEt2.0ZnEt + 2HjO = 
 
 COjEt.CEtj.OH + Zn(OH)j + C^U^. 
 
 7. By reduction of ketonio acids. 
 
 Beacticms. — The action of PCI5 and of Na, and 
 the characters of the resulting compounds have 
 been discussed above. The oxy-acids act as half 
 alcohol and half acid. Thus they form two kinds of 
 monoethylic ethers.one of the form E"(0H).C02Et, 
 the other of the form R"(0Et).C02H. The 
 ethers 'R"{0'B.).OOJEt possess all the characters 
 of an ethyl salt of an acid. Thus they may be 
 prepared in the usual way from the acid, 
 alcohol, and HCl ; they may be saponified easily 
 by alkalis ; they are converted by ammonia 
 into amides K"(0H).C0NH2 ; they are neutral 
 to litmus. The ethers of the form E"(0Et).C02H 
 can be prepared by saponifying the diethylio 
 ethers E"(0Bt).C02Et and these are got from 
 B"Cl.COjEt by action of NaOEt. The ethers 
 B"{OEt).COijH cannot be saponified by alkalis ; 
 are only converted into ammonium salts, 
 B"(OEt).COjNH„ by ammonia ; and are acid 
 to litmus. 
 
 o-oxy-acids are spht up by boiling cone. HCl 
 into formic acid and aldehydes : 
 
 CHa.CHiOHj.CO^H = CH3.CHO + HCO,H. 
 /3-oxy-acids boiled with cone. HCl give HjO and 
 an acid of the acrylic series : 
 
 CH2OH.CHj.CO2H = GHjiCH.COjH + HjO. 
 y-oxy-aoids split up, when their solution is 
 warmed, into water and lactones {q. v.). 
 CH3.CH(OH).CH2.CH2.C02H = 
 CH3.CH.CH2.CH2CO.O + H2O 
 
 On dry distillation, the a-oxy-acids of the form 
 B'.CH(0H).C02H produce lactides, or compound 
 
 ethers of the form E'.CH<°^q> CH.E'. The 
 
 3-oxy-acids are oonverted by dry distillation 
 into unsaturated acids : 
 
 E'.CH(0H).CH2.C0,H = E'.CH:CH.C0jH + H,0, 
 or into an aldehyde and an acid ; 
 
 CH3.CH(0H).CEE'.C0s,H = 
 CH3.OHO + HCEE'.COjH. 
 Ketoulc acids. Carboxylic acids represented 
 by formulte in which carbonyl is united to two 
 atoms of carbon. The preparation and pro- 
 perties of the ketonio acids got by displacing one 
 or two atoms of hydrogen in aceto-acetic acid by 
 hydrocarbon radicles are described under Aceto- 
 AOETic ACID. Homologues of aoetoacetio acid in 
 which carbonyl and carboxyl are not both united 
 to the same atom of carbon are described 
 as alkoyl-derivatives of fatty acids; thus, 
 CHs.CH2.CO.CHj.CH2.CO2H is described as Pko- 
 
 PIONyL-PEOPIONIO ACID. 
 
 Ketonio acids containing two oarboxyls are 
 described as derivatives of di-basic acids, thus 
 CH3.CO.CH{C02H).CH2.C02H is described as 
 acetyl-succinic acid. 
 
 Ketonio acids of the form E'CO.^JOjH can be 
 prepared from cyanides of the form E'.CO.CN, 
 and also, in thf aromatic series, by the action of 
 HgPhj &o., on ClCO.COjEt. 
 
 Si-basic acids, C„H2„.204. 
 
 Formation. — 1. By oxidation of the corre- 
 sponding glycols.^2. By boiling the cyanides of 
 alkylenes with potash. Alkylidene cyanides do 
 not exist (Claus). — 3. By saponification of cyano- 
 acids, C„H2„-,Cy02.— 4. By reduction of un- 
 saturated di-basic acids. — 5. By action of 
 reduced silver upon iodo-acids (e.g. formation of 
 adipic from iodo-propionic acid). — 6. By oxida- 
 tion of fats, fatty acids, ketonic acids, unsatu- 
 rated acids and many other bodies. — 7. By 
 reducing polyhydric di-carboxylio acids by HI, 
 e.g. tartaric acid to succinic. — 8. From aceto- 
 aoetic ethers by acting with NaOEt and the 
 ethyl salt of a chloro- or bromo-acid, and sapo- 
 nifying the product with cone. KOH {v. Acetyl- 
 succinic ethek). — 9. From sodio-malonic ether 
 and alkyl iodides : 
 
 CHNa.(C02Et)2 -F HI = CHE(C02Et)2 + Nal. 
 
 The product still contains hydrogen dis- 
 placeable by sodium: CHE(C02Et)2 -h Na = 
 CNaR(C02Bt)2 + H whence alkyl iodides form 
 di-alkylated malonio ether : 
 
 CNaB(C02Bt)2 + E'l = CE'E(C02Et)2 -I- Nal 
 (v. MAiiONic acid). 
 
 Properties. — Solid and not volatile. Fre- 
 quently produce anhydrides when heated. 
 Malonic acid and itw derivatives are split up by 
 heat into CO2 and acids of the acetic series. In 
 the oxalic series the acids containing an even 
 number of carbon atoms in the molecule have 
 higher melting-points, and lower solubility in 
 water than the acids with an uneven number of 
 carbon atoms (Baeyer, B. 10, 1286 ; Henry, C.B. 
 99, 1157 ; 100, 60). 
 
 For the characters of the homologues of 
 benzoic and salicylic acids see Aeomatio Seeies. 
 See also amido-, beomo-, chloeo-, iodo- and 
 NixEo-AciDs, and stjlphowo acids. 
 
 ACONIC ACID 
 
 G,-Rfl^i.e. C02H.CH2.C<^°>0 
 
 M. w. 128. [163°-164°]. S. 17-8 at 15°. Formed by 
 boiling itadibromopyrotartaric acid with a caus- 
 tic alkali, C3HeBr204 = 2HBr + C,H,0j (Kekule, 
 A. Suppl. 1, 338), or with water (10 pts.) (Beer, A. 
 216, 92). In like manner from bromoitaconic acid, 
 O-HsBrO^ (Swarts, /. 1873, 584). To prepare it, 
 a "Bolution of itadibromopyrotartaric acid neutral- 
 
5ft 
 
 ACONIC ACID. 
 
 iaed with soda is heated to the boiling point, 
 then gradually mixed with more soda till it con- 
 tains 3 mol. NaOH to 1 mol. of the acid. On 
 evaporating the solution, sodium aoonate crys- 
 tallises out and aconio acid may be obtained 
 from it by decomposition with sulphuric acid 
 and agitation with ether (Meilly, A. 171, 158). 
 
 Separates from water in rhombic crystals ; 
 from ether in elongated laminae (M.). 
 
 Bt.zctions. — 1. Decomposed slowly by boiling 
 water, forming a, brown syrup. — 2. Does not 
 combine with bromine. — 3. Unites with HCl and 
 HBr forming chloro- and bromo-itaconic acids 
 (Swarts). — 4. Eeduced by Sn or Zn to itaconio 
 acid. — 5. Boiling baryta produces formic, suc- 
 cinic and oxy-itaconic acids : 
 
 C5H,04-|-2H,0 = CH20., + C,H,0, and 
 
 Salts. — BaA'^: v. sol. water, ppd. by alcohol ; 
 crystallises from hot alcohol in shining prisms; 
 gives off 2| aq. at 150°. — CuA'._,4aq : blue prisms. 
 — AgA' : sparingly soluble laminse. — NaA'Saq : 
 efflorescent triclinic crystals : a : 6 : c = 
 •538 : 1 : -099; a = 103°6', /3 = 104° 27', y = 
 84° 49'. Got by boiling ita-di-bromo-pyrotartaric 
 acid with the calculated quantity of aqueous 
 Na^COj. It is decomposed by long boiling with 
 water (B.). — ZnA'^Saq : large shining crystals, 
 melting below 100° in their water of crystallisa- ; 
 tion. I 
 
 Methtjl Ether. MeA' [85°]. From AgA' and ' 
 Mel. Long thin prisms, v. sol. ether, m. sol. 
 alcohol, si. sol. water. H. W. 
 
 ACONITANILIC ACID v. Aniline. 
 
 ACONITE ALKALOIDS. — 1. Aconitine. 
 C3,H„NO,2.[183° cor.]. S. -13 ; S (benzene or chlo- 
 roform) 18 ; S. (ether) 1-56 ; S. (alcohol) 2-7 ; S. 
 (petroleum) -036 (Jiirgens, Ar. Ph. [3] 24, 127). 
 
 Occurrence.— In the root of monk's-hood, 
 Aconilwm Napellus (Geiger a. Hesse, A. 7, 276 ; 
 Planta, A. 74, 237). 
 
 Preparation. — The ground root is exhausted 
 with alcohol containing tartaric acid ; the con- 
 centrated extract, after exposure to the air in 
 shallow dishes to remove the last traces of alco- 
 hol, is mixed with water ; the aqueous solution 
 is filtered to separate resin, the last portions 
 of which are removed by agitation with light 
 petroleum, and then precipitated with potassium 
 carbonate ; the precipitate, consisting chiefly of 
 aconitine, is dissolved in ether, which leaves 
 behind a small quantity of humous substance ; 
 the solution is mixed with aqueous tartaric acid 
 and precipitated with sodium carbonate ; the 
 precipitate is dissolved in ether ; and the etheric 
 solution left to evaporate. The residue consists 
 of nearly pure aconitine, which may be further 
 purified by converting it into hydrobromide, 
 decomposing this salt, after recrystallisation, 
 with sodium carbonate, and finally recrystallising 
 the precipitate from ether (Duquesnel, C. B. 73, 
 207; Wright, 0. /. 31, 150). 
 
 Properties. — Crystallises in rhombic or hexa- 
 gonal plates. Soluble in alcohol, ether, benzene, 
 very soluble in chloroform, insoluble in light 
 petroleum. Extremely poisonous ; the minutest 
 particles, inhaled or blown into the eye produce 
 excessive irritation (W., C. J. 31, 154 ; Wright 
 a. Luff, G. J. 33, 325). Lajvogyrate (D.). 
 
 Reactions.— Slightly alkaline : lorms well- 
 
 crystallised salts. Eesolved by heating with 
 alcoholic KOH into benzoic acid and aconine: 
 
 C3,H„N0„ -h H„0 = (3,H„0, + C,„H,„NO„ ;— 
 partly also in the same manner by dilute mineral 
 acids, but another portion is at the same tiine 
 resolved into water andapoajsonitine. Acetic 
 and benzoic anhydrides convert it into acetyl 
 and benzoyl-apoaconitine (W. a. L.). The 
 hydrobromide forms crystals containing 
 C33H„NO,„HBr,2iH20 ; the hydrochloride 
 Cs3Hj3NO,2,HCl,3H20, forms with auric chloride 
 the salt C.,3Hj3NO,„,HCl,Au 01,, which separates 
 in pale yellow amorphous flakes very slightly 
 soluble in water (W.). • 
 
 ^^oacowiiimeCjjH^iNO,,. [186°].— Formed, 
 together with benzoic acid and aconine, by pro- 
 longed boiling of aconitine with sulphuric acid 
 (5 p.c.) or with a saturated solution of tartaric 
 acid. The benzoic acid which separates is dis- 
 solved out by ether and the apoaconitine is pre- 
 cipitated by sodium carbonate, while the aconine 
 remains dissolved. Crystals soluble in ether. 
 As poisonous as aconitine. The hydrobromide 
 C33Hj,N0,„HBr.2iH20 is crystalline (W. a. L.). 
 Ace tyl-apo aconitine CssH^(|AcN0„.[181°]. 
 Soluble in ether, separates therefrom in small 
 crystals. Dissolves easily in acids, forming amor- 
 phous salts (W. a. L.). Benzoylapoaconitine 
 Cj||HjiNO,2 = Cs3H„BzO|„ obtained by heating 
 aconitine or aconine with Bz^O, is indistinctly 
 crystalline, softens at about 130°, forms amor- 
 phous salts. Nitrate nearly insoluble (W. a. L.). 
 Aconine C^sHj^NO,, [130°]. Formed, to- 
 gether with benzoic acid, by the action of aqueous 
 alkalis, or more completely by that of alcoholic 
 NaOH, on aconitine {v. sup.). V. sol. water, 
 alcohol, alkalis and chloroform, insol. ether. 
 Amorphous. Beduces gold and silver salts at 
 ord. temp., Fehling's solution when heated. 
 
 SaZ<s.— 3C2jH3gNO,„2HCl and B'jH^SOj 
 are amorphous and probably only mixtures. 
 B'HClAuClj is a yellow flocculent pp. B'HIHgl, 
 is a white flocculent pp. (W. a. L.). 
 
 Apoaconine, CjsHsjNO,,, is formed by heating 
 the hydrochloride of aconine at 140°. 
 C2„H3,N0,|,HC1 is amorphous, soluble in water, 
 precipitated by alkalis. 
 
 2. Picroaoonitine CsiHjjN,,,. — Found by 
 T. B. Groves in a commercial aconite root, sup- 
 posed to be that of A. Napellus. Amorphous 
 varnish, having a bitter taste, but not producing 
 any prickly sensation on the tongue. Not 
 poisonous. Does not melt at 100°. Salts 
 crystallise well. The hydrochloride contains 
 C3,Hj5N0,„HCl,|H20. The gold salt B'HClAuCl,, 
 is a canary-yellow amorphous precipitate very 
 slightly soluble in water (W.). 
 
 Picroaconine CjiHjiNOa. Formed, to- 
 gether with benzoic acid, by the action of alco- 
 holic KOH on picroaoonitine. Closely resembles 
 aconine. Forms CjjHiiNOjHIHglj (W. a. L.). 
 
 3.PBeudaconitiiieC3jH„NO,2[104°-105°]. 
 The chief basic constituent of the root of Aconi- 
 turn ferox, from which it is obtained by exhaust- 
 ing with alcohol and sulphuric acid (0'05 p.c. 
 of the weight of the alcohol), or with methylated 
 spirit (640 c.c.) containing a little HClAq (1 c.c), 
 leaving the alcohol to evaporate, precipitating 
 the remaining solution with ammonia, dissolv- 
 ing the precipitate in ether, and evaporating. 
 The crystals which separate are purified by 
 
ACONITIO ACn). 
 
 60 
 
 recrystallisation from a mixture of ether and 
 light petroleum, or hy means of the nitrate. 
 
 Properties. — More soluble in alcohol and ether 
 than aconitine ; crystallises in transparent 
 needles and sandy crystals ; remains syrupy after 
 rapid evaporation. The air-dried base contains 
 1 mol. HjO, given off at 80° in a stream of air, 
 more quickly at 100° ; decomposes, -vrith separa- 
 tion of water at 130°-140°- Decomposed by 
 alcohoho soda at 100° into pseudaconine and 
 Y'gj'jitric 8iCid * 
 
 C,,H,5n6„ + H,0 = C„H„KO, + C,H,.0, 
 at 140° into veratric acid and apopseudaconine, 
 CjjHjjNOg. By mineral acids it is resolved into 
 water and apopseudaconitine ; with acetic acid 
 it forms acetylapopseudaeonitine. Salts mostly 
 amorphous ; nitrate CajH^NOij NO3H SH^O, 
 crystalline. B'HClAuClj crystallises from alcohol 
 in small needles, slightly soluble in cold alcohol. 
 B'H] Hgl^ is an amorphous Hocoulent pp. (W. a. L.) 
 
 Apopseudaconitine CjsH^jNO,, [103°]. 
 Formed, together with pseudaconine and veratric 
 acid, by heating pseudaconitine with dilute 
 mineral acids, or with veratric acid alone when 
 pseudaconitine is heated at 100° with a saturated 
 aqueous solution of tartaric acid. Crystallises 
 from ether in the same forms as pseudaconitine. 
 The nitrate is crystalline. The aurochloride 
 CjjH^NOiiHClAuCla crystallises from alcohol in 
 small needles (Wright a. Luff). 
 
 Acetyl-apopsetidaconitine C3i,H.,„AoNO|,aq. 
 Formed by heating pseudaconitine at 100° with 
 acetic anhydride or glacial acetic acid, and 
 separated by agitation with ether. Crystalline. 
 Nitrate and aurochloride crystalline. Benzoyl- 
 apopseudaconitine C3iiH|jBzN0,,aq. Indistinctly 
 crystalline. Nitrate and aurochloride crystallise, 
 the latter from alcohol in anhydrous rosettes 
 (W. a. L.). 
 
 Pseudaconine. C„H„NOs [100°]. 
 Formed, together with veratric acid, by heating 
 pseudaconitine with dilute mineral acids, or 
 better with alcoholic soda. Light yellow varnish, 
 moderately soluble in water forming a strongly 
 alkaline bitter solution, which, however, does 
 not produce any prickly sensation on the tongue. 
 Soluble in ether. Forms amorphous sails. Be- 
 duces silver solution and alkaline copper solution 
 when heated.^CjjHjiNOgHIHglj is a white 
 amorphous precipitate (W. a. L.). 
 
 Apopseudaconine C^jHjgNOg. Formed, to- 
 gether with veratric acid, by heating pseud- 
 aconitine with alcoholic soda at 140°. Closely 
 resembles pseudaconine. — CjjHj.ACjNOg is an 
 amorphous varnish melting below 100°, spar- 
 ingly soluble in water. Salts amorphous. 
 CjjHjjBzjNOj is nearly insoluble in water (W. 
 a. L.). 
 
 4. Japaconitine. CssHssNjOj,. In the root 
 of Aconitwm Japonicum. Prepared by exhaust- 
 ing the root with alcohol containing 1 p.c. 
 tartaric acid, concentrating the extract when 
 adding water, and repeatedly agitating the 
 filtered liquid with ether to remove resinous 
 constituents ; precipitating the alkaloids with 
 sodium carbonate ; agitating it with ether ; dis- 
 solving it in aqueous tartaric acid; again 
 precipitating it with Na^CO^, and dissolving in 
 ether. The resulting solution when left to 
 evaporate deposited crystals which after being 
 freed from adhering syrup, were re-crystallised 
 
 from ether, and after repeated fractional crystal- 
 lisation gave by analysis numbers agreeing with 
 the formula CB„H,iN,0..., , confirmed by the 
 analysis of the gold-salt. The hydrobromide 
 C„„Ha8N.,0„ 21-IBr 5H.,0, and the nitrate 
 crystallise well (Wright a. Luff, 0. /. 35, 387). 
 
 Japaconine, G.^^S^^'NO ^„ is obtained, to- 
 gether with ber zoic acid, by heating japaconitine 
 with alcoholic potash: Cj^HgsNjOj, -h 3H.,0 = 
 2C,H„0, + 2C,„H^,N0,„. Yellowish varnish, 
 easily soluble in ether, alcohol, and chloroform ; 
 insoluble in water. Forms a mercuriodide 
 C,„H,,NO,„HIHgI,. 
 
 Japaconitine and japaconine heated with 
 benzoic anhydride yield the same product, viz. 
 C.,5H3„NO,(OC,H-,0)4, which is flocculent, dis- 
 solves in ether, and does not crystallise. Salts 
 non-crystalline, nitrate very sparingly soluble in 
 water (W. a. L.). 
 
 5. Lycaconitine C.,,H3jN20„2aq. A non-crys- 
 tallisable alkaloid obtained from wolf's bane, 
 aconitum lycoctonum (Dragendorff a. Spohn, 
 J. Ph. [5] 10, 361 ; 0. /. 48, 403). If heated 
 with water under pressure it is converted into 
 crystalline lycoctonic acid, C,,H,|,NjO„ and 
 two alkaloids, lycaconine and acolyctine. 
 
 6. Myoctonine, C2,H,„N20j5aq. Is an amor- 
 phous alkaloid also present in A. lycoctomim. 
 
 H. W. 
 
 ACONITIC ACID Cfifi, i.e. C,H3(C0.,H), or 
 C0jH.CHj.C(C02H) ; CH.CO.H [186°-187°] 
 
 S. 18-6 at 13°. S. (80 p.c. alcohol) 60 at 12°. 
 Equisetic acid, citridic acid. Occurs as calcium 
 salt in the roots and leaves of monk's-hood 
 (Aconitum Napellus) and other aconites, in the 
 herb of Delphinium Consolida collected after 
 flowering (Wicke, A. 90, 98) ; in the horse-tail 
 (Equisetum fluviatile) (Baup, A. 77, 293) ; in 
 millefoil (Zanon, A. 68, 21 ; Hlasiwetz, J. pr. 
 72, 429) ; in the juice of the sugar-cane (Behr, 
 B. 10, 351), and in that of sugar-beet (0. v. 
 Lippmann, B. 12, 1649) ; as calcium and potas- 
 sium salt in the leaves of Adonis vernalis 
 (Linderos, A. 182, 3G5). 
 
 Formation. — 1. By the action of heat on 
 citric acid, or by prolonged boiling of that acid 
 with hydrochloric acid: C,H,0, - H.,0 = C„HbOj 
 (Dessaignes, C. B. 42, 494) ; more quickly by 
 heating citric acid with HCl in a sealed tube at 
 130°-140° (Hergt, J.pr. [2] 8, 372), or by boiling 
 it with HBr (Mercadante, G. 7, 248).— 2. In 
 small quantity, together with citraconio acid, by 
 heating citric acid with HI in a sealed tube 
 (Kammerer, A. 139, 209). 
 
 Preparation. — Citric acid, in portions of 
 100 grams each, is heated in small flasks pro- 
 vided with bent distillation-tubes J met. long, 
 till the whole tube is lined with small oily drops, 
 and the residue is heated on a water bath with 
 15 g. water till it solidifies to a crystalline mass. 
 On pulverising this mass and treating it with 
 pure ether, aconitic acid dissolves and oiirio 
 acid is left behind (Pawolleck, A. 178, 150). 
 Huniius (B. 9, 1751) heats citric acid at 140° 
 for a day in a stream of HCl-gas, dissolves the 
 product in a small quantity of water, evaporates, 
 and treats the residue by Pawolleck's method. 
 
 Properties and Reactions. — Crystallises in 
 small four-sided plates, melting at 187° and 
 resolved at the same time into CO.^ and itaoonio 
 acid CiHPj; also when heated with water at 
 
00 
 
 ACONITIO AOm. 
 
 180° (Pebal, A. 98, 94). Dissolves easily in 
 absolute ether, whereby it is distinguished from 
 sitrio acid. Converted by sodium-amalgam into 
 tricarljallylio acid CsHsOj (Hlasiwetz, J. 
 18G4, 396). Unites with fuming HBr, at 100°, 
 forming bromocitrio acid CgHjBrOj.and with 
 hypochlorous acid, forming ehlorooitric acid 
 CjHjClO,. The calcium salt fermented with 
 cheese yields succinic acid (Dessaignes, C. B. 
 31, 432). 
 
 Salts. The acid is tribasic. The NH,, K, 
 Na, Mg and Zn salts dissolve readily in water, 
 the rest are insoluble or only sparingly soluble. 
 The soluble aconitates form, with lead and silver 
 solutions, white flocculent precipitates (distinc- 
 tion from fumaric and maleic acids). 
 
 (NHJHjA'": nodules or lamina. S. 15-4 at 
 15°.— (NH^j^HA'".— K3A"'2aq. S. 9 at 15° 
 (Baup, A. 77, 299). Slender, silky, very deU- 
 quescent needles; lose aq at 100° and aq at 
 190° (Guinochet, C. B. 94, 455).— K^HA'" 2aq. 
 S. 87-7 at 16°: smallprisms(G.).— KH^A'". S.ll 
 at 17° ; minute elongated prisms. — NajA'" 2aq: 
 retains its water in a current of air at 60° but 
 gives it up at 15° in vacuo. — ^Li^ A'" 2aq: v. 
 Bol. water; solution is alkaline. — CaHA"'aq: 
 guramy; v. sol. water.— CajA'"^ 3aq: gummy; 
 V. sol. cold water, but at 80°-100° this solution 
 deposits rhombic prisms, si. sol. cold water. 
 The latter gradually dissolve, changing to the 
 gummy variety.— Ca3A"'j 6aq. S. 1-01 at 15° (B.).— 
 SrjA'''^ 3aq. S. -625 at 16° (G.). Ppd. on boiling 
 the solution.— BaH^A"'2 : prisms. S. 4-2 at 17° 
 (G.). — ^BajA"'2 Baq : gelatinous pp. got by adding 
 BaCl, to aconitic acid or a solution of an aconi- 
 tate.— MgsA"'j 3aq. S. 10-4 at 17°- Elongated 
 octahedra (G.).— CosA^jBaq. S. 3-5 at 16°. Pink 
 powder. — Ni3A"'2aq. Pp. changed by long boil- 
 ing to Ni,&."', 6aq.— Cd3A"'2 6aq. S. -113 at 17°. 
 Prisms. — ZUjA^jSaq : insoluble in water. — 
 PbjA'''^ 3aq(?) : flocculent precipitate (Buchner). 
 — PbsA"'j2Pb02Hj,0 : obtained by prolonged 
 boiling of the NH^-salt with basic lead acetate 
 (Otto, A. 127, 180).— MujA'''^ 12aq : small 
 rose-coloured octahedra, slightly soluble in 
 water (Baup). — ^AgjA'" prepared by adding AgNOj 
 to the normal ammonium salt, is a thick 
 flocculent precipitate, becoming crystalline on 
 drying ; slightly soluble in water. 
 
 A solution of aconitic acid mixed vrith ferric 
 chloride is precipitated by ammonia, but the 
 presence of citric acid even in small quantity 
 prevents the precipitation {Bti. 1, 648). 
 
 Ethers. — The ethers of aconitic acid are 
 formed by heating the acetyl derivatives of the 
 corresponding citric ethers, 03H4(OAc)(C02K)j, 
 at 250°-280°, acetic acid being split olf ; yield 
 75 p.c. of the theoretical (Anschiitz a. Klinge- 
 mann, B. 18, 1953). 
 
 Me3A"' (271°) (Hunaus, B. 9, 1750) ; (161°) 
 at 14 mm. (A. a. K.) From aconitic acid, MeOH, 
 and HCl (H.). 
 
 EtsA'" (275°) (Mercadante, G. 1, 248); (252°) at 
 250 mm. (Conen, B. 12, 1655) ; (171°) at 14 mm. 
 (A. a. K.). S.G. f 1-1064 (C.) ; i* 1-074 (Crasso, 
 
 A. 34, 59). From tetra-ethyl citrate and PCljat 
 100° (Conen). 
 
 PrjA'" (195°) at 13 nun. (A. a.K.) 
 Di-aniZida. [217°]. Yellow needles; formed 
 by boiling aqueous aniline aconitato (Michael, 
 
 B. 19, 1374). 
 
 Iso-aconltic ether 
 COjEt.CH:CH.CH(COjEt)s(?) (248°)S.G.|f 1-0505. 
 A product of the action of hot HCl upon di-car- 
 boxy-glutaeonio ether {q. v.). An oil ; sol. aloo 
 hoi or ether (Conrad a. Guthzeit, A. 222, 255). 
 
 Fseudo-aconltic acid 
 
 C02H.CH2.CH(C02H).C".C02H [217°] 
 
 Formed at 180° from propylene tetra-carboxylio 
 
 acid [q. v.), obtained from bromo-maleio ether 
 
 and sodium malonio ether (Schacherl, 4. 229, 95). 
 
 SaZ«.— BajA^aq. H. W. 
 
 ACOBIN Cj^HjoOs. A glucoside extracted from 
 the common reed {Acorus calamus). Sol. alcohol 
 or ether; ppd. by benzene from its ethereal 
 solution (A. Faust, Bl. [2] 9, 392 ; Thorns, Ar. 
 Ph. [3] 24, 465). 
 
 ACKALDEHYDE v. Acbolein. 
 
 ACKIDINE C,3HsN i.e. 
 
 CH CH CH 
 
 CH 
 
 CH 
 
 CH N CH 
 
 M. w. 179. [106°] (Bernthsen) ; [111°] (Fische» 
 a. Korner). V. D. 6-10 (Graebe, B. 5, 15). 
 
 Occurrence. — In coal tar (Graebe a. Caro, 
 A. 158, 265). The portion that boils between 
 300° and 360° is extracted with H^SOjAq and 
 the extract ppd. by Kfirfi,. 
 
 Formation. — 1. By heating formyl-diphenyl- 
 amine (23 g.) with ZnCLj (45 g.) at 190°-220° : 
 
 H.C0.N(C3H.)j= 0,3H,N + H,0. 
 2. From crystallised oxalic acid, diphenyl- 
 amine, and ZnCl^ at 120° -260°.— 3. From chlo- 
 roform, dipheuylamine, and ZnCl^ or AICI3. 
 In this way 2 g. of acridine can be got from 
 25 g. dipheuylamine. It is better to heat chloro- 
 form (1 pt.) with diphenylamine (1 pt.), ZnCl, 
 (1 pt.), and ZnO (^ pt.) , for 8 hrs. at 200° (Fischer 
 a. Korner, B. 17, 101). (C,K^)^S + CCI3H + ZnO 
 = C,3HgN,HClH-ZnCl2 + H20. — 4. By passing 
 phenyl-o-toluidine through a red hot tube 
 fGraebe, B. 17, 1370). — 5. In small quantity 
 (5 p.c.) by heating aniline and ZnClj with o- 
 or p- oxy-benzoic aldehyde or even with benzoic 
 aldehyde (Mbhlau, B. 19, 2451). 
 
 Preparation. — Heat formic acid (50 g. of 
 S.G. 1-22) with diphenylamine (175 g.) and 
 ZnCl^ (100 g.) gradually from 150° to 270°, avoid- 
 ing evolution of CO. Dissolve the product in 
 alcohol, and pour into aqueous NaOH. Acridine 
 and diphenylamine are in the alcoholic layer ; 
 evaporate this, and dissolve the residue in 
 ether ; shake the ether with dilute hydrochloric 
 acid. The acridine is then in the acid solution. 
 The yield is small (Bernthsen, A. 224, 3). 
 
 Properties. — Long needles (from much water) 
 or prisms, a: b: c = -656 : 1 : -335. Pungent odour 
 and burning taste. The base and its hydro- 
 chloride attack the tongue even when in minute 
 quantities. Volatile with steam. Very slightly 
 soluble in water. Dilute solutions exhibit a 
 characteristic greenish-blue fluordsoence. 
 
 SaZis.- (Bernthsen, A. 224, 3 ; B. 16, 1802 
 Graebe, B. 16, 2828 ; Medicus, B. 17, 196.)— 
 B'HCl : yellow plates, soluble in water impart- 
 ing a bluish-green fluorescence. — B'^HaPtCl,! 
 sparingly soluble minute yellow needles. — 
 
AOROLElK 
 
 ffl 
 
 B'jHNOj 3aq ! [151°], yellow pp. got by adding 
 Bodium nitrite to a solution of an acridine salt. 
 Long yellow silky needles ; si. sol. ether or cold 
 water, m. sol. hot water, v. e. sol. alcohol; some- 
 what volatile with steam. — ^B'jHjSO,: formed 
 by adding aqueous SOj to a solution of the 
 hydrochloride. Yellowish-red needles, v. si. sol. 
 water. — B'HNaSOj : got by mixing solutions of 
 Bodium sulphite and acridine hydrochloride. 
 Colourless, easily soluble, prisms. 
 
 Picrate. C,s,H5NC(,H2(N02)30H. Minute 
 yellow prismatic needles. Melts at a high tem- 
 perature. V. si. sol. cold alcohol, cold water or 
 cold benzene. Boiling water partially decom- 
 poses it (Anschiitz, B. 17, 438). 
 
 Acridine forms no carbonate. 
 
 Reactions. — 1. HgClj giv«>s a yellow crystal- 
 line pp. (C,3HjN,HCl)2HgCl2.— 2. KfiijO, gives 
 a yellow pp. CigHgNHjOrOj. — 3. I dissolved in 
 EIAq gives a brownish pp. (CijHjNHI),!^. — 
 4. Reduced in alcoholic solution by sodium 
 amalgam to hydro-acridine which is soluble in 
 alcohol ; at the same time a white powder in- 
 soluble in alcohol is formed. Hydro-acridine, 
 
 CjHj<^„-rv'NCjHj, is not a base. It forms 
 
 prisms, [169°], si. sol. cold alcohol, v. sol. hot 
 alcohol or ether, insol. water. Sol. cone. H2S04 
 and reppd. by water, unaltered. It is oxidised 
 by A.g.fl or CrOa back to acridine. — 5. KMn04 
 oxidises acridine to a quinoline di-oarboxylio 
 acid (acridinio acid) (Graebe a. Caro, B. 13, 99). 
 
 Octo-hydro-acrldine (acridine-octo-hydride) 
 C,3H„N[84°]. (320°). Colourless plates or tables. 
 
 Formed by heating acridine or hydroaoridine 
 with HI and P at 220°. — B',HC1 : colourless 
 tables, soluble in hot water, sparingly in cold 
 (Graebe, B. 16, 2831). 
 
 ACBIDIKES.— Compounds having the general 
 formula ^CE' 
 
 
 OeHj. 
 
 They are characterised by basic properties, 
 fluorescence in dilute solutions, capability of 
 directly uniting witfl Mel, and of forming 
 neutral dihydrides which may readily be re- 
 converted into the original base. v. Buttl- 
 icRiDiNE, Methyl-aokidine, and Phentl-aobi 
 DINE. See also Amzdo-phenyl-acridiiie, Oxy- 
 
 rHENYI-ACKiniNE, AMIDO-HTDiiO-ACKlDINB KETONE. 
 
 ACEIDINIC ACID v. {Py. 2:3)-QniNOLiNE-Di- 
 
 CABBOXTLIO ACID. 
 
 ACEIDYL-BENZOIC ACID v. Phbnyl-aoei- 
 
 DINB CaBBOXTLIC AcID. 
 
 ACBOI.ACTIC ACID 
 C,H,0s,i.e.CH0.CH2.C0jH or CH(0H):CH.C02H. 
 Formed by boiling ethyl jS-ohloro-acrylate 
 CHClrCH.COjEt, with baryta water (Pinner, B. 
 7, 250 ; A. 179, 91). The acid is a thick syrup. 
 Its silver salt, AgA', blackens quickly on exposure 
 to light, and is m. sol. water. 
 
 ACBOLEIN CsH.O, i.e. CH2:CH.CH0. Acrylic 
 aldehyde, Acraldehyde. Mol. w. 56. (52-4°). 
 V.D. 1-897. S. 2-5. S.G.f -841 ; f.^1-4089 ; 
 Boo 25-31 (Briihl). 
 
 Formation. — 1. By oxidation of allyl alcohol 
 CH2:CH.CH20H, with platinum-black or chromic 
 acid mixture.— 2. By dehydration of glycerin, 
 CaHgO,, and therefore in the destructive distil- 
 lation of fats.— 3. By distillation of acetone 
 4)bromide : C3H,0Brj= 2HBr + C,H,0.— 4. From 
 
 di-iodaoetone and silver cyanide (M. Simpaon, 
 J. pr. 102, 380). — 5. By exploding ethylene with 
 a large excess of oxygen, the carbon being 
 partly oxidised to CO, which with the ethylene 
 forms acraldehyde, C^Hj -i- CO = CjH^O. This 
 effect, however, is produced only by nascent, not 
 by ready-foimed CO (E. v. Meyer, J. pr. [2] 
 10, 113). 
 
 Preparation. — Anhydrous glycerin (1 pt.) is 
 distilled with KHSO, (2 pts.), and the vapour, 
 after passing over calcium chloride and lead 
 oxide to remove water and acrylic acid, is con- 
 densed by a freezing mixture (Aronstein, j4. Suppl. 
 3, 180). — Obtained also in large quantity as a 
 by-product in the preparation of oenanthalde- 
 hyde, from castor-oil (Sohorlemmer). 
 
 Properties. — Mobile strongly refracting liquid. 
 Vapour extremely irritating to the nose and eyes. 
 Taste pungent and burning. It is readily con- 
 verted into dis acryl, a white amorphous body 
 (isomeric or polymeric?), insoluble in water, 
 alcohol, acids, and alkalis. 
 
 Reactions. — 1. Oxidised quickly in the air, 
 or by silver-solution to acrylic acid, in the latter 
 case with formation of a silver speculum -, by 
 nitric acid to glycoUic and oxalic acids (Claus. 
 A. Suppl. 2, 118). — 2. Converted by nascent 
 hydrogen (Zn and HCl) into allyl alcohol, 
 C3H5O, isopropyl alcohol, CjHjO, and acro- 
 pinacone 2C3H.fi + 112 = ^t^mOi (Linnemann, 
 A. SuppV 3, 257).- 3. With PCI5 acrolein yields 
 aUylene chloride CjHjClj (84-5°), the isomeric 
 dihydrochloroglycideor3-epidichlorhydrin(102°), 
 and trichlorhydrin OsHiCl, boiling at 152°-156° 
 (Geuther, Z. 1865, 24).— According to Eomburgh 
 \BI. [2] 36, 549) the three liquids are allylidene 
 chloride CaH^Clj (85°), its isomeride, (110° cor.), 
 and iS-chloro-allyl alcohol CHChCH.CH^OH 
 (153° cor.). — 4. Bromine forms di-bromo-pro- 
 pionic aldehyde (g. v.). — 5. Acrolein heated with 
 ethyl-alcohol and its homologues and a little 
 acetic acid, yields glycerides ; e.g. triethylin 
 C3H5(CjH5)30„ from 1 vol. C3H4O and 1 vol. 
 alcohol and 0-5 vol. acetic acid ; trimethylin 
 C3H5(CH3)303, from 1 vol. CaH^O, 3 vol. methyl 
 alcohol, and 0-5 vol. acetic acid ; and triamylin 
 C3H5(C5H„)303, in like manner. On passing HCl- 
 gas into a mixture of acrolein and 2 vol. abso- 
 lute alcohol, diethylchlorhydrin C3H5(C2H5)3C10, 
 is obtained as a heavy oil having a sweetish 
 ethereal odour and S. G. 1-03 at 10-5° (Alsberg, 
 J. 1864, 494). — 6. Acrolein acts strongly on 
 aniline, forming diallylidene-di-phenyl-di-amine, 
 (CsH3),(C3HJjN2(Sohiff, J. 1864, 414). 
 
 Combinations. — 1. With Sodium Hydrogen 
 Sulphite bydirect combination C5H40,2NaHSO, = 
 CH3.CH(NaS03).CH(0H)(NaS03). Crystalline 
 nodules. With acids gives off SO, but no 
 acrolein. By NH, and BaCl, only half the 
 sulphurous acid is precipitated as BaSO,, the 
 o-sulphopropionic aldehyde remaining in solu- 
 tion. Sodium amalgam converts it into oxypro- 
 pane sulphonic acid. Silver oxide oxidises it 
 to a-sulpho-propionic acid (Max Miiller, B. 6, 
 lUl.—Bn. 360). 
 
 2. With Acetic Anhydride. CjHiO.C^HsO, 
 or C3H4(OAo)2. Formed by direct combination 
 at 100°. Liquid (180°). S.G.S3 1-076 (Hiibner a. 
 Geuther, A. 114, 47). 
 
 3. With Acetyl Chloride. C,H40,20jH,OCl. 
 Liquid boiling at 140°-145° (Arousteia). 
 
83 
 
 AOKOLElN. 
 
 4. With Ethyl Chloride. 
 CH,:gH.CHCl(0CjH5). Formed together with 
 acrolein-aoetal, by the action of sodium etbylate 
 on allylidene chloride, CH^iCH.CHCl^ at 120°. 
 Liquid. (115°-120°). 
 
 5. With Ethyl Alcohol. C.H,„02 i.e. 
 CHj,:CH.CH(0H)(0C.H5). From acrolein hydro- 
 chloride and sodium etbylate : 
 
 CH,:CH.CH0,HC1 + NaOEt = 
 
 NaCl + CH2:CH.CH(0H)0Et. 
 
 Liquid boiling, with partial decomposition at 
 
 130°. S.G. 2 0-946. Soluble in water, alcohol and 
 
 ether (Geuther a. Cartmell, A. 112, 3). 
 
 6. With ammonia, acrolein forms a conden- 
 sation-product CjHjNO = 2C,,H,0 + NHj - H^O, 
 prepared by passing the vapour of anhydrous 
 acrolein into alcoholic ammonia (Hiibner a. 
 Geuther, A. 114, 35), or more readily by passing 
 the vapour of crude acrolein into aqueous ammo- 
 nia, expelling the excess of ammonia by a gentle 
 heat and precipitating the remaining liquid with 
 a mixture of ether and alcohol (Glaus. A. 130, 
 186). — Red amorphous body easily soluble in 
 water and in acids, sparingly in hot alcohol, 
 insoluble in cold alcohol and in ether. Converted 
 by dry distillation, first into a non-volatile oxy- 
 genated base (Glaus. ^.158, 222), then intopico- 
 line and water (Baeyer, A. 155, 288). Acrolein- 
 ammonia unites directly with bases, forming 
 brown amorphous salts. The platinochloride 
 (C„H,|N0HCI)2PtCl.| is a yellow amorphous pp. 
 
 Polymerides. l.Metaorolein (0311^0)3. [50°]. 
 V.D. 5-9. Formed with evolution of hydrogen, 
 when acrolein hydrochloride is heated with 
 potassium hydroxide (not NaOH). Needle- 
 shaped crystals lighter than water, having an 
 aromatic odour. Partly reconverted by distilla- 
 tion into acrolein. Volatilises undecomposed 
 with aqueous vapour. Insoluble in cold, sparingly 
 soluble in hot water, easily in alcohol and ether. 
 Exerts only a feeble reducing action on ammo- 
 niacal silver solution. Not affected by dilute 
 alkalis, but changed more or less into acrolein 
 by heating with mineral acids. Does not com- 
 bine with ammonia. Unites with dry HCl-gas 
 forming )3-chloropi'opionic aldehyde 
 CH,C1.CH,.CH0 (Geuther a. Cartmell, A. 112, 8). 
 
 2. Acrolein resin. Formed by heating 
 acrolein for a week with 2-3 vol. water at 100°, 
 as a brown resin which begins to melt at 100°, 
 is moderately soluble in hot water, easily in 
 alcohol and in ether. Heated with ammoniacal 
 silver solution, it reduces the silver in specular 
 form. Reconverted into acrolein at 100° (G. a. C). 
 
 3. Hexacroleio acid C„H2.,05. Formed 
 fty treating acrolein with alcoholic or aqueous 
 potash or with moist silver oxide. Yellow 
 amorphous body, insoluble in water, easily 
 soluble in alkalis, alcohol, and ether. Has a 
 slight acid reaction. Salts: NaCjgHjjO,,: brown 
 and amorphous. Ca(C,jH230j),^ : yellow flocculent 
 precipitate insoluble in water and in alcohol. 
 Barium salt ; amorphous ; decomposed by COj 
 (Claus. A. Suppl. 2, 120). H. W. 
 
 ACEOLEIN - DIPHENYIAMINE v. Di- 
 
 PHENYL-AMINE-ACROLEIN. 
 
 ACKOLEIN-UREA C^HgN^O, i.e. 
 
 C0N,H,(C3H,). 
 
 Formed by the action of acrolein on urea in 
 
 ulcoholic solution (Leeds, A.O.J. 4, 58 ; B. 15, 
 
 yeo). White powder; sol. ^loohpl, ether, or 
 
 CSj. Other bodies are also formed (Sohiff, Ai 
 151, 206 ; B. 15, 1393). 
 
 ACROLElN-m-XYLIDINE v. to-Xylidinb- 
 
 ACKOLEIN. 
 
 ACEOPINACONE G^S^fi^, 
 i.e. CH2:CH.CH(0H).CH(0H).CH:CHj (160°- 
 180°) S.G.l^ -99. Formed by action of zinc and 
 dilute HjSO, upon acrolein (Linnemann, A. 
 Suppl. 8, 268 ; L. Henry, J. pr. [2] 9, 477). It 
 is extracted with ether. It turns brown in air. 
 V. sol. alcohol or ether, insol. water. 
 
 ACBOTHIALDIHE. C5H,3NS25aq. A base 
 produced by the action of ammonium sulphy- 
 drate on acrolein at 0° (Schiff, Bl. [2] 8, 444). 
 Insol. water, v. si. sol. alcohol, ether, or CSj. 
 
 ACEYL-COLLOIDS v. j8-Bkomo-acrylic acid. 
 
 ACRYL-ALDEHYDO- PHENOXY- ACETIC 
 ACID C„H,„0,i.e. CHO.CHiCH.CsH^.O.CHj.CO^H 
 [153°]. TO [100°]. p [182°]. These three acida 
 are prepared by adding a cold aqueous solution 
 of aldehyde to a dilute solution of sodium o- 
 aldehydo-phenoxy-acetate at 60° (Elkan, B. 19, 
 3048). 
 
 ACEYLIC ACID G,Ufi„ i.e. CH^ : CH.CG.H. 
 Mol. w. 72. [8°] (140°) (Linnemann, A. 171, 294). 
 Formation. — 1. By oxidation of acrolein (p. 61) . — 
 2. By heating /3-iodopropionic acid with sodium 
 etbylate: CH2l.CH5,.CO.,H -h NaOEt = 
 
 Nal + EtOH + CHj : CH.CO.,H. 
 (v. Schneider a. Erlenmeyer, B. 3, 339).— 3. By 
 heating ;3-iodopropiomc acid with lead oxide. — 
 4. Together with propyl alcohol and other pro- 
 ducts, by heating allyl alcohol with KOH (Tol- 
 lens, Z. [2] 6, 457).— 5. From iodoform and 
 sodium ethylate (Butlerow, A. 114, 204).— 6. By 
 debromination of o-j8-dibromopropionio acid 
 with zinc-dust, 
 
 CHjBr.CHBr.C02H-Br, = 0H, : CH.CO^H. 
 7. By heating dichlorallylene with water : 
 CClj : C : CH^ + 2H2O = 2HC1 -1- CHo : CH.CO^H 
 (Pinner, B. 7, 66). -8. By the distillation o{ 
 hydracrylates C3H5O3 = CjHjOj + H^O (Beilstein, 
 A. 122, 372). 
 
 Preparation. — Acrolein mixed with 3 vol. 
 water is poured upon recently precipitated silver 
 oxide suspended in water in a vessel protected 
 from light ; the liquid is heated to boiling ; so- 
 dium carbonate added to slight alkaUne reaction; 
 and the mass, after evaporation to dryness, is 
 treated with dilute sulphuric acid. The liquid 
 is filtered (hexacroleic acid and reduced silver 
 remaining on the filter) and the filtrate is dis- 
 tilled, acrylic acid then passing over (Claus. A. 
 Suppl. 2, 117). 
 
 Properties. — Colourless Uquid having a pun- 
 gent odour like that of acetic acid ; solidifying 
 at low temperatures ; misoible with water. 
 
 Reactions.— 1. Converted by sodium-amalgam 
 and by boiling with zinc and dilute sulphuric 
 acid into propionic acid (Linnemann, A. 125, 
 317) . — 2. Fusion with KOH gives formic and acetic 
 acids : C3H^0j -1- 2Hfi = CH A -t C^H^Oj + H, 
 (Erlenmeyer, A. 191, 376).— 3. Unites directly 
 with bromine forming o;3-dibromopropionio acid, 
 CH2Br.CHBr.CO2H, and with hydriodic acid, 
 forming /8-iodopropionio acid, CHjI.CHj.COjH 
 (WislicenUB, .4. 166, 1). — 4. Its alcoholic solution 
 saturated with HCl, yields ethyl j8-chloropro- 
 pionate, CHjCl.CHj.COjCjHs (Linnemann, A. 
 163, 96). — 5. Unites with hypochlorfiys acid^ 
 forming /3-chlprpli|<ctic aoi4 
 
ABIPIO AOID. 
 
 es 
 
 OHj : CH.COja + ClOH = CH^Ol.CHOH.OO.H 
 (Mellikow, B. 12, 2227 ; 13, 2154). 
 
 Salts. — All except the silver salt are easily 
 soluble in water. Give off part of their acid at 
 100°, leaving basic salts ; the K-, Ba-, and Zn- 
 salts decomposing in this manner even at ordi- 
 nary temperatures. — KCjHjOjis'very deliquescent 
 (Clausius). — NaA', microscopic needles. 100 
 pts. cold alcohol dissolve 0'7 pt. of this salt 
 (Zotta, A. 192, 105). Dissolves easily in 90 p.c. 
 alcohol. Melts with deoomposition above 250° 
 (Linnemann). Converted by heating with 
 aqueous soda at 100° into the isomeric bydra- 
 crylio acid CHjOH.CH^.OOjH (Linnemann, B. 
 8, 1095). — CaA'j: needles (Caspary a. ToUens). 
 — SrA', : small rhombic plates very soluble in 
 water. — ZnA'^: small scales (Clausius).—PbA'2: 
 shining needles soluble in alcohol. — AgA' : floo- 
 sulent precipitate crystallising from boiling 
 water in prisms (Caspary a. ToUens, A. 1G7, 
 2-10). 
 
 Ethers.— MeA' (80-3°) (Weger) S.G.2 -934. 
 From methyl o-j8-di-bromo-propionate, MeOH, 
 Zn andH.,SO, (C. a. T. ; Kahlbaum, 5. 13, 2349). 
 — EtA' (98-5°) (W.) ; (101-5°) (C. a. T.). From 
 ethyl a-j8-di-bromo-propionate, EtOH.Zn and 
 H,SO^.— PrA' (122-9°)(W.). From propyl a-j3-di- 
 bromo-propionate, PrOH, Zn and H^SOj. — AUyl 
 ether. 03H5A'_(119°-124°) (0. a. T.). 
 
 Other derivatives of acrylic acid are described 
 
 as : BliOMO-AOKYLIO acids, CHLOBO-AOKYLiC ACIDS, 
 
 CnLOEo-BKOMO-ACKTiiio ACID, Amido-aoeylio acid, 
 Beojio-iodo-aobylic acid, Iodo-aceylio acid. See 
 also HYDBACBYiiic acid. 
 
 Paraorylio Acids (CjH^O^jn. — An acid pro- 
 bably having this composition is formed by the 
 action of potassium cyanide on ethyl a-chloro- 
 propionate at 150°. Short prisms melting at 
 180°-182°. Gives a brown red pp. with ferric 
 chloride (Karetnikoff, /. M. 9, 116). — Another 
 paracrylic acid is formed by boiling aqueous 
 Is-iodopropionic acid with excess of silver oxide, 
 till the solution becomes coloured, and metallic 
 silver begins to separate. The same acid is 
 formed when hydraorylio acid C3H11O3 is left in 
 contact for several days with 1 mol. bromine. — 
 Small crystals melting at 69° ; insol. in water, 
 slightly sol. in cold, easily in hot, alcohol. Easily 
 takes up HI at 157° and is converted into /3-iodo- 
 propionio acid. — The sodium salt is indistinctly 
 crystalline, dehquescent, does not melt at 180°. 
 The lead salt is soluble in water (Klimenko, J. B. 
 12, 102). 
 
 Di-acrylic acid CjHjO^. 
 
 At 260° sodium hydracrylate is decomposed 
 into water, sodium aerylate, and sodium di- 
 acrylate. On treating this mixture with water it 
 becomes very hot, and the sodium di-acrylate 
 takes up aq being converted into para-adipo- 
 malate, NajGjHjOs. The latter is thrown down 
 as a viscid syrup when an equal volume of alcohol 
 is added. At 200°-250° it loses aq, changing to 
 sodium di-acrylate, an amorphous deliquescent 
 mass, which becomes warm when breathed 
 upon, combining again with aq. Salts. — 
 NajA".— BaA". — CaA" : from calcic hydracrylate 
 at 220' (Wislicenus, A. 174, 285). 
 
 Para-adipomalic acid isa syrup. It is 
 reduced by HI to para-adipio acid CuH,„Oj. 
 Salts. — NaAHA aq.— BaA".- CuA" aq.— 
 VbA". All are amorphoiis. S- W. 
 
 ACTINOMETEH Instrument for measuring 
 
 chemical intensity of light. V. Physioal 
 Methods, sect. Optical. 
 
 ADENINE OjH.NsSaq. Occurs amongst the 
 decomposition-products of the contents of all 
 growing animal and vegetable cells. Formed, 
 amongst other products, by boihng nuolein 
 with dilute H^SO,. 
 
 Long rhombic needles (from NHjAq. (V. sol. 
 hot water, and in NaOHAq, v. si. sol. Na^COjAq. 
 Neutral to litmus. Insol. ether or CHCl... — By 
 nitrous acid it is converted into hypoxanthine 
 (KoBsel, B. 18, 79, 1928 ; H. 10, 248). C^HjAg^N,: 
 insol. NHjAq. (C5H,N,,),H.,S0^2Aq. SI. sol. wa'ter. 
 
 ADIPIC ACID C„H,„0„ 
 i.e. C0,H.CH,.CH2.CH.,.CH,.C02H. Mol. w. 146. 
 [149°]. S. 1-44 at 15°; S. (ether) -633 at 19° 
 (Dieterle a. Hell, B. 17,^ 2221) ; S. 7-73 at 18° 
 (Wirz, A. 104, 257). 
 
 Formation. — 1. By the oxidising action of 
 nitric acid on sebacio acid, and on natural fats, 
 e.g. hog's lard, coooanut oil, &o. — the first pro- 
 duct of the action being sebacio acid, which by 
 further oxidation is converted into adipic acid 
 (Laurent, A. Ch. [2] 66, 166 ; Bromeis, A. 35, 
 105 ; Malaguti, A. Ch. [3] 16, 84).— 2. By the 
 action of HI and phosphorus at 140° on muoio 
 acid (Crum Brown, A. 125, 19), or saccharic acid 
 (De la Motte, B. 12, 1572).— 3. From muconic 
 acid CjH^Oj and sodium-amalgam (Marquardt, 
 B. 2, 385). — 4. From fl-iodopropionio acid and 
 silver atl00°-160°; 2(CH2LCH,.C0,H) -1- Ag.,= 
 2AgI-H(CH2)^(C0,H)j (Wislicenus,^. 149, 22'l). 
 5. By reduction of di-acetylene di-carboxylio 
 acid, CO^H.C-C.C-C.COaH, or of hydro-muoonio 
 acid, CjH||(C02H)2, with sodium-amalgam 
 (Baeyer, B. 18, 680). — 6. By heating butane-m- 
 tetra-carboxylic acid (Perkin, B. 19, 2040). 
 
 Preparation. — Sebacio acid is boiled with 
 nitric acid, whereby it is converted into a mix- 
 ture of adipic and succinic acids, which are 
 soluble in water. The nitric acid is then eva- 
 porated off, and the residue crystallised from 
 water. It is then fused and the solidified mass 
 is pulverised and treated with ether, which 
 dissolves the adipic acid, leaving a small quan- 
 tity of succinic acid (Arppe, Z. 1865, 300). 
 
 Properties. — Monoolinio laminas, flat needles, 
 or feathery groups of needles. Sparingly soluble 
 in cold water, freely in alcohol and ether. It 
 has a tendency to form supersaturated solutions. 
 Converted into butane by distilling with large 
 excess of CaO (Hanriot, G. B. 101, 1156). 
 
 Salt s. — The ammonium salt (NHJjA" forms 
 monoclinic crystals resembling augite ; a : 6 : = 
 ■688 : 1 : -979 ; /3 = 82°14' (A. 217, 143). S. 40 at 14°. 
 At 150° it gives off all its NH3.— NajA"2aq.— 
 Na2A"Aaq : very soluble pearly plates. — K^A" — 
 BaA": white pp. S.12-04 at 12°; 7-47 at 100°. 
 SrA"|aq.— CaA"aq. — CaA"2aq : minute needles 
 (from alcohol), giving up their water at 
 100° (Laurent, 0. R. 31, 351).— MgA"4aq: 
 prisms. S. 25 at 15°.— ZnA"2aq.— CdA"2aq.— 
 CuA"aq.— CuA"2aq. — PbA" : small glistening 
 plates, S. -021 at 16°.— HgA" : white crystalline 
 pp.— Ag.jA": small glistening plates, S. '016 at 
 14°. — The ferric salt is a brown-red insoluble pp. 
 For more detailed description of salts v. Dieterle 
 a. Hell, B. 17, 2221. 
 
 Ethyl ether.— Ei\M' (245°) (Ajppe, ^. 
 1865, 302), 
 
64 
 
 ADIPIO AOID. 
 
 Amide 0,Ha(CO2NHj)2 [220°] S. -44 (Henry, B/. 
 43, G18).— Dimethyl-amide OjHa^COjNHMe), 
 [151°-153°] (H.). 
 
 Derivatives of adipic acid v. Bbomo-adipio 
 
 ACID, OXY-ADIPIO ACID. H. W. 
 
 Para-adipic Aci4. — ^Formed by the action of 
 HI on paradipimalio acid, CbHidOs — a decompo- 
 Bition product of sodium hydraorylate v. di- 
 AoEYLio ACID. — Syrupy. — ZnOjHgOj.SHjO. Vis- 
 cid flooculent pp. (Wislicenus, A. 174, 295). H. W. 
 
 Iso-adipic acid C4Hs(COjH)j.[192°].S. 1 at 22°. 
 A product of the action of bromine on the sul- 
 phate of cyanethine (g;. v.). The product is 
 extracted with ether ; on evaporation this leaves 
 an oil which reacts violently with strong NHj, 
 forming crystals of the amide of butane dicar- 
 boxylic acid, CjH8(CONH2)2. Converted by 
 boiling dilute H^SOj or HCl into the acid. 
 (E. V. Meyer, J. pr. [2] 26, 358). 
 
 Properties. — Bows of prisms, or, from hot 
 concentrated solution in water, globular aggre- 
 gates. Begins to sublime at 100°. Eeadily 
 soluble in alcohol and ether. 
 
 Salts. — A"H(NHj). Solutions of this salt give 
 the following precipitates : FejClj, reddish-white ; 
 AgNOj, white ; CuSO,, green ; Pb(0Ac)2, on agi- 
 tation, prisms crossing one another; HgClj, 
 CaClj, BaClj give no pps.— A"Ag2.— A"Cu.— 
 A"Pb,iact. 
 
 Amide. — (See above.) — Does not melt at 260°. 
 Prisms with pyramidal ends (from water). 
 
 Adiplc acid C4Hj(C02H)2 (Myd/ro-pyro-cin- 
 chonic acid) [194°]. Small white needles or 
 glistening prisms ; easily soluble in alcohol and 
 ether, less in water. Is the chief product of reduc- 
 tion of pyrocinchonio acid C02H.CMe:CMe.C0.^H 
 or of the reduction of di-chloro-adipio acid 
 COjH.CClMe.CClMe.COjH. By conversion into 
 the anhydride and redissolving in water it is 
 converted into the isomeric adipio acid melting 
 at [240°]. 
 
 Salts.— CaA." IJaq: very sparingly soluble 
 white silky needles. — SrA" IJaq: sparingly soluble 
 needles. — PbA" 3aq : white crystalline pp. — 
 A"Cu : green pp. 
 
 ^wMriie.-9^j^^j-^0>0. [187°] (Otto 
 
 a. Beckurts, B. 18, 838 ; Eoser, B. 15, 2012 ; 
 Iieuckart, B. 18, 2344). 
 
 Co7istitution. — Probably identical with the 
 above iso-adipic acid. 
 
 Adipic acid (G,B.,(G0.,I1).X [240°]. Glisten- 
 ing plates, or prismatic needles. Formed by 
 isomeric change from the preceding adipio acid 
 [194°] by conversion into the anhydride and re- 
 dissolving in water. 
 
 Salt. — Ag^A" : sparingly soluble white crys- 
 talline pp. The acid does not give an anhydride 
 on heating (Otto a. Beckurts, B. 18, 843). 
 
 Adipic acid C,B.^(CO^B.)^ [165°-167°]. Di- 
 viethyl-succinic acid (?) — From aceto-acetic ether 
 by means of sodium, a-bromo-propionic ether, 
 and Mel (Hardtmuth, A. 192, 142). 
 
 Salts.— 'ShK" : flocculent pp.— Ag^A". 
 
 Adipic acid CjH^Oj [142°-143°].— From tro- 
 pilene {q. v.) and HNOs(S.G. 1-285) (Ladenburg, A. 
 217, 140). 
 
 Salts. — AgjA". — Ammonium salt forms tri- 
 clinio crystals : a : b : c - -8474 ; 1 : -6496 a = 
 90° 2Q'. = 95°10'. y - 100° §^'. 
 
 Constitution.— PtdbMj identical with «-di- 
 methyl-snocinic acid (g. v.), 
 CO2H.CMej.CH2.COaH. 
 
 Other Isomerides of adipio acid are described 
 
 as MEIHYL-ETHYL-MALONia, PboPYL-MALONIO, ISO- 
 
 Peopyl-malonic, di-Methyii-sdocinio, Ethyl- 
 SDOciNio, and Methyl-olutabio acids. 
 
 Adipic (?) aldehyde ObH,„Oj.— Formed by 
 treating acetic aldehyde with zinc-turnings at 
 100°3C2H,O-H2O = CsH,„O2. Smells like wild 
 mint, and appears to be decomposed by prolonged 
 distillation, with formation of H^O and higher 
 condensation products. Unites with alkaline 
 bisulphites, forming crystalline compounds (Ri- 
 ban, G. B. 75, 98). H. W. 
 
 ADIFOCEBE. — A fatty substance produced 
 in the decomposition of animal substances in 
 moist ground; first found by Fourcroy in the 
 Gimetiire des Irmocens at Paris. Consists of 
 palmitic, stearic, and oleic acids (Gregory, A. 
 61, 362 ; Wetherill, /. 1855, 517). According to 
 Ebert (B. 8, 775) it consists essentially of pal- 
 mitic acid, together with margaric and oxymar- 
 garic acids, CijHjjOj and CiiHjjOj. H. W. 
 
 ADIPOMALIC ACID CsH.oOs, is formed by boil- 
 ing bromadipic acid with potash, as a viscid mass 
 which becomes crystalline. — PbCjHgOsSHjO. 
 White precipitate which dissolves in hot solution 
 of lead acetate and separates therefrom in na- 
 creous scales. Gives off 2H2O at a moderate heat 
 (Gal a. Gay-Lussac, C. B. 70, 1175). H. W. 
 Para-adipo-malic acid v. di-AoBYUO acid. 
 ADIPOTARTARIC ACID C„H|„Os. Formed 
 by heating pulverulent dibromadipic acid with 
 water at 150°. Moderately soluble in alcohol 
 and ether. Much more soluble in hot than in 
 cold water, and separates in monoclinic laminsB. 
 Optically inactive. Solution agitated with KOH 
 yields a crystalline pp. resembling cream of 
 tartar (Gal a. Gay-Lussac). H. W. 
 
 ADONIDIN. Aglucosidein Adonis vemalis, 
 resembling digitalin in physiological action 
 (Cervello, Ph. [3] 13, 129 ; Mordagne, Ph. [3] 
 16, 145). 
 
 ADONINIDINE. A poisonous substance in 
 Adonis cupaniana (Cervello, G. 14, 493). 
 
 .ffiSCIGENIN 0,2Hz„0,. Formed, together 
 with glucose, by passing HCl-gas into a boiling 
 alcoholic solution of teleGsoiu (infra) 
 
 OisHaoOj -I- H^O = CijHjjOj + CbHijOu 
 Indistinctly crystalline powder, insoluble in 
 water, soluble in alcohol. Strong sulphuric acid, 
 in presence of sugar, dissolves it with blood-red 
 colour. Acetyl chloride converts it into a 
 diacetate (Eochleder, J. 1867, 751). H. W. 
 
 .ffiSCINIC ACID Cj^H^Oj. Occurs in small 
 quantity in the cotyledons of ripe horse-chestnut 
 seeds. Formed, together with propionic acid, 
 by boiling argyrsescin with potash-lye : 
 
 C2,H„0,j -I- 2K0H = KOjjHasO.j + KCHjOj, 
 and together with butyric acid by similar treat- 
 ment of aphrodiEscin : 
 
 CsjHgjOjs 4 3K0H = 2KC2jHsoO, J + KC,H,Oj. 
 Gelatinous mass, becoming partially crystal- 
 line. 
 
 Eesolved by hydrochloric acid into glucose 
 andtelaescin: 
 
 CzjHjjO,! -^ HjO = CjHijOj + C,sH,,0,. 
 The acid potassium salt EC2jH,gO,2,C24H„0,„ 
 forms silky needles, si. sol. water (Bochledei). 
 
 H. W. 
 
^DuTJLETIN. 
 
 06 
 
 JESCIOBGEtiT 0,H,NO,. A Eubstance re- 
 sembling orcein, formed by the action of ammonia- 
 Tapour on moist paraaesculetin : 
 
 CHjO. + NH, + = H,0 + C,H,N05 
 (Eochleder, J. 1867, 753). H. W. 
 
 ^SCIORCIN CsHsO,, is formed by the 
 action of sodium amalgam on eesooletin. Dis- 
 solves in alkalis OTth green colour quickly 
 changing to red. Converted by ammonia into 
 lesoioroein (Eochleder, ibid. 751). H. W. 
 
 .ffiSCIOXALIC ACID CjH^O^H^O. Produced, 
 together with formic and oxalic acids, sometimes 
 also protooateohuio acid, by boiling eesculetin 
 ■with very strong potash lye. More easily 
 obtained pure by boiling SESculetin for several 
 hours with baryta water in an atmosphere of 
 hydrogen. Very minutely crystalline mass. 
 Gives with ferric chloride a red-brown colour, 
 changing to purple-violet on addition of sodium 
 carbonate ; with ferrous sulphate and a small 
 quantity of sodium carbonate, a deep blue 
 colour {Eochleder, /. 1867, 752). H. W. 
 
 ffiSCULETIC ACID CaHgOs, 
 i.e. C5H2(0H),CH:CH.C02H. Formed by boiling 
 tESCuletin with baryta (Eochleder, J. pr. 69, 211). 
 
 Salts.— BaK',.—5FhC^fi„G,B.fi,. Acids 
 •which contain the group CH:CH.C02H, such as 
 f umario and maleic acids and the coumaric acids, 
 are usually capable of existing in two forms, 
 one of which can be easily transformed into the 
 other, ^sculetic acid and its methyl deriva- 
 tives are at present known in one form only, but 
 tri-ethyl asculetic acid and its ether have been 
 obtained in two forms, which are described below 
 as derivatives of (a) and {$) sesculetic acid. 
 
 Tri-methyl derivative C5H2(OMe)3.C2H2.C02H 
 [168°]. Needles. Solubleinalcohol,ether,benzene, 
 and hot water, sparingly in cold water. Formed 
 by the action of alcoholic KOH on the following 
 body. Its neutralised solution gives pps. with 
 AgNOa, CuS04,ZnS0„ and Pb(0Ae)2. 
 
 Methyl ether CsHj(OMe)3.C2Hj.C02Me 
 [109°]. Prisms. Distils undecomposed at a very 
 high temperature. Soluble in alcohol, ether, 
 and benzene, insoluble in water. Formed by 
 evaporating dimethylfesculetin (1 mol.) with a 
 solution of NaOH (2 mols.) nearly to dryness 
 and digesting the residue dissolved in methyl 
 alcohol with methyl iodide (Tiemann a. Will, B. 
 15, 2082). 
 
 (o)-iEsoTii,ETio Aon) C,H5,(OH),.CH:CH.C02H 
 Tri-ethyl-derivative CeH2(OEt)3.C2H2.C02H 
 [103°]. Prepared by saponification of its ether. 
 Changes when heated to its boiling point or boiled 
 with strong HClinto the (;3)-isomeride. 
 
 On reduction vrith sodium-amalgam the tri- 
 ethyl-derivatives of both (o)- and (/3)- sesculetic 
 acid give the same tri-ethoxy-phenyl-propionic 
 acid, CjH2(0Et)3CH2CH2C02Et, and with alkaline 
 KMnOj the same tri-ethoxy-benzoio aldehyde, 
 t!,H,(OEt),CHO. 
 
 Ethyl-Ether CjH2(OEt),.C5,H2.COjEt 
 [51°], thick yellow prisms, very soluble in alcohol, 
 ether, and benzene, insoluble in water ; prepared 
 by heating di-ethyl-sesculetin with sodium 
 ethylate and ethyl-iodide at 100°, avoiding an 
 excess of ethyl-iodide and longer heating than 
 four hours ; on heating to its boiling point 
 (above 230°) it changes into the (;8)-isomerida 
 (Will, i?. 16, 2110). 
 
 (Bj-^souLBiio Aoro C,Hj(0H)j.CH:CH.C02H 
 
 Vot. I. 
 
 Tri-ethyI-derivativeCJB.,{0^i)s.C^n,.COfi 
 [144°], colourless silvery crystals, easily soluble 
 in alcohol, ether, and benzene, nearly insoluble in 
 water ; formed by saponification of its ether, or 
 by heating the (o) -isomer to its boiling point. 
 
 Ethyl-Ether C5H,(0Bt)s.CjHj.C0,Et 
 [75°], glistening tables, easily soluble in alcohol^ 
 ether and benzene, insoluble in water, distils 
 undecomposed above 360° ; prepared by heating, 
 di-ethyl-cesculetin with ethyl iodide and sodium 
 ethylate at 100° for 8 hours ; it is also formed 
 by heating the (o) -isomeric ether to its boiling: 
 point (Will, B. 16, 2108). 
 
 a:SCULETIN 
 
 >CH:CH 
 CAO„ i.e. C,H,(0H)2< I 
 \o . CO 
 Occurs in very small quantity in horse-chestnut ■ 
 bark. Formed by the action of dilute acids or 
 of emulsin on tesouliu (Eochleder, /. 1863, 589). 
 
 Preparation. — A solution of sesoulin in warm- 
 strong hydrochloric acid is boiled till it solidifies- 
 to a crystalline pulp ; this after washing with' 
 water is dissolved in warm alcohol ; the solution' 
 precipitated with lead acetate ; the precipitate' 
 of lead-iBsculetin is washed with alcohol andi 
 afterwards 'with boiling water, then suspended 
 in boiling water and decomposed by hydrogen 
 sulphide ; the liquid is filtered at boiling heat ; 
 and the sesculetin which separates on cooling is 
 recrystallised (Zwenger, A. 90, 68). 
 
 Properties. — Very thin shining needles or 
 scales consisting of C9H,04,H20 ; bitter, slightly 
 soluble in cold, more soluble in warm, water and 
 alcohol, nearly insoluble in ether. Aqueous 
 solution exhibits a very faint blue fiuorescence, 
 considerably exalted, however, by addition of a 
 small quantity of ammonium carbonate. Deep 
 green coloration with ferric chloride ; yellow 
 precipitate 'with lead acetate. ^souletin dis. 
 solves in hydrochloric acid ; and is oxidised by 
 nitric acid to oxalic acid. By boiling with very 
 strong potash-lye, it is converted into formic, 
 oxalic, protocatechuio, and ffiscioxaho acids ; by 
 sodium amalgam into sesoiorcinol. 
 
 A hydrate CjHjO^.JH^O, isomeric with 
 daphnetin, occurs in horse-chestnut bark in 
 larger quantity than anhydrous eesculetin. 11 
 is less soluble in water than the latter, and 
 crystallises therefrom in small granules. Sub- 
 limes at 203°, and melts above 250°, converted 
 into sesculetin by heating at 200° in COj-stream, 
 also when crystallised from hot hydrochloric 
 acid or from absolute alcohol mixed with strong 
 hydrochloric acid (Eochleder, J. 1863, 588). 
 
 JSsculetin unites with MgO (Schiff, B. 13, 
 1951), and with solution of lead acetate forms, 
 a lemon-yellow precipitate ha'ving the oomposi-, 
 tion PbCjH^O^ (Zwenger, A. 90, 63). 
 
 Diace iyZcEscitZe^ira CijHiijOj i.e. CgHjAcjO,, 
 [134°] formed by treating ssculetin with acetic 
 anhydride and sodium acetate. Crystallises from 
 alcohol. in prisms ; from water in needles ; dis- 
 solves in alcohol and ether; is not coloured by 
 ferric chloride ; is easily saponified by heating 
 with strong sulphuric acid at 30° to 40° (Nach- 
 bauer, A. 107, 248). 
 
 Bromomsculetins. — CjH^BrjO,, formed 
 by treating dibromoesculin with strong sulphuric 
 acid, crystallises from alcohol in yellowish 
 needles melting at 233°, slightly Eolnble in 
 
 F 
 
^SCULETIN. 
 
 water.— CsHsBrjOj, formed by adding bromine 
 to a hot solution of lesouletiu in glacial acetic 
 acid, crystallises from alcohol in long yellow 
 needles, melting with decomposition at 240° 
 (Liebermann a. Knietsch, JB. 13, 1591). 
 
 Di-acetyl-di-bromo-cBsculetin 
 CisHsBr^Os i.e. CpH^Ao^BrjO, [177°]. 
 Formed by aoetylation of di-brom-sesculetin 
 crystallises from alcohol in slender needles. 
 
 Di-acetyl-tri-bromo-asculetin 
 C,3H,Brj08 i.e. CgHAo^BrjOj, formed by aoetyla- 
 tion of tri-bromsesculetin, or by bromination of 
 diacetylsesculetin, crystallises in long very thin 
 needles, melting, with decomposition at 180°- 
 182° ; insoluble in water (L. and K. ; Liebermann 
 a. Mastbaum, B. 14, 475). 
 
 Methyl-asculetin C,„'B.gOi i. e. 
 CgHi02(0H)(0Me) [184°] is formed by heating 
 Bssculetin (6 pts.) with methyl iodide (15 pts.) and 
 KOH (4 pts.) dissolved in a small quantity of 
 methyl alcohol till the liquid becomes neutral. 
 On treating the product, after the greater part of 
 the methyl alcohol has been given ofi, with 
 water and hydrochloric acid, methylsesculetiu 
 crystallises out, while dimethylsesouletin re- 
 mains in solution. 
 
 Shining needles. Soluble in cold dilute 
 alkalis and in ammonia, and precipitated there- 
 from by acids. Decomposed by boiling aqueous 
 alkalis like sesculetin. Insoluble in cold, but 
 soluble in hot water ; easily soluble in alcohol, 
 ether and benzene, insoluble in light petroleum 
 (Tiemann a. Will, B. 15, 2075). 
 
 Dimethyltesculetin, C„H,j04 i. e. 
 CsH,0j(0Me)2 [144°], is deposited from the 
 mother-Hquor of the preceding compound on 
 addition of ammonia. Shining needles. Easily 
 ■soluble in alcohol, ether, and benzene, nearly 
 insoluble in light petroleum ; insoluble in cold, 
 soluble in hot, water. Dissolved by H2SO4 and 
 precipitated by water. H. W. 
 
 Ethyl-tssculetin CjHA (OH) (OEt) 
 [143°], colourless crystals, soluble in alcohol, 
 ether, benzene, alkalis, and hot water, insoluble 
 in cold water. 
 
 Bi-ethyl-cssculetin C9H402(0Et)2 
 1^109°], colourless silvery plates, soluble in alco- 
 hol, ether, and benzene, sparingly in hot water, 
 insoluble in cold water and cold aqueous alkalis 
 (Will, B. 16, 2106). 
 
 Constitution. — .SIsouletin contains two hy- 
 droxyls, for it forms a di-acetyl derivative. The 
 formation of protooatechuic and of tri-ethoxy- 
 propionio acids and of tri-ethoxy-benzoic alde- 
 hyde from teaculetin and tri-ethyl-sesculetio 
 acids respectively show them to be aromatic 
 bodies. If we compare, the formulae for cou- 
 marin CsHjOj, umbelliferon, CgHjOj and sescu- 
 letin, CjHijO,, we see that the two latter may be 
 regarded as oxy- and di-oxy-coumarin. That 
 umbelliferon is oxy-coumarin has been proved 
 by synthesis (Tiemann a. Reimer, B. 12, 993). 
 All three bodies are fluorescent in alkaline solu- 
 tion, but methyl-umbelliferon, CgH502(0Me) and 
 methyl-jBsculetin fluoresce more strongly than 
 umbelliferon and sesculetin respectively, while 
 di-methyl-ffisculetin, C8H402(OMe)j, fluoresces 
 most strongly of all. 
 
 When coumarin (1 mol.) is evaporated with 
 KaOH (2 mols.) and the residue digested with 
 
 MeOH and Mel, it tales up the elements ol 
 MCjO, becoming methylio methyl-o-coumarate ; 
 .CH:CH 
 aH,< I + 2K;OH + 2MeI = 
 
 \o .00 
 C5HiOE).CH:CH.C02K + H^O -^ 2MeI - 
 CsH4(0Me).CH:CH.C02Me + H^O + 2KI. 
 But two isomerides may be got in this way, one, 
 (a), when excess of Mel is avoided and the diges- 
 tion is for 3 hours at 100°, the other (;3) by di- 
 gesting for a longer time at 150° (W. H. Perkin, 
 C. J. 81, 417 ; 39, 409). Precisely the same re- 
 action occurs when di-ethyl-sesouletin is digested 
 with NaOEt and EtI, the two isomeric ethers, 
 CBH4(OEt)3.CH;CH.C02Et, being formed, the (a) 
 compound when excess of EtI is avoided and 
 the heating kept up for only four hours, the (;8) 
 compound by more prolonged heating. In both 
 cases the (a) compounds are changed by distil, 
 lation into the (;3) compounds. These reactions 
 indicate analogous structure. 
 
 It is however, remarkable that di-methyl- 
 sesculetin does not form a dibromide as cou- 
 marin does. 
 
 Parasesouletin. — C5H5O4 (?). — Obtained by 
 treating sesculetin with aqueous NaHSO,, at 
 boihng heat, then adding rather dilute sulphuric 
 acid and afterwards alcohol, whereby NajSO^ is 
 first thrown down, and then the compound 
 CjHjOj.NaHSOs, which when decomposed by 
 sulphuric acid yields hydrated parasesculetin 
 0511,04,231120 in indistinct crystals easily soluble 
 in water, sparingly in ether, more freely in alco- 
 hol, less easily in wood-spirit, nearly insoluble 
 in acetone and chloroform, soluble in glacial 
 acetic acid. Parasesculetin exerts a strong re- 
 ducing action in alkaline solution, throws 
 down metallic copper from Fehling's solution at 
 50°-70°, and reduces indigo at ordinary tempera- 
 ture. Not attacked by acetic anhydride. Ex- 
 posed in the moist state to ammonia-vapour, it 
 quickly turns red, then dingy- violet, and changes 
 after a few minutes to a sky-blue liquid, which 
 when left over sulphuric acid gives off ammonia, 
 and again turns red, from formation of sesoiorcein 
 (p. 65). Converted by heating with aniline into 
 sesculetanilide(Eoohleder, ^.1868, 589 ; 1867, 752). 
 
 CBH|iOi,NaHS03,iH20 forms small needles. 
 According to Liebermann a. Knietsch {J. 1880, 
 1028), the true formula of this compound is 
 CjHgOjjNaHSOj ; it probably therefore contains 
 a hydro-SBSCuletin. H. W. 
 
 .ffiSCULIir CisHiA [204-5°-205°] (H. 
 Schifi, B. 14, 802).— Occurs in the bark of the 
 horsechestnuty (Msculus Hippocastanum) es- 
 pecially in March before the buds open (Minor, 
 B. J. 12, 274 ; Jonas, A. 15, 266). 
 
 Preparation. — 1. Horsechestnut bark is ex- 
 hausted by boiling with water ; the extract is 
 precipitated with lead acetate, and the filtrate, 
 freed from lead by hydrogen sulphide, is evapo- 
 rated to a syrup. The sescuUn then crystallises 
 out after a few days, and may be purified by 
 washing with water, and crystallising, first from 
 weak spirit (40 p.c), then from boiling water 
 (Eochleder a. Schwarz, A. 87, 186).— 2. The 
 bark is exhausted with weak aqueous ammonia ; 
 the solution evaporated to dryness ; the residue, 
 mixed with alumina and exhausted with alcohol 
 of 95 p.c. ; and the sesculin which crystallises 
 from the alcohol is agitated with water and 
 
AFFINITY. 
 
 67 
 
 ether, and finally washed with benzene (Fair- 
 thorne, C. N. 26, 4). 
 
 Properties. — Small prisms, composed oJ 
 C,5H,j09,2HjO. Bitter, sparingly soluble in cold, 
 easily in boiling water, the solution coagulating 
 on cooling. 1 pt. dissolves in 24 pts. boiling 
 alcohol. Very slightly soluble in absolute ether, 
 soluble in glacial acetic acid and ethyl acetate 
 (Trommsdorff, A. 14, 200). The aqueous solu- 
 tion is slightly acid, and exhibits a blue fluores- 
 cence which disappears on addition of acids, 
 but is restored by alkalis. Dissolves in alkalis 
 more readily than in water. 
 
 Reactions. — 1. .ffisoulin is resolved at 230° 
 into gluoosan and CBSculetin : 0,5H,|j09 = 
 CsHijOs + CsHsOi(Schifi) ; by digestion with 
 dilute mineral acids or by treatment with 
 emulsin, into glucose and sesculetin (Eochleder 
 a. Schwarz, A, 88, 356) ; by boiling with baryta- 
 water into glucose and sesculetic acid (Bochleder 
 /. pr. 69, 211).— 2. Converted by sodium- 
 amalgam into hydrsBsculin (Eochleder). — 3. 
 Agitated with a small quantity of nitric acid, it 
 yields a yellow solution which assumes a deep 
 blood-red colour on addition of ammonia, this 
 reaction affords a delicate test for assculin 
 (Sonnenschein). — 8. Cone. HjSO, (4 drops) 
 followed by NaOClAq gives a violet colour (Eaby, 
 .f. Ph. [5] 9, 402). 
 
 ^sculin forms with magnesia, the compound 
 2C,5H,|,09Mg(0H)2, which is yeUow and dis- 
 solves readily in water (Schiff, B. 13, 1952). 
 PentacetylcEsculin 
 
 CjsHzsOh i.e. CisHjiAosOg. 
 Formed by heating sesculin with acetic oxide 
 crystallises from alcohol in small needles melt- 
 ing at 130° (Schift, A. 161, 73 ; B. 13, 1952). 
 
 Di-bromo -CBSCulin C,5H,4Br209. 
 Is obtained by gradually adding bromine in 
 calculated quantity to a solution of sesculin in 
 glacial acetic acid. Crystallises from glacial 
 acetic acid in small needles ; melts and decom- 
 poses at 193°-105°. Sparingly soluble in alcohol, 
 still less in all other solvents (Liebermann 
 a. Knietsch, B. 13, 1594). 
 
 Pentacetyl-dibromo-CBSCulin 
 C25H24Br20n i.e. CjsHjBrjACsOg, prepared in like 
 manner from dibromsesculin, forms slender 
 needles, melting at 203°-206°, converted by 
 strong sulphuric acid into dibromssculetin. 
 
 PentabenzoylcBsculin C5JH35O,, i.e. 
 CijHuBZjOj, forms nodular groups of crystals 
 sparingly soluble in ether, freely in hot alcohol 
 (Schiff). 
 
 Trianilsesculin 
 CjsHjiNjOsi.e. 0,5H,5(NC,H5)308, from ssculin and 
 aniline by prolonged heating at 200°- Amor- 
 phous brown powder, soluble with red colour in 
 alcohol (Schiff, B. 4, 472). H. W. 
 
 JBTHAL V. Cettl Alcohol. 
 .ffiTHOKIERIN. The yellow colouring matter 
 of the flowers of ArMrrhm/wm Linaria. H. W. 
 
 APriNITY.— Chemical affinity is that pro- 
 perty of bodies in virtue of which, when brought 
 into contact, they react on each other, forming 
 new bodies. It can be called a force, in so far 
 as by its action energy is produced, namely, heat, 
 light, electrical or mechanical energy. And, 
 vice versd, energy must be employed to reverse 
 the action of chemical affinity, and to decompose 
 the combined substances. 
 
 Nothing is known as yet about the nature of 
 chemical affinity, nor has a satisfactory hypothesis 
 been suggested concerning it. The oldest con- 
 ceptions concerning the reasons why substances 
 react on each other reach back to Greek philo- 
 sophy ; nothing has survived of them except the 
 name affinity, which preserves the notion that 
 those substances which are of the same origin or 
 of the same kind, and which therefore are as it 
 were related to each other, possess the power of 
 mutual reaction. It is now known that the con- 
 trary of this is more correct. Moreover, the 
 reason of the greater or smaller facility with 
 which substances react chemically was conceived 
 to be somewhat similar to human qualities — sym- 
 pathy and antipathy. These conceptions held 
 sway as long as the philosophy of Aristotle 
 reigned. The breach with these ideas, which was 
 brought about by Galileo's mechanics, intro- 
 duced mechanical ideas into chemistry also. 
 The ultimate particles of substances were ima- 
 gined as furni jhed with points, edges, and hooks, 
 by the aid of which were brought about their 
 decompositions and combinations. Sir Isaac 
 Newton's discovery of the general mutual action 
 of masses introduced a new phase into the con- 
 ception of nature. The idea of an attractive 
 action between one small particle and another at 
 a distance was introduced by Newton himself 
 into chemistry, in order to explain the mutual 
 reactions of bodies. He did not, however, con- 
 sider the cause of chemical actions as identical 
 with that of general gravitation, but as different 
 from it, especially as regards the law concerning 
 action at a distance. 
 
 Later investigators, Buffon, Bergmann, Ber- 
 thollet, assumed, on the contrary, that both 
 forces are of the same nature, and that only the 
 circumstances under which chemical forces act — 
 especially the close proximity of the reacting 
 particles— cause an apparent difference. 
 
 An influence similar to that due to Newton's 
 astronomical discovery was exerted at the be- 
 ginning of this century by a physical discovery, 
 that of the electric current. The great chemical 
 activity of the current was soon noticed. By its 
 help Davy decomposed the alkalis and earths ; 
 and Berzelius made use of the phenomena of 
 electrical decomposition for the foundation of a 
 theory concerning chemical compounds, which 
 rested on the supposition that chemical attrac- 
 tion was nothing but the attraction of the oppo- 
 site electricities concentrated on the smallest 
 parts of substances. 
 
 The electro-chemical theory of Berzelius was 
 the first chemical theory which was based on 
 facts. Owing to this it obtained great import- 
 ance. Taking into account the needs of the 
 time, Berzelius developed his theory only with a 
 view towards classification ; but it did not con- 
 tribute anything towards the investigation of the 
 nature of chemical affinity. 
 
 The last great change in the views concern, 
 ing affinity took place in the middle of this cen- 
 tury, and was brought about by Mayer's and 
 Joule's discovery of the equivalence of ' forces,' 
 or more strictly, of ' the actions of forces.' It 
 was recognised that chemical affinity was to be 
 classed with mechanical, electrical, and thermal, 
 energy, in so far as it is convertible into any of 
 these, and can be produced from each of them. 
 
 7 2 
 
63 
 
 AFFINITY. 
 
 When this was known, the need to trace back the 
 mode of action of the forces of affinity to other 
 known actions of forces ceased to exist, as a 
 great many inferences could be drawn from this 
 experimental fact, and a special hypothesis did 
 not seem called for. 
 
 Two different views have been held concern- 
 ing the way in which chemical forces act, and 
 each of these has still its followers at the present 
 day. First it was imagined that the force acting 
 between two different kinds of matter is similar 
 to that acting between two masses ; it brings 
 the ultimate particles nearer together, and, if 
 under the given circumstances this is possible, it 
 produces combination. It would be difficult to 
 entertain different ideas concerning the simple 
 process of combination. The task becomes far 
 more difficult when it is a question of simulta- 
 neous decomposition and combination. Very 
 often a substance acta on another which is a 
 compound without combining with it as a whole, 
 but only combining with one of its constituent 
 parts, and expelling the other from the original 
 compound. The hypothesis indicated above re- 
 fers these facts to the opposite action of two 
 forces, similar to two mechanical forces opposite 
 in direction and unequal in magnitude, which 
 produce motion in the direction of the greater. 
 It was imagined that the stronger chemical 
 affinity overcame the weaker, and produced 
 chemical action in its own direction. 
 
 It was in accordance with this conception that 
 ' tables of affinity ' were compiled which were to 
 give an account of the force of chemical affinity 
 according to its order. Such tables were first 
 published in 1718 by H. Geoiifroy. They con- 
 tained, under the head of any one substance, a 
 series of others, all of which could enter into 
 chemical combination with the specified body. 
 They were so arranged that the preceding body 
 would always replace all the following bodies from 
 their combinations with the one at the head of 
 the list. Such tables of affinity, which were very 
 popular during the last century, culminated in the 
 works of Bergmann, who collected the ideas in- 
 dicated above in a theory of affinity. Bergmann 
 recognised that substances can react differently 
 according to circumstances, and therefore he 
 gave two tables for each substance, one for the 
 action in aqueous solution — ' in the wet way ' ; 
 the other for the action at the temperature of 
 fusion—' in the dry way.' Beyond this he kept 
 to the idea that chemical affinity always acts 
 exclusively in one direction, so that under all 
 circumstances a smaller affinity is overcome by 
 a greater. 
 
 To Claude Louis BerthoUet is due the great 
 merit of having shown this view to be too nar- 
 row. According to him, besides 'the intensity 
 of the forces,' the 'mass' of the reacting sub- 
 stances is of importance, in so far as under the 
 same conditions the action is the greater the more 
 of the reacting substances there is present. ' Toute 
 substance qui tend A entrer en combmaison, agit 
 en raison de son affiniti et de sa quantiti ' {Sta- 
 tique chimique,'p. 2). This is the concise expres- 
 sion of the new idea which BerthoUet introduced 
 into the theory of affinity. But it was reserved for 
 a much later time to develop this idea scienti- 
 iiaally, since one of the chief applications which 
 ii< author made of it — namely, the inference 
 
 that compounds according to fixed proportions 
 do not exist, but only such as vary in composi- 
 tion within fixed limits — was proved to be false. 
 The proof of this error which was given by 
 Proust, BerthoUet's compatriot, brought aho 
 the correct foundation into discredit. To this 
 must be added, that in the discoveries of Eichter, 
 Dalton, and Berzelius, the science found such 
 important and productive tasks that there was 
 no inducement to investigate what of truth was 
 left in the partially refuted hypothesis of Ber- 
 thoUet. The idea of ' influence of mass ' is the 
 first, but not the only, conception which tho 
 science owes to Berthollet. This chemist fur- 
 ther recognised the decided influence of the 
 physical states of the reacting bodies on the 
 final results of the actions of affinity. He 
 taught that the simple action, according to the 
 measure of affinity and mass, holds only for 
 homogeneous mixtures, but holds no longer when 
 by the appearance of certain substances in a 
 different state of aggregation the chemical equi- 
 librium is disturbed. The influence of ' cohesion ' 
 ajid -' Alasticiti,' on the results of chemical ac- 
 tions, were explained by him perfectly clearly ; 
 how first equilibrium is established in the usual 
 manner, but is afterwards disturbed by one of 
 the substances separating out in a different state 
 of aggregation ; in consequence of this, a fresh 
 quantity of this substance is formed, and is 
 again separated, and thus the process repeats 
 itself until the substance in question — gaseous 
 or solid — has been entirely, or almost entirely, 
 removed from the changing system. A chemical 
 reaction carried to completion, which had been 
 taken by Bergmann to be the normal case, ap- 
 pears, according to Berthollet, as the exceptional 
 case, and occurs only because of differences in 
 the states of aggregation of the reacting sub- 
 stances. 
 
 The decision between these two fundamen- 
 tally different views has not yet been completely 
 made. Even now, Bergmann's theory is pro- 
 pounded by some investigators, though in a 
 somewhat modified form. In place of the 
 greater or smaller affinity, the greater or smaller 
 production of heat is considered by these inves- 
 tigators as decisive of the course of a chemical 
 action ; the fundamental idea, however, the ' ex- 
 clusiveness ' of the reaction, is presupposed by 
 them also. In order to explain those partial re- 
 actions in the opposite direction, which certainly 
 occur, those who maintain the theory of Berg- 
 mann are obliged to admit that such partial re- 
 actions are possible under certain conditions, 
 notably under the influence of heat. These 
 authorities are therefore under the necessity of 
 proving the presence of such special conditions 
 in aU those cases wherein we deal with incom- 
 plete reactions. BerthoUet's theory, on the 
 other hand, by making use of one and the same 
 principle, embraces both kinds of chemical ac- 
 tion, and teaches us to consider the one as the 
 limiting case of the other. Apart from 'this 
 logical advantage it has another ; it allows ua 
 to apply definite laws, which can be stated in a 
 mathematical form, to the action of affinity 
 taken in conjunction with the action of mass. 
 But this cannot be done by Bergmann's theory, 
 whether in its old or in its new form. 
 
 BerthoUet's views met with respect and ap- 
 
AFJTNITY. 
 
 09 
 
 preoiation from his oontemporaries, but not with 
 continuation and development ; because che- 
 mistry began at this time to follow auottier path 
 which had been opened up by Dalton and Ber- 
 zelius. Thus it was possible for the funda- 
 mental fact of the influence of mass, the fact, 
 namely, that chemical action decreases and in- 
 creases with the relative quantities of the acting 
 substances, to be denied ; and it became neces- 
 sary to prove this fact at length by many special 
 cases before it could be regarded as a secure 
 property of science. One of the first investi- 
 gators to whom the merit of this proof is due 
 was H. Eose (P. 82, 545), who showed that in 
 the formation of many carbonates of the heavy 
 metals, by precipitating aqueous solutions of the 
 salts of these metals by sodium carbonate, the 
 precipitates contained less carbonic acid and 
 more metalho hydroxide the more water was 
 presen* in the original solutions. It followed 
 therefore that the water, according to its quantity, 
 expelled the carbonic acid from its combination 
 with the metal. Eose found further (P. 94, 481 ; 
 95, 96) that when barium sulphate was fused 
 with an equivalent quantity of potassium car- 
 bonate it was only partially converted into car- 
 bonate. If the quantity of potassium carbonate 
 was increased, appreciably more barium sulphate 
 was decomposed, but only with a proportion of 
 "6 to 7 equivalents did the decomposition become 
 approximately complete. 
 
 Another case of the influence of mass was 
 investigated by Bunsen {A. 85, 131). If to a 
 mixture of carbonic oxide and hydrogen a 
 quantity of oxygen is added, less than sufficient 
 for the complete combustion of the two gases, a 
 division of the oxygen between the two com- 
 bustible gases take place. The proportion in 
 which the oxygen combines with either gas 
 depends on the relative masses of these gases. 
 Bunsen's further result, that these proportions 
 can be expressed by some small multiples of 
 the atomic weights of the gases, has been re- 
 cognised to be an error. Debus (A. 85, 103) 
 proved- in Bunsen's laboratory the fact of the 
 influence of mass on the precipitation of mixed 
 solutions of lime and baryta by insufficient quan- 
 tities of carbonic acid. In 1865 Gladstone {Tr. 
 1855, 179 ; and O. /. 9, 54) proved the general 
 truth of the influence of mass in various ways. 
 His method consisted in using certain definite 
 physical properties, especially colour, and the 
 rotation of the plane of polarisation of a ray of 
 light, from measurements of which to draw con- 
 clusions concerning the arrangement of com- 
 pounds in a homogeneous solution. Thus, by 
 comparing the colour of pure ferric sulphooyanide 
 with the colour produced in mixed solutions of 
 iron salts and potassium sulphooyanide, the same 
 amount of iron being present in both solutions, 
 he established the fact, that by the reaction of 
 three equivalents of potassium sulphooyanide 
 and one equivalent of an iron salt, only 13 per 
 cent, of ferric sulphooyanide was formed, and 
 that even in the presence of 375 equivalents of 
 potassium sulphooyanide the whole of the iron 
 had not been converted into sulphocyanide. 
 
 By this and similar methods Gladstone esta- 
 blished the following laws : 
 
 1. When two or more binary compounds are 
 mixed so that all resulting compounds have the 
 
 power of reacting on each other, each electro- 
 positive element enters into combination with 
 each electronegative element, and it does so 
 according to fixed and constant proportions. 
 
 2. These proportions are independent of the 
 manner in which the different elements are ini- 
 tially arranged. They are also not only the 
 resultants of the various forces of attraction 
 between the different substances, but depend 
 also on the mass of each of these substances. 
 
 8. An alteration in the mass of one of the 
 binary compounds produces a change in the 
 quantity of each of the other binary compounds, 
 and it does so in a ratio which progresses regu- 
 larly. Sudden changes occur only when a sub- 
 stance can combine with another in more than 
 one proportion. 
 
 4. The equilibrium of affinities is generally 
 established after a very short time, but in some 
 cases the elements attain their final condition 
 only after hours. 
 
 5. The resulting efEeots are completely al- 
 tered when precipitation, volatilisation, crystal- 
 lisation, and similar phenomena, occur ; in such 
 cases the equilibrium which had been established 
 at first is again disturbed by the removal of 
 some of the chemically active substances. 
 
 Harcourt and Esson (0. /. [2] 5, 460) ex- 
 amined the reaction between hydrogen peroxide 
 and hydriodic acid, and also that between potas- 
 sium permanganate and oxalic and sulphuric 
 acids. They concluded that 'when any substance 
 is undergoing a chemical change, of which no 
 condition varies except the diminution of the 
 changing substance, the amount of change oc- 
 curring at any moment is directly proportional 
 to the quantity of the substance.' 
 
 The principle, first established by Steinheil 
 {A. 48, 153), of determining the chemical com- 
 position of a homogeneous liquid by means of 
 physical measurements, was put to practical 
 use by Gladstone in various ways. His measure- 
 ments might have served as a direct basis of a 
 theory concerning the influence of mass, had 
 such a theory existed. But even the extensive 
 investigations of Berthollet and St. Giles on the 
 etherification of acids and alcohols {A. Oh. 61, 
 65 ; 66, 68), by which the chemical influence of 
 mass had been confirmed and the magnitude of 
 this influence had been measured, did not give 
 rise to the formulation of a mathematical theory 
 of affinity. 
 
 Meanwhile a number of theoretical concep- 
 tions, some of old standing, were pointing in 
 the same direction. As far back as 1851 Wil- 
 liamson (A. 77, 37 ; and 0. J. 4, 110) in his 
 fundamental researches on etherification, had 
 propounded a theory concerning the course of 
 chemical reactions, which explained, better than 
 had been done before, the nature of the chemical 
 infiuence of mass. According to him, substances 
 which react on each other, when in contact or 
 mixed together, are by no means in a state of 
 neutral equilibrium, but rather in one involving 
 a continuous exchange of constituents. The 
 final result of the reaction depends on the direc- 
 tion in which this exchange of constituents can 
 take place most easily and most frequently. The 
 state of chemical equilibrium arrived at under 
 any conditions is thus not a statical one, in which 
 the forces balance each other and so no more 
 
70 
 
 AFFINITY. 
 
 produce any effect, but is rather a dynamical 
 state, in which two opposite reactions occur con- 
 tinually to the same extent, so that the average 
 state of the system remains the same. 
 
 Williamson's theory was accepted for the 
 special case for which it had been propounded. 
 Neither the author nor any of his contemporaries, 
 however, made an application of it to the general 
 explanation of chemical reactions. Meanwhile, 
 hypotheses were developed on an entirely 
 difierent basis, which agreed with this theory in 
 a most remarkable manner. These are the 
 views concerning the gaseous state, which, first 
 propounded by D. Bernoulli, and afterwards, in- 
 dependently, by Herapath, Joule, Kronig, and 
 Clausius, were developed by Clausius and Max- 
 well in a mathematically well-founded theory of 
 the states of aggregation. According to this 
 theory, bodies are made up of molecules, which 
 are in a state of continual motion. In the case 
 <nf gases this motion is rectilinear, until the 
 molecules meet with some resistance, whereby 
 they are caused to rebound according to the laws 
 of collision of elastic bodies. The velocity of 
 motion increases with the temperature, and is 
 inversely proportional to the square root of the 
 molecular weight of the gaseous body. Like- 
 wise, there is motion within the molecules, which 
 motion is of the nature of oscillations, the in- 
 tensity of which bears a constant ratio to the 
 motion of the molecule as a whole. Moreover, 
 at any specified temperature, the molecules of a 
 homogeneous gas have not all the same velocity, 
 but have different velocities varying from the 
 mean value in such a manner that deviations from 
 this value are the fewer the greater they are. 
 In the case of liquids, the molecules have no 
 longer the power of translational motion, but 
 are compelled to fill a definite space owing to 
 the forces which act between them. In other 
 respects the statements made for gases hold good 
 for liquids also, especially those referring to the 
 differences of condition of the various molecules 
 of a homogeneous substance at a constant tem- 
 perature. The theory has been least developed 
 for the case of solids ; here it is to be assumed 
 that the intermolecular forces assign to the 
 various molecules very definite relative positions 
 of equilibrium {v. Aggeegation, States op, p. 87). 
 
 The application of these ideas to chemical 
 processes has been made by L. Pfaundler (P. 
 131, 55). It can easily be seen how they directly 
 lead to conceptions which do not appreciably 
 differ from those of Williamson. The molecular 
 conceptions are, however, a decided improve- 
 ment on those of Williamson, since, in the 
 differences of the conditions of various mole- 
 cules, they supply a reason for the continuous 
 interchange of atoms which Williamson supposed 
 to occur. When the velocity of motion exceeds 
 a certain amount, there wUl always be present 
 some molecules in which this velocity is so great 
 that the connection between the atoms is 
 loosened or destroyed. These molecules are 
 then ready to interchange their constituent 
 atoms, while other molecules, which have a 
 smaller velocity, will not do so. This is the 
 explanation for partial reactions. The same 
 conceptions, when slightly modified, lend them- 
 selves to the explanation of the influence of mass 
 find to that of reversible reactions. 
 
 At the same time as these hypotheses coo- 
 cerning the mechanism of chemical processes 
 were developed, Guldberg and Waage {Etitdes 
 sur Us Affinites chimigues, Christiania, 1867) 
 laid the foundation for the exact development of 
 the theory of aflSnity by establishing a mathe- 
 matical law for the influence of mass. Their 
 work marks an epoch in the history of affinity. 
 It was they who first gave a possibility of deter- 
 mining numerically the intensity of chemical 
 affinities, though at first only as relative magni- 
 tudes. 
 
 The law established by these two investigators 
 states ' that chemical action is proportional to 
 the active masses of each of the substances 
 participating in the reaction.' By ' active mass ' 
 is understood that quantity of the substance 
 participating in the reaction, measured in 
 equivalents or in molecular weights, which is 
 contained in unit volume of the system. This 
 is the same idea as underlay the views of 
 Berthollet ; it is the same, only freed from the 
 errors which were attached to it in his time and 
 thrown into an exact mathematical form. 
 Guldberg and Waage lay special stress on the 
 fact that, when the action of several substances 
 on each other is proportional to the active mass 
 of each separately, the intensity of the reciprocal 
 actions among the substances ismeasuredby the 
 product of these masses. 
 
 In their earlier paper Guldberg and Waage 
 developed the equations for the chemical equiU- 
 brium of opposite reactions by putting the 
 chemical forces as proportional to the product 
 of the active masses. On the other hand, as 
 proportional to these same forces they put the 
 velocities of the reactions, i.e. the relation be- 
 tween the quantity of substance changed and 
 the time necessary to effect the change. In 
 their later papers it was found better to refer the 
 considerations, not to the forces, but to the 
 velocities of the reactions, since these are capable 
 of exact definition, and to leave out of account 
 altogether the somewhat vague idea of chemical 
 forces. According to this conception, chemical 
 equilibrium results when the velocities of the 
 opposite reactions have become equal, i.e. when 
 the quantity of substance undergoing a certain 
 change is equal to the quantity formed by the 
 reverse process. It is evident that this is the 
 same theory as had been framed by Williamson, 
 and developed by Pfaundler. The empirical 
 law of the influence of mass thus receives a 
 reasonable foundation in the molecular theory 
 of matter. The effect is proportional to the 
 active mass, because the number of molecules 
 which can react is proportional to the mass. 
 On these lines Van't Hoff (B. 10, 669) has de- 
 duced the law of the influence of mass. He 
 retains exactly the form given to it by Guldberg 
 and Waage ; and in a later paper (J. pr. [2] 19, 
 69) these authors accepted this formal improve- 
 ment. 
 
 In the following part I propose to give a short 
 systematic review of chemical kinetics, or the 
 doctrine of the course of chemical actions, and 
 to deduce from it the conditions and equations 
 of chemical equilibrium ; further on, the theo- 
 retical conceptions thus gained will be used in 
 the practical determination of the magnitudes of 
 affinities. The theoretical part is based mainly 
 
AFFINITY. 
 
 71 
 
 on the paper of Guldberg and Waage mentioned 
 above. A book recently published by Van't 
 HofE (Etudes de Dynamigue chimique) is also 
 of importance, and has been of great use to the 
 author, though he by no means agrees with the 
 ■whole of its contents. 
 
 Chemioaii Kinetios. — Let us suppose some 
 substance to be undergoing chemical change. 
 Then in any time, dt, some quantity, dx, will 
 have been changed. We define the velocity of 
 the chemical reaction, c, as the ratio of the 
 quantity changed to the time taken for the 
 
 change, and we therefore put c = — . The quan- 
 
 titles of the reacting substances are in every 
 case measured by formula-weights. 
 
 The quantity of substance changed will be 
 dependent on many conditions. Among these 
 we find such as are constant, or can be kept 
 constant, during the whole process. Such are 
 temperature, pressure, volume, &c. One condi- 
 tion, namely, the quantity of substance under- 
 going change, necessarily varies during the pro- 
 cess, and we have to find an expression for the 
 velocity of the change as a function of this 
 quantity. This may be done by putting 
 
 c = fj = fc/ (x,x,), 
 
 where the constant factor h represents the con- 
 stant conditions, and / (aiiSj) the conditions vary- 
 ing with the quantities a;,, aij. . . . Concerning 
 the form of the function / (aJiSj) information has 
 been sought and found in various ways. All 
 the results arrived at are concordant, and show 
 the function to be one of direct proportion. This 
 result has been arrived at empirically, and also 
 theoretically as a deduction from various assump- 
 tions. Guldberg and Waage did the first ; Horst- 
 mann, and others after him, showed that for 
 certain cases, especially for gaseous compounds, 
 the law of direct proportionality between chemical 
 action and mass follows as a necessary conse- 
 quence from the second law of thermodynamics. 
 Gibbs has made this result perfectly general. 
 The kinetical theory of the constitution of matter 
 leads to the same result, by considering the pro- 
 babilities for the occurrence of those arrange- 
 ments of particles which make chemical change 
 possible. 
 
 Before, however, the proof for the law of 
 direct proportion between chemical action and 
 mass can be attempted we must distinguish be- 
 tween the various types of chemical reactions. 
 As a rule, chemical action does not take place in 
 the presence of one substance only, but more 
 than one is needed to bring about the final result. 
 Since the final result is proportional to the mass 
 of each separately, we have quite generally 
 
 — r = K, a!|, 3J2, IC3, X^J . . • Xn 
 at 
 where »„ a;,, a;,, . . . a;„ are the quantities of the 
 various substances, and x the quantity of sub- 
 stance formed by their reaction. All these quan- 
 tities are measured according to the ratios of the 
 molecular weights of the various substances. 
 
 The simplest case is that in which one sub- 
 stance only undergoes change during the reac- 
 tion, or that in which the change of only one 
 substance has to be taken into account. The 
 Grst case occurs when, for example, a substance 
 
 is decomposed, or when it undergoes a molecular 
 transformation ; the second occurs when the 
 other substances participating in the reaction axa 
 present in such quantities that the diminution of 
 them occasioned bythe chemical change isnotap- 
 preciable. Since, then, the factors x^, x,, . , ,x 
 disappear or become constant, we have 
 
 0=1 = .... 
 
 The velocity of the reaction at any instant is 
 proportional to that quantity of substance un- 
 dergoing change which is still within the sphere 
 of action. 
 
 This equation was first established by Wil- 
 hehni (P. 81, 413) in 1850 for the inversion of 
 cane-sugar. Since that time it has been con- 
 firmed in many ways. In order to compare it 
 with the empirical results it must be integrated. 
 If we put the quantity of substance present at 
 the beginning of the change = a, then, after any 
 time t, a quantity x wiU be decomposed, and, 
 since we are dealing with molecular units, x wUl 
 at the same time represent the quantity of the 
 product of decornposition formed. The quantity 
 X, of substance present at the time t is (a—x), 
 and we have therefore 
 dx 
 
 dt 
 dx 
 
 -k (a-x) 
 
 (1) 
 
 = k.dt 
 a—x 
 —log (a — x)- A;.i + constant, 
 where log represents the natural logarithm. In 
 order to determine the constant of integration, a 
 definite pair of values for x and t must be taken. 
 We put both simultaneously equal to zero, i.e. 
 we begin the time from the instant when the 
 decomposition begins, and thence we get 
 —log a = constant, and 
 
 log a— log (a— x) =log - 
 
 = kt. 
 
 In order to pass from the natural to the common 
 logarithms we have only to multiply the con- 
 stant k by its modulus. 
 
 Some series of experiments illustrative of 
 this equation will now be given. The first of 
 these refers to a simple decomposition, the 
 change of dibromosuccinic acid into dibromo- 
 maleic acid and hydrobromio aoid, 
 
 CjHjBr^fCOOH)^ = C2HBr(C00H)j + HBr, 
 a change which occurs in aqueous solution at 
 100'. This reaction has been studied by Van't 
 Hoff (Etudes de Dynamigue chimigue, p. 13). 
 The progress of the decomposition can be traced 
 by titrating with standard alkali. The amount 
 of alkali required for neutralisation before the 
 action began was 10-25 (arbitrary units), and 
 when the change was finished the amount of 
 alkali was 15"32. The excess of alkali used, 
 over 10-21, at any stage of the change is put as 
 equal to x. For a we have 5-11, since two 
 equivalents of dibromosuccinic aoid give one 
 equivalent of hydrobromic acid. Van't Hoff's re- 
 suits are presented in the table given onnext page. 
 The constancy of the value of k, as shown in 
 the last column, furnishes a proof of the truth 
 of the equation used. 
 
 A second series of experiments dealing with 
 the inversion of cane-sugar by means of sul- 
 phuric acid is taken from the experiments of W. 
 Ostwald (J.pr. 29, 394). The action is one ol 
 
f2 
 
 AFFINITY. 
 
 t (minutes) 
 
 units 
 alkali 
 
 X 
 
 
 * 
 
 
 
 10-21 
 
 0-00 
 
 __ 
 
 
 
 a 
 
 10-63 
 
 0-32 
 
 0-0281 
 
 0-0141 
 
 4 
 
 10-79 
 
 0-68 
 
 00624 
 
 0-0131 
 
 e 
 
 11-05 
 
 084 
 
 0-0776 
 
 0-0129 
 
 8 
 
 11-25 
 
 1-04 
 
 0-0988 
 
 0-0124 
 
 10 
 
 11-66 
 
 1-34 
 
 0-1320 
 
 0-0132 
 
 13 
 
 11-94 
 
 1-73 
 
 0-1796 
 
 0-0133 
 
 16 
 
 12-29 
 
 2-08 
 
 0-2269 
 
 00142 
 
 19 
 
 12-63 
 
 2-31 
 
 0-2612 
 
 00138 
 
 22 
 
 12-84 
 
 2-63 
 
 0-3116 
 
 0-0143 
 
 26 
 
 13-03 
 
 2-82 
 
 0-3487 
 
 00134 
 
 30 
 
 13-30 
 
 3-09 
 
 0-4027 
 
 0-0136 
 
 31 
 
 13-57 
 
 3-36 
 
 0-4647 
 
 0-0137 
 
 39 
 
 13-71 
 
 3-60 
 
 0-6009 
 
 0-0129 
 
 45 
 
 14-05 
 
 3-84 
 
 0-6038 
 
 0-0135 
 
 52 
 
 14-32 
 
 4-11 
 
 0-7077 
 
 0-0137 
 
 60 
 
 14-62 
 
 4-31 
 
 0-8041 
 
 0-0135 
 
 71 
 
 14-69 
 
 4-48 
 
 0-9066 
 
 0-0128 
 
 90 
 
 16-03 
 
 4-83 
 
 1-2441 
 
 0-0133 
 
 the type called catalytic, i.e. the substance which 
 brings about the change (in this case sulphuric 
 acid) does not itself undergo any change. The 
 sugar, by taking up water, is changed into 
 dextrose and lavulose. The rotatory power 
 changes in the same proportion as the decom- 
 position proceeds ; the course of the change can 
 therefore be traced by means of the polariscope. 
 The original solution rotated 25°04' ; when com- 
 pletely inverted it rotated — 8°15', so that the 
 total angle passed through was 33°19'; this 
 number is at the same time the measure of the 
 total amount of sugar, and must therefore be 
 put = a. For x we have the difference 25°0i' — w, 
 where w is the angle of rotation produced by the 
 solution undergoing change at time t. 
 
 i (minutes) 
 
 w 
 
 X 
 
 
 68 
 
 20=20 
 
 4-84 
 
 0-0684 
 
 114 
 
 16=28 
 
 8-76 
 
 0-1331 
 
 197 
 
 11=34 
 
 13-70 
 
 0-2316 
 
 263 
 
 8=30 
 
 16-74 
 
 0-3052 
 
 394 
 
 3=35 
 
 21-69 
 
 0-4602 
 
 685 
 
 -1=39 
 
 26-43 
 
 O-6909 
 
 0-0001180 
 1163 
 1175 
 1161 
 1169 
 1182 
 
 Similar experiments have been made for many 
 other oases and have given like results. For 
 non-reversible chemical reactions, which depend 
 on the quantity of a single substance only, the 
 above formula holds good quite generally ; it can 
 however be proved only in the case of reactions 
 which are sufficiently slow to allow of measure- 
 ment. 
 
 A second main division of chemical processes 
 is formed by those which involve the presence 
 of two different substances. In such oases the 
 general equlation (1) takes the form 
 
 ^^ = fc.x..x, (2) 
 
 Two cases have to be distinguished here ; either 
 the quantities of the reacting substances are 
 equivalent -with respect to the chemical change 
 considered, or one of them is present in excess. 
 Putting these quantities = a and 6, then either 
 B = 6 or a > 6. In the first case we have to put 
 e, = a;j = a— s and we get 
 
 dr^io-^)' (3) 
 
 and integrating 
 
 z^-aJcJ {A) 
 
 where the constant of integration is detennined 
 on the same suppositions as before. 
 
 Decompositions of this type have often been 
 investigated experimentally. The example given 
 here is a series of experiments by Ostwald {J.jar. 
 27, 1), on the decomposition of acetamide by 
 acids, especially by trichloracetic acid. _ This 
 change takes place according to the equation : 
 CH3.CONH2 + CCI3.CO2H -I- H2O = 
 CCle.COONH^ + CHj.COjH. 
 The quantities both of acetamide and trichlor- 
 acetic acid diminish, with production of inert 
 ammonium trichloraoetate, and acetic acid, which 
 acid under the conditions of the experiment 
 exerts little or no influence on the change. In 
 the following table t stands for the time in 
 minutes, x for the quantity of ammonium salt 
 formed (or, what is the same thing, for the 
 quantity of acetamide decomposed) measured in 
 units such that the total quantity a = 26'80. 
 
 15 
 
 30 
 
 45 
 
 60 
 
 90 
 
 120 
 
 150 
 
 180 
 
 240 
 
 3-13 
 
 5-52 
 
 7-61 
 
 9-23 
 
 12-01 
 
 13-82 
 
 15-51 
 
 16-59 
 
 18-33 
 
 0-132 
 0-260 
 0-397 
 0-52S 
 0-811 
 1-065 
 1-375 
 1-623 
 2-169 
 
 ak 
 
 0-0088 
 0-0087 
 0-0086 
 0-0088 
 0-0090 
 0-0089 
 0-0092 
 0-0090 
 0-0090 
 
 These results show that the quantity 
 
 t a — x 
 is constant, as is required by theory. 
 
 A second series of experiments by E. Warder 
 (B. 14, 1361) on the saponification of ethylio 
 acetate gave similar results. Equivalent quan- 
 tities of ethylic acetate and soda were mixed, 
 and portions taken from time to time were neu- 
 tralised by dilute acid. The quantities of acid 
 used^these will be called s — give the quantities 
 of the substances not yet decomposed. In each 
 experiment the soda alone would have used 
 16-00 CO. of acid ; hence we have a = 16-00 and 
 i2;=16— s, therefore also a—x = s 
 
 t (minutes) 
 
 • 
 
 X 
 
 X 
 
 a—x 
 
 ok 
 
 5 
 
 10-24 
 
 5-76 
 
 0-563 
 
 0-113 
 
 15 
 
 6-18 
 
 9-87 
 
 1-601 
 
 0-107 
 
 25 
 
 4-82 
 
 11-68 
 
 2-765 
 
 0-108 
 
 35 
 
 3-41 
 
 12-59 
 
 3-69 
 
 0-106 
 
 55 
 
 2-31 
 
 18-69 
 
 5-94 
 
 0-108 
 
 120 
 
 1-10 
 
 14-9 
 
 18-55 
 
 0-113 
 
 Again ah is sufficiently constant. When a and 6 
 are different, a, becomes a—x, and x, becomes 
 b — x; then 
 
 jl. = h(a-a)(h~x) = k{x''-(a+h)x + ab}{S) 
 the integral of this equation is 
 
 The validity of this equation has been proved by 
 T. Flood (P. M. IS] 6, 371). 
 
AEFINITY. 
 
 73 
 
 These two tjrpes of non-reversible chemical 
 actions which have been just considered com- 
 prise all non-reversible actions which have been 
 accurately studied. To be consistent, we must 
 assume that in chemical reactions which involve 
 more than two, say three, substances, an equation 
 corresponding with those given ought to hold 
 good. Thus when three substances are present 
 
 in equivalent quantities, -r = 7c(a— k)'; and 
 
 x,2ax—x'' 
 
 ^a\U. 
 
 (7) 
 
 ^ (a-x)-' 
 
 But no reaction has been observed with sufiS- 
 oient certainty the course of which proceeds 
 according to this, or according to a higher, equa- 
 tion. 
 
 Moreover, a complication may arise from the 
 simultaneous occurrence of several reactions. 
 For such a case the principle of the ' coexistence 
 of reactions ' is important ; this principle states 
 that every reaction proceeds as if it alone took 
 place. This principle is of paramount import- 
 ance ; it forms the connecting link between the 
 simple reactions, and those of so-called chemical 
 equilibrium. For the mathematical expression 
 of the coexistence of reactions, when one and 
 the same substance is affected by the various 
 changes, we have the following. 
 
 dx 
 Si' 
 
 h.x^Xi ■•• + k'x'iX'^ ... + h"x^'x^' . 
 
 If, however, the coexistent reactions take place 
 among different groups, which are themselves 
 without effect on each other, the equation of 
 velocity has to be developed for each separately 
 without regard to the others. 
 
 No experimental investigation of the law of 
 coexistence has as yet been published. The 
 application of this law in the theory of affinity 
 leads, however, to results which agree with ex- 
 perience, and the law may therefore be considered 
 to be experimentally proved. 
 
 Beversible Beactions. 
 
 The processes investigated above frequently 
 represent only one part of the actual reactions. 
 In many oases the substances formed mutually 
 react to reproduce the original substances. In 
 such cases the process does not end with de- 
 composition ; but a permanent final state is 
 arrived at in which the original substances, as 
 well as the products of their double decomposi- 
 tion, are coexistent. In such a case the final 
 system is said to be in chemical equilibrium. 
 Here we have to consider on the one hand the 
 velocity of the reaction, on the other hand the 
 proportion of the masses for which chemical 
 equilibrium results. As aids in the first part of 
 this inquiry we have the equations given above, 
 together with the principle of coexistence : in 
 investigating the second part of the problem we 
 have the following condition ; — chemical equili- 
 brium results when the velocities of the opposite 
 reactions have become equal. 
 
 The establishment of chemical equilibrium is 
 connected with the second type of chemical reac- 
 tions [equations (3) (4), and (5) (6)], respectively. 
 For the velocity of each of the reactions we have 
 /Zar' dx" 
 
 dt 
 
 dt 
 
 and equilibrium results when 
 dx' dx" 
 
 di =dr °' T'%'^2'='k"x^"x/. 
 Thts is the equation first established by Guld- 
 berg and Waage. Putting the initial quantities 
 of the substances as p, q, p', and q', when the 
 substances p' and q' are formed by the reaction 
 of p and 2 and vice versd, equilibrium will re- 
 sult when a certain quantity 4 of ^ and q has 
 been decomposed. Then the quantities p — ^, 
 q~^,p' + i,q' + i are in equilibrium; and | has 
 the same value throughout, since the quantities 
 p, q, &o. are measured according to equivalents. 
 The quantity | may be positive or negative. 
 
 The equation of equiKbriimi then takes ths 
 following form : — 
 
 k'{p-i)(q-^) = ¥'{p' + i)(q' + Sj; (8) 
 from which a value for J is found, 
 t = k'{p + q) + k"(p' + q') 
 ' 2{k'-k") 
 
 /f k'{p + q) + k"{p' -i-q 'Y k'p'q' ~ k^q 
 V V 2{k'-k") J + k'-k" 
 
 k' 
 The minus sign holds when c/z/'li 
 
 and vice versd. 
 
 By making certain assumptions, this ex- 
 pression may be considerably simplified. If at 
 the beginning of the reaction the substances p 
 and q only are present, in equivalent quantities, 
 p = g andy = 2' = o, and it follows that 
 k' £^ 
 
 (9) 
 
 , and 
 
 i=p 
 
 Vi 
 
 (9a) 
 
 F' + l 
 The equation of velocity takes the following 
 
 form. The resultant velocity ^ is the differ- 
 ence of the partial velocities : 
 
 ^^V(p-x){q-x)-k"(p' + x)[q' + x) (10) 
 
 Introducing a new constant h we have 
 k'(p + q)+k"{p' + q') 
 "■- k'-k" «' 
 
 the equation can then be brought to the form 
 
 %={k'-k")[i-x]{h-x); 
 and from this by integration, we obtain 
 
 The form of this equation is analogous to 
 that already deduced for simple reactions 
 (equation (6), p. 72). If now it is assumed, as 
 before, that p = q, and p' = g^ = o, J assumes the 
 simple form given in (9a) 
 
 and h=p 
 
 Vp 
 
 Vp-1 
 
 The preceding equations are deductions 
 from the laws of the influence of mass, and 
 the coexistence of chemical reactions. Both 
 laws are of about the same importance in the 
 theory of affinity as the laws of gravitation and 
 the coexistence of motions are in astronomy. 
 
74 
 
 AFFINirY. 
 
 Each indiyidual practical case really comprises 
 several difierent relations; but there are com- 
 binations in which so great a part of the result 
 depends on one single cause only, that the ob- 
 served phenomena may be represented almost as 
 if this were the only cause. And as little as we 
 doubt the law of gravitation because the motions 
 of the moon cannot yet be expressed completely 
 in equations, so little have we cause to doubt the 
 laws stated above because certain phenomena 
 cannot yet be represented as simple deductions 
 from them. 
 
 We have hitherto assumed that the constant 
 of velocity does not alter its value throughout 
 the whole reaction. It is, however, not im- 
 possible that reactions exist in which the reason 
 for the change of k is to be found in the chemical 
 process itself; in such cases the problem be- 
 comes considerably complicated. 
 
 Chemical Dynamics. 
 
 In general dynamics the magnitude of any 
 force is defined and measured by the velocity 
 which it imparts to a mass of known magnitude. 
 Another way of measuring forces consists in esta- 
 blishing equilibrium between the given force and 
 a force acting in the opposite direction, which 
 latter is of a magnitude already known or easily 
 determined. This can be considered as a special 
 case of the first method, as a case in which. the 
 velocity due to the given force is reduced to 
 nothing, by means of one equal in magnitude 
 but opposite in direction. The second method, 
 though not a direct one, possesses all the im- 
 portant experimental advantages belonging to a 
 zero method and is therefore the more usual. 
 The measurement of the intensity of chemical 
 forces can be accomplished by two methods, 
 analogous to those employed in general dyna- 
 mics. The more usually employed method 
 (because of experimental advantages) is the 
 statical, or the method of equilibrium, in which 
 a chemical process is reduced in a certain pro- 
 portion by another action occurring in the oppo- 
 site direction. This corresponds to the statical 
 method used in measuring mechanical forces. 
 Analogous to the kinetical method, or the method 
 of velocity, is the process of obtaining a measure 
 of the intensity of the acting forces by measuring 
 the velocity of the chemical change. The two 
 chemical methods are connected in a similar 
 manner as the two mechanical methods, since, 
 as has been shown above, the equilibrium of 
 chemical changes can be regarded as the con- 
 sequence of the mutual counteraction of changes 
 which are equal in magnitude, but opposite in 
 direction. 
 
 Statical methods. 
 
 The first attempts to measure affinities were 
 made by Wenzel, in 1777 (Die Lehre von der 
 Chemischen Verwandtschaft, p. 28, Dresden, 
 1777). He used the method of velocities, but 
 his process was very imperfect. His experi- 
 ments related to the solution of metals by 
 various acids. Later experiments dealt almost 
 exclusively with the affinity between acids and 
 bases, and were mostly carried out by the method 
 of equilibrium. 
 
 Solutions of acids and bases were mixed in 
 proportions such that difEerent acids competed 
 for an insufficient amount of a base, or vice 
 
 versd ; and an attempt was then made to deter- 
 mine the distribution of the base between the 
 competing acids (or vice versd). Ordinary 
 analyses could give no information as to this 
 distribution ; since such analyses could determine 
 only the absolute quantities of the acids and 
 bases, and not their distribution. Steinheil (A. 
 48, 153) (although with an entirely different 
 aim) was the first to show how we must proceed 
 in order to get a knowledge of the arrangement 
 of the constituents of a solution without inter- 
 fering with its composition. Since each of the 
 constituents of a solution changes the physical 
 properties — such as density, refractive index, 
 colour, &c.— of the solution, a knowledge of the 
 laws governing these changes indicates how to 
 solve the problem, by measuring 8 sufficient 
 number of constants and forming the necessary 
 equations. 
 
 It has been already explained how Gladstone 
 used these means for establishing a number of 
 facts concerning the chemical statics of solu- 
 tions of salts. He could not, however, utilise 
 his measurements further, as there did not then 
 exist a general theory of chemical affinity. Such 
 a theory was first given by Guldberg and Waago 
 {Etudes sur les AffiniUs chimiques, Christiania, 
 1867) and was also applied by them to a number 
 of measurements. This theory has met with 
 such wide confirmation that we hope to be able 
 some day to reconcile with it those facts which 
 do not appear at present to be in keeping with it. 
 J. Thomsen (P. 138, 65) was the first to 
 apply the theory of Guldberg and Waage to the 
 case of homogeneous solutions. He found that 
 sulphuric acid when acting on soda gives a heat- 
 production of 31,378 gram-units, while nitric acid 
 gives 27,234 units only. Now, when sulphuric 
 acid and nitric acid simultaneously act on soda, 
 all three substances being present in equivalent 
 quantities, three cases may arise. Either the 
 sulphuric acid exclusively combines with the 
 soda, or the nitric acid exclusively does so, or 
 the soda divides itself between the two acids in 
 some fixed proportion. In the first case 31,378 
 gram-units of heat, and in the second case 
 27,234 units, wouldbe produced, while in the third 
 case the heat-production would be represented 
 by a number between these two. Therefore the 
 number found by experiment gives a measure of 
 the distribution of the soda between the acids. 
 
 Similarly sodium sulphate is allowed to 
 react with nitric acid. If no chemical action 
 results there will be no production of heat. If 
 the nitric acid combines with all the soda, 
 liberating all the sulphuric acid, a disappear- 
 ance of heat must result, numerically equal to 
 the difference between the two heats of neutral- 
 isation; that is to say, 81,378-27,234=4,144 
 units of heat will disappear. If, however, a 
 division of the base between the acids results, a 
 quantity of heat less than 4,144 units will dis- 
 appear. Experiment shows that 3504 units of 
 heat are used ; therefore the soda divides itself 
 between the two acids. 
 
 If no secondary thermal action takes place 
 between the substances used in the experiment, 
 we can deduce directly from these numbers that 
 
 JT71 = 0-845 of the total quantity of sodium sul- 
 phate is decomposed. Free sulphuric acid does, 
 
AiTmiTY. 
 
 75 
 
 however, react with sodium sulphate, and the 
 action is accompanied by production of heat. 
 The extent of the reaction depends on the 
 relative quantities of the reacting substances 
 present. Thomsen has measured this effect for 
 a great many proportions, and has expressed 
 his results by the equation : 
 n 
 Q= — Q.o .3,30Q gram-units of heat ; 
 
 where n represents the number of equivalents of 
 sulphuric acid present for each equivalent of 
 sodium sulphate. By the help of this formula 
 Thomsen found empirically that soda divides 
 itself in such a proportion that ^ of it goes to 
 the sulphuric acid, and f of it to the nitric acid. 
 Calculating the heat production on this supposi- 
 tion, the result is —3,547; experiment gives 
 —8,504; the difference lies within the limit of 
 experimental error. 
 
 Guldberg and Waage's theory gives an ex- 
 tremely simple expression for this case. Since 
 sodium sulphate and nitric acid were present in 
 equivalent quantities at the beginning of the re- 
 action, but sodium nitrate and sulphuric acid 
 were absent, we have to put in equation (8) 
 2) = g = l andy=2'=0; 
 this gives fc(l-i)^ = fc'f, 
 & P 
 &'°(1-Jr 
 As I is the quantity of soda combined with the 
 nitric acid, and (1 — J) that combined with the 
 sulphuric acid, it follows that the ratio of the 
 velocities of the reaction is equal to the square 
 of the ratio of distribution. Thomsen calls the 
 endeavour of the acids to combine with bases 
 the avidity of the acids, and defines it by the 
 ratio of distribution. According to this, the 
 avidity of sulphuric acid is half as great as 
 that of nitric acid, or putting the latter = 1, the 
 avidity of sulphuric acid is = 0-5. The avidities 
 are in the ratio of the square roots of the 
 velocities of reaction. 
 
 Thomsen {ThermochemischeUntersuchungen, 
 i. 808) has made further experiments concern- 
 ing the avidity of other acids towards soda, using 
 a method similar to that described above. His 
 numbers are given in the following table, where 
 the avidity of nitric acid has been put = TOO. 
 Hydrochloric acid . = 1"00 
 Hydrobromio „ . 0-89 
 
 Hydriodio „ . 0-79 
 
 Sulphuric „ . 0-49 
 
 Selenic „ . 0-45 
 
 Trichloracetic „ . 0'36 
 
 Orthophosphoric acid . 0-25 
 
 Oxalic „ . 0-24 
 
 Monochloracetic „ . 0'09 
 
 Hydrofluoric „ . 0-05 
 
 Tartaric „ . 0-05 
 
 Citric „ . 0-05 
 
 Acetic „ . 0-03 
 
 Boric, siUcio, and hydrocyanic acids do not give 
 any appreciable values. 
 
 Taking the squares of these numbers we get 
 the relative velocities of the reactions between the 
 acids and the soda, which values cannot be ob- 
 tained directly owing to their great magnitude. 
 
 The question now presents itself as to whether 
 the avidities thus found have constant values, 
 or whether they change when a base other than 
 
 soda is employed. Thomsen made similar ex- 
 periments for hydrochloric and sulphuric acids, 
 using different bases (P. 138, 497), viz. potash, 
 ammonia, and magnesia, the oxides of manganese, 
 iron, cobalt, nickel, zinc, and copper ; for the 
 avidity of sulphuric acid he obtained numbers 
 which increase from 0*5 up to 0-8, and vary, for 
 the alkalis between 0'5 and 0-57, and for 
 the bases of the magnesia series between 0-70' 
 and 0-81. These results induced Thomsen to 
 conclude that the relative avidity of acids de- 
 pends on the nature of the base. 
 
 Berthelot (A. Oh. [4] 30, 516), however, 
 raised the just objection that Thomsen's method 
 does not allow of the measurement of the 
 relative avidities without the introduction of 
 errors. The free sulphuric acid reacts on the 
 neutral salt, forming acid sulphate, and thus 
 loses part of its active power, and it does this 
 the more the greater the quantity of acid-sul- 
 phate which can be formed. 
 
 Thomsen's experiments were repeated by W. 
 Ostwald (P. Ergzbd. 8, 167 ; /. pr. [2] 19, 468), 
 who used a different method based on measuring 
 the changes of volume which accompany 
 chemical reactions in aqueous solutions. The 
 volume of the solution of a salt is different from 
 the sum of the volumes of the solutions of the 
 acid and the base, which by their mutual action 
 produce the salt ; and further this change of 
 volume is different for different bases and acids. 
 If we use solutions which contain one gram- 
 equivalent of the acid or base per kilogram of 
 solution then the volume of two equivalents of 
 soda is 1913"26 c.c, and that of two equivalents 
 of nitric acid is 1933-25 c.c. ; the sum of these 
 two is 3846-51 c.c. ; but the volume of the corre- 
 sponding solution of sodium nitrate is 3886-05 c.c, 
 that is to say, 89-54 c.c. more than the sum of 
 the volumes of acid and base. Eepetition of the 
 experiment with sulphuric acid gives an increase 
 of volume of 29-96 c.c. only. Hence the volume- 
 changes can be used for determining the com- 
 position of the solution, in the same manner as 
 the heats of neutraUsation had ■ been used by 
 Thomsen. Eesults were obtained by this method 
 exhibiting the behaviour of nitric acid and sul- 
 phuric acid towards soda ; these results agreed 
 entirely with those of Thomsen. Thomsen's 
 conclusion that nitric and hydrochloric acids are 
 stronger acids than sulphuric acid — a result 
 opposed to the older views — was thus confirmed 
 by Ostwald. The same chemist investigated at 
 length the question as to whether the relative 
 afiBnity of an acid varied with the nature of the 
 base. By experiments to which Berthelot's ob- 
 jection cannot apply, he arrived at the result 
 that the relative avidity of an acid is independent 
 of the base. Thus with hydrochloric and nitrio 
 acids he found the following numbers : — 
 Potash . . 0-97 
 Soda . . . 0-96 
 Ammonia . . 0-96 
 Magnesia . . 0-99 
 Zinc oxide . 0-95 
 
 Copper oxide . 0-97 
 The differences are not greater than the probable 
 errors of the experiment. 
 
 The question concerning the influence of 
 temperature on the relative affinities of acids 
 has also been investigated by Ostwald. He 
 
76 
 
 AFFINITY. 
 
 measured the expansion due to heating the Bame 
 
 solutions wMcli had served for the volumetric 
 
 experiments with soda. The ratio of the avidity 
 
 or aflBnity of hydrochloric acid to that of nitric 
 
 acid towards soda proved to be as follows ; — 
 
 At 0° . 1-02 
 
 20° . 0-96 
 
 40° . 0-98 
 
 60° . 1-00 
 
 In both cases the number for sulphuric acid 
 is not quite constant ; but, as already mentioned, 
 this acid seems to be the stronger the less acid 
 sulphate is formed, and vice versd. 
 
 At a subsequent time Thomsen (Thermoch. 
 Vnters. i. 89) also attacked the problem of the 
 influence of temperature on relative avidities, 
 and arrived at the same results as Ostwald. 
 
 The refraction of light was used by Ostwald 
 as another method for determining the com- 
 position of a homogeneous solution by means of 
 its physical properties. Dale and Gladstone 
 (T. 1863, 317), and also Landolt (P. 133, 1), 
 showed that the function v{n—l), in which n is 
 the refractive index and t) the specific volume of a 
 liquid body, depends only on the elementary 
 composition of the body and not. on the tempera- 
 ture, nor (within certain limits) on the chemical 
 arrangement of the constituents of the body. 
 Hence the specific volume is inversely propor- 
 tional to the refractive index diminished by 1, 
 and the volume-changes attendant on chemical 
 reactions must be accompanied by opposite 
 changes in the refractive indices. Experiment 
 has most fully borne out these conclusions. 
 The optical method is, however, less accurate 
 than the volumetric method, when the ordinary 
 apparatus only is used. 
 
 The numerical results of Ostwald's experi- 
 ments are collected in the following table. The 
 numbers have the same meaning as those of 
 Thomsen given before (p. 75), i.e. they give the 
 relative avidities of the various acids, putting 
 that of nitric acid = 1. 
 
 Acid 
 
 
 Thomsen 
 
 Nitric 
 
 1-00 
 
 1-00 
 
 Hydrochloric . 
 Trichloracetic . 
 
 0-98 
 0-80 
 
 1-00 
 0-36 
 
 Dichloraoetio . 
 
 0-33 
 
 — 
 
 Monochloracetio 
 
 0-070 
 
 0-09 
 
 Glycolio . 
 Formio . 
 
 0-050 
 0-039 
 
 — 
 
 Citric 
 
 0-033 
 
 — 
 
 Acetic 
 
 0-0123 
 
 0-03 
 
 Propionic . 
 Butyric . 
 Isobutyric . . 
 Succinic . 
 
 00104 
 0-0098 
 0-0092 
 0-0145 
 
 — 
 
 Malic • . . 
 
 0-0282 
 
 — 
 
 Tartarie . 
 
 0-052 
 
 0-05 
 
 Thomson's values have also been given as 
 far as they refer to the acids considered here. 
 They agree as well as can be expected; tri- 
 chloracetic acid alone shows an appreciable 
 difference. Thomson's number for this acid is 
 undoubtedly much too small; this has been 
 proved beyond doubt by other measurements. 
 
 The ratios of avidities given in the preceding 
 table remain the same \Thethei determined for 
 
 potash, soda, or ammonia ; they are independent 
 of the nature of the base. 
 
 Besides these three methods which are of 
 general application to the case of solutions, 
 some investigators have employed others, which 
 can, however, be used only in special cases. 
 Thus G. Wiedemann {W. 5, 45) has shown that 
 from the magnetic properties of ferric salts in 
 solution we can argue as to the amounts of these 
 salts decomposed by the water into free acid and 
 colloidal soluble iron oxide. This method is, 
 however, restricted to the case of these special 
 salts. A. Muller (P. Ergzhd. 6, 123) has drawn 
 conclusions from the change in colour as to the 
 distribution of iron oxide between hydrochloric 
 acid and sulphuric acid. Jelett (/. 25, 371) 
 determined the relative affinities of codeine, 
 quinine, and brueine, by means of the rotation 
 of the plane of polarisation, and found for the in- 
 fluence of mass the same law as had been es- 
 tablished by Guldberg and Waage. The experi- 
 ments of Dibbits (P. Ergzhd. 7, 462), Bruoke 
 (SiU. W. 77, April 1877), and others, are of a 
 more qualitative nature. 
 
 Besides these statical methods, based on the 
 determination of the composition of a homo- 
 geneous solution, others are available in which 
 the chemical reactions take place in heterogeneous 
 media, viz. between solids and liquids, or 
 liquids and gases, or lastly between solids and 
 gases. The theory of these methods has been 
 also given by Guldberg and Waage, and Ostwald 
 has developed the methods for the purpose of 
 determining aflSnities. 
 
 According to Guldberg and Waage the 
 chemical action of solids in contact with solu- 
 tions is independent of their mass ; in other 
 words, the chemical mass of the solids is 
 constant. Otherwise the laws of the influence 
 of mass hold good. If, for example, an acid 
 acts on the salt of another acid, which latter 
 salt is insoluble in water (or more strictly, 
 scarcely soluble), and with the base of which the 
 first acid forms a soluble salt, then the same 
 equation holds good as applies in the case of 
 substances which are all soluble, with this ex- 
 ception that the term corresponding to the in- 
 soluble salt becomes constant or independent of 
 X. Putting in the equation k.p.c[ = k'.p'.ct' 
 p = hydrochloric acid, and g = calcium oxalate, 
 then J)' = calcium chloride, and 3' = oxalic acid. 
 
 If the experiment is arranged so that hydro- 
 chloric acid acts on an excess of calcium 
 oxalate and that undissolved calcium oxalate is 
 always present, then at all stages of the change 
 oxalic acid and calcium chloride are present in 
 equivalent quantities. Putting the original 
 quantity of hydrochloric acid = l, and that oJ 
 th> oxalate dissolved = |, the equation becomes 
 k(l-i)c = k'.i.i;henoB 
 
 l = ^)'^"^\/|' = *= * 
 
 where c stands for the constant chemical mass 
 of calcium oxalate. In this equation k, k', and 
 c are unknown, while f can be measured directly. 
 Eepeating the experiment with a different acid, 
 say nitric acid, a new expression of the form 
 
 *.- -^ 
 
 V6(l-U 
 
AFFiNiry. 
 
 77 
 
 Is obtained, in wliioh e has the same value as 
 referring to calcium oxalate, which is used in 
 both experiments under the same conditions. 
 Dividing the one equation by the other we get 
 the relative affinities 
 
 expressed in quantities which can all be directly 
 measured. This method has been used by W. 
 Oslwald and his pupils for determining the 
 relative affinities of various acids, and has given 
 results which agree well with those found for 
 homogeneous solutions. It has great experi- 
 mental advantages over the physical methods, 
 as the ordinary methods of chemical analysis 
 can be used. The insoluble, or scarcely soluble, 
 salts used were these; zinc sulphide, calcium 
 oxalate, zinc oxalate, barium chromate, cream 
 of tartar, and the sulphates of barium, strontium, 
 and calcium. As a rule the coefficients of 
 affinity thus determined for various salts agree 
 very well amongst themselves, but there are 
 some deviations which are not yet fully explained. 
 As an example of the method the following 
 numbers are given {J. pr. [2] 28, 493) ; these 
 numbers were obtained by the action of acids on 
 calcium oxalate, a substance lending itself 
 particularly well to these experiments. Experi- 
 ments were made both with normal and deci- 
 normal solutions of acids. Nitric acid is again 
 put = 1. 
 
 Acid 
 
 Normal 
 
 ^Normal 
 
 Hydrochloric . 
 
 1-00 
 
 0-98 
 
 Hydrobromio . 
 
 0-95 
 
 0-99 
 
 Nitric 
 
 1-00 
 
 1-00 
 
 Chloric 
 
 1-04 
 
 100 
 
 Sulphuric . 
 
 0-70 
 
 0-74 
 
 Formic 
 
 0-0259 
 
 0-129 
 
 Acetic 
 
 0-0105 
 
 0-735 
 
 Monoehloracetio 
 
 0051 
 
 0-213 
 
 Dichloracetic . 
 
 0-183 
 
 0-488 
 
 Trichloracetic . 
 
 0-642 
 
 0-899 
 
 Lactic 
 
 0-041 
 
 0-133 
 
 Succinic . 
 
 0-0205 
 
 0-093 
 
 Malic 
 
 0-0505 
 
 0-121 
 
 Tartaric . 
 
 0-0462 
 
 0-141 
 
 Citric 
 
 0-0306 
 
 0-144 
 
 The numbers in the first column, which 
 refer to normal solutions (one gram-equivalent 
 in a litre), agree well with those before obtained 
 by the volumetric method. Along with them is 
 given a second series referring to solutions ten 
 times as dilute. While the stronger acids ex- 
 hibit scarcely any change by the dilution, the 
 values for the weaker acids have increased very 
 considerably, and this the more the weaker are 
 the acids. We shall consider this phenomenon 
 at length later on, and find the general law 
 underlying it. 
 
 Of further results which have been arrived 
 at by this method one must be noticed as im- 
 portant, viz. that the action of the acids varies as 
 they are present alone or along with their 
 neutral salts {J.pr. [2] 23, 209). 
 
 Some Bucii result was to be expected in the 
 case of dibasio acids which combine with their 
 neutral salts to form acid salts. The mono- 
 
 basic acids, however, exhibit no tendency to 
 combine with their neutral salts, and yet they 
 too show a change which in the case of the 
 strong acids, such as hydrochloric and nitric, is 
 an increase in the affinity. This increase ia 
 proportional to the quantity of the neutral salt 
 present, and decreases rapidly with increasing 
 dilution. This statement does not, however, 
 hold for all monobasic acids, but only for the 
 strong acids. The weak monobasic acids, on 
 the contrary, are considerably more weakened 
 by the presence of their neutral salts, and this 
 the more the weaker are the acids. These facts 
 are of great importance in the interpretation of 
 experiments undertaken for the purpose of 
 determining the relative affinities of acids by 
 the division of a base between two competing 
 acids. Since in this case the acids always act 
 in presence of their own salts, this condition 
 doubtlessly exerts some influence, making the 
 strong acids appear stronger and the weak acids 
 appear weaker. This shows that too much im- 
 portance must not be attached to the numerical 
 values obtained by the preceding methods ; they 
 certainly give the order of the affinities correctly, 
 but the numerical values deviate from the true 
 value in the sense that the large numbers are 
 too large and the small values are too small. 
 We shall see later on that other determinations 
 of the same quantities, which are more likely to 
 give the true values, show deviations in this 
 sense from the above numbers. 
 
 Einetical Ilethods. 
 
 The second way of measuring the intensity 
 of chemical forces is based on determinations of 
 the velocities of the reactions produced by these 
 forces. The theoretical introduction concerning 
 this method has been already considered, and we 
 have seen that many reactions proceed according 
 to a course which agrees well with that cal- 
 culated from the influence of mass. 
 
 This method does not, however, lend itself 
 to direct applications to the majority of the re- 
 actions investigated by the statical method. 
 This statement applies particularly to the effects 
 of affinity between acids and bases, because 
 these processes are of too short duration to 
 allow of measurements being accurately made 
 of their velocities. If, however, the magnitudes 
 in question can be measured by kinetical 
 methods, this is because of a general and im- 
 portant principle. 
 
 It has been already shown that the nature 
 of the base exerts no influence on the relative 
 avidities or affinities of the acids which react 
 with the base. If the affinity between an acid 
 a and a base b is designated ijf{a, b), then the 
 following equations hold good : 
 
 f(a,b) f(a,b') f{a,b") 
 f{a',b)-f(a',b'rf(a',b"r 
 These equations can be true only if each ex- 
 pression / {a, b) is the product of two factors 
 one of which depends on the acid only and the 
 other on the base only ; /(a, 6) = (()(a).i|/(6). 
 
 The affinity between acids and bases is 
 therefore the product of speci/io affinity-co- 
 efficients. All reactions due to acids and bases 
 as such must, on this view, be proportional 
 among themselves. From this it follows that 
 processes which, taken by themselves, have 
 
78 
 
 AFFINITY. 
 
 nothing to do witli the formation of salts, may 
 be employed for finding numerical values for 
 the affinities which come into play during the 
 formation of salts, provided the reactions in 
 question have been accomplished by the acids 
 and bases only. Dete'rminationa of the specific 
 affinity-coefficients of acids and bases are thus 
 of the greatest importance. It -will be our task 
 to show first that the above conclusions are 
 verified by experiment, and then to use the 
 numbers thus arrived at for drawing further 
 deductions. 
 
 The first reaction which was used to check 
 the values of the coefficients of affinity of acids 
 determined in the statical way, by means of a 
 kinetical method, was the change of acetamide 
 into ammonium acetate (Ostwald, J. pr. [2] 
 27, 1), which takes place according to the equa- 
 tion CH3CONH2 + H20 = CH3COONHi. When 
 water only is present the reaction does not pro- 
 ceed to a sensible extent, but when anacidis added 
 the latter exerts a predisposing influence, and 
 the process takes place to the degree which is 
 possible under the existing conditions of affini- 
 ties, concentration, and temperature. 
 
 By ' predisposing affinity ' is usually under- 
 stood the cause of reactions between certain 
 substances, which reactions could take place, 
 but do not actually occur, without the presence 
 of another substance, which has affinity towards 
 one of the possible products of the reaction. 
 In the case just discussed, water and acetamide 
 do not react unless an acid capable of combining 
 with the ammonia produced (or a base which 
 has affinity for acetic acid) is present. The 
 strange assumption expressed in the name pre- 
 disposing affi/minj, viz. that the affinity of the 
 predisposing substance towards a body not yet 
 formed induces the other substances to produce 
 this special body, has been given up, since the 
 molecular theory of Williamson and Clausius, 
 as developed by Pfaundler, gives a much more 
 simple view of such reactions. When applied 
 to the case just considered, this theory tells us 
 that the atoms which form the molecules of 
 acetamide and water only very seldom get a 
 chance of forming ammonium acetate during 
 the movements and collisions of the molecules 
 in question, since the forces which tend to re- 
 tain the original condition of the system are 
 greater than the forces which tend towards de- 
 composition. If, however, a strong acid or base 
 is added, the forces tending towards decomposi- 
 tion are correspondingly increased, and, in many 
 collisions, in which previously no change occurred, 
 decomposition now takes place {v. also Men- 
 del6eff, B. 19, 456). 
 
 The experiments were conducted by keeping 
 equivalent quantities of acetamide and acid for 
 some time at 65° and 100°. The quantity of 
 ammonium salt formed was determined by de- 
 composing it with sodium hypobromite and 
 measuring the volume of nitrogen evolved. The 
 reaction takes place in the presence of acids, 
 such as hydrochloric acid, according to the equa- 
 tion, 
 CH3CONH2 + H^O + HCl = CH3COOH + NH4CI. 
 Three different kinds of molecules are therefore 
 always necessary for the reaction. Moreover, 
 only two Bobstances, acetamide and hydrochloric 
 acid, undergo an appreciable change of mass 
 
 during the reaction. The water is present in 
 such excess (about 800 H^O to 1 HCl) that the 
 change in its mass is uuappreciable. Hence, if 
 there are no secondary reactions, the change will 
 proceed according to equations (3) and (4). An 
 example in which the actual reaction agrees with 
 theory has already been given. 
 
 But the reaction is by no means free from 
 secondary changes. Particularly (as has been 
 already noticed), the presence of the neutral 
 ammonium salt of the acid added has the effect 
 of increasing the strength of strong acids, and 
 decreasing the strength of weak acids. Conse- 
 quently when strong acids are used the process 
 is accelerated, compared with its normal value, 
 and the acceleration is the greater the further 
 the change has proceeded. With weak acids, on 
 the other hand, the process is retarded. Owing 
 to the formation of acid salts, the polybasic 
 acids are influenced by similar but much more 
 pronounced secondary reactions. All these con- 
 ditions have to be taken into account in the in- 
 vestigation of the progress of the reaction, as is 
 seen most conspicuously in the graphical repre- 
 sentation given in the original paper. These 
 circumstances are disadvantageous if it is de- 
 sired to make absolute determinations of the 
 velocity of the reaction, but they are of advan- 
 tage in the comparison of the kinetical and 
 statical methods, since the results obtained by 
 the latter are also influenced in the same way by 
 similar sources of error. 
 
 The time taken to convert half the acetamide 
 into the ammonium salt was taken as the reci- 
 procal measure of the velocity of the reaction. 
 The velocity in minutes was found to be as fol- 
 lows : — 
 
 Aoid 
 
 At 650 
 
 At 100° 
 
 Ratio 
 
 Hydrochloric . 
 
 72-1 
 
 4-98 
 
 14-5 
 
 Nitric . 
 
 75-2 
 
 5-35 
 
 14-4 
 
 Hydrobromio 
 
 74-0 
 
 5-14 
 
 14-4 
 
 Trichloracetic 
 
 112-8 
 
 — 
 
 
 
 Dichloracetic 
 
 433-7 
 
 
 
 ^ 
 
 Monochloracetic . 
 
 4,570 
 
 
 
 
 
 Formic . 
 
 28,950 
 
 2,138 
 
 13-6 
 
 Sulphuric 
 
 180 
 
 14-1 
 
 12-8 
 
 Oxalic . 
 
 1,516 
 
 118-6 
 
 12-8 
 
 Tartaric 
 
 35,310 
 
 929 
 
 14-7 
 
 Mahc . 
 
 — 
 
 
 
 
 
 Succinic . 
 
 
 
 7,976 
 
 
 
 Citric . . 
 
 44,810 
 
 3,088 
 
 14-5 
 
 Phosphoric . 
 
 — 
 
 3,880 
 
 
 
 Arsenic 
 
 — 
 
 4,005 
 
 — 
 
 In order to make these numbers comparable 
 with the coefficients of affinity as found by the 
 volumetric method they must be referred to 
 HC1=1, by dividing the times corresponding to 
 the several acids each into that corresponding to 
 hydrochloric acid. The relative velocities of the 
 reaction are thus obtained for hydrochloric acid 
 = 1. Further it must be borne in mind that by 
 theory the ratio of the afSnities is equal to that 
 of the square roots of the velocities of the reac- 
 tion. In the following table I have collected the 
 acids the relative affinities of which are known. 
 Under I. are given the velocities of the reaction, 
 under II. their square roots, and under III. the 
 relative affinities : — 
 
^FINITY. 
 
 79 
 
 Acid 
 
 I. 
 
 11. 
 
 III. 
 
 Hydroohlorio . 
 
 1-00 
 
 1-00 
 
 0-98 
 
 Nitric 
 
 0-96 
 
 0-98 
 
 1-00 
 
 Hydrobromio . 
 
 0-97 
 
 0-98 
 
 0-95 
 
 Trichloracetic . 
 
 0-639 
 
 0-80 
 
 0-80 
 
 Dichloracetio . 
 
 0-166 
 
 0-41 
 
 0-33 
 
 MonocUoracetic 
 
 0-0169 
 
 0-13 
 
 0-07 
 
 Formic 
 
 000266 
 
 0-052 
 
 0-039 
 
 Acetic 
 
 0-000547 
 
 0-0234 
 
 0-0123 
 
 Sulphuric . 
 
 0-428 
 
 0-65 
 
 0-67 
 
 Tartaric • 
 
 0-00564 
 
 0-075 
 
 0-052 
 
 Malic 
 
 0-00218 
 
 0-0467 
 
 0-0282 
 
 Succinic • 
 
 0-00065 
 
 0-0255 
 
 0-0145 
 
 The numbers in the two last columns agree as 
 well as could be expected. The deviations are 
 in the direction of a greater value for 11. than for 
 III. in the case of weak acids. The reason for 
 this lies in the fact that in the enunciation of 
 the equation of velocity no attention was paid 
 to the acetic acid formed in the reaction, by the 
 presence of which the change is accelerated. 
 This action of acetic acid scarcely comes into 
 play when strong acids are employed. 
 
 The examination of the action of acids on the 
 change of acetamide into acetic acid and ammo- 
 nium salt has established the connection between 
 equilibrium and velocity which is predicted by 
 theory ; but the reaction employed was not of a 
 kind to give completely accurate values for the 
 velocity of the change, since too many secondary 
 reactions exert their influence on the primary 
 process. Another reaction studied by Ostwald 
 (J. pr. [2] 28, 449) lends itself better for this 
 purpose. This is the decomposition of ethereal 
 salts by water in the presence of acids. Aqueous 
 solutions of methyl acetate (or of similar com- 
 pounds) undergo only very slow decomposition 
 at ordinary temperatures ; if, however, an acid is 
 present the process is greatly accelerated. The 
 acid does not undergo a permanent change, since 
 at the end of the reaction exactly the same 
 quantity of acid is found as was present at the 
 beginning. It is doubtless by its affinity for the 
 methyl alcohol that the acid influences the rate 
 of the change. It predisposes in the sense already 
 explained, only the compound which the acid 
 forms with the methyl alcohol cannot exist in the 
 presence of the great excess of water. The che- 
 mical process is represented by the equation 
 CH0COOCH3 + B.fi = CH3OH -t- CH3COOH. Two 
 substances are required ; but the quantity of 
 water is so great that its change need not be 
 taken into account. Equations (1) and (2) must 
 therefore hold good. This conclusion is verified 
 by experiment. Thus for example 10 c.c. of nor- 
 mal hydrochloric acid were mixed with 1 c.c. of 
 methylaoetate and diluted with water to 15 c.c. 
 One c.c. of this solution required for neutralisa- 
 tion 13-33 c.c. of baryta. Owing to the decompo- 
 sition of the methyl acetate the acidity increased ; 
 the results are given in the first table of next 
 column. The numbers in the last line repre- 
 sent the results when the decomposition was 
 completed. 
 
 In the third column, under x, is given the 
 increase in the number of c.c. of baryta used to 
 neutralise the acid ; the values in this column 
 are always proportional to the quantity of methyl- 
 
 acetate decomposed. The last value 14-11 gives 
 the quantity a in the equation 
 
 Calculating the expression log — ~ (for simpli- 
 
 city's sake in ordinary logarithms), and dividing 
 it by the time t,k{ = the coefBoient of velocity) 
 is obtained ; the value of k is given in the last 
 column ; it is nearly a constant. 
 
 
 
 X 
 
 t 
 
 After 14 minutes 
 
 14-25 
 
 0-92 
 
 000209 
 
 34 „ 
 
 15-47 
 
 2-14 
 
 0-00211 
 
 59 
 
 16-85 
 
 3-52 
 
 0-00212 
 
 89 „ 
 
 18-24 
 
 4-91 
 
 000209 
 
 119 
 
 19-48 
 
 6-15 
 
 0-00209 
 
 159 
 
 20-92 
 
 7-59 
 
 0-00211 
 
 199 
 
 22-15 
 
 8-82 
 
 0-00214 
 
 239 
 
 23-10 
 
 9-77 
 
 0-00214 
 
 299 
 
 24-21 
 
 10-88 
 
 0-00214 
 
 399 
 
 25-46 
 
 12-13 
 
 0-00214 
 
 539 
 
 26-42 
 
 13-09 
 
 0-00213 
 
 00 
 
 27-44 
 
 14-11 
 
 — 
 
 The same method was used for determining 
 the velocity of decomposition of methylacetate 
 by many other acids ; the coef6cients, referred 
 to H01 = 1, are collected in the following table : — 
 
 Acid 
 
 Hydroohlorio . 
 Hydrobromio . 
 Hydriodio . 
 
 Nitric 
 Chloric 
 Sulphuric . 
 Methylsulphurio 
 Ethylsulphuric . 
 Propylsulphuric 
 Isobutylsulphuric 
 Isoamylsulphurie 
 Ethylsulphonic . 
 Isethionio . 
 Benzenesulphonic 
 Formic 
 Acetic 
 Propionie . 
 Butyric 
 Isobutyric . 
 Monochloracetio 
 Dichloracetio . 
 Trichloracetic . 
 Lactic 
 
 Hydroxyisobutyric 
 Trichlorolactic . 
 Pyruvic . 
 Oxalic . . 
 Malonio . . 
 Succinio • . 
 Malic . 
 Tartaric . . 
 Bacemic . . 
 Citric . . 
 
 1-00 
 
 0-98 
 
 0-96 
 
 0-92 
 
 0-94 
 
 0-547 
 
 1-00 
 
 0-99 
 
 0-98 
 
 0-97 
 
 0-96 
 
 0-98 
 
 0-98 
 
 0-99 
 
 0-0131 
 
 0-00345 
 
 000304 
 
 0-00299 
 
 0-00268 
 
 0-0430 
 
 0-2304 
 
 0-682 
 
 0-00901 
 
 000921 
 
 0-069 
 
 0-067 
 
 0-1746 
 
 0-0287 
 
 0-00496 
 
 0-01181 
 
 0-02296 
 
 0-02296 
 
 0-01635 
 
 11. 
 
 1-00 
 
 0-99 
 
 0-98 
 
 0-96 
 
 0-97 
 
 0-739 
 
 1-00 
 
 0-99 
 
 0-99 
 
 0-98 
 
 0-98 
 
 0-99 
 
 0-99 
 
 0-99 
 
 0-115 
 
 0-0587 
 
 0-0551 
 
 00551 
 
 0-0518 
 
 0-208 
 
 0-480 
 
 0-826 
 
 0-0949 
 
 0-0960 
 
 0-263 
 
 0-259 
 
 0430 
 
 0-169 
 
 0-0704 
 
 0-1086 
 
 0-1515 
 
 0-1515 
 
 0-1279 
 
 In the second column I have given the square 
 roots of the velocities of reaction ; these nunc ■ 
 bers ought to be proportional to the affinities, if 
 
80 
 
 AFFINITY. 
 
 the detennination of the affinities were free from 
 the influence of all Beoondary reactions. Com- 
 paring these numbers with those already ob- 
 tained, the same order of affinities appears, but 
 in this case the values are more nearly equal. 
 This agrees entirely with what had been ex- 
 pected ; for it has been often emphasised that, 
 owing to the presence of neutral salts, the stati- 
 cal methods make the strong acids appear too 
 strong, and the weak acids appear too weak. 
 The numbers found in the present case can 
 therefore be justly considered as approaching 
 nearer to the true coefficients of affinity than the 
 previous values. 
 
 It is of special interest that a reaction such 
 as the catalysis of methylacetate, which is only 
 very remotely connected with the process of the 
 formation of salts, is yet doubtlessly brought 
 about by that very property of acids which pro- 
 duces the latter class of reactions. This leads 
 to the conclusion that the numerical values of 
 all reactions exhibited by acids as such depend 
 on that one property which till now has been 
 somewhat vaguely termed the strength of the 
 
 Acid 
 
 I. 
 
 II. 
 
 III. 
 
 Hydrochloric . 
 
 1-00 
 
 1-00 
 
 1-00 
 
 Hydrobromio . 
 
 1-114 
 
 1-05 
 
 0-99 
 
 Nitric . 
 
 1-000 
 
 1-00 
 
 0-96 
 
 Chloric . 
 
 1-035 
 
 1-02 
 
 0-97 
 
 Sulphuric 
 
 0-536 
 
 0-732 
 
 0-739 
 
 Ethylsulphurio 
 
 1-000 
 
 1-00 
 
 0-99 
 
 Isethionic 
 
 0-918 
 
 0-96 
 
 0-99 
 
 Ethylsulphonic 
 
 0-912 
 
 0-95 
 
 0-99 
 
 Benzenesulphonie . 
 
 1-044 
 
 1-02 
 
 0-99 
 
 Formic . 
 
 0-0153 
 
 0-124 
 
 0-115 
 
 Acetic . 
 
 0-00400 
 
 0-0632 
 
 0-0587 
 
 Isobutyrio 
 
 000335 
 
 0-0579 
 
 0-0518 
 
 Monochloracetic . 
 
 00484 
 
 0-220 
 
 0-208 
 
 Dichloracetic . 
 
 0-271 
 
 0-521 
 
 0-480 
 
 Trichloracetic 
 
 0-754 
 
 0-868 
 
 0-826 
 
 Glycolic 
 
 0-01308 
 
 0-114 
 
 
 
 Lactic 
 
 0-01066 
 
 0-103 
 
 0-0949 
 
 Methylglycolio 
 
 0-01815 
 
 0-135 
 
 
 EthylglycoUo . 
 
 0-01372 
 
 0-117 
 
 
 
 Methyllactio . 
 
 0-01390 
 
 0-118 
 
 
 
 Diglycolic 
 
 0-0267 
 
 0-163 
 
 
 
 Pyruvic . , 
 
 0-0649 
 
 0-255 
 
 0-259 
 
 Glyceric 
 
 0-01715 
 
 0-131 
 
 
 
 Oxyisobutyrio 
 
 0-01062 
 
 0-103 
 
 0-0960 
 
 Oxalic . 
 
 0-1857 
 
 0-430 
 
 0-430 
 
 Malonic . 
 
 0-0308 
 
 0-175 
 
 0-169 
 
 Suooinio 
 
 0-0545 
 
 0-0738 
 
 0-0704 
 
 Pyrotartaric . 
 
 00107 
 
 0-103 
 
 
 Malic . 
 
 00127 
 
 0-113 
 
 0-109 
 
 Citric . 
 
 0-0173 
 
 0-131 
 
 0-128 
 
 Phosphoric . 
 
 0-0621 
 
 0-249 
 
 
 Arsenic . 
 
 0-0481 
 
 0-219 
 
 — 
 
 acids. In order to verify this assumption 
 Ostwald {J. pr. [2] 29, 385, [1884]) investigated 
 another process which is not connected with the 
 formation of salts, viz., the inversion of cane 
 sugar. The reaction proceeds, as in the case 
 of methylacetate, by the addition of water— 
 Ci5Hj20„ + H20 = 2CjH|20j — without an appa- 
 rent intervention of an acid. Yet it takes place 
 only in the presence of acids. It is a catalytic 
 reaction in the same sense aa that already con- 
 
 sidered. As again only one substance, the sugar, 
 undergoes change, the same equation holds good. 
 As an example has already been given which 
 shows that the process is represented by equa- 
 tions (1) and (2), the velocities of inversion are 
 now given directly (v. table in last column). 
 
 In the second column are given the square 
 roots of the velocities of inversion, in the third 
 column the corresponding values for the cata- 
 lytic change of methylacetate. The agreement 
 is evidently sufficiently great to prove the iden- 
 tity of the causes which produce the inversion 
 of cane sugar and the decomposition of. methyl 
 acetate. This agreement also forms the com- 
 plete experimental verification of the assumption 
 that there exist constants of specific activity, 
 which numerically determine all the manifesta- 
 tions of affinity exerted by acids as such. The 
 numbers found for methylacetate and for cane 
 sugar represent these constants with great ex- 
 actitude. The process of the inversion of cane 
 sugar had been already used by Lowenthal 
 and Lenssen (/. pr. 85, 321, 401) for the pur- 
 pose of measuring constants of affinity. These 
 chemists did not, however, deduce the constants 
 of inversion from their experiments, although 
 the theory of inversion had been established long 
 before by Wilhelmy (P. 81, 413), nor did they 
 give a proof of the fact that there are other 
 chemical reactions which proceed according to 
 a course analogous to that observed by them in 
 the inversion of cane sugar. 
 
 Besides the chemical methods for the deter- 
 mination of the affinities of acids, there is yet 
 another method which, by means of physical 
 measurements, allows very accurate determina- 
 tion of these values to be made. It has been 
 proved beyond doubt that the electrolytic con- 
 ductivities of acids are closely connected with 
 their chemical properties ; so that this conduc- 
 tivity is proportional to the velocity of the 
 reactions produced by the acids. As the elec- 
 trolytic conductivity can easily be measured to 
 a high degree of accuracy, we have here a 
 method of much importance for the solution of 
 the problems connected with affinity. The exist- 
 ence of this relation was first recognised and 
 enunciated by W. Hittorf (W. 4, 391), who had, 
 however, almost no measurements at his dis- 
 posal. Arrhenius (Bijh. K. Svensk. Vet. Ah. 
 Hand. 8, Nos.13, 14 (1884)) developed a theory 
 of the chemical changes among electrolytes, 
 starting with the supposition that the power of 
 conducting eleotrolytically and the power of 
 participating in chemical reactions were iden- 
 tical. 
 
 This theory leads to equations which agree 
 with those of Guldberg and Waage. Finally W. 
 Ostwald has considerably increased the some- 
 what scanty material available for comparisons 
 between the power of inducing chemical reac- 
 tions and electrolytic conductivity. He fully 
 proved the proportionality between the velocity 
 of the reactions induced by an acid and the 
 electrolytic conductivity of the acid (J", pr. [2] 
 30, 93 ; ih. 30, 225 [1884] ; ib. 31, 433 ; ib. 32, 
 300 [1885]). The following table shows this 
 agreement. Under I. are given the electrolytic 
 conductivities for normal solutions; under II. 
 the velocities of inversion of cane sugar for semi- 
 normal solutions ; under III. the velocities of 
 
AFFINITY. 
 
 Si 
 
 decomposition of methylaoetate for f normal 
 lolations; all the numbers are referred to bydro- 
 chlorio acid=l. 
 
 Aoid 
 
 I. 
 
 II. 
 
 in. 
 
 Hydroohlorio 
 
 1-002 
 
 1-00 
 
 1-00 
 
 Hydrobromio 
 
 101 
 
 1-11 
 
 0-98 
 
 Eydriodio . 
 
 1-01 
 
 — 
 
 0-96 
 
 Nitric 
 
 1-00 
 
 1-00 
 
 0-92 
 
 Sulphuric . 
 
 0-65 
 
 0-73 
 
 0-74 
 
 Formic . 
 
 0-0168 
 
 0-0153 
 
 00131 
 
 Acetic 
 
 0-00424 
 
 0-004 
 
 0-00345 
 
 Monochloracetic. 
 
 0-049 
 
 0-0484 
 
 00430 
 
 Diehloraoetio 
 
 0-253 
 
 0-271 
 
 0-230 
 
 Trichloracetic . 
 
 0-623 
 
 0-754 
 
 0-682 
 
 Glyoolio 
 
 0-0134 
 
 0-0131 
 
 
 
 Methylglycolio . 
 
 0-0176 
 
 0-0182 
 
 — 
 
 Ethy glyoolio . 
 
 00130 
 
 0-0137 
 
 — 
 
 Diglyoolic . 
 
 0-0258 
 
 00267 
 
 — 
 
 Propionic . 
 
 0-00325 
 
 — 
 
 0-00304 
 
 Lactic 
 
 0-0104 
 
 0-0107 
 
 00090 
 
 * Oxypropionio . 
 
 0-00606 
 
 0-0080 
 
 — 
 
 Glyceric . 
 
 00157 
 
 0-0177 
 
 — 
 
 Pyruvic 
 
 0-0560 
 
 0-0649 
 
 0-0670 
 
 Butyric 
 
 0-00316 
 
 — ■ 
 
 0-00300 
 
 IsobutyriB . 
 
 0-00311 
 
 0-00385 
 
 0-00268 
 
 Oxyisobutyric . 
 
 0-0124 
 
 0-0106 
 
 00092 
 
 Oxalic 
 
 0197 
 
 0-186 
 
 0-176 
 
 Malonio . 
 
 0-0310 
 
 0-0308 
 
 0-0287 
 
 Succinio . 
 
 0-00581 
 
 0-0055 
 
 0-0050 
 
 Malic . . 
 
 0-0134 
 
 0-0127 
 
 00118 
 
 Tartaric , 
 
 0-0228 
 
 — 
 
 0-0230 
 
 Bacemio . 
 
 0-0228 
 
 — 
 
 0-0230 
 
 Pyrotartaric 
 
 0-0108 
 
 0-0107 
 
 — 
 
 Citric . 
 
 0-0166 
 
 00173 
 
 0-0163 
 
 Phosphoric 
 
 0-0727 
 
 00621 
 
 — 
 
 Arsenic 
 
 0-0538 
 
 0-0481 
 
 — 
 
 The agreement of the numbers in the three 
 columns is evident, and proves the truth of the 
 assertion made above. 
 
 In order to understand the relation between 
 conductivity and the power of taking part in 
 chemical changes, we must go back to the theory 
 of Clausius and Williamson. According to this 
 theory the molecules of the electrolytic sub- 
 stances are continually interchanging their con- 
 stituent atoms. These atomic exchanges gene- 
 rally take place to an equal amount in all 
 directions ; but when an electric current is 
 passing they are so influenced that the electro- 
 positive or basic constituents go to the one side, 
 and the electronegative or acid constituents to 
 the other side, each constituent separating from 
 the solution on one of the electrodes. This 
 motion of the constituents occurs to a greater 
 extent the greater the difference of potential 
 between the electrodes, i.e. the greater the 
 electromotive force. The change proceeds ac- 
 cording to Faraday's law of electrolysis, which 
 states that the quantity of electricity passed is 
 proportional to the equivalents of the parts of 
 the molecules separated out. Put into a slightly 
 different form, this means that each electrified 
 atom, or group of atoms, conveys the same 
 quantity of electricity quite vndependently of its 
 nature. 
 
 Since the electric current only exerts a direc- 
 tive influence on the electrolyte, but does not 
 Vol. 1. 
 
 itself induce the action, the conducting power 
 of substances depends entirely on the power of 
 interchanging their ions. But on that same- 
 power depends also the velocity of the chemical 
 changes produced by these substances; hence- 
 it follows that the velocities of the reactions- 
 must be proportional to the conductivities of the 
 reacting substances. The experimental proof of 
 this proportionality is in itself an important 
 point in favour of the theory of Williamson and 
 Clausius. (In Faraday's works we also find 
 views which agree in the chief points with those 
 explained above.) For the experimental details 
 of the method the reader must be referred 
 to the papers of Kohlrausch, Arrhenius, and 
 Bouty. A short account of the conceptions and 
 definitions used will, however, be given here, 
 since the assumptions generally used in phy- 
 sics proper do not lend themselves well for our 
 purpose. 
 
 Imagine a vessel having the form of a paral- 
 lelepiped, the two parallel sides of which form the 
 electrodes, and imagine the distance between the 
 two to be equal to unit length. Into this vessel we 
 imagine a quantity of the electrolyte to be placed, 
 either by itself or in solution, such that its weight 
 in grams is numerically equal to its molecular 
 weight. Let us further suppose that the electro- 
 motive force between the two electrodes is unity ; 
 then the quantity of electricity passed through 
 in unit time represents the molecular conduc- 
 tivity. Since equal quantities of electricity are 
 conveyed by each electrolytic molecule, the total 
 quantity of electricity passed is proportional to 
 the number of double exchanges which take 
 place in unit of time in one molecular weight of 
 the substance 
 
 The electrolytic conductivity can be very easily 
 and accurately determined. The possibility of 
 solving a great many problems connected with, 
 the values of afifinities is thus presented. W. 
 Ostwald has specially investigated the influence- 
 of dilution, and has established the laws which 
 hold for it. The simplest relations are foundi 
 for the strong monobasic acids, hydrochloric, 
 hydrobromic, hydriodio, nitric, chloric, and per- 
 chloric. For normal solutions all these acids 
 have nearly the same conductivity, and this in- 
 creases by about 10 per cent, to 12 per cent, 
 with increasing dilution, gradually approaching 
 a maximum value, which in the units used 
 by Ostwald was equal to 90. Sulphocyanio and 
 bromic acids approximate to the acids named 
 above. 
 
 The other monobasic acids, which are weaker, 
 and which therefore have smaller conductivities 
 than those already mentioned, exhibit a greater 
 change in conductivity with increasing dilution, 
 the weaker they are, and they all do this accord- 
 ing to the same law. This law states that the 
 dilutions at which two acids have the same 
 molecular conductivity always bear the same 
 ratio to each other. 
 
 Thus, when measured in the units mentioned 
 above, formic acid of the dilution i—i.e. 
 H2C02 = 46 grams, in two litres of the solution — 
 has the molecular conductivity 1-76; butyric 
 acid reaches the value 1-81 only at 32 litres 
 dilution. On further dilution the followinji 
 relation is manifested : — 
 
 G 
 
AFFINITY. 
 
 FoBMio Acid 
 
 BnTTiiic Acid 
 
 DUation 
 
 Conductivity 
 
 Dilution 
 
 Conductivity 
 
 4 
 8 
 
 16 
 32 
 
 64 
 128 
 
 256 
 
 512 
 
 1024 
 
 2-47 
 3-43 
 4-80 
 6-63 
 9-18 
 12-6 
 17-0 
 22-4 
 29-0 
 
 64 
 
 128 
 
 256 
 
 512 
 
 1024 
 
 2048 
 
 4096 
 
 8192 
 
 16384 
 
 2-56 
 3-50 
 5-04 
 7-02 
 9-74 
 13-4 
 18-0 
 23-8 
 31-5 
 
 Butyric acid and formic acid have always 
 nearly the same molecular conductivity when 
 the former is sixteen times as dilute as the 
 latter. The same holds good for dilute solu- 
 tions of all the monobasic acids. Plotting a 
 curve, with the molecular conductivities as 
 ordinates and the logarithms of the dilutions 
 as abscissae, we find it to have the shape indi- 
 cated in the annexed figure. In this, the 
 
 logarithms are not referred to the base 10, but 
 to the base 2, since in Ostwald's experiments 
 the dilutions increase as the powers of two. 
 They are the exponential powers, 'p, of the dilu- 
 tion v; D = 2!' . 
 
 The curve appears to be symmetrical about 
 two lines at right angles to each other, and has 
 a point of contrary flexure when the conductivity 
 reaches the value 45. The equation to the curve 
 can be approximately expressed — using the given 
 units — by the empirical formula 
 
 /« \ -4518 
 tan. »ra = I - I 
 
 where m is the molecular conductivity ; % the 
 dilution (in litres per gram-equivalent) for 
 which the conductivity is 45 ; and v any dilu- 
 tion for which the conductivity is to be cal- 
 culated. The same curve holds for all acids if 
 the abscissa d„ is chosen properly. The value 
 »„ is charaoterietio for each acid. For the 
 above-mentioned strong acids, it is found in 
 high concentrations: — for iodic acid, at 2-8 litres 
 approximately ; for hypophosphorous acid, 8 
 litres ; for dichloracetic acid, at 10 litres ; for 
 imonochloracetio acid, between 400 and 500 
 litres ; far formic acid, at about 1000 ; and for 
 S)utyric acid, at about 60,000 litres. 
 
 The influence of the dilution, on the relative 
 affinities varies widely for the different acids, as 
 has already been seen. It seemed therefore very 
 doubtful whether much importance could be 
 attached to these values as natural constants 
 on which the action of the acid as such de- 
 pends. In the law of dilution, as enunciated 
 above, there has been found the proof that we 
 
 are dealing with important and oharaoteristia 
 values, with values which do not alter with the 
 nature of the reaction induced by the acid, and 
 which are related to the dilution in a perfectly 
 fixed manner. The general truth of this law 
 for the case of chemical reactions has been 
 separately proved by Ostwald {/. pr. [2] 31, 307). 
 The values of affinities sought by men of 
 science in the last century have thus been 
 found by means of a method which had been 
 even then indicated by the famous opposer of 
 the old theory of afiinity. 
 
 It has already been mentioned that the 
 above law of dilution holds primarily for mono- 
 basic acids. Polybasic acids behave differently 
 according to their constitution. Some dibasic 
 acids, such as phosphorous, selenious, &o., in 
 which the second hydrogen atom is of the 
 nature of a weak acid (this is shown by the 
 alkaline reaction of their normal salts), behave 
 on dilution at first exactly like monobasic acids, 
 the conductivity being referred to molecular and 
 not to equivalent weights. Hence electrolysis 
 of these solutions takes place at first according 
 to the type H | HE". It is only on reaching 
 very great dilutions that the second hydrogen 
 atom begins to participate in the reaction. Di- 
 basic acids whose normal salts are neutral 
 behave differently. It is true that they, too, 
 conduct at first according to the type H | HE"; 
 but the second hydrogen atom exerts its in- 
 fluence even in moderately dilute solutions. 
 The conductivity increases much more rapidly 
 than in the case of monobasic acids, and ap- 
 proaches a maximum Which is double that 
 observed for monobasic acids. Oxalic acid may 
 be taken as a typical acid of this class. In the 
 case of very strong dibasic acids, such as sul- 
 phuric acid, it is the last part of the phenome- 
 non just described which becomes prominent. 
 Even for a concentrated solution the molecular 
 conductivity exceeds the maximum of mono- 
 basic acids, and rapidly approaches, a value 
 double that found with these acids. Hence 
 conduction takes place from the beginning, for 
 the most part, according to the type H^ | E". 
 
 Ostwald has recently (J. pr. [2] 32, 300) 
 examined the conductivity of a number of acids, 
 and has shown that the relations already stated 
 hold in all cases. He has also established many 
 relations between the conductivities of acids and 
 their chemical constitution. This investigation 
 opens up the possibility of drawing many in- 
 ferences concerning the action of chemical forces. 
 The following tables exhibit an abstract of the 
 measurements of the molecular conductivities of 
 various acids for the dilutions of 4, 82, and 256 
 litres : — 
 
 Acid 
 
 4 
 
 32 
 
 256 
 
 
 litres 
 
 litres 
 
 litres 
 
 Hydrochloric HCl . 
 
 80-9 
 
 87-0 
 
 89-2 
 
 Hydrobromic HBr . 
 
 83-4 
 
 87-9 
 
 89-6 
 
 Hydriodic HI 
 
 83-2 
 
 89-6 
 
 89-7 
 
 Hydrofluoric UJb' 
 
 6-54 
 
 13-14 
 
 30-3 
 
 Hydrocyanic HON . 
 
 0-077 
 
 0-108 
 
 
 Sulphocyanic HSCN. 
 
 79-3 
 
 84-2 
 
 8R-fS" 
 
 Sulphydric H^S . 
 
 
 
 0-214 
 
 
 FerrocyanicHjFe(CN)5 
 
 
 
 205-9 
 
 250-j; 
 
 'd 
 
AFFINITY. 
 
 8S 
 
 The acids which do not contain oxygen show 
 great differences : HOI, HBr, HI, form a group 
 of strong acids, while HF is much weaker ; HON 
 can scarcely he called an acid ; H2S is slightly 
 stronger ; but if cyanogen combines with sul- 
 phur and hydrogen sulphocyanio acid is formed 
 the strength of which approaches that of hydro- 
 chloric acid. Perrocyanio acid is also a strong 
 acid, though made up of the neutral iron cyanide 
 and the weakly acid hydrogen cyanide. 
 
 Acid 
 
 4 
 litres 
 
 33 
 
 litres 
 
 356 
 
 litres 
 
 Nitric HNO3 
 Chloric HCIO, . 
 Perchloric HClOi . 
 Bromic HBrOj . 
 Iodic HIO3 . 
 Periodic H5IO, . 
 
 80-4 
 80-2 
 82-2 
 
 50-6 
 23-7 
 
 86-3 
 85-8 
 88-1 
 79-4 
 72-3 
 49-2 
 
 88-4 
 88-7 
 89-9 
 86-3 
 81-8 
 76-7 
 
 HNO3, HCIO3, HCIO, closely follow the halogen 
 hydracids ; HBrOa is weaker ; HIO3 is still weaker ; 
 and HsIOj shows this decrease in strength to a 
 marked extent. A similar relation is shown by 
 the acids of phosphorus. 
 
 Acid 
 
 4 
 Utres 
 
 32 
 
 litres 
 
 256 
 litres 
 
 Hypophosphorous H3PO2 
 Phosphorous HjPOj 
 Orthophosphorio HjPO, 
 
 37-91 
 34-29 
 17-00 
 
 62-1 
 
 56-96 
 
 34-41 
 
 77-84 
 74-54 
 61-8 
 
 Here too the acids become weaker as the amount 
 of oxygen increases. The opposite relation is 
 shown by the acids of sulphur and selenion. 
 
 Acid 
 
 4 
 litres 
 
 32 
 litres 
 
 256 
 litres 
 
 Sulphurous HjSOj 
 Sulphuric HjSO, . 
 Dithionio H^SjOs . 
 Tetrathionio H^S^O, . 
 Selenious H^SeO, . 
 Selenic H^SeOi . 
 
 19-19 
 96-4 
 
 9-74 
 103-2 
 
 41-6 
 116-3 
 166-4 
 170-6 
 
 21-73 
 127-0 
 
 66-5 
 150-6 
 178-0 
 181-5 
 
 45-11 
 157-9 
 
 The strength increases with increase of oxygen 
 as well as with increase of sulphur. 
 
 As regards organic acids, the members of the 
 acetic series are weak acids, and the strength de- 
 creases as we ascend in the homologous series. 
 
 
 4 
 
 32 
 
 256 
 
 Acta 
 
 litres 
 
 litres 
 
 litres 
 
 Formic HCO H 
 
 2-47 
 
 6-63 
 
 17-0 
 
 Acetic CH3CO2H . 
 
 0-755 
 
 2-12 
 
 5-64 
 
 Propionic G.^HsCO^H . 
 
 0-601 
 
 1-77 
 
 4-92 
 
 Butyric GJi^GO^'B. . 
 
 0-604 
 
 1-81 
 
 5-04 
 
 Isobutyrio C.H^OOjH . 
 
 0-608 
 
 1-81 
 
 4-95 
 
 Valeric C^H^CO^H 
 
 0-615 
 
 1-87 
 
 5-16 
 
 Caproic CfiifiO^B , 
 
 — 
 
 1-70 
 
 4-78 
 
 Appreciable differences are shown in the first 
 three members only. 
 
 When chlorine, bromine, iodine, or cyanogen, 
 is substituted for hydrogen, the acid character 
 increases. 
 
 Acid 
 
 4 
 litres 
 
 32 
 litres 
 
 266 
 
 litres 
 
 Monochloracetio OHaOICOaH 
 
 6-93 
 
 ir-3 
 
 37-8 
 
 Diohloraoetio CHCIjCO^ . 
 
 34-3 
 
 60-3 
 
 76-2 
 
 Trichloraoetio C01,00,H . 
 
 6S-9 
 
 76-0 
 
 78-1 
 
 MonobromaoetioOH.BrOO.H 
 
 — 
 
 16-1 
 
 36-8 
 
 Oyanaoetio CH,CNOO,H . 
 
 10-6 
 
 S5-3 
 
 67-8 
 
 ■Bromopropionic 
 
 
 
 
 OH.CHBrCO,H 
 
 7-87 
 
 17-8 
 
 36-3 
 
 ^lodopropionic 
 
 
 
 
 CH,IOH.OO,H 
 
 1-634 
 
 4-386 
 
 11-8 
 
 The chlorinated acids are seen to increase in 
 strength as the amount of chlorine increases ; 
 but even trichloracetic acid does not reach the 
 value for hydrochloric acid. The substitution 
 of bromine, or cyanogen, for hydrogen acts in 
 the same way as the substitution of chlorine ; 
 the action of cyanogen is much more marked 
 than that of bromine. Introduction of the group 
 OH for H in the fatty acids increases the strength 
 of the acids, although not to so great an extent 
 as is noticed in the preceding table. 
 
 Acid 
 
 4 
 Utres 
 
 32 
 Utres 
 
 256 
 lities 
 
 GlycolioCH.OHOO^H . . . 
 
 2-08 
 
 6-77 
 
 15-09 
 
 Glyoxylio COH.CO,H . . . 
 
 3-66 
 
 9'83 
 
 24-51 
 
 Lactic CH,CHOHCO.H 
 
 1-94 
 
 6-49 
 
 14-42 
 
 /soxypropionic OHaOHCH^CO.H . 
 
 0-896 
 
 2-63 
 
 7-18 
 
 TricWorolaoticCCljCHOHOOaH: . 
 
 11-0 
 
 27-7 
 
 64-8 
 
 Pyruvic CHjCOOO.H . 
 
 9-06 
 
 22-1 
 
 43-8 
 
 Glyceric CH.OHOHOHCO.H . 
 
 2-46 
 
 6-87 
 
 17-9 
 
 "Oxybutyric 0,H.CHOHCO,H . 
 
 1-44 
 
 3-99 
 
 10-08 
 
 TOxybutyricCH,CHOHCH,CO,H 
 
 1-31 
 
 3-4 
 
 7-70 
 
 Oxyisobutyrio (CH,)jOOHCO,H . 
 
 1-98 
 
 6-07 
 
 12-81 
 
 Methoxyaoetic CH,OCH,CO,H . 
 
 2-99 
 
 8-29 
 
 20-75 
 
 Ethoxyacetic CHaOC,H,CO.H , 
 
 2-40 
 
 6-94 
 
 17-93 
 
 Diglycolic 0(CH,CO,H), . , 
 
 8-00 
 
 13-78 
 
 33-68 
 
 Thiodiglyoolio S(OH,CO^H). . 
 
 — 
 
 11-73 
 
 28-22 
 
 The influence of the relative positions of the 
 OH groups appears to be of importance. In the 
 cases of the isomeric lactic acids and the oiy- 
 butyrio acids, that one is the strongest in which 
 the OH is nearest the COOH group. Pyruvic 
 and glyceric acids seem to obey the same law. 
 The following members of the oxalic acid series 
 have been investigated: 
 
 Acid 
 
 4 
 litres 
 
 32 
 litres 
 
 256 
 Utres 
 
 OxaUo(00,H) 
 
 36-82 
 
 61-4 
 
 79-8 
 
 Malonic 0H,(00aH), . 
 
 6-34 
 
 16-6 
 
 37-7 
 
 Succinic C,H.(CO»H), . 
 
 1-30 
 
 3-72 
 
 10-03 
 
 Metbylmalonio OHOH,(00aH)a . 
 
 — 
 
 12-91 
 
 30-8 
 
 PyrotaxtaricC,H.OH,(00,H), . 
 
 2-29 
 
 6-74 
 
 13-19 
 
 Dimetbylmalonio 0(Ca:,),(00,H). 
 
 — 
 
 12-14 
 
 29-69 
 
 Ethylmalonic CH(0,H.)(00,H)j . 
 Suberic C.H„(CO,H), . . . 
 
 — 
 
 16-18 
 
 36-06 
 
 — 
 
 — 
 
 6-99 
 
 Sebacic C,H„(CO,H), . 
 
 — 
 
 — 
 
 6-6» 
 
 Malic 0,H3(0H)(C0,H).. . 
 
 2-97 
 
 8-63 
 
 22-28 
 
 Tartaric 0,Ha(OH),(COsH), . 
 
 6-06 
 
 13-68 
 
 33-15 
 
 Eacemic OaH^(OH)j(C03H), . 
 
 6-07 
 
 13-64 
 
 33-19 
 
 Saccharic O.H.(OH),(CO,H). 
 
 — 
 
 12-14 
 
 29-73 
 
 Muoic O.H.(OH).(CO.H), . 
 
 — 
 
 — 
 
 16-39 
 
 * By extrapolation. 
 
 As the distance between the two oarboxyls in- 
 creases the dibasic acids become rapidly weaker ; 
 sebacic acid is scarcely stronger than the higher 
 acids of the acetic series. Of the two isomerides, 
 succinic acid and isosuccinic or methylmalonic 
 acid, the latter has the carboxyls nearer together, 
 and is therefore the stronger. Tartaric acid and 
 raoemic acid show no difference; hence the 
 latter when in solution is not a compound of 
 
 9,2. 
 
84 
 
 AFFINITY. 
 
 right-handed and left-handed tartaric acid, as ia 
 the case in the crystalline form, but it is rather 
 a mixture of the two. 
 
 The derivatives of benzoic acid are of special 
 interest owing to the conditions under which 
 isomerism occurs in this series. The following 
 have been investigated : — 
 
 Acid 
 
 32 litres 
 
 256 litres 
 
 Benzoic 0,H,COaH .... 
 
 ^ 
 
 9-95 
 
 Oxybenzoio 1:2' O.H.OH00,H . 
 
 — 
 
 33-02 
 
 1:3 
 
 4-31 
 
 11'24 
 
 1:*: 
 
 J-39 
 
 6-65 
 
 Nltiobenzoio 1:2 O.H.NO,CO,H . 
 
 — 
 
 64-34 
 
 1:3 
 
 — 
 
 20-83 
 
 l:t 
 
 .— 
 
 22-0» 
 
 Chlorobeniolo 1:2] O.H.aCO^ . 
 
 — 
 
 32'64 
 
 [1:3] 
 
 — 
 
 1513 
 
 [1:*] 
 
 — 
 
 12-7* 
 
 Bromobenzoio [1:2] 0,H^rCO,H . 
 
 -« 
 
 38-89 
 
 £1:3] 
 
 — 
 
 14-8 
 
 * By extrapolation. 
 
 The substituting radicle always exerts most in- 
 fluence on the strength of the acids when it is in 
 the ortho position. There is little difference 
 between the meta and para positions. It is 
 strange that para-oxybenzoic acid should be 
 weaker than benzoic acid itself, as in all other 
 oases the introduction of OH increases the 
 strength of the acid. This points to the con- 
 clusion that the af&nity-foroes are of the nature 
 of vector quantities, that is, that they are directed 
 forces the resultants of which cannot be put as 
 simply equal to the sums of the components. 
 The other acids of the aromatic (or benzenoid) 
 group for which measurements have been made 
 are as follows ; — 
 
 Add 
 
 33 
 litres 
 
 256 
 
 litres 
 
 AmJdobenzene Bnlpbonic [1:3] 
 
 
 
 C.H.NH,SO.H 
 
 4-55 
 
 16-13 
 
 Amidobenzene Bulpbonic [1:4] 
 
 
 
 O.H.NH,SO,H 
 
 10-84 
 
 26-36 
 
 Mononitropbenol [13] 0,H.NO,OH 
 
 — 
 
 1-02 
 
 [1:3] 
 
 0-14 
 
 0-26 
 
 ,; [1:4] 
 
 0-177 
 
 0-41 
 
 Dinitrophenol [1 :2, 1 :4] C.H.(NO,).OH 
 
 ^- 
 
 10-96 
 
 Trinitrophenol [1:3:6] O.H,(NOJ,OH 
 
 _- 
 
 79-7 
 
 Anisic C.H.OCH,COjH 
 
 — 
 
 5-00 
 
 aToluio C.H.CHjCO^H 
 
 3-61 
 
 9-1 
 
 Pbenylgljcolio C.H.CHOHCO,H 
 
 9-02 
 
 22-76 
 
 Phenoxyaoetio C,B.,OCRJOO^ . 
 
 13-57 
 
 29-86 
 
 Phtbalic [1:2] O.H.(C0aH), 
 
 16-15 
 
 35-23 
 
 . „ [1:3] „ . . 
 
 — 
 
 20-0 
 
 Nitropbthalio O.H.(NO.) (CO;.H), . 
 
 38-62 
 
 66-67 
 
 » » . • 
 
 29-22 
 
 ( 57-50 
 125-00 
 
 The introduction of NH^ into benzene sul- 
 phonic acid, which is nearly as strong as hydro- 
 chloric acid, is accompanied by the production 
 of a much weaker acid. The meta-acid is weaker 
 than the para-acid. The three nitrophenols 
 show the gradation ortho, para, meta, in the 
 same way as the nitrobenzoic acids. The phe- 
 nols rapidly increase in strength with the 
 number of NO, groups they contain. Another 
 point of interest is the difference exhibited by 
 the isomerides anisic acid, phenylglycolio acid, 
 and phenoxyacetic acid. Orthophthalic acid 
 greatly exceeds metaphthalic acid in strength ; 
 while of its two nitro derivatives, the a compound, 
 in which the NO, group is adjacent to the car- 
 boxyl, proves itself superior to the j8 derivative 
 in which there ia a greater distance between the 
 
 KO, and the COOH groups. As regards the un- 
 saturated acids, the following numbers show that 
 they are the stronger the less hydrogen they 
 contain. 
 
 Acid 
 
 4 
 litres 
 
 32 
 litres 
 
 266 
 
 litres 
 
 Acrylic OjH^COjH . . 
 
 1-25 
 
 3-46 
 
 9-20 
 
 Crotonio OjH.COjH . 
 
 0-728 
 
 2-16 
 
 6-88 
 
 Fumaric \ c-a nnvr 
 
 Maleic }0»H,CO,H . . . 
 
 17-46 
 
 13'52 
 39-15 
 
 32-6 
 66-49 
 
 Citraconic 
 
 9-66 
 
 24-05 
 
 49-67 
 
 Itaconio 0,H.CO,H 
 
 1-92 
 
 6-33 
 
 14-66 
 
 Mesaconlc 
 
 — 
 
 11-93 
 
 29-45 
 
 Hydroolnnammio 0,H,O.H.COjH 
 
 — 
 
 2-26 
 
 6-08 
 
 Cinnammic O.^fi^HjOOJI . 
 
 — 
 
 — 
 
 7-66 
 
 Phenjlpropiolio C.H,CaOO,H . 
 
 — 
 
 27-66 
 
 62-0 
 
 Hydrosorbio C,H,CO,H; . 
 
 — 
 
 2-29 
 
 6-29 
 
 SorbioO,H,CO,H. 
 
 •^ 
 
 .— 
 
 6-ro 
 
 «TlTnTnnninnamTm-fi 
 
 
 
 
 i;.ll.U,iLBrUO,li 
 
 — 
 
 
 
 62-70 
 
 isBromocinoammic 
 
 
 
 
 C,H.O.HBrCO^ 
 
 _ 
 
 — 
 
 33-1 
 
 Meoonio 0,HOaOH(COaH), . 
 
 — 
 
 102-1 
 
 141-8 
 
 Quinio C.H,(OH),CO,H . . 
 
 _ 
 
 r-81 
 
 19-92 
 
 Oampboric C.H,CjH,COjH . 
 
 — 
 
 — 
 
 6-07 
 
 On comparing acrylic with propionic acid, 
 crotonic with butyric acid, f umaric and maleie 
 -with succinic acid, and citraconic, itaconic, and 
 mesaconic with pyrotartario acid, it is evident 
 that for each withdrawal of H, the acid becomes 
 stronger. These relations become very con- 
 spicuous when we compare hydrocinnammic with 
 cinnammic and phenylpropiolio acid, and hydro- 
 sorbio with sorbic acid. As regards the peculiari. 
 ties of the dibasic unsaturated acids, they can 
 only be just mentioned. Meconic acid, which 
 stands by itself, is conspicuous by its great 
 strength. It is the strongest of all acids which 
 consist of carbon, oxygen, and hydrogen only, 
 and it approaches very near to sulphuric acid. 
 There is evidently some connexion between 
 this property and the small amoimt of hydrogen 
 this acid contains. 
 
 The introduction of amidogen and similar 
 radicles makes the acids weaker. 
 
 Acid 
 
 8 
 litres 
 
 32 
 
 litres 
 
 266 
 
 litres 
 
 AtnidoaoeticOHaNHjCOjH . 
 Hippuric, 
 
 CH,NH(O.H.CO)COaH . 
 Acetylamidoacetie 
 
 CH,NH(CH.OO)OO.H . 
 Oxamio CONHjCO^H . 
 Oxaluric 
 
 00(NHC0irH,)CO,H 
 Parabanic (CONH),CO 
 
 0-236 
 
 21-07 
 43-36 
 
 0-257 
 
 6-68 
 
 6-88 
 35-88 
 
 57-03 
 48-23 
 
 0-32 
 
 17-38 
 
 17-78 
 62-26 
 
 74-28 
 63-96 
 
 The introduction of the NH, group into acetic 
 acid is attended with a great reduction of the 
 strength of the acid. This acid is considerably 
 less weakened when one of the hydrogens in the 
 NHj group is replaced by the negative radicle 
 benzoyl or acetyl. Oxalic acid is also weakened 
 by introducing the NH, group. On the other 
 hand the introduction of the urea residue 
 (ISfHCONH,) into oxalic acid only slightly 
 decreases the conductivity of the oxalic acid. 
 Farabanic acid does not contain the carboxyl 
 group, nor does it behave at all hke an acidi 
 since its conductivity increases but slightly with 
 dilution. 
 
 The conditions of affinity among acids form 
 the best-known part of the theory of affinity. 
 
AFFINITY. 
 
 65 
 
 Oar knowledge eonoerning the bases is much 
 more scanty. From the fact that the relative 
 afBnities of acids are independent of the nature 
 of the bases, we can infer that the relative 
 affinities of the bases must also be independent 
 of the nature of the acids {J. pr. [2] 16, 422). 
 It is highly probable that the same laws hold 
 for bases as for acids. 
 
 It must, however, be admitted that there is 
 great lack of experimental data in this depart- 
 ment. Some experiments of Meuschutkin (C. B. 
 96, 256), who drew from them the conclusion 
 that Berthollet's law of the influence of mass 
 does not hold, prove only that under the condi- 
 tions of the experiment the relative afi&nities of 
 the bases compared — potash to aniline, to tri- 
 methylamine, and to ammonia, in alcoholic 
 solutions — are very different. The same f ac t was 
 proved by some thermo-chemical experiments of 
 Berthelot. 
 
 Nor have many experiments been made by 
 the kinetioal method. Warder (B. 14, 1361) 
 who first applied this method to bases, measured 
 the velocity of decomposition of ethylic acetate. 
 An investigation made by Eeicher (Van't Hoff, 
 Dyn. chim. 107) in connexion with Warder's 
 work, showed that the velocity of the reaction 
 is nearly the same for potash, soda, and baryta, 
 the electrical conductivities being also nearly 
 the same. 
 
 Ostwald {/. pr. [2] 33, 352) has recently in- 
 vestigated the electrical conductivities of some 
 bases. The alkalis KOH, NaOH, LiOH, are 
 strong bases ; they have nearly the same con- 
 ductivities. TIOH acts as an alkali. The con- 
 ductivities of CaOjHj, SrOjHj, and BaOjH^, 
 referred to masses equivalent to NaOH, &c., are 
 the same as those of NaOH, &o. ; the molecular 
 conductivities of CaO^II;, &c., are, however, 
 double those of NaOH, &o. Ammonia is a 
 weak base ; its conductivity is much influenced 
 by dilution ; the variations in the molecular con- 
 ductivity follow the same law as was observed 
 for acids. Substitution of H or Hj in NH3 by 
 CH3, C2H5, and other alkyl groups, increases the 
 strength of the base ; but N(CH3)3 and NfCjHj), 
 are weaker bases than NH(CH3)2 and NH(C2Hj)j. 
 These bases all follow the same law of dilution. 
 The non- volatile ammonium bases, e.g. NMe^OH 
 — and also the base (C2H5)3S{OH)2 — exhibit con- 
 ductivities nearly the same as those of the 
 alkahs ; guanidine is a little weaker, but belongs 
 more to the ammonium bases than to the de- 
 rivatives of ammonia. 
 
 In a memoir not yet published, Ostwald shows 
 that these conclusions are confirmed by kinetical 
 experiments on the saponification of ethylic 
 acetate. 
 
 Besides the investigations which have led to 
 numerical values for certain constants of afliuity, 
 there are numerous others from which such 
 quantities cannot be deduced, because the re- 
 actions investigated were too complex. To this 
 class belong principally the works of Berthelot 
 and P. de St. Gilles on etherification, and the 
 investigations of Menschutkin (collected in A. Ch. 
 15] 30, 81) on the same subject. 
 
 The importance of the first of these in 
 chemical dynamics has already been emphasised. 
 The latter have brought out interesting connec- 
 tions between the reactions observed and the 
 
 chemical constitution of the acids used. The 
 values obtained do not, however, lend themselves 
 to the determination of coefficients of affinity ; 
 and the investigations themselves cannot there- 
 fore be considered here at greater length. The 
 work of Horstmann (B. 12, 64), and of Dixon 
 {T. 1884. 617), on incomplete combustion can 
 likewise only be mentioned. 
 
 Little attention hag as yet been directed to 
 the investigation of the influence of temperature 
 on the velocities of reactions, and on the con- 
 stants of affinity. For the case of the inver- 
 sion of cane sugar there are the investigations of 
 Wilhehny, Urech, and Spohr ; for the velocity 
 of etherification there are those of Berthelot and 
 P. de St. Gilles, as well as those of Menschutkin. 
 The whole question has been thoroughly investi- 
 gated by Van't Hoff. By applying the dynamical 
 theory of heat he finds that the equation for the 
 relation between the temperature and the velo- 
 city of the reaction. A;, must be of the form 
 
 <Zlog k 
 dr 
 
 A 
 
 ::?+B 
 
 where t is the absolute temperature, and A and 
 B are constants. 
 
 Van't Hoff has also shown that for several 
 reactions the observed facts can be very well re- 
 presented by such a formula. For details the 
 book of Van't Hoff which has been mentioned 
 must be consulted. 
 
 Berthelot and P.de St. GiUes have found that 
 the chemical equilibrium of etherification is in- 
 dependent of the temperature within a wide 
 range. Ostwald established the same general- 
 isation for the relative affinities of various acids, 
 Van't Hoff shows by the help of the dynamical 
 theory of heat that this will occur when the 
 reactions producing equilibrium do not give an 
 appreciable thermal effect as their resultant. 
 Moreover, when this is not the case, with a fall 
 of temperature the equilibrium shifts in favour 
 of that reaction which produces more heat than 
 the reverse one {I. c. 167). 
 
 We have now arrived at the point where we 
 must take up the problem concerning the rela- 
 tion between affinity and production of heat. As 
 soon as it had been recognised that the thermal 
 action accompanying a chemical reaction was 
 the measure of the chemical energy used up 
 therein, an attempt was made to apply this to 
 the question of affinity. 
 
 In 1854, J. Thomseu enunciated the following 
 laws (P. 92, 34). The magnitude of the force 
 evolved in the formation of a compound is equal 
 to the quantity of heat produced. When a com- 
 pound is decomposed by another body the reason 
 for this is that the stronger affinities satisfy them- 
 selves ; hence decomposition must be accompa- 
 nied by an evolution of force. Since chemical 
 force when hberated under ordinary conditions 
 generally manifests itself as an evolution of heat, 
 it follows that ' every simple or complex effect of a 
 purely chemical nature is accompanied by pro- 
 duction of heat.' 
 
 This deduction, plausible though it seems at 
 first sight, is not correct. Heat does not measure 
 forces but quantities of energy; hence the 
 chemical production of heat does not tell us any- 
 thing concerning the intensity of chemical forces : 
 it is only the product of their (mean) value (if 
 
AFFINITY. 
 
 ■we imagine them to be forces of attraction) into 
 the space passed over by the atoms that is a 
 quantity of energy, and as such is measurable 
 by thermal methods. Since we know nothing 
 about the spaces passed over by the atoms, and, 
 moreover, cannot assume that the spaces are the 
 same for all compounds, no conclusion regarding 
 the chemical forces can be accurately drawn 
 from measurements of the quantities of heat 
 produced in chemical reactions. 
 
 To point out the old mistake would have 
 been uncalled for, were it not that Berthelot has 
 of late years enunciated an analogous erroneous 
 'law,' which he has defended with great 
 warmth. It is the more necessary to submit 
 this theory to criticism, as, owing to the great 
 prestige which the renovator of this old mistake 
 enjoys — a prestige he owes to his excellent ex- 
 perimental researches — the theory is surrounded 
 as it were by a halo which has deterred many 
 from closely examining it. Berthelot formu- 
 lates his law as follows : ' Tout changenient 
 chimigue accompli sans I' intervention d'une 
 inergie itrangire tend vers la prodiLction du 
 corps, ou du systime de corps, qui digage le phis 
 de chaleur.' And further : ' Toute riaction 
 cMmigue susceptible d'etre accomplie sans le 
 concours d'un travail priliminaire et en dehors 
 de I'mtervention d'une inergie itrangire a cells 
 des corps presents dans le sysUme, se produit 
 nicessaArement, si elle digage de la chaleur.' 
 
 By a vague connexion with general dynamics, 
 Berthelot calls this the principle of maximum 
 work. He assumes it to follow as a natural 
 consequence from the dynamical theory of heat. 
 This view is erroneous. There is no such 
 thing as a law according to which a dynamical 
 system is in equilibrium when the greatest pos- 
 sible quantity of its potential energy has been 
 changed into actual energy ; but this would be 
 the dynamical analogue of the so-called chemical 
 law. 
 
 There does, however, exist a law in the dyna- 
 mical theory of heat according to which a system 
 is in equilibrium when it has attained to the 
 maximum entropy. This function, which was 
 first introduced by Clausius, is, like the energy 
 of a system, entirely dependent on the condition 
 of the system; it is defined by the equation, 
 
 dS = -mt where S stands for entropy, Q for a 
 
 quantity of heat given to the body, and Tforthe 
 absolute temperature. Horstmann {A. 170, 192), 
 was the first to apply this law to chemical 
 phenomena. The investigation has also been 
 carried out very fully by Willard Gibbs. Unfor- 
 tunately, the law is of very limited application. 
 The integration can only be accomplished if the 
 substances experimented with are perfect gases : 
 Horstmann has shown that the law of entropy 
 then leads to the same result as is attained by ap- 
 plying Guldberg and Waage's law of the influence 
 of mass. This law has thus been supplied from 
 the theoretical side with a valuable confirmation. 
 As far as we can tell, the law of entropy does 
 not generally lead to reactions which are quite 
 completed on one side, but rather to conditions 
 of chemical equilibrium between opposite pro- 
 cesses. According to Van't Hoff {I.e. p. 153), 
 these processes vary with the temperature, if 
 
 they are aooompanied by a positive or negative 
 production of heat, and the law is that the 
 equilibrium shifts the more in favour of the 
 positive thermal production the lower is the tem- 
 perature. It is, however, only at absolute zero 
 that the reaction would take place in one 
 direction only (if at this temperature chemical 
 reactions are at aU possible) ; and it is only for 
 this hmiting case that a law of maximum 
 thermal efieot would hold good. 
 
 This is all that the law of the maximum 
 thermal effect reaUy contains ; it is a limiting 
 case from which the actual conditions differ the 
 more the higher is the temperature. Since the 
 temperature at which ordinary chemical re- 
 actions occur is not very high, the reactions ac- 
 companied by production of heat preponderate. 
 This had been already noticed by Thomsen, and 
 the approximation to truth contained in the law 
 we certainly owe to him. 
 
 What Berthelot has added refers to the 
 cases of chemical equilibrium which have been 
 established beyond doubt, and which, according 
 to the principle of maximum work, ought not to 
 occur ; this law asserts that because one of two 
 reciprocal reactions is attended with production 
 of heat that one ought to take place exclu- 
 sively. It is Berthelot's endeavour to reduce 
 all reactions in which chemical equilibrium has 
 been observed to cases of partial dissociation, 
 wherein the masses of the reacting bodies do 
 not act as wholes. To accomplish this, he is 
 obliged to call reactions of a purely chemical 
 nature, dissociations ; for example, the decom- 
 position of acid sodium sulphate in aqueous 
 solution, a reaction brought about by the affinity 
 between sulphuric acid and water. The whole 
 explanation resolves itself into reasoning in a 
 circle. It need scarcely be said that an explana- 
 tion of this kind cannot account for the laws by 
 which the chemical equihbrium, the velocity of 
 chemical reactions, and the electrical conduc- 
 tivities of the reacting bodies, are connected. 
 
 There is no doubt that, with the possibiUty 
 of a more general application of the laws rf 
 entropy to chemical reactions, thermochemical 
 data will become important and fundamental 
 means for the investigation of the relations of 
 affinity. Moreover, there is httle doubt that 
 Bergmann's theory of affinity, revived in a 
 thermochemical form, is not the solution of the 
 problem, and that, in spite of its modern 
 appearance, it can as httle keep its ground 
 againstBerthollet's far-reaching views as it could 
 in its older form. 
 
 Of aU the great old-standing problems of 
 chemistry, that of chemical affinity has been 
 least developed. The general relations and laws 
 given in this article refer only to a limited number 
 of substances, and to a hmited number of reac- 
 tions ; many parts of the question have not yet 
 been investigated at all. Great and important 
 progress has, however, been achieved by Berthol- 
 let's enunciation, and Guldberg and Waage'g 
 rational formulation, of the law of active masses. 
 It must, however, be admitted that there are some 
 reactions which seem to contradict this law, and 
 which cannot be explained by it when taken in 
 its simple form. It is not necessary to reject the 
 law on this account, as has been done by some. 
 The actual conditions of each experiment we make 
 
AQGEEGATION, STATES OF. 
 
 87 
 
 lire BO complex that we are not able to completely 
 apply the law of the influence of mass. We 
 must content ourselves with an approximation 
 which does not always lie -within the limits of 
 experimental errors. The motions of the stars 
 cannot yet be represented in strict accordance 
 with the law of gravitation; yet the first ap- 
 proximation is sufficient to remove any doubts 
 as to the validity of the law. The law of the 
 influence of mass in its simple application is also 
 only true to a sufficient approximation in those 
 cases in which the effects considered are of great 
 magnitude as compared with those neglected. 
 (In connexion with affinity v. Pny sioal methods ; 
 section Optical.) W. 0. 
 
 AGAH-ACrAS or Bengal Isinglass. 
 
 A vegetable gum obtained in China from sea- 
 weeds : Eucheuma spinosum, sphcsrococcus 
 lichenoides, spinosus, and tenax. Transparent 
 colourless strips, almost completely soluble in 
 water : forms a large quantity of thick, taste- 
 less, and odourless jelly. Dilute H^SO, forms 
 galactose, characterised by its conversion into 
 galactonic acid by Brj and AgjO. This galactose 
 is formed from a carbohydrate, CjHmOs, present 
 in the agar-agar (Bauer, J.pr. [2] 30, 367). 
 
 AGARICIC ACID 
 C,„H,„05aq. [139°] (J.) ; [145-7°] (F.). S. -8 at 15°. 
 Obtained, together with agaric resin, from the 
 larch-fungus (Boletus Laricis) by extraction 
 with dry ether (Fleury, C. B. 70, 53) or with 
 90 p.c. alcohol (Jahns, Ar. Ph. [3] 21, 221, 260). 
 
 Four-sided, silvery plates (from 90 p.o. 
 alcohol at 50°) or prisms (from dry alcohol). 
 V. sol. hot glacial HOAo or oil of turpentine, 
 m. sol. chloroform or ether, v. si. sol. benzene or 
 cold water. Swells up and dissolves in boiling 
 water but crystallises out again on cooling. 
 Oxidised by HNOj to butyric and succinic acids. 
 
 Salts. — Amorphous, insoluble pps. The 
 neutral salts, U.C^Ji^O^ lose H^O at 120° 
 becoming MaCiAoO,.— NH^HA".— Na^A" (at 
 120°).— KjA".— BaA".— AgjA" : gelatinous pp. 
 Hot alcoholic solutions give, with AgNOj, a pp. 
 of AgjCisHj^O, (Jahns). 
 
 AGAIIICIN. The fly-agaric {Agaricus albus) 
 yields to alcohol a non-nitrogenous crystalline 
 powder having a sweet taste with bitter pungent 
 after taste ; slightly soluble in water, insoluble 
 in ether ; decomposed by boiling with dilute 
 acids, or by contact with saliva, yielding a 
 substance which exerts a slight reducing power 
 on alkaline copper-solution (Schoonbroodt, J. 
 1864, 613). According to Jahns (/. 1883, 1400) 
 it is identical with agaricic acid. H. W. 
 
 ACrABIC BESIN v. Agaeicio Acid. 
 
 Red, amorphous, solid ; melts at 89'7° ; dis- 
 solves in absolute alcohol, ether, wood-spirit, 
 and cliloroform, but is insoluble in water, 
 benzene, and CS^ ; slightly bitter ; dissolves in 
 alkalis. Na salt precipitated by alcohol in flocks 
 changing in 24 hours into long needles. Forms 
 precipitates, mostly crystalline with metaUio 
 salts (Fleury, 0. B. 70, 53). H. W. 
 
 ACrABICTTS. A genus o£ Fungi. Many 
 fungi, especially the agarics, contain an amount 
 of nitrogen exceeding that in peas and beans, 
 varying from 3-19 p.c. to 7-26 p.o. (Schlossberger 
 a. Topping, A. 52, 106). 
 
 The solid tissue consists of cellulose. Agarics 
 contain mannite and fermentable sugar, but no 
 
 starch. Many agarics contain fumaric acid,, 
 sometimes associated with malic or citric acid. 
 
 Agaricus bulbosus and A, integer yield 
 crystallisable hydrochlorides and platino- 
 chlorides of basic bodies (Thorner). 
 
 Agaricus ruber or sanguineus contains & 
 colouring-matter, ruberiiie, soluble in water 
 and in alcohol. It is rose-red by transmitted 
 light, having two absorption bands in the green, 
 but it exhibits strong blue fluorescence. Dilute 
 HCl extracts an alkaloid, agarythrine, from 
 the fungus ; this alkaloid is converted by 
 oxidising agents into a red substance, possibly 
 ruberine (T. L. Phipson, G, N. 46, 199). 
 
 Agaricus integer, contains an acid, with 
 following properties : white needles [70°], very 
 soluble in ether, benzene, CS^, CHCI3, hot 
 alcohol and acetic acid, insoluble in water, and 
 cold alcohol and acetic acid. — A'^Pb : insoluble 
 white pp. [114°]. The alkaline salts are sparingly 
 soluble in cold water, and the salts of the heavy 
 metals, insoluble (Thorner, B. 12, 1635). 
 
 Agaricus atramentosus yields to boiling ether 
 a dioxyquinone C„H|jOa(OH)j. Dark brown 
 metallic-shining laminae, dissolving with yellow 
 colour in alkalis, insoluble in water, ether, light 
 petroleum, benzene, chloroform and CSj. Sub- 
 limes with great difficulty in yellow microscopic 
 tablets. It is reduced by boiling its alcoholic 
 solution with zinc-dust, the resulting colourless 
 liquid becoming yeUow-green again on exposure 
 to the air. The ammonium salt is a green 
 crystalline powder, dissolving readily in water 
 with violet colour, nearly insoluble in boiling 
 absolute alcohol. — Ba soZi : dingy flesh-coloured 
 crystalline precipitate (Thorner, B. 11, 533). 
 The diacetyl derivative C,5H,204 = C„H802(OAc)j 
 forms small reddish yellow tablets. 
 
 Boletus Laricis contains besides agaricio 
 acid and (25 p.c. of) agaric resin also 3 to 5 p.c. 
 of a neutral body, which crystallises in needles, 
 [272°], and may be sublimed (B. Jahns, /. 1883, 
 1400). H. W. 
 
 AGAVE. Well preserved juice of Agave 
 americana, sp. gr. 1-046 at 15° was found by 
 J. Boussingault (A. Ch. [4] 11, 447) to contain 
 in 1000 parts : 26-45 levulose, 61-71 saccharose, 
 3-53 malic acid, 5-45 gum, 10-13 albumin, 0-06 
 ammonia, 6'21, inorganic salts, and 88646 water. 
 
 H. W. 
 
 AGE or AXIN. The fat of Coccus Axin grow- 
 ing in Mexico, consists of the glycerides of laurio 
 and axinic acids (Hoppe, J. 1860, 324). H. W. 
 
 AGGKEGATIOir, STATES OF.— In this ar- 
 ticle the differences between the properties of 
 bodies in the solid, the liquid, and the gaseous, 
 condition, are looked upon as due to differ- 
 ences in the state of aggregation of those small 
 particles, of which, according to the molecular 
 theory of the constitution of matter, all bodies 
 are composed. According to this theory, our 
 power of subdividing matter cannot be carried 
 beyond a certain limit, whatever means — chemi- 
 cal, physical, or mechanical — we employ. In 
 other words, the theory asserts that the largest 
 quantity of a body which we cannot subdivide by 
 any means in our power is of finite size ; it i^ 
 called the atom of the substance of which the 
 body is composed. Each elementary body has 
 its peculiar atom, and the union of atoms oi 
 different kinds forma the smallest quantity 
 
88 
 
 AGGREGATION, STATES OF. 
 
 ■which can exist of a compound substance ; this, 
 however, cannot, in accordance with the defini- 
 tion, be called an atom, since, by the nature of 
 the case, it can be divided by chemical, and often 
 even by physical, means. Though matter can be 
 divided down into atoms by chemical means, 
 yet we have reason to believe that when only 
 physical processes are going on the sub-division 
 of matter is not in general carried so far ; and 
 that just as in an army, though the unit is the 
 individual soldier, yet for military purposes the 
 soldiers forming a regiment always act together, 
 so in matter, groups of atoms, called molecules, 
 remain together for a considerable time. The 
 molecule, however, is a very much less definite 
 thing than the atom, and it must not be assumed 
 without proof in each case that the term has 
 always a definite meaning, or that there may 
 not in the same body be molecules consisting of 
 very different numbers of atoms. There is 
 strong evidence, too, that, in some cases at any 
 rate, the molecule does not always consist of the 
 same atoms ; the molecule after a time seems to 
 break up and the constituent atoms find fresh 
 partners. In some cases, however, such as 
 those of the permanent gases, we have reason 
 to believe that the number of molecules which 
 consist of the same number — say n — of atoms, 
 is enormously greater than the number of those 
 consisting of any other number of atoms. If, 
 however, we raise the temperature, then, in the 
 case of some gases at any rate, dissociation sets 
 in ; that is, there are now a considerable number 
 of molecules in which the number of atoms is 
 less than N ; this is shown by the abnormally 
 small densities of such gases at high temperatures. 
 On the other hand, the density of a vapour near 
 its point of condensation is often abnormally 
 great, as in the case of acetic, formic, and mono- 
 chloracetio, acid; a part at any rate of this 
 increase in density would seem to be due to the 
 formation of molecules consisting of a greater 
 number of atoms than those formed when the 
 temperature was raised far above that of the 
 point of condensation. 
 
 According to the molecular theory of matter, 
 the difference between the molecular constitution 
 of bodies in the solid, liquid, and gaseous, state 
 is that in the solid state the molecules oscillate 
 about a position of equilibrium and never get 
 far from their original position in the body ; in 
 the liquid state the molecules are supposed not 
 to oscillate about positions of equilibrium, but 
 to be comparatively free to move in any direc- 
 tion; they cannot, however, move far without 
 coming under the influence of other molecules, 
 so that their courses are constantly being 
 changed and do not bear any approximation to 
 straight lines ; in the gaseous state the mole- 
 cules are so far apart that for the greater part 
 of the time they are describing straight lines, 
 the time during which they are under the influ- 
 ence of other molecules being an exceedingly 
 small fraction of the whole time. 
 
 We must be careful to remember that there 
 is no evidence that the molecules in the liquid 
 or solid state consist of the same number of 
 atoms as those of the same substance in the 
 gaseous state ; but that on the contrary it seems 
 most probable that in the solid and liquid states 
 the molecules are systems whose complexity is 
 
 not only very different from the molecules in 
 the gaseous state but that these molecular aggre- 
 gations vary very much in complexity among 
 themselves. These molecular aggregations are 
 probably not permanent but are continually 
 breaking up and their constituents changing 
 partners ; this breaking up and re-formation of 
 the molecular aggregations would produce the 
 same effect as the collisions between the mole- 
 cules of a gas, that is, it would tend to equalise 
 the distribution of momentum and energy, so that 
 it would make the substance possess viscosity, 
 and be able to conduct heat. In fact, the 
 collision between two molecules of a gas is the 
 formation and breaking up of a molecular aggre- 
 gation, and the difference between this case and 
 that of a solid or a liquid is that the ratio of the 
 time the molecular aggregation lasts to the time 
 which elapses between the formation of suc- 
 cessive aggregations is much smaller in the case 
 of the gas than in that of the liquid or solid. 
 The simplest state of aggregation we can imagine 
 is one where the molecule and the atom are 
 identical, that is, where the molecule consists of 
 only one atom ; this case is realised by a mon- 
 atomic gas such as mercury, and possibly by all 
 gases when the temperature is sufficiently high. 
 The properties of matter in this state have not 
 been investigated with special regard to the 
 differences between this and more complex 
 states of aggregation; Schuster (Pr. 1885), how- 
 ever, has shown that the phenomena of the 
 electric discharge through mercury vapour are 
 quite different from those occurring in a gas 
 whose molecules are polyatomic. 
 
 In the case of most elementary gases the 
 molecules consist generally of two atoms, and 
 this ease has received by far the largest amount 
 of attention both from the experimental and the 
 theoretical point of view. The most important 
 results of the kinetic theory of gases from the 
 chemical point of view are: — firs t,Avogadro's law, 
 which states that in equal volumes of all gases 
 at the same temperature and pressure there are 
 the same numbers of molecules. Prom this it 
 follows at once that, as long as all the molecules 
 consist of the same number of atoms, the ratio 
 of the molecular weights of two gases is the 
 same as the ratio of their densities. It must, 
 however, bo clearly understood that this result 
 is only true for perfect gases, that is, for gases 
 in which the pressure is produced entirely by 
 the striking of the molecules against the sides 
 of the vessel containing the gas, and not at all 
 by the force between the molecules. If a gas 
 obeys Boyle's law it is a perfect gas for this 
 purpose, and we may apply Avogadro's law to it ; 
 this law is not, however, applicable when Boyle's 
 law does not hold. If the departure from the 
 law be slight, and if Sp be the deviation of pres- 
 sure from that given by Boyle's law, then the 
 number of molecules in unit volume will equal 
 the number in the same volume of a perfect gas 
 at the same temperature and pressure multiplied 
 
 by < 1--^V, wherep is thepressure. This correc- 
 tion is quite appreciable in the case of all but 
 the most permanent gases. Maxwell investi- 
 gated the distribution of velocity among the 
 molecules of a gas, and showed that when the 
 
AGGREGATION, STATES OF. 
 
 89 
 
 gas was in a steady state the moleoulea could 
 not all be moving with the same velocity ; he 
 gave (P.M. [4] 19, 22) a formula which tells how 
 many molecules there are whose velocities are 
 between any assigned limits. We shall here, 
 however, only give a few numbers calculated from 
 that formula. To take the case of oxygen at 
 CO., about ^ the molecules are moving with 
 velocities of between 300 and 600 metres per 
 second, about J between 300 and 100, only 
 about J55 with velocities less than 100 metres 
 per second, and not j^ part with velocities 
 greater than 1,200 metres per second. The 
 velocities with which the molecules of the same 
 gas are moving at diffeient temperatures are 
 proportional to the square roots of the absolute 
 temperatures ; thus the distribution of velocity 
 among the molecules of oxygen at 278°0. would 
 be got by multiplying by i/'2 all the velocities at 
 0°0. The velocities with which the molecules 
 of different gases are moving at the same tem- 
 perature are inversely proportional to the square 
 roots of their molecular weights ; thus, for 
 example, the velocities of the hydrogen mole- 
 cules are on a scale four times as great as that 
 of the oxygen molecules. 
 
 "We can estimate by the methods of the 
 kinetic theory of gases (see Meyer, Die Kine- 
 tische Theorie der Gase) the number of mole- 
 cules in a cubic centimetre of the gas, and the 
 diameter of the molecule, if the molecule is 
 looked on as a hard elastic sphere ; or if the 
 molecule be considered as a system, we can 
 estimate the distance between two molecules 
 when their paths become appreciably curved. 
 We find as the result of such calculations 
 that there are about 21 trillion molecules 
 in a cubic centimetre of gas under the 
 pressure of 760 mm. of mercury at 0°C ; so 
 that the mean distance between the mole- 
 cules is between 3 and i millionths of a 
 millimetre, or about 3-5 x 10"' centimetres ; the 
 diameter of the molecule is probably between 
 1 X 10 -' centimetres and 3 x 10"" centimetres, 
 or between J and ^Jg of the mean distance 
 between the molecules. Another quantity which 
 it is important to know is the mean distance 
 through which the molecule passes between two 
 collisions ; this is called the mean free path of 
 the molecule, and it is inversely proportional 
 to the density. For hydrogen at the pressure 
 of 760 mm. of mercury the mean free path is 
 about 1-8 X 10"= centimetres ; at the pressure of 
 1 mm. the free path is about n of a millimetre ; 
 and at a pressure of a millionth of an atmosphere 
 about 18 centimetres. When the free path is 
 comparable with the dimensions of the vessel 
 in which the gas is inclosed, the gas can exhibit 
 phenomena of a different character from those 
 shown when the free path is indefinitely small 
 compared with the dimensions of the vessel. 
 The radiometer exhibits effects of this kind, and 
 Crookes has called a gas rarefied so much as to 
 show rotation in a radiometer, matter in the 
 fourth or ultra gaseous state. But this is using 
 the word state in a different sense from that in 
 which it is used in the phrases solid, liquid, 
 and gaseous, states; for these states do not 
 depend upon anything but the matter itself, 
 while the ultra-gaseous state depends upon 
 the ratio of the free path to the other lengtha 
 
 involved; if we increased all the lengths pro- 
 portionately to the rarefaction, the gas would 
 not show any of those properties which character- 
 ise the so-called nltra-gaseous state, while, on 
 the other hand, if we experimented with small 
 enough instruments we could get all the ultra- 
 gaseous effects manifested by a gas at the atmo- 
 spheric pressure. 
 
 The distribution of energy among the mole- 
 cules is of much chemical interest. It seems, 
 however, that in one respect the results of 
 theory have been misinterpreted; it has been 
 said that because iodine, for example, is dis- 
 sociated at a temperature a little over 600°, and 
 since in iodine at any temperature there are 
 some molecules possessing the same amount of 
 energy as those which are split up at 600°, that 
 therefore these molecules ought to be split up, 
 and if any substance were present capable of 
 combining with free iodine the whole of the 
 iodine would ultimately combine with this sub- 
 stance. Now although there are apparently no 
 experiments which may be called secular to say 
 whether or not this would ultimately happen, 
 yet it is certain that it does not happen so quickly 
 as theory would indicate, if every molecule 
 which possessed the same kinetic energy as 
 that possessed by the average molecule at 600° 
 were straightway dissociated and entered into 
 combination with the other substances present ; 
 there seems, however, to be no reason why this 
 should be the case, for though one molecule at 
 0° may have the same energy as one at 600°, 
 yet dissociation must depend upon the surround- 
 ing molecules as well as upon the molecule 
 itself. Now the molecule at 600°, though it 
 possesses at any instant the same energy as one 
 at 0°, is yet surrounded by molecules which are 
 moving very much faster than itself, and whose 
 energy is much more nearly equal to its own, so 
 that it is not bo likely to lose its energy by 
 collision with other molecules as the molecule 
 at 0° which is surrounded by molecules with 
 much less energy than itself. For this reason the 
 tendency to dissociate will be very much greater 
 at 600° than at 0°, and a molecule at the former 
 temperature may dissociate while the latter may 
 lose its energy before this can happen. 
 
 The distribution of energy affects the speciflo 
 heat very much ; so that if we know the 
 value of the specific heat we can tell a good 
 deal about the energy of the molecule, as the 
 following theoretical investigation will show. 
 Let us begin with the case of a gas the molecule 
 of which is of any degree of complexity, measured 
 by the number of degrees of freedom,^. There 
 is a theorem due to Boltzmann which states 
 that the mean energy corresponding to each 
 degree of freedom is the same, so that the mean 
 
 n 
 
 total energy of the molecule is w times the mean 
 
 energy due to the translatory motion of the 
 centre of gravity. Though there is very strong 
 evidence against the truth of the theorem in this 
 form, and the mathematical proof of it is un- 
 satisfactory, yet a very special case of it is pro- 
 bably true, viz. that if we have a molecule con- 
 sisting of n atoms approximately symmetrically 
 arranged (that is, if the distance between a par- 
 ticular pail of atoms is not always very muoh 
 
80 
 
 AGQKEQATION, STATES OF. 
 
 = 1, 
 
 less than the distances between the other pairs), 
 then the ratio of the mean total kinetic enerpty of 
 the molecule to the energy due to the translatory 
 motion of its centre of gravity is proportional 
 to n, the number of atoms in the molecule. 
 
 Let the ratio of the total kinetic energy to 
 the translatory energy of the centre of gravity, 
 which by the kinetic theory of gases is measured 
 by the absolute temperature, be Pn. Then the 
 total kinetic energy in the gas = 2i3»9 = /3ii'9, 
 when n' is the number of atoms in the gas. If 
 all the atoms be of the same mass, vi, and the 
 quantity of gas be the unit of mass, then m'tn = 1, 
 BO that the total kinetic energy in the gas 
 
 = —, which, if J3 be the same for all elementary 
 m 
 
 gases, is inversely proportional to the atomic 
 weight of the gas. If the gas had been a com- 
 pound such that each molecule consisted of a 
 atoms of mass m, 6 of mass to', c of mass to", 
 and so on, then for unit mass of the gas, 
 N'(ma + m'b + m"c) _ 
 {a + b + c) 
 go that the energy in unit mass 
 = n'j89 
 PB{a+b + c) 
 ~ ma + m'b + m"e. 
 Now a+6 + c is the number of atoms in the 
 molecule, and ma + m'b + m"c is the mass of a 
 molecule, so that the energy of unit mass 
 _ ^8(number of atoms in the molecule) t , 
 mass of the molecule. 
 US first suppose that all the energy in the gas is 
 kinetic, then the energy in unit mass of the gas 
 
 at temperature B is — so that the specific heat is 
 
 TO, 
 Bd 
 — or the product of specific heat into the mass 
 
 TO, 
 
 of an atom, which is called the atomic heat, is 
 equal to j3, and, as experiment shows, does not 
 vary much from gas to gas. For a compound, 
 we see from the expression given above for the 
 energy, that the product of the specific heat into 
 the mass of a molecule equals i8(number of atoms 
 in the molecule), so that for all perfect gases, 
 simple or compound, the product of the specific 
 heat into the mass of the molecule = ;8(number of 
 atoms in the molecule). We may remark that 
 with our assumptions the ratio of the specific heat 
 at constant pressure to that at constant volume 
 
 2 r, . sp\ 1 
 
 .1+ 
 
 3.(^^ = 
 
 p /number of atoms in the 
 molecule, 
 
 when Sp is the deviation of the pressure from 
 that given by Boyle's law. The experimental 
 results show that for most perfect gases, simple 
 or compound, the molecular heats are constant, 
 showing that )3 is constant for such gases, or 
 that the whole kinetic energy is proportional to 
 the product of the number of atoms in the mole- 
 cule and the energy due to the translatory 
 motion of the centre of gravity. There are, 
 however, some simple gases, such as chlorine 
 and bromine vapour, whose atomic heats are 
 much higher than the value given by the above 
 rule. These gases are, however, easily liquefied, 
 and so when heat is applied, work is done in 
 altering the molecular state as well as in raising 
 the temperature; this will produce an effect 
 
 equivalent to increasing P, and will therefore 
 explain the large value of the atomic heat. 
 We should expect a large value for this quantity 
 too if the gas were dissociating. There are 
 some compound gases, on the other hand, such 
 as ammonia, ethylene, and marsh gas, whose 
 molecular heats are too small to agree with the 
 above rule, if we suppose that the number at 
 different systems in the molecule is the same aa 
 the number of atoms indicated by the chemical 
 formula of the gas. If, however, two or more 
 atoms always remain close together, they will 
 for our purpose count as one atom, as it is only 
 when the molecules are approximately symme- 
 trically arranged that we can assume that the 
 total energy is proportional to the number of 
 atoms. The total energy is proportional to the 
 number of distinct systems ; and if a group of 
 atoms always remain close together they only 
 count as one system, however many atoms there 
 may be. If, for example, the atoms in a radicle 
 always remain together, the radicle, for this 
 purpose and in the formula for the ratio of the 
 specific heats, will only count as one atom. We 
 may therefore regard those compounds which 
 have too small atomic heats, as consisting of but 
 few separate systems, though there may be a 
 great number of atoms in the molecule. 
 
 The determinations by Dulong and Petit and 
 others of the specific heats of elementary bodies 
 in the solid state show that for these bodies the 
 atomic heat is approximately constant, while 
 Kopp's experiments on the specific heats of com- 
 pound solid bodies show that for many such 
 solids the product of the mol. w. and the specific 
 heat is proportional to the number of atomS in 
 the molecule, just as for gases. The expression 
 for the kinetic energy of unit mass of a solid will 
 probably be of the same form as that which we 
 found for a gas ; for this only depends upon tho 
 assumptions that the absolute temperature is 
 proportional to the mean energy due to the 
 translatory motion of the centre of gravity of 
 the molecules, and that the ratio of the mean 
 total kinetic energy of the molecule to the 
 mean energy due to the translatory motion of 
 the centre of gravity is proportional to the num- 
 ber of atoms in the molecule. These assump- 
 tions win probably hold for the solid and liquid 
 as well as for the gaseous state. We must re- 
 member that when heat is applied to a solid or 
 liquid, work is done in altering the molecular 
 configuration as well as in increasing the kinetio 
 energy of the molecules. All solids and liquids 
 appear to be able to get into a condition in 
 which the specific heat does not alter with the 
 temperature, and it is in this condition that the 
 atomic heat is constant. Now if the speoifio 
 heat is independent of the temperature, tha 
 work spent in altering the molecular configura- 
 tion must bear a constant ratio to the work 
 spent in increasing the kinetic energy ; and if 
 the atomic heat is constant this ratio must be 
 the same for aU substances ; so that Dulong and 
 Petit's experiments show that when heat is 
 applied to a solid or liquid it is divided between 
 the energy of molecular configuration and the 
 mean kinetio energy, in the same proportion for 
 all substances ; and since for many substances, 
 such as iodine, bromine, mercury, &a., the 
 speoifio heat in the solid state ia twice that in 
 
AGGREGATION, STATES OF. 
 
 01 
 
 the gaseous, it is equally divided between these 
 two forms of energy, a result which purely 
 dynamical considerations would also lead us to 
 regard as the most probable one. The specific 
 heats of liquids seem to be more irregular than 
 those of either solids or gases, but the 
 bodies for which this is the case are those whose 
 melting and boUing points are comparatively 
 close together, and we may suppose that the 
 nature of the molecular configuration alters 
 with each change in temperature, and this 
 makes the specific heat abnormally large. The 
 specific heats of those substances which exist in 
 the fluid state through wide ranges of tempera- 
 tare seem to be the same in the solid and fluid 
 states. 
 
 When the specific heat of a solid compound 
 is much smaller than the number of atoms in it 
 would lead us to expect, we may, just as in the 
 case of a gas, conclude that two or more atoms 
 always remain close together in the molecule. 
 It is important to notice, however, that the 
 specific heat cannot give us any information 
 about what we may call the molecular aggrega- 
 tion of the solid or liquid, that is it aSords no 
 information as to whether the molecules are 
 isolated or form groups, for if we suppose the 
 molecules to unite and form more complex ones 
 the atomic heat would remain the same as long 
 as the energy was equally divided among the 
 atoms or radicles forming the molecules. 
 
 Chanoe of State. — Gaseous to Liquid. 
 
 By the application of great pressure accom- 
 panied when necessary by intense cold, all gases 
 have been liquefied, and during this process they 
 pass through all intermediate states, so that at 
 some stage of the process it is impossible to tell 
 whether the substance is a gas or a liquid. It is 
 found that there is for each gas a temperature 
 above which it cannot be liquefied by the appli- 
 cation of the most intense pressure, so that at a 
 temperature higher than this the substance can 
 only exist as a gas. This temperature is called 
 the critical temperature, and Andrews has pro- 
 posed to call a substance at a temperature 
 higher than its critical temperature a gas, and 
 one which though in a gaseous condition is yet 
 at a temperature lower than the critical tem- 
 perature, a vapour. Van der Waals {Continuitat 
 des Qasformigen und flUssigen Zustandes, 87), 
 and Clausius {W. 9, 1880), have shown how to 
 calculate the critical temperature from the 
 difference between the pressure of the gas in 
 any state and that given by Boyle's law. 
 
 We shall here confine ourselves to showing, by 
 general reasoning, that a critical temperature 
 must exist. When a body is in the liquid state the 
 ratio of the work required to separate the parti- 
 cles to an infinite distance to the kinetic energy 
 of the molecules must exceed a certain limit, for 
 the substance will behave as a liquid or a gas 
 according as the forces between the molecules 
 are or are not able to change their kinetic energy 
 appreciably in the interval from one collision 
 to another. The molecules will change their 
 kinetic energy appreciably if the ratio of the 
 alteration in the mutual potential energy of the 
 molecules to their initial kinetic energy is finite; 
 but for this to be the case the ratio of the work 
 required te separate the molecules to an infinite 
 
 distance must be finite, so for a body to be in 
 the liquid condition this ratio must exceed a 
 certain quantity, say, B. Let v be the work re- 
 quired to separate one of the molecules from the 
 remainder, and i the kinetic energy of the transla- 
 tory motion which is proportional to the absolute 
 temperature; then the substance will behave 
 
 like a liquid if — be greater than n, but like a 
 
 T 
 
 gas if — be less than this quantity. Now 7 
 
 I 
 cannot be greater than the work, v', required to 
 separate the molecules when they are quite close 
 
 v' 
 together, so that when i>— the substance 
 
 B 
 
 will always behave like a gas. Now t is pro- 
 portional to the absolute temperature, so that 
 when the absolute temperature exceeds a certain 
 value the substance will always behave like a gas, 
 that is, it cannot be liquefied. This shows that 
 there must be a ' critical temperature,' and it also 
 shows that the critical temperature is propor- 
 tional to the work required to separate the mole- 
 cules ; a measure of this will be the amount of 
 heat required to convert the substance from a 
 liquid into a gaseous state under infinite pres- 
 sure. We can take as a practical measure the 
 latent heat of the substance. The mean kinetic 
 energy of the translatory motion equals the 
 absolute temperature, so that if h be the latent 
 heat, S the critical temperature, Nv' will be pro- 
 portional to h, where n is the number of mole- 
 cules in unit mass, and i is proportional to 9, 
 
 v' 
 so that since — is constant, we should expect 
 
 I 
 to find that the critical temperature multiplied 
 by the number of molecules in unit mass — or, 
 what is proportional to it, the reciprocal of the 
 molecular weight — ought to be related to the 
 latent heat so that when one is great the other 
 is great also. The following table will show 
 that this condition is approximately fulfilled : — 
 
 
 Abso- 
 
 
 
 
 lute- 
 
 Critical 
 
 
 
 criti- 
 
 tempera- 
 
 liEltCIlfe 
 
 Sabstanoe 
 
 cal 
 
 ture 
 
 heat 
 
 
 tem- 
 
 divided 
 
 
 pera- 
 
 bymoLw. 
 
 
 
 ture 
 
 
 
 Alcohol O2H5O . 
 
 510 
 
 11-1 
 
 20a 
 
 Acetone C^nfi . 
 
 505 
 
 8-7 
 
 140 
 
 Carbon disulphide OS2 . 
 
 646 
 
 7-3 
 
 105. 
 
 Benzene CjIIe 
 
 558 
 
 7-17 
 
 109 
 
 Methyl acetate C^Rfi^ . 
 
 503 
 
 6-8 
 
 lift 
 
 Ethyl formate CaHeOj . 
 
 503 
 
 6-8 
 
 105 
 
 Sulphurous oxide SO^ . 
 
 429 
 
 6-7 
 
 94 
 
 Ether C<H,„0 
 
 468 
 
 6-3 
 
 94 
 
 Ethyl acetate C^HjOj . 
 
 518 
 
 5-83 
 
 105 
 
 Chloroform CHCl, 
 
 533 
 
 4-51 
 
 67 
 
 Carbon tetrachlorideCOl^ 
 
 557 
 
 3-6 
 
 52 
 
 Passage fbom the Liquid to the Gaseous 
 State. 
 Though it requires the application of pressure 
 and cold to make a substance pass from the 
 gaseous to the liquid state, yet the substance 
 will always to a limited extent pass of itself 
 from the liquid into the gaseous state. In thei 
 space over a liquid in the equihbrium conditiuni 
 
G2 
 
 AGGREGATION, STATES OF. 
 
 there ia always a quantity of the vapour of the 
 liquid, the quantity of vapour in unit volume 
 depending only on the nature of the liquid and 
 the temperature ; in other words, the vapour 
 exerts a definite pressure called the vapour pres- 
 sure (often erroneously the vapour tension). If we 
 have a quantity of liquid in a vessel furnished 
 with a piston the liquid will evaporate until 
 there ia a certain quantity of vapour in each 
 unit of volume above the liquid ; if we depress 
 the piston so that this volume diminishes by 
 V then a quantity of vapour equal to that in 
 volume V will condense ; if the piston be raised 
 again the vapour will be re-formed. In this 
 way we can have a continual transference from 
 the gaseous into the liquid state and back again. 
 In this process, however, we have only matter 
 in these two states and have no continuity of 
 state from the gaseous to the liquid as we had 
 in the process by which the permanent gases 
 are liquefied. The vapour pressures of different 
 liquids vary enormously ; thus for sulphuric acid 
 the vapour pressure is so small as to be almost 
 inappreciable ; for sulphuric acid, mixed with its 
 ■own volume of water, it is about one-eighth of a 
 mm. at 15°C; for water at the same temperature 
 it is about 12-6 mm. ; for alcohol, 82 mm. The 
 vapour pressure always increases as the tem- 
 perature rises, but until the temperature reaches 
 a certain value depending on the pressure, the 
 liquid which evaporates is always that on the 
 surface, and none of the liquid in the interior 
 passes into the gaseous condition. When, how- 
 ever, the vapour pressure becomes greater than the 
 pressure on the surface of the liquid, the bubbles 
 of vapour which form on the sides will be at a 
 pressure equal to or greater than the pressure 
 in the surrounding fluid, and so will expand 
 .and be able to reach the top without con- 
 densing. When this takes place, i.e. when 
 portions of the liquid not on the surface are 
 ■converted into gas, the liquid is said to boil. 
 ■ The temperature of the boiling-point wiU increase 
 with the pressure ; it cannot, however, even by 
 the application of an infinite pressure, be raised 
 above the critical temperature of the substance. 
 Bodies which have small vapour pressures at 
 •ordinary temperatures have high boiling-points ; 
 but it does not follow that because the vapour 
 pressure of one substance is at some tempera- 
 ture greater than that of another its boiling- 
 point will be lower; for example, at 15°C. the 
 vapour pressure of carbon tetrachloride is greater 
 than that of methyl alcohol, though its boiling 
 point is higher. According to the molecular 
 theory, some of the molecules manage to escape 
 from the liquid, we may suppose because they 
 are moving so fast as to be able to escape from 
 the attraction of the other molecules ; on the 
 •other hand, some of the molecules of the vapour 
 strike the surface and get caught by the mole- 
 'Cules of liquid. When things are in a state 
 of equilibrium as many molecules escape from 
 •the liquid as are caught by it. 
 
 Although the vapour densities of many sub- 
 stances have been determined, few experiments 
 seem to have been made on the rate of evapora- 
 tion and condensation. The knowledge of these 
 irates would very much increase our knowledge 
 of the constitution of fluids. 
 
 The forces between the molecules in the 
 
 liquid state must be sensible, otherwisewe should 
 not be able to spend work upon a liquid without 
 increasing the kinetic energy, as we do when W8 
 convert water into steam at the same tempera- 
 ture. The latent heat may be taken as a mea- 
 sure of the potential energy lost by the transi- 
 tion from the gaseous to the Uquid state. In a 
 fluid the potential energy of the molecular con- 
 figuration seems to depend only on the mean 
 distance between the molecules ; for the fluid 
 resists anything tending to diminish its volume, 
 but does not resist anything tending to change 
 its shape. When the fluid is in such a condition 
 that its specific heat is independent of the tem- 
 perature then any increase in the kinetic energy 
 must be accompanied by a proportionate increase 
 in the potential energy of the molecular con- 
 figuration. Now, if the forces between the mole- 
 cules are large it will require a smaller increase 
 in the distance between them to increase the 
 potential energy by a given amount than if they 
 were smaller ; so that for a, given increase in the 
 kinetic energy, that is, a given rise in tempera- 
 ture, the increase in volume will be less when 
 the forces between the molecules are great than 
 when they are small, so that the coefficient of 
 expansion will be small when the forces between 
 the molecules are great, but when the forces 
 between the molecules are great the fluid is in- 
 compressible and the product of the mol. w. and 
 latent heat is large ; so that we should expect a 
 small coefficient of expansion, incompressibiUty, 
 and large latent heat for equal volumes to go 
 together, and we find by the following tables 
 of these quantities that this seems to be the 
 case. 
 
 
 Product of 
 
 OoefS- 
 cient of 
 
 Com- 
 
 Substance 
 
 latent heat 
 
 pressi- 
 
 
 aadmol.w. 
 
 expan- 
 sion 
 
 bility 
 
 ■Water, H,0 .... 
 
 11,088 
 
 ■000065 
 
 4-Sl 
 
 Benzene, 0.11. ... 
 
 8,502 
 
 ■00138 
 
 
 Acetone, C,H,0 . 
 
 8,120 
 
 ■00172 
 
 
 Chloroform, CHCI, . 
 
 7,906 
 
 ■00140 
 
 
 Carbon tetrachloride, COlj 
 
 7,904 
 
 ■00140 
 
 
 Ether (C,H,)jO . 
 
 6,956 
 
 •0021 
 
 10^8 
 
 Carbon bisulphide, CS, . 
 
 6,810 
 
 ■00146 
 
 6-2< 
 
 A peculiarity of water is that it is denser at 
 4°C. under atmospheric pressure than at any 
 other temperature under the same pressure ; we 
 may perhaps suppose that this is due to some- 
 thing of the following kind. We know that 
 when water freezes it expands and crystallises 
 in the hexagonal system ; now we may suppose 
 that, before thp water solidifies, molecular aggre- 
 gations are formed which possess the same pro- 
 perty as is possessed by the ice crystals, ■viz. 
 that when the molecules are arranged in this 
 way they occupy a greater volume than when 
 arranged uniformly — the formation of these 
 aggregations would tend to increase the volume 
 and might be sufficient to more than counter- 
 balance the diminution due to the nearer approach 
 of those particles which do not form these aggre- 
 gations. 
 
 Chahqb of State trou Solid to Liquid. 
 
 When the temperature of a solid is raised 
 sufficiently high it begins to melt. There are 
 two kinds of melting ; in the one, as in the case 
 of ioe, if the heat is applied slowly the tempera- 
 
ALACREATmiNB. 
 
 93 
 
 toie remains constant until all the substance 
 has passed from the solid into the liquid 
 Btate In this case there is a definite melting- 
 point. In the other case, of which an example 
 is the melting of sealing-wa,:, the substance 
 first begins to soften, then as more heat is applied 
 it gets softer and softer, its temperature, however, 
 increasing until when a certain temperature is 
 reached the substance is liquid; in this case 
 there is no definite melting-point, as the process 
 is spread over a considerable range of tempera- 
 ture. This would seem to imply that the sub- 
 stances which melt in the second way are not 
 perfectly homogeneous in structure, but contain 
 molecular aggregations of various degrees of 
 complexity, which get gradually split up as the 
 temperature rises ; while those substances which 
 melt like ice have a more uniform constitution, 
 BO that any change of state takes place simul- 
 taneously through the molecules. This would 
 obviously tend to make the transition more 
 definite. This view is in accordance with the 
 fact that crystalline bodies, which are generally 
 regarded as being more uniform in structure 
 than non-crystalline, all melt in the same way 
 as ice. Sealing-wax in the state of transi- 
 tion is what is called a viscous body ; so that 
 on this view a viscous substance is regarded as 
 a mixture of molecules some of which are in the 
 same state as they are when the substance is 
 liquid, and some are in the same state as they 
 are when the substance is solid. A dynamical 
 illustration will enable us to see how such a 
 body might behave like a rigid body under the 
 action of rapidly changing forces, and like a 
 fluid under constant or slowly varying forces. 
 Suppose we have a series of heavy spheres con- 
 nected by strong springs placed upon a hori- 
 zontal table, and that one end of this row of 
 spheres is fastened to a peg which cannot sustain 
 a tension greater than T without breaking ; 
 then if a steady pull, i, be exerted at the other 
 end of the row of spheres the string wiU break, 
 but if the tension at the end, instead of being 
 steady, be periodic, and if the period of vibration 
 be greater than the natural period of vibration 
 of the spheres and springs, then if the number 
 of spheres be great enough the string will not 
 break, though a tension enormously greater than 
 1 is acting at the other end. This is quite a 
 parallel case to that of the viscous fluid; the 
 springs and spheres correspond to those mole- 
 cules which are in the same condition as when 
 the substance is solid, the string to those in the 
 fluid condition. 
 
 The change of state from solid to Hquid 
 seems to be always accompanied by a change in 
 volume, and when this is so the melting-point 
 — as J. Thomson proved — must be altered by 
 the application of pressure. Thomson showed 
 that this followed from thermodynamical con- 
 siderations ; and that when the substance expanded 
 on solidification, like ice, the melting-point was 
 lowered by pressure, but when the substance con- 
 tracted on solidification the melting-point was 
 raised by pressure. The most important sub- 
 stances which expand on solidification are water, 
 bismuth, antimony, and cast-iron ; none of these 
 crystallises in the regular system, so that we may 
 suppose that the molecules are arranged unsym- 
 tnetrically, that while some are nearer together 
 
 
 than when in the liquid state, others are further 
 apart, producing on the whole an increase of 
 volume. 
 
 The specific heat of a body in the solid 
 condition is in general less than when it is in 
 the liquid, except for those substances whose 
 melting and boiling-points are very far apart, 
 when it seems to be about the same in the two 
 states ; if we know the specific heat of a sub- 
 stance in both the fluid and the solid state at 
 all temperatures, we can find the amount of 
 heat necessary to convert unit mass of the sub- 
 stance from the solid to the liquid state. Por 
 Clausius has proved that if \ be the latent heat 
 at the temperature t, s, and s^ the specific heats 
 in the solid and liquid states respectively at 
 the same temperature, then 
 
 A 
 
 ' T 
 
 A similar equation wiU apply to the change 
 from the liquid to the gaseous state. Soma 
 bodies, such as camphor and iodine, sublime, 
 that is pass directly from the BoUd to the gaseous 
 state, and as these bodies exhibit a definite 
 vapour-pressure — they must also pass directly 
 from the gaseous into the solid states. 
 
 In the solid and liquid states the molecule is 
 probably a very much more complex thing than 
 the gaseous molecule, it is probably also not 
 nearly so definite. Maxwell, in the article 
 ' Atom ' in the Encyclopedia Britanmca, shows 
 how the hypothesis of groups of molecules of 
 different degrees of stability would explain the 
 residual effects of elasticity, and states that in 
 his view a solid consists of groups of molecules, 
 some of which are in difEerent circumstances 
 from others. J. J. T. 
 
 AGONIADIN 0,„H„05. A crystalline bitter 
 substance occurring in Agoniada bark (from 
 Plumeria longifolia), which is used in Brazil as 
 a remedy for intermittent fever. Needles, very 
 bitter, v. si. sol. ether, v. sol. hot alcohol, and 
 CS2. Nearly insoluble in cold, easily soluble in 
 boiling water. When boiled with sulphuric acid 
 it yields a sugar (Peckolt, Ar. Ph. [2] 144, 34). 
 
 H. W. 
 
 ALACEEATINE C4H„N302 i. e. 
 NH2.C(NH).NH.CHMe.COjHa-g'Mamiio-2)ropio»i(j 
 acid. S. 8-3 at 15°. Formed by mixing cone, 
 solutions of alanine and cyanamide, adding a 
 little NH3, and allowing the mixture to stand 
 (Baumann, A. 167, 83). Small prisms, v. si. 
 sol. cold alcohol. At 180° it changes into its 
 anhydride, alacreatinine. Boiling baryta-water 
 forms alanine and urea, or its decomposition- 
 products, CO2 and NH3. HgO oxidises it, forming 
 guanidine. 
 
 Methyl-alacreatine 
 NH2.C(NH).NMe.CHMe.C02H. _ From a-methyl- 
 amido-propionio acid, cyanamide, and a little 
 NH3 (Lindenberg, J. pr. [2] 12, 253). Mono- 
 clinic prisms, si. sol. cold water or alcohol. 
 
 AIACEEATININE C^H^NaO aq. Formed by 
 dehydration of alacreatine by the action of heat or 
 dilute acids, crystallises from water in long prisms, 
 which give off aq in dry air or at 100°. M. sol. 
 alcohol, more soluble in water than alacreatine. 
 With zinc chloride it forms crystalline scales 
 (C4H,NgO)jZnCl2, S. 4-35 at 20°, T. bL sol. 
 aloobol (Baumann, B. 6, 1371). 
 
64 
 
 ALANINE. 
 
 AXANINE C,H,NOp. i.e. CH3.CH(NHJC0jH 
 a-amido-propionic acid. Mol. w. 89. S. 2-2 at 
 17° ; S. (cold alcohol of 80 p.o.) -2. 
 
 Fcn-mation. — 1. From ethylio o-ohloropro- 
 pionate and ammonia (Kolbe, A. 113, 220; 
 Streoker, A. 75, 29). — 2. From a-bromopropionio 
 acid and alcoholic ammonia (Kekul6, A. 130, 18). 
 
 Preparation. — An aqueous solution of 2 pts. 
 aldehyde-ammonia is mixed with aqueous hydro- 
 cyanic acid containing 2 pts. HCyj hydrochloric 
 acid is added in excess ; the mixture is evaporated 
 to dryness over a water-bath ; the residue is 
 digested with a mixture of alcohol and ether, 
 which leaves NH^Cl undissolved (Strecker). 
 
 Properties. — Tufts of colourless needles or 
 oblique rhombic prisms, having a nacreous lustre. 
 Sublimes at 200°. V. si. sol. cold alcohol, insol. 
 ether. The aqueous solution has a sweet taste, 
 does not affect vegetable colours and gives no 
 precipitates with any of the ordinary reagents. 
 Alanine is isomeric with urethane, lactamide, 
 and sarcosine ; distinguished from the two former 
 by not melting below 100°, and from the last by 
 its solubility in water and its behaviour to 
 metallic oxides. 
 
 Beactions. — 1. Not altered by boiling with 
 dilute acids or with alkaUs. — 2. Fused with 
 KOH, it gives off hydrogen and ammonia and 
 forms cyanide and acetate of potassium. — 3. 
 Besolved by boiling its aqueous solution with 
 PbO^.into aldehyde, carbon dioxide, andammonia ; 
 CaHjNOu -^ = Gfifi -h CO2 -I- NHj.— 4. Decom- 
 posed in aqueous solution by nitrous acid, with 
 evolution of nitrogen and formation of lactic 
 acid. H. W. 
 
 ALANT CAMPHOR C,^,fl. Occurs in 
 elecampane root, and is obtained together with 
 solid alantic anhydride by distilling with water. 
 Liquid smelling like peppermint, boiling at 200°. 
 Heated with PjOj, it yields a hydrocarbon C|„Hi4 
 which boils at 175°, and is converted by oxidisa- 
 tion with chromic acid into terephthalic acid 
 (KaUen). H. W. 
 
 ALAHTIC ACID C.^H^^O, [91°].— Obtained 
 from its anhydride (v. sup.). Slender needles 
 (from alcohol). Dissolves sparingly in cold, more 
 readily in boiling water, very easily in alcohol. 
 The barium salt forms warty masses moderately 
 soluble in water. The silver salt AgCisHjiOj 
 forms small scales having a silvery lustre (Kal- 
 len, B. 9, 156). 
 
 Alantic Anhydride Ci^^fi^ [66°], (275°), 
 crystallises from dilute alcohol in prismatic 
 needles. Easily sublimable. Dissolves very 
 sparingly in water, very easily in alcohol, ether, 
 &c.— The chloride Ci^HjiOjCl [140°] formed 
 by passing HCl-gas into a solution of alantic 
 acid in absolute alcohol, crystallises in large 
 rhombic tablets, melting, with evolution of HCl, 
 at 140°. It unites with bases, forming salts 
 which readily decompose, with separation of 
 metallic chlorides. By excess of caustic alkali it 
 is converted into dialantio acid, G^^^f>^ (?) 
 —The amide G.^^^fi.-'^n^ [210°], obtained by 
 passmg ammonia-gas into an alcoholic solution 
 ■of the anhydride, forms small crystals, melting, 
 with decomposition at 210°, slightly soluble in 
 alcohol, resolved by potash into ammonia and 
 »lantic acid. H. W. 
 
 ALBUMEN V. Peoieids. 
 
 ALCAMINES v. Alkaminbs. 
 
 ALGOGEL, A gelatinous compound of eiliois 
 acid with alcohol (g. v.). 
 
 ALCOHOL CjHjO or EtOH {ethyl alcohol, 
 aqua vita). Mol. w. 46. (78-2°) at 762-7 mm. 
 (R. Schiff); (78-3°) (Eegnault); (78-4°) at 760 
 mm. (Kopp, A. 92, 9) ; (78-5°) (Perkin) ; (12-8°) 
 at 20-9 mm. ; (21°) at 41-B mm. (Eahlbaum, B. 
 16, 2480). S.G. y -79367 (S.) ; • \\ -79503 (P.) ; 
 II- -78820 (P.) ; =j» -8000 (Bruhl). S.V. 62-18 (S.) ; 
 62-7 (Ramsay). V.D. 1-613 (for 1-591, Gay- 
 
 Lussao). S.H. -615 (Kopp) ; -659 (20° to 78°) 
 (Reis) ; -6019 (16°-20°) ; -6067 (16°-35°) ; -6120 
 (16°-40-5°) (J. H. Schiiller, P. Erghd. 5, 116, 
 192). H. F. p. 58,470. H. F. v. 57,020 {Th. iv. 
 229). fn^ 1-3667 Ra, 20-81 (B.). M.M. 2-78 (P.). 
 
 Name. — The term alcohol was used in the 
 time of Libavius (1595) to denote a powder. 
 Spirit dried over powdered potassic carbonate 
 was called spiritus alcolisatus. Kopp [Oeschichte, 
 iv. 281) suggests that this term does not mean 
 spirit that has been treated with the powder, but 
 that it is a corruption of spiritus alcalisatus, or 
 spirit that has been treated with alkali. Aloolised 
 or alcoholised spirit was then shortened to alcohol. 
 
 Occurrence. — 1. In fermented saccharine 
 juices. — 2. In putrid, and even in healthy, 
 tissues, such as ox-brain (Bfiobamp, C. B. 89, 
 573).— 3. In crude coal-tar benzene (about 2 
 parts per million) (0. N. Witt, C. 0. 1878, 416).— 
 4. In the fruits and juices of some living plants 
 (Gutzeit, A. 177, 344).— 5. In bread (Bolas, C. N. 
 27, 271). — 6. In crude wood-spirit (V. Heniulian, 
 B. 8, 661). — 7. Together with acetone, in the 
 urine of diabetic patients (Markownikoff, B. 9, 
 1441, 1608). 
 
 Formation. — 1. By the decomposition of 
 glucose under the influence of ferments (v. 
 Fermentation) : CsH,208= 2C2H5O + 200^. Levu- 
 lose, maltose, and melitose also give alcohol 
 on fermentation. — i. From defiant gas by dis- 
 solving it in cone. H^SO^, diluting and distilling 
 (Hennel, P. M. 1826, 240; Berthelot, A. Ch. [3] 
 48,385): C^H^ -f H^SO^ = C^H^SCH 
 
 C^H^SO^H + H^O = C2H5OH + HSO.H. 
 The absorption of ethylene is greatly facilitated 
 by heating the H^SO, to 100° or, better still, 
 170° (Goriainow a. Butlerow, A. 169, 147).— 8. 
 By reduction of acetic anhydride (Liimemann, 
 A. 148, 249), acetyl chloride (Saytzeff, J. pr. 
 [2] 3, 76), or aldehyde, by means of sodium- 
 amalgam. — 4. By heating ether at 170° with 
 water slightly acidulated with H^SOj (Erlen- 
 meyer a. Tscheppe, Z. [2] 4, 343). 
 
 Preparation. — When aqueous solutions of 
 grape-sugar are fermented by yeast, 95 p.o. of 
 the sugar splits up into alcohol and carbonic 
 acid, but 4 p.c. goes to form succinic acid and 
 glycerin, while 1 p.c. is used by the yeast as 
 food. Small quantities of w-propyl, iso-butyl, 
 andthetwoiso-amyl,alcohols,MeaCH.CHj.CH20H 
 and MeEtCH.CHjOH, are also formed. The 
 mixture of these four alcohols is known as fusel 
 oil. According to Eabuteau (C B. 87, 500), 
 potato spirit contains also iso-propyl, w-butyl, 
 and secondary amyl alcohols. 
 
 The liquid to be fermented must contain 
 nitrogenous matter and some inorganic salts to 
 serve as food for the yeast ; grape-juice, or a 
 mixture of water with germinating barley (malt), 
 to which a mash of potatoes may be added, are 
 
ALCOHOL. 
 
 95 
 
 the liquids usually employed. Diastase, an 
 unorganised ferment in malt, converts the starch 
 of the potatoes into a sugar, maltose, which then 
 undergoes alcoholic fermentation. 
 
 When any of these alcoholic liquids are 
 distilled the first portions of the distillate are 
 rich in alcohol. By repeated rectification 
 ' rectified spirit ' containing 91 p.o. of alcohol 
 may be got. Fusel oil may be removed by 
 adding to the spirit about -7 of its weight of 
 coarsely powdered charcoal, leaving the mixture 
 to stand for several days, and stirring repeatedly, 
 then decanting and distilling. Animal or blood 
 charcoal may also be used. 
 
 Absolute Alcohol. — The last traces of water 
 may be removed by repeated rectification over 
 freshly heated EjCO,, CaO, BaO, CuSOj, or CaClj. 
 The best way is to digest strong spirit with quick 
 lime at 40° for two hours, and then, on distil- 
 ling, to reject the first and last portions 
 (Mendel6efE, Z. 1865, 260). If the spirit contain 
 more than 5 p.c. of water a second treatment 
 with lime will be necessary (Erlenmeyer, A. 160, 
 249). If dry baryta be used to complete the 
 drying, as soon as the alcohol is absolute it will 
 become yellow, dissolving a little BaO (Berthelot, 
 J. 1862, 392). 
 
 References.— C. Bullock, Ph. [3] 4, 891 ; J. 
 Ij. Smith, Am. Ch., 5 120 ; Dittmar a. Stewart, 
 C. N. 33, 53 ; Friedel a. Crafts, A. Ch. [4] 9, 5. 
 Properties. — A transparent, colourless, mo- 
 bile, liquid. It has a characteristic odour and 
 burning taste. When undiluted it acts as an 
 inflammatory poison. It solidifies at — 130-5° 
 (Wroblewsky a. Olszewsky, M. 4, 338). Very 
 hygroscopic. Misoible with water. Burns with 
 a pale flame. Snow (1 pt.) mixed with alcohol 
 (2 pts.) produces a freezing mixture (-20°, Bn. 
 i, 237). 
 
 Alcohol dissolves fats, oils, resins, alkaloids 
 and most organic substances. It dissolves CaCl2 
 and SrClj but not BaClj,; Ca(N03)2 but not 
 Sr(N03)2 and Ba(N03)2 ; LiCl but not ECl and 
 NaCl. It does not dissolve carbonates or 
 sulphates. It dissolves I, Br, P, and S. 
 
 The critical point of alcohol is 284-6° at 
 48,900 mm. At this point 1 g. occupies 3-5 c.e. 
 (Eamsay a. Young, Pr. 38, 329). Alcohol vapour 
 in contact with liquid acquires its normal 
 density, 23, at 50° (B. a.Y.). 
 
 When alcohol is mixed with water contrac- 
 tion takes place and heat is evolved. The 
 maximum contraction occurs when 49-8 vols, 
 water and 53-9 vols, alcohol at 0° produce 100 
 vols, of mixture instead of 103-7 vols. This 
 corresponds to a possible compound, EtOH 3aq 
 (Mendeldeff, Z. 1865, 262). 
 
 The greatest difference between the observed 
 specific heats of solutions of alcohol and the 
 values calculated on the assumption of mere 
 mixture occurs in a solution containing about 
 80 p.c. of alcohol by weight, corresponding to 
 the formula EtOH 6aq. The greatest difference 
 between the observed and calculated boiling- 
 points and between observed and calculated 
 capillarity also occurs in the same mixture, but 
 the maximum deviation from calculated (or 
 mean) compressibility is exhibited by a solution 
 containing 40 p.c. of alcohol by weight (Dupr6 a. 
 Page, Pr. 17, 333 ; P. M. [4] 38, 158). The 
 maximum rate of transpiration through capillary 
 
 tubes is exhibited by the solution EtOHSaq 
 (Graham, A. 123, 102). 
 
 Detection of Water in Alcohol. — 1. CuSO^ 
 ought not to turn blue (Cassoria). — 2. Benzene 
 ought not to form a cloudiness, due to water- 
 drops (Gorgeu, O. iJ. 30, 691).— 3. Wet alcohol 
 produces a pp. of BaO when added to a solution 
 of BaO in absolute alcohol (Berthelot, A. Ch. 
 [3] 46, 180).— 4. If alcohol be added to a mixture 
 of anthraquinone ("001 g.) with a little sodium 
 amalgam, a jjreen coloration indicates absence 
 of water, otherwise a red colour is produce-1 
 (Glaus, B. 10, 927). 
 
 The following table gives the percentages of 
 absolute alcohol, determined by Tralles : 
 
 Volumes 
 
 Weights 
 
 Speoifio 
 
 Volumes 
 
 Weights 
 
 dpacifio 
 
 per 
 
 per 
 
 gravity 
 
 per 
 
 per 
 
 gravity 
 
 cent. 
 
 cent. 
 
 at 16-56° 
 
 cent. 
 
 cent. 
 
 at 15-560 
 
 
 
 
 
 l-OOOO 
 
 51 
 
 43-47 
 
 •9315 
 
 1 
 
 0-80 
 
 •9976 
 
 52 
 
 44-42 
 
 •9295 
 
 2 
 
 1-60 
 
 •9961 
 
 53 
 
 4o-36 
 
 •9275 
 
 3 
 
 2-40 
 
 •9947 
 
 54 
 
 46-32 
 
 •9254 
 
 4 
 
 3-20 
 
 •9933 
 
 55 
 
 47-29 
 
 -9234 
 
 5 
 
 4-00 
 
 •9919 
 
 56 
 
 48-26 
 
 •9213 
 
 6 
 
 4-81 
 
 •9906 
 
 57 
 
 49-23 
 
 •9192 
 
 7 
 
 5-62 
 
 •9893 
 
 58 
 
 50-21 
 
 •9170 
 
 8 
 
 6-43 
 
 •9881 
 
 59 
 
 51-20 
 
 ■9148 
 
 9 
 
 7-24 
 
 •9809 
 
 60 
 
 52-20 
 
 ■9126 
 
 10 
 
 8-05 
 
 •9857 
 
 61 
 
 53-20 
 
 ■9104 
 
 11 
 
 8-87 
 
 •9845 
 
 62 
 
 64-21 
 
 ■9082 
 
 12 
 
 9-69 
 
 •9834 
 
 63 
 
 55-21 
 
 •9059 
 
 13 
 
 10-51 
 
 •9823 
 
 64 
 
 56-22 
 
 ■9036 
 
 14 
 
 11-33 
 
 •9812 
 
 65 
 
 57-24 
 
 ■9013 
 
 15 
 
 12-15 
 
 •9802 
 
 66 
 
 58-27 
 
 ■8989 
 
 16 
 
 12-98 
 
 •9791 
 
 67 
 
 59-32 
 
 •8965 
 
 17 
 
 13-80 
 
 •9781 
 
 68 
 
 60-38 
 
 ■8941 
 
 18 
 
 14-63 
 
 •9771 
 
 69 
 
 61-42 
 
 ■8917 
 
 19 
 
 15-46 
 
 •9761 
 
 70 
 
 62-50 
 
 ■8802 
 
 20 
 
 16-28 
 
 •9751 
 
 71 
 
 63-58 
 
 •8867 
 
 21 
 
 17-11 
 
 •9741 
 
 72 
 
 64-66 
 
 ■8842 
 
 22 
 
 17-95 
 
 •9731 
 
 73 
 
 65-74 
 
 ■8817 
 
 23 
 
 18-78 
 
 •9720 
 
 74 
 
 66-83 
 
 ■8791 
 
 24 
 
 19.62 
 
 •9710 
 
 75 
 
 67-93 
 
 •8765 
 
 25 
 
 20-46 
 
 •9700 
 
 76 
 
 69-05 
 
 •8739 
 
 26 
 
 21-30 
 
 •9689 
 
 77 
 
 70-18 
 
 ■8712 
 
 27 
 
 22-14 
 
 •9679 
 
 78 
 
 71-31 
 
 ■8685 
 
 28 
 
 22-99 
 
 •9668 
 
 79 
 
 72-45 
 
 ■8658 
 
 29 
 
 23-84 
 
 ■9657 
 
 80 
 
 73-59 
 
 ■8631 
 
 30 
 
 24-69 
 
 •9646 
 
 81 
 
 74-74 
 
 ■8603 
 
 31 
 
 25-55 
 
 •9634 
 
 82 
 
 75-91 
 
 ■8575 
 
 32 
 
 26-41 
 
 •9622 
 
 83 
 
 7709 
 
 ■8547 
 
 33 
 
 27-27 
 
 •9609 
 
 84 
 
 78-29 
 
 -8518 
 
 34 
 
 28-13 
 
 •9596 
 
 85 
 
 79-50 
 
 ■8488 
 
 35 
 
 28-99 
 
 •9583 
 
 86 
 
 80-71 
 
 ■8458 
 
 36 
 
 29-86 
 
 •9570 
 
 87 
 
 81-94 
 
 ■8428 
 
 37 
 
 30-74 
 
 •9550 
 
 88 
 
 83-19 
 
 •8397 
 
 38 
 
 31-62 
 
 •9541 
 
 89 
 
 84-46 
 
 ■8365 
 
 39 
 
 32-50 
 
 •9526 
 
 90 
 
 85-75 
 
 •8332 
 
 40 
 
 33-39 
 
 •9510 
 
 91 
 
 8709 
 
 ■8299 
 
 41 
 
 34-28 
 
 •9494 
 
 92 
 
 88-37 
 
 -8265 
 
 42 
 
 35-18 
 
 •9478 
 
 93 
 
 89-71 
 
 ■8230 
 
 43 
 
 36-08 
 
 •9461 
 
 94 
 
 91-07 
 
 ■8194 
 
 44 
 
 36-99 
 
 •9444 
 
 95 
 
 92-46 
 
 ■8157 
 
 45 
 
 37-90 
 
 ■9427 
 
 96 
 
 93-89 
 
 ■8118 
 
 46 
 
 38-82 
 
 -9409 
 
 97 
 
 95-34 
 
 ■8077 
 
 47 
 
 39-75 
 
 •9391 
 
 98 
 
 96-84 
 
 ■8034 
 
 48 
 
 40-66 
 
 •9373 
 
 99 
 
 98-39 
 
 ■7988 
 
 49 
 
 41-59 
 
 •9354 
 
 100 
 
 100-00 
 
 ■7939 
 
 50 
 
 42-52 
 
 •9335 
 
 
 
 
96 
 
 ALCOHOL. 
 
 Ths specific gravity of aqueous alcohol is 
 given by MendeWeff (P. 138, 103,230) as follows : 
 
 Weight P.O. 
 
 SpeoiQo Sravity, referred to Water at 4" 
 
 Alcohol 
 
 atO" 
 
 at 10° 
 
 at 20° 
 
 at 30° 
 
 
 
 •99988 
 
 •99975 
 
 •99831 
 
 •99579 
 
 5 
 
 •99135 
 
 •99113 
 
 •98945 
 
 •98680 
 
 10 
 
 •98493 
 
 •98409 
 
 •98195 
 
 •97892 
 
 15 
 
 •97995 
 
 •97816 
 
 •97527 
 
 •97142 
 
 20 
 
 •97566 
 
 •97263 
 
 •96877 
 
 ■96413 
 
 25 
 
 •97115 
 
 •96672 
 
 •96185 
 
 •95628 
 
 30 
 
 •96540 
 
 •95998 
 
 •95403 
 
 •94751 
 
 35 
 
 •95784 
 
 •95174 
 
 •94514 
 
 •93813 
 
 40 
 
 •94939 
 
 •94255 
 
 •93511 
 
 •92787 
 
 45 
 
 •93977 
 
 •93254 
 
 •92493 
 
 •91710 
 
 50 
 
 •92940 
 
 ■92182 
 
 •91400 
 
 •90577 
 
 65 
 
 •91848 
 
 •91074 
 
 •90275 
 
 •89456 
 
 60 
 
 •90742 
 
 •89944 
 
 •89129 
 
 •88304 
 
 65 
 
 •89595 
 
 •88790 
 
 •87961 
 
 •87125 
 
 70 
 
 •88420 
 
 •87613 
 
 •86781 
 
 •85925 
 
 75 
 
 ■87245 
 
 •86427 
 
 •85580 
 
 •84719 
 
 80 
 
 •86035 
 
 •85215 
 
 •84366 
 
 •83483 
 
 85 
 
 ■84789 
 
 •83967 
 
 •83115 
 
 •82232 
 
 90 
 
 •83482 
 
 •82665 
 
 •81801 
 
 •80918 
 
 95 
 
 •82119 
 
 •81291 
 
 •80433 
 
 •79553 
 
 100 
 
 •80625 
 
 •79788 
 
 •78945 
 
 •78096 
 
 The following table is given by Fownes 
 {Manual, 3id ed. 691), the specific gravities 
 being taken at 15-6° 0. : 
 
 Percent- 
 age by 
 Weight 
 
 Specific 
 Gravity 
 
 Percent- 
 age by 
 Weight 
 
 Specific 
 Gravity 
 
 Percent- 
 age by 
 Weight 
 
 Specific 
 Gravity 
 
 0'5 
 
 0-9991 
 
 34 
 
 0-9511 
 
 68 
 
 0-8769 
 
 1 
 
 0-9981 
 
 35 
 
 0-9490 
 
 69 
 
 0-8745 
 
 2 
 
 0-9965 
 
 36 
 
 0-9470 
 
 70 
 
 0-8721 
 
 3 
 
 0-9947 
 
 37 
 
 0-9452 
 
 71 
 
 0-8696 
 
 4 
 
 0-9930 
 
 38 
 
 0-9434 
 
 72 
 
 0-8672 
 
 6 
 
 0-9914 
 
 39 
 
 0-9416 
 
 73 
 
 0-8649 
 
 6 
 
 0-9898 
 
 40 
 
 0-9396 
 
 74 
 
 0-8625 
 
 7 
 
 0-9884 
 
 41 
 
 0-9376 
 
 75 
 
 0-8603 
 
 8 
 
 0-9869 
 
 42 
 
 0-9356 
 
 76 
 
 0-8581 
 
 9 
 
 0-9855 
 
 43 
 
 0-9335 
 
 77 
 
 0-8557 
 
 10 
 
 0-9841 
 
 44 
 
 0-9314 
 
 78 
 
 0-8533 
 
 11 
 
 0-9828 
 
 45 
 
 0-9292 
 
 79 
 
 0-8508 
 
 12 
 
 0-9815 
 
 46 
 
 0-9270 
 
 80 
 
 0-8483 
 
 13 
 
 0-9802 
 
 47 
 
 0-9249 
 
 81 
 
 0-8459 
 
 14 
 
 0-9789 
 
 48 
 
 0-9228 
 
 82 
 
 0-8434 
 
 15 
 
 0-9778 
 
 49 
 
 0-9206 
 
 83 
 
 0-8408 
 
 16 
 
 0-9766 
 
 50 
 
 0-9184 
 
 84 
 
 0-8382 
 
 17 
 
 0-9753 
 
 51 
 
 0-9160 
 
 85 
 
 0-8357 
 
 18 
 
 0-9741 
 
 52 
 
 0-9135 
 
 86 
 
 0-8331 
 
 19 
 
 0-9728 
 
 53 
 
 0-9113 
 
 87 
 
 0-8305 
 
 20 
 
 0-9716 
 
 64 
 
 0-9090 
 
 88 
 
 0-8279 
 
 21 
 
 0-9704 
 
 55 
 
 0-9069 
 
 89 
 
 0-8254 
 
 22 
 
 0-9691 
 
 56 
 
 0-9047 
 
 90 
 
 0-8228 
 
 23 
 
 0-9678 
 
 57 
 
 0-9025 
 
 91 
 
 0-8199 
 
 24 
 
 0-9665 
 
 58 
 
 0-9001 
 
 92 
 
 0-8172 
 
 25 
 
 0-9652 
 
 59 
 
 0-8979 
 
 93 
 
 0-8145 
 
 26 
 
 0-9638 
 
 60 
 
 0-8956 
 
 94 
 
 0-8118 
 
 27 
 
 0-9623 
 
 61 
 
 0-8932 
 
 95 
 
 0-8089 
 
 28 
 
 0-9609 
 
 62 
 
 0-8908 
 
 96 
 
 0-8061 
 
 29 
 
 0-9593 
 
 63 
 
 0-8886 
 
 97 
 
 0-8031 
 
 30 
 
 0-9578 
 
 64 
 
 0-8863 
 
 98 
 
 0-8001 
 
 31 
 
 0-9560 
 
 65 
 
 0-8840 
 
 99 
 
 0-7969 
 
 82 
 
 0-9544 
 
 66 
 
 0-8816 
 
 100 
 
 0-7938 
 
 33 
 
 0-9528 
 
 67 
 
 0-8793 
 
 
 
 Proof spirit was a term originally intended 
 to denote spirit that was just strong enough to 
 ignite gunpowder when burnt upon it, but it 
 was defined by law in the reign of George III. 
 to be spirit ' such as shall at the temperature of 
 51° F. weigh exactly twelve-thirteenth parts of 
 an equal amount of distilled water.' It has, 
 therefore, S.G. -920 at 15-6° C, and contains 
 49-24 pts. alcohol to 50-76 pts. water by weight, 
 or 100 vols, alcohol to 81-82 vols, water. 
 
 Alcoholic Drinks. — Beer contains from 2 to 
 6 p.c. of alcohol ; hoch and claret from 8 to 10 
 p.o. ; iport and sherry from 15 to 20 p.c. ; gin, 
 rum, and whisky from 51 to 54 p.o. 
 
 Detection. — 1. The liquid supposed to con- 
 tain alcohol is repeatedly rectified, after drying 
 with KjCOj. The alcohol is recognised by its 
 boiling-point, and by converting it into ethyl 
 iodide, and noting the boiling-point of the iodide 
 (72°). — 2. The suspected liquid ia distilled and 
 some of the distillate (8 c.c.) mixed with water 
 (10 c.c.) and HjSO, (5 c.c.) ; some KMnO^Aq, 
 and after five minutes a solution of magenta, 
 bleached by SOj, are added. A red colour indi- 
 cates that aldehyde had been formed by the 
 oxidation of the alcohol. Acetone, formic acid 
 and methyl alcohol do not show this reaction, so 
 that it may be used to detect ethyl alcohol in 
 wood spirit. Other primary alcohols behavo 
 more or less like ethyl alcohol (Biche a. Bardy, 
 C. B. 82, 768).— 3. An aqueous solution of 
 alcohol warmed with EOH and iodine deposits 
 iodoform. This ' iodoform reaction ' is given 
 also by aldehyde, acetone, w-propyl, w-butyl, sec. 
 butyl, and octyl alcohols, by propionic and 
 butyric aldehydes, by lactic, quinic, and meconio 
 acids, by acetophenone, methylic butyrate, acetio 
 ether, and oil of turpentine. 
 
 The ' iodoform reaction ' is not given by 
 methyl and amyl alcohols, by formic, acetic, 
 butyric, valeric, oxalic, succinic, malic, tartaric, 
 racemio, citric, pyrotartario, suberic, sebacic, 
 uric, mucic, isethionic, benzoic, salicylic, anisic, 
 cinnamic, and picric acids, phenol, valeric alde- 
 hyde, benzoic aldehyde, glycol, glycerin, mannite, 
 glyoocoU, leucine, chloral, ethyl chloride, ethy- 
 lene chloride and bromide, chloroform, tetra- 
 chloride of carbon, sulphide of carbon, toluene, 
 and ether (Lieben, A. Sii^l. 7, 226). Sugar 
 and dextrin give a small amount of iodo- 
 form. 
 
 The formation of ethyl acetate and benzoate 
 is also recommended as a test for alcohol. 
 
 Estimation. — The liquid is distilled and the 
 S.G. of the distillate taken. 
 
 Detection of Fusel Oil. — 1. The liquid ia 
 diluted with water until it contains about 12 p.o. 
 alcohol ; it is then shaken with chloroform. 
 This extracts the amyl alcohol, which it 
 leaves behind on evaporation ; by warnjing with 
 KOAo and HjSOj this is converted into amyl 
 acetate, smelling like pear-drops. — 2. The alco- 
 hol is diluted until it forms a 50 p.c. solution. 
 100 c.c. are then shaken with 20 c.c. chloroform 
 at 15° in a graduated cylinder. If the chloroform 
 layer is 37"1 c.c. the alcohol is free from higher 
 homologues, but if it occupy a larger volume, 
 fusel oil is present. Thus 39-1 c.c. indicates 
 1 P.O. amyl alcohol (Rose, B. 19, E. 184).— 3. 
 The height to which the alcohol will rise in 
 capUlary tubes of known diameter is observed. 
 
ALCOHOL. 
 
 07 
 
 I*are alcohol rises higher than alcohol adulte- 
 rated with fusel oil (J. Tiaube, B. 19, 892). 
 
 iJeactJoiM. — 1. Potassium and sodium act 
 upon alcohol, evolving hydrogen and forming 
 EtOK and EtONa respectively. — 2. Phosphorus 
 trichloride forms EtCl, HCl, ethyl phosphite, 
 and phosphorous acid (Beohamp, C. B. 40, 944) : 
 6EtOH + 2PCI3 = SEtCl + 3HC1 + EtjPO, + HjPO, 
 A smaller quantity of PCI3 acts in the cold 
 thus: PCl3 + HOEt = PCl2(OEt) + HCl (Men- 
 schutkin, A. 139, 343).— 3. PCI5 reacts thus : 
 EtOH + PCI5 = EtCl + CIH + PCI3O. 
 
 4. PjSj produces mercaptan : 
 
 5EtOH + PjSj = 5EtSH + P A- 
 
 5. Alcohol coagulates albumen, and, partly 
 on this account and partly by arresting the 
 development of low organisms, it prevents 
 the putrefaction of dead animal matter. — 
 
 6. Vapour of alcohol passed through a red Jiot 
 tube produces COj, water, hydrogen, CH^, C^H,, 
 naphthalene, and charcoal. If the tube be filled 
 with pumice, benzene, phenol, and perhaps 
 also aldehyde and acetic acid, are also formed 
 (Berthelot, A. Ch. [3] 33, 295; A. 81, 108).— 7. 
 Zinc dust at 300°-B50° forms ethylene and hy- 
 drogen : CjHjO + Zn = ZnO + CjHi + H.,. Alcohol- 
 vapour passed over zinc dust at a duU red heat 
 forms CO, CH„ and Hj (Jahn, M. 1, 378).— 8. 
 Alcohol scarcely conducts an electric current, 
 but when acidulated with 5 p.o. HjSO, the 
 current passes, hydrogen comes off at one pole 
 and, at the other, aldehyde, ethyl formate sul- 
 phate and acetate, together with small quantities 
 of aoetal, and CH3.CH(0H)(0Et) are formed 
 (Benard, A. Ch. [6] 17, 295). Alcohol con- 
 taining a little potash produces hydrogen at the 
 negative pole and aldehyde-resin at the positive 
 pole (Connell). — 9. Alcohol bums with a pale 
 flame forming CO.^ and HjO. Alcohol vapour 
 undergoes rapid, but incomplete, combustion 
 when mixed with air and exposed to finely 
 divided platinum ; acetic acid, aldehyde, formic 
 acid, acetal, and acetic ether are formed. Hence 
 a coil of red hot platinum wire will keep red hot 
 if placed round the wick of a spirit lamp that is 
 not burning (glow-lamp of Sir H. Davy). — 10. 
 Finely divided rhodiwm, iridium, and ruthenium, 
 in presence of an alkali, decompose alcohol, with 
 elimination of H and foi-mation of an acetate 
 (Deville a. Debray, C. B. 78, 1782).— 11. Oxygen 
 does not attack cold pure alcohol, but ozone 
 forms acetic and formic acids (Boillot, G. B. 
 76, 1132). — 12. Chromic acid mixture oxidises 
 alcohol to aldehyde and acetic acid. — 13. An 
 amjnoniacal solution of CuO at 180° attacks 
 alcohol, forming acetic acid and Cu^O (A. Le- 
 tellier, C. B. 89, 1105).— 14. KMn04 in acid, but 
 not in alkaline, solution forms aldehyde and 
 acetic acid (Chapman a. Smith, G. 3. 20, 301). 
 15. Strong 'mtric acid acts violently, giving 
 off copious red fumes containing nitrous ether, 
 nitric oxide, COj, aldehyde, acetic and formic 
 acids. If the action be moderated by making 
 three layers of fuming HNO3, water, and alcohol, 
 and allowing them to mix slowly by diffusion, 
 the following bodies are formed : aldehyde, 
 acetic acid, glyoxal, glyoxylic acid, glycollic acid, 
 and oxalic acid (Debus). — 16. In presence of 
 wrea, nitric acid converts alcohol into ethyl 
 nitrate (3. «.). — 17. In presence of mercuric ni- 
 trate, nitric acid acts upon alcohol with produc- 
 
 VoL. L 
 
 tion of fulminate of mercury (3. v.) ; in a similar 
 way fulminate of silver may be made. 
 
 If mercury (1 pt.) be dissolved in HNO, 
 (12 pts.) (S.G. 1-3) and the liquid left for soma 
 days till no more nitrous fumes appear and the 
 liquid is colourless, and then alcohol (12 pts. of 
 S.G. '8) be added and the mixture be warmed, a 
 pp. is produced which is not mercuric fulminate. 
 It may be crystallised from diluted (4 vols.) 
 HNO3 (1 vol.). It is Cj,H„Hg30,(N03),. At 
 120°-130° it explodes. It is insoluble in 
 water, alcohol, and ether. Potash con- 
 verts it into C2H2Hg30.;(OH)j; while cold K^CjO, 
 slowly converts it into the oxalate,C2H2Hg302C204, 
 a body which is browned by sunlight. A mix- 
 ture of HNO3 and alcohol converts it into 
 mercuric fulminate (Cowper, O. J. 39, 242 ; v. 
 Gerhardt, A. 80, 101).— 18. Chlorine is rapidly 
 absorbed by alcohol, and in sunlight the liquid 
 may even take fire. The ultimate product is 
 chloral alcoholate, CCl3.CH(0Et)(0H), but this 
 is probably the result of a long series of reactions 
 (v. Chloral). Besides chloral, there are formed 
 HCl, aldehyde, acetal, acetic acid, EtCl and 
 other chlorinated bodies. — 19. Bromine forms 
 HBr, water, EtBr, bromal, and bromal alcoholate 
 (E. Hardy, O. B. 79, 806).— 20. Dry chlorine 
 passed into alcohol mixed with Kfirfi, gives 
 aldehyde, EtCl, acetyl chloride, and EtOAo 
 (Godefroy, BZ. [2] 40, 168).— 21. When alcohol 
 is distilled with much water and bleaching 
 powder, chloroform (5. v.) is formed. When 
 bleaching powder (300 grms.) is mixed with 
 absolute alcohol (67 grms.) in 10 minutes thsi 
 mixture gets hot and alcohol distils over to- 
 gether with a green oil, which explodes when; 
 exposed to sunlight or heated, and among tha 
 products of the explosion are mono- and di- 
 chloro-acetal (Sohmitt a. Goldberg, J. pr. [2] 
 19, 393), aldehyde, and small quantities of 
 chloroform (Goldberg, /. pr. [2] 24, 97).— 22.. 
 Hydric chloride produces ethyl chloride : 
 
 EtOH + HCl = EtCU HjO. 
 But when excess of alcohol is used and the solu- 
 tion heated in a sealed tube at 240°, ether is; 
 also formed: EtOH -HCIEt = Et20 + HCl (Rey- 
 noso, A. Ch. [3] 48, 385).— 23. Sulphuric. 
 acid mixes with alcohol with evolution of heat 
 and formation of hydrogen ethyl sulphate : 
 
 EtOH + H^SO^ = EtHSOj -1- H,,0. 
 About half the alcohol and H^SOj take part in 
 the reaction ; when more dilute acid is used 
 hydrogen ethyl sulphate is not formed until 
 heat is applied. If a mixture of alcohol with 
 an equal volume (or less) o£ H^SO^ be heated, 
 a further reaction sets in at 120°-150°, ether 
 and water distilling over ; this is due to action 
 of alcohol upon hydrogen ethyl sulphate 
 (Williamson, C. /. 4, 106, 229 ; v. Ether) : 
 
 HEtSO, + EtOH = Hi,S04 4- EtOEt 
 When alcohol is heated with twice its volume 
 (or more) of H^SO, the mixture begins to 
 blacken between 160°-180°, and then gives oft 
 ethylene, mixed with SO^, acetic acid, acetic 
 ether, COj, CO, ethyl sulphate, and formic acid. 
 The main reaction is expressed by the equation 
 C^HjO = CjH, + H„0 (compare Erlenmeyer, A. 
 162, 373). — 24. Anhydrous sulphuric acid, SO3, 
 dissolves in alcohol forming di-ethyl sulphate, 
 EtjSO,. Vapour of SO, passed into dry 
 alcohol forms crystals of ethionic anhydride, 
 
98 
 
 ALCOHOL. 
 
 OzH^^gQ'^O, or ' carbyl sulphate,' together 
 
 with ethionio, isethionic, and sulphuric acids, 
 and HEtSOj. — 25. Heated with sulphurcnts acid 
 at 200° it forms HEtSO„ ether, H^SO.,, mer- 
 captan, and S (PagUani, /. 187*?, 518).— 26." 
 CISO3H forms EtHSOj and other bodies 
 (Baumstark, A. 140, 75).— 27. When alcohol is 
 dropped upon hot zinc chloride the greater part 
 is decomposed in accordance with the equation : 
 
 2C,H„0 = C^HjO + Hj + C^H, + H.O. 
 Hydrogen, ethane, HCl, and polymerides of alde- 
 hyde are also formed (W. H. Greene, O. B. 86, 
 1140). When wet alcohol is heated with ZnClj 
 at 155°, ether is formed, as well as EtCl, basic 
 zinc chloride being left. — 28. Phosphoric acid 
 mixed with alcohol forms some di-hydrogen 
 ethyl phosphate, EtH2P04. Alcohol heated 
 with P2O5 forms HEt^PO, and EtjPO^ (Carius, 
 A. 137, 121).— 29. Alcohol heated with B.fi, 
 forms EtEOj and Et^BOj.— 30. PJiosphorus 
 sulpho-chloride, PSCI3, forms di-hydrogen ethyl 
 thio-phosphate (Chevrier, Z. [2] 5, 413) : 
 
 PSCI3 -I- 3H0Et = PS(0H)2(0Et) + 2EtCl + HCl. 
 31. Chloride of sulphur, SjClj, acts upon 
 alcohol forming ethyl chloride, ethyl sulphite, 
 and a small quality of mercaptan (Carius, A. 
 106, 316). — 32. Chloride of antimony dissolves 
 in alcohol ; if the solution be heated to 150° 
 the following reaction ensues (H. Schiff, A. 
 Suppl. 5, 218) : 
 
 SbCl3 -e 4EtOH = SbOCl + 2EtCl + Et,0 -K 2H ,0. 
 33. Heated with carbon tetrahromide at 100° 
 for 12 hours, bromoform is produced (Bolas a. 
 Groves, O. J. [2] 9, 784): CBr4 + C2H„0 = 
 CHBrj -t- OjHjO -^ HBr. Alcohol here acts as a 
 reducing agent, as it does also in the next 
 reaction. — 34. Heated with a di-azo salt, nitrogen 
 is evolved and the entire di-azo group displaced 
 by hydrogen : 
 
 C„H,.N2C1 + C^H^O = C^H^H -H N^ -f HCl + C^H^O. 
 In some cases the di-azo group is displaced by 
 ethoxyl. — 35. Heated with ammoniacal zinc 
 chloride at 260°, alcohol is converted into a 
 mixture of mono-, di-, and tri-ethylamine ; the 
 yield of mixed bases amounts to 45 p.c. of the 
 alcohol used (Merz a. Gasiorowski, B. 17, 637). — 
 
 36. Zinc acetate heated with excess of alcohol at 
 100° is converted, in about 30 hours, into zinc 
 ethyl acetate and zinc oxide (Kraut,^. 156, 323). 
 
 37. When stannic chloride is distilled with 
 alcohol, ether and EtCl pass over at 140°-170° ; 
 afterwards a compound of EtCl with SnClj (Kuhl- 
 maim, A. 33, 106, 192).— 38. Crystallised stan- 
 nous chloride distilled with alcohol yields ether, 
 but no EtCl (Marchand) ; the same decomposi- 
 tion takes place in a sealed tube at 240°. 
 Crystallised chloride of inanganese, and ferrous 
 chloride also etherif y alcohol completely at 240° ; 
 the chlorides of cadmium, nickel, and cobalt 
 partially (Beynoso, A. Ch. [2] 48, 385).— 39. 
 Platinic chloride (1 pt.) dissolved in alcohol 
 (10 pts.) of S.G. -82 and distilled to ^, yields 
 aldehyde,ethyl chloride,HCl, and the solution con- 
 tains the so-called inflammable chloride of plati- 
 num OjHiPtClj, which is left as a sticky mass when 
 the liquid is evaporated (Zeise, P. 9, 632 ; 21, 
 498 ; 40, 249).— 40. Platimous chloride boiled 
 with alcohol forms a black explosive powder 
 called detonating platinum deposit, CjHjPtO(?) 
 (Zeise, Joe. cit.).— 41. Mercuric chloride is slowly 
 
 reduced to calomel by alcohol. — 42. Alcohol 
 heated with soda-lime, air being excluded, is 
 converted into sodic acetate, with evolution of 
 hydrogen; at a higher temperature the sodio 
 acetate breaks up into sodio carbonate and 
 marsh-gas. — 43. Chloride of cyanogen is readily 
 absorbed by alcohol but does not decompose it 
 immediately. After a few days, or more quickly 
 at 60°, NHjCl separates, and the liquid then 
 contains ethyl chloride, ethyl carbamate (or 
 urethane), and ethyl carbonate (Wurtz, A. 79, 
 280). 
 
 Combinations. — Alcohol combines with many 
 salts, acting like water of crystallisation. — 
 SbClsEtOH [67°] needles (from alcohol); re- 
 solved by heat into HCl, EtCl, Sb.Oj, and SbCl,. 
 Soluble in ether and chloroform, but decomposed 
 by water (W. C. Williams, C. J. 30, 463).— 
 AsCl^EtOH (148°) : liquid ; fumes in the air ; 
 decomposed by water (Luynes, A. 116, 368). — 
 CaCl24EtOH : got by cooling an alcoholic solu- 
 tion of CaClj with ice.— CaCl^SEtOH : got by 
 evaporation of such solution over H^SO^ (Heindl, 
 M. 2, 207).— LiC14EtOH (Simon, J. pr. [2] 
 20, 376).— MgCl,6EtOH (S.).— Mg(N03)26EtOH 
 (Chodnew, A. 71, 256) : a crystalline mass 
 deposited from boiling solution. — PtCl42EtOH 
 (Schiltzenberger, J. 1870, 388).— SnCl42EtOH: 
 crystals formed by evaporation over HjSO, 
 (Lewy, C. R. 21, 371 ; Bobiquet, J. Ph. [3] 26, 
 161) ; heated with acids, this compound readily 
 forms ethyl salts.— TiCliEtOH [105°-110°] crys- 
 tals ; decomposed by water (Demar9ay, B. 8, 75). 
 
 Alcoholates or Ethylates are formed 
 by displacing the typical hydrogen by metals. 
 They are decomposed by water : 
 
 MOEt -I- HjO = HOEt + MOH. 
 
 Aluminium ethylate Al(0Et)3 [130°] 
 S.G.4 1-147. Aluminium does not attack alcohol, 
 but if iodine be present and the liquid be 
 warmed, hydrogen is evolved and aluminium 
 ethylate is formed (Gladstone a. Tribe, Pr. 30, 
 646): 2Al + 6HOEt = Al,(OEt)5-l-3H,,. The re- 
 action probably takes place in three stages : 
 3H0Et + Aljlj = Alil3(OEt)3 -f 3HI 
 Al2(OEt)sl3 + SHOEt = Al2(0Et)s + 3HI 
 Alj-K6HI = Al2ls + 3H2. 
 Aluminium (4 g.) , iodine (2 g.), and alcohol (40 0.0.), 
 are heated in a flask with inverted condenser ; 
 when no more H comes off, the contents are 
 distilled in vacuo at 300°. (Good yield (12 g.). 
 G. a. T., C. /. 39, 2). When aluminium ethylate 
 has been fused it remains liquid for a long time 
 even at 70°. It is decomposed by water thus : 
 
 Al^jOEt), H- 6H2O = Alj(0H)3 H- 6H0Et. 
 When distilled under atmospheric pressure it 
 decomposes : Al2(0Et)j = AlA + SCjHj -i- SHOEt, 
 (G. a. T., a. J. 41, 5). 
 
 Barium ethylate Ba (0Et)2Aq (Berthelot, 
 A. Ch. [3] 46, 180), Ba(0Et)jBa(0H)2 (Destrem, 
 A. Ch. [5] 27, 8, 22 ; C. B. 90, 1213). A granular 
 pp. formed by boiling an alcoholic solution of 
 BaO, or by heating alcohol with BaO in a 
 digester at 150°. A white powder, turned yellow 
 by oxidation. Converted by CO, into bario 
 ethyl-carbonate. Destructive distillation gives 
 CjHj, methane, H, and BaCOj. 
 
 Calcium ethylate Ca(0Et)2 resembles the 
 barium compound. 
 
 Ferric ethylate ''Pe2(0Et), (?).- Whentho 
 proper quantity of sodic ethylate is added to an 
 
ALCOHOLS. 
 
 09 
 
 slooholic solution of PajClj, all the chlorine is 
 ppd. as NaCl, and the filtrate leaves, after 
 evaporation, a black pasty mass, sol. alcohol, 
 MeOH, ether,, benzene, chloroform, or benzoline 
 (Grimaux, O. B. 98, 105). A solution of ferric 
 ethylate poured into water produces a solution 
 of coUoidal ferric hydroxide. 
 
 Potassium ethylate KOEt. — Similar in 
 character to sodic ethylate. 
 
 Sodic ethylate NaOEt. — When sodium is 
 dissolved in dry alcohol, H is evolved, and 
 ultimately crystalline lamina of NaOEt 2H0Et 
 separate. If the solution be evaporated in vacuo 
 at 20° needles of NaOEt SHOEt are got (For- 
 crand, Bl. 40, 177). The alcohol of crystallisa- 
 tion may be driven off at 180°. 
 
 Reactions. — 1. When mixed with water and 
 distilled, alcohol passes over and NaOH is left. — 
 
 2. Converted by EtI into ether (Williamson). — 
 
 3. Forms ether when it acts on EtNOj : but it 
 acts like Na upon ethers of organic acids ; thus 
 it converts formic ether into CO and alcohol, 
 oxalic ether into CO and carbonic ether, carbonic 
 ether into NaCOjEt and EtjO, benzoic ether 
 into NaOBz and Et^O, acetic ether into sodium 
 aoeto-acetic ether (Geuther). — 4. CO combines 
 with NaOEt at 100' forming sodic propionate. 
 Carbonic oxide passed over a mixture of NaOEt 
 and NaOAc at 205° produce n-butyrio acid, di- 
 ethyl-aeetic acid, mesityleuic acid, an acid 
 C.oHnOj (250°-260°), and two ketones CsH.sO 
 and CisH^jO (Geuther, A. 202, 305).— 5. PCl^ 
 gives NaCl, P0(0Et)3, and EtCl.— 6. With chloro- 
 form it forms ortho-formic ether, CH(0Et)3 
 (Williamson a. Kay, C. J. 7, 224).— 7. Chlorine 
 forms aldehyde and acetic acid (Maly, Z. [2] 5, 
 345).— 8. Bromine forms bromal, EtBr, and 
 acetic ether (Barth, B. 9, 1456). — 9. Ghloro- 
 acetic acid forms sodium ethyl-glyoolate (Heintz, 
 P. 109, 301).— 10. Iodine forms Nal, sodic for- 
 mate, and iodoform. — 11.- Iodoform is reduced 
 by NaOEt to methylene iodide. — 12. Nitrobenzene 
 is reduced to azoxybenzene, azobenzene, and 
 aniline (B^ohamp a. Saint-Pierre, G. R. 47, 24). 
 
 Thallium ethylate "TlOEt. S.G. 3-5 to 
 3-685.— Formed by heating EtOH with thallium 
 at 100° (Church), or by exposing thallium to the 
 vapour of alcohol in a bell-jar full of oxygen 
 <Lamy, A. Oh. [4] 3, 373). It may be solidified 
 by great cold. It dissolves in dry alcohol or 
 ether, hut addition of a trace of water causes 
 separation of thallous hydrate. TlOEt is slowly 
 decomposed by CHCI3 with separation of TlCl. 
 
 ALCOHOLS The term alcohol, originally 
 
 limited to one substance, viz. spirit of wine, is 
 now applied to a large number of compounds, 
 many of which, in their external characters, 
 exhibit but little resemblance to conmion alcohol. 
 All alcohols are compounds of carbon, hydrogen, 
 and oxygen, and are derived from hydrocarbons 
 containing even numbers of hydrogen-atoms by 
 substitution of one or more hydroxyl-groups, 
 OH, for an equal number of tydrogen-atoms : 
 thus from propane CsHj or CH3.CHj.CH3, are 
 derived the three following alcohols : — 
 Propyl alcohol C3HSO = C3H,(0H) 
 Propylene alcohol CaHaOj = C3H,(OH)2 
 Propenyl alcohol! OHO ^ C3H,(0H)3 
 orglycerm j a b 3 3 ^\ 13 
 Alcohols are classed as monohydric, di- 
 hydrio, trihydrio, &o., or generally as mono- 
 
 and poly-hydric, according to the number of 
 hydroxyl-groups which they contain. 
 
 An alcohol is saturated or unsaturated 
 according to the nature of the hydrocarbon 
 from which it is derived. Thus, all the three 
 alcohols derived from propane CgH,, which is a 
 saturated hydrocarbon, are themselves saturated 
 molecules not capable of forming addition- 
 compounds ; but from the unsaturated hydro- 
 carbon C3H5 is derived the unsaturated compound 
 allyl alcohol, CgHeO or C3H5(OH), which is 
 capable of taking up 2 at. bromine and forming 
 the compound C3H3BrjO. 
 
 The replacement, partial or total, of the 
 hydroxyl in an alcohol by CI, Br, I, or F, gives 
 rise to haloid ethers; thus: 
 
 From C3H.(0H) are derived C3H,C1, C3H,Br, 
 &o. 
 
 From C3H3(0H)2 are derived CjHjO^OH), 
 C3H,Cl2, &c. 
 
 From C3H3(OH)3 are derived CaHsC^OH)^, 
 C3H3Cl2(OH), C3H5CI3, &c. These substitutions 
 are effected by treating the alcohols with the 
 chlorides, bromides, and iodides of hydrogen and 
 phosphorus, as in the formation of ethyl chloride 
 from ethyl alcohol : 
 
 CjH,OH + HCl = H(OH) + C„,H,C1 
 3C3H5(OH) +PCl3 = P(OH)3 + 3C,H3Cl 
 
 3C^3(OH) i- POCI3 = P0(0H)3 ^ SCaH^Cl. 
 Instead of the bromides and iodides of phos- 
 phorus, a mixture of phosphorus and bromine or 
 iodine, in the proportions required to form them, 
 are often used in these processes. — The haloid 
 ethers are also formed in many instances by 
 direct substitution of chlorine &o. for hydrogen 
 in hydrocarbons. 
 
 The treatment of the alkyl chlorides, bro- 
 mides, or iodides with aqueous caustic alkalis 
 gives rise to a substitution opposite to that 
 shown in the above equations, reconverting the 
 ethers into alcohols; e.g. C2H5C1 + K0H = 
 KC1 + C2H5(0H). A considerable portion of the 
 alcohol thus formed is, however, converted by 
 dehydration into the corresponding olefin: e.g. 
 C3H80-H20 = C3H5. A better yield of alcohol 
 is obtained by heating the haloid ether with 
 moist silver oxide, which acts like a hydroxide 
 AgOH ; and a still better method is to convert 
 the alcoholic chloride, &c. into an acetate by 
 heating it with silver acetate or potassium ace- 
 tate, and to boil the resulting alkyl acetate 
 with caustic potash or soda ; 
 
 CjHjCl + KC2H3O, = KCl -I- CjHj.CjHjOj 
 CjHj.CjHjOj + KOH = KC2H3O2 + CjHjOH. 
 This reaction is of great importance in the pre- 
 paration of some of the higher alcohols. 
 
 The replacement of the hydroxyl in an alco- 
 hol by the corresponding radicles, methoxyl 
 OCH3, ethoxyl OC2H5, &o. — or of the hydrogen 
 in the OH by Me, Et, &o., gives rise to simple or 
 mixed alkyl oxides or ethers: thus EtOH 
 yields EtOK, EtOMe, and EtOEt ; and ethylene 
 alcohol C2H<(0H)j, yields C2H,(0H)(0Et) and 
 02Hj(0Bt)2. These substitutions may be effected 
 in various ways, the simplest being to replace a 
 H-atom in the alcohol by K or Na, and act on 
 the resulting compound with a haloid ether; e.g. 
 
 2C2H,(0H)2 -I- Naj = 2C2H,(0H)(0Na) + H^ ; 
 
 C2H,(0H)(0Na) -(-EtI = NaI + C2H4(0H)(0Et). 
 
 These oxides toay be looked upon as anhydrides 
 
 formed by elimination of one molecule of watejr 
 
100 
 
 ALCOHOLS. 
 
 from two molecules of the same or different 
 alcohols. 
 
 In the polyhydrio alcohols, where the two 
 hydroxyls occur in the same molecule, the elimi- 
 nation of water gives rise to another class of 
 oxides ; thus from ethylene alcohol C^i^OE.)^ is 
 derived ethylene oxide OjH^O. 
 
 The replacement of the hydrogen in an 
 alcohol by acid radicles produces alkyl salts 
 (also called compound ethers or esters) ; thus 
 from methyl alcohol, MeOH, are derived a nitrate 
 MeON02, an acetate MeOAc, an acid sulphate 
 Me.O.SOjH and a normal sulphate {MeO)2S02. 
 These alkyl salts may also be derived from the 
 corresponding acids by substitution of alkyl- 
 radicles for hydrogen, being indeed related to 
 the alcohols in the same manner as metallic 
 salts to metallic hydroxides. They may also 
 be looked upon as anhydrides formed by elimi- 
 nation of a molecule of water between one 
 molecule of an alcohol and one molecule of an 
 acid. By distillation with alkalis they are re- 
 solved into acid and alcohol ; e.g. 
 
 EtOAo + EOH = KOAo + EtOH. 
 
 MoNOEyDBio Alcohols. 
 
 1. Series C„'B^^fi or CaH2„+,0H. Of this 
 series the following members are at present 
 known, each being derived from the correspond- 
 ing paraffin OJS.^^f by substitution oi OH forH: 
 thus 
 
 CH3.OH 
 CjHj.OH 
 CjHj.OH 
 C4H,.0H 
 
 CaH.i.OH 
 
 C,H„.OH 
 
 C27H55.OH 
 CaoHjpOH 
 
 Methyl Alcohol . . 
 Ethyl „ . . . 
 Propyl „ . . . 
 Butyl „ . . . 
 Amyl ,t • • . 
 Hexyl „ . . . 
 Heptyl „ . • • 
 
 Octyl , UgMij.UU. 
 
 Ennyl or Nonyl Alcohol . . CgH,g.OH 
 Deoyl Alcohol .... CmHji.OH 
 Hendeoyl „ ... C„Hj3.0H 
 
 Dodeoyl „ ... CuH^s.OH 
 
 Tetradeoyl „ ... ChHjj.OH 
 
 Hexadecyl or Cetyl Alcohol . CisHjj.OH 
 Ootadecyl Alcohol . . ~ ~ 
 
 Oeryl Alcohol . 
 MeUssyl or Myricyl Alcohol 
 
 The first and second of these alcohols do 
 not admit of isomeric modifications ; for sup- 
 posing, as is most probable, that all the hydrogen- 
 atoms in the paraffins methane CH4 and ethane 
 CHg.CHj have the same value and are attached 
 to their respective carbon-atoms in the same 
 way, the result of the substitution of OH for H 
 in them must be the same, whichever of the 
 hydrogen-atoms is thus replaced. But in all the 
 higher terms of the series the case is different. 
 Thus in propane, CHs.CHj.CHj, the substitution 
 may take place either in one of the exterior 
 groups CH3, or in the middle group CHj, giving 
 rise to two alcohols of different structure, distin- 
 guished as primary and secondary, viz. 
 CH8.OH2.CH2OH OH3.CHOH.CH, 
 
 Primary Secondary 
 
 _ In the primary alcohols the carbon-atom 
 joined to the hydroxyl is connected immediately 
 with only one other carbon atom, that namely 
 in the group CHj ; but in the secondary alcohol 
 it is linked to two other carbon-atoms, and 
 
 these are the only forms of a 3-carbon alcohol 
 of the series. 
 
 The 4-carbon alcohol of the series admits ol 
 a greater number of modifications. For in the 
 first place, the hydrocarbon, butane, OaHj, from 
 which it is derived, is itself susceptible of two 
 forms, viz.. Normal butane CH3.CH2.CHj.CHj 
 and Isobutane CH3.CH(CH3)2 ; and further the 
 first of these hydrocarbons is capable of yielding 
 one primary and one secondary alcohol — these 
 terms having the meanings above explained — 
 while the second yields another primary alcohol, 
 and likewise a tertiary alcohol, in which 
 the C-atom joined to the hydroxyl is linked 
 also to three other atoms of carbon.' These 
 four derivatives are represented by the following 
 formulffi : — 
 
 Normal Primary CH3.CH2.CH2.CH2OH. 
 
 Isoprimary {Gn,)fin.CU^OU. 
 
 Secondary OH3.CH(OH).CH2(CH3). 
 
 Tertiary (CH3)2C(0H).CH3. 
 The higher alcohols of the series admit of 
 a still larger number of isomeric modifications ( 
 but all these alcohols must be either primary, 
 secondary, or tertiary ; for the C-atom joined to 
 the OH cannot be joined to a number of othei 
 carbon-atoms greater than three. In other 
 words the replacement of an H-atom by the 
 group OH must take place, either in a methyl- 
 residue CHj, a methylene-residue OHj, or a 
 methenyl residue CH, producing respectively a 
 primary, secondary, or tertiary, alcohol. 
 
 A very convenient nomenclature for these 
 isomeric alcohols has been introduced by Kolbe 
 {A. 132, 102). Methylalcoholis called carbinol 
 and the higher alcohols named as its substitution- 
 products, thus : 
 
 Carbinol or Methyl Alcohol CH3OH. 
 Methyl-carbinol or Ethyl Alcohol MeCHjOH. 
 Ethyl-carbinol or Propyl Alcohol EtCH20H. 
 Dimethyl-carbinol or.Isopropyl Alcohol 
 
 McjCHOH. 
 Propyl-oarbinol or Butyl Alcohol PrCHjOH. 
 Isopropyl-carbinol or Isobutyl Alcohol PrCHjOH, 
 Methyl-ethyl-carbinol or Secondary Butyl 
 
 Alcohol MeBtCHOH. 
 Trimethyl-carbinol or Tertiary Butyl Alcohol 
 
 McjCOH. 
 Primary, secondary, and tertiary alcohols are 
 distinguished from one another by their pro- 
 ducts of oxidation. The primary alcohols 
 of the series C^H^+jO, containing the group 
 CHjOH, are converted by oxidation with ohromio 
 acid mixture, first into the corresponding 
 aldehydes, by removal of Hj, or conversion ot 
 CHjOH into CHO, and then by further oxidation 
 into fatty acids C^Hj^Oj ; thus : 
 CH3.CH2.CH2OH -h = HjO -h CH3.CH2.CHO 
 Propyl Alcohol Propionic Aldehyde 
 
 CH3.CH2.CH20H-^ 02=H20 + CH3.CH2.COOH 
 
 Propionic acid 
 A secondary alcohol on the other hand 
 which contains two alcohol-radicles united by 
 CHOH, is converted, by removal of H^ from this 
 group, into a ketone, i.e. a compound consisting 
 of two alcohol-radicles united by the group CO, 
 thus: 
 
 CH3.CHOH.CH, -1- = HjO h CH3.CO.CH, 
 
 Secondary Propyl Dimethyl Ketone 
 
 Alcohol 
 
 Conversely tha aldehydes treated with nascent 
 
ALCOHOLS. 
 
 101 
 
 hydrogen (action of sodium-amalgam) are con- 
 verted into primary alcohols, and tlie ketones 
 into secondary alcohols. 
 
 Tertiary alcohols do not yield by oxida- 
 tion either aldehydes or ketones, or acids con- 
 taining the same number of carbon-atoms as 
 themselves, but are split up into bodies contain- 
 ing smaller numbers of carbon-atoms — tertiary 
 butyl aloohol for example into formic and pro- 
 pionic acids : 
 
 (CH3)3COH + 0t= CH2O2 4 CjH A + HA 
 The three classes of alcohols may also be 
 distinguished by the following test : — A quantity 
 of dry silver nitrite, mixed with an equal weight 
 of dry sand, is introduced into a small distilla- 
 tion-flask fitted with a side-tube ; the iodide of 
 the alcohol under examination is then added; 
 the mixture, after the reaction has begun, is 
 distilled ; and the distillate, received in a test- 
 tube, is shaken up with potassium nitrite 
 and potash-ley, and then acidulated with dilute 
 sulphuric acid. If no coloration of the mass 
 ensues, the alcohol-radicle present is a tertiary, 
 whereas a red coloration indicates the presence 
 of a primary, and a blue coloration that of a 
 secondary, radicle. The reaction maybe re- 
 cognised with great distinctness with the use 
 of not more than 0'3 to 0'5 grm. of the alcoholic 
 iodide (Meyer a. Locher, B. 7, 1510). Secondary 
 hexyl iodide does not give this test. 
 
 2. Series 0„H2„0. The most important mem- 
 ber of this series is allyl aloohol O3H5O, which 
 is a primary aloohol, convertible by oxidation 
 into acrylic aldehyde CjHjO, and aoryho acid 
 CaHjOu. They are unsaturated compounds 
 capable of taking up 2 at. bromine, and forming 
 the compounds C^iJirfi. 
 
 3. Series 0„H2„.20. This series includes pro- 
 pargyl alcohol, di-allyl-carbiuol, and the higher 
 homologues of the latter. 
 
 i. Series C^H^^.jO. These alcohols are 
 derived from the aromatic hydrocarbons, 
 C„H2„_5, in the same manner as the fatty 
 alcohols C„H2„+jO from the paraffins. The 
 lowest member, viz., p h e n 1 C5H5O or 65115(011) , 
 which may be formed from benzene, CjHj, by 
 oxidation with HA or with nascent ozone 
 (Leeds, B. 14, 96), is the only alcohol of the 
 series containing 6 at. carbon. The higher 
 terms admit of isomeric modifications : for all 
 the homologues of benzene may be regarded as 
 derived from benzene by substitution of one or 
 more of its hydrogen atoms by alcohol radicles 
 C„H2„+,, and the formation of an alcohol from 
 Buch a hydrocarbon by substitution of OH for H 
 may take place either in the benzene nucleus or 
 in one of the substituting alcohol-radicles : thus 
 from toluene C^Hs.CHs may be obtained the two 
 alcohols, C5H5.CH2OH (benzyl alcohol) and 
 CjHj(OH).CH, (cresol), and the higher hydrocar- 
 bons of the series are capable of yielding a still 
 greater number of metameric alcohols. The 
 properties of the compounds thus formed differ 
 considerably, according as the hydroxyl is 
 introduced into the benzene nucleus, or into one 
 of the associated alkyls. The compounds formed 
 in the latter case — benzyl aloohol for example 
 — are true alcohols analogous in all their reac- 
 tions to those of the fatty series ; but those in 
 which the OH replaces a hydrogen-atom in the 
 benzene nucleus (phenols) exhibit very different 
 
 properties, the hydroxyl being much less easily 
 displaced by other radicles (01, Br, &c.), v. 
 Phenols). 
 
 5. Series 0„Hj„.gO. To this series belong 
 cinnamyl alcohol CgH,„0, cholesterin 
 OjijHjiO, and allyl-phenol 0„H,|,0. 
 
 DiHYDEio Alcohols. 
 
 These alcohols are derived from hydrocar- 
 bons by substitution of two HO-groups for two 
 H-atoms, and may therefore be regarded as com- 
 pounds of divalent alkyls with hydroxyl. Two 
 series of them are known, viz., glycols derived 
 from the fatty hydrocarbons, and dihydrio 
 phenols from the aromatic hydrocarbons. 
 
 H. W. 
 
 The lower glycols are described as Glycol, 
 Pboptlene glycol, and Jn-MEiHYLEKB qlyool, 
 but the higher members as di-OxY-BTiTANE,-PEN- 
 TANE, &0. Unsaturated glycols are described aa 
 
 <?i-OxY-BUTINENE, -HEXINENB, and -HEPTINENB. 
 
 The chief di-hydric phenols are Pybo-caiecbin, 
 Eesoboin, and Hyoeoquinone. Di-OXY-NAMHA- 
 LENB and tZi-OxY-ANTHKAOENB belong to this 
 class. 
 
 Teihydrio Alcohols. 
 This class is represented by five fatty alcohols : 
 Glycerin, and Jri-OxY-EnTANE,-PENTANE,-EEX- 
 ANE, and -HEXiNENE. There are also several 
 aromatic representatives, e.g. Pyeogallol, Phlo- 
 
 EOOLUOIN, and (ri-OxY-NAPTHALENE. 
 
 Teteahydb c Alcohols. 
 Erythrite is the only fatty tetra-hydric aloohol 
 known. Tetra-oxy-benzene and tetra-oxy. 
 tetra-phenyl-ethane, and tetra-oxy-tri. 
 phenyl-me thane are aromatic tetra-hydrio 
 alcohols. 
 
 Peniahydeio Alcohols. 
 Pinite and quercite are the only ones known. 
 
 Hbxahydeic Alcohols. 
 Mannite, duloite, sorbite, perseite and 
 hexa-oxy-diphenyl make a complete hst. 
 
 Form,ation of Alcohols. — 1. From haloid 
 ethers as described above. — 2. From aldehydes 
 or ketones by reducing with sodium-amalgam. — • 
 3. From acid anhydrides by reduction with 
 sodium-amalgam (Linnemann). — 4. From pri- 
 mary amines by the action of nitrous acid ; this 
 reaction is, however, accompanied by an intra- 
 molecular change in the case of aU fatty amines 
 except ethylamine and methylamine. As a result 
 of this change w-propylamine gives rise to 
 secondary as well as «-propyl alcohol. — 5. Se- 
 condary Alcohols may be got by the action of 
 zinc alkyls upon aldehydes : 
 
 BCHO + ZnEt2 = E.CHEt.0ZnEt 
 
 B.CHEt.0ZnEt-HH20 = 
 
 B.CHEt.OH + EtH + ZnO 
 
 6. Tertiary alcolwls can be formed, similarly, 
 
 from zinc alkyls and acid chlorides : 
 
 CHa.C0.01 + ZnMe2 = CH3.CClMe.0ZnM8 
 
 CH3.CClMe.0ZnMe -i- ZuMe^a 
 
 CHs.CMe,.0ZnMe H- ClZnMo 
 
 CH3.CMe2.0ZnMe + H^O = 
 
 CHj.CMe^OH + ZnO + OH, 
 
 V. ZiNO-METHYL.— 7. Fiom olcfiues, by dissolving 
 
 them in H^SO, and distilling the product with 
 
 water : McjCiOHj + HjSO, = MejC.O.SOjH 
 
 Me,C.O.SO,H + H,0 = McjCOH + H,SOj. 
 
102 
 
 ALCOHOLS. 
 
 Just as : CJH, + HjSO< = CjH^SO^H 
 
 By this reaction primary alcohols can be turned 
 into secondary.— Thus cone. HjSO, converts 
 propyl alcohol into propylene, which is converted 
 by the above treatment into iso-propyl alcohol. 
 
 Eeactions of Alcohols. — Besides the general 
 reactions mentioned above, the following are 
 important: — 1. Any reaction that might be 
 expected to produce an alcohol of the form 
 B.CH:CH.OH, produces an aldehyde, E.CHj.CHO, 
 instead (Erlenmeyer, B. 13, 309 ; 14, 320). Simi- 
 larly an alcohol of the form E.CH:CB'.OH be- 
 comes a ketone, E.CH^.CB'O. — 2. On heating 
 methyl, ethyl, butyl, octyl, and capryl alcohols 
 with ammoniacal ZnClj at 240°-280° a mixture 
 of the mono-, di- and tri-alkylamines is got, the 
 yield of which amounts to 50-75 p.c. of the 
 alcohol (Merz a. Gasiorowski, B. 17, 623). — 3. 
 Tertiary alcohols differ from primary and secon- 
 dary alcohols in not combining with baryta 
 (Menschutkin, J. B. 10, 368). — i. Cone. HNO3 
 converts tertiary alcohols into nitro-alkylenes, 
 thus (CHJjCOH becomes nitro-iso-butylene 
 OjHjNOa (Bn. 1, 232).— 5. The boiling-points of 
 tertiary alcohols are lower than those of the 
 isomeric secondary alcohols, and these again 
 lower than those of the isomeric primary alco- 
 hols. — 6. The alcohols C„H2„^.20 are decomposed 
 by zinc dust at 300°-B50° into define, C„Hj„, and 
 water. Methyl alcohol gives, however, CO and 
 hydrogen (Jahn, M. 1, 378). — 7. Carbonic oxide 
 above 100° acts upon sodium alcoholates (EONa) 
 mixed with sodium salts (C„H2„.,02Na) as follows : 
 EONa -F CO -f C„H,„_,02Na = 
 CHNaOj + C„H2„.2E02Na 
 the elements of NaOH being abstracted so that 
 B displaces H. A secondary reaction is 
 
 EONa + CO=ECOjNa 
 (Geuther a. Froehlich ; Looss ; Poetsch, A. 
 218, 56). But GO does not act on a mixture 
 of sodic phenylate and sodic acetate at 200° 
 (Schroeder, A. 221, 35), or on one of sodic 
 ethylate and sodic benzoate at 200°. On a 
 mixture of sodic ethylate and sodio phenyl- 
 acetate CO forms various acids including one 
 (310°-320°) which may be phenyl-vinyl-butenyl 
 acetic acid, Ph.C(C.,H3)(C2H.,Et)C0,H. On 
 a mixture of NaOEt and sodio cinnamate, 
 carbonic oxide forms di-ethyl-cinnamic acid, 
 C,H5.CEt:CEt.C02H and di-butyl-cinnamio acid, 
 C„H5.C(C,H„):C(0^H5).C02H. Both are oils.— 8. 
 Primary alcohols heated with soda-lime form acids 
 and give off hydrogen thus : ECH^OH + KOH = 
 ECOjK+ 2H2 (Dumas a. Stas, A. 35, 129). But 
 at a higher temperature a second reaction 
 occurs: EC02K + K0H = EH + C03K2. If the 
 hydrogen evolved be measured, some conclusion 
 may be drawn as to the molecular weight of 
 the alcohol; but the lower alcohols cannot 
 give good results, as the hydrocarbons EH 
 are gases. Myricyl alcohol gives off {^ of 
 the calculated hydrogen (C. Hell, A. 223, 269).— 
 9. When an alkyl carbonate is heated with 
 an alcohol, exchange of radicles occurs if the 
 radicle of the alcohol contains more carbon 
 atoms than that of the ether (Eose, A. 205, 
 240). But when an alcohol is heated with an 
 acetal, exchange takes place only if the alcohol 
 has the smaller radicle (Geuther, A. 218, 45). 
 "When an alcohol is boiled with a simple 
 
 ether or with an ether of acetic or butyrio 
 acid with inverted condenser, no change occurs 
 (G.).— 10. If a small quantity of a secondary 
 alcohol, other than isopropyl alcohol, be 
 moistened with HNO3 and then mixed with 
 water and shaken with ether, on adding alco- 
 holic KOH to the residue left after evapo- 
 rating the ether, yellow prisms of a potassium 
 alkyl nitrite separate (Chiancel, 0. B. 100, 601). 
 — 11. Benzoin, isohydrobenzoin, and pyrocate- 
 chin give, when their sodium compounds are 
 treated with ClCOjEt, neutral carbonates of 
 the form E"C03, while resorcin, hydroquinone, 
 and oroin give di-carbonates, E"(C03Et)2 (M. 
 Wallach, 4.226, 87).— 12. Onthe Bate of Etheri- 
 flcation of alcohols v. Chemical Change. — 13. 
 FcjCls gives a colour -reaction with all oxy-com- 
 pounds whether aromatic or fatty, though in the 
 latter case the reaction is faint and a nearly 
 colourless solution of the reagent is required. 
 Such a solution can be prepared by diluting two 
 drops of 10 p.c. solution of Fe^Clg with 60 o.c. 
 of water. If an excess of the substance to be 
 tested is added to this solution a sulphur-yellow 
 colour will be produced if a fatty alcohol, oxy- 
 acid, or carbohydrate is present (Landwehr, B, 
 19, 2726). 
 
 ALDASE, A term proposed by Eiban (C. B, 
 75, 98) to designate products formed by the 
 union of two or more molecules of an aldehyde, 
 with elimination of water — e.g. crotonic aldehyde 
 CH3.CH:GH.CH0 from aldehyde. 
 
 Si-aldane CjH,j0s i.e. 
 CH3.CH(OH).CH3.CH:CH.CH(OH).CH3.CHO 
 [130°]. S. (ether) -87 at 22°. Formed by the 
 condensation of aldol, CH3.CH(OH).CH2.CHO, 
 under the influence of hydrochloric acid (Wurtz, 
 Bl. [2] 24, 100; 28, 169). Crystallised from 
 water. SI. sol. cold water, v. e. sol. boiling 
 alcohol. May be distilled in vacuo. It reduces 
 silver solution. Aqueous NH3 at 100° forms a 
 crystaUine base, CuHjjN^Os, v. sol. water, 
 alcohol or ether (Wurtz, C. B. 91, 1030). The 
 aqueous solution of the base deposits, after some 
 time, an amorphous isomeride. 
 
 Iso-di-aldane C8H„03 [114°]. Formed by 
 heating aldol at 125° (W.) or by slow action of 
 aqueous HON upon aldol (Lobry de Bruyn, Bl. 
 [2] 42, 161). 
 
 Di-aldanic acid CsH^O, i.e. 
 
 CH3.CH(OH).CH3.CH:CH.CH(OH).CHj.COjH 
 [80°]. (198°) at 20 mm. Formed by treating an 
 aqueous solution of di-aldane with Ag^O or 
 KMnOj (Wurtz, G.B. 83, 255, 1259). Monoclinio 
 crystals. V.e. sol. alcohol or water, m. sol. ether. 
 Salts: — KA' deliquescent crystals (from 98 p.c. 
 alcohol). — NaA': plates (from alcohol). — BaA'^; 
 ppd. as powder by adding ether to an alcoholic 
 solution. — CaA'j xaq : v. e. sol. water, but not 
 deliquescent. — AgA' : small laminae (from boiling 
 water) ; insol. alcohol. 
 
 Oi-aldanic alcohol C„H,e03 i.e. 
 CH3.CH(0H).CHj.CH:0H.CH(0H).CH2.CH20H 
 [49°_53°]. (162°-165°) at 10 mm. Prepared by 
 reducing di-aldane in aqueous solution with a 
 large excess of (1 p.c.) sodium amalgam, the 
 liquid being kept slightly acid with HCl. The 
 liquid is neutralised and evaporated, freed from 
 NaCl by alcohol, and the alcohoUc solution 
 distilled (Wurtz, O. B.92, 1371). White, crystal- 
 line, deliquescent mass. V. e. sol. water and 
 
ALDEHYDE (AOETIO). 
 
 105 
 
 alcohol; v. sol. ether. Ao^O forms an acetate 
 OgllnAOaO, (o. 159°) at 20 mm. Di-aldanio 
 alcohol does not reduce ammoniacal AgNO,. 
 
 Constitution. — The formation of a di-aoetate 
 seems inconsistent with the constitution assigned 
 to di-aldanio alcohol. Di-aldane may be oon- 
 Eidered to be derived from di-aldol, 
 
 CH,.OH(OH).CH,.CH{OH).CH,.OH(OH).OH,.OHO, 
 by removal of H^O. If this dehydration is to 
 destroy two hydroxyls an anhydride must be 
 formed : 
 
 CH3.CH.CH,.CH.CH2.CH(OH).CH,.CHO 
 
 6 1 
 
 and the formula of dialdane derivatives must 
 be altered accordingly. 
 
 ALDEHYDE (ACETIC) C^H.O, i.e. CH3.CHO. 
 M0I.W.44. (21°). S.a. fi-800 (Kopp, ^.64, 214); 
 \» -7799 (Briihl) ; ia -7951 ; i| .7876 (Perkin, C. /. 
 45, 475). S.V. 56-6 (Eamsay). /ig 1-3359. 
 E a> 18-18 (B.). H.P.p. 48,740 (Thomsen) ; 
 46,000 (Berthelot). H.F.v. 47,870. M.M. 
 2-383 at 16-3°. V.D. 1-532 (for 1-520). 
 
 Occurrence. — In the first portions obtained 
 by rectifying spirit that has been filtered through 
 charcoal, where it is perhaps formed by oxida- 
 tion in the charcoal (Kramer a. Pinner, B. 2, 
 403 ; 4, 787 ; Keknlfi, B. 4, 718). The name 
 aldehyde was invented by Liebig as a contrac- 
 tion of alcohol dehydrogenatum. 
 
 Formation. — 1. In the oxidation of alcohol, 
 either by slow combustion in contact with pla- 
 tinum black, or by the action of CrOj, chlorine 
 water, HNO3, or a mixture of HjSO, and MnO^ 
 (Liebig, A. 14, 133). Also by oxidation of acetic 
 ether and other ethyl compounds {e.g. ethyla- 
 mine, Carstanjen, J. pr. 89, 486), and by slow 
 combustion of ether. — 2. By action of ZnClj ou 
 glycol: CjHj(OH)2 = H20 + 02HjO (Wurtz, A. 
 108, 86). — 3. From ethylene bromide and water 
 at 160° (Carius, A. 131, 172) C.B.fir^ + 'B.fi = 
 C^fi + 'iBSx. From ethylene bromide and 
 mercuric acetate (Linnemaun, A. 143, 347). — 
 4. From ethylene and CO2 at 400° (Schutzen- 
 berger, Bl. 31, 482). — 5. From acetylene and 
 aqueous HgEr^ (KutscheroS, B. 14, 1540). — 
 6. By electrolysis of potassic lactate (Kolbe, A. 
 113, 244), of sugar solutions (H. T. Brown, 0. J. 
 25, 578), or of alcohol containing H2SO4 or KOH 
 (Jaillard, G. B. 58, 1203).— 7. By dissolving 
 acetylene in dilute H^SO^ (S.Gr. 1-35) and dis- 
 tilling the product with water (Lagermark a. 
 Eltekoff, B. 10, 637).— 8. By the dry distillation 
 of a mixture of calcic acetate and calcic formate 
 Ca(COjOH3)j+ Ca(C02H)2= 2CaC0, -^ 2HCO.CH3 
 (Bitter, A. 97, 369).— 9. By oxidation of ethylene 
 with aqueous CrOj at 120° (Berthelot, 0. B. 68, 
 834). — 10. By reducing chloral with zinc and 
 dilute HjSO^ (Peraoune, G. B. 71, 227).— 11. To- 
 gether with formic acid by heating lactic acid 
 with dilute H^SO^ at 130° : 
 
 CH3.CH(0H).C02H= CH3.CHO + HCO^H 
 (Erlenmeyer, Z. [2] 4, 343). Also, together 
 with lactide, by the dry distillation of lactic 
 acid. — 12. Among the products of the action of 
 H2SO4 and MnOj or E^Cr^O, upon albumen, 
 fibrin, casein, gelatin (Guckelberger, A. 64, 46, 
 86), or gluten (Keller, A. 72, 31).— 13. By heat- 
 ing acetal with glacial acetic acid at 180° for 
 two days (Beilstein, G. B. 48, 1121).— 14. By 
 passing alcohol through a red-hot tube. From 
 hemp oil in the same way (Hess, P. 38, 380). 
 
 Aldehyde occurs among the products of the dry 
 distillation of wood (Kane, A. 19, 288 ; Kramer, 
 a. Grodzki, B. 9, 1921 ; Mabery, Avi. 5, 258), and 
 of sugar (Volekel, A. 87, 303).— 15. By distilling 
 o-di-alkylated-^-oxy-propionic acids : 
 CH3.CH(OH).CEt2.C02H = 
 CH3.CHO + CHEt,,C02H. 
 
 Preparation. — 1. From the 'first runnings' 
 in the rectification of fermented liquors. — 2. 
 Alcohol (3 pts. of S.G. -842) and K^Cr^O, (3 pts.) 
 are placed in a retort and cone. H^SO^ (4 pts.) is 
 slowly run in. The heat evolved causes the 
 aldehyde to distil off (W. a. E. Eodgers, J. pr. 40, 
 240). It is collected in dry ether, which is after- 
 wards saturated with dry NH3; aldehyde- 
 ammonia separates in cubes, and this is distilled 
 with HjSO^ (3 pts.) mixed with water (4 pts.), 
 the receiver being cooled with ice and salt. The 
 product is dried over CaClj and rectified. 
 
 Properties. — Characteristic odour, miscible 
 with water, but separated by CaClj from solu- 
 tion. Neutral. Eeadily polymerised. Mixes with 
 alcohol and ether. A mixture of aldehyde (1 pt.) 
 and water (3 pts.) boils at 37°. Aldehyde dis- 
 solves S, P, and I. Burns with blue flame. It 
 dissolves 7 times as much SO^ as water does. 
 
 Tests. — 1. Heated with ammoniacal silver 
 nitrate forms a mirror. — 2. Heated with aqueous 
 potash forms a yellow body (aldehyde resin) and 
 gives off a characteristic odour (Weidenbusch, 
 A. 66, 153). The solution then contains form- 
 ate and acetate. — 3. Eestores the colour to a 
 solution of a rosaniline salt that has been 
 bleached by SOj. — 4. Eeacts with hydroxylamine 
 forming a liquid oxim (v. infra). — 5. Eeacts 
 with phenylhydrazine forming a crystalline 
 phenyl-hydrazide {v. infra). — 6. Combines with 
 NaHSOj.- 7. Combines with NH,.- 8. H,S 
 passed into an aqueous solution forms an oil, 
 converted by acids into solid thio-aldehyde 
 (q.v.).—9. Alkaline aqueous solutions produce 
 a red coloration when treated with diazo-ben- 
 zene sulphonic acid and a little sodium-amalgam. 
 
 Beactions. — 1. Oxidised to acetic acid slowly 
 by air, more rapidly in presence of platinum 
 black, most rapidly by oxidising agents. — 2. 
 Passed over red-hot soda lime, it forms sodio 
 acetate and hydrogen. Passed over red-hot 
 quicklime, it gives acetone and various ketones 
 and gases (Sohloemilch, Z. [2] 5, 336).— 3. HI at 
 high temperatures reduces it to ethane (Berthelot, 
 Bl. [2] 7, 59). — 4. Sodijim amalgam reduces it 
 to alcohol, some di-oxy-butane being also formed 
 (Kekule, A. 162, 309).— 5. Converted into 
 orotonic aldehyde (g. v.) by ZnCl^ or by aqueous 
 solutions of sodic acetate or Bochelle salt at 
 100°. Zinc shavings at 100° produce an alde- 
 hyde CsHijOj (220°) ; it is an oil and combines 
 with NaHSOj (Eiban, BZ. [2] 18, 63).— 6. With 
 chlorine forms, in sunlight, acetyl chloride 
 (Wurtz, A. 102, 93).— 7. Chlorine passed into 
 aqueous aldehyde forms chloral, butyro-chloral, 
 dichloraldehyde, and other bodies (Pinner, A. 
 179, 21; B. 8, 1321, 1561; Wurtz a. Vogt, 
 Bl. 17, 402). Bromine converts aldehyde, 
 dissolved in aoetio ether, into bromal and 
 di-bromo-aldehyde. — 8. PCI5 gives ethylidene 
 chloride, CHa.CHClj (Beilstein, A. 113, 110). 
 COCI2 acts similarly (Eckenroth, B. 18, 518).— 
 9. PCljBrj gives ethylidene bromide, CHj.CHBrj 
 (Paterno a. Pisati, B. 5, 289).— 10. Dry HCl 
 
104 
 
 ALDEHYDE (ACETIC). 
 
 passed into coW aldehyde forms ethylidene ohlor- 
 hydrin CH3.CHCI.OH, (25°) at 40 mm. This 
 changes spontaneously, or more quickly it heated 
 ortreatedwithHCl,into' ethylidene oxy-ohloride, ' 
 CfHgClfi, (0. 59°) at 40 mm. A small quantity 
 of another body, O^JiifiljO, (c. 100°) at 40 mm., 
 is also got. Ethylidene oxy-chloride is probably 
 di-ohloro-di-ethyl oxide (CHj.CHC^jO. It is 
 converted by boiling water into aldehyde and 
 HCl, and by ammonia into efflorescent needles 
 of (CH3.CHNH2)jO 2HC1 (Lieben, 0. B. 46, 662 ; 
 Kessel, A. 175, 46; Hanriot, C. B. 92, 302). 
 Aldehyde saturated with HCl is converted into 
 crotonic aldehyde (2. 'i'.),chloro-butyric aldehyde, 
 and a compound C,„H,8CL,03 [98°J (Kekulfi, A. 
 162, 102). — 11. Aldehyde left for some days with 
 aqueous HCl forms aldol {q. v.). — 12. HCl passed 
 into a mixture of aldehyde and alcohol forms 
 chloro -ethyl ether (g. v.). — 13. HCl passed into a 
 mixture of aldehyde and mercaptoi forms di-thio- 
 acetalCHs.CH(SEt)2, a mobile liquid (Baumann, 
 B. 18, 884). — 14. Aldehyde forms with zinc ethyl 
 a compound which is decomposed by water with 
 production of secondary butyl alcohol (g. v.). — 
 16. When paraldehyde (1 g.) is added to cold 
 HjSO, (100 g.) and the solution is shaken with 
 benzene, di-phenyl-ethane is got : 
 
 CH3.CHO + 20,H, = CH3.CH(C,H,), + HjO 
 (Baeyer, B. 7, 1190). — 16. With cyanamide it 
 forms a compound (C2H,)3N3Cy3Aq (Knop,4. 131, 
 258).— 17. With HON it gives lacto-nitrile (g. v.). 
 18. With HCN, HCl, and NH, in aqueous 
 solution it gives, on boiling, alanine [q. v.). A 
 mixture of aldehyde-ammonia and HCN in 30 
 p.o. solution acidified by HCl gives in the cold 
 amido-propionitrile, which changes first to 
 imido-propionitrile, and then, in about a month, 
 to hydrocyanaldine. 
 
 HydrocyanaldineC^t„^i.W\.b°]. S.-18at 
 20°. S. (alcohol) 1-27 at 18°. Prisms (from 
 ether). May be sublimed. V. sol. acetone, m. 
 Bol. ether, v. si. sol. CSj. Decomposed into its 
 components by boiling AgNOj or boiling KOH. 
 
 Parahydrocyanaldine CaHi^N^. [232°]. 
 S. -01 at 20° ; S. (alcohol) -04 at 18°. This is a 
 similar body formed by allowing the liquid con- 
 taining hydrocyanaldine to stand several months, 
 and also by warming a mixture of amido- and 
 imido- propionitrile with HCl. Rhombic crystals 
 (from acetone). Insol. ether, v. e. sol. acetone. 
 Decomposed by AgN03 or KOH like hydrocyan- 
 aldine. 
 
 Combinations. — 1. With bisulphites of the 
 alkalis : C^HjONaHSO-iAq : pearly plates by 
 evaporation overHiSO,; satiny needles when 
 ppd. by alcohol.— CjHjOKHSOj : hard indis- 
 tinct crystals composed of minute needles. — 
 (C2HjO)2Ba(HS03)2 : soluble scales.— If a solu- 
 tion of (NHJHSO3 be mixed with aldehyde and 
 evaporated, it deposits crystals of C2H,OSOi,NH3, 
 S. 16 at 16°_ (Bunte, A. 170, 305). But by 
 passing SOj into alcoholic aldehyde-ammonia, 
 Eedtenbaoher (A. 65, 37) got unstable needles of 
 an isomeric body, S. 70 at 16°. When strongly 
 heated withpotash-lime.this decomposed withpro- 
 duotion of di-methyl-amine or ethylamine (Goss- 
 mann, A. 91, 122).— It may be C^H.ONH.HSO, 
 (Beilstein) . — The compound of aldehyde with acid 
 sodium sulphite may perhaps be represented 
 by the formula CH,.CH(0H).S03Na, as o-oxy- 
 ethyl sodium sulphite. 
 
 2. With ammonia: CH3.CH(0n).NH,. 
 Aldehyde-ammonia [70°-80°]. (100"^. 
 
 V.D. 80-36. By passing NH3 into ethereal solu- 
 tion of aldehyde (Liebig, A. 14, 133). Ehombo- 
 hedra, best got by mixing a cone, alcoholic solu- 
 tion with ether, very soluble in water, hardly 
 soluble in ether. Alkaline. Turns brown in air. 
 Decomposed by dilute acids, even by CO^, giving 
 off aldehyde. Eeactions. — (a) H^S forms thi- 
 aldine (q. v.). — (6) HjSe forms selen-aldine 
 C,.H|3NSea.— (c) Alcoholic CSj forms carbo-thi- 
 aldine (q. v.).—(d) HCN and HCl form, in the 
 cold, hydrocyanaldine, C„H|jN.„ or on heating, 
 alanine (q. v.). — (e) At 120° in a sealed tube it 
 forms tri-methyl-pyridine, oxy-tetraldine 
 CsHijNO, axidiOxypentaldine C|(,H,5N0. The 
 two latter are monacid amorphous bases, si. sol. 
 water (Babo, J. -pr. Ti, 88 ; Heintz a. Wislicenus, 
 J. 1858, 347 ; Schiff, A. Suppl. 6, 10).— (/) Ac- 
 tion of SO., is described above. — (g) CSj forms 
 carbothialdine CjH||,N2Sj(g.«.).— (7i) NaOEt and 
 Mel in the cold form isooholine iodide, C^H, ,NOI 
 (G. Meyer, B. 16, 207). 
 
 3. With ammonia and silver nitrate or sul- 
 When AgNOj (100 c.c. of a | normal 
 
 solution) is added to aqueous NH, (15 0.0. four 
 times normal) and, after filtration, aldehyde is 
 added as long as the pp. first formed redissolves, 
 a liquid is got in which moreNH, (15 o.c.) causes 
 separation of the compound C,H,„N303Ag Jaq, 
 which must be washed with alcohol and ether 
 and dried at a low temperature (Eeychler, B. 
 17, 41). It forms unstable white six-sided plates. 
 SI. sol. water, v. si. sol. alcohol, insol. ether. 
 Its warm aqueous solution deposits a silver 
 mirror. — It the same solutions be mixed in the 
 following proportions: 20 c.c. NHjAq, 33 c.c. 
 AgNOjAq and 20 c.c. aldehyde, and 250 c.c. 
 alcohol be added, a white microcrystalline pp. 
 C|H|„N303Ag is got. This body is represented 
 by Liebermann a. Goldschmidt (B. 10, 2179 ; 
 11, 1198) as AgN032C2HjNH ; 
 
 Eeychler writes AgO.N «^^(^>CH.CH,)j.— 
 
 Ag2SO,(C,H,NH)38aq.— Ag,S0,(C.,HJNH)^6aq.— 
 Ag,S0 JC,H^NH)3NH3 3aq (W. G.'Mixter,^m.S. 
 [8] 17, 427). 
 
 4. A solution of aldehyde in alcoholic am- 
 monia in six months becomes brown. It it be 
 then evaporated, tri-ethylidene diamine, or 
 hydracetamide (CH3.CH)3N2, is left as a yellow 
 amoT'jhous powder, soluble in water. Its hydro- 
 chloride is CaH,,,N22HCl. Boiling water or acids 
 convert it into oxy-trialdine C„H|,NO, an 
 amorphous yellow powder, soluble in water; 
 salts.— C5H„N0.HCl.—(C„H„N0),H,S0, (H, 
 Schiff, Bl. [2] 8, 443 ; A. Swppl. 6, 1). 
 
 5. With Prussia acid : C^H^OCNH i. e. 
 C2H4(OH)CN, ethylidene cyanhydrin or 
 lacto-nitrile (q. v.). — 6. With ethyl nitrate; 
 C,Hj02EtN03 (86°). S.G. 12 1-045. Formed by 
 distilling a mixture of KEtSO< with KMO,. It 
 is an oil. Vapour explosive. Decomposed by 
 potash into aldehyde (Nadler, A. 116, 173). 
 
 7. With ethyl chloride v. Chloro- )i-ethii. 
 
 OXIDE. 
 
 8. With alkoyl chlorides or bromides. The 
 following compounds may be viewed as derived 
 from ethylidene glycol chlorhydrinCHs.CH,'OH) C] 
 {v. reaction 10), by displacement of H by acid 
 radicles. 
 
ALDEHYDE (AOETIC). 
 
 105 
 
 (a) With acetyl chloride: C^B. fi, C^HjO.Clor 
 C2H4(OAo)Cl, ethylidene chloracetin (121-5° cor.) 
 E.G. i^ 1-114. Combination takes place at 
 100° (M. Simpson, Pr. 27, 120 ; Pranehimont, B. 
 1, 246; Eiibencamp, A. 225, 274). The com- 
 pound was discovered by Wurtz \z. 1871, 362 ; 
 A. Ch. [3], 49, 58 ; 0. R. 73, 528). Decomposed 
 by potash into KCl, acetic acid, and aldehyde. 
 KOAo forms CH3.CH(0Ac)j (Schiff, B. 9, 304). 
 Chlorine at 120°, in presence of iodine, forms 
 CHCI2.CHCI.OA0, tri-chloro-ethyl acetate (250°- 
 280°). Bromine dropped into it at 100° forms 
 bromethyl bromo-acetate CHs.CHBr.O.CO.CHjBr 
 {v. Bbomo-aoetic acid). 
 
 (b) With acetyl bromide forms a corre- 
 sponding, but unstable, compound (c. 140°) 
 (Tawildarofi, A. 176, 21). 
 
 (c) With propionyl chloride : CgHjClOj or 
 CH3.CHC1.0(C3H50), chloro - ethyl -propionate 
 (135° unoor.). S.G. i5 1-071. 
 
 {d) With butyrylchloride: CH3.CHC1.0(C,H,0) 
 (149° uncor.). S-G. ^ 1-038. 
 
 (e) '^iXh.valerylchloride:CB.,.CKCl.O(C^O) 
 (0. 168°). S.G. i£ -997. 
 
 Derivatives of Obtho-Aldehyde. 
 
 The following combinations between alde- 
 hyde and compounds of the form M^O may be 
 viewed as derivatives of ortho-aldehyde, 
 CH3.CH(OH)2. Ortho-aldehyde itself is not 
 known, but chloral hydrate is tri-chloro-ortho- 
 aldehyde. 
 
 Alhyl derivatives, Acetals or Alde- 
 hydates. The term 'acetal,' originally applied 
 to CH3.CE[(OEt)2, is now often extended to the 
 whole series of di-alkylated ortho-aldehydes. 
 
 These bodies are formed, together with other 
 products, by the oxidation of alcohols. Each 
 of them may be formed from one of its higher 
 homologues, by heating the latter at 120°, with 
 an alcohol containing a lower radicle. Thus 
 di-ethyl-acetal heated with methyl alcohol yields 
 dimethylaoetal, whereas the latter heated with 
 ethyl, propyl, isobutyl, or amyl alcohol yields 
 only traces of an acetal containing difierent 
 alcohol-radicles. Similarly diethyl-acetal heated 
 with methyl-alcohol is converted, for the most 
 part, into dimethylacetal, but is practically un- 
 altered by propyl and amyl alcohols (Bachmann, 
 
 A. 218, 38). Aldehydates may also be formed 
 by heating aldehydes with alcohols and HCl 
 (Wurtz a. Frapolli, A. 108, 226 ; Glaus a. Trainer, 
 
 B. 19, 3004). 
 Ethyl-ortho-aldehyde CH3.CH(0H)(0Et) 
 
 (80°-90°) (Eeuard, B. 8, 132) (c. 50°) (Jacobsen, 
 B. 4, 215). Among the products of electrolysis 
 of mixture of alcohol and dilute HjSOj (B.). 
 By action of water on chloro-ethyl-ether, 
 CH3.CHCl.OEt (J.). 
 
 Di-methyl-acetalGtB.,i,02i.e.CH3.CH.{OM.e)^ 
 (62-7°-63-3°) at 751-6 mm. S.G. ^ -8655 (Bach- 
 mann) ; -8590 at 14° (Dancer, A. 132, 240). V.D. 
 3-10 (for 3-11). S.V. 110-81 (E. Schiff, A. 220, 
 104). Occurs in crude wood spirit (D.). Formed 
 by oxidising a mixture of MeOH and EtOH with 
 MnOj and H2S04 (Wurtz). Prepared by heating 
 aldehyde (4 vols.), methyl alcohol (8 vols.), and 
 glacial HOAo (1 vol.) at 100° (Alsberg, J. 1864, 
 485). A colourless liquid burning vrith a white, 
 blue-edged flame (Wurtz, A. Ch. [3] 48, 373). 
 EtOH at 120° has hardly any action, traces of 
 
 methyl-ethyl-acetal being formed. Propyl, iso- 
 butyl, and iso-amyl alcohols act similarly. 
 
 Methyl-ethyl-acetal CH3.CH(0Me)(0Et). 
 Eeaotions that might be expected to produce 
 this body yield only a mixture of di-methyU 
 acetal and di-ethyl-acetal (A. Genther, A. 225, 
 265). 
 
 Di-ethyl acetal «. Acetal. 
 
 Methyl-jaropyl-acetal CgH^Oj i. «. 
 CH3CH(0Me)(0Pr) (103°-105°). Very little is 
 formed from di-methyl-aoetal and PrOH at 120°. 
 
 Ethyl-propyl-acetal CiH^Oj i.e. 
 CH3.CH(OEt)(OPr)(124°-126°). Very little ia 
 formed from di-ethyl-acetal and PrOH at 120°. 
 
 Methyl-isobutyl-acetal CjHjsOj 
 (126°). Dimethyl-acetal (15 g.) heated with iso- 
 butyl alcohol at 120°1orms a httle (1 g.) of this 
 body. 
 
 Methyl-iso-amyl-acetal CgHuOj 
 (14i°-144°). A little got from di-methyl-acetal 
 and iso-amyl alcohol at 120°. 
 
 Di-propyl-acetal CsH.jOj (146°-148°). S.G. 
 ^£1 -825. Got by passing pure PH3 into a mix- 
 ture of aldehyde and PrOH at -21° (Girard, G. 
 B. 91, 629). 
 
 Di-iso-butyl-acetal C.oHjA (168°-170°). 
 S.G. — -BIG. Prepared like the preceding, 
 
 Di-iso-amyl-acetal C,2H2802 i.e. 
 CH3.CH(0C5H„)2 (c.l95°) (Bachmann); (210-8° 
 cor.) (Alsberg, J. 1864, 485 ; Claus a. Trainer, B. 
 19, 3008). S.G. ^ -801 (B.); is -835 (A.). Alde- 
 hyde (1 vol.) and iso-amyl alcohol (5 vols.) are 
 mixed, saturated with SO2 and warmed with 
 glacial HOAo (1 vol.). A small quantity is got 
 by heating amyl alcohol with acetal at 120°. 
 
 Ethylene-acetal CjHjOj i. e. 
 
 CH3CH<^>C2H^ (82-5°) at 766 mm. S.G. 21-002. 
 
 S. 67. From aldehyde and glycol at 100° 
 (Wurtz, A. 120, 328). Separated by CaClj from 
 its aqueous solution. Not attacked by EOH. 
 Acetic acid gives glycol di-acetin. 
 Propyl ene-acetal C5H,„02 i.e. 
 
 CH3.CH<^^>03H5 (93°). From aldehyde and 
 
 propylene glycol at 160° (Gramont, Bl. 41, 361). 
 Decomposed by water into aldehyde and propy- 
 lene glycol. 
 
 Oxy-propylene-acetal C^Hifi, 
 
 i.e.CH,.CH<3>C3H50H (c. 186°) S.G. 2 1-081. 
 
 From aldehyde and glycerin at 180° (Har- 
 nitzky a. Menschutkin, A. 136, 126). Decom- 
 posed by water into its components. 
 
 Di-(ff)-naphthyl-acetal C^^fi^ i.e. 
 CH3.CH(0.C,„H,)2. [201°]. Slowly formed when 
 (3)-naphthol and aldehyde are dissolved in acetic 
 acid and a few drops of HCl are added (Claisen, 
 B. 19, 3318). Crystals; insol. aqueous alkalis. 
 Changed by warming with HOAo and HCl into 
 ethyhdene-di-naphthyl oxide, 
 
 CHs.CH<^-oHp>o. 
 
 Alkoyl derivatives 01 ethylidene salts. 
 When both alkoyls (acid radicles) are the same, 
 these bodies may be viewed as compounds of 
 acid anhydrides with aldehyde. They are slowly 
 decomposed by water, more rapidly by potash, 
 into aldehyde and acids. Mono-alkoyl deri- 
 vatives, CH3.CH(0H)(0E) are not known ; they 
 appear to split up into water and the an- 
 
106 
 
 ALDEHYDE (ACETIC). 
 
 hydrides {CH3.CH(OE)}jO. These anhydrides 
 may be formed from di-ohloro-di-ethyl oxide, 
 (CHjCHCljjO and sodium salts. They are vola- 
 tile liquids, decomposed by water into aldehyde 
 and acid (Geuther, A. 226, 223). 
 
 Di-acetyl derivative CB^.GB.(Ok.o)2 
 (168-4° cor.). S.G. i£ 1-073. /i = l-40 at 28°. 
 1. From CH3.CHCl(0Ac) and AgOAc (Biiben- 
 camp, A. 225, 274). — 2. From aldehyde and ACjO 
 at 180° (Geuther, A. 106, 249).— 3. From alde- 
 hyde and AcCl at 100° (Franchimont, B. 1, 248). 
 
 Di-propionyl derivative 
 CH3.CH(OC3H50)2 (192-2° cor.). S.G. l^ 1-020 
 li = 1-407. From CHj.CHC^OCaH^O) and 
 AgO(C3H,0). 
 
 Di-butyryl deriv ativ eCH.2.GB.{OGfifi)2 
 (215-5° cor.). S.G. IS -9855. m = 1-411. 
 
 Di-valeryl derivativeCE.3.Gli{0C^'H.fi)2 
 (225° cor.). S.G. is -947. ^1 = 1-414. 
 
 Acetyl-propionyl derivative 
 CH3.CH(0Ac) (OC3H5O) (178-6° cor.) . S.G. is 1-044 
 M = 1-402. From AgOCsH,0 and CH3.CHCl.OAc 
 or from AgOAo and CH3.CHCI.OC3H5O (Geuther 
 a. Biibencamp, A. 225, 281). 
 
 Acetyl-hutyryl derivative 
 CH,.CH(OAc)(OCjH,0) (192-6° cor.). S.G. is 1-015 
 ju = 1-047. From AgOC^H,0 and CH3.CHCI.OA0, 
 or from AgOAo and CHj.CHCl.OC.HjO. 
 
 Acetyl-valeryl derivative 
 CH3.CH(OAc)(OC5HsO) (194°-199° cor.). S.G. i* 
 •991/4=1-408. Similarly prepared. 
 
 POLYMEBIDES OP ALDEHYDE. 
 
 Aldehyde reauily polymerises, forming aldol 
 CjHjOj (3. v.), paraldehyde CjHijOj, or metal- 
 dehyde C2„Hj„0„. Pure aldehyde may be kept 
 without change, but when impure it spon- 
 taneously changes to paraldehyde or metalde- 
 hyde (Weidenbusch, A. 66, 155 ; Fehling, A. 
 27, 319 ; Geuther a. Cartmell, A. 112, 16 ; Lie- 
 ben, A. Suppl. 1, 114; Ketul6 a. Zincke, A. 
 142, 141 ; B. 3, 468). Metaldehyde is formed 
 from aldehyde at a low temperature by the same 
 reagents that cause the formation of paraldehyde 
 at high temperatures (K. a. Z.). Neither of these 
 bodies is affected by hot potash, but both of 
 them are converted by PCI5 into ethylideue 
 chloride, CHj.CHClj, and by HCl into ' ethylidene 
 oxy-chloride ' {v. supra). A little alcohoUo KOH 
 converts aldehyde into a mixture of metalde- 
 hyde, paraldehyde, and a little crotonic alde- 
 hyde (Perkin, C. /. 43, 88). 
 
 Paraldehyde C^Hi^O,. Mol. w. 132. [10°-12°]. 
 (124°i.V.) (K.a. Z.); (124-4'') at 752mm.(E.Sohifl, 
 A. 220, 104). S.G. f -9943 (Briihl) ; i| -9993; 
 II -9900 (Perkin, 0. /. 45, 479). S.V. 150-7 (S.). 
 V.D. 4-35 (for 4-55, S.). /»p 1-409^5. Ea, 52-48 (B.) 
 M.M. 6-662 at 17-3°. S. 12 at 13° ; 6 at 100°. 
 
 Preparation, — In presence of a small quantity 
 of HCl, COCI2, or SO2, aldehyde gradually 
 becomes hot, often reaching 40°. It is then 
 changed to paraldehyde. HjSO, and ZnClj 
 effect this change even more vigorously. The 
 product is cooled to 0°, when paraldehyde 
 crystallises. 
 
 Properties. — Colourless liquid, smelling like 
 acetal and aldehyde. It is partially converted 
 into aldehyde by distillation. Distillation with 
 HjSO<, HCl, ZnClj, HgBr^, or COClj completely 
 effects this change. The reactions of paralde- 
 hyde, in presence of any of these bodies, are 
 
 therefore the same as those of aldehyde. It also 
 forms CH3.CH(OAc)2 with Ac^O. But it does 
 not react with ammonia. HNO3 oxidises it to 
 glyoxal (Liubawin, J. B. 13, 496). 
 
 Constitution. — The S.V. agrees with that 
 required by Kekul^'s formula 
 
 ^2H<aC H*>° (^'*^^' ^- 203.44). 
 
 Metaldehyde CsHjjOj. S. (chloroform) l-03'4 
 at 26° ; 4-235 at 60° ; S. (benzene) -12 at 23°, 
 •181 at 80°. Formed by passing a few bubbles 
 of SO2 or HCl into aldehyde in a freezing mix- 
 ture; metaldehyde crystallises out, and the 
 mother liquors are distilled and treated as before 
 (K. a. Z.). CaClj effects the same transformation 
 at the ordinary temperature. 
 
 Properties. — Long striated prisms, sublimes 
 about 115° without melting. Insoluble in water, 
 sMghtly soluble in cold alcohol or ether. It may 
 be converted into aldehyde : (a) by heating for 
 a day in vacuo at 180°, (b) by repeatedly dis- 
 tilling under atmospheric pressure, (c) by heat- 
 ing its solution in chloroform. The vapour 
 density may be found in the usual way, due 
 allowance being made for its partial dissociation, 
 the amount of undeoomposed metaldehyde being 
 estimated after cooling. The V.D. is thus found 
 to lie between 72-2 and 59-1, the mean value 
 being 62-5. Metaldehyde is not attacked in the 
 cold by KMnO,, chromic mixture, or NH3. Chlo- 
 rine forms chloral; PCI5 gives ethylidene chloride 
 (Hanriot a. Oeconomides, C. B. 93, 463 ; A. Oh. 
 [5] 25, 226). 
 
 Si-aldehyde v. Aldoi>. 
 
 ALDEHYDE-ACETAMIDE C^H^NjOj i.e. 
 CH3.CH(NHAc)2 M-aceiyl-ethylidene diamine 
 [169°]. Got by heating aldehyde with acetamide 
 (Tawildaroff, B. 5, 477). 
 
 ALDEHYDE ACETATE v. p. 106, 1. 6. 
 
 ALDEHYDE ACETYL CHLORIDE v. p.lOS.Z. 1. 
 
 ALDEHYDE ALCOHOLATE v. p. 105, I. 58. 
 
 ALDEHYDE GBEEX v. Bosaniline. 
 
 ALDEHYDE GUM C,„H,30,. The barium 
 salt is formed by allowing a solution of aldehyde 
 in baryta- water to stand for some time. From 
 this salt HjSO, liberates the ' gum ' as a syrup, 
 soluble in water and alcohol. It reddens 
 rosaniHne decolorised by SOj, and it gives iodo- 
 form with I and Na2C03. Eeduces hot Fehling'9 
 solution— Ca(C,|,H„04)j: amorphous (ToUens, 
 B. 17, 660). 
 
 ALDEHYDE FHENYL-HYDBAZIDE 
 CsH,„N2 i.e. CH3.CH:N2HPh. 
 From aldehyde and phenyl-hydrazine in ether 
 V. Aldehydes, reaction 4. Crystallised from 
 benzoline. Deliquescent. V. sol. alcohol 01 
 ether. Besolved by boiling water or dilute acids 
 into its constituents. 
 
 ALDEHYDE EESIN. Formed by the action 
 of aqueous or alcoholic potash, hot or cold, 
 upon aldehyde, or by heating aldehyde with 
 NaOAc in sealed tubes at 100°. It is accom- 
 panied by a strongly smelling yellow oil which 
 may be removed by distillation. Aldehyde resin 
 resembles colophony. It produces, when fused 
 with potash, oxy-iso-phthalio acid [283°], o-oxy- 
 m-toluio acid [173°], and m-xylenol, C„H3Me20H 
 When strongly heated with zinc dust it gives 
 ethyl-benzene, to- and p- methyl-ethyl-benzene 
 and methyl-naphthalene. Cone. HNO3 gives 
 
ALDEHYDES. 
 
 10? 
 
 igo-plithalio aoid (Weidenbusoh, A. 66, 153 ; 
 Ciamician, M. 1, 199). 
 
 ALDEHYDES — An aldehyde is a body de- 
 rived from a primary aloobol by removal of two 
 atoms of hydrogen from each molecule, and 
 having the general formula E.CO.H. It may 
 therefore be looked upon as a ketone in which 
 one alkyl is represented by H. Aldehydes may 
 also be viewed as hydrides of aoid radicles, 
 hence OHj.CO.H is called acetic aldehyde and 
 not ethyl aldehyde, although the latter name is, 
 etymologically, the more correct (p. 103). 
 
 Enumeration. — In the following list the 
 numbers denote values of n. C„Hj„0. 1. For- 
 mic ; 2. Acetic ; 3. Propionic ; 4. Butyric ; 5. 
 Valeric; 6. Hexoic; 7. Heptoio; 10. Decoio ; 
 12. Laurie; 14. Myristic; 16. Palmitic; 17. 
 Stearic. — C„Ha,.20. 3. Acrylic (acrolein) ; 4. 
 Crotonic; 5. Tiglio; 6. Hexenoic; 8. Octenoio; 
 14. Tetradecenoic ; 15. Cimicic ; 21. Tri-oenan- 
 thic. — 0„H2„_jO. CasHsijO, Tetra-oenanthic. — 
 OjHj^.gO. Benzoic ; Phenyl-propionic. — 
 O^Hj^.jjOj. Ciimamio. — C„H2„_„0. Naphthoic. 
 — 0„Hj„.,80. Di-phenyl-acetic— 0„H2„O2. Gly- 
 oollic (?). Oxypropionic. Oxybutyric (aldol). — 
 C.Ha,.A- Glyoxal. — GJ^ia-fi^. Maleio. — 
 Gn^-fii- Furfurol.— C„H2„_s02. Oxy-benzoio; 
 Furfur-aorylio, Furfurorotonic. — C„H„„.20s. 
 Suberic. Azelaio and Brassylic. — C^H^^sOj. 
 Di-oxy-benzoic ; Piperonal. — C„H2„_,|,0, Di-alde- 
 hydo-resorcin ; Di-aldehydo-orcin. 
 
 Formation. — 1. By oxidation of primary 
 alcohols by air and platinum-black, by aqueous 
 chromic acid or by HjSOj and MuO^ : 
 
 2E.CH,.0H -I- Oj = 2B.C0.H + 2H2O. 
 2. By distilling a mixture of barium or calcium 
 formate with some barium or calcium salt : 
 Ca(O.CO.E)j + Ca(O.CO.H), = 2CaC03 + 2H.CO.R 
 (Limpricht, A. 97, 368 ; Piria, A. Ch. [3] 48, 
 113; Krafft, B. 16, 1717). This process is a 
 particular case of Williamson's method of pro- 
 ducing mixed ketones. Instead of calcic formate, 
 a mixture of calcic oxalate and lime may be 
 used (Bogusch, /. B. 7, 47). — 3. From chlorides 
 of the type E.CH.Clj by heating with dry oxalic 
 acid (Anschutz, A. 226, 19).— 4. Chromyl di- 
 ohloride, CrOjCLj, unites with toluene and its 
 homologaes when added to their solution in 
 CSj, forming brown powders, possibly of the 
 form ECH(0.CrCLj.0H)2, which are decomposed 
 by water with production of aldehydes (A. Etard, 
 0. B. 90, 534 ; 97, 909 ; Bornemann, B. 17, 
 1462). — 5. Aromatic aldehydes may be prepared 
 by heating dichlorides E.CHCL, with NaOHAq, 
 or the monochlorides, E.CHjCl with aqueous 
 lead or copper nitrate. — 6. Alcohols of the form 
 E.CH:OH.OH appear to change, at the moment 
 of their formation into aldehydes, E.CHj.CHO. 
 The formation of acrolein from glycerin, and of 
 aldehyde from bromo-ethylene are instances. — 
 
 7. Some aldehydes, as benzoic, acetic, propionic, 
 and butyric, are produced by distilling albumen, 
 fibrin, casein, or gelatin, with MnOj and H^SO,. 
 
 8. Many aldehydes can be obtained from essen- 
 tial oils derived from plants ; e.g., benzoic, cin- 
 namic, cuminic, and sahoylio aldehydes. 
 
 Properties. — ^Almost all are volatile liquids. 
 
 Beactions. — 1. Are readily oxidised to acids, 
 and consequently are powerful reducing agents. 
 Ketonio alcohols, E.CO.CHjOH, resemble alde- 
 liydos in reducing power (Ziacke, A. 216, 317). — 
 
 2. Many are converted by alcoholic potash 
 or by potash-fusion into an alcohol and an acid r 
 2C5H5.CHO + KOH = C„H5.G0.,K -I- CjHs.CHjOH. 
 Glycols with double the number of carbon atoms 
 in the molecule are often formed. — 3. Sodium- 
 amalgam, or zinc and glacial HOAc, reduce thenn 
 to alcohols (Krafft, B. 16, 1714 ; Tiemann, B. 
 19, 355).— 4. They combine with NaHSO,. 
 These compounds are usually soluble in water 
 and in alcohol, but insoluble in saturated solu- 
 tions of the bisulphites. Hence by shaking a 
 liquid containing an aldehyde with excess of 
 such a saturated solution, the aldehyde may be 
 completely separated in the form of a crystalline 
 compound. From these compounds the alde- 
 hyde may be set free by dilute HoSO, or NajCOs, 
 and may then be distilled with steam (Bertagnini, 
 
 A. 85, 179, 268).— 5. They combine with phenyl- 
 hydrazine (q. v.). A solution of phenyl-hydra- 
 zine hydrochloride (1 pt.) and sodic acetate 
 (I5 pts.) in water (8 pts.) when added to an 
 aqueous solution of an aldehyde or ketone, pro- 
 duces an insoluble compound, usually an oil 
 appearing in drops producing a milkiness, but 
 sometimes a crystalline pp. These compounds 
 are not volatile with steam, but on boiling with 
 dilute HCl they are resolved into phenyl-hydra- 
 zine hydrochloride and the aldehyde or ketone 
 (E. Fischer, A. 190, 131; B. 15, 2252).— 6. They 
 form a silver mirror when heated with cone, 
 ammoniaeal silver nitrate. The reduction is 
 promoted by adding NaOH (ToUens, B. 15, 1635). 
 7. A solution of a rosaniline salt, bleached by 
 SO2, is reddened by aldehydes, in the cold 
 (Schiff, Z. 1867, 175 ; Caro ; V. Meyer, B. 13, 
 2342). This test is not infallible (Tiemann, B, 
 14, 791) ; it is given by aldehyde, paraldehyde, 
 propionic, iso-valeric, and oenauthic aldehydes, 
 chloral, butyro-chloral, acrolein, furfurol, ben- 
 zoic, oinnamic, and furfurcrotonic aldehydes, 
 furfuraorolein, salicylic aldehyde, cimicic alde- 
 hyde ; it is not given by chloral hydrate, formic 
 acid, carbo-hydrates, propyl alcohol and higher' 
 alcohols, pinacone, glycol, the phenols, or qui- 
 none ; a faint colour is produced after some time 
 by acetone, and methyl and ethyl alcohols (G. 
 Schmidt, B. 14, 1848). — 8. Alkaline aqueoua 
 solutions produce a coloration like magenta 
 when treated with diazo-bemene sulphonic acid. 
 and a little sodium-amalgam. Acetone and aceto- 
 acetic ether give a dark red coloration without 
 the violet shade (Penzoldt a. E. Fischer, B. 16, 
 657). — 9. Aldehydes are converted by hydroxyl- 
 amine into aldoxims : 
 
 E.CHO + HjNGH = E.CHiNOH -1- H^O 
 (V. Meyer, B. 15, 1164, 1324, 1525, 2784; 16, 
 822, 2992). — 10. u-di-methyl-p-phenylene diamine 
 acts vigorously on aldehydes in alcoholic solu- 
 tion forming crystalline compounds (A. Calm, 
 
 B. 17, 2938) : Ph.CHO + NH2.CjHj.NMe2 = 
 
 Ph.CH:N.CjHj.NMe2 -1- H^O. 
 11. Homologues of acetic aldehyde form crys- 
 talline compounds with aTOi«oma5,E.CH{NHJOH. 
 These are converted by H^S into sulphur base* 
 (fl. p. 104, 1. 9). The aromatic aldehydes are con- 
 verted by ammonia into hydramides : 
 
 3Ph.CH0 + 2NH3 = (Ph.CH),N2 + 3H2O. 
 Some fatty aldehydes, e.g. iso-butyric aldehyde' 
 (Lipp, A. 211, 344) behave similarly. Acrolein 
 loses only half its oxygen : 
 
 2C3H^O + NH3 = C,H,NO -^ HjO. 
 
108 
 
 ALDEHYDES. 
 
 Primary and secondary bases act upon aldehydes 
 with elimination of water. The neutral pro- 
 ducts are split up by HOI into their components. 
 
 12. Chlorine forms derivatives by substitution. — 
 
 13. PCI5 displaces by 01^.— U. H^S displaces 
 O by S, forming thio-aldehydes, or their poly- 
 merides. — 16. PCI3 combines with aldehydes; the 
 -compounds are converted by water into phos- 
 phinic acids (3. T.).— 16. PH^I forms crystalline 
 compounds [v. Phosphines). — 17. Aldehydes re- 
 act with alcohols forming acetals (p. ) : 
 
 E.CHO + 2H0R' = E.CH(OB% + H^O. 
 :SimiIarly, mercaptans form meroaptals (Bau- 
 Tnann, B. 18, 884). — 18. Alkyl chlorides form 
 chlorinated ethers (e.g. CHsCHCl.OEt). Alkoyl 
 chlorides act similarly (p. 105, 1. 1). — 19. Hydric 
 cyanide combines with aldehydes, forming a-oxy- 
 nitriles. These nitriles give (a) on saponification, 
 oxy acids, (6) on treatment with ammonia, 
 amido-nitriles, whence araido acids may be got 
 (Tiemann, B. 14, 1905).— 20. Aldehydes may 
 be converted into amido-aoids by allowing them 
 to stand for 30 minutes with a 3 p.c. solution of 
 NH4CN, and then boiling with HCl (Liubawin, 
 -J. B. 13, 506). — 21. Benzoic aldehyde reacts with 
 nitro-paraffins thus : Ph.CHO + H2C(NO2).0H3 = 
 Ph.CH:C{N02).CH3 + H,0 (Priebs, A. 225, 319). 
 22. Aldehydes condense with aromatic com- 
 ^pounds with elimination of H^O and formation 
 of tri-substituted methanes. Thus aldehyde 
 and benzene give di-phenyl-methyl-methaue ; 
 benzoic aldehyde and phenol give di-oxy-tri- 
 phenyl-methane ; benzoic aldehyde and aniline 
 .give di-amido-tri-phenyl-methane. — 23. In pre- 
 sence of small quantities of acids, aldehydes 
 form red resins when warmed with phenols. 
 'ill&Tij of these are converted by excess of acids 
 into crystalline isomerides. Thus benzoic alde- 
 hyde forms with pyrogallic acid prisms (from 
 ether) of CjjHojOs; this forms an acetyl deri- 
 vative C25H24AC2O5. Benzoic aldehyde and resor- 
 cin form C^^LJH^. If a few drops of a liquid 
 ■containing an aldehyde be boiled with an alco- 
 holic solution of resorein and a little HCl, and 
 be then poured into water, a pp. is formed. 
 "This may be used as a test for presence of alde- 
 iydes (Baeyer, B. 5, 25 ; Michael a. Eyder, B. 
 19, 1388). — 24, In dilute alkaline solution alde- 
 hydes condense with ketones or other aldehydes 
 with elimination of H2O, and production of com- 
 plicated aldehydes or ketones. — 25. For the re- 
 ;action between aldehydes and o-di-amincs v. 
 Aldehydines. 
 
 Pekkin's Synthesis of Unsaturated 
 Acids. — Benzoic aldehyde, acetic anhydride and 
 eodic acetate, heated together form sodic cin- 
 namate. 
 
 In this reaction the sodic acetate may be 
 -exchanged for sodic butyrate or valerate, but the 
 product wiU still be sodic cinnamate : hence 
 Perkin concludes that the reaction takes place 
 between the aldehyde and the anhydride. Pittig 
 came to the opposite conclusion, viz., that the 
 aldehyde acted on the sodium salt and that the 
 nature of the anhydride was immaterial, thus if 
 sodic succinate and acetic anhydride were used, 
 the condensation took place with the sodic suc- 
 cinate. To this Tiemann (B. 15, 2061) objected 
 that possibly the acetic anhydride acting on the 
 .sodic succinate formed sodic acetate and suc- 
 •cinic anhydride, and that the latter reacted upon 
 
 the aldehyde. Stuart (B. 16, 1436) then showed 
 that when sodic malonate was used condensa- 
 tion took place between it and the benioio 
 aldehyde, although no malonio anhydride is 
 known. He also showed that in this case glacial 
 acetic acid might be substituted for acetic an- 
 hydride. According to Fittig, aldol-like condensa- 
 tion-products are first formed, and these, when 
 they split off water, give the unsaturated acids 
 (A. 227, 49). This is shown by the action of 
 sodic iso-butyrate on benzoic aldehyde in pre- 
 eence of isobutyrio anhydride, when the anhydride 
 of the isobutyric derivative of j3-oxy-j8-phenyl- 
 valerio acid Ph.0H(0Hj.0Me2.C02H (j.t).) is 
 formed ; in which there is no H for the OH to 
 split off vrith. If NaOAo be used instead of 
 sodium isobutyrate oxy-phenyl-valerio acid is 
 stiU formed, a result that supports Perkin'* 
 view (Perkin, C. 3. 49, 317). 
 
 CEnanthol and valeric aldehyde may bs 
 substituted for benzoic aldehyde in these syn- 
 theses, while the sodium salt and anhydride ot' 
 propionic or w-butyrio acid may be used instead 
 of the correspondiag derivatives of acetic acid. 
 Condensation then takes place in the a position : 
 Ph.CHO + CH3.CH2.C02Na = 
 Ph.CHiCMe.COjNa -^ H3O. 
 
 A dibasic acid can unite with one equivalent 
 of an aldehyde for each CHj.CO^H contained in 
 its formula; the product may then lose H^O, 
 becoming a lactonic acid or an unsaturated acid. 
 
 ALDEHYDINES.— This name was formerly 
 applied to the base CgHuN obtained by heating 
 aldehyde-ammonia, since shown to be tri-methyl- 
 pyridine (g. ■«.). The same name has since been 
 used by Ladenburg (B. 10, 1126 ; 11, 590, 1660) 
 to denote bases obtained by mixing dUute 
 aqueous solutions of aromatic (but not m, or p) 
 di-amine hydrochlorides with aldehydes. Con- 
 densation occurs with evolution of heat ; the 
 yield of aldehydine after crystallisation is 60 to 
 70 p.c. of the theoretical. CiHy(NH3)j -f 2H.C0.E = 
 CxHyN2C2H2E2 -f 2H2O. Thus o-tolylene-di-amine 
 hydrochloride and benzoic aldehyde give rise to 
 CjHjNjCjHjPhj tolylene benzaldehydine. 
 
 The same body is formed by the action of 
 benzyl chloride on anhydro-benzoyl-tolylene di- 
 N = C.Ph 
 
 Hinsberg con- 
 
 amine at 160°, C,h/ / 
 
 \nh 
 
 eludes from this that its formula is 
 
 >N = C.Ph 
 0,H3< / (B. 19,2025). Under the con. 
 
 \N— CHjPh 
 ditions of this experiment molecular change is 
 more likely to occur than in the usual prepara- 
 tion of aldehy dines in aqueous solution. All 
 other considerations point to a symmetrical 
 formula ; and since in stability and other pro- 
 perties these bodies resemble the quinozalines 
 it is probable that, together with the latter, they 
 belong to the class of azines: tolylene benzalde- 
 
 .N-CHPh 
 hydine would then be 0,H|,^ | | . Ths 
 
 \n-( 
 
 formula given by Ladenburg is 
 .N._,CHPh 
 
 o,hZ X 
 
 ^N^^CHPh 
 Fhenylene-anis-aldehydine C^jHaN^, 
 [129°]. Needles. Soluble in alcohol. Prepar<»d 
 
 -CHPh 
 
ALDEnYDO-OXY-BENZOIC ACIDS. 
 
 ll)9 
 
 by shaking anisio aldehyde with an aqueous 
 iolution of o-phenylene-diamine hydrochloride. 
 
 B'HCl : needles ; difficultly soluble in water, 
 
 Fhenylene-benzaldehydiue C„|,H,,N, i.«. 
 ,N._,CH.O„H, 
 C„H,< >< [133°-134°]. • 
 
 \n^CH.0,H5 
 Six-sided prisms. Insoluble in water, easily 
 soluble in alcohol and benzene. 
 
 Preparation. — (1) By heating o-phenylene- 
 diamine with benzaldehyde. (2) By shaking 
 benzaldehyde with an aqueous solution of o- 
 phenylenediamine hydrochloride. 
 
 Salts. — B'HCl : colourless prisms. 
 (B'HCl).,PtCl4: yeUow precipitate. B'HNOj. 
 Slightly soluble prisms. B'^jSO,: colourless 
 
 I/IQ flp + Q 
 
 Ethylo-iodide C^^t^^^iajB.^)! [211°-213°]. 
 Colourless prisms. 
 
 Methylo-iodide C2|,H,8N2(CH3)I. Prisms. 
 Fhenylene-furfur-aldehydiue C,eH,2NjOj i.e. 
 .(1)N_-,CH.0,H30 
 CsH,< X [95°-96°]. 
 
 \(2)N''^CH.C,H30 
 Colourless crystals. Soluble in alcohol and CjIIj, 
 with difficulty in ligroin, insoluble in water. 
 Prepared by shaking furfurol with an aqueous 
 solution of o-phenyleuediamine hydrochloride. 
 
 Salts. — (B'HCl)2PtCl4 : yellow leaflets. 
 B'HNOj : slightly soluble needles. 
 
 Methylo-iodide 0,5H,jNA(CH3)I. [192°- 
 195°]. Prisms. 
 
 Tolylene-anisaldehydine CjjILjNjOj i.e. 
 ^(l)N^^CH.O^,{OMe) 
 
 C,H3(CH3)< 
 
 
 [152°-156°] 
 
 ' \(2)N^^CH.C3H,(0Me) 
 Needles. Prepared by the action of anisic alde- 
 hyde on an aqueous solution of o-tolylene- 
 diamine hydrochloride. 
 
 Tolylene-benzaldehydine C^jH^Nj i.e. 
 ^(l)N^CH.0eH3 
 
 CeH3(CH,)^ 
 
 \ 
 
 ,^. 
 
 [195-5°]. 
 
 (2)N^^CH.C„H, 
 
 Forms unstable salts with 
 
 Colourless prisms, 
 
 acids. Prepared by heating benzaldehyde with 
 
 o-tolylene diamine to 140°. Yield 45 p.c. of the 
 
 diamine. 
 
 B'HCl + H2O: long needles: difficultly soluble 
 in strong HCl. 
 
 Ethylo-iodide [180°-181°]. Needles or prisms 
 (-I-JH2O). Soluble in water. With iodine it 
 forms a periodide C2,H,8N2(C2H5)l3 [123°]. 
 
 Gives a strongly alkaline solution with AgjO 
 which on neutralising with HCl and adding 
 PtClj gives a crystalUne platino-ohloride 
 (C^H«N,Cl),PtCl,. 
 
 Methylo-iodide [209°]. Thin white needles. 
 
 Pheuylene-benzaldehydine carboxylic acid 
 .(1)N — CH.C,H, 
 C,,H,,NA*-«-C0,H.C3H,<' V 
 
 \(2)N^CH.C,H, 
 Prepared by the oxidation of tolylene-benz- 
 aldehydine with KMnO,. Is not altered by 
 heating with HCl to 200°. 
 
 Salts : A'Ag: white precipitate. A'jCa; diffi- 
 cultly soluble needles. 
 
 Tolyleue-farfuraldehydine 
 
 C.,H„NA i-^ O.H3(CH,)/ 
 
 ^(2)N^ 
 
 -,CH.C,H30 
 ^CH-CAO 
 
 [128J°J. Thin white prisms. Easily soluble in. 
 alcohol, ether, (fee, with difficulty in cold ligroin. 
 
 Preparation. — (1) By heating furfurol with 
 o-tolylenediamine. (2) By adding furfurol 
 (20 pts.) to a solution of o-tolylenediamine 
 hydrochloride (20 pts.) in 80 pts. of water ; on 
 standing the hydrochloride separates out and ia 
 purified by crystallising the base repeatedly 
 from ligroin ; yield 56 p.c. of the theoretical. 
 
 Salts : B'HNOa : needles. B'^H^SO^ : prisma- 
 (B'HCl)2PtCl, : yellow crystals. 
 
 Methylo-iodide [195-5°]. Leaflets. Difficultly- 
 soluble in water ; bitter taste ; powerful poison. 
 
 Methylo-chloride:lea&eta ; easHj soluble in^ 
 water. Powerful poison. 
 
 Methylo-triiodide 0„HnN202(CH3)l3 [126°- 
 128°]. Light brown needles. 
 
 Methylo-pentiodide C„H„NA(CH3)l5 [109°]. 
 Steel-blue pillars. 
 
 j)-ALDEHYDO.BENZOIC ACID C,H„0, i.«. 
 C„H,(CH0)(C02H) [c. 246°]. Formed by careful 
 oxidation of terephthalio aldehyde with chromio 
 mixture (Low, A. 231, 365 ; B. 18, 947). Needles 
 (from water). Small needles when sublimed. 
 M. sol. ether or chloroform, si. sol. hot water. 
 
 Salt.—AgA'. Ether. — ^EtA'. Shows charac- 
 ters of benzoic aldehyde. 
 
 Reactions. — 1. Does not reduce ammoniacal 
 AgNOa. Its ethyl ether, however, reduces am- 
 moniacal AgN03.— 2. Does not give Perkin's 
 reaction with NaOAo and Ac^O. — 3. With ZnCl, 
 and alcoholic NPhMe, it forms the zinc carboxy* 
 late of leuco-malachite green, [147°]. 
 
 Phenyl hydrazide [226°]. 
 
 ]p-Aldehydo-nitro-benzoic acid 
 
 (2) (1) (4) 
 
 CsH3(N02) (CH0)C02H. Nibro-terephthaUc-aUe- 
 %de-aci(j [160°]. Large four-sided prisms. Easily 
 soluble in alcohol and ether, sparingly in chloro- 
 form. Formed by nitration of ^J-aldehydo-ben- 
 zoic acid. 
 
 With acetone it gives the indigo-reaction 
 (Low, B. 18, 948). 
 
 ALDEHYDO-CINNAMIC ACID v. Cmnamio 
 
 ACID. 
 
 AIDEHYDO-NAPHTHOL v. Oxy-naphihoio 
 
 ALEEHIDB. 
 
 ALDEHYDO-OXY ACIDS. Got by heating 
 aromatic oxy acids with chloroform and aqueous 
 NaOH (Tiemann a. Beimer, B. 9, 1268). 
 C„H<(ONa)CO,Na + SNaOH -H CHCI3 = 
 
 C3H3(COH)(ONa)C02Na -H 3NaCU 2H2O. 
 The COH takes either or ^ position towards 
 the hydroxyl. 
 
 ALDEHYDO-OXY-BENZOIC ACIDS C3H5O,. 
 
 m-Aldehydo-salicylio acid 
 C5H,(OH)(CHO)(COjH)[l:4:2]. [249°]. S.-7 at 
 100° ; -038 at 25°. 
 
 Preparation. — Salicylic acid (14 pts.), NaOH 
 (25 pts.), water (50 pts.) and chloroform (15 pts.), 
 are boiled for some hours, the product dissolved 
 in water, and acidified with HCl. A yellow 
 pp. is formed and is extracted with ether. The 
 ethereal solution is shaken with aqueous 
 NaHS03 -, this solution, when boiled with dilute 
 HjSO,, deposits t, crystalline pp. consisting of the 
 (1, 2, 6) acid ; the (1, 4, 2) acid remaining in the 
 solution, from which it may be extracted by ether 
 (Tiemann a. Keimer, B. 9, 1268 ; 10, 1563). 
 
 Properties.— Jjong delicate yellowish needles. 
 V. sol. ether or hot alcohol, v. si. sol. chloroform. 
 
iio 
 
 ALDEIIYDO-OXY-BENZOIC ACIDS. 
 
 FejClj turns its aqueous, solution cherry-red. 
 Decomposes NajCOj. Combines with NaHSOj. 
 Eeduoed by sodium-amalgam to oxy-methyl- 
 «aKcyUc acid, C,H3fOH)(CH,OH)CO,H (Beimer, 
 B. 11, 791). Distillation with lime yields ^i-oxy- 
 ienzoic aldehyde. Potash-fusion gives oxy-iso- 
 phthalio acid. The copper salt dissolves in 
 NHjAq and is not precipitated by boiling. 
 Hydroxylamine converts the acid into its oxim, 
 ■C,H3(OH)(OH:NOH)C02H aq. This aldoxim- 
 salicylic acid is si. sol. water, [179°] (Piirth, B. 
 16, 2182). 
 
 AldeKydo-salicylic acid 
 C,H3(0H)(CH0)C0,H aq [1 : 2 : 6]. [179°]. S. 6-5 
 at 100° ; -065 at 24°. Dehoate needles. Prepared 
 as above. Aqueous solution turned yellow by 
 NaOH and red by Fe^Cl,. Alcoholic solution 
 shows blue fluorescence. Decomposes Na^COjAq. 
 Combines with NaHSOj. Distillation with lime 
 gives salicylic aldehyde. Beduced by sodium- 
 amalgam to (1,2,6) oxy-methyl-salicylic acid, 
 C,H,(0H){CH20H)C02H [142°]. Potash-fusion 
 gives an oxy-iso-phthalic acid. The copper 
 salt dissolves in NH3Aq but is ppd. as CuCjHjO^ 
 on boiling ; this difference from the (1, 4, 2) 
 acid may be used in their separation. Hydroxyl- 
 amine converts this acid also iuto an oxim 
 •C„H3(0H)(CH:N0H)C0.,H, [139°], which forms 
 yellowish needles, soluble in hot water. 
 
 Aldehydo-m-oxy-benzoic acids 
 <3sH3(OH){CHO)COjH [1:2:5], [234°]. and 
 £1 : 4 or 6 : 5]. These two acids are formed in the 
 same way as the aldehydo-salioylic acid, fromjra- 
 oxy-benzoic acid, CHCI3 and NaOH. Easily sepa- 
 rated by water, the (1,2,5) acid being only slightly 
 soluble in boiling water, the other acid being 
 an excessively soluble syrup. The (1,2,5) acid 
 forms white needles, v. sol. alcohol or ether, 
 combines with NaHSOj, has soluble Ba and Ca 
 salts, and on oxidation produces oxy-terephthalio 
 acid. The other acid reduces Fehling's solution 
 with great readiness, and has a soluble silver salt 
 <Tiemann a. Landshoff, B. 12, 1334). 
 
 Aldehydo-p-oxybenzoic acid 
 C,H3(OH)(CHO)C02H[l : 2 : 4]. [244°]. 
 Formed as above from ^-oxy-benzoic acid, 
 CHCI3, and NaOH. Thin yellow prisms (from 
 water). Sublimes in long white needles. SI. 
 sol. water or CHCI3, v. sol. alcohol or ether. 
 Aqueous solution turned yellow by NaOH, brick- 
 red by FejClj. Decomposes aqueous Na2C03. 
 Combines with NaHSOj. Its calcium salt yields, 
 on dry distillation, salicylic aldehyde. Beduced 
 by sodium-amalgam to oxy-methyl-jj-oxy-benzoio 
 acid C3H3(OH)(CH20H).CO,H, [270°]. 
 
 o-ALDEHYDO-PHENOXY-ACETIC ACID 
 
 C„H,0, i.e. [1 : 2] C,H^(C0H).0.CH2.C0,H 
 Aldehydo-phenyl-glycollic acid [132°]. Formed 
 Iby the action of chloro-acetic acid upon sodio- 
 salioylio aldehyde. Sublimable. Yellow plates. 
 V. sol. hot water, alcohol, and ether ; v. si. sol. 
 cold water. By boiling with acetic anhydride 
 and sodium acetate it is converted into oouma- 
 ■rone. — A'Ag : large white needles. 
 
 BisulpmeG^B.lOCB^.GO.^).GB.{OB)O^O^^a,. 
 White crystals. 
 
 Ethyl ether.— A'Et [114°] ; needles ; v. sol. 
 :aloohol and ether, insol. water. 
 
 Phenyl-hydrazide 
 
 C„Hj(0CH2.C02H).CH:N3HC3H3. [0. 105°] ; 
 crystalline powder. Sol. alcohol and ether, si. 
 
 sol. benzene, insol. water. By gently warminjt 
 with H.SOj it is converted into a bluish-green 
 colouring matter, (CjH^NOs):! [108°]. This body 
 may also be got by heating ehloro-aoetic acid 
 with the sodium compound of the phenyl-hydra- 
 zide of salicylic aldehyde. It is a glistening 
 black powder, insol. water, ether, benzene and 
 chloroform, but dissolving in alcohol with a deep 
 bluish-green colour, and in alkalis with a red 
 colour (Bossing, B. 17, 2988). 
 
 Oxim 0„H,(CH:NOH).O.CH2.CO2H. [138°] ; 
 white plates, v. sol. water, alcohol, and ether 
 (Elkan, B. 19, 3051). 
 
 Bromo-aldehyda-pheuoxy-acetic acid 
 C^H^BrOj. [163°]. Formed by the action of 
 bromine water upon o-aldehydo-phenoxy-acetio 
 acid C,H,(CH0).0CH,.C02H (Bossing, B. 17, 
 2992). White sOky needles. Easily soluble in 
 alcohol, ether, and chloroform, sparingly in 
 benzene, nearly insoluble in cold water. 
 
 m-Aldehydo-phenoxy-acetic acid. [148°]. 
 Prepared like the compound. Bromine water 
 gives a pp. of GJELfiiO^ [154°].— AgA'. 
 
 Ether. EtA'. [c. 120°]. 
 
 Oxim. [145°]: large pointed needles. 
 
 Phenyl hydrazide. [0. 140°] : needles. 
 
 ^-Aldehydo-phenoxy-acetic acid. [198°]. 
 Prepared in the same way as its isomerides. 
 Small plates (from hot water). Br gives C^HjErOj 
 [185°].— AgA'. 
 
 Oxim. [168°]: slender needles. 
 
 Phenyl-hydrazide. [159°]. Slender 
 needles. 
 
 ALDEHYDO-OXY-ISOPHTHALIC ACIDS 
 C H O 
 
 " (a)''b3H,(C02H)3(CH0)0H[l:3:5:6]. [265°]. 
 Formed by boiUng (o)-oxy-iso-phthalio acid 
 (1 pt.), with EOH (U pts.), water (3 pts.), 
 and chloroform (IJ pts.) for 5 or 6 hours. It is 
 isolated by means of its bisulphite compound 
 (Beimer, B. 11, 793). It forms white felted 
 needles. SI. sol. cold water, v. sol. hot water. 
 Its alkaline solutions are yellow with green 
 fluorescence. Fe^Clj gives red colour. AgjA" aq. 
 
 (;3) C„Hj(C02H),(CHO)OHiaq[l:2:3:5] [238°]. 
 Formed as above from (i8) -oxy-iso-phthalic acid 
 (E.). It forms long slender needles. Its alkaline 
 solutions are colourless. 
 
 (Py. 3)-ALDEHYD0-ftT;iN0LINE 
 
 C,„H,NO i.e. OeH,< 
 
 /' 
 
 \> 
 
 .CH:CH 
 I 
 
 [71°]. 
 
 N : C(CHO) 
 
 Monoclinic tables. Easily soluble in alcohol 
 and benzene, sparingly in water and cold petro- 
 leum-ether. Formed by oxidation of quinolyl- 
 acryhc acid with KMuO^. It reduces ammo- 
 niacal AgN03. 
 
 Phenyl-tvydrazide CisH,3N3. [195°-198°] ; 
 yellow plates (Miller a. Spady, B. 18, 3404 ; 19, 
 130). 
 
 ALDEHYDO-VANILLIC ACID C^nfis i.e. 
 C,H,(0H)(0Me)(CH0)(C02H) [1:2:6:4]. [222°]. 
 Formed, together with vanillin by boiling 
 vauiUio acid with NaOH, water, and chloroform 
 (Tiemann a. Mendelsohn, B. 9, 1278 ; 10, 395). 
 Silky yeUowish needles (from water). V. sol. 
 alcohol or ether, v. si. sol. cold water. Decom- 
 poses Na2C03Aq. Unites with NaHSO,. 
 Aqueous solution is coloured yellow by NaOH, 
 red by FejCl,,. Does not reduce Fehling's solu< 
 tion. 
 
.T.KALI. 
 
 Ill 
 
 Methyl Ether 0„H,(OH){OMe)(CHO)(CO,Me) 
 [135°]. YeUow needles. Sol. Na^COsAq. 
 
 Methyl derivatii) e 
 C„H2(OMe)2(OHO)C02H [211°]. Formed, to- 
 gether 701111 preceding, by heating aldehydo- 
 vanillic acid with Mel, KOH, and MeOH. Slender 
 needles (from water). Forms colourless solution 
 with NaOH, and gives no colour with FejClj. 
 Combines with NaHSOj. Is isomeric with opianio 
 acid. 
 
 Methylether 0„H,(OMe),(CH0)(CO2Me) [99°]. 
 Slender needles (from water). Insol. NaOHAq. 
 
 ALDOL C^HsO^ i.e. CH3.CH(OH).CH2.CHO 
 P-oxy-butyric aldehyde, (c. 90°) at 20 mm. 
 S.G. 2 1-208; 12 1-1094. /i„ 1-458. 
 
 Formation. — 1. By polymerisation of alde- 
 hyde under the influence of solutions of HCl, 
 Zn0l2, or alkaline salts, or of dry KjCOj but not 
 Na^COj (Wurtz, C. B. 74, 1361 ; 76, 1165 ; 
 Michael a. Kopp, Am. 5, 185). 2. From o-crotonio 
 aldehyde and dilute HCl at 0° (Wurtz, Bl. 42, 
 286). 
 
 Preparation. — Aldehyde (2 kilos), water 
 (2 kilos), and HClAq (2 kilos), are mixed and 
 left for three days at 15°. When the mixture 
 has become yellow and has nearly lost the 
 emeU of aldehyde, it is neutralised with solid 
 NajCOjlOaq. and extracted with ether. The 
 ether is distilled ofl, and the residue rectified in 
 vacuo. Fair yield (495 g.) (Wurtz, 0. B. 92, 1438). 
 
 Theory of the Process. — 
 
 CHs.CHO + HCl = CH3.CH(0H)C1 
 
 CH3.CH(0H)C1 + CH3.CHO = 
 
 CH3.CH(OH).CH2.CHO -i- HCl. 
 
 The condensation may also be explained thus : 
 
 CH3.CHO -I- H,0 = CH3.CH(OH)2 
 
 CH3.GH(0H)j-h CH3.CHO 
 = CH3.0H(OH).CH2.CHO -1- H^O 
 
 Properties. — A viscid liquid. In the course 
 of an hour its temperature rises greatly, owing to 
 polymerisation. The product is still more viscid. 
 Aldol has an aromatic and bitter taste, mixes 
 with water and alcohol, sol. ether. 
 
 Beactions. — 1. Gives pp. of Cu^O with 
 Fehling's solution.— 2. Gives silver mirror with 
 ammoniacal AgN03. — 3. At 135° splits up into 
 H2O and orotonio aldehyde (g. v.). Small quan- 
 tities of iso-di-aldane (v. Aldane) and di-aldehyde 
 (q. V.) are also formed. The same decomposition 
 takes place when heated with glacial HOAo. — 
 4. Nitric acid forms aldehyde, oxalic acid, &o. — 
 6. Moist silver oxide forms iS-oxy-butyric acid. 
 6. Sodium-amalgam in neutral solution re- 
 duces it to di-oxy-butane (q. v.). — 7. Gaseous 
 HCl at 10° is absorbed, forming a thick oil. — 8. 
 With acetic anhydride at 100° for three days, aldol 
 forms an oil separated by distillation into CuHuOs 
 (c. 100°at20mm.)andCsH,2O^(o.l5o° at 20 mm.). 
 The former is perhaps CH3.CH(OAo).CH2.CHO, 
 but the latter is probably a derivative of orotonio 
 aldehyde, CH3.CH:CH.CH(OAo)2 (Beilstein, Bn. 
 1, 786). 
 
 Paraldol(04Hs02)j. [c. 80°], {o.9B°)invacico. 
 8. (alcohol) 26 at 25°. S. (ether) 5 at 22°. 
 
 Deposited as crystals from aldol that has 
 been kept several weeks (Wurtz, C. B. 83, 
 255). 
 
 Triclinic prisms (from alcohol). Sol. water. 
 Partly converted by distillation in vacjio into 
 aldol. Converted by moist AgjO into /S-oxy- 
 butyrio acid. 
 
 Di-aldehyde C^HsGj (?). (170°) at 15mm. 
 (280°) at 760 mm. S.G.a 1-095. V.D. about 
 8. Formed by heating paraldol in sealed tubes 
 for four hours at 170°- Colourless liquid. SoL 
 water. 
 
 Beactions. — 1. Sodium-amalgam forms di- 
 oxy-butane, OH3.CH(OH).CH2.CHjOH.— 2. 4ce<2/J 
 chloride gives off HCl and forms an acetyl deri- 
 vative. BzCl behaves similarly. — 3. PCI3 gives 
 off HCl. — 4. Does not combine with cold bro- 
 mine.— 5. ACjO at 100°-110° forms a liquid 
 (176°) at 15mm., (275°) at 760mm., S.G.a 1-095, 
 insol. water, but saponified on heating with it in 
 sealed tubes for some days. It would appear to bo 
 CHs.OH(OAo).CH2.CH2.0.CO.CH,.CH(OAo).CH3 
 or di-acetylated oxy-butyl oxy-butyrate (?). 
 (Wurtz, C. B. 97, 1625). 
 
 Di-aldehyde may perhaps be di-oxy-tetra- 
 
 methylene, CH(0H)<;^^2>0H(0H). 
 
 ALDOI-AMMONIA C^HgO^NHj. Obtained 
 in a crystalline condition by passing NH3 at 0° 
 into aldol dissolved in ether. It melts when 
 gently warmed, and is soluble in water (Wurtz, 
 C. B. 76, 1165 ; 88, 940, 1154). When distilled 
 in a current of NH3, it forms tri-methyl-pyridine 
 (aldehydine),abaseC8H,3NO (160° at 20 mm.) 
 and apparently another, CjHuKO^. By heating " 
 aldol with aqueous NH3 at 140°-180°, tri-cro- 
 tonylene-amine C,2H24Nj (g. v.) is formed. 
 
 ALDOXIM CjHsNO i.e. CH3.CH:N(0H). 
 (115°). Colourless fluid. Miseible with water, 
 alcohol, and ether. Formed by the action of an 
 aqueous solution of hydroxylamine on aldehyde. 
 By acids it is resolved into its constituents. 
 
 Paraldehyde and metaldehyde do not form 
 oxims (Petraczek, B. 15, 2784 ; 16, 829). 
 
 ALLOXIMS. Aldehydes react, even in the 
 cold, with hydroxylamine in aqueous solution. 
 For this purpose an aqueous solution of 
 hydroxylamine hydrochloride is exactly neutral- 
 ised with 10 p.c. NaOHAq (V. Meyer, B. 15, 
 1526). The aldoxims are liquid, soluble in ether, 
 and differ from hydroxylamine in not reducing 
 Fehling's solution. Boiling HCl splits them up 
 into the aldehyde and hydroxylamine : 
 
 B.qH:N.OH-hH,0 = E.CO.H + H.N.OH. 
 The various aldoxims are described under the 
 aldehydes from which they may be formed. 
 Aldoxims are converted by AcCl into nitriles: 
 
 E.CH:N.OH + AcCl = E.C-N + HCl + AcHO. 
 
 In this respect they differ from ketoxims, 
 which form acetyl derivatives, E'EC:N.OAc. 
 An exception is terephthalic aldoxim, converted 
 by AcCl into C„H,(CH:N.0Ac)3 (Westenberger, 
 B. 16, 2995 ; Laoh, B. 17, 1571). On the other hand, 
 ketoxims of the form EE'CH.C(NOH).CHE"E"', 
 such as di-isopropyl-ketoxim Pr2C:N.0H, and 
 camphor-oxim, are converted by AcCl into an- 
 hydrides, by abstraction of water (V. Meyer, 
 B. 19, 1618). 
 
 Aldoxims are readily reduced, in alcoholic 
 solution, by means of sodium-amalgam and acetic 
 acid to the corresponding amines (Goldschmidt, 
 B. 19, 3232). 
 
 ALIZASIN V. Di-OxY-ANTHEAQUDfONE. 
 
 ALKALI (.4ra6ic = the ash). This term was 
 originally applied to the ashes of sea-plants; but it 
 was soon extended to include substances which, 
 like the ash of sea-weed, easily dissolved in 
 water, forming solutions which had a soap-like 
 
133 
 
 ALKALI, 
 
 action on the skin, affected the colour of many 
 plants, and reacted with acids with effervescence 
 and the production of new substances wherein 
 neither the properties of the acids nor those of 
 the alkalis were prominent. Van Helmont and 
 his successors recognised two kinds of alkali, 
 fixed and volatile; Duhamel, in 1736, divided 
 fixed alkali into two classes, vegetable (potash), 
 and mineral alkaU (soda). Little or nothing was 
 known regarding the composition of alkali until 
 the year 1755, when Black (on the occasion of 
 graduating as M.D. at Edinburgh) published his 
 dissertation on 'Magnesia Alba, Quicklime, and 
 other AlkaUne Substances.' Magnesia alba 
 dissolved in acids with effervescence ; but after 
 being strongly heated no effervescence attended 
 the solution of this alkali. The notion of Basil 
 Valentine (end of 15th and begiiming of 16th 
 century), that lime when burnt combined with 
 • matter of fire,' had been accepted by many as 
 an explanation of the difference in the behaviour 
 towards acids of burnt and unburnt lime. If 
 this explanation applied to magnesia it should be 
 possible perhaps to get hold of this ' matter of 
 fire,' which combined with the magnesia alba 
 when that body was heated. But Black found 
 that a given mass of magnesia alba weighed more 
 than the calcined magnesia obtained from it. 
 Hence something was lost instead of gained 
 during the process of heating. This something 
 proved on further quantitative examination to be 
 a gas different from common air ; to it Black 
 gave the name of fixed aAr. The effervescence 
 or non-effervescence of alkalis with acids was 
 proved by Black to accompany the presence or 
 absence of fixed air (carbonic acid). From this 
 time a distinction was clearly drawn between 
 alkaUs, which dissolved in acids without effer- 
 vescence, and carbonated alkalis, the solution 
 of which in acids was accompanied by the escape 
 of carbonic acid gas. It was recognised that 
 whether a caustic or a carbonated alkali were 
 dissolved in an acid, the body which remained 
 in solution, and which had no close resemblance 
 either to the acid or the alkali, was one and the 
 same. 
 
 The properties of the alkalis were supposed 
 by the older chemists to be due to a 'principle of 
 alkalinity,' or sometimes to a ' principle of salt- 
 ness,' which latter principle was common to 
 acids, alkalis, and the products of their mutual 
 action, i.e. salts. Closely allied to, and some- 
 times regarded as identical with, the alkalis, was 
 the group of earths. These bodies were known 
 to neutralise acids and affect colouring matters 
 like alkahs, but they were much less soluble in 
 water than the alkahs. It was taught by some 
 chemists that an alkah is hidden in every earth, 
 and by others that an alkali is an earth refined 
 by the presence of acid and combustible matter. 
 Black's exact quantitativeinvestigations tended to 
 disparage all such explanations as these ; but it 
 yet remained to find the precise composition of 
 the alkalis and the earths. Lavoisier thought 
 that these bodies must be compounds ; but, as he 
 had no means of proving this, he classed them 
 with the elements, whUe suggesting that the 
 earths were probably compounds of oxygen with 
 unknown metals. In 1807 Davy decomposed 
 two alkalis, potash and soda, by passing an 
 electric current through these substances when 
 
 molten ; and a year later he succeeded, by the 
 same agency, in separating the earthy bodie* 
 Hme, baryta, and strontia, into oxygen and, io 
 each case, a metal. 
 
 The name alkali is now generally applied to 
 the compounds of hydrogen and oxygen with on(» 
 or other of the five metals, hthium, sodium^ 
 potassium,' rubidium, caesium (v. AiiXALis, Metals 
 OF the) ; an aqueous solution of ammonia ia. 
 also regarded as containing an alkali, viz. a com- 
 pound of hydrogen and oxygen with the radicle 
 ammormim (v. Ammonium compounds). The: 
 alkalis are classed with the hydroxides, i.e. com- 
 pounds of hydrogen and oxygen with a third 
 element, rather than vnth the hydrates, i.e, 
 compounds of water vrith an oxide or a salt (v, 
 Eydbaies). The general formula of the alkalis 
 is written MOH rather than M^OHjO ; M = Li» 
 Na, K, Cs, Bb, or NH,. The alkalis are very 
 soluble in water ; these solutions neutraUse acida 
 forming salts, and also precipitate most of the 
 heavy metals from their solutions in the form 
 of oxides or hydrated oxides ; aqueous solutions 
 of the alkahs act corrosively on animal and 
 vegetable substances, and also alter the tint of 
 many colouring matters. When moist, tha 
 alkalis, with the exception of ammonia, readily 
 combine with carbonic acid to form carbonates. 
 Lithia is much less soluble in water than the 
 other alkalis. The solid alkalis are not de- 
 composed by the action of heat alone. 
 
 M. M. P. M, 
 
 ALKAIil-BITTE v. Phbnyl-bosaniline sul- 
 
 PHONATE or soda. 
 
 ALKALIMETST — The estimation of alkahs 
 by volumetric methods, v. Analysis. 
 
 ALKALINE EABTHS, METALS OF THE. 
 — Calcium, Stboniium, Babium. — Certain sub- 
 stances, more or less alkahne in their properties, 
 but differing from alkali chiefly in being in- 
 soluble in water, were known from early times ; 
 these substances were called earths. After a 
 time some of the earths were found to dissolve 
 in water, although to a less extent than alkahs; 
 these comparatively soluble earths were se- 
 parated from the others and classed together as 
 the alkahne earths. The best known alkaline 
 earth is lime; this substance was long con- 
 sidered identical with baryta and strontia, but 
 in 1774 Scheele proved that baryta was different 
 from hme, and in 1792 Hope distinguished 
 strontia from the two other alkahne earths. 
 After decomposing the alkalis potash and soda, 
 Davy apphed the agency of electricity to tha 
 three substances just named, and in 1808 ha 
 succeeded in separating each into oxygen and a 
 metal. Davy made his experiments quantita- 
 tive; he also synthesised the three alkaline 
 earths from oxygen and the meta,l3 he had 
 himself discovered ; thus he proved the alkaline 
 earths to be metallic oxides. The metals cal- 
 cium, barium, and strontium were not obtained 
 in a state of approximate purity until 1855, 
 The metal magnesium is sometimes classed 
 with calcium, barium, and strontium ; but, on 
 the whole, it seems better to place magnesium 
 with zinc and cadmium {v. p. 114, also Maonb- 
 siuM Group op MeiaiiS), 
 
 Some of the principal data regarding the 
 metals of the alkaline earths are presented in 
 the following tables. 
 
ALKALINE EAETHS, METALS OF THE. 
 
 lis 
 
 Oaloium 
 
 Strontium 
 
 BABinM 
 
 Atomic weights . . I 89-9 87-3 | 186-86 
 
 No compounds gasified. Combining weights determined; and most probable formulte of 
 oxides and chlorides deduced from considering analogies with other oxides, &c. Molecular 
 weights unknown. 
 
 Melting points 
 (data uncertain) 
 
 Specific gramties 
 (approximate) 
 
 Specific heats 
 
 Atomic weight 
 Spec. grew. 
 
 high red-heat 
 
 above strontium 
 
 1-58 
 
 017 
 25-3 
 
 moderate red-heat 
 above barium 
 2-5 
 
 not determined 
 34-9 
 
 below red-heat 
 
 3-75 
 
 not determined 
 36-5 
 
 Heats of formation in aqueous solutions (Th 
 (1) Of haloid salts: 
 
 jmsen). 
 
 [M,C!l',Aq] . 
 [M,Br«,Aq] . . . 
 IM,F,Aq] . . , 
 
 187,600 
 165,800 
 135,000 
 
 195,700 
 173,800 
 143,400 
 
 196,800 
 174,900 
 144,600 
 
 
 (2) Of oxides: 
 
 
 [M,O.Aci] . . . 
 
 149,260 1 157,780 
 
 168,760 
 
 [M,0',H»,A(i] , . 1 
 
 (8) Of hydroxides : 
 217,620 1 226,140 
 Heats of hydration (Thomsen). 
 
 (1) Of haloid salts : 
 
 227,120 
 
 [MOlSeffO] . . . 
 
 81,750 
 
 18,640 
 
 [Ba01»,2H'O] 
 7,000 
 
 [BaBr^2H''0] 
 9,110 
 
 [WBt»,6H«0] . . . 
 
 25,600 
 
 23,330 
 
 [MO,H,0] 
 
 [MOAq,H'SO«Aq] 
 
 [MOAq,H^OPAc|] 
 
 |>IOAq,H^'0»Aq] 
 
 (2) Of oxides: 
 . I 15,540 I 17,700 I 
 
 Heat$ of neutralisation of oxides in solution (Thomsen) ; 
 
 31,150 
 27,640 
 
 31,150 
 27,640 
 
 22,260 
 
 81,160 
 27,640 
 
 Malleability, 
 lour, &o. 
 
 co- 
 
 Wave-lengths of 
 mosteha/racteris- 
 tic Unes in spectra. 
 
 Ohemieal proper- 
 ties. 
 
 Oeewrenet and 
 pr^aration. 
 
 CALcnru 
 
 Very ductile, but when 
 hammered becomes brit- 
 tle ; whitish - yellow ; 
 hardness about same as 
 lead. 
 
 Ca,/3 (yellow) 5588. 
 H (violet) 3969. 
 K ( do. ) 3933-8. 
 
 Quickly oxidises in moist 
 air ; decomposes cold 
 water rapidly ; heated 
 to redness in air, burns 
 without smoke ; readily 
 combines vrith 01, Br, I, 
 F, and S, at high tem- 
 peratures. 
 
 Very widely diffused in 
 rocks, waters, plants,and 
 animals, as carbonate, 
 sulphate, phogphate,and 
 silicate : prepared by 
 electrolysis of mixture 
 CaOlj, SrOIj, and NH<01. 
 
 Stkontium 
 
 Ductile and malle- 
 able ; colour re- 
 sembles calcium 
 but clearer ; harder 
 than lead. 
 
 Sr, (blue) 4604 
 
 Closely resembles 
 calcium ; decom- 
 poses water more 
 rapidly. 
 
 Not very widely dif- 
 fused; occurs as 
 carbonate and sul- 
 phate in rocks, and 
 waters ; prepared 
 by electrolysis of 
 fused SrCl» 
 
 BARI0JJ 
 
 Somewhat ductile ; 
 gold-yellow colour. 
 
 Ba, (yellow) 6688. 
 
 Besembles oalolom ; 
 burns when heated iii 
 0-E flame. 
 
 Not very widely diffused; 
 occurs as carbonate, 
 sulphate, and sili- 
 cate, in rooks, waters, 
 and certain plants: 
 prepared by electro- 
 lysis of BaOL mixed 
 with NH^Cl. 
 
 Vol. I. 
 
114 
 
 ALKALINE EARTHS, METALS OF THE. 
 
 Oeneral Formuliz and Character of Salts. 
 
 MO, MOj, MOjH^, MS, MS^H^, MX2(X = C1, 
 Br, I, P, ON), MSO,, M2NO5, MCO3, &o., where 
 M= Ca, Sr, or Ba. MO2 decomposed by heat. 
 Salts for the most part white ; no great tendency 
 to form double salts ; polysulphides known, 
 SrSjeHjO and BaS^HjO, in definite crystals. 
 Oxides and hydroxides markedly basic ; latter, 
 except that of Ba, decomposed by heat alone 
 into oxides and water ; almost all similar salts 
 isomorphous ; many salts isomorphous with cor- 
 responding compounds of Mg, e.g. carbonates ; 
 most, with corresponding compounds of lead ; 
 MO and MOjHj not very soluble in water, solu- 
 bility increases as atomic weight of metal in- 
 creases ; MClj and MBr^ easily soluble, solubi- 
 lity decreases as atomic weight of metal increases ; 
 CaSO^ very slightly soluble (S. -272 at 38°), 
 SrSOi nearly insoluble (S. -01 at 100°), BaSOj in- 
 soluble. CaCOs slightly soluble (S. 1-lB at 100°), 
 SrCOa and BaCOs nearly insoluble. Nitrates all 
 soluble, solubility decreases as atomic weight of 
 metal increases ; Ca2N03 S. 93-1 at 0°. Sr2N03 
 S. 54-9 at 10°. Ba2NOs S. 7 at 10°. 
 
 These data show that the metals of the alka- 
 line earths differ from the alkali metals (com- 
 pare data for latter on p. 115) ; the former are 
 not so readily oxidised as the latter ; the heats 
 of formation of the oxides of the alkaline earth 
 metals are smaller than those of the alkalimetals; 
 the hydroxides of the alkali metals cannot, but 
 the hydroxides of the alkaline earth metals ex- 
 cept that of Ba can, be separated into oxides and 
 water by the action of heat alone. The alkali 
 metals are specifically lighter than those of the 
 alkaline earths ; the composition of the oxides 
 and chlorides of the former is represented by 
 formulae containing two atoms of metal to one 
 of oxygen or two of chlorine, while that of the 
 corresponding salts of the latter is represented 
 by formulae containing one atom of metal to one 
 of oxygen or two of chlorine. The salts of the 
 alkali metals, as a class, are much more soluble 
 in water than those of the alkaline earth metals ; 
 the hydroxide, carbonate, and phosphate of 
 lithium are, however, considerably less soluble 
 than the corresponding salts of the other alkali 
 metals {v. AiiKalis, Metais of the, p. 115). Al- 
 though magnesium forms the oxide MgO, the 
 chloride MgClj, and the sulphate MgSOj, salts 
 analogous in composition to the oxides, chlorides, 
 and sulphates of the metals of the alkaline earths, 
 nevertheless this metal is clearly cut off from 
 these by the following, among other, character- 
 istics. The heats of formation, in aqueous solu- 
 tions, (1) of the haloid salts of Ca, Sr, and Ba, (2) 
 of Mg, Zn, and Cd, indicate the existence of two 
 groups, in the first of which (Ca, Sr, Ba) the 
 value of the reaction increases, and in the second 
 of which (Mg, Zn, Cd) the value of the reaction 
 
 u 
 
 [M,OnAq] 
 
 [M,Br%Aq] 
 
 [M,P,Aq] 
 
 Ca. . . 
 Sr. . . 
 Ba. . . 
 
 Mg . . 
 Zn. . . 
 Cd. . . 
 
 187,600 
 195,700 
 196,300 
 
 186,900 
 
 112,800 
 
 96,300 
 
 165,800 
 173,800 
 174,400 
 
 165,000 
 90,900 
 74,400 
 
 135,300 
 143,400 
 144,000 
 
 134,600 
 60,500 
 44,000 
 
 decreases, as the atomic weights of the metaU 
 increase. The data are from Thomsen. 
 
 Magnesium is scarcely oxidised in ordinary 
 air ; it does not decompose cold water ; nor does 
 it combine so readily with the halogens as the 
 metals of the alkaline earths do. The spectrum 
 of magnesium, as produced in the electric arc, is 
 marked by a series of triplets alternately sharply 
 marked and diffuse, and diminishing in bright- 
 ness towards the more refrangible side ; the 
 spectra of barium and strontium show no trip- 
 lets, but a series of lines only ; the spectrum of 
 calcium is marked both by lines, perhaps homo- 
 logous with those of barium and strontium, and 
 also by well -marked triplets (Liveing and Dewar). 
 Magnesium sulphate is very soluble in water; 
 this salt, and also the carbonate and chloride, 
 readily combines with salts of the alkali metala 
 to form double compounds. Magnesium oxide 
 is scarcely if at all soluble in water ; the forma- 
 tion of the hydroxide by the action of water 
 on the oxide is attended with the production ot 
 very little heat : [MgO, H'O] = (approx.) 3,000 
 (Thomsen). 
 
 The mutual relations of the two groups of 
 elements — the alkaline earth metals and the 
 magnesium metals — are suggested by the posi- 
 tion they occupy in the classification based on 
 the periodic law (3. v. ; v. also Classitioahoii). 
 Both belong to Group II. ; but Ca, Sr, and Ba 
 occur, along with Be, in even series, and Mg, Zn, 
 andCd, along with Hg,in odd series, of that group. 
 The metal beryllium exhibits analogies both with 
 the alkaline earth, and with the magnesium, 
 metals ; it is one of those elements called ' typi- 
 cal ' by Mendel^eff {v. Beryllidm). For accounts 
 of the metals of the alkaline earths and their 
 binary compounds 1;. the articles Baeium, Calcium, 
 and Strontium ; and for the other salts of the 
 metals v. Cabbonates, Nitrates, Sulphates, &o. 
 
 M. M. P. M. 
 
 ALKALIS, METALS OF THE. (Lithium, 
 Sodium, Potassium, Rubidium, Caesium.) — The 
 history of the name alkali has been briefly 
 traced in the article under that heading. The 
 alkalis potash and soda were decomposed by 
 Davy in 1807 ; lithia (discovered by Arfvedson 
 in 1817) was decomposed by the same chemist 
 about 1818; csesia and rubidia were discovered 
 by Bunseu and Kirchoff in 1860-61, rubidium 
 being obtained in the same year by Bunsen, by 
 electrolysing the chloride ; approximately pure 
 CEesium was not prepared until 1882, in which 
 year Setterberg obtained the metal by electro- 
 lysing the double cyanide of caesium and barium. 
 The more important properties of these metals 
 and of their principal salts are presented in the 
 tables on the next page and page 116. 
 
 Thermal values of reaction withwater. — When 
 an alkali metal reacts with water an alkaline hy- 
 droxide is formed and dissolved, and hydrogen 
 is evolved ; thus : — 
 
 M2 + ibHjO = 2M0HAq +(x- 2)H20 + Hj. 
 
 This reaction would be expressed in the nota tioD 
 of thermal chemistry thus : — 
 
 [M^2H^0] = - acH^.O] -H [M^O^m,AcL!. 
 
 The value of 2[H2,0] is 136,720 gram-units 
 when HjO represents 18 grams liquid water ; 
 when the value of [M^O^,H^Aq] considerably 
 
ALKALIS, METALS OF THE. 
 
 115 
 
 
 llTHroM 
 
 Sodium 
 
 PoTisaiuM 
 
 BuBmrou 
 
 OiBSIUH 
 
 AUnme weights 
 
 7-01 
 
 23 
 
 39-04 
 
 85-2 
 
 132-7 
 
 No compounds gasified. Combining weights determined ; and most probable formulsa of 
 oxides and chlorides deduced by chemical methods from considering smallest masses of these 
 salts which take part in chemical changes. Molecular weights unknown. 
 
 Melting points 
 Specific gravitiei . 
 Specific heats 
 Atomic weight 
 Spec. grav. ' 
 
 180° 
 0-59 
 0-94 
 
 11-9 
 
 95°-5° 
 0-98 
 0-29 
 
 23-5 
 
 68°-62° 
 0-87 
 0-17 
 
 44-9 
 
 
 Heats of formation in ag^ueous solutions 
 (1) of haloid salts : 
 
 EM',OP,Aq] . 
 [M2,Br^Aq] . 
 [MSFAq] 
 
 204,500 193,000 
 182,600 171,200 
 152,200 140,600 
 
 (2) Of oxides and 
 
 202,300 
 180,500 
 150,000 
 
 hydroxides 
 
 [M^O,Ac|] . . 
 
 [M^o•^H^Aq] . . 
 
 166,500 
 234,900 
 
 155,300 
 223,600 
 
 164,600 
 232,900 
 
 88° 
 
 1-52 
 
 not determined 
 
 56-1 
 
 26°-27° 
 1-88 
 not determined 
 
 70-6 
 
 Seats of neutralisation of oxides in solution (Thomsen) ; 
 
 [M'0Aq,H2S0*Aq] . 
 [M''OAq,H-CPAq] i 
 [M^OAq,H«N'0»Aq] f 
 
 31,150 
 27,640 
 
 31,150 
 27,640 
 
 31,150 
 27,640 
 
 exceeds 136,720, we should expect the metal M 
 to decompose liquid water. Thomsen has deter- 
 mined these values : — 
 
 M [M^O^H^Aq]. 
 M = Iii2 234,900 
 
 Naj 223,600 
 
 Kj 232,900 
 
 General formulce and characters of salts. — 
 Ufi, (MA. M,0<), MOH, M,S, (M,S„ M,SJ, 
 MSH, MX(X = C1, Br, I,P, CN), M,SO„MHSO„ 
 MNO3, MjCOs, MHCOs, &o., where M = Li, Na, K, 
 Bb, or Cs. No oxides or sulphides of Eb and 
 Cs have been prepared in a state of purity. 
 LijO is the only oxide, and Li^S the only sul- 
 phide, of Li known with certainty. NajOj and 
 Kfit are very stable towards heat, but quickly 
 decompose in moist air, giving off oxygen and 
 forming NaOH and KOH. Salts for the most 
 part white, and very soluble in water ; but 
 LiOH is much less soluble than the other hy- 
 droxides, and Li2C03 and LiaPO, than the other 
 carbonates and phosphates — (Li^COs, S. -769 
 at 13°, S. -778 at 100° ; LijPO,, S. -04 at 18° [ap- 
 prox.].) Chlorides, except LiCl, form many 
 double salts with chlorides of heavy metals, e.g. 
 MjPtCla, SbClsBMCl, &o. Sulphates, except 
 Li2S04, form alums, also double salts with 
 sulphates of magnesium group. Most salts are 
 isomorphous, but some of the lithium salts 
 are not strictly isomorphous with corresponding 
 salts of the other metals ; some compounds of 
 silver and thallium are isomorphous with those 
 of the alkali metals. All the metals of this 
 group are electropositive towards any other 
 elements ; their oxides and hydroxides are 
 strongly basic. The latter cannot be decom- 
 posed by heat alone into oxides and water. 
 Lithium differs from the other members of the 
 group in the comparative insolubility in water 
 of its hydroxide, carbonate, and phosphate, in 
 
 the non-formation of an alum, and in some 
 other respects (compare heats of formation of 
 analogous salts) ; this element serves to connect 
 the group of the alkali metals with that of the 
 metals of the alkaline earths in somewhat the 
 same way as the latter group is connected with 
 zinc and cadmium by the element magnesium 
 {v. ALKAI/rUE EABIHS, Metals OP the). The 
 metals copper and silver are to some extent 
 connected with the alkali metals. Copper forms 
 two series of salts represented by CUjO and 
 CuO respectively; the former, so far as com- 
 position goes, are analogous to the alkali salts. 
 They are, however, much more insoluble in 
 water than these, and, with the exception of 
 the iodide and cyanide and some double salts, 
 are much less stable than the salts formed from 
 the oxide CuO. The salts of silver, as a class, 
 are much less soluble in water than those of the 
 alkali metals ; their composition is similar — 
 AgjO, AgNOs, AgjSO,, &c. ; some of them are 
 isomorphous with corresponding sodium salts, 
 e.g. AgjSOj. Silver forms an alum, and its 
 oxide is markedly basic. 
 
 The alkali metals are placed in Group I., 
 according to the classification of elements based 
 on the periodic law, and this group also con- 
 tains the metals Cu, Ag, and Au. Li, K, Cs, 
 and Eb belong to even series, and Na, Cu, Ag, 
 and Au, to odd series, of Group I. There can be 
 no doulst, however, that sodium is closely con- 
 nected with the other alkali metals, and that 
 the three heavy metals (Cu, Ag, Au) present 
 only feebly marked analogies to each other, and 
 to the metals of the alkalis. In considering the 
 classification of elements which the periodic 
 law presents, attention must be paid, not only 
 to the group in which any given family of 
 elements occurs, but also to the character of 
 the elements which precede and those which 
 
 i2 
 
116 
 
 ALKALIS, METALS OF THE. 
 
 loUow the given family in the same series ; the 
 liosition of the family in the complete scheme 
 must also be considered (v. Pebioeio Law). 
 
 In some respects thallium exhibits a marked 
 chemical lesemblance to the alkali metals ; it 
 forma an oxide TLjO and a hydroxide TIOH, 
 both of which dissolve in water, producing a 
 strongly alkaline and basic liquid, marked by 
 most of the properties which characterise 
 aqueous solutions of soda and potash; it also 
 
 forms salts— TljCO,, T1,S0„ TINO3, *c— 
 which, as a class, are easily soluble in water, 
 and many of which are isomorphous with the 
 corresponding alkali salts. Some of the thalloua 
 salts, however, resemble those of lithium in 
 being comparatively insoluble, e.g. TlCl and 
 TI3PO4. Thallium also forms an alum, and a 
 double platinum chloride Tl^PtClij. On the 
 other hand, the metal itseU differs much from 
 the alkali metals ; it is heavy, is not very easily 
 
 FOTASSnTH 
 
 EUBIDItTM 
 
 CESIUM 
 
 MalUdbility, 
 
 colour, dc. 
 
 Wave-lengths of most 
 characteristic 
 Unes in spectra. 
 
 Chemical proper- 
 ties. 
 
 Occurrence and 
 preparation. 
 
 Silver-white; easily 
 drawn into wire, 
 but less tenacious 
 than lead ; very 
 soft, may be 
 welded at or- 
 dinary tempera- 
 ture ; not vola- 
 tile at red heat. 
 
 Li. (red) 6705 
 (blue) 4602 
 
 Oxidises in ordi- 
 nary air but not 
 so rapidly or 
 completely as 
 other metals of 
 the group ; de- 
 composes cold 
 water rapidly but 
 without itself 
 melting ; ignites 
 at temperature 
 
 • much above its 
 melting - point; 
 readily combines 
 with halogens 
 and sulphur. 
 
 Widely diffused in 
 rocks, waters, 
 plants, and some 
 animal secre- 
 tions ; occurs as 
 silicate and phos- 
 phate with other 
 alkali metals ; 
 prepared by elec- 
 trolysis of mix- 
 ture of LiCl and 
 NH.Ol. 
 
 Silver-white ; 
 soft as wax 
 at ordinary 
 tempera- 
 ture ; very 
 ductile at 
 0° ; can be 
 distilled at 
 red heat. 
 
 D, (orange) 
 5895 
 
 D2 (orange) 
 5889 
 
 Oxidises ra- 
 pidly in air; 
 decomposes 
 water ra- 
 pidly; com- 
 bines very 
 energetic- 
 ally with ha- 
 logens and 
 sulphur, de- 
 composes 
 many ha- 
 loid salts at 
 high tem- 
 peratures. 
 
 In large quan- 
 tities as 
 chloride, si- 
 licate, fluo- 
 ride, nitrate, 
 &o., pre- 
 pared by de- 
 oxidising 
 NajCOa by 
 hot carbon. 
 
 White ; brit- 
 tle at 0°, 
 malleable 
 at 5° or so, 
 pasty at 
 15°: can be 
 distilled at 
 700°-800''. 
 
 (yellow) 5800 
 
 Kfl (violet) 
 4044 
 
 Oxidises very 
 rapidly in 
 air ; decom- 
 poses water 
 rapidly; 
 combine s 
 with halo- 
 gens and 
 sulphur. 
 
 Silver-white; 
 soft as wax 
 at -10°. 
 
 Inlarge quan- 
 tities as ni- 
 trate, sili- 
 cate, sul- 
 phate &e. ; 
 prepared as 
 Na. 
 
 Bb, (red) 
 
 7800 
 Bb, (orange) 
 
 6297 
 
 Oxidises in 
 air so ra- 
 pidly that 
 usually 
 takes fire ; 
 decomposes 
 water most 
 rapidly; 
 burns bril- 
 liantly in 
 vapours of 
 halogens, 
 sulph ur, 
 and arsenic. 
 
 Very widely 
 diffused, but 
 in very 
 
 small quan- 
 tities ; in 
 most Eand 
 Naminerals; 
 in waters ; 
 no special 
 Bb mineral 
 known ; pre- 
 pared as 
 Na and E 
 
 Silver-white; 
 soft at or- 
 dinary tem- 
 perature. 
 
 Cb« (blue) 
 4697 
 
 Cs. (blue) 
 
 4560 
 
 Exceedingly 
 easily oxi- 
 dised. Pro- 
 perties not 
 yet exactly 
 studied. 
 Most elec- 
 tropositive 
 of aU ele- 
 ments. 
 
 As silicate in 
 a rare min- 
 eral. In mi- 
 nute quan- 
 tities in 
 many rocks 
 and waters; 
 prepared by 
 electrolysis 
 of double cy- 
 anide of Cs 
 andBausing 
 Al poles. 
 
 oxidised, does not decompose water except at 
 a red heat, and is much more electro-negative 
 than the alkali metals. Thallium forms an 
 oxide, TljOj, from which a series of salts— 
 TljSSO,, TlCl,, &c.— is obtained ; these salts 
 exhibit analogies with those of the earth metals. 
 The heats of formation of thallous oxide, hy- 
 droxide, and chloride, are much smaller than 
 those of the alkali salts ; Thomsen gives these 
 numbers: [T1^0,Aq] =39,200; [T1^0^H^Aq] = 
 107,600 ; [TP,CP,Aq] = 76,900 {v. Eabths, Meiam 
 OF IBB, and Teallium). 
 
 An aqueous solution of ammonia is strongly 
 alkaline; when neutralised by acids salts are 
 obtained which, as a class, closely resemble those 
 of the alkali metals, with which they are, for the 
 most part, isomorphous. These salts are con- 
 sidered to be compounds of the radicle am- 
 monium (NH^) with acid radicles ; the general 
 formulfB given for salts of the alkali metals 
 apply to the ammonium salts if M be taken to 
 represent NH,. This radicle ammonium re- 
 places the elements Li, Na, K, Bb, or Cs, ia 
 most compounds without altering the crystalline 
 
ALKALOIDS. 
 
 117 
 
 form, and without changing the ohemioal type, 
 ot these compounds. The salts of ammonium 
 are, therefore, classed with those of the alkali 
 metals. (For more details regarding the consti- 
 tution of these salts, and for an account of their 
 properties, see Ammonium Compounds.) For ac- 
 counts of the individual alkali metals and their 
 binary compounds, see the articles Cesium, 
 Lithium, Potassium, Bubidium, and Sodium ; and 
 for the other salts of these metals see Cae- 
 
 BONATES, NiTBATES, SULPHATES, &0. 
 
 M. M. p. M. 
 ALKALIS, Action on Organic Gomponnds. 
 The tendency of alkalis is to form salts. Thus 
 they react with acids and other hydroxylic com- 
 pounds by displacing the hydrogen by potas- 
 sium or sodium (p. 53). Keutral substances are 
 frequently saponified by alkalis, i.e. turned 
 into salts. Saponification means soap-making ; 
 in the narrowest sense it means boiling a fat 
 with potash or soda : C3H5{0CisH350)3 + 3K0H = 
 C3H5(0H)3-h3E0C,8H350. In a broader sense 
 it means the splitting up of any compound 
 ether into its alcohol and its acid, whether by 
 means of an alkali, an acid, or by water alone. 
 In the broadest sense it means the conversion 
 of a neutral substance into an acid or the salt 
 of an acid. Alkalis saponify compound ethers, 
 nitriles, amides, and amic acids. In the case 
 of nitriles the reaction takes place as follows : 
 E.CN + KOH + Hfi = R.CO2K + NH3. Alkalis 
 act upon chlorinated or brominated substances 
 with production of haloid salts : the reaction 
 is either one of substitution; CHsCl + KOH = 
 CHj.OH-l-KCl: or elseHClorHBr is abstracted; 
 CH2Br.CH.^r + KOH = CHjjtCHBr + KBr -f H^O. 
 The latter equation represents the action of 
 alcoholic KOH on chlorinated or brominated 
 hydrocarbons. Hydrogen and halogen are 
 always taken from contiguous carbon atoms. 
 Alcoholic potash sometimes displaces halogen 
 atoms byethoxyl: CH^CLCO^K + KOH -1- EtOH = 
 OHj(OEt).COjK + KCl + H3O. 7-Chloro-aoids are 
 converted by neutralisation with potash into 
 lactones (g. v.). When the halogen is in place 
 of hydrogen in the benzene nucleus, it cannot 
 be turned out liy aqueous potash unless a nitro- 
 group is also present. Thus chloro-benzene is 
 not affected by potash, while o- and p- chloro- 
 nitro-benzenes are converted into nitro-phenols. 
 When phenol is boiled with chloroform and 
 NaOHAq, oxy -benzoic aldehyde results (Tiemann 
 a. Eeimer's reaction): CsHjONa + 3NaOH + CHOlj 
 -CBH,(ONa)COH + 3NaCl-^2H30 (B. 9, 824). 
 
 By the same method the group CHO can be 
 introduced into many derivatives of phenol 
 (p. 109). 
 
 If tetrachloride of carbon be used instead of 
 chloroform, carboxyl enters the phenol, forming 
 a oarboxylic acid: OsH50Na + 5NaOH-!-C01,= 
 C|iH,(0Na).C02Na + 4NaCl + 3HjO. Alcoholic 
 potash sometimes acts as a reducing agent 
 (p. 99, 1. 42). 
 
 Potash-fusion {or soda fusion). 
 
 1. Converts aromatic sulphonates into phenols : 
 
 C5H5.SO3K -1- KOH = C3H3OH -H KjjSO.. 
 
 2. Displaces halogens by hydroxyl : 
 CH^CLCO^K + KOH= C^<(0H).C02K + KCL 
 
 However, owing to the high temperature re- 
 quired, a subsequent migration of the hydroxyl 
 
 sometimes takes place. Thus when any halogen 
 benzene sulphonate or halogen phenol is fased 
 with potash at 235°-270°, resorcin is produced. 
 
 3. Converts oarboxylates into hydrocarbons : 
 CH3.CO2K + HOK = CHj + COsKj. Soda-lime, 
 lime, or baryta may also be used for this purpose. 
 
 4. Converts the higher fatty aldehydes and 
 aromatic aldehydes into alcohol and salt of the 
 acid : 2Ph.CH0 -1- KOH = Ph.CO^K + Ph.CHjOH. 
 In other cases also, potash acts by oxidising 
 one portion of the substance and reducing 
 another. Thus glycerin distilled with potash 
 gives (a) by reduction, propylene glycol, (&) by 
 oxidation, potassic acetate and formate. Simi- 
 larly anthraquinone sulphonate gives (a) by 
 reduction, anthracene, (6) by oxidation, alizarin. 
 
 5. Splits up unsaturated acids at the point of 
 non-saturation into two salts : 
 
 CH3.CH:0H.C02H + 2K0H = 20H3.COjK + H,. 
 
 6. Eesins usually give ^-oxy-benzoate proto- 
 catechuate, and phlorogluoin. 
 
 ALKALOIDS The term alkaloid was first 
 
 applied to any organic base. It is now usually 
 restricted to organic bases that are of vegetable 
 origin and produce marked toxicological effects. 
 Thus such bodies as ethylamine, asparagine, and 
 leucine, are not usually classed as alkaloids. All 
 the alkaloids contain nitrogen, and all except 
 coniine, nicotine, and sparteine contain oxygen. 
 These three alkaloids are volatile, the others are 
 fixed. The vegetable alkaloids are ammonia-, not 
 ammonium-, bases, that is, they combine with " 
 HCl without elimination of H3O. The following 
 alkaloids have been described : 
 
 From Achillea Moschata: aohilleine, mos- 
 chatine. 
 
 From Aconitum Ncvpellus, ferox, dc. : aco- 
 nitine, picro-aconitine, pseudo-aconitine, japa- 
 conitine, lycaoonitine, myoctonine. 
 
 From !^thusa Gynapium : cynapine. 
 
 From Agarictis : agarythrine. 
 
 From Alstonia constricta : alstonine, por- 
 phyrine, alstonidine, alstonioine. 
 
 From Arariba rubra : aribine. 
 
 From Artemisia abrotanum : arbrotin«. 
 
 From Asjpidosperma ; aspidospermine, aspi- 
 dospermatine, aspidosamine, hypoquebraohine, 
 quebrachine, quebraohamine, paytine, payta- 
 mine. 
 
 From Angustura bark : cusparine, gasipeina, 
 
 From Atherosperma : atherospermine. 
 
 From Atropa: atropine, hyoscyamine, hy- 
 oscine, belladonine. 
 
 From Baccharis : bacoharine. 
 
 From BapUsia tincioria : unnamed. 
 
 From Bebeeru : beberine. 
 
 From Berberis : berberine, ozyaoanthine, 
 hydrastine. 
 
 From Buxus : buxine, buxidine. 
 
 From Calabar beams : physostigmine or 
 eserine. 
 
 From Capsicum: oapsicine. 
 
 From Cannabis indica: an unnamed alkaloid 
 (M. Hay, Ph. [3] 13, 998). 
 
 From CheUdomum: ohelerythrine, oholi- 
 donine. 
 
 From Cinchona: quinine, oinchonine, con- 
 quinine, quinicine,homoquinine, hydroquinidine, 
 cinchonidine, aricine, cusconine, cusconidine, 
 oinchoUne, cuscamine, ouscamidine, quinamine, 
 oinchamidine, cinchotine, hydrooinobonine, oon- 
 
118 
 
 ALKALOIDS. 
 
 qninamine, hydroquinine, dioinchonine, dicon- 
 quinine, javanine, paricine. 
 
 From Coca lea/ves : cocaine, eogonine, hy- 
 grine. 
 
 Prom Cocoa beans : theobromine. 
 
 From Coffee berries : caffeine. 
 
 From ColcMcum : colchicine. 
 
 From Conessi bark : conessine. 
 
 From Cordum : coniine. 
 
 From CorydaUs : corydaline. 
 
 From Crossoptera : orossopterine. 
 
 From Cv/rare : curarine. 
 
 From Cytisus : cytisine. 
 
 From DeVpMmwm: delphinine, delphinoid- 
 ine, delphisine, staphisagrine. 
 
 From Dita bark : ditamine or ditaane, eohita- 
 tuine, echitenine. 
 
 From Duboisia : duboisine or hydrocyamine. 
 
 From Ergot: ergotine. 
 
 From Erythrophlewm : erythrophleine. 
 
 From Msenbeckia : esenbeckine. 
 
 From Fraxinus americana: an unnamed 
 alkaloid (F. B. Power, Ph. [3] 12, 812). 
 
 From Fumaria : fumarine. 
 
 From Oelsenium : gelsenine. 
 
 From Oeselmium : geselmine. 
 
 From Glaucium : glaucine, glaucopicrine. 
 
 From Harmala : harmaline, harmine. 
 
 From Sumulus Vwpulus (Hops) : lupuline 
 (hopeine), neurine. 
 
 From Hymenodictyon: an uimamed alkaloid. 
 
 From Ipecacuanha : emetine. 
 
 From Isopyrum : isopyrine, pseudo-isopyrine. 
 
 From Lobelia : lobeline. 
 
 From Lotur bark: loturine, colloturine, 
 loturidine. 
 
 From Loxopterygium : loxopterygine. 
 
 From Lupimis : lupinine, lupinidine. 
 
 From Lycopodium : lycopodine. 
 
 From Macleya : mackleyine, sanguinarine. 
 
 From Menispermum : menispermine. 
 
 From Mustard : sinapine. 
 
 From Nicotiana tabacum : nicotine. 
 
 From Nymphcea alba : an unnamed alkaloid 
 (Gruning, B. 16, 969). 
 
 From Oleander : oleandrine. 
 
 From Opium : morphine, codeine, thebaine, 
 papaverine, narcotine, naroeine, hydrocotarnine, 
 pseudomorphine, codamiue, laudamine, laudano- 
 sine, meconidine, lanthopine, protopine, crypto- 
 pine, crytopine, oxynarootine. 
 
 From Papaver rhceas : rhoeadine. 
 
 From Papaver somniferum : v. Opium. 
 
 From Pennius : boldine. 
 
 From Piper nigrum (Pepper) : piperine. 
 
 From Pereiro bark : geissospermine, pereirine. 
 
 From Pilocarpus leaves : pilocarpine, jabo- 
 rine, pUocarpidine. 
 
 From Pomegranate bark : pelletierine. 
 
 From Poppy : rhoeadine. Opium Poppy v. 
 Opium. 
 
 From Batany root : ratanhine. 
 
 From Bicinus (castor-oil plant) : ricinine. 
 
 From Salamandra : samandrine. 
 
 From Saphora : saphorine. 
 
 From Sinapis : sinapine. 
 
 From Spartium : sparteine. 
 
 From Stroplmntus : strophantine. 
 
 From Strychnos : strychnine, bruoine. 
 
 From Thalictrum: thalictrine. 
 
 From Taxus : taxine. 
 
 From Tea leaves : caffeine. 
 
 From Tobacco : nicotine. 
 
 From Trigomella : trigomeUine, neurine. 
 
 From Veratrum: veratrine, veratridine, ceva- 
 dine, cevadilline, jervine, rubijervine, pseudo- 
 jervine, veratralbine. 
 
 From Vetch : vicine. 
 
 Formation of alkaloids in plants. Most ol 
 the above alkaloids are pyridine derivatives. 
 They are probably produced by the action of 
 ammonia or amido compounds upon non-nitro. 
 genous bodies. Pechmann a. Welsh (B. 17, 2384) 
 consider that the non-nitrogenous bodies are such 
 acids as meconic, chelidonic, and cumalic, which 
 are probably f urfurane derivatives. These three 
 acids are converted by ammonia into oxypyridine 
 carboxylic acids. CumaUc acid is formed arti- 
 ficially from malic acid by action of cone. H^SO, ; 
 and it is probable that the two other acids are 
 also formed by condensation of simpler acids. 
 
 V. Meyer has suggested that hydroxylamine 
 by acting upon aldehydes may also play some 
 part in the production of the nitrogenous con- 
 stituents of plants. 
 
 Extraction: The tissue is extracted with 
 dilute acid and the extract ppd. by ammonia, 
 potash, soda, lime, or magnesia. Volatile alka- 
 loids are then distilled, fixed alkaloids are 
 crystallised from a suitable solvent. The ex- 
 traction of alkaloids from animal matter, as in 
 cases of poisoning, is described in the next 
 article. 
 
 Beactions. — 1 . Sodic phosphomolybdate added 
 to solutions acidified with nitric acid gives, in 
 the cold, a yellowish-white flocculent pp. Ani- 
 line, the alkylamines, and quinoline, as well as 
 silver, mercurous, and lead, salts are also ppd. 
 by this reagent (Sonnenschein, A. 104, 45). To 
 recover the alkaloid, the pp. is boiled with 
 baryta, when volatile alkaloids distil over. The 
 residue is saturated with COj, evaporated to dry- 
 ness and extracted with alcohol. Sonnenschein'a 
 reagent is prepared by dissolving yellow am- 
 monic nitro-molybdate in NajCOjAq, drying and 
 strongly heating ; if reduction of molybdic acid 
 take place, the product is moistened with HNOj 
 and again heated. It is then heated with water, 
 nitric acid is added, and the liquid diluted until 
 10 parts of the solution contain 1 part of solid 
 residue. 
 
 2. Phosphotungstic acid may be used instead 
 of phospho-molybdic acid (Scheibler, Fr. 12,315; 
 J. 1860, 157). The reagent, which is a mixture 
 of sodic tungstate and phosphoric acid, is added 
 to solutions acidified with HjSO^. Phospho- 
 antimonic acid got by dropping antimonio 
 chloride into aqueous phosphoric acid, precipi- 
 tates morphine, narcotine, and nicotine, but not 
 atropine (F. Schulze, A. 109, 177). 
 
 3. Potassio-mercuric iodide produces floccu- 
 lent yellowish-white pps., insoluble in acids and 
 in dilute alkalis, slightly soluble in excess of 
 the reagent, easily soluble in alcohol, and gene- 
 rally also in ether (F. Mayer, J. 1863, 708 ; A. 
 133, 236 ; De Vrij, J. 1867, 602). Theobromine, 
 caffeine, glucosides, carbohydrates, and organic 
 acids give no pp. with Mayer's solution. Albu- 
 minous and gelatinous substances, in presence 
 of free acid (but not in alkaline solutions) give 
 sticky pps. (Valser, Fr. 2, 79). To separate the 
 alkaloid from the pp., the latter is triturated 
 
ALKALOIDS. 
 
 119 
 
 witb SnCLj and excess of aqueous KOH ; this 
 reduces the mercury to the metallic state, and 
 the base is then extracted by its proper solvent. 
 Mayer's solution contains 13-5g. mercuric 
 chloride and 49'8g. potassio iodide per litre. 
 
 4. Potassio-bismuthous iodide is prepared 
 by dissolving Bi(0H)jN03 (80 g.) in HNO3 
 (200 0.0. of S.G. 1"18) and adding a cone, solu- 
 tion of KI (272 g.). The solution is cooled until 
 KNO3 crystaUises, and the mother liquor is then 
 diluted to a litre (Dragendorff, Fr. 5, 406 ; Kraut, 
 A. 210, 310). The solution is added to the 
 alkaloid dissolved in dilute HjSO, or HI. 
 Double iodides of the alkaloid and of bismuth are 
 ppd. The alkaloid can be recovered by decom- 
 posing these double iodides with aqueous NaOH, 
 and extracting with a proper solvent. 
 
 5. Fotassio-cadmic iodide forms white 
 flooculent pps. when added to solutions of 
 alkaloids acidulated with H^SO^. The pps. soon 
 become orystaUine ; they are soluble in alcohol, 
 insoluble in ether. They dissolve in excess of 
 the reagent. The alkaloid can be recovered by 
 treatment with NaOHAq and a solvent (MarmI, 
 Bl. [2] 9, 203). 
 
 6. Poiassio-platinic iodide ani potassio-aurio 
 iodide also pp. alkaloids (Sehni, G. 5, 255). 
 These solutions are prepared by adding KI to 
 solutions of PtCl, or AuClj until the pp. first 
 formed is redissolved. The platinum salt gives, 
 in acetic acid solution, a black pp. with nicotine, 
 but none with conessine ; it also gives a wine- 
 red pp. with solanidine but none with solanine. 
 The gold salt gives, on evaporation, arborescent 
 crystallisation with nicotine, but only oily drops 
 with ooniine. 
 
 7. A solution of iodine (1 pt.) in KI (1 pt.) 
 dissolved in water (100 pts.) gives brown, often 
 crystalline, pps. of the periodides. These polarise 
 light like tourmaline. The alkaloids can be 
 recovered by treating the pp. with SO^Aq. 
 
 8. Animal charcoal removes most of the 
 alkaloids from aqueous solution. The alkaloid 
 can then be extracted from the charcoal by a 
 suitable solvent (Graham a. Hofman, C. J. 5, 
 173). 
 
 9. Picric acid pps. many alkaloids, even in 
 presence of a large excess of H^SOj. Morphine, 
 caffeine, and glucosides are not so ppd. The 
 reagentpps. English but not German preparations 
 of atropine (Hager, Fr. 9, 110). 
 
 10. Tannin gives a white or yellowish-white 
 pp. The salts of morphine, with the exception 
 of the acetate in strong solution, are not ppd. by 
 tannin. The alkaloids can be recovered by 
 treating the pp. with lime. 
 
 11. Platinic chloride gives, in cone, solu- 
 tions, a yellowish-white or yellow pp. Chloride of 
 gold does the same (cf. Coninck, Bl. [2] 45, 131). 
 
 12. Sodie nitroprusside usually forms oily 
 drops of the nitroprusside, which crystallises on 
 standing (Horsley, C. N. 5, 355 ; B. W. Davy, 
 Ph. [3] 11, 756). 
 
 13. The electrolysis of solutions of salts of 
 alkaloids has been studied by Bourgoin (Bl. [2] 
 12, 438). 
 
 14. The alkaloids are ppd. by sodium salts of 
 glycocholic, hyoglycocholic, and taurocholic acids. 
 The pps. appear to be acid salts of the alkaloids 
 <W. F. de I'Abre, 0. C. 1872, 231). 
 
 15. Hydrie sulphide passed into alcoholic 
 
 solutions of alkaloids forms compounds contain- 
 ing sulphur (Palm, J. 1868, 433 ; B. Schmidt, B. 
 8, 1267). 
 
 16. The absorption-spectra of various alka- 
 loids have been mapped by A. Meyer (P. [3] 13, 
 413). 
 
 17. A solution of iodine monochloride in HOI 
 added to a solution of an alkaloid in HOI gives a 
 pp., usually yellow and sparingly soluble (Tilden, 
 C. J. 21, 145; Dittmar, B. 18, 1612; Oster- 
 mayer, B. 18, 2298). According to Dittmar, if 
 the alkaloid contain one pyridine ring, the pp. 
 is of the form XIOl ; if it contain two pyridine 
 groups it is of the iormYIfil^. However, NEtjCl, 
 NEtjHOl, caffeine hydrochloride, and pyrrol, all 
 give pps. though they contain no pyridine ring, 
 while B-oxy-quinolines, and tetra-hydroquinoline 
 give no such pps. The pps. may also be got by 
 using a mixture of KI, KNOj, and HCl, instead 
 of 101. The chloro-iodides are converted by 
 excess of chlorine into unstable compounds XICIj. 
 Ammonia converts the chloro-iodides into iodo- 
 amides, XINH, ; these are dark-green or dark- 
 red unstable bodies, insoluble in water, but 
 converted back into the chloro-iodides by HCl, 
 and decomposed by boiling with alcohol accord- 
 ing to the equation : 
 
 6XINH2 = 3X + 3XIj -1- 4NH3 + Nj. 
 These iodo-amides are also produced by the 
 combination of the alkaloids with iodide of 
 nitrogen. 
 
 Tests for alkaloids. — The above reactions are 
 general. The following tests may be used in dis- 
 tinguishing the alkaloids from one another: — 
 1. The alkaloid is sublimed. -Sublimation begins 
 below 100° in the case of caffeine, theobromine, 
 and cantharidiue ; between 150°-200° in the 
 case of strychnine, morphine, and pilocarpine 
 (Wynter Blyth, O. J. 33, 318). The foUowing 
 give no sublimate, but melt : (a) below 100° 
 hyoscyamine, atropine ; (6) between 100°-150° 
 papaverine; (c) above 200° solanine. The 
 sublimate is then examined microscopically 
 (Helvig, Fr'. 3, 43 ; Deane a. Brady, O. /. 18, 34). 
 — 2. Cone. H^SOj produces colours with certain 
 alkaloids, e.g. a blood-red colour with thebaine 
 and a crimson with veratrine. — 3. Nitric acid 
 usually produces a yellow solution, but morphine 
 and brucine give a red colour. — 4. Sulphuric acid 
 containing a little molybdic acid, so-caUed sul- 
 phomolybdio acid, gives a violet colour with 
 morphine, and characteristic colours with other 
 alkaloids. — 5. Brdmann's solution is prepared 
 by adding HNO3 (6 drops of S.G. 1-25) to water 
 (100 c.c.) and adding ten drops of the diluted 
 acid to 20 c.c. of cone. H2SO4. This solution 
 gives a blue colour when warmed with solutions 
 of codeine, and characteristic colours with other 
 alkaloids. — 6. Chlorine water, followed by am- 
 monia, gives a green colour with quinine, a red 
 colour with narceiue, and an orange colour with 
 narcotine. — 7. A mixture of an alkaloid (1 pt.) 
 with sugar (7 pts.) often gives colours with cone. 
 HjSO^. Morphine and codeine give a purple, 
 aconitine a rose-red (B. Schneider, P. 147, 128), 
 —8. HjSO, and a httle Ce./), give with strych- 
 oine a fine blue colour ; with brucine, orange ; 
 narcotine, brown, cherry-red, finally wine-red; 
 morphine, olive-brown, finally brown ; codeine, 
 olive green, finally brown ; quinine, pale yellow ; 
 cinohonine and caffeine, no coloui; veratrine. 
 
120 
 
 ALKALOIDS. 
 
 Rtiapine, solanine, emetine, brown ; colchicine, 
 green becoming brown ; papaverine, almost black 
 (Sonnenschein, B. 3, 632). 
 
 Optical Properties. — When the solution of 
 an alkaloid affects a ray of polarised light the 
 specific rotatory power of solutions of its normal 
 Baits is independent of the nature of the acid if 
 the alkaloid is mono-acidic and the salt is not 
 decomposed by water, but if the alkaloid is di- 
 acidic the basic salts usually rotate much less 
 than the normal salts (Oudemans, B,. 1, 18). 
 AIKAIOIDS, CADAVERIC v. Piomaikes. 
 ALKALOIDS, FOISONOUS, Detection and 
 Estimation of. — This article will be directed to 
 the simple detection of the chief alkaloids ; but 
 incidentally their quantitative estimation will be 
 touched upon. The detection and complete recog- 
 nition of an alkaloid by chemical tests is often a 
 matter of great difficulty, even in the case of 
 some well-known and potent alkaloids. Indeed, 
 in some cases these difficulties are at present 
 insurmountable by chemical means alone, and 
 physiological experiments have to be called in 
 aid. The obstacles to the recognition of these 
 bases, when several are present, is stiU greater. 
 Indeed, it may be stated that the complete 
 separation of a mixture of commonly occurring 
 alkaloids is a problem stiU awaiting solution. 
 The toxicologist has too often to content himself 
 with the identification of one or two alkaloids in 
 organic mixtures, and the determination of their 
 aggregate quantity, being unable to ascertain 
 their individual amounts. 
 
 History. — The earhest methods devised for 
 the detection of alkaloidal poisons in forensic 
 research were those found effective for the 
 separation of the vegetable alkaloids from the 
 other matters with which they are found asso- 
 ciated in nature; and modifications of these 
 methods are even now employed for this pur- 
 pose. The material to be operated on was 
 extracted with diluted acids, aided by gentle 
 heat, gummy and other substances removed by 
 lead acetate, the excess of lead ppd. with 
 hydrogen sulphide, and the alkaloid obtained 
 as a salt — generally an acetate — in a greater or 
 less degree of purity by evaporation of the 
 solution. This and other crude processes were 
 mostly abandoned when Stas (A. 84, 379) pub- 
 lished his classical paper on the separation of 
 alkaloids from organic mixtures, and devised a 
 new and refined process, which was subsequently 
 modified and improved by Otto {A. 100, 39), 
 DragendorfE (Gerichtl. chem. Ermit. v. Gift., 
 1876), and others. In one form or another, this 
 process, generally known as that of Otto-Stas, 
 is still the one most generally employed in, 
 lorensic analyses, though Sonnenschein (A. 105, 
 45), Selmi (0. J. 1877, 93), and more recently 
 L. Brieger (Die Ptomaine, Pt. I., 1885 ; Pt. II., 
 1885; Pt. III., 1886) have each employed 
 different but less refined methods for the general 
 separation of the organic bases from the matters 
 with which they are commonly associated. 
 
 Methods of Procedure. — If an apparently 
 fairly pure solid body has to be examined, e.g. 
 a orystaUine medicinal powder, its alkaloidal 
 nature may be demonstrated by ascertaining 
 in the ordinary way that it contains both organic 
 carbon and nitrogen; by its sparing solubility 
 in aqueous alkaline, and ite ready solubility in 
 
 aqueous acid, solutions; and by adding to the 
 acid solution reagents that react with the al- 
 kaloids as a class. The alkaloid will usually 
 be ppd. from its acid or aqueous solution, if this 
 be not too dilute, by caustic and by carbonated 
 alkalis ; and will appear either in the form of oily 
 droplets (liquid and volatile alkaloids), or as an 
 amorphous pp., becoming crystalline on stand- 
 ing. If the pp. redissolves in excess of the 
 caustic alkali, as in the case of morphine, it 
 will again separate when the alkali becomes 
 carbonated, as by exposure to the air. Since 
 none of the alkaloids are altogether insoluble in 
 water, no pp. may form in very dilute solutions, 
 and yet an alkaloid be present. There are, 
 however, certain group reagents that pp. the 
 alkaloids from their barely acid solutions, even 
 when these are highly dilute ; and these re- 
 agents are generally employed where the presence 
 of an alkaloid is suspected. Such general re- 
 agents are the following ; but it must be borne 
 in mind that as any one of them may fail to 
 give a precipitate with a given organic base, 
 two or more of them must be used, under appro- 
 priate conditions, in order to prove or disprove 
 the presence of an alkaloid in the solution to be 
 tested. — 1. A weak solution of iodine in potas- 
 sium iodide. This reagent gives a more or less 
 coloured pp. with extremely dilute solutions of 
 most of the vegetable alkaloids. — 2. Bromine 
 water yields similar pps., but has the dis- 
 advantage of yielding pps. with the phenols 
 also. — 3. Tannin pps. most of the vegetable 
 alkaloids from their not too dilute solutions. — 
 4. Mercuric chloride in aqueous, and also in 
 alcoholic solution, is a valuable pptant., and is 
 especially useful in the separation of the organic 
 bases resulting from putrefaction (ptomaines), 
 for the separation of which the Otto-Stas method 
 to be presently described is inadequate (L. Brieger, 
 op. cit.), — 5. Potassio-mercuric iodide solution 
 is perhaps the most generally useful pptant. of 
 the alkaloids ; and from the ppts. thus produced 
 the alkaloids may be recovered in a high state 
 of purity by trituration with stannous chloride 
 and solution of NaOH, and extraction of the al- 
 kaloid thus liberated, with ether.— 6. Phospho- 
 molybdic acid in nitric acid solution pps. the 
 alkaloids from acid solutions. The alkaloids 
 may be recovered from these pps. by decomposing 
 them with barium hydrate, and either distilling 
 ofi the alkaloid (volatile alkaloids), or after re- 
 moving the baryta by means of a stream of car- 
 bon dioxide, subsequently extracting the alkaloid 
 with absolute alcohol. — 7. Picric acid is also a 
 useful pptant., and from the pps. thus produced 
 the alkaloids may be separated by acidification 
 with HCl and agitation with ether. — Many other 
 general pptauts. of the alkaloids have been pro- 
 posed, but the above fulfil almost every useful 
 purpose ; and on the ppn. of organic natural bases 
 by alkalis, and their resolution and extraction 
 by ether and other special solvents— or on their 
 removal from organic solutions by one or other 
 of the above pptants. — are based the most ap- 
 proved general methods for the separation of the 
 poisonous alkaloids in forensic analysis. 
 
 The method most generally employed for the 
 extraction of the vegetable alkaloids from ad- 
 mixture with animal matters is that originally 
 devised by Stas for the separation of nicotine in 
 
AXKALOIDS, POISONOUS. 
 
 121 
 
 the course of a forensic analysis, and now known 
 with modifications as the Otto-Staa method. The 
 writer of this article has introduced further 
 modifications which are embodied in the follow- 
 ing description, and have been found by him 
 necessary in those cases where unstable and 
 easily hydrolysed alkaloids are to be sought 
 ior, such as morphine, which is readily decom- 
 posed by heating its acidified solutions, and 
 aoonitine, which is unstable in alkaline and 
 especially in ammoniacal solutions. In all 
 cases the method, which is a quantitative one, 
 is greatly dependent for success upon the care 
 with which the preliminary operations are con- 
 ducted. 
 
 The organic material to be operated upon, if 
 Bolid, is brought into as minute a state of 
 division as its nature permits, and is then 
 digested with twice its weight of rectified spirit 
 of wine at a temperature of about 35°. Liquids 
 are also treated with twice their volume of 
 rectified spirit. Bedistilled methylated spirit of 
 wine may be used for these operations. After 
 several hours' digestion the liquid is poured off 
 from the deposited solids, and the digestion is 
 repeated with a fresh quantity of spirit. This 
 is again poured off, and mixed with the previous 
 alcoholic infusion. If solid matter, e.g. liver, is 
 operated on, the liquid is squeezed from the solid 
 portion at each digestion in a piece of fine 
 cambric which acts as a crude filter ; and the 
 liquids thus obtained are added to the other alco- 
 holic liquids. After two or more digestions, ac- 
 cording to the nature of the organic matter, the 
 undissolved portions are subjected to a new diges- 
 tion, also at 35°, with spirit faintly acidified with 
 acetic acid. Some recommend tartaric in pre- 
 ference to acetic acid, but this is objectionable, 
 when, as is usually the case, morphine has to be 
 Bought for : others use oxalic acid, but this acid 
 may have to be sought for as well as the alkaloids. 
 Enough acid must be added to keep the liquid just 
 perceptibly acid, excess being avoided. After a 
 prolonged digestion jvith the acidified alcohol, 
 this is poured off, the solids squeezed, and the 
 digestion repeated, but this time with unacidified 
 spirit. A final digestion may be required, the 
 rule being to continue the exhaustion with spirit 
 of wine so long as any colour is imparted to this. 
 The alcoholic liquids obtained before acidification 
 after mixing are momentarily and rapidly raised 
 to a temperature of 70°, cooled, and the insolu- 
 ble residue filtered and washed with spirit ; and 
 those obtained with and after the use of acetic 
 acid are similarly treated. But the two liquids, 
 the unacidified and the acidified are not mixed 
 till a later stage is reached. In this way, by 
 keeping the liquids separate, danger of hydrolysa- 
 tion of unstable alkaloids is as far as possible 
 avoided. The alcoholic infusions are now eva- 
 porated at a temperature never exceeding 35° to 
 the consistency of a syrup. It is advisable during 
 the course of the evaporations to neutralise a 
 portion of the free acid with caustic soda from 
 time to time, so as to keep the liquids just per- 
 ceptibly acid. The evaporations are easily effected 
 with tolerable rapidity by placing the liquids 
 in shallow basins supported on large beakers 
 some inches above the floor of an ordinary 
 oven, which is heated by a gas flame playing on 
 Uki top. The door is kept a little ajar. Tlie 
 
 advantages of this arrangement of the author's 
 are, that overheating is avoided, evaporation is 
 more rapid than by any other method, and all 
 creeping of the liquids up the sides of the basing 
 is obviated. This course of procedure is greatly 
 preferable to distilling off and recovering the 
 alcohol, as usually recommended. The syrupy 
 liquid is now drenched with about 30 c.c. of 
 absolute alcohol, with constant stirring or 
 grinding in a mortar ; the alcohol is poured off 
 from the pasty mass which usually separates, 
 and replaced by successive quantities of 15 c.c. 
 alcohol so long as a colour is imparted to this. 
 The alcoholic liquids are mixed, filtered, the 
 filter washed with alcohol, and the filtrate eva- 
 porated in the oven, as before, at a temperature 
 not exceeding 35°. The syrupy residues— that 
 from the plain and that from the acidified spirit 
 of wine — are diluted with a small quantity of 
 water, filtered, the filters washed with water, and 
 the filtrates mixed. They should, together, 
 measure 15-20 c.c. The liquid is introduced 
 into an accurately stoppered tube, partially 
 neutralised, if necessary, with caustic soda, taking 
 care, however, to leave it slightly acid. If the 
 method laid downhas been scrupulously followed, 
 we have now a liquid containing the whole of the 
 alkaloids, and free from albuminoids. The 
 aqueous and faintly acid liquid in the tube is now 
 covered with twice its volume of washed ether, 
 and the whole is mixed by gently and repeatedly 
 inverting the tube, care being taken not to 
 emulsify the mixture by any violent agitation. 
 The ether is allowed to separate, and this is 
 favoured by giving an occasional sharp rotatory 
 shake to the tube. The supernatant ether is 
 then pipetted off, and replaced by a new and 
 smaller quantity of ether. The tube is again 
 shaken ; and the operation of extraction with 
 ether is continued till a few drops on evaporation 
 leave no residue. Four or five extractions will 
 generally suffice. The ethereal solutions as they 
 are pipetted off are successively washed by 
 vigorous shaking in a second stoppered tube with 
 5 c.c. water to which a few drops of dilute 
 sulphuric acid have been added. The ether on 
 evaporation may yield an oily residue which may 
 be reserved for further examination and for 
 physiological tests. But the acid liquid sub- 
 jected to ethereal extraction will stiU contain 
 nearly all the alkaloids, as the acid salts of these 
 are mostly practically insoluble in ether ; but the 
 salts of some of the alkaloids being perceptibly 
 soluble in ether may be met with in the ' acid- 
 ether ' extract. The acid aqueous solution, and 
 the acidulated water with which the ether has 
 been washed, are mixed, alkalised with sodium 
 carbonate, and again exhausted four or five times 
 as before with washed ether ; only in this case 
 the first exhaustion is made with a mixture of 
 1 vol. chloroform and 3 vol. ether, and the final ex- 
 tractions with ether alone. These successive 
 ethereal extracts are washed in a tube by shaking 
 anew with 5 c.c. water. They are then trans- 
 ferred to a third and finally to a fourth tube, the 
 first containing 10 c.c. water acidulated with a 
 few drops of sulphuric acid, and the last contain- 
 ing 5 c.c. water alone, and agitated. By these 
 operations the alkaloids are first liberated from 
 their salts by the alkali, then transferred to the 
 ether-chloroform in which theyane solable; then 
 
122 
 
 ALKALOIDS, POISONOUS. 
 
 again converted into sulphates, -which, being 
 Ineoluble in ether and chloroform, again pass into 
 the acid solutions, impurities being left behind in 
 tha ether. We have now again the alkaloids in 
 acid solution, but in a much purer state than 
 before. The acid liquid and the final wash- 
 water are mixed, washed with a little ether once 
 or twice, then re-alkalised with sodium carbonate, 
 and well re-extracted with chloroform-ether and 
 ether. These ethereal solutions are washed with 
 water barely alkalised with sodium carbonate, 
 then filtered through a dry filter, and evaporated 
 to dryness in the oven below 35° in tared glass 
 basins about eight centim. in diameter. Once 
 dry, the residue may be transferred for a few 
 minutes to the water-oven, dried at 100°, and 
 weighed after cooling over sulphuric acid. This 
 weight fairly represents that of the alkaloids. 
 It is well before evaporating the bulk of the 
 solution to evaporate a few o.c. only; if an 
 oily odorous residue be left the presence of a 
 volatile alkaloid is indicated ; the evaporation 
 is then modified by mixing the ether-chloroform 
 with BO much ether previously acidulated by 
 agitation with a strong solution of hydrochloric 
 acid as is necessary to render it acid. In this 
 case it is not the free alkaloids, but their non- 
 volatile hydrochlorides which are left and 
 weighed. The residue may therefore be dissolved 
 in water and subjected to appropriate tests — 
 first for the alkaloids generally (vide ante), and 
 secondly specifically for the volatile alkaloids. 
 But if the solid free alkaloid has been obtained 
 it must first be converted into a hydrochloride 
 by moistening it with a very slight excess of very 
 dilute hydrochloric acid, and evaporating to dry- 
 ness in vacuo over sulphuric acid. The residue 
 may then be dissolved in water and subjected to 
 tests, which may be obtained from the ethereel 
 extract either before or after conversion into 
 hydrochloride and solution of this in water. 
 
 Morphine is practically insoluble in ether 
 except immediately after ppn. from its solutions, 
 hence if this alkaloid were present in the matters 
 submitted to examination, but little of it would 
 be removed by the chloroform and ether, more 
 especially if, as is advisable, the agitation with 
 these solvents was not executed immediately 
 after the addition of sodium carbonate. In order 
 to obtain the morphine, the first alkalised solu- 
 tion from which the other alkaloids have been 
 removed must be re-extraoted a few times with 
 a well-washed mixture of equal volumes of acetic 
 ether and ethyl ether, which is preferable to 
 amyl-alcohol, and in which mixture morphine is 
 soluble. The mixed ethers are washed with a 
 little water, filtered through a dry filter, and 
 evaporated just as the chloroform-ether was 
 evaporated for the other alkaloids. The residue 
 is usually not pure morphine, as acetic ether 
 takes up other non-alkaloidal bodies, but these 
 do not usually interfere with the morphine 
 reactions. 
 
 G. Drageudorff (Oerichtl. chem. Ermit. v. 
 Gift., 1876, p. 141) has devised a process which 
 proceeds upon the same general lines as that 
 of Stas, but is much more elaborate. It re- 
 quires, moreover, a, higher temperature for the 
 preliminary evaporation. The finely divided 
 substance, if soHd, is digested for several hours 
 at a temperature of 40°-S0° with dUute sulphuric 
 
 acid — about 2 p.o. by volume of the acid. Liqaids 
 are acidulated with the same proportion of acid. 
 The digestion is continued for several hours, 
 and the mixture is then pressed, and filtered. 
 !rhe operation of extraction with dilute sulphuric 
 acid is repeated two or three times, 100 c.c. of 
 liquid being a convenient quantity for each ex- 
 traction. The mixed filtrates, containing the 
 alkaloids, are partially neutralised with magnesia, 
 and carefully evaporated to a syrup at a temper- 
 ature much below 100° ; but never to dryness. 
 It is certain that in this operation some alkaloids 
 may be destroyed, and it is also asserted that 
 basic bodies are formed by the decomposition of 
 the albuminoids. A useful modification (L. 
 Brieger, op. cit.) is to partially neutralise the 
 liquid from time to time during the course of the 
 evaporation, so that it is never more than very 
 slightly acid in its reaction to litmus. The 
 syrupy residue from the evaporation is mixed 
 with three or four times its volume of rectified 
 methylated spirit of wine, and a few drops of 
 sulphuric acid, and allowed to digest at about 
 30° for twenty-four hours. The insoluble matter 
 is separated by filtration and washed with spirit, 
 and the filtrate and washings are distilled in a 
 retort so as to recover the alcohol. The aqueous 
 residue in the retort is diluted with water to 50 c.c, 
 filtered, and introduced into a stoppered tube 
 and exhausted successively with petroleum ether, 
 benzene, and chloroform, 20-30 c.c. of each at a 
 time, in the manner in which exhaustions are 
 made with ether in Stas's process. The aqueous 
 solution is then made alkaline with ammonia, 
 and again exhausted successively with petro- 
 leum-spirit, benzene, chloroform, and amyl- 
 alcohol. On evaporation of the respective 
 solvents (consult what has been said under 
 Stas's process as to volatile alkaloids) alkaloidal 
 residues are obtained, which when taken up with 
 water, either with or without previous conver- 
 sion into hydrochlorides as necessity demands, 
 may be submitted to appropriate tests for the 
 alkaloids, and specially for the various suspected 
 alkaloids. 
 
 Among the commoner alkaloids,andpoisonous 
 neutral substances : — 
 
 Petroleum ether removes from the acid 
 aqueous solution: — some piperiue, resins such 
 as capsioin, camphor, and phenol. 
 
 Benzene further removes from the acid 
 solution: — more piperine, caffeine, colchicine, 
 santonin, digitalin, cubebin, colocynthin, aloetin, 
 picric acid, elaterin, and cantharidin. 
 
 Chloroform, again, removes from the acid 
 aqueous solution : ' — cinchouine, theobromine, 
 papaverine, narceine, jervine, more digitalin, 
 picrotoxin, smilacin, and senegin. 
 
 On rendering the solution alkaline with 
 ammonia : — 
 
 Petroleum sj>irit removes from the alkaline 
 solution: — strychnine, brucine, quinine, vera- 
 trine, aconitine, emetine, and the volatile 
 alkaloids coniine, nicotine, lobeline, and trime- 
 thylamine (from putrefaction), the pimento- 
 alkaloid, and aniline. If the presence of aco- 
 nitine or emetine be suspected, the operation 
 must be performed quickly, since these alkaloids 
 rapidly decompose in alkaline solutions. 
 
 Benzene further removes from the alkalint 
 solution : — atropine, hyoscyamine, physostig- 
 
ALKALOIDS, POISONOUS. 
 
 129 
 
 mine (eserine), thebaine, codeine, narcotine, and 
 additional quantities of stryohnine, bruoine, 
 quinine, cinchonine, veratrine, aoonitine, and 
 emetine. 
 
 Chloroform, again,removes from the alkaline 
 solution : — some morphine, and additional quan- 
 tities of cinchonine, narceine, and papaverine. 
 
 Amyl-alcohol finally removes from the alka- 
 line solution: — morphine, narceine, and some 
 neutral bodies, such as salicin. 
 
 Not all the substances enumerated above are 
 poisonous ; but they are bodies that may be 
 present in medicinal mixtures, and hence are 
 likely to come under the notice of the toxico- 
 logist in forensic analyses. 
 
 Selmi proposed another method of extract- 
 ing the poisonous alkaloids, and applied it to 
 the extraction of the ptomaines (<?. 6, 153 ; 
 C. J. 31, 93). The viscera are exhausted with 
 alcohol and dilute sulphuric acid. This acidi- 
 fied alcoholic extract is filtered and evaporated 
 at a temperature of 65°, again filtered, and 
 evaporated to a syrup. The residue is taken 
 up with water, filtered, the filtrate treated with 
 basic lead acetate, and the mixture exposed 
 to the air for twenty-four hours. It is then 
 filtered, the excess of lead removed by hydrogen 
 sulphide gas, and the filtrate concentrated. 
 This is then repeatedly extracted with ether. 
 The ethereal solution is then saturated with a, 
 stream of dry carbon dioxide gas, which gene- 
 rally causes a pp. of droplets containing some 
 of the alkaloids, and adherent to the side of 
 the vessel. The ethereal solution is poured 
 off, mixed with about half its volume of water, 
 and a current of carbon dioxide is again passed 
 for twenty minutes, which may cause the ppn. 
 of other alkaloids not ppd. by dry carbon 
 dioxide. Usually the whole of the alkaloids are 
 thrown down by these means, but if not, the 
 ethereal solution is dehydrated by shaking with 
 barium oxide, and then a solution of tartaric 
 acid in ether is added to the clear liquid, taking 
 care not to employ an excess of acid; any 
 alkaloid that may remain in solution is thus 
 thrown down. As a matter of precaution, the 
 remains of the viscera or other matters operated 
 on are mixed with barium hydrate and a little 
 water, and agitated with pure amyl alcohol. 
 The alkaloids may then be extracted from the 
 alcohol by shaking it in a stoppered tube with 
 very dilute sulphuric acid. 
 
 Sonnenschein (A. 104, 45) separates the alka- 
 loids by ppn. with phosphomolybdic acid. In 
 extracting the bases, the organic matter to be 
 examined is repeatedly exhausted with very 
 dilute hydrochloric acid, the mixed solutions 
 filtered, and the filtrate evaporated in the oven at 
 a temperature not exceeding 35° to a thin syrup ; 
 then diluted with water, cooled, and filtered. 
 An excess of phospho-molybdic acid is added to 
 the filtrate, and the pp. is washed with water con- 
 taining nitric and phosphomolybdic acids. The 
 still moist pp. is washed into a flask, made 
 distinctly alkaline by the addition of Isarium 
 hydrate, and distilled into a bulb apparatus 
 charged with hydrochloric acid, which absorbs 
 ammonia and the volatile bases. The residue 
 in the flask, containing the non-volatile bases, 
 is freed from barium hydrate by a current of 
 oarbon dioxide, evaporated to dryness, and the 
 
 bases extracted by means of strong alcohol. 
 The filtered alcoholic solution often yields oa 
 evaporation the alkaloids in a sufficient state of 
 purity to admit of their being weighed, con- 
 verted into hydrochlorides, and submitted to- 
 tests. Sometimes, however, they must be puri- 
 fied by re-solution and re-crystallisation from 
 absolute alcohol, ether, chloroform, Ac. 
 
 The method of Uslar and Erdmann {A. 120, 
 121) is not much employed in this country, the 
 evaporation of amyl alcohol being a disagreeable 
 operation ; but it is nevertheless a valuable process 
 for the separating of strychnine and morphine. 
 It is practised as follows : — The suspected matter,, 
 if solid, is made into thin paste with water, 
 slightly acidulated with hydrochloric acid, and. 
 digested at a temperature of 70° for an hour or 
 two. It is then strained through a moist piece of 
 cambric, and the solid residue on the cloth ia 
 well exhausted with hot very dilute hydrochloric- 
 acid. The combined liquids after filtration are- 
 made slightly alkaline with ammonia, mixed 
 with clean sand, and evaporated to dryness on 
 the water-bath. The residue from the evapora- 
 tion is extracted three or four times with hot 
 amyl alcohol and the mixed liquids are filtered. 
 The filtrate is shaken violently in a stoppered 
 tube -with several times its volume of hot water- 
 acidulated with hydrochloric acid, which removes 
 the alkaloids, leaving colouring matters and fat in 
 the alcohol. The alcohol is pipetted off, and the- 
 hot acid solution is repeatedly washed by agita- 
 tion with fresh portions of amyl alcohol until aU. 
 fat and colouring matter is removed, after which, 
 the clear aqueous liquid is concentrated by 
 evaporation, made alkaline with ammonia, and 
 well shaken with fresh hot amyl alcohol four or 
 five times. These alcoholic liquids are mixed,, 
 filtered through a filter moistened with amyl 
 alcohol to remove water, and evaporated in a 
 tared basin, when the alkaloids will be left in a 
 sufficiently pure condition to be dissolved and 
 tested, previous to which they should be weighed.. 
 Occasionally a coloured residue is obtained which 
 requires re-solution in aqueous acid, agitation, 
 with amyl alcohol, alkalisation with ammonia, 
 and re-extraction with amyl alcohol, in order to^ 
 obtain the alkaloids in a sufficiently pure state 
 for testing. With morphine the process, though 
 tedious, works well. 
 
 Scheibler's process is based upon the precipita- 
 tion of the alkaloids by phosphotungstic acid, a . 
 reagent prepared by treating sodium tungstate 
 in solution with half its weight of phosphoric 
 acid, when crystals of phosphotungstic acid 
 slowly form. These are dissolved, and the pro- 
 cess in detail is carried on in the same manner 
 as Sonnenschein's phosphomolybdic acid process,, 
 substituting the phosphotungstic for the phospho- 
 molybdic solution as a precipitant. It is some- 
 times recommended to precede the ppn. of the 
 alkaloid by the addition of lead acetate to remove 
 colouring matter, and then to remove the excess ■ 
 of lead by hydrogen sulphide ; but some of the 
 alkaloid present is apt to be removed with the- 
 lead pps. Nor should animal charcoal be used 
 as a decolorant, as this is still more effective in 
 withdrawing the alkaloids from solution. In- 
 deed the obstinacy with which the alkaloids- 
 adhere to animal charcoal has been utilised by- 
 Graham, Hofmann, and Bedwood as a means of 
 
!S4 
 
 ALKALOIDS, POISONOUS. 
 
 separating strychnine from beer and other 
 liquids (O. J. 5, 173). 
 
 The following scheme serves for the detection 
 of the more commonly occurring poisonous 
 alkaloids. The alkaloids are brought into 
 acid aqueous solution, and this is shaken with 
 «ther : — 
 
 I. The ether withdra/ws from the acid aqueous 
 solution, and leaves on evaporation : 
 
 1. Colchicine. — Its solution is yellow, and is 
 turned to a violet colour by strong nitric acid. 
 Its solution in HClAq, when made alkaline with 
 •caustic soda, develops an orange-red colour. 
 
 2. DigitaUn. — When dissolved in cone. H^SO^ 
 and a minute quantity of bromine water is 
 added, a reddish-violet tint is produced, which, 
 on the addition of water changes to a green. 
 
 3. Picrotoxin. — Eeduces Fehling's solution. 
 The solution is made alkaline vnth sodium 
 
 'bicarbonate, and again shaken with ether. 
 
 II. Ether removes from the alkaline solution, 
 and leaves on evaporation : 
 
 1. NicoHme. — Oily droplets, having a tobacco- 
 like odour. Its aqueous solution is not ppd. by 
 •chlorine water, nor does it become coloured when 
 warmed. Warmed with hydrochloric acid the 
 •alkaloid becomes violet, and then on the addition 
 •of nitric acid orange-coloured. 
 
 2. CanUne. — Oily droplets having a mouse- 
 like odour. Its aqueous solution is ppd. by oMorine 
 ■water, and becomes coloured when warmed. Dry 
 hydrochloric acid gas turns the alkaloid at first 
 led, and then to a violet colour. 
 
 3. Lobeline. — Oily droplets yielding no very 
 •definite chemical reactions. 
 
 4. Brucine. — Turned rosy-red by strong sul- 
 phuric acid not quite free from oxides of nitro- 
 gen. The alkaloid is reddened by strong nitric 
 •acid, and the red solution changes to a bluish 
 violet on the addition of a solution of Stannous 
 •chloride.. 
 
 5. Strychnme. — No coloration on the addi- 
 tion of strong HjSO,. On the further addition 
 of solid potassium dichroniate, MnO^, or PbO.j, 
 a violet-blue coloration is immediately produced, 
 passing gradually into a cherry-red, the colour 
 •only slowly disappearing. 
 
 6. Narcotime.—lt become first yellow, then 
 bluish- violet when warmed -with strong sulphuric 
 acid. Its solution in strong H2SO4 becomes 
 red on the addition of a trace of nitric acid. 
 iSnlphomolybdic acid turns the alkaloid green. 
 
 7. Veratrine. — With strong sulphuric acid it 
 'becomes yellow, orange, and finally cherry-red. 
 Its solution in cold concentrated hydrochloric 
 acid is colourless, but gradually changes to a 
 ■deep red when boiled. 
 
 8. Jervine. — The salts of this alkaloid, except 
 the acetate and phosphate are only very sparingly 
 soluble in water and acid solutions. Its solution 
 in acetic acid is ppd. by nitrio acid and by 
 potassium nitrate. 
 
 9. Atropine.— Ml odour of hawthorn is deve- 
 loped when the alkaloid is warmed with strong 
 sulphuric acid and potassium dichromate ; and 
 the solution becomes green from reduction of 
 •chromic acid. Evaporated to dryness with 
 fuming nitric acid, and the residue touched with 
 an alcoholic solution of potash, a fine purple 
 •eolour is produced. 
 
 10. Aconitine can only be identified by its 
 
 physiological properties. The chemical tests for 
 pure aeonitine are not characteristic. 
 
 11. Gelsemine. — With strong sulphuric acid 
 and potassium dichromate, a reddish-purple 01 
 cherry-red colour is developed, quickly passing 
 into bluish-green or blue. 
 
 12. PhysosUgmine. — Its solutions, whether 
 acid or alkaline, become reddish on exposure, and 
 this colour is discharged by sulphurous acid and 
 the thiosulphates. Treated •with sulphuric acid 
 and bromine-water, it yields a brown-red colour. 
 
 III. There remain in the alkaline aqueous 
 solution : — 
 
 Morphine, curarine, and cytisine. The first 
 may be separated by shaking with acetic ether, 
 and is identified by the usual tests — nitric acid, 
 ferric chloride, iodic acid and starch, and sul- 
 phomolybdio acid. Curarine may be ppd. by 
 phosphomolybdic acid after acidification with 
 nitric acid. The pp. is decomposed by barium 
 hydrate, and the alkaloid extracted by absolute 
 alcohol {v. Sonnenschein's process, ante) ; it 
 gives a reddish colour with sulphuric acid, and 
 reacts somewhat like strychnine with sulphuric 
 acid and potassium dichromate. Curarine, how- 
 ever, is not precipitated from its solutions by 
 potassium dichromate. 
 
 Cytisine yields no definite chemical reactions. 
 
 The following are the chief trustworthy tests 
 for the more commonly occurring poisonous 
 alkaloids, &o. : — 
 
 Aeonitine. — this alkaloid, as well as the 
 closely allied alkaloids pseud-aconitine and japa- 
 conitine, when pure, yield no characteristic 
 chemical reactions. The colour reactions 'with 
 sulphuric and phosphoric acids that have been 
 described by authors are untrustworthy, and 
 due to impurities. 
 
 Ajpomorphine. — Its salts turn green on ex- 
 posure to light and air, and its solutions on 
 boiling. With sodium bicarbonate its solutions 
 yield a pp. which turns green on standing, 
 and forms with ether a purple, and with chloro- 
 form a violet, solution. Its solutions strike 
 a red colour with ferric chloride and with nitric 
 acid. 
 
 Atropine. — When warmed with strong sul- 
 phuric acid — or, more quickly, when evaporated 
 to dryness with baryta-water, and the residue 
 heated— an odour of stale hawthorn flowers is 
 developed. 
 
 Brucine. — It is turned of a blood-red colour 
 by nitrio acid; and the red solution becomes 
 violet on the cautious addition of a solution of 
 stannous chloride. It yields an orange-red with 
 Bulphomolybdio acid ; and with sulphuric acid 
 and potassium dichromate a deep orange-red 
 colour. 
 
 Caffeine. — Crystallises in silky needles. Eva- 
 porated to dryness with dilute hydrochloric acid 
 and a fragment of potassium chlorate, a pink 
 residue is left, which turns violet on the addition 
 of ammonia. 
 
 Cinchonine. — It is diflScult to get any charac- 
 teristic reaction for this base. Its sulphate is 
 soluble in chloroform, and is non-fluorescent — 
 characters which distinguish it from quinine. 
 
 Cocaine. — Is not coloured by concentrated 
 acids. When evaporated to dryness with alco- 
 holic potash, the residue when w!»rmed vnth 
 
ALKANET. 
 
 125 
 
 dilute sulphurio acid evolves an aromatic odour 
 oi benzoic acid. 
 
 Colchicine. — Nitric acid strikes a violet 
 colour, which on the addition of sodium hydrate 
 changes to a fine orange. Strong sulphurio acid 
 dissolves the alkaloid to a greenish yellow 
 colour, and on the addition of a drop of dilute 
 nitric acid a play of colours, beginning with 
 violet, is manifested. The subsequent addition 
 of caustic soda yields a fine rose tint. 
 
 OonUne. — Oily, and of a mouse-like odour. 
 Its dilute aqueous solution fumes with strong 
 hydrochloric acid, and after acidification gives 
 no pp. with bromine-water until supersaturated 
 with sodium hydrate, when a white pp. forms. 
 
 Curarine. — Is turned blue violet when 
 touched with sulphuric acid and potassium 
 diohromate added ; but the colour is more per- 
 sistent than in the case of strychnine. 
 
 Cytisine. — This alkaloid is insoluble in ether, 
 benzene, chloroform, and carbon disulphide. It 
 dissolves in sulphuric acid without colour, but 
 the subsequent addition of nitric acid produces 
 an orange coloration. Nitric acid dissolves 
 cytisine without colour, but on warming the 
 mixture becomes orange-red. 
 
 Emetine is said to strike a blood-red colour 
 with strong nitric acid, but the writer believes 
 that this is due to impurities, and that tests for 
 emetine are desiderata. 
 
 Oelsemine. — Sulphuric acid and potassium 
 dichromate produce an inunediate but evanescent 
 violet coloration, and the chromate is quickly 
 reduced. The alkaloid is naturally associated 
 with gelsemic acid, a substance which in alkaline 
 solution fluoresces strongly, and is yellow by 
 transmitted, blue by reflected light. 
 
 Eyoscyamine. — No good chemical test for this 
 alkaloid is known. 
 
 Jervine. — The salts of this alkaloid, especially 
 the acetate, are ppd. by nitric acid and by 
 potassium nitrate. 
 
 Morphine gives with nitric acid a deep red 
 colour, not materially altered by the subsequent 
 addition of stannous chloride. With sulphuric acid 
 and potassium dichromate a green coloration 
 is gradually developed. Ferric chloride gives a 
 blue or blue-green coloration. It liberates 
 iodine from iodic acid, and the mixture shaken 
 with chloroform imparts a violet tint to this; 
 but the brown colour is only deepened and 
 altered in tint by ammonia. Sulphomolybdic 
 acid gives an immediate purple coloration. 
 
 Na/rcotine. — Uncoloured by sulphuric acid, 
 except this contains a trace of nitric acid, when 
 a fine cherry-red colour is gradually developed, 
 and is persistent. Its acidulated solution when 
 warmed with bromine-water, added drop by drop, 
 develops a purple or violet tint. 
 
 NicoHne. — Oily, and having the odour of 
 tobacco. Freely soluble in water. Its acidu- 
 lated solutions give a copious pp. with bromine- 
 water, and this pp. disappears when excess of 
 sodium hydrate is added. 
 
 PhysosUgmine. — Sulphurio acid gradually 
 produces a reddish colour. Its solutions acquire 
 a red colour on standing, and at once when 
 treated with sodium hydrate and warmed, and 
 on evaporation leave a bluish residue which on 
 ocidulation affords a dichroic (red and blue} 
 
 solution, which becomes permanently red oc 
 standing. 
 
 Pilocarpine afEords no very characteristic 
 chemical reactions. With sulphuric acid and 
 potassium dichromate a green colour, due to 
 reduction, is developed. 
 
 Piperine has the pungent fragrant odour of 
 pepper. It is turned of a deep red colour by 
 sulphuric, and of an or«uge colour by nitric acid. 
 
 Quinine. — Its solution in sulphuric acid is. 
 fluorescent. Treated with bromine-water and 
 then excess of ammonia added, an emerald 
 green coloration is produced. 
 
 Salicm. — A neutral glucoside. It is not 
 withdrawn from its acid or alkaline solutions by 
 ether, benzene, or chloroform, and hence is 
 not obtained in the ordinary processes for the 
 separation of the alkaloids. It is turned of a 
 cherry-red colour by sulphuric acid, and then on 
 the addition of potassium dichromate an odour 
 of meadow-sweet is evolved. Fused and par- 
 tially sublimed in a test-tube, and then dissolved 
 in water, ferric chloride strikes a violet colour. 
 
 Strychnine. — Sulphurio acid gives no colour 
 tiU potassium dichromate, MnOz, PbO^, or 
 ferricyanide of potassium is added, when im- 
 mediately a fine blue-violet colour is produced 
 which gradually passes into reddish-violet, red, 
 and finally cherry-red. Evaporated to dryness 
 with fuming nitric acid, and the residue 
 moistened with alcoholic potash a deep orange 
 colour is produced. 
 
 Veratrine. — Touched with strong sulphurio 
 acid, this alkaloid gradually develops a fine 
 red colour, or immediately on warming. Its 
 solution in cold strong hydrochloric acid is 
 colourless, but becomes intensely red on boUing. 
 
 T. S. 
 
 ALEAMINES, alcamines, alkines, or alcines. 
 Names used by Ladenburg to denote substances 
 that contain both alcoholic hydroxyl and amido- 
 gen, such as oxy-ethyl-amine, C2H<(0H).NHj. 
 
 ALKANET. The commercial name of two 
 different plants. True alkanet is Lawsonia 
 inermis,ialse alkanet is Anehusa tinctoria. The 
 leaves of Lawsonia contain a yeUow dye, its 
 roots contain a red pigment, used as a cosmetic. 
 The root of Anchvsa (Orcannette, Radix Al- 
 canncB spurice) contains anchusin. 
 
 Anchusin or Alkannin Cj^H^gO, (Bolley a. 
 Wydler, A. 62, 141) or C^HjoO^ (Pelletier, A. 
 6, 27) or CisHijO^ (Carnelutti a. Nasini, Q. 1880, 
 283 ; B. 13, 1514). Obtained by extracting the 
 root of Anehusa tinctoria with petroleum; the 
 crude product is treated with dilute potash, the 
 filtrate is shaken with ether, and the alkannin is 
 ppd. by a current of 00^. It is a brownish-red 
 mass with a metallic lustre ; sol. ether, chloro- 
 form, and acetic acid, si. sol. alcohol. Softens 
 below 100°. AleohoUc solutions give with 
 baryta-water a blue pp. of a barium compound. 
 N^OAc and Acfl produce a crystalline di-aoetyl 
 derivative : C,5H,jAc204(?). Nitric acid forms 
 oxahc and succinic acids. Alkannin appears to- 
 be allied to santalin. An alcoholic solution of 
 alkannin dyes cotton mordanted with alum, 
 violet; iron mordants give a grey colour. Turned 
 blue by alkalis, especially ammonia (Bottger, J. 
 pr. 107, 46; Enz, J. 1870, 935). Alkannin, 
 unlike rosaniline, is not abstracted by cubes ,of 
 gelatin from its solution. Its absorption-spec- 
 
126 
 
 ALKANET. 
 
 trum Bhow3 3 bands, dividing the spectrum 
 between D and the blue strontium line into 
 4 equal parts. On adding ammonia the red 
 solution turns blue, now showing 2 bands, one 
 at D, the other in the red, two-thirds of the way 
 towards the lithium line (A. Dupr4, 0. J. 37, 572). 
 
 ALKARSIN. Name given by Bunsen to 
 caoodyl or arsenic di-methide (g. v.), C^HijAs, as 
 being empirically alcohol in which has been 
 displaced by As (A: 24, 271). 
 
 ALKYL. An alcohol radicle. 
 
 ALKOYI. An acid radicle. 
 
 ALLANIC ACID Cfi^nfiM- 
 
 Formed, together with urea and allanturio 
 acid by the action of nitric acid in the cold on 
 allantoin (E. Mulder, A. 159, 353). Stellate 
 needles (from water). SI. sol. cold water. De- 
 composes at 210°-220° without melting. Does 
 not give off gas with HNO3 containing NjO,. 
 Gives no pp. with CaCI^Aq and NHjAq. Gives 
 pps. with AgNOjAq and NHjAq, and with basic 
 lead acetate, but not with neutral lead acetate. 
 
 SaZfe.— NH4A': prisms.— HO.Pb.A': ppd. by 
 basic lead acetate.— 2PbA'25Pb(OH)2 — AgA'aq: 
 amorphous pp. 
 
 ALLANTOIC ACID 
 04HgN40<i.e.NH2.C0.NH.CH(C02H).NH.C0.NHj 
 A solution of allantoin in aqueous potash which 
 has stood for sorne days, no longer gives a pp. 
 with acetic acid, even after some time ; but if 
 a little alcohol be also added, and the liquid be 
 left in an exsiccator over lime, crystalline 
 potassic allantoate, KA', separates (E. Mulder, 
 A. 159, 362 ; Sohlieper, A. 67, 231 ; Ponomarew, 
 J. B. 11, 13). The solution of potassic allan- 
 toate gives crystalline pps. with Pb(0Ac)2 and 
 AgNOj, but not with BaClj. BaClj and alcohol 
 give a hygroscopic curdy pp. 
 
 SaZ«s.— NH^A'— NaA' aq.— KA'.-BaA', 2aq. 
 — PbA'^aq.- AgA'. 
 
 ALLAHTOlN C,H„N,Oa »•«• 
 .NH.CO 
 C0< I 
 
 ,NH.CH(OH) 
 or C0< I 
 
 \NH.C:N.CO.NHj 
 Mol. w. 158. S. -62 at 20° ; 3-3 at 100°. 
 
 Occurrence. — In the allantoic liquid of the 
 cow (Lassaigne, A. Ch. [2] 17, 301 ; compare 
 Vauquelin, A. Ch. 33, 269). In urine of sucking 
 calves (Wohler, A. 70, 229). Occasionally in 
 urine of dogs (Salkowski, B. 9, 721; 11, 500; 
 Meissner a. Jolly, Z. 1865, 131). In the young 
 leaf-buds of the plane and maple, and in the 
 bark of the horse-chestnut tree (E. Schulze, B. 
 14, 1602; J.pr. 133, 147; H. 9, 425). In wheat, 
 to the amount of -5 p.c. of the embryo (Eiohard- 
 son a. Crampton, B. 19, 1181). 
 
 ^Formation. — 1. By treating uric acid with 
 boiling water and PbOj (Liebig a. Wohler, A. 
 26, 244; B. Mulder, A. 159, 349), with KOH 
 and potassic ferrioyanide (Schlieper, A. 67, 216), 
 or with KMnOj (Glaus, B. 7, 227).— 2. By heat- 
 ing glyoxylic acid (1 pt.) with urea (2 pts.) eight 
 hours at 100° (Grimaux, C. B. 83, 62).— 3. By 
 the action of nitrous acid on dialurio acid (Gibbs, 
 A. Suppl. 7, 337).— 4. By heating mesoxalic 
 BOid with urea at 110° (Michael, Am. 5, 198). 
 
 JProperties. — Glassy monoclinic prisms 
 
 JDauber, A. 71, 68). Tasteless. Neutral, 
 Eeadily soluble in alcohol. 
 
 Beactions. — 1. Dry distillation gives am- 
 monic carbonate and cyanide, and charcoal. — 2. 
 Gently heated with hydrochloric or nitric acid 
 it gives urea and allanturio acid. — 3. Hot 
 sulphuric acid forms 00^, CO, and NH3. — 4. 
 Boiled with baryta-water, CO2, NH„ oxalic acid, 
 and hydantoin are got (Baeyer, A. 180, 161). — 
 5. Hot cone, potash forms CO2, NHj, oxalic acid, 
 and acetic acid. — 6. Cold potash slowly forms 
 allantoic acid {q. v.). — 7. Nitric acid of S.G. 1-35 
 forms, on boiling, allanic acid (j. v.). — 8. 
 Potassic ferricyamde and KOH form allantoxanio 
 acid (Mulder, B. 8, 1291).— 9. Sodium amalgam 
 forma glyeoluril, CJHJN4O2 (Streokera.Bheineck, 
 A. 131, 119).— .10. Hydric iodide reduces it to 
 urea, and hydantoin or glycolyl-urea (Baeyer, A, 
 117, 178). 
 
 Tests. — 1. A cone, solution of furfurol, to 
 which a little HCl has been added, gives a violet 
 colour with an aqueous solution of allantoin 
 (Schiff, B. 10, 771).— 2. Mercuric nitrate (but 
 not chloride) gives a pp., as with urea. 100 g. 
 of dry allantoin require 172 g. of mercuric oxide. 
 The pp. is (C4H5N,03),5HgO. 
 
 Compounds with Bases. — These are 
 formed by boiling aqueous solutions of allan- 
 toin with metallic oxides. They are sparingly 
 soluble (Limprioht, A. 88, 94). — 
 
 (04H5N403)2CdO.— OAN.OsZnO.— 
 
 (C4H3N40,),5HgO.-(C4H,N403)32HgO.- 
 (C,H,NA)43PbO.-(C4H3N,0,)eCuO. 
 The following are described as true salts : 
 Ag04H5Ni03, got as a pp. by ammoniacalAgNOj. 
 — KC4H5N403: from allantoin, KOHAq, and 
 alcohol, in exsiccator. 
 
 Nitrate C^HsN^OsHNOj. Amorphous. De- 
 composed by water or alcohol into HNO, and 
 allantoin. 
 
 Constitution. — The constitutional formules 
 given above are chiefly based upon Formation 
 2 and Beaction 10. 
 
 ALLANIOXA^iDIIT 
 
 /NH.CO 
 CjHjNjOj aq i.e. C0<^ | aq. 
 \nH.C:NH 
 When allantoxanio acid is liberated from its 
 salts, it at once splits up into COj and this body 
 (Ponomarew, J. B. 11, 47). Glittering prisms or 
 tables. V. sol. boiling water, si. sol. cold water 
 or alcohol, insol. ether. Decomposed by heat, 
 giving off HON, HCNO, and NH3. Acid reaction. 
 Boiled with water, or treated with cold Na^COjAq, 
 it splits up into formic acid and biuret. 
 
 Salts. — KA' : ppd. by alcohol. — AgA'. 
 
 ALLANTOXAKIC ACID C^H^NA i.e. 
 
 <NH.CO 
 I 
 NH.C:N:C02H 
 Formation. — 1. Allantoin dissolved in aque- 
 ous KOH is treated with potassic ferrioyanide 
 until the colour is permanent. Acetic acid is 
 then added, when 04H2KN304 is ppd. (Van 
 Embden, A. 167, 39).— 2. From allantoin, KOH, 
 and KMn04 (Mulder, B. 8, 1292; Ponomarew, 
 J. B. 11, 19). — 3. From oxalyl-di-ureide and 
 aqueous potash (P. B. 18, 982). 
 
 Properties. — The acid, liberated from its lead 
 
 salt by HjS, splits up into aUantoxaidin and CO,. 
 
 Salts.— NH4A': needles. — (NH4),C4HN304. 
 
ALLOPHANIO AOID. 
 
 127 
 
 — KA': silky needles. S. -SO. Boiled with water, 
 it gives CO.^, biuret, and formic aeid. Eeduoed 
 by sodium-amalgam to iiydroxonio acid. — 
 ^CiHNaO, aq: v. sol. water, insoluble in dry 
 aloohol.— Ba(C4H2N304)j 6aq. — BaC^HNaO, 2aq. 
 — Pb(CjE[,N304)2 ijaq: very thin needles. — 
 PbC^HNaO,. — AgCjHjNsOj : crystalline pp. — 
 Ag2C4HNjO, : gelatinous. 
 
 Ethyl ether C,H2EtNj04 : from AgA' and EtI. 
 
 AIIANTTJRIC ACID OsH.N A *•«• 
 xNH.CO Olyoxyl-urea. 
 C0< I 
 
 \nH.CH(OH) 
 
 Formation. — 1. By boiling allantoin with 
 HNO3, HCl or PbOj or heating with water at 
 140° (Pelouze, A. Ch. [3] 6, 71 ; Mulder, A. 159, 
 359). — 2. Formed, together with glycoluril and 
 urea, by action of sodium-amalgam on allantoin 
 (Eeinecke, A. 134, 220). — 3. By boiling allantoic 
 acid or alloxanic acid with water (Fonomarew, 
 J. R. 11, 15; SchUeper, A. 56, 5).— 4. By 
 oxidation of hydantoin (Baeyer, A. 117, 179 ; 
 130, 160). — S. By boiling uroxanio acid with 
 water (Medious, B, 9, 1162 ; Ponomarew, B. 11, 
 2155). 
 
 Properties. — ^A deliquescent gummy mass. 
 Insol. alcohol. Boiling potash forms GO2, NH„ 
 acetic acid, and oxalic acid (Medicus, B. 10, 544). 
 —Salts. These are amorphous.— KA'H A' 2aq. 
 S. 10.— BaA'2 3aq. 
 
 ALLENE. Name sometimes used instead of 
 Alltlkne. 
 
 ALLITTJBIC ACID OsHeN^Oi. 
 S. 5 or 6 at 100°. Obtained from an aqueous 
 solution of alloxantin, mixed with HCl, by 
 rapidly evaporating to a small bulk, and treating 
 the resulting powder with HNO3 which dissolves 
 alloxantin but not allituric acid. The latter 
 crystallises from water as a bulky yellowish- 
 white powder (Schlieper, A. 56, 20). Not at- 
 tacked by cone. ELjSO^ or HNO3. Evolves NH, 
 when boiled with KOH. 
 
 AILO.— A prefix proposed by Michael (B. 19, 
 1378) to denote unexplained isomerism; thus 
 lumario acid would be called allo-maleio acid. 
 
 ALLOCAFFEIhE C8H5N3O5. 
 [196°]. (E. Fischer, A. 215, 276). 
 
 Formation. — 1. Obtained by action of water 
 on the unstable product of addition of bromine 
 to caffeine methylo-hydroxide. — 2. One of the 
 products of action of HOI and KClOj on caffeine 
 methylo-hydroxide (Schmidt a. Schilling, A. 
 228, 162). 
 
 Small white trimetric crystals, a:6:c = 
 •6953: 1: '5401, soluble in benzene, chloroform, 
 and hot water, nearly insoluble in cold water, 
 sparingly in alcohol or ether. 
 
 Beactions. — 1. Decomposed by boiling water 
 into CO2 and methyl-caffuric acid. Allocaffeine 
 is therefore probably methyl-apocaffeine.— 2. 
 HNOj (S.G. 1'2) gives cholestrophane, methyl- 
 amine, and COj.— 3. HCl and KCIO3 form di- 
 methyl-alloxan, amalic acid, cholestrophane, 
 methylamine, and COj. — 4. Brormme appears to 
 form an addition product, but it is decomposed 
 by water into allocaffeine, cholestrophane, and 
 methylamine hydrobromide. — 5. BoUing baryta 
 forms sarcosine, formic acid, and CO^. 
 
 GoTuStitut/ion. — Inasmuch as it splits off 
 NMeHj in reactions where caffeine splits off 
 NH„ the Me (and oonsequently OH also) must 
 
 be attached to nitrogen, the formula being 
 either : 
 
 MeN— CH MeN— CO 
 
 I II II 
 
 CO C— NMe or OC C— NMe 
 I I >C0 I II >CH 
 
 MeN— C = NMe.OH MeN-0— NMe.OH 
 (after Fischer) (after L. Medicus) . 
 
 ALLOPHANIC ACID C^H^NA 
 i.e. NHj.CO.NH.COjH Urea v-carboxylic acid. 
 The free acid splits up at once into COj and 
 urea. Its ethers are formed by passing vapour 
 of cyanic acid into alcohols: 2C0NH-HH0Et = 
 NH2.00.,Et + CONH = NHj.CO.NH.CO^Et. The 
 ethers are sparingly soluble crystalline solids. 
 
 Salts. — ^BaA'^: obtained from the ether by 
 cold baryta-water (Liebig a. Wohler, A. 59, 291). 
 When boiled with water it gives off CO^, deposits 
 BaCOj, and urea is left in solution. Dry dis- 
 tillation produces basic oyanate, NH,, and COj. 
 It gives no pp. with AgNOj. — Salts of Ca, K, and 
 Na have been prepared. 
 
 Methyl allophanate NHj.C0.NH.C02Me 
 (Biohardson, A. 23, 138). 
 
 Ethyl allophanate EtA'. [191°]. 1. From 
 alcohol and the vapour of cyanic acid (L. a. W.). 
 2. From ClCO^Et and urea (Wilm a. Wisehin, 
 Z. [2] 4, 6). — 3. Together with oxamide and 
 alcohol by heating urea with oxalic ether at 
 135°-170° (Grabowski, A. 134, 115).— 4. From 
 potassio cyanate, alcohol, and chloro-acetic ether 
 (Saytzeff, A. 135, 230) or chloroformic ether, 
 ClCOjEt (Wihn, A. 192, 244).— 5. From potassio 
 cyanate, alcohol, and HCl (Amato, G. 3, 469). 
 Small needles. Tasteless. SI. sol. cold water, 
 more soluble in alcohol. V. si. sol. cold ether 
 (difference from oarbamio ether). At 190° it 
 slowly changes to alcohol and oyanuric acid. 
 Alcohol at 160° converts it into carbamic ether : 
 NH,.00.NH.C02Et + HOEt = 2NH2C02Et (Hof- 
 mann, B. 4, 268). 
 
 Acetyl derivative, NHAc.CO.NH.COjEt. 
 [107°]. Silky needles (from alcohol) (Seidel, /.2>r. 
 [2] 32, 273). 
 
 Benzoyl derivative NHBz.C0.NH.C0jEt. 
 [163°]. Together with alcohol, HCl, and CO^ 
 from benzoyl chloride and urethane (Eretsch- 
 mar, B. 8, 104). 
 
 H'ropyl allophanate PrA'. [150°-160°]. 
 (Cahours,/. 1874,834). 
 
 Amyl allophanate CjHuA'. [162°]. From 
 cyanic acid and amyl alcohol (Schlieper, A. 59, 23). 
 From amyl aldoholand urea (Hofmann, B.4, 267). 
 Unctuous pearly scales (from water). 
 
 Oxethyl allophanate H0.C2H4A'. [160°]. 
 From glycol and cyanic acid vapour. Shining 
 laminae (from alcohol) (Baeyer, A. 114, 160). 
 
 Di-oxy-propyl allophanate C3H5(0H)jA'. 
 [160°]. From glycerin and cyanic acid vapour 
 (B.). Plates (from alcohol). Sol. water. Heated 
 with baryta-water, it forms BaCO,, urea, and 
 glycerin. 
 
 Phenyl-allophanate PhA'. Cyanic acid 
 vapour is passed into phenol; the product is 
 dissolved in alcohol and ppd. by ether. 
 Slender crystals. At 150° it splits up into 
 cyanic acid and phenol (Tuttle, J. 1857, 451). 
 
 Propenyl-methozy -phenyl-allopha- 
 nate Ci^HnNjO, *•«• 
 
 NH2.C0.NH.C0.0.0eH3(CKHs).0CH,. 
 From eugeuol and cyanic acid vapour (Baeyer. 
 
128 
 
 ALLOTEOPY. 
 
 A. 114, 164). Needles. Insol. water. SI. sol. 
 cold alcohol. 
 
 Amide of allophanic acid 
 NH,.CO.NH.00.NH2 v. Biueet. 
 
 ALLOTBOFY (otherwise turned, otherwise 
 formed, from iXKos = another, and rp6iros = man- 
 ner) denotes the appearance of one and the 
 same substance in several different states, dis- 
 tinguished from each other by different proper- 
 ties. The term was introduced by Berzelius in 
 1840 IJ. No. 20 for 1839, pt. ii. p. 13), because 
 he held the term ' isomerism ' to be inadmissible 
 where the subject of modification is an elemen- 
 tary substance, isomeric states being traceable 
 to different modes of combining equal numbers 
 of atoms of the same elements. In the view of 
 Berzelius, accordingly, the allotropio modifica- 
 tions of the elements are not to be explained by 
 differences in the arrangement of their atoms, 
 but he expressed no opinion whatever about 
 their actual cause. Since, however, he indicated 
 it as probable that even in compounds the ele- 
 ments retain their allotropic states, and thereby 
 often occasion isomeric forms of compounds 
 (J. No. 23, p. 51 ; No. 24, p. 32), he appears to 
 have been of opinion that the cause of the aUo- 
 tropic transformation is to be sought in a 
 change in the atoms themselves. Now that we 
 have learned to appreciate more correctly the 
 doctrine of Avogadro, and so have become 
 accustomed to consider the molecules of the 
 majority of elements as particles composed, like 
 those of compounds, of several atoms, the dis- 
 tinction introduced by Berzelius between allo- 
 tropy and isomerism has lost its original mean- 
 ing. But the term allotropy has been retained, 
 being used, however, with reference not to ele- 
 ments only but also to compounds. Accordingly 
 we distinguish between allotropy of elements and 
 allotropy of compounds. The former, accord- 
 ing to the modem use of the expression, embraces 
 all the different forms in which an element ap- 
 pears ; the latter only those cases in which, 
 while the composition remains the same, there 
 is a change in the physical, but none, or at any 
 rate none of any consequence, in the chemical, 
 properties, thus apparently warranting the as- 
 sumption that there has been no change in the 
 linkage of the atoms by which, doubtless, chemi- 
 cal behaviour is essentially determined. Allo- 
 tropy of compounds is accordingly synonymous 
 with physical, as opposed to chemical, isomerism. 
 But since the two groups of properties are closely 
 connected, and any change of the physical is 
 usually accompanied by a change, however 
 small, of the chemical also, no sharp line is to be 
 drawn between the two kinds of isomerism. 
 
 On the other hand, the transformation of one 
 allotropio form into another offers so many 
 analogies to the transformation of one state of 
 aggregation into another that, strictly speaking 
 the three states of aggregation of any substance 
 should be described as three allotropio modifica- 
 tions of it (Lehmann, Z.K. 1877. 1, 97) . Hitherto, 
 however, it has not been usual so to describe the 
 states of aggregation, and, consequently, on this 
 side also, the notion of allotropy is not to be 
 defined with perfect exactness. The melting of 
 ice, for example, is a transformation of the 
 lighter into the heavier modification of water, 
 for the particles of the lighter are still retained 
 
 in the liquid state for some degrees above the 
 melting point, and bring it about that the 
 maximum of density appears not at 0° but at 
 + 4°. Something similar probably takes place 
 in many, if not in all, other substances, only the 
 difficulties of observation are greater. But as it 
 has been observed that changes in the properties 
 of a substance usually proceed differently and 
 follow different laws according as the substance 
 is near to, or more remote from, its melting- 
 point (no matter whether above or below it), we 
 may conclude that immediately below the melt- 
 ing point the solid substance already contains 
 isolated portions of the liquid modification, and 
 that above the melting point the liquid body 
 stUl contains portions of the solid modification. 
 But even if we do not account these changes of 
 aggregation as instances of allotropy, the num- 
 ber of cases of allotropy as yet known, while 
 suffering a very important diminution, will still 
 remain pretty considerable. 
 
 I. Allotkopt or the Elements. — ^Allotropy, 
 taken in the narrower sense, has hitherto been 
 observed only in the non-metallic or semi- 
 metallic elements. Among metals proper it has 
 been found only as regards crystalline form, in 
 which case it is usually known as dimorphism or 
 polymorphism. Since, to the best of our present 
 knowledge, the gaseous molecules of the metals 
 consist of single atoms,' while those of the semi- 
 metals and non-metals are composed of several 
 atoms, the absence of allotropic modifications of 
 the metals proper tells in favour of the present 
 view, which is different from that of Berzelius, and 
 is to the efieotthat allotropy of the elements, Uke 
 isomerism of compounds, depends on differencesin 
 the mode of union of the atoms, and not on any 
 changes in the atoms themselves. Polymor- 
 phism, occurring as it does even among metals, 
 may be explained by supposing that there are 
 differences in the arrangements of the atoms as 
 well as of the molecules, while the existence of 
 allotropic modifications in the melted, the dis- 
 solved, or the gasified, state points to differences 
 in the constitution of the molecules, i.e. to dif- 
 ferent modes of uniting the atoms to form mole- 
 cules. 
 
 The appearance of allotropy seems to be 
 favoured by smallness of atomic weight, for not 
 unfrequently in one and the same natural family 
 aUotropy shows itself only in the first members, 
 while the members with higher atomic weights ex- 
 hibit it either in some properties only or not at all. 
 In the family of the halogens, F, CI, Br, I, allo- 
 tropy has not been observed, unless we consider 
 as such the splitting of molecules at high tem- 
 peratures into separate atoms (Victor Meyer). 
 Hydrogen does not exhibit allotropy. On the 
 other hand aUotropy is found very notably in 
 the first members of the oxygen-sulphur family. 
 Ozone exhibits much more strongly marked 
 chemical characters, and moreover a greater 
 density, than oxygen. If the molecular weight 
 of ordinary oxygen is represented by Oj, that of 
 ozone is probably 0,, ozone being thus a poly- 
 meride of oxygen. Sulphur in each of its states 
 of aggregation exhibits allotropio modifications, 
 and these to some extent correspond with each 
 other. In the solid state it is: (1) rhombic; 
 
 * It should not be forgotten that the data are most 
 meagre, — Ed. 
 
ALLOTEOPY. 
 
 v:u 
 
 D. = 2-07, melting-point 113" (Gernez), soluble 
 in CSj: (2) monoolinic ; D.= l-06, M.P. 117° 
 (Gernez), soluble in CSj : (3) amorphous plastic ; 
 D. = l-90 to 1-93, insoluble in CS.,: (4) according 
 to Gernez (0. B. 98, 144) and Sabatier (C. R. 100, 
 1 34G) crystallised in little rods with a lustre like 
 that of mother-of-pearl. The last modification 
 Maqueune (C. B. 100, 1499) considers to be dis- 
 torted rhombic crystals, which according to 
 Gernez are very easily produced out of the fourth 
 modification (0. B. 100, 1584) without being 
 identical with it. Liquid sulphur is : (1) imme- 
 diately above the melting-point thin and clear : 
 (2) at about 200° thick and dark : (3) at about 
 340° thin and dark. The vapour : (1) between 
 the boiling-point (446 ') and about 500° has 
 V.D. = 6-6, molecular weight = S„ : (2) above 700° 
 V.D. = 2-2, molecular weight = S... The behaviour 
 of seUnion is analogous to that of sulphur. 
 When solid this substance is : (1) red, amor- 
 phous, vitreous, or pulverulent, D. = 4'26, soluble 
 in OSj'. (2) red, crystallised, monoclinic, iso- 
 morphous with sulphur, D. = 4'51, soluble in 
 CSj ; (3) gray, granularly crystalline, D. = 4-80, 
 insoluble in CSj. Whether the black foliated 
 crystals, insoluble in CSj, D. = 4-80, obtained from 
 a solution of potassium selenide, are identical 
 with the third modification remains to be deter- 
 mined. Liquid selenion is: (1) at low tem- 
 peratures in a thin stratum light-red and 
 transparent : (2) at higher temperatures, dark. 
 Gaseous selenion under 1400° consists in part of 
 molecules composed of more than two atoms : 
 above 1400° all the molecules are diatomic, 
 V.D. = 5'G8, molecular weight Se^. Of tellurium 
 no allotropic form is known with certainty, yet 
 it is worthy of remark that its electrical con- 
 ductivity, like that of selenion, but contrary to 
 that of aU other conductors of the first class, 
 increases with rising temperature. This may be 
 explained by supposing the production of a modi- 
 fication with better conductivity. As regards the 
 nitrogen family, the existence of any allotropic 
 forms of nitrogen has not yet been conclusively 
 proved, but solid phosphorus exists in three 
 forms : (1) colourless, very easily burnt, soluble 
 in CS2 and in many oils, crystallising out of 
 these solutions according to the regular system, 
 D. = 1-83 : (2) red, amorphous, D. = 2-18 : (3) dark- 
 red crystallised in rhombohedral forms, in the 
 highest degree indifferent, D. = 2-34. The last 
 two forms perhaps represent one and the same 
 modification. In the liquid state there seems 
 to be only one modification — the colourless ; in 
 the gaseous state, on the contrary, there appear 
 to be two, since the vapour-pressure over colour- 
 less phosphorus is greater than that over red at 
 the same temperature, and the vapour condenses 
 under certain circumstances into the one modi- 
 fication and under other circumstances into the 
 other. Arsenic is: (1) amorphous, D. = 4'72, 
 less easily oxidised than the following variety : 
 (2) crystallised in rhombohedral forms, D. = 5-73. 
 Whether explosive antimony (Gore), D. = 5-83, is 
 a distinct modification cannot be quite definitely 
 determined, since it cannot be obtained free from 
 chloride. Por ordinary antimony D. = 6-71. Of 
 bismuth no allotropic modification is known. 
 
 In the carbon family carbon exists : (1) as 
 diamond, regular, very hard, D. = B-52: (2) as 
 graphite, either lihombohedral (Kenngott), or 
 
 Vnl.. I. 
 
 monoolinic (Clarke, NordenskiBld), D. = 2-38; 
 (3) amorphous charcoal, D. = 1-87 to 2-30, agree- 
 ing with graphite in many properties and hence 
 perhaps not to be regarded as a distinct modi- 
 fication. Silicon : (1) amorphous, easily oxi- 
 dised : (2) crystallised according to the regular 
 system, D. = 2-20 to 2-49. The so-called graphi- 
 toidal variety consists of distorted regular 
 crystals. Of titanium and thorium allotropic 
 forms are not known. Zirconium has been ob- 
 tained amorphous and crystallised. Tin also 
 appears to be dimorphous. 
 
 The element boron is probably capable of 
 allotropic modification, yet hitherto it has been 
 obtained pure only in the amorphous form. 
 The crystallised always contains aluminium or 
 carbon. Some of the platinum metals, namely 
 iridium and palladium are said to occur in two 
 forms, regular and hexagonal. 
 
 II. Allotuopt of Compounds, or Physical 
 IsoMEKiSM, may be theoretically defined as iso- 
 merism with Identity of atomic linkage. The 
 following inorganic compounds exhibit remark- 
 able instances of allotropy : calcium carbonate 
 (as oalc-spar and arragonite) ; silica (quartz, 
 tridymite, agate) ; titanium oxide (ru'tile, brookite, 
 auatase) ; the nitrates of sodiwn, potassium, am- 
 monium, and silver ; sodium metapJiosphate ; 
 arsenious and antimonious oxides ; the sulphates 
 of magnesium, iroti, and copper ; potassium di- 
 chromate ; silver iodide ; zinc chloride ; mercuric 
 chloride ; manganvus chloride ; and indeed many 
 other substances. Many instances of allotropy 
 have also been observed among the compounds 
 of carbon, particularly in the following sub- 
 stances : bemophenone \ isohydrohenzoin diace- 
 tate (Zincke) ; dibromopropionic acid (Tollens) f 
 tolylphenyl ketone (Van Dorp, Zincke) ; meta- 
 chloronitrobenzene; chlorodinitrobenzene (1:3:4)' 
 (Laubenheimer) ; oxycamplioronic acid (Zepha- 
 rowich) ; the benzoylated and anisylated hy- 
 droxylamines (Lessen) ; hydroguinone ; para- 
 nitrophenol ; stilbene chloride ; dibromofluorene 
 (Lehmann) ; tetramethyldiamido-triphenyl-meth-- 
 ane ; diphenylnaphthylmethane ; pentamethyl- 
 leukaniline (E. Fischer, Lehmann) ; dibenzoyU 
 diamidodibromodiphenyl (E. Lellmann). No 
 definite and regular relation between the compo- 
 sition of carbon compounds and the existence oi 
 allotropic forms of these compounds has as yet 
 been recognised. 
 
 The production of allotropic modifi- 
 cations, and the transformation of one 
 modification into another, are effected, as 
 a general rule, by changes of temperature. The 
 cases in which we are entirely ignorant of the 
 conditions under which allotropic modifications 
 are produced, are but few. The most notable is 
 that of one of the modifications of carbon — the 
 diamond, but on the other hand the transforma- 
 tion of diamond into graphite has been observed. 
 One of the allotropic states usually corresponds 
 to a specified interval of temperature, so that at 
 a definite limit of temperature the one modifica- 
 tion passes into the other. Yet we frequently 
 succeed in cooling the modification belonging to 
 the higher temperature below the lower limit, 
 and sometimes also in heating the other modi- 
 fication above this limit, without any transfor- 
 mation taking place. But when such a modifi- 
 cation is preserved above its fixed limit, tho 
 
 K 
 
180 
 
 ALLOTROPY- 
 
 state of equilibrium attained by its particles is 
 unstable, and is often destroyed by very trifling 
 ■causes, a particularly easy means of upsetting it 
 leing to bring the substance into contact with a 
 ■crystal of the modification that is stable at the 
 ;prevailing temperature. On transformation into 
 the stable form thereupon ensuing, heat is pro- 
 ■duced or disappears, according as contraction or 
 ■expansion takes place. This thermal effect may 
 ■be very considerable. 
 
 The temperature of transformation has been 
 •determined for rhombic and monoclinic sulphur 
 by L. Th. Beicher (Z. K. 1884. 8, 6) to be 95-6°. 
 Below this the rhombic form is stable, above it 
 the monoclinic, the other being unstable. The 
 amorphous form is unstable at all temperatures 
 below, and also for a considerable interval above, 
 the melting point ; the temperature at which it 
 becomes stable has not been determined, but 
 probably it lies not far below the boiling point. 
 When cooled quickly both the monoclinic and 
 the amorphous form may be kept a considerable 
 time at comparatively low temperatures. One 
 might be tempted to suppose that the modifica- 
 tions that have thus become unstable would pass 
 into the stable forms the more easily the greater 
 the distance of their temperature from that of 
 transformation ; yet below the temperature of 
 transformation this is not the case ; on the con- 
 trary, transformation into the rhombic modifi- 
 ■oation ensues the more easily the higher the 
 temperature and therefore the nearer it comes 
 to the temperature of transformation. This is 
 undoubtedly due to the circumstance that the 
 mobility of the particles increases as the tempe- 
 ■rature increases. The behaviour of selenion is 
 similar to that of sulphur. Amorphous selenion 
 is produced only above the melting point, which 
 is 217°, nevertheless when this variety is quickly 
 ■cooled it remains stable for some time, and 
 •begins to pass into the grey crystalline form only 
 at 80° (Hittorf) ; the progress of this change is 
 however more rapid at 125°. The temperature 
 of transformation of the red soluble crystals of 
 selenion is about 110° (Mitscherlich). 
 
 The conditions under which phosphorus 
 passes from one of its modifications into another 
 are very remarkable. If colourless phosphorus 
 is vaporised in a vessel too small to contain 
 the whole of the phosphorus as vapour, the red 
 variety is formed at 210° and upwards ; the 
 change proceeds more rapidly at 260°, and very 
 quickly above 300°. Conversely, red phosphorus, 
 if it can transform itself freely into vapour, and 
 if the vapour is allowed to cool, is re-converted 
 at 260° into the colourless form : the red modi- 
 fication is formed only if the vapour has been 
 heated above a red heat and then allowed to 
 cool (Hittorf). Arsenic vapour condenses below 
 220° to form amorphous arsenic ; at a higher 
 temperature to form crystallised. At 360° the 
 former passes into the latter with production of 
 Iheat. Tin is converted by very great cold, under 
 •conditionsnot yet exactly determined, into loosely 
 ■cohering columnar aggregations of grey colour 
 anddiminished density (Fritsohe, Petri, Schertel). 
 iLight too may bring about the production of 
 'aUotropic modifications ; through its influence 
 (Selenion and tellurium temporarily acquire a 
 ibetter electric conductivity — a fact which has 
 ibeen applied in telegraphy. Phosphorus be- 
 
 comes red through the action of light. Elee^ 
 tricity likewise may convert phosphorus, in 
 vacuo, into the red modification, but perhaps the 
 transformation may be due only to the heai 
 produced. 
 
 Among compound substances the phenome- 
 non of the transformation of one allotropio 
 modification into another has been observed by 
 many authors, but it has been studied with 
 special attention by 0. Lehmann {passim, and 
 in later papers in Z. K.) He has proved that 
 it obeys the same laws that hold for the ele- 
 ments. In most cases an unstable modification, 
 differing from the ordinary stable one, is ob- 
 tained by raising a substance to a high tempera- 
 ture and then cooling it quickly to a temperature 
 a long way below that of transformation. It is 
 supposed that in such circumstances the parti- 
 cles do not find time and opportunity to assume 
 the position of equilibrium corresponding to the 
 lower temperature. The unstable state thus 
 produced may be assumed alike by solid, melted, 
 and dissolved, substances, and may be main- 
 tained, especially at pretty low temperatures, for 
 a long time. In many cases, e.g., in that of 
 hydroquinone, the one modification (in this case 
 the unstable) is obtained by melting or sublim- 
 ing ; the other form is obtained from solutions. In 
 other cases, either form may be obtained from the 
 same melted body, or from the same solution, 
 according as it is brought into contact with a 
 crystal of the one form or of the other. If frag- 
 ments of crystals of both modifications are in- 
 troduced simultaneously, both of them at first 
 increase in size ; but as soon as the two crystal- 
 line masses come into contact the form that is 
 stable at the prevailing temperature grows into, 
 and at the expense of, the unstable, while the 
 latter dissolves or is consumed. As a general 
 rule the modification that is unstable at a low 
 temperature has a lower melting point than the 
 stable, so that many substances on being heated 
 are observed first to melt, then to solidify again, 
 with transformation into the other modification, 
 and finally to melt a second time. This pheno- 
 menon may be observed with special distinctness 
 in the case of dibenzoyldiamidodibromodiphenyl, 
 because here the melting points of the two forms 
 lie unusually far apart. The needles of this 
 substance crystallised out of alcohol melt at 
 195°, when quickly cooled the melted substanca 
 solidifies to a vitreous mass, which, when again 
 heated, melts at 99°, re-solidifies in a crystalline 
 form between 125° and 130°, and then melts 
 once more at 195° (Lellmann). 
 
 Many compounds, especially inorganic com- 
 pounds, behave like selenion; the form pro- 
 duced at high temperaturesmay remain stable far 
 below the temperature of transformation, and 
 may become unstable only on being heated to 
 the neighbourhood of the temperature of trans- 
 formation. Arragonite, the rhombic form of 
 calcium carbonate, which separates from hot 
 solutions (and according to G. Bose from very 
 dilute cold solutions also) is perfectly stable at 
 ordinary temperatures. If, however, a crystal is 
 heated, it breaks up, long before giving off car- 
 bon dioxide, into a mass of small crystals ol 
 calc-spar (Haidinger), thus passing over into 
 the rhombohedral form, which is produced at 
 lower temperatures. Eock-orystal and amorphous 
 
ALLOXANTIN. 
 
 131 
 
 silioft are perfectly stable at ordinary tempera- 
 tures, but at the temperatures of the poroelain- 
 kiln they are changed into tridymite, the third 
 modification, which in turn is likewise stable at 
 lower temperatures. As regards other substances, 
 particularly organic compounds, the forms to be 
 classed as unstable usually possess much less 
 stability, but still of course they are not alto- 
 gether destitute of it. This persistence in a state 
 Qo longer completely stable may be explained by 
 supposing that a certain impulse, or an increase 
 cf the proper motion of the particles, is required 
 to change the state — to make the particles leave 
 their respective positions and pass over into new 
 ones. That the change is attained most easily 
 and most surely by contact with a crystal of the 
 stable modification, is undoubtedly due to the 
 power of every crystal to give to the particles 
 settling on it a definite and regular orientation 
 and arrangement. L. M. 
 
 ALLOXAN C,H.,NjO^ aq (and 4aq.) 
 
 i.B. CO<;^g^Q>CO. Mesoxalyl-urea. Mol. 
 
 w. 142. — Discovered in 1817 by Brugnatelli, who 
 named it erythric acid. Subsequently examined 
 by Liebig a. Wohler (A. 26, 256), and by 
 Schlieper (A. 35, 253). 
 
 Fcn-mation. — 1. By oxidation of uric acid by 
 HNOg (S.G. 1-42) diluted with water (9 pts.) at 
 70°. By adding SnCl^, alloxantin is ppd., and, 
 after washing, is re-oxidised to alloxan by nitric 
 acid (2 pts. of S.G. 1-52 mixed with 1 pt. of 
 S.G. 1-42) in the cold (Liebig, A. 147, 366, Bl. 
 [2] 9, 152). — 2. From uric acid and aqueous Br, 
 01, or I (M.E. Hardy, Bl. [2] 1, 445).— 3. From 
 xanthine, KCIO3, and HCl (E. Fischer, A. 215, 
 310). 
 
 Properties.— A. warm saturated aqueous solu- 
 tion deposits on cooling trimetric efflorescent 
 crystals (with 4aq). If the solution is kept 
 warm while evaporating monoclinic prisms (with 
 aq) are got. V. sol. water or alcohol, ppd. from 
 solution by HNO3. Astringent taste, reddens 
 litmus, does not decompose CaCO,. Aqueous 
 solution turns the skin purple, imparting a pecu- 
 liar smell. 
 
 BeacUons. — 1. Hot dilute nitric acid forms 
 COj and parabanic acid, the latter then becoming 
 CO2 and urea. — 2. Boiling potash forms mes- 
 oxalic acid and urea.- 3. Boiling very dilute 
 sulphuric acid forms ammonic hydurilate. — 4. 
 Boiling aqueous HCl or H2SO4 forms alloxantin, 
 which separates ; dialuric acid, ammonic oxalate 
 etc., remain in solution. — 5. Boiled a long time 
 with water, it forms CO2, parabanic acid, and 
 alloxantin. — 6. By reducing agents (H^S, SnClj, 
 Zn and HCl) it is converted into alloxantin, and 
 finally into dialuric acid. — 7. Boiled with 
 ammonia and sulphurous acid, it forms ammonic 
 thionurate {q. v.). —8. KHO or baryta converts it 
 into alloxanic acid ; baryta or lime-water giving 
 white pps. of baric or calcic alloxanate. If the 
 alkali be in excess, the pp. contains mesoxalate. 
 9. Warm aqueous ammonia forms a yellow 
 jelly of the ammonium salt of ' mycomelic acid ' 
 C^HjNjOz (L. a,. W.). — 10. Ferrous sulphate gives 
 a deep blue colour. — 11. Boiled with water and 
 PbOa there results COj, PbCOs, and urea. — 12. 
 Boiling aqueous lead acetate forms lead mes- 
 oxalate and urea.— 13. Boiling aqueous NaNO, 
 and acetic acid form sodio oxalurate (Gibbs, 
 
 Am,. S. [2] 48, 215). — 14. Hydroxylamine hydro- 
 chloride forms violuric acid. — 15. With a dilute 
 solution of pyrrol it forms crystalline pyrrol, 
 alloxan (Ciamician a. Silber, B. 19, 106, 1708).— 
 16. PCI5 mixed with POCI3 at 130° forms tetra- 
 chloro-pyrimidine (Ciamician a. Maguaghi, B. 18, 
 3444). 
 
 Metallic derivatives. — C^Ag^N^Oj. — 
 OjHjN^OjHgO 7aq : ppd. by mercuric nitrate.— 
 
 Compounds with Bisulphites. — 
 CjH^N^OjNaHSOjlJaq: large crystals, v. sol. 
 water. — C^H^N^OjEHSOa aq : m. sol. cold water, 
 V. sol. hot water.— C,H.,N204NH4HSOs (Lim- 
 pricht a. Wuth, A. 108, 41). 
 
 ALLOXANIC ACID C^H.N^O, 
 i.e. NH,,.CO.NH.CO.CO.CO,H. Mesoxaloxyl-urea. 
 S. (alcohol) about 20. (Liebig a. Wohler, A. 26, 
 292 ; Schlieper, A. 55, 263 ; 56, 1 ; Stadeler, A. 
 97, 122 ; Baeyer, A. 119, 126 ; 130, 159). Formed 
 from alloxan by treatment with aqueous fixed 
 alkalis or alkaline carbonates. White needles or 
 warty masses. V. sol. water ; si. sol. ether. 
 
 Reactions. — 1. Boiling the aqueous solution 
 produces CO2, leucoturic acid (q. v.), allanturio 
 acid and hydantoin. — 2. AUoxanates are con- 
 verted by boiling water into mesoxalates and 
 urea.— 3. Nitric acid forms CO2 and parabanic 
 acid. — 4. HI reduces it to hydantoin, giving off 
 CO2 (Baeyer). 
 
 Salts. The alkaline alloxanates are soluble 
 in water. The normal salts of other metals 
 are usually insoluble. Ferrous sulphate 
 gives a dark blue pp. with potassic alloxanate. 
 NHiCjHjNjOs. S. about 30.— BaH^A''^ 2aq.— 
 BaA"4aq. — CaH2A"2 6aq. S. 5.— CaA"5aq. — 
 CuA"4aq. S. 17 to 20. — CuA"Cu(0H)2. — 
 PbH2A"2 2aq. — Pb3H2A",7aq. — PbA"aq. — 
 Pb3A"2(OH).,.— MgA" 5aq.— NiA" 2aq. — KHA".— 
 K2A"3aq. — Ag,A".— SrA"4aq.— ZnH2A"24aq.— 
 Zn30A"2 8aq. 
 
 Iso-allozanic acid C^^fiy Obtained by the 
 action of alkalis upon the red substance got by 
 heating alloxan at 260° (L. Hardy, A. Gh. [4] 
 2, 372). A similar body may be got by the 
 action of bromine-water on uric acid (Magnier 
 de la Source, Bl. [2] 22, 56). Its solution then 
 gives with baryta-water a splendid violet pp. of 
 baric iso-alloxanate, which, however, when 
 exposed to moist air soon changes to colourless 
 baric alloxanate. 
 
 Salts. — (NHJjA" : red powder : v. sol. water 
 forming a purple solution, which gives with 
 AgN03 an indigo blue pp., and with KjOOj a 
 violet colour. 
 
 ALLOXANTIN CsH^N^O, 3aq. 
 (Liebig a. Wohler, A. 26, 262 ; Fritzsche, J. pr. 
 14, 237). 
 
 Formation. — 1. By action of warm dilute 
 HNO3 on uric acid. — 2. By action of electrolysis 
 or of reducing agents on alloxan (q. v.). — 3. By 
 dissolving alloxan in a concentrated aqueous 
 solution of dialuric acid : OjHjNjO, + CjHjNjOj = 
 CsHjNjO, 4- HjO. — 4. By heating uranil or am- 
 monium thionurate with dilute H^SO,. — 5. By 
 action of air on dialuric acid. — 6. In the deoom. 
 position of caffeine by chlorine. — 7. By heating 
 a mixture of malonio acid and urea with excess 
 of POCI3 (Grimaux, C. B. 87, 752 ; 88, 85).— 8. 
 By the prolonged action of HjS upon di-bromo- 
 barbituric acid (G.). 
 
 Properties. — Small oblique rhombic prisma. 
 
133 
 
 ALLOXANTTN. 
 
 ReddenB litmus. V. si. sol. cold water. Gives 
 with baryta- water a violet pp. Eeduces AgNOj. 
 
 Reactions. — 1. At 170° gives hydurilic acid, 
 oxalic acid, COj, CO, and NHj.— 2. Oxidation 
 gives alloxan. — 3. Bedziction forms dialurio 
 acid. — 4. Ammonia gas turns it red, forming 
 murexide. — 5. Aqueous ammonia forms a purple 
 solution, long boiling bleaches it, uranil being 
 formed. This is then converted into murexide 
 by atmospheric oxidation. — 6. The purple pp. 
 produced by baryta-water disappears on boiling, 
 baric alloxanate and dialurate being formed. 
 
 ALLOYS. — The word alloy was originally 
 employed to designate the product obtained by 
 mixing gold or silver with other metals ; its ap- 
 plication is now general, all mixtures or com- 
 pounds of metals with each other being named 
 alloys, except those containing mercury, which 
 are termed ' amalgams.' For a detailed descrip- 
 tion of special alloys, reference must be made 
 to one of the constituent metals ; only the 
 general properties of the alloys will be here 
 considered. 
 
 On melting two metals together, or on melt- 
 ing one and adding the other, complete assimi- 
 lation takes place in some cases and not in 
 others. Thus, silver easily mixes or alloys with 
 gold, copper, or lead ; but neither silver nor 
 copper can be readily induced to unite with 
 iron. In the cases of those metals which do not 
 completely mix when melted together it usually 
 happens that a small quantity of one is taken 
 up by the other ; thus, Faraday and Stodart 
 found that iron is able to absorb ^Jpth of its 
 .weight of silver with production of a homogeneous 
 alloy, the properties of which are considerably dif- 
 ferent from those of iron ; but that if more silver 
 than 5 Jjth of the mass of the iron is present, the 
 greater part of the silver separates during cooling, 
 and that which remains can be detected by the 
 microscope. If silver is melted with addition of 
 a small quantity of iron, the latter metal alloys 
 to some extent; but it is impossible to obtain 
 mixtures of these metals in any desired propor- 
 tion. On the other hand, silver and copper, or 
 silver and gold, form alloys in which the propor- 
 tion of the two metals may be varied at will. 
 
 The physical properties of alloys are in some 
 cases nearly the mean of those of their con- 
 stituent metals ; but in other cases a wide 
 difference is observable between the properties 
 of the alloy and the properties of the metals 
 which have been used to form it. Matthiessen, 
 to whom we owe most of our knowledge of the 
 properties of alloys, divides all metals into two 
 classes : (1) those which impart to an alloy their 
 own physical properties, to a less or greater degree, 
 according to the proportion in which they them- 
 selves exist in the alloy ; and (2) those which do 
 not come under class (1). To the first class 
 belong the metals lead, tin, zinc, and cadmium ; 
 and to the second, in all probability, the other 
 metals. The alloys themselves may also be 
 divided into three groups : (a) those made of the 
 metals belonging to class (1), (6) those made of 
 metals of class (1) with class (2) ; and (c) those 
 made of class (2) with one another. This classi- 
 fication IS largely based on the relative conduc- 
 tivity for electricity of the metals and of the 
 alloys _ which they form with each other. 
 Matthiessen found that the metals placed in 
 
 class (1), when alloyed with each other, givb 
 products the conducting powers of which for 
 heat and for electricity are proportional to the 
 relative quantities by volume of the constituent 
 metals ; but that this is not the case with alloys 
 of the metals of class (1) with those of class (2), 
 nor with the alloys of metals of class (2) with 
 each other. As regards conductivity for heat 
 and for electricity, Wiedemann and Franz have 
 added to our knowledge by showing that the 
 conducting powers of metals and their alloys for 
 heat vary in a similar manner to that in which 
 their conductivity for electricity varies. This 
 statement has been confirmed and amplified by 
 Sundall. 
 
 Matthiessen regards alloys of the metals of 
 class (1) as solidified solutions of one metal in 
 the other ; but supposes that metals of class (2) 
 enter into alloys in an allotropic form ; and he 
 further supposes that when metals are alloyed 
 together one or more of the metals may undergo 
 allotropic change. Thus, he regards as solidified 
 solutions of the metals, alloys of lead with tin, 
 cadmium vrith tin, zinc with tin, cadmium with 
 lead, zinc with cadmium, and zinc with lead. 
 He supposes that in the alloys of lead or tin 
 with bismuth, tin or zinc with copper or with 
 silver, one metal is dissolved in an allotropic 
 modification of the other ; and that in alloys of 
 bismuth with gold or silver, palladium or plati- 
 num with silver, or of gold with copper or 
 silver, both metals exist in allotropic forms. 
 Matthiessen does not, however, ignore the fact 
 that certain alloys contain their constituent 
 metals in simple atomic proportions ; for ex- 
 ample, the alloys whose composition may be 
 expressed by the formules AuSnj, AuSuj, and 
 AuSn; but he regards aUoys of intermediate 
 composition as solidified solutions of such de- 
 finite compounds in each other. It is known 
 that zinc wiU not aUoy with more than 1-2 p.c. of 
 lead, nor will lead alloy with more than 1-6 p.c. 
 of zinc; yet, by stirring, it is possible to ob- 
 tain mechanical mixtures of such alloys with 
 excess of one or other metal. Such mixtures 
 are placed by Matthiessen in a class by them- 
 selves. Most of the alloys of silver and copper 
 with each other are regarded by him as mixtures 
 of various soUdified solutions. The hypothesis 
 of the existence in an alloy of one of the con- 
 stituent metals in an allotropic form has re- 
 ceived a certain degree of confirmation from 
 experiments by Deville and Debray, who have 
 observed that the iridium separated by the action 
 of an acid on an alloy of that metal with zino 
 explodes when heated to 300°, and is changed by 
 the explosion into ordinary iridium. Wiedemann 
 has suggested that the contraction of alloys after 
 solidification, which sometimes goes on for days, 
 is due to the gradual occurrence of an aUotropio 
 change in the constituent metals, one modifica- 
 tion Ijeing stable at high, and the other at low, 
 temperatures. If the hypothesis of the occurrence 
 of allotropic change during the formation of cer- 
 tain alloys is tenable, it is remarkable that such 
 allotropic modifications of metals should be pro- 
 ducible by pressure; for Spring has succeeded 
 in producing Wood's alloy (containing bismuth, 
 cadmium, and tin), and also brass, but the latter 
 only partially, by exposing mixtures of the metal« 
 in fine powder to very high pressures. 
 
UJ-ALLYJ^-ACETIO ACID. 
 
 183 
 
 On the whole, there appears to be a marked 
 analogy between alloys and solutions. It is well 
 known that the conductivity of water for elec- 
 tricity is nearly nil, but becomes considerable 
 when the minutest trace of any salt is dissolved 
 in it. Similarly, the conductivity of copper is 
 greatly diminished by the admixture with it of 
 minute quantities of other metals. Moreover, 
 in many other cases a great modification is pro- 
 duced in the tenacity, malleability, &c.,of metals 
 by very small additions of foreign substances ; 
 as, for example, by the addition of small quan- 
 tities of carbon, silicon, sulphur, or phosphorus, 
 to iron, of phosphorus to copper, or of mag- 
 nesium to nickel. And just as an aqueous 
 solution of a salt must be heated to a tempera- 
 ture higher than that of the boiling-point of 
 water before the whole of the water is removed, 
 so it has been found that alloys of zinc, sodium, 
 mercury, &c., must be heated to temperatures 
 above those at which these metals volatilise 
 before the metals in question are entirely re- 
 moved from the alloys. The analogy between 
 alloys and solutions has been strikingly shown 
 by Guthrie. This physicist has found that that 
 alloy of two metals which has the lowest melting- 
 point does not contain the metals in atomic pro- 
 portion, but is strikingly similar to an ' alloy ' 
 of two salts, such as that of nitrate of potassium 
 and nitrate of lead. Alloys were obtained by 
 him of bismuth and zinc (Bi = 92-8.5 p.o. 
 Zn = 7'15 p.c), melting at 248° ; of bismuth and 
 tin (Bi = 46'l p.c. Su = 53'9 p.c), melting at 
 133°; of bismuth and lead (Bi = 55-58 p.o. 
 Pb = 44-42 p.o.) , melting at 122-7° ; and of bismuth 
 and cadmium (Hi = 59-19 p.o. Cd = 40-81 p.c), 
 melting at 144°. None of these alloys contains 
 the metals in the proportion of their atomic 
 weights, and the melting-point of each alloy is 
 the lowest of aU possible alloys of the specified 
 pair of metals. Such alloys are termed by 
 Guthrie eutectic alloys ; they appear to be in 
 some sense solidified solutions, resembling cryo- 
 hydrates. We are stiU ignorant of the true 
 nature of such mixtures, if mixtures they be. 
 
 Spring {B. 15, 595) has prepared several 
 alloys by sutpjeoting mixtures of the constituent 
 metals to pressures of about 7,000 atmos. In 
 this way he obtained brass, Wood's alloy (Bi, 
 Cd, and Sn), and Rose's alloy (Bi, Pb, and Sn). 
 
 References. — Matthiessen, B. A. 1863, 37 ; 
 and 0. /. Trans. 1867, 201 ; also P. B. I. March 
 20th, 1868. Deville and Debray, O. B. 94, 1557. 
 Spring, B. 15, 595. Wiedemann, W. 3, 237-250. 
 Crookewit, A. 68, 290. Furstenbaoh, Bayerisches 
 Industrie- und Qewerhehlatt, 1869. Sundall, 
 A. Ch. 149, 144. Crace-Calvert a. Johnson, A. 
 Cli. 45, 454. Guthrie, P. M. June, 1884. 
 
 W.E. 
 
 ALLTJEANIC ACID C.H^N^Oj (?). Formed 
 by evaporating an aqueous solution of equiva- 
 lent quantities of urea and alloxan (Mulder, B. 
 6,1012). Crystals ; si. sol. water. AgA'2aq. 
 
 ALLYL The radicle CH2:CH.CH2 is called 
 
 Allyl, the isomeric radicle CHj.CHiCH being 
 termed Propenyl. 
 DI-ALLYLO,H,„i.e.OHj:CH.OH,.CHj.CH;CH,. 
 
 Bexinene. Mol. w. 82. (59-3°) at 769 mm. 
 (B. Schiff, A. 220, 91) ; (59-5°) (Zander, A. 214, 
 148), S.G. '-^ -6983 ; J -7074 (Z.) ; f -688 (Briihl). 
 
 C.E. (0°-10°) -00138; (ll-9°-59-3°) 00156. 
 S.V. 125-8 (S.) ; 125-7 (Z.). V.D. 2-84 (for 2-84). 
 H.F.p. - 9260, H.F.v. - 11580 (Thomsen). 
 u^ 1-4079. Eoo 45-99 (B.). Critical temperature 
 234-4°- 
 
 B'ormation. — 1. Prom allyl iodide and Na 
 (Berthelot a. de Luca, A. 100, 361), an alloy of 
 sodium and tin (Wiirtz a. Leolanoh^, A. Ch. [4] 
 3, 15.5), or iron (Linnemann, BI. [2] 7, 424). — 
 2. By heating mercury allyl iodide, IHgCaH^. 
 alone (Linnemann, A. 140, 180) or with aqueous 
 ECy (Oppenheim, B. 4, 672). 
 
 Reactions. — 1. Oxidised by chromic acid 
 mixture gives carbonic and acetic acids. — 2. 
 Oxidised by KMnO, in neutral solution gives 
 CO2, acetic, oxalic, and succinic acids. — 3. 
 Oxidised by KMnO^ in acid solution gives CO2, 
 acetic acid, and succinic acid (E. Sorokin, J. pr. 
 131, 1). 
 
 Constitution. — The formation of acetic acid 
 by oxidation of di-allyl seems to favour the 
 formula CH3.CH:CH.CH:CH.0H3 ; while the for- 
 mation of succinic acid is more in accordance 
 with the formula GHj-.CH.CHj.CHj.CHiCHj, a 
 formula that is further supported by the con- 
 version of di-allyl into di-propargyl. The oxalic 
 acid may be supposed to be formed by oxidation 
 of the succinic acid. Acetic acid may be con- 
 sidered to be formed from intermediate hydrates, 
 CH3 CH(OH).CH2.CH2.CH:CH3 
 
 andCH3.GH(OH),CH2.CH2.CH(OH).CH3. 
 These bodies do, in fact, yield acetic acid when 
 oxidised. According to Sabaneeff {J. R. 1885, 
 35) di-allyl forms two tetrabromides and must 
 therefore be a mixture of two hydrocarbons. 
 
 Combinations. — 1. When gaseous HIispassed 
 into strongly cooled di-allyl, combination takes 
 place, the product CH3.CHI,CH2.CH2.CHI.CH3 
 being formed, v. Iodo-hexanes. — 2. A smaller 
 quantity of HI forms the mono-hydro-iodide, 
 CjHijHI, (165°), also formed from preceding by 
 alcoholic EOH(«.Iodo-bexylene).— 3. Similarly, 
 fuming HCl forms two hydrochlorides. — 4. 
 HOCl forms C,H,„(H0C1)2, di-chloro-di-oxy- 
 hexane (g. v.). — 5. Br forms tetra-bromo-hexane. 
 
 ALLYL ACETATE C5H3O2 i.e. 0,B.fi.,B^O,. 
 M0I.W. 100. (103°-103-5°) at 735 mm.(E. Schiff, 
 A. 220, 109), S.G. f -9276 (Bruhl). S.Y. 121-87 
 (S.). Mpl-il06. Boo 42-21 (B.j. 
 ■ ALLYL-ACETIC ACID 
 
 C^H^O^ i.e. CH2:CH.CH2.CH2.C02H. Fetitenoie 
 acid. (185°_188° cor.). S.G. l| -9866; if 
 -9842 ; 5-i -9767. M.M. 6-426 at 14° (Perkin, 
 C. J. 49, 211). Prepared by heating allyl- 
 malonic acid (Conrad a. Bischoff, B. 13, 598) or 
 from allyl-aceto-acetic ether (Zeidler, B. 8, 1035). 
 Combines with Br^ or HBr. Not reduced by 
 sodium-amalgam. Oxidised by chromic acid 
 to succinic and formic acids. 
 
 S alts. — KA' : scales ; v. sol. water ; solution 
 not ppd. by Fe^CIj.— CaA'^ 2aq. : laminas.— 
 BaA'„ 2aq.— AgA' (Messersohmidt, A. 208, 92). 
 
 E t h e r.— Et A' : (142°-144°) . 
 
 DI-ALLYL-ACETIC ACID CsHi.O^ i.e. 
 (C3H,)..CH.C02H. Octinoicacid. (220°) (0. a. B.); 
 (218-'-222°) (H.) ; (224°-226°) (R.) ; (227° cor.). 
 S.G. II -9576 ; 15 -9555 ; || -9491. M.M. 10-344 
 at 16-4° (Perkin, C. J. 49, 212). 
 
 Formation.— Fiom di-allyl-aceto-aoetio ether 
 (Wolff, A. 201, 49 ; Eeboul, BI. [2] 29, 228) or 
 from di-allyl-malonio acid (Conrad a. BisohofE, 
 
134 
 
 DI-ALLYL-ACETIO ACID. 
 
 B. 13, 598). Prom iodo-di-allyl-acetic aoid 
 (2. V.) by reduction (Sehatzky, J. B. 17, 79). 
 
 Properties. — Oil, of disagreeable odour. 
 Insol. water. Volatile with steam. 
 
 BeacHons. — 1. Cone. HBr forms, probably, 
 an addition product (CH3.CHBr.GHj2CH.CO,H 
 which instantly splits o£E HBr forming 
 
 ,CH2.CH.CH3 
 CH3.0HBr.CH2.CH< | 
 
 \co.o 
 
 V. Bbomo-oxt-ootoic aoid (Hjelt, A. 216, 73). — 
 2. Br in CHCI3 forms, probably, an addition 
 compound, (CHjBr.CHBr.CHJjCH.CO.H, but 
 this instantly splits up into HBr and a lactone 
 
 ,CH2.CH.CH2Br 
 
 OH3r.CHBr.CH2.CH/ 
 
 \co.o 
 
 V. TH-BROMO-OXY-OOTOIO ACID. 
 
 —3. HNO3 (S.G 1-3) forms tri-carballylio acid 
 (W.). 
 
 Salts.— CaA'j2aq:leaiiets.— AgA'. S. -41 at 
 15°. Ether .— Et A' (195°) (B.) . 
 
 ALLYL-ACETO-ACETIC ETHES v. pp. 23, 25. 
 
 ALLYL-ACETONE 
 C^H.oO i.e. OH2:CH.OH2.0H2.CO.CH, 
 
 Methyl butenyl heUme. (129°). S.G. ,^5 -SSi. 
 From allyl-aceto-acetic ether (Zeidler, A. 187, 35). 
 Unpleasant smell. Forms with NaHSOj an 
 amorphous compound, C|jH|„0 2NaHS03 (0. 
 Hofmann, A. 201, 81). Eeduced by sodium- 
 umalgam to hexenyl alcohol (j. v.). 
 
 DI-ALLYL-ACETONE 
 
 C„H,.0 i.e. (03H,),CH.CO.CH3. (175°). 
 
 From di-allyl-aoeto-aoetic ether (Wolff, A. 
 201, 47). 
 
 ALLYL-ACETOPHENONE d.Phenyij butenti. 
 
 KETONE. 
 
 ALLYL-ACETOXIM 
 
 0„H„ON i.e. C3H,.CHj.C(N.OH).CH3 
 (188°corr.). Formed by the action of hydroxyla- 
 mine on allyl-acetone. Liquid. Soluble in alcohol, 
 ether, benzene, CS2, ligroine, acids, and alkalis. 
 By aqueous acids it is resolved into its consti- 
 tuents. It combines with bromine to form a 
 di-bromide (Nageli, B. 16, 496). 
 
 ALLYL ALCOHOL 
 C,B.S> i.e. CH,:OH.CH,OH. [-50°]. (96-6°). 
 S.G. g -8706 Sil^j -8576. S.V. 74-19. C.E. (0°-20°) 
 •00104 (Thorpe, G. J. 37, 208). S.H. -6569 
 (Eeis, P. [2] 13, 447). H.F.p. 31,200. 
 
 H.F.V. 29,750. Eoo 27-09 (Bruhl, A. 200, 175). 
 
 Occurrence. — Crude wood spirit contains not 
 more than one-fifth per cent. (Aronheim, B. 
 7, 1381 ; Grodzki a. Kramer, B. 7, 1492). 
 
 Formation. — 1. Dry gaseous ammonia is 
 passed into oxalate of allyl till a solid mass of 
 oxamide, saturated with allyl alcohol, is 
 obtained. The latter is then distilled off 
 (Zinin, A. 96, 362).— 2. Produced, together with 
 isopropyl alcohol and acropinacone (j. v.), 
 when acrolein is treated with zinc and hydro- 
 chloric acid (Linnemann, A. Suppl. 3, 257). — 
 3. By the action of sodium on dichlorhydrin 
 (Hubner a. Miiller, Z. 6, 344). — 4. The two 
 atoms of chlorine may also be removed from 
 dichlorhydrin by sodium-amalgam (Lourenijo, 
 A. Ch. [3] 67, 323), or by copper and potassio 
 iodide (Swarts, Z. 1868, 259).— 5. Allyl iodide 
 (1 pt.) is heated with water (20 pts.) for 60 
 
 hours in a soda-water bottle at 100°. Thi 
 yield is excellent (Niederist, A. 196, 350). 
 
 Preparation.— Qlyoer'me (400 pts.) is slowly 
 distilled with crystallised cxalic acid (100 pts.) 
 and a little ammonic chloride (1 pt.), to con- 
 vert any potassic oxalate into chloride. Tha 
 receiver is changed at 190°, and the distilla- 
 tion continued up to 260°. The distillate, 
 containing aqueous allyl alcohol, allyl formate, 
 acrolein, and glycerin, is rectified, dried, first 
 with KjCOs, then over solid potash, and dis- 
 tilled. It then boils at 90°, but when the last 
 traces of water are removed by quicklime, it 
 boils at 96°. The yield is one-fifth of the 
 weight of oxalic acid used (ToUens a. Hen- 
 ninger, Bl. [2] 9, 394; Briihl, A. 200, 174; 
 Linnemann, B. 7, 854). 
 
 Theory of the Process. — Carbonic acid is 
 first evolved freely (at 130°), but formic acid 
 which must be produced at the same time 
 (H20.20i= OOj-H H2CO2) reacts upon glycerin, 
 producing monoformiu : C3H,(0H)s -i- H^COj 
 = H.fl + CJl,{OB.UOCBO). The monoformin 
 can be extracted with ether, and boils about 
 165° in vacuo. When distilled, monoformin ' 
 splits up into allyl alcohol and carbonic acid : 
 
 C3H,(OH)3(OCHO) = CO2 -I- H2O + 03H,(0H) 
 (ToUens, A. 156, 140). When a large quantity 
 of oxalic acid is used, the excess of formic acid 
 does not produce diformin, but comes off as 
 formic acid {q. v.). 
 
 Properties. —A pungent liquid, with a burning 
 taste. It mixes with water, alcohol, and ether. 
 
 Constitution That allyl alcohol has the for- 
 mula OH2:CH.OH20H and not CHj.OHiCH.OH 
 may be inferred from the fact that it yields 
 no acetic acid when oxidised by nitric acid. 
 A similar remark applies to allyl iodide (Kekul6 
 a. Einne, B. 6, 386). 
 
 Beactions. — 1. Chromic acid oxidises it to 
 CO2 and formic acid ; no acrylic acid is formed, 
 but a pungent odour, which may be due to 
 acrolein, is observed (Hofmann a. Cahours, A. 
 100, 257 ; Einne a. ToUens, A. 159, 110).— 2. 
 When allyl alcohol is heated, with inverted con- 
 denser, for 5 hours in a water-bath with zinc 
 and dilute H^SOj, about 16 p.o. is reduced 
 to TC-propyl alcohol: CH2:CH.0H20H 4- H^ = 
 CH3.CH2.OH.OH (Linnemann, B. 7, 862).— 8. 
 Solid potash' &t 100°-150°, in a flask with in- 
 verted condenser, forms n.-propyl alcohol (by 
 reduction), formic acid (by oxidation), ethyl 
 alcohol, hydrogen, and other products (ToUens, 
 A. 159, 92). — 4. Potassium displaces hydrogen, 
 forming gelatinous potassic allylate. — 5. H^SO, 
 forms (03H5)HSO,.-6. Dilute H^SO, or HCl at 
 100° forms an aldehyde, Gfi^fi (c. 137°) (Solo- 
 nina, J. B. 1885, i. 145). 
 
 Combinations. — 1. With chlorine it forma 
 M-dichlorhydrin OH^Cl.CHCl.OH^OH (g. v.) — 
 
 2. With bromine it forms a dibromide, called 
 also dibromhydrin, OH^Br.CHBr.OHjOH, (214°). 
 60 grms. Br are dissolved in 300 grms. CSj and 
 dropped slowly (in 4 hours) into a solution of 
 20 grms. of aUyl alcohol in 100 grms. of CSj. 
 The product is distilled in vacuo (Michael a. 
 Norton, Am. 2, 16 ; compare KekuU, A. Suppl. 
 1, 138; Markownikoff, J. 1864, 490). Linne- 
 mann says there are two bromides (B. 7, 859).— 
 
 3. When iodine is added to a solution of allyl 
 alcohol in CHOI,, it combines, and on evapora- 
 
Al.LXL. UARBAMINE. 
 
 135 
 
 Una OH2I.CHI.CH2OH separates as needles. 
 Dilute Na^COj converts this into iodallyl alcohol 
 1160'] (Hubner a. Lellmann, B. 14, 207).— 4. ICl 
 unites, forming OsHsIC^OH) (Henry, B. 3, 
 351). -5. With cyanogen it unites, forming 
 CsH,(CN),(OH), (151°) (ToUens, B. 5, 1045).— 0. 
 BaO combines, forming BaO,2C3H^O.— 7. HCIO 
 unites, forming a little chlorhydrin {q. v.). — 8. 
 Chloral combines with allyl alcohol ; the com- 
 pound, CCl3.CH(OH)(OC3H5) [20-5°], (116°), is 
 analogous to chloral alooholate (Oglialoro, O. 
 4, 463). 
 
 DI-ALLYL-p-AMIDO-BENZOIC ACID 
 C.aH.jNOj i.e. (C3H,),N.C„H^.C0jH [127°]. From 
 allyl iodide and potassic ^-amido-benzoate 
 (Michael a. Wing, Am. 7, 198). 
 
 Di-allyl-m-amido-benzoic acid [90°] (Griess, 
 B. 5, 1041).-HA'HC1 aq. 
 
 DI-ALLYL-AMIDO-ETHYL ALCOHOL v. 
 
 OXYETHYL-DI-ALLYLAMINE. 
 
 ALLYLAMINE CjHjN i.e. CU^\OB..CR^.^B.^ 
 Mol. w. 57. (56°) (E. Schiff, B. 19, 565) ; (58°) 
 (Oeser, A. 134, 7). S.G. ia .864 (0.) S.V. 78-38 
 (S.). H.F.p.-1140. H.F.V.-2880. 
 
 Formation. — 1. From ally] cyanate (Cahours 
 a. Hofmann, A. 102, 301).— 2. From oil of 
 mustard, Zn, and HCl (0.). — 8. From oil of 
 mustard and cone. HjSO, (Hofmann, B. 1, 182 j 
 Einne, A. 168, 262). 
 
 Properties. — Liquid with pungent ammoniaoal 
 odour. Misoible with water. Strong base. 
 Dissolves ppd. Cu(0H)2 and Ag.^0. 
 
 Beactions. — 1. Combines with bromine. — 2. 
 H^SOj at 140° forms a compound which, on 
 pouring into water, produces oxy-propyl-amine 
 HO.C3Hj.NH2. 
 
 Salts.— (B'HCl)^tCl4 : monoclinio tables. 
 Changed by boihng into (B'HClj^PtClj (Lieber- 
 mann a. Paal, B. 16, 530). — B'^ H2S04(Andreasch, 
 M. 5, 33). 
 
 Di-allyl-amine C„H„N i.e. (CjHJ^NH 
 (111°) (Ladenburg, B. 14, 1879). 
 
 Tri-allyl-amine CaHuN i.e. (C3H5)3N. 
 (156° i.V.) S.G. § -8206. S.V. 200-3 (Zander). 
 C.E. (0°-10°) -00103. Formed when tetra- 
 allyl-ammonium hydroxide is distilled (C. a. H. ; 
 Pinner, B. 12, 2054 ; Grosheintz, Bl. 31, 391).— 
 B'HCl.— B',H.,PtCle. 
 
 Tetra-allyl-ammoniam hydrate (CjHJ^NOH : 
 liquid. — ((C3H3)jNCl)jPtClj. — (CsH_)^NBr. — 
 (C3H5)4NI. The three last are crystalline 
 (C. a. H.). 
 
 ALLYL-AMYL-AMINE CaH„N i.e. 
 (C3H,)(C,H„)NH. (c. 150°). S.G. Ji -777. 
 From amyl bromide and allyl-amine (Lieber- 
 mann a. Paal, B. 16, 531). 
 
 ALLYL AMYL OXIDE C,H,„0 i.e. C,H, ..O.CjHj 
 (120°) (Berthelot a. de Luca, A. Ch. [3] 48, 292). 
 
 ALLYL-ANILINE 0„H„N i.e. PhN(C3H,,)H. 
 (209°). S.G. 25 -982 (Sohiff, A. Suppl. 3, 364). 
 
 Di-allyl-aniline C.jH^N i.e. PhN(C3HJ,. 
 (244°). S.G. § -9680. S.V. 225-2 (Zander, A. 
 214, 149). C. B. (0°-10°) -00083. 
 
 ALLYL-BENZENECsH,„i.e.Ph.CH:CH.CH3(?) 
 Phenyl-propylene. Propenyl-benzene. Mol. w. 
 118. (175°) (P.) ; (178°) (E.). S.G. 3^ -92. 
 
 Formation. — 1. By-product in action of 
 sodium-amalgam on warm aqueous cinnamyl 
 alcohol (Fittig a.Kriigener,B.6,214; Eiigheimer, 
 A. 172, 129). — 2. From propyl-benzene by Br at 
 160° and distilling the product (Eadziszewski, 
 
 C. B. 78, 1153): PhC3H„Br = PhC,n, + HBr. 
 So prepared it boils at (165°), audits di-bromide 
 forms needles. — 3. From bromo-hydro-phenyl- 
 crotonic acid (Perliin, O. J. 32, 660).— 4. From 
 chloro-propyl-benzene and alcoholic potash 
 (Errera, O. 14, 504). 
 
 Di-bromide OgH.jBr^ [66-5°]. Plates or 
 needles. On distillation it yields an allyl- 
 benzene (178°), which polymerises forming a 
 viscid solid (330°). 
 
 Iso-allyl-benzene Ph.CH2.CH:CH2(?) (155°). 
 Chojnacld (C. R. 76, 1418) got this body from 
 allyl iodide or bromide, benzene, and zinc dust at 
 100°. Others have failed to get it. Allyl 
 chloride, benzene, and Al^Clj give di-phenyl pro- 
 pane, CH3.CHPh.CH2Ph, and »-propyl-benzene 
 (2. V.) (Wispek a. Zuber, A. 218, 378). 
 
 ALLYL BENZOATE v. Benzoic acid. 
 
 ALLYL-BENZOYL -ACETIC ACID C,,H|„0, 
 i.e.BzGH(C3HJC0.B [122°-125°]. Frombenzoyl- 
 acetio ether, NaOEt, and allyl iodide. The result- 
 ing ether is saponified by standing for three 
 weeks with dilute alcoholic KOH (W. H. Perkin, 
 jun., O. J. 45, 186 ; 47, 240). Colourless crystals. 
 
 iJeaciion.— Boiled with dilute alcoholic KOH 
 forms phenyl butenyl ketone (g. v.), benzoic acid 
 and (probably) aUyl-acetio acid. 
 
 Ether.— EtA' (220°) at 100 mm. j (241°) at 
 225 mm. Combines with Br. 
 
 ALLYL BORATE CsH.jBOj i.e. (C3HJ3BOS 
 (168°-175°). From BA and allyl alcohol at 
 130° (Councler, /. pr. [2] 18, 376). Combines, 
 with bromine, forming (C3H5Br.,)3B03. 
 
 ALLYL BROMIDE C3H3Bri.e.CHj:CH.CH Br 
 (71°). S.G. 2 1-459; i^ 1-436. S.V. 90-5. 
 (Zander, A. 214, 144). CE.(0°-10°) -00123. 
 H.F.p. -340 ; H.F.v. -1500. 
 
 Formation. — 1. From allyl alcohol, bromine, 
 and phosphorus (ToUens, A. 156, 152). — 2. From., 
 glycerine and PBr, (Henry, Z. [2] 6, 575).— 
 3. From allyl iodide and cupric bromide:, 
 2C3HjI-i-2CuBr2 = Br2-HCu2l3 ^ 2C3H5Br (Oppen- 
 heim, B. 3, 442). 
 
 Preparation. — Potassic bromide, hydric sul- 
 phate (2 pts.), and water (1 pt.) are warmed till 
 hydric bromide begins to come off. Allyl alcohol 
 is then dropped in (Grosheintz, Bl. 30, 98). 
 
 Combinations. — 1. With concentrated hydric 
 bromide forms a mixture of propylene bromide 
 (CHj.CHBr.CH^Br) and trimethylene bromide 
 (CH^Br.CHj.CH^Br) which may be separated by- 
 distillation (Geromont, A. 158, 369).— 2. With 
 dry HBr it forms chiefly trimethylene bromid» 
 (g. v.). — 3. With bromine it forms tribromhydrin 
 {q. v.).—i. With ICl it forms C3H5lClBr.— 5. 
 With ClBr at 20° forms CaHjClBrj, but at lOO'' 
 forms CjH-.CljBr (M. Simpson, Pr. 27, 119).— 
 
 6. With HCIO it produces C3Hj(0H)BrCl.— 
 
 7. It combines with NEtj. 
 
 ALLYL BUTYBATE v. Butybio acid. 
 
 ALLYL-ISO-BUTYL-MALONIC ETHER 
 C,,n,fi, i.e. (C3H,)C(C,H3)(CO,Et)2 (247°-250°). 
 From di-sodio-malonic ether, allyl iodide, and 
 iso-butyl iodide (Ballo, B. 14, 335). On saponi- 
 fication it gives an acid [129°] which appears ta 
 be propyl-iso-butyl-malonic acid. 
 
 ALLYL CAEBAMINE C^H^N i.e. 
 CH2:CH.CHj.NC (96°-106°). S.G. U -794. 
 Produced by the action of silver cyanide on allyl 
 iodide. It is a liquid of disagreeable odour 
 Somewhat soluble in water (Lieke. A. 112, 31(5^ 
 
ISO 
 
 ALLYL CARBINOL. 
 
 BI-ALLTL CARBINOL v. Heptisxl alcohoi,. 
 
 DI-ALLTL-DI-CHLOEHYDEIN C.Hi.Cl.O^ 
 i.e. C,H,„(0H)2CLi. From HCIO and di-allyl 
 (Przybytek, B. 18, 1350; Lauoh, B. 18, 2288). 
 
 ALLYL CHLOBIDE C,B.fiU.e. CH,:OH.CH,OI 
 (46«) (Thorpe); (44-6°) at 744 mm. (Briihl). 
 S.Ot. g -9547 ; f -9379 (Briihl). C.E. (0'-10°) 
 •00137. S.V. 84-7 (Zander). S.H. -3084 
 (Eeis). fifi 1-4225. Ea, 32-63 (Bruhl). 
 H.F.p. 7100. H.F.V. 5940. M.M. 6008 at 
 19-6°. 
 
 Formation. — 1. From allyl iodide and HgCl^. 
 
 2. From allyl oxalate, calcic chloride, and 
 alcohol (Oppenheim, A. 140, 205). — 3. From 
 allyl alcohol and HCl in sealed tubes. 
 
 Preparation.— From allyl alcohol and PCI3 
 (ToUens, A. 156, 154). 
 
 Properties. — 1. Alcoholic potash, even below 
 100°, converts it into ethyl allyl oxide. The 
 isomeric chloropropylene (26°) is converted by 
 alcoholic potash at 120° into allylene. — 2. HCIO 
 unites, forming unsymmetrical dichlorhydrin, 
 CH2C1.CHC1.CH,0H, or dichloride of allyl alcohol. 
 This body, when oxidised by HNO3, is converted 
 into dichloropropionic acid (Henry, B. 7, 757). — 
 
 3. HCl combines, forming CHj.CHCl.CH^Cl.— 
 
 4. HBr forms CH.,Br.CH2.CH,Cl, together 
 with a little CHs.CHBr.CHjGl.— 5. Warmed 
 with HjSOj and then dilated and distilled, 
 propylene chlorhydrin is produced (Oppen- 
 heim, A. Suppl. 6, 367). — 6. Bromine com- 
 bines, forming CjHjCl.Brj. — 7. With potassic 
 cyanide in presence of dilute alcohol it forms 
 chiefly pyrotartario acid, also propylene cyanide 
 (Glaus, A. 191, 38) and triaflylamine (Pinner, 
 B. 12, 2053). The reactions in this case are : (a) 
 
 CH,:CH.CH,,C1 + KCN = KCI + CH2:CH.CH,.CN. 
 (6) CHjiCH.CH^CN + HCN = CH3.CH(CN).CH,CN 
 (c) CH3.CH(CN).OH,CN + 2KOH + 2H20 = 
 2NH3-h CH3.CH(C02k).CH2.C02K (pyrotartrate). 
 The liberated ammonia forms the triallylamine. 
 8. With benzene, in presence of aluminium 
 chloride, forms diphenylpropane : C-iH^Cl + 20 Hj 
 = HC1 + (C„H,),C,H, (Silva, O.R. 89, 606). 
 
 ALLYL-PSETTDO-CUMYL-PHTHAL-AMIDE. 
 Cj„Hj2N303i.e.C,H2Me3.NH.C0.C,H,.C0.NHC3H5. 
 [179°J. Silky needles. Easily soluble in alcohol. 
 Formed by the action of allylamine on phthal- 
 pseudo-cumidine (Frohlich, B. 17, 1808). 
 
 ALLYL CYANAMIDE 
 CjHjOjIaq. i.e. (CN.NHCjHJx. Sinamine 
 [100°]. From allyl-thio-urea and Pb(OH)j 
 or HgO. (Will, A. 52, 15 ; Andreasch, M. 2, 
 780 ; Eobiquet a. Bussy, J.pr. 19, 234). Alka- 
 line. Sol. water, alcohol, and ether. Forms 
 compounds with HgClj, ^PtClj, and oxalic acid. 
 
 ALLYL CYANATE C^H.NO i.e. C3H5N.CO. 
 Allyl carbimide. (82°). V.D. 3-05 (for 2-88). From 
 allyl iodide and silver oyanate (Cahours a. Hof- 
 mann, Tr. 1857, 555). 
 
 ALLYL CYANIDE CjH3N i.e. CH/.CH.CH,CN. 
 Omtonitrile. Mol. w. 67. (119° cor.). S.G.2-8'i91; 
 is-8351; i2gS: -8398. 
 
 Formation.— 1. By ppg. potassic myronate 
 (2. V.) with silver nitrate and treating the pp. 
 with hydrio sulphide C,H^g,NS,Oj + H^S = 
 0^11,^ + Ag^ -I- S + HjSO,.— 2. During the fermen- 
 tation of black mustard. — 3. From allyl mustard 
 oil by zino dust : C3H5NCS i- Zn = ZnS + C3H5CN 
 (Sehwarz, B. 15, 2508).— 4. From allyl 
 siiiphocyanide aad sodium (Billeter, B. 8, 4C6). 
 
 Preparation. — Allyl iodide is heated with 
 KCy for two days at 110°. The product is 
 washed, dried, and heated again with KCy at 
 110°. It is then washed, dried over CaCl^, dis- 
 tilled, freed from carbamine by shaking with a 
 little HNO3, and rectified (Binne a.. ToUens, 
 A. 159, 106). 
 
 Properties.— 'hiqm.di smelling faintly of garlic. 
 
 Reactions.— 1. Aqueous or alcoholic ^otes7i 
 forms NH3, and solid erotonic acid [72°] . The 
 formation of this erotonic acid may be explained 
 by the assumption that j8-oxybutyrate is first 
 formed: CH^-.CH.CHjCN + KOH + 2B..p = 
 NH, + CH3.CH(OH).CH3.CO,K, and that this 
 splits oft water : CH3.CH(0H).CHj.C0,K = 
 HoO + CHs.CHiCH.CO^K, forming potassic 
 orotonate. This view is supported by the be- 
 haviour of allyl cyanide- towards HCl. — 2. With 
 fuming hydric chloride at 60° it forms /3-chloro- 
 butyric acid : CH.,:CH.CH2.CN -I- 2HC1 + 2H,0 = 
 NHjCl + CH3.CHCI.CH2.CO2H. This is an un- 
 stable acid, which easily changes to crotouio 
 acid. — 3. HNO3 forms acetic and oxalic acids. — 
 4. CrOj forms acetic acid. 
 
 Combinations. — 1. With alcohol. When 
 potassic cyanide acts on allyl iodide in alcoholic 
 solution, a compound of allyl cyanide and 
 alcohol, of boiling point (174°), is obtained : 
 CH3:CH.CH,0N + HOEt = CH3.CH(0Et).CH,.CN. 
 Saponified by strong HCl, this forms ethoxy- 
 butyramide, CH3.CH(0Et).CH,.00NH3 [71°], 
 which, when warmed with HCl, gives ethoxy- 
 butyric acid, CH,.CH(0Et).CH,.C02H, boiling 
 about 215°. Saponified by potash, the com- 
 pound of allyl cyanide and alcohol (;8-ethoxy. 
 butyronitrile) gives ordinary erotonic acid as 
 follows : CH3.CH(0Et).CH,.CN + KOH + H,0 = 
 NH3 + H0Et + CH3.CH:CH.C0.,K (Rinne, B. 
 6, 389). Dry hydrogen chloride converts the 
 compound of allyl cyanide and alcohol into 
 the chloride of /3-chlorobutyrimid-ether (166°), 
 CH3.CHCl.CHj.C(0Et)NH. 'This last compound 
 is converted by alcoholic potash into erotonic 
 acid (Pinner, B. 17, 2007). 
 
 2. With allylalcohol. A similar compound, 
 CH3.CH(OC3Hj.CH3CN(96°),isformedwhenKCy 
 acts on allyl chloride mixed with allyl alcohol. 
 
 Constitution. — From its mode of preparation, 
 allyl cyanide ought to be CH2:CH.CH2.CN, but 
 from its reaction with potash it should be the 
 nitrile of ordinary erotonic acid CHj.CHiCH.CN. 
 From the fact that allyl cyanide and erotonic 
 acid both produce acetic acid on oxidation, while 
 allyl iodide and allyl alcohol yield no acetic 
 acid, Kekul6 assumes the presence of a methyl 
 group in the two former and its absence in the 
 two last named (B. 6, 386). This reasoning 
 seemed conclusive until the experiments of 
 Pinner, mentioned above, showed that, when 
 the cyanide is converted into erotonic acid by 
 hydric chloride, an intermediate compound 
 fl-chlorobutyric acid) is produced, and it is 
 therefore possible that when nitric or chromio 
 acid is used, an unstable derivative of butyric 
 acid (say, 3-oxybutyric acid) is first formed, and 
 that it is this which gives acetic acid on oxida- 
 tion. 
 
 ALLYLENE C,K^ i.e. Me.O-CH. Methyl- 
 acetylene. Propinene. Mol-w.40. S. (ether) 30 at 
 16°. H.F.p. -39950 (Thomson); -87500 (Ber- 
 thelot). H.F.V.-41530 (Th.). 
 
ALLYL IODIDE. 
 
 137 
 
 Formation. — 1. By action of alcoholic NaOH 
 upon bromo -propylene (Sawitsch. 0. B. 52, 399), 
 chloro-propyleue, or propylene bromide (Mias- 
 nikoff, A. 118, 332).— 2. By the action of Na 
 upon CH,.CCl2.CHCl2 (Borsche a. Fittig, A. 133, 
 111), CH2CI.CCI2.CH2CI, or CHj:CCl.CH,Cl 
 (PfeSer a. Fittig, A. 185, 357).— 3. By electro- 
 lysis of calcium mesaconate or citraconate (Aar- 
 land, J.pr. [2J 7, 142).— 4. By heating (oitra-) 
 bromo-pyrbtartaric anhydride with ammoniacal 
 AgNOaAq at 130° (E. Bourgoin, 0. B. 85, 710). 
 Colourless gas, with unpleasant smell; burns 
 with smoky flame. V. sol. alcohol, sol. water. 
 
 Beactions. — 1. Ammoniacal cuprous chloride 
 gives a canary coloured pp. — 2. Absorbed by 
 cone. H2SO4 much more readily than acetylene, 
 allylene sulphonic acid, CjHjSOjH, being 
 produced. An aqueous solution of this acid, 
 when heated, yields mesitylene and acetone 
 (A. Schroke, B. 8, 17, 367).— 3. Aqueous mer- 
 curic salts form pps. containing the mercuric 
 salt, HgO, and allylene. These pps. are de- 
 composed by acids with formation of acetone 
 (Kutscheroff, B. 14, 1541 ; J. B. 1882, 326).— 
 
 4. KMnOjAq forms, in the cold, malonic, oxalic, 
 and formic acids (Berthelot, A. Suppl. 5, 97). — 
 
 5. CrOjAq forms propionio acid (Berthelot, A. 
 Suppl. 8, 47). 
 
 Metallic Derivatives. — CHj.C-CNa : 
 white powder, decomposed by water into NaOH 
 and allylene (Berthelot, A. Oh. [4] 9, 395 ; /. B. 12, 
 288). — (C3Hs)2Hg: crystalline pp. formed by 
 passing allylene into Nessler's solution (Kut- 
 soherofi, B. 17, 25). 
 
 Combinations. — 1. Cold fuming HCl forms 
 CH3.CCI2.CH3 ; HBr, and HI act simnarly.— 2. 
 Bromine forms di-bromo-propylene (g. v.) and 
 tetra-bromo-propane (g. v.). Iodine acts simi- 
 larly. 
 
 Iso-allylene CH2:C:CH2. 1. Formed by 
 electrolysis of potassio itaconate (A.). — 2. By 
 the action of sodium on di-chloro-propylene, 
 CHChCH.CHjCl (from symmetrical tri-chlorhy- 
 drin, Hartenstein, J. pr. [2] 6, 295). 
 
 Properties. — A gas that does not pp. am- 
 moniacal silver or cuprous solutions. Forms a 
 tetrabromide. 
 
 Di-allylene CjHj or CH2:CH.CH2.CH2.C:CH 
 Allyl-allylene (70°). S.G. la -858. V.D. 2-79'(for 
 2-76). AJlyl-acetone is converted by PCI5 into 
 C3H5.GH2.CCI2.CH3, which is converted by 
 alcoholic KOH into di-allylene (L. Henry, O. B. 
 87, 171). 
 
 Beactions. — 1. Aqueous silver nitrate gives a 
 pp. CjHjAg aq. — 2. Ammoniacal cuprous chlo- 
 ride gives a canary-yellow pp. CuH^Cu aq.— 3. 
 Alcoholic AgNOj gives a pp. CjH,AgEtOH.— 
 4. Bromine forms CsHgBrj. 
 
 Iso-allylene tetra-oarboxylio acid v. Pbopanb 
 
 TETKA-CARBOXTLIC ACID. 
 
 ALLYLENE DI-CHLOSIDE v. Di-chloko- 
 
 pnOPYLENE. 
 
 ALLYLENE OXIDE C3H4O (63°). Formed 
 by oxidising allylene with CrOjAq (Berthelot, 
 Bl. 14, 116). Pungent neutral liquid. Not 
 attacked by baryta-water at 150° or by KOHAq 
 at 300°. Eeduces AgNOjAq. 
 
 ALLYL ETHANE v. Pentindnb. 
 
 ALLYL ETHEB v. Alml oxidb. 
 
 ALLYL ETHYL OXIDE v. Ethyl allyi, 
 
 DI-ALLYL HYDSATE v. Hexenyl ALOonot. 
 
 DI-ALLYL-DI-HYDRATE v. Di-oxy-hexanh. 
 
 ALLYLIN V. Glyoeein. 
 
 ALLYL IODIDE C3HJ i.e. CH,:CH.CH2l 
 (102-7° i. v.). S.G. § 1-8696. C.E. -00106. 
 S.V. 100-9 (Zander, A. 214, 145) ; V. D. 5-77 (obs.). 
 
 Formation. — 1. AUyl alcohol, P, and iodine 
 (Tollens, Bl. [2] 9, 396).— 2. Glycerin and PI, 
 (Berthelot a. de Luca, A. Ch. [3] .43, 257).— 3. 
 Glycerin distilled with hydriodic acid; excess 
 of the latter is to be avoided, as it would con- 
 vert the allyl iodide into isopropyl iodide : 
 CHjiCH-CHJ -I- 2HI = CH3.CHI.CH2I + HI - 
 
 CHj.CHiCHj -H I, + HI = CH3.CHI.CH3 + Ij 
 (Erlenmeyer, A. 139, 211).— 4. From allyl chlo- 
 ride and calcic iodide (Eomburgh, B. 1, 151 ; 
 Spindler, A. 231, 270). 
 
 Preparation. — 200 grms. of glycerin, pre- 
 viously dried by heating to 280°, are mixed with 
 125 grms. of iodine. The tubulus of the retort 
 is connected by a flexible tube with a flask con- 
 taining 40 grms. of clear phosphorus in small 
 pieces ; this flask has also a side tube through 
 which carbonic acid is passed until the air is 
 cleared out of the entire apparatus. The clear 
 phosphorus is added to the contents of the re- 
 tort by tilting the flask from time to time. Allyl 
 iodide distils over rapidly. The addition of 
 phosphorus takes about 2^ hours. The distilla- 
 tion is then continued until the contents of the 
 retort begin to carbonise and vapours of acrolein 
 are given off. The distillate is washed with 
 dilute NaOH, dried over CaClj, and rectified. 
 Yield 110 grms. (98°-102°). 
 
 Theory of the Process. — It is usually held 
 that triiodhydrin is first formed : 
 
 CH,(0H).CH(0H).CH2(0H) + P 4- 13 = 
 
 H3PO3-1-CH3I.CHI.CH2I, 
 and that this splits up into iodine and allyl 
 iodide : CHjI.CHI.CHJ = I^ + CH„ : CH.CH^I. 
 But the fact that allyl alcohol accompanies the 
 allyl iodide renders it quite likely that the in- 
 termediate body is diiodhydrin : 
 
 CH2I.CHI.CH2OH = I2 -I- CHjiCH-CHjOH. 
 The allyl alcohol formed in this way being con- 
 verted into iodide by HI (Henry, B. 14, 403). 
 
 Beactions. — 1. Zinc and HGl reduce it to 
 propylene. — 2. Salts of silver form silver iodide 
 and salts of allyl. — 3. Viy hydric iodide converts 
 it into isopropyl iodide (Simpson, Pr. 12, 533). 
 
 4. With sine ethyl at 100° it forms amylene, 
 pentane, and diallyl (Wurtz, C. B. 56, 387).— 
 
 5. With cacoiij/ Ht reacts thus: As2Me4-H2C3H.I=i 
 AsMe.J. + ks.Me.,{G,}i,).J. (Cahours, A. Ch. [3] 62, 
 291).— 6. With dry copper zinc couple at 100° it 
 forms diallyl : 2C3H J -h Zn = Znl^ + (C3H3).,. — 7. 
 With wet copper-zinc couple it forms propylene : 
 CaHJ -I- B..JO + Zn = IZnOH -I- C3H3.— 8. With zint 
 and alcohol (S.G. -805) it also forms propylene 
 (Gladstone a. Tribe, O. /. 27, 208).— 9. With 
 HgBrj at 200° it gives Hgl2, HBr and propane 
 (Montgolfier a. Girand, B. 12, 1211).— 10. Heated 
 at 100° for a long time with water it forms allyl 
 alcohol (3. «.).- 11. With EON and alcohol it 
 forms a di-cyanide which, when boiled with KOH, 
 produces potassic pyrotartrate (Glaus, 4. 191, 38). 
 
 Combinatio7is. — 1. With chloride of iodine it 
 unitea, forming GjHjIjCl (205°-210°), a colour- 
 less oil (M. Simpson, Pr. 13, 540). — 2. BromiMe 
 forms GsHsBrj.— 3. Mercury unites with it, form- 
 ing G3HjHgI, mercurio-allyl iodide. 
 
138 
 
 ALLYL-MALONIC ACID. 
 
 ALLYL-MALONIC ACID 
 
 C„H,04 i.e. CaH,CH(C0,H)2. [103°]. 
 (Conrad a. Bischoff, B. 13, 597 •, A. 204, 166 ; 
 Hjelt, A. 216, 52). Large prisms. V. sol. water, 
 alcohol, and ether. At 180° it splits up into 
 COj and allyl-acetio acid. Combines with HBr 
 forming liquid (C02H)2CH.C3HsBr which, when 
 boiled with water gives a lactone of oxy-propyl- 
 malonic acid (g. v^. Combines with Br^ forming 
 di-bromo-propyl-malonio acid (g. v.). 
 
 Salts. — CaA": crystalline powder. — Ag^A". 
 
 Si/ier.— Et2A"(218°-225°) ; (194°) at 380 mm. 
 S.G. IS i-ois (0. a. B.) ; i| 1-014. M.M. 11-28 
 at 13-7° (Perkin). From sodio-malonic ether 
 and allyl iodide. 
 
 Si-allyl-malonic acid 
 
 C^H.^Oj i.e. (C3HJ,C(C0jH),. [133°]. 
 Ehombie prisms ■,a:h:c = -9916 : 1 : 1-0179 (Haus- 
 hofer, Z. E. 11, 147). Sol. water, alcohol, and 
 ether; v.sl. sol. CS^. 
 
 Reactions, — 1. Heat splits it up into COj 
 ttnd di-allyl-acetic acid. 
 
 EtherSt^k". (240°) (C. a. B.); (203°) at 225 mm. 
 S.G. 11 -996 (C. a. B.) ; ^ 1-000 ; |l -993 (Perkin). 
 M.M. 15 at 22°. From aUyl iodide and sodio- 
 malonio ether (Conrad a. Bischoff, B. 13, 598 ; 
 A. 201, 171 ; Hjelt, A. 216, 61). 
 
 ALLYL MEKCAPTAN O3H5SH. Mol. w. 74. 
 (90°) (Hofmann a. Cahours, A. 102, 292).— 
 CjHjSHgCl : pearly plates (from alcohol) 
 (Gerlich, ^.178,88). 
 
 ALLYL METHYL ETHER v. Methyl allh, 
 
 OXIDE. 
 
 ALLYL MTJSTAED OIL 
 
 V. Allyl thio- 
 
 GABBIMICE. 
 
 ALLYL NITRATE CaH^NOj. (106°). 
 S.G. la 1-09. V.D. 3-54 (for 3-56). From allyl 
 bromide and AgNOj (Henry, B. 6, 452). 
 
 ALLYL NITRITE CsH.NO^ i.e. C3H5.O.NO. 
 (44°). S.G. 2-955. Prepared by distilling glyceryl 
 tri-nitrite with allyl alcohol. An oil. Decom- 
 posed by MeOH into allyl alcohol and methyl 
 nitrite. Its vapour explodes at 100° (Bertoni, 
 G. 15, 361). 
 
 ALLYL OXALATE v. Oxalic acid. 
 
 SI-ALLYL-OXALIO ACID (so called) v. 
 
 OXY-OOTINOIC ACID. 
 
 DI-ALLYL-OXAMIDE CsH.^NjOj i.e. 
 C,H5NH.CO.CO.NHC3Hs. [154°]. (274°). White 
 plates. Soluble in hot water. Prepared by the 
 action of allylamine on oxalic ether. 
 
 Tetrabromide CACNHCjH^Br^)^. In- 
 soluble in most ordinary solvents, except hot 
 acetic acid (Wallach a. Strieker, B. 13, 513). 
 
 DI-ALLYL OXIDE C„H,„0 i.e. (C3HJ2O. 
 Allyl ether. Mol. w. 98. (82°) (Cahours a. 
 Hofmann, A. 102, 290) ; (94-3° i.V.) (Zander, A. 
 214,146). S.G.g-8223. S.V. 135-5. C.E. (0°-10°) 
 •00127. H.F.p. 12460. H.F.v. 9850 (Thomsen). 
 
 DI-ALLYL DI-OXIDE 
 
 CH3 . CH.CH2.CHj.CH . CHj 
 (180°). V.D. = 3-7 (obs.). Mobile colourless 
 fluid of slight smell and burning taste. Heavier 
 than water. Combines with acids, and pps. 
 magnesia from a solution of MgClj. Obtained 
 by the action of solid caustic alkalis upon di- 
 allyl-di-chlorhydrin. By boihng with water it 
 13 converted into the alcohol-oxide 
 
 /n 
 
 \ 
 
 IH2 . CH.CH3.CHj.CH(0H).CH.,(0H), 
 which only by long heating with water is con. 
 verted into the tetra-hydric alcohol 
 CH,(OH).CH(OH).CH2.CH2.CH(OH).CHj(OH) 
 (Przybytek, B. 18, 1350). 
 
 - ALLYL - PHENOL. Methyl derivativs 
 C.oH.jO i.e. C,H,(0Me).CH2.CH:CHj,. (233°). 
 S.G. if -9972 ; |g -9884 ; *f -9793. Formed by tha 
 action of NajCOsAq on the product of the union 
 of HI with the methyl derivative of (a)- or (;8). 
 oxy-phenyl-crotonic acid (g. v.). It is an oil; 
 combines with bromine ; forms a red solid with 
 HjSO, (Perkin, C. J. 39, 425). 
 
 p - AUyl-phenol. Methyl derivative. (232°) 
 S.G. |§ -985. Prepared as above from cor- 
 responding ^-compound. Anethol {q. v.) is 
 isomeric with this body. Anol (j. v.) is isomeric 
 with allyl-phenol. 
 
 ALLYL-PHENYL-THIO-UEEA C,„H.,2N.,S 
 i.e. C3H5.NH.CS.NHPh. [98°]. S. (alcohol) 
 71 at 18°. From oil of mustard and aniline 
 (Zinin, A. 84, 348) ; from allyl-amine and 
 phenyl thio-carbimide (Weith, B. 8, 1529). 
 Monoclinic crystals ; v. sol. ether, insol. water. 
 Cyanogen passed into an alcoholic solution 
 forms C,„H,2N2S(CN)2, ppd. by water (Maly, Z. 
 1869, 261). When this is warmed with alcohol 
 and dilute H^SO, it forms the oxalyl derivative. 
 
 Oxalyl Derivative 
 CO.NC3H,. 
 
 I >CS [161°]. Lemon-yellow needles. 
 
 CO.NO.H,'^ 
 insol. water, si. sol. cold alcohol. 
 
 ALLYL-PHENYL-TJREA C,„H,2N20 i.e. 
 C3H5.NH.CO.NHPh. [97°]. Needles. Got from 
 its oxalyl derivative by baryta (Maly, Z. 
 1869, 263). 
 
 CO-NO3H., 
 
 Oxalyl-derivative 
 
 '\ 
 
 CO. 
 
 Co-nc^h/ 
 
 From the oxalyl derivative of allyl-phenyl-thio- , 
 urea (g,.v.) and warm AgNOj in alcoholic solu- 
 tion. Long needles. Insol. water, v. sol. 
 alcohol, benzene, and CS2. 
 
 ALLYL-PHTHALIMIDE v. Phthalio Acid, 
 Allylamide. 
 
 ALLYL - PROPYL ALCOHOL v. Hexenyl 
 
 ALCOHOL. 
 
 ALLYL-PROPYL-AMINE CjH.sN i.e. 
 CsH^NHCaHj. (c. 112°). S.G. i| =-7708 
 Colourless fluid. S. = about 6. Prepared by 
 the action of propyl bromide on allylamine. 
 
 Salts : B'jHjCljPtClj : orange crystals. — 
 'B'n.fi.fi,: si. sol. needles.— B'jHjCP/ : thin 
 plates (Liebermann a. Paal, B. 16, 525). 
 
 Allyl-di-propyl-amine(C3H,)jNC3H3. (0. 147°). 
 Colourless fluid. S = about 2. Formed by tho 
 action of propyl bromide on allylamine. 
 
 Salts. — B'jHjCljPtClj : orange-red trimetria 
 crystals, a-.h-.c = •9831:1:1-1217. 
 B'HClPtClj -. sparingly soluble yellow needles 
 [152°] ; formed by boiling the preceding salt 
 with water (Liebermann a. Paal, B. 16, 527). 
 
 ALLYL-ISO-PROPYL-BENZENE v. Pro. 
 
 PENYL-ISO-PEOPYL-BENZENE. 
 
 ALLYL DI-PROPYL CARBINOL v. Decenyi 
 
 ALCOHOL. 
 
 Di-allyl propyl carbinol v. Decinyl alcohol. 
 a-ALLYL-PYRIDINE CjHj(C3HJN. (o.l90°). 
 
ALLYL THIO-CARBIMIDE. 
 
 138^ 
 
 H.G. 2 -gsOS. Colourless refractive oil ; si. sol. 
 water. Prepared by heating pure (a)-picoline 
 with paraldehyde for 10 hours at 250°-2G0°. 
 On oxidation it gives pioolinio acid [133°]. On 
 reduction in alcoholic solution by means of 
 eodium it yields (o) -propyl-pyridine (inactive 
 ooniine). 
 
 SaZfa.— (B'HCl)2Ptai4 : [188°], sparingly 
 soluble needles. -B'HClAuCla" : [136°], oily pp. 
 solidifying to small needles.— (B'HCljjHgCl/ : 
 very sparingly soluble crystalline pp. (Laden- 
 burg, B. 19, 2578). 
 
 v-ALLYl-PYREOL 0,Hs,N i.e. CjH.N.CjH,. 
 [105°] at 48 mm. Formed by the action of allyl 
 bromide on pyrrol-potassium. Colourless oil. 
 Volatile with steam. Almost insoluble in water. 
 HgCl^ gives a white pp. (Ciamician a. Dennstedt, 
 B. 15, 2581 ; G. 13, 17). 
 
 ALLYI-BESOKCIN C„H3(C3H3) (OH)^. Mono- 
 methyl ether CeH3(C3H5)(OMe)(OH). (245°-250°) ; 
 V.D. 165 (obs.) ; colourless oil (Pechmann a. 
 Cohen, B. 17, 2132). 
 
 ALLTL-STTCCINIC ACID 
 C,H,„04 i.e. C02H.CH2.CH(CsH5).002H. 
 [94°]. Plates (from alcohol). Prepared by heat- 
 ing allyl-ethaue tri-carboxylic acid to 160°, COj 
 being evolved. Strong aqueous HBr converts it 
 into the corresponding laotonio acid — 
 
 CH3.CH.OH2.CH.CHj.CO2H 
 I I 
 
 O CO 
 
 Salts : A"Ca'' : crystalline, soluble.— A'TBa" : 
 easily soluble, amorphous. — A"Ag2'' : sparingly 
 soluble, amorphous. — FeS04 gives a flocculent 
 pp. (Hjelt, B. 16, 334). 
 
 ALLYL SULPHATE CgHeSOi i.e. 
 C3H5O.SO2.OH. Hydrogen allyl sulphate. Allyl- 
 sxdphuric acid. From allyl alcohol and H^SO^ 
 (Cahours a. Hofmann, 0. J. 10, 316). 
 
 SaZis.— (Szymanski, A. 230, 43.) BaA'^.— 
 SrA'j.- CaA'j 2aq.— CuA'j 4aq.— PbA'^PbO 6aq.— 
 MgA'2 4aq.-KA'.— NaA'.— NH,A'. 
 
 ALLYL SULPHIDE C,H,„S i.e. {p^B.^)S- Oil 
 of Garlic. M. w. 114. (140°). 
 
 Occurrence. — In the essential oils obtained 
 by distilling, with steam, the leaves, seeds, or 
 bulbs, of various plants (allium sativum, alliaria 
 officinalis, allium cepa, thlaspi arvense). Often 
 associated with allyl-thio-carbimide (g.u.) (Wert- 
 heim, A. 51, 289 ; 55, 297 ; Pless, A. 58, 36). 
 
 Formation. — From allyl iodide and alcoholic 
 KjS (Hofmann a. Cahours, A. 102, 291). 
 
 Properties. — A light oil, smelling of garlic. 
 
 Combinations. — 1. Forms pps. with salts of 
 Au, Hg, Pd, Pt, and Ag.— (CjHJ.SPtSj (W.)— 
 (C3H5).,SAgN0j (Ludwig, A. 139, 121). 
 
 HgS(HgCy,2(C,H,)2S (W.) 
 2. Combines with Mel (Cahours, Z. 1865, 438). 
 
 ALLYL SULPHOCYANIDE CjH^NS i.e. 
 C3H5.S.CN. Allyl thio-cyanate. (161°). 
 
 S.G. 2 1-071 ; is 1-056. 
 
 Formation. — 1. From lead salt of allyl 
 mercaptan and cyanogen chloride in ethereal 
 solution (Billeter, B. 8, 464) : 
 
 (C3H,S).,Pb + 2C1(CN) = 2C3H5.S.CN + PbClj. 
 2. From ammonium sulphocyanide and a cold 
 alcoholic solution of allyl bromide (Gerlioh, A. 
 178, 85). 
 
 Prqperfes.— Changes spontaneously into the 
 isomeric allyl-thio-carbimide, especially when 
 boiled. Alcoholic KOH forms ESCN. P«esnot 
 
 give immediate pps. with ammoniacal AgNOa or 
 alcoholic HgClj. Zn and HCl in alcohol form 
 (CaHJjS and HON (G.). Sodium amalgam toima- 
 NajS and allyl oarbamine (B.). 
 
 ALLYL-SULPHOHIC ACID v. Propylene 
 
 SULPHONIO ACID. 
 
 ALLYL STJLPHYDRATE «. Allyl mekcapian. 
 
 ALLYL-TATJEINE C^H.iNSOa i.e. 
 CsH5NH.CH2.CHj.SO3H. [190°-195°]. From 
 CH,C1.CH2.S03H and allylamine at 160° (James,, 
 C. J. 47, 369). Prisms (from alcohol). V. e. sol. 
 
 ALLYL-THIO-CARBAMIC ACID Mhyl ether 
 CsH„NSO i.e. C3H3NH.CS.OEt. Allyl-thio- 
 urethane (210°-215°). S.G. a 1-036. From oil 
 of mustard and alcohol at 110° : 
 
 OjHjNiCS + HOEt = C3H3NH.CS.OEt 
 (Hofmann, B. 2, 119). Ppd. by HgCl.,Aq. 
 
 Allyl-di-thio-carbamic acid CH^NH.CS.SH. 
 From allyl thio-carbimide and alkaline sulphy- 
 drates : CaHjNiCS + HSK = C3H3NH.CS.SK. The 
 free acid is unstable. 
 
 Salts. — NHjA' : unstable laminsB. — KA': 
 large rhombic plates. — NaA' 3aq : unstable- 
 nacreous laminsB. — BaA'^ 4aq : laminas ; v. sol. 
 water.— PbA'2 : white pp. (Will, A. 52, 30). 
 
 ALLYL THIO-CARBIMIDE O^H^NS i.e.- 
 C3H5N:CS. Oil of mustard, allyl mustard oil, 
 allyl thio-cyanate, allyl iso-thio-cyanate, allyl' 
 sulphocyanide, allyl iso-sulpho-cyanMe, allyl 
 sulpho-carbimide. M. w. 99. (151°). S.G. ^ 1-028. 
 S.V. 118-12 (B. Schift, B. 19, 568). H.F.p_ 
 -45,540. H.F.V.- 46,700. V.D. 3-54 (for 3-42).. 
 
 Occurrence. — In the oil distilled from the- 
 seeds of black mustard {sinapis nigra). Also pre- 
 sent in oil of garlic, and in horse-radish. 
 
 Formation. — 1. Seeds of black mustard con- 
 tain potassic myronate, and also an unorganised-) 
 nitrogenous ferment, myrosin. When treated 
 with water, the ferment splits up the potassie- 
 myronate thus : 
 
 C,„H,3NS,0,„K = C3H3.NCS + CjH.jOe -I- KHSO^. 
 At low temperatures a little allyl sulphocyanide- 
 is also foriiied (B. Schmidt, B. 10, 187).— 2.. 
 Allyl sulphocyanide (g. v.) changes, slowly at 
 15°, quickly on boiling, into allyl thio-carbimide- 
 Consequently, when allyl iodide is distilled with, 
 alcoholic potassic sulphocyanide (Zinin, A.. 
 95, 128; Berthelot a. De Luca, A. Ch. [3] 
 44, 495), or allyl sulphide (Wertheim, A. 55, 297),- 
 the product is allyl thio-carbimide. 
 
 Properties. — Oil with pungent odour and. 
 burning taste. Blisters the skin. SI. sol. water,. 
 V. sol. alcohol or ether. Slowly decomposed by 
 water, sulphur being liberated. 
 
 Beactions. — 1. Zinc and hydric chloride re- 
 duce it to allylamine and thio-formic aldehyde : 
 C3H,NCS-(-2H2=C3H3NH2-t-H,CS, the latter 
 being partly reduced to methane and HjS- 
 (Hofmann, B. 1, 179).— 2. HClAq at 200° forms 
 allylamine, CO2, and H^S (H.). — 3. Alcohol at 
 100°, or alcoholic potash, forms allyl-thio-car- 
 bamic ether {q. v.). — 4. Aqueous alkalis, or 
 water and the oxides BaO, PbO, AgjO, or HgO,. 
 form di-allyl-urea : 2C3H5NCS -h 3PbO -i- H^O = 
 (C3H3)2N„H,CO-H2PbS-fPbC03.— 5. K^S at 100""^ 
 forms potassic sulphocyanide and allyl-sul- 
 phide. — 6. NH3 forms allyl-thio-urea {thio-sina- 
 mine). — 7. Aldehyde-ammoma forms needles:- 
 of C.eHjiNsSjOj [108° I (B. Schifl B. 9, 571).. 
 — 8. Furfv/ramide in alcoholic solution at 
 
140 
 
 ALLYL TinO-OARBIMIDE. 
 
 100° forme CuHuNACsHsNOS [118°] (R.Sohifl, 
 B. 10, 1191).— 9. Boiling oono. KHSO3 forms 
 C^HsHH-CS-SOaK. Pearly plates (form alcohol) 
 ^Bohler, A. 154, 59). 
 
 Combination.— Gg'B.^'SCS Ag^SO^. Formed by 
 -adding AgNOjAq to aqueous potassio myronate 
 r<Will a. Korner,4.125, 267). 
 
 Additional References. — Boutron a. Eobiquet, 
 J. Ph. 17, 296 ; Henry a. PlissoUi J. Ph. 17, 
 451 ; Dumas a. Pelouze, A. Ch. [2] 53, 181 ; 
 Asehoff, J. pr. i, 314 ; Eobiquet a. Bussy, A. Ch. 
 [2] 72, 328 ; Boutron a,. Fremy, J. Ph. 16, 112 ; 
 Xowig a. Weidmann, J. pr. 19, 218 ; Will, A. 
 .52, 1 ; Gerhardt, A. Ch. [3] 14, 125 ; Hubatka, 
 A. 47, 153 ; VoUrath, /. 1871, 408 ; Grabowski, 
 A. 138, 173. 
 
 ALLYL-THIO-HYDANTOIN GjHjNjSO i.e. 
 
 HN:CK I 
 
 \S CH2 
 
 Formation. — (1) By the action ol ohloro- 
 .aoetio acid on allyl-thio-urea in aqueous solution 
 ;at 100°. (2) By the action of aUyl-cyanamide 
 on thio-glycollio acid. 
 
 Minute needles. Sol. hot, si. sol. cold, water. 
 
 The hydrochloride (B'HCl) forms glistening 
 ;prisms. (Andreasch, B. 15, 326; M. 2, 775). 
 
 AILYL-THIO-PAEABANIC ACID v. Tmo- 
 
 TAEAEANIO ACID. 
 
 ALLYL - THIO - URAMIDO - BENZOIC ACID. 
 
 <i„n,^^SOJ.e. OsH5NH.CS.NH.CjH,.C02H. [1:3] 
 [189° uncor.]. Formed by boiling m-amido- 
 benzoio acid with an alcoholic solution of allyl- 
 thio-oarbimide. Plates. (Aschan, B. 17, 431.) 
 
 AXLYL-THIO-TJREA. C^HgN.S i.e. 
 <C3H,NH.CS.KH2. Thiosinamine. M. w. 116. [74°]. 
 Formation. — From allyl mustard oil and 
 -ammonia (Dumas a. Pelouze, A. Ch. [2] 53, 181 ; 
 Asohoff, J. pr. 4, 314; Lowig a. Weidmann, 
 ■J. pr. 19, 218 ; Eobiquet a. Bussy, J. pr. 19, 
 232 ; WiU, A. 52, 1). 
 
 Properties. — Prisms, without smell. M. sol. 
 water, v. sol. alcohol, and ether. 
 
 Reactions. — 1. HgO or PbO converts it into 
 «llyl-cyanamide (j. v.). — 2. Warm AgNOjAq 
 forms allyl-urea. 
 
 Combinations. — (CiHjNjS HC^jPtClj. — 
 -C4H8N2S2HgCl2:curdywhitepp.— C^HsN^SAgNOj. 
 — CjHgNz SBr^ [147°], six-sided columns ; sol. 
 water, and alcohol. Converted by moist Ag^O 
 into alkaline C4HgN2S BrOH, whence HCl forms 
 ■C,HgN,,SBrCl [130°]. (Maly, Z. 1867, 42).— 
 (C^HsN^SBrJ^PtCl^. — (O^HsN.SBrCn^PtCl^. — 
 -C.HgN.SBrClAuBrj. — C^HgN^SI^ [90°]. — 
 C,Hi,Nj,SClI.— CjHsN^SCyj; converted by hot 
 ■dilute H2SO4 into allyl -thio-pababanio acid 
 •te- «.). (Maly, Z. 1869, 259). -C.HsNjSICyAgCy. 
 Ethyloiodide OjHaNjSEtl. [72°] (Welzien, 
 A. 94, 103 ; M.). 
 
 ALLYL-TJEEA C^HgN^Oi.e. CjHgNH.CO.NH^. 
 Allyl ca/rbamide. [85°]. Formation. — 1. From 
 allyl cyanate and hot NHjAq (Hofmann a. 
 <!ahours, Tr. 1857, 555).— 2. From aHylamine 
 sulphate and potassic cyanate (Andreasch, M. 5, 
 -31). — 3. From allyl thio-urea and AgNOjAq, the 
 •liberated HNO3 being neutralised by baryta. 
 'The yield is 92 p.c of the theoretical. 
 
 Properties. — Needles, V. e. sol. water, and 
 mlcohol, V. si. sol. CHGI3, and ether. Br^ forms 
 tdi-bromo-propyl-urea.— S a It.— B'HNOj. 
 
 Di-aUyl-urea(O,HjNH)jCO.Smai)oKTCe.[100°]. 
 
 Formation.— 1. By action of water and PbO 
 or baryta on aUyl thio-carbimide (Simon, P. 50, 
 377; Will, A. 52, 25).— 2. By heating aUyl 
 cyanate with water or aqueous potash. 
 
 Properties. — Unctuous shining laminte. T. soL 
 alcohol, ether or hot water ; volatUe with steam. 
 Its aqueous solution is ppd. by HgClj and PtOl^. 
 Dry HCl liquefies sinapoline forming B'HCl. 
 
 ALMONDS. — Bitter almonds contain a gluco- 
 side, amygdalin (g. v.), and a nitrogenous un- 
 organised ferment, emulsin. Sweet almonds 
 contain amygdalin but not emulsin. When 
 bitter almonds are ground up with cold water, 
 the amygdalin is split up by emulsin : 
 C2„H„N0„ + 2H,0 = C,HgO + CNH + 2CsH, A. 
 The essential oil of bitter almonds is obtained 
 by distilling the product with steam. It con- 
 tains benzoic aldehyde, prussio acid and man- 
 delonitrile, the product of their union. The 
 presence of mandelonitrile is indicated by the 
 formation of phenyl-ethylamine when the oil is 
 acted upon by nascent hydrogen (Fileti, (?. 9, 
 446). Both sweet and bitter almonds yield by 
 pressure a fixed oil, S.G. is -gis ; this consists 
 of olein with some stearin and palmitin. It is 
 called oil of almonds. 
 
 ALNEIN.— A golden yellow colouring matter 
 in the alder, birch, and beech (Savigny a. Col- 
 Uneau, O. 0. 1881, 703 ; 0.^.42, 309). 
 
 ALOES. — The thickened juice of various 
 species of aloe. 
 
 ALGETIC ACID CnH^N^O,, aq, i.e. 
 GjfK^(^02)fl.2a-il('!).Tetra-nitro-anthraquincme{1) 
 Obtained, together with chrysammic acid, by 
 warming aloes with HNO3 (Schunck, A. 39, 24 ; 
 65, 235 ; G. J. Mulder, A. 72, 286 ; Finck, A. 
 134, 236). Yellow amorphous powder. SI. sol. 
 cold water, m. sol. hot water or alcohol, forming 
 purple solutions, which become yellow on 
 addition of acids, and red again when neutral- 
 ised. It has a bitter taste. Boiling HNO3 con- 
 verts it into chrysammic acid, and ultimately 
 into picric acid. Warm potassium or ammonium 
 sulphide containing excess of alkali forms 
 an indigo-blue gelatinous mass. Salts: 
 BaCiiHjNjOij. AgjA" : insoluble, dark red 
 powder. 
 
 ALOIN. — The purgative principle in aloes. 
 There are several varieties classified by Shen- 
 stone (Ph. [3] 13, 461) as follows : (1) Naia- 
 lo'ins. — Are not reddened by HNO3, but converted 
 by it into picric and oxalic acids. — (2) Barba- 
 loins — are reddened by HNO3, aloetic, chrysam- 
 mic, picric and oxalic acids being formed. These 
 may be subdivided into laj-barbalcfCns, reddened 
 by ooldHNOj (S.G. 1-4), (^)-6aj-6aZoi'MS, reddened 
 by fuming HNO3, not by cold HNO3 (S.G. 1-4). 
 The aloiins may be extracted by hot water or 
 hot spirit from the various aloes, and purified 
 by re-crystallisation. They dissolve in caustic 
 and carbonated alkalis, forming orange solu- 
 tions. Their solutions are ppd. by lead 
 subacetate. 
 
 (a)-Barbaloin, 0,^3.,/), and (0) - Barbaloin, 
 Zauzaloin or Socaloin CuHuO, occur in aloes 
 from Barbadoes, Socotrina, Zanzibar and Jaffer- 
 abad (T. a. H. Smith, Ohem. Gaz. 1851, 107 ; 
 Stenhouse, P.M. [3] 37, 481 ; Tilden, O. J. 25, 
 488 ; 28, 1270). 
 
 Reactions, — 1. By distilling with zinc dust 
 a very little methyl-anthracene may be got (E. 
 
ALUMINIUM. 
 
 Ul 
 
 Schmidt, B. 8, 1275).— 2. Fotash-fusion gives 
 orcin, p - oxybenzoio acid, and aloreinio acid. — 
 8. Boiling dilute sulphuric acid forms p-coumario 
 acid. — 4. HGl and KClOj form tri-ohloro-aloin, 
 CibHijCIjO,, yellow prisms (from alcohol). — 5. 
 Bromine forms tri-bromo-aloin ; yellow needles 
 (from alcohol). — 6. Ac.O forms tri-aoetyl-aloin, 
 CisHijAcaO, : amorphous. 
 
 Nataloin 0,8H,gOj (?). Occurs in Cape aloes 
 (Fliickiger, Ar. Ph. [2] 149, 11 ; Bl. 17, 328 ; 
 Tilden, 0. /. 25, 153). Thin bright yellow 
 scales; si. sol. water, benzene, ether, CS^, and 
 CHCI3. Its solution in H^SO^ is turned green by 
 KNO3, the colour changing through red to blue. 
 
 Additional References. — T. B. Groves, Ph. 16, 
 128 ; Orlowski, Fr. 5, 309 ; Hlasiwetz, A. 184, 
 287 ; Kemboia, A. 138, 186 ; Borntrager, Fr. 20, 
 234; E. H. Groves, Ph. [3] 11, 1045; Lenz, 
 Fr. 21, 220 ; Plenge, Ph. [3] 15, 330 ; Cripps a. 
 Dymond, Ph. [3] 15, 633). 
 
 ALOKCIC ACID C^H^Oa aq. [97°]. Cfi.fi, 
 [115°] i.e. C„H2(OH)Me2.C02H. Formed in small 
 quantity, along with ^-oxy-benzoic acid and 
 orcin, by fusing aloes with KOH (Weselsky, A. 
 167, 65). Long needles. SI. sol. cold water, t. 
 Bol. hot water, alcohol, and ether. The aqueous 
 solutionis not coloured by Fe^CljAq, but alkaline 
 solutions are turned cherry-red by air. Hypo- 
 chlorites turn the aqueous solution of the acid 
 purple-red, colour destroyed by excess. Basic, 
 but not neutral, lead acetate gives a pp. Aloroio 
 acid reduces silver nitrate and FehUng's solution. 
 Fused with potash it forms orcin and KjCOj. 
 
 Salts. BaA'2 6aq: small needles. — CaA'j : 
 needles — CuA'j 4aq. 
 
 Acetyl derivative CgHjAcOj: [125°] ; 
 needles. 
 
 Anhydride CsHsOa : [138°]; formed by 
 distilling the acid. 
 
 ALOXANTHIN C,^U,fi^ Le. 0,4H3Me(OH) ,0^. 
 From barbaloin and socaloin, but not from 
 nataloin, by chromic mixture. Eeduced, by 
 distillation with zinc dust, to methyl-anthracene. 
 Its alkaline solutions are cherry-red. Nitric 
 acid converts it into aloetio and ehrysammio 
 acids (Tilden, Ph. [3] 8, 231 ; 0. J. 32, 903). It 
 forms an acetyl derivative CisHgAcOj. 
 
 ALPHA. To find compounds beginning with 
 this prefix, remove the prefix and look for the 
 remaining word. 
 
 AlPININ CijH.jOj. [174°]. Light yeUow 
 needles (-(-HjO). Occurs, together with oam- 
 phoride and galangin in the galanga-root (Jahus, 
 B. 14, 2810). 
 
 AISTONIDINE. [181°]. An alkaloid occurring 
 along with alstonine (j. v.) and porphyrine {q. «.) 
 in the bark of Alstonia constricta. It may be 
 separated from porphyrine by its more sparing 
 solubility in petroleum. It crystallises in radia- 
 ting needles, sol. alcohol, chloroform, and ether. 
 Its solutions display intense blue fluorescence. 
 It is not coloured by cone. HjSOj or HNO3. 
 Its salts crystallise in colourless needles. The 
 gold and platinum salts are golden flocculent 
 pps. (Hesse, A. 205, 368). 
 
 ALSTONINE G,^B,„t^fi, 3|aq. Chlorogenine 
 (F. V. Miiller a. L. Rummel, C. J. 35, 31 ; Oberlin 
 a. Sohlagdenhauffen, Ph. [3] 10, 1059; 0. 
 Hesse, A. 205, 360). An alkaloid in the bark of 
 Alstonia oonstricta (F. v. M.), from which it may 
 
 be extracted by alcohol. The extract is evapo- 
 rated, treated with very dilute HCl, filtered, ppd. 
 by NH3, dissolved in ether and evaporated. 
 
 Prqp«)-iMS.— Orange-yellow, brittle, pellucid, 
 bitter, mass. It melts below 100°. When dry, 
 it melts at 195°- It dissolves easily in alcohol, 
 ether, chloroform, and dilute acids, but sparingly 
 in water. All dilute solutions show blue fluo- 
 rescence. Salts. Ppd. by excess of acid. — 
 (B'HCl),PtCl,4aq.— (B'H01)2HgCl,.— B',H,Cr,0,. 
 
 ALUMINA. — Oxide of Aluminium, Al^Oj, v. 
 ALnMiNiuM, Oxide op. 
 
 ALUMINATES.— Certainminerals are known, 
 e.g. AljOjMgO, Al.OjBeO, &c., which may be re- 
 garded as deri^ ed from the hydrate AljOj.H^O 
 (v. Aluminium, Hydroxides oe), by replacing H, 
 by Mg, Be, &c. Some of these minerals have been 
 prepared by Ebelmen (A. Ch. [8] 22, 211) by dis- 
 solving Al.fi, and the other metallic oxide in 
 molten boric acid, and removing part of the sol- 
 vent by long-continued heating ; in this way h& 
 prepared spinelle Al^O^Mg, chrysoberyl AljOjECr 
 &o. By heating AI2F5 with boric acid and ZnF^, 
 Deville and Caron obtained gahnite AljO^Zn. 
 
 Barium aluminate Al204Ba.4H20 was ob- 
 tained in crystals by fusing AljO, and oarboa 
 with BaO, BaCOa, Ba2NOs, or BaSO„ dis- 
 solving in water and crystallising (Deville, G. B. 
 54, 327 ; v. also Gaudin, 0. B. 64, 687 ; also- 
 Beckmaun, J.pr. [2] 26, 388 a. 474). Compounds: 
 of AI2O3 and BaO obtained by action of BaOA^ 
 on AljOj and Al^Cl^Aq are described by Beck- 
 mann (B. 14, 2151). 
 
 Potassium aluminate A1204K2.3H20 was 
 obtained in crystals by Fremy (A. Oh. [8] 12, 
 362) by fusing AljOj and KOH in a silver dish, 
 dissolving in water, and evaporating in vacuo ; 
 this salt may be recrystaUised from con. aqueoua 
 solutions, from dilute solutions Al^OuHj separates 
 out. 
 
 Sodium aluminate has not been obtained 
 crystallised. An impure salt is used in manu- 
 factures ; it is obtained by heating cryolite and 
 CaO, or bauxite and NaOH, in steam, dissolving 
 in water and evaporating to dryness (Morin, J. 
 1862. 668). Tissier (O. B. 48, 627) described 
 four compounds to which he assigned the com- 
 positions AljOjNaj, AljOjNas, AljOjNaj, and 
 AljO^Na,; but no analyses are given in the 
 original paper. M. M. P. M. 
 
 ALUMINIUM.— Al. At w. 27-02 (Mallet, T. 
 171, 1003). Mol. w. unknown as V.D. has not 
 been determined. [About 700°]. S.G. f (fused) 
 2-583 (Mallet, T. 171, 1003) ; (after pressure of 
 6,000 atmos.) 2-562 (Spring, A. Ch. [5] 22, 170). 
 S.H. -218 (Louguinine, A. Ch. [5] 27, 398) ; 
 (0°-100°) '2253 (Mallet, I.e.). C.E. (lin. at 40°) 
 ■002313; (lin. 50°) -002336 (Fizeau, C.R. 68, 
 1125) T.O. (Ag = 100) 31-33 (Lorenz, W. 13, 422). 
 E.G. (Hg at 0° = 1) 20-97 at 0°, 16-15 at 15° 
 (Lorenz, I.e.). S.V.S. 10-4. Chief lines in spec- 
 trum, 3960-9, 3943-4, 3612-4, 3091-9, 3081-2, 
 2815-3, 2630-6 (Hartley, T. 175, 101). 
 
 Occurrence. — The metal aluminium does not 
 occur native ; but as silicate (in all clays and in 
 very many minerals, especially the felspars), and 
 oxide (corundum, diaspore, &c.) , and fluoride (cry 
 lite), it is very widely and largely distributed, 
 forming nearly ^ of the earth's crust. Alumina 
 was shown to be a distinct earth by Marggraff in 
 1764 ; the metal was separated by Wohler in 
 
ALUMINIUM. 
 
 1828 (P. 11, 14G), and in purer form in 1854 (A. 
 S3, 422). 
 
 Preparation. — Wohler decomposed AIjCIb by 
 K ; in 1854 Deville employed Na and decomposed 
 •2NaCl.Al,Cl„ (J.pr. 61, 83, 113, 219, 386). Bun- 
 sen (P. 92, 648) decomposed fused 2NaCl.Al2Cl5 
 ■by an electric current. Eose (P. 96, 152) decom- 
 posed eNaF.AljFs (cryolite) by fusing it with KCl 
 and Na. Basset {J. 1869. 753) reduced 
 2NaCl.Al2Cle by Zn, and heated the Zn-Al alloy 
 ■to ■white heat to remove the Zn. The A1.,C1„ may 
 also be reduced by KCN (Wagn, /. 1858. 1) ; a 
 compound of Al and S may be reduced by Pe, or 
 by hydrocarbons (Petitjean, J. 1858. 136) ; and in 
 ■other ways. The usual method of preparation is 
 to heat 2NaCl.Al2Cl„ ■with about 36 p.o. Na and 
 40 p.c. cryolite (as a flux), on the hearth of a 
 reverberatory furnace, and to run off the molten 
 Al into iron moulds. The 2NaCl.Al2Clj is pre- 
 pared by heating bauxite (silicate of Al containing 
 Fe) with Na^COa, whereby Na aluminate is formed, 
 dissolving in water, ppg. Al^Oj by a stream of 
 COj, collecting, washing, and drying the AI2O3, 
 mixing it with charcoal and NaCl and heating 
 strongly in CI whereby 2NaCl.Al2Cl, is formed 
 and distilled o& into receivers. Mallet (T. 171, 
 1003), prepared very pure Al by fusing AljEr,, 
 with KCl and NaCl in the ratio 2(KCl.NaCl):Al2BrB, 
 and then heating with Na in clay crucibles lined 
 ■with AI2O3 and Na aluminate ; the reduced metal 
 was heated on a support of M.fi,, washed with 
 HGlAq, then with water, and dried at a gentle 
 heat. 
 
 Properties. — A tin-white metal; grey when 
 in powder. Odourless and tasteless. After fusion 
 about as hard as silver ; hammered metal is about 
 as hard as soft iron. Very malleable, and ductile ; 
 very sonorous ; may be highly polished. Tena- 
 city nearly equal to that of Cu (V. Burg, D.P.J. 
 151, 286) ; less than that of Zn (Karmarsoh, D.P.J. 
 152, 441; 172, 55). Very feebly magnetic. 
 Melts fairly easily (about 700°) and crystallises, 
 apparently in regular octahedra, on cooling. 
 Non-volatile, and non-oxidisable in air; heated 
 in Qxygen becomes covered with film of AI2O3. 
 Unacted on by HjS or ammonium sulphides, and 
 by S only at high temperatures. Scarcely 
 attacked by HNOjAq, but dissolved by 
 HClAq, H^SO^Aq, KOHAq, and NaOHAq. Most 
 specimens of Al contain Fe and Si ; they are 
 more easily oxidised than the pure metal. 
 
 Aluminium forms one series of salts the 
 simplest formulss of which represent them as 
 derived from acids by replacement of H3 by Al ; 
 e.g. Al^.SSOt, AI3NO3 cSic. 
 
 The atom of A! is trivalent in the gaseous 
 molecule AICI3. Many experiments have been 
 conducted to detei'mine the mol. w. of Al chloride ; 
 Nilson a. Pettersson have finally shown (Z. P. C. 
 4, 206) that the only molecules which exist 
 throughout a considerable range of temperature 
 have the composition AICI3. Odling (P. M. [4] 
 29, 316) stated the V.D. of Al methide to be 36-2 
 at temperatures above 200' (and 72-4 at 130°) ; 
 and hence mol. w. A^CHj),. It remained, how- 
 ever, uncertain whether the gas was homogeneous 
 or not {v. Wanklyn, P. M. [4] 29, 313 ; William- 
 son, ibid. 395 ; Le Roux a. Louise, C. B. 106, 
 73). Quincke (Z. P. C. 3, 164) has shown 
 that the molecular formula of Al methide is 
 Al(CIl3).. 
 
 The atomic weight of Al has been deter- 
 mined; (i.) by analyses and determination of 
 V.D. of AljClj, AljBr^, and AI2IB ; (ii.) by measure- 
 ments of S.H. of Al; (iii.) by comparison of 
 various compounds {e.g. Al„03, and alum) with 
 isomorphous compounds of Cr and Fe ; (iv.) by 
 analyses of ammonia-alum and Al^Br^, and by 
 measuring the H evolved by the action of Al on 
 NaOHAq (Mallet, T. 171, 1008 i.; v. also for older 
 determinationsBerzelius, P. 8, 187 ; Dumas, A.Ch. 
 [3] 55, 151 ; Tissier, C.E. 46, 1105 ; Terreill, Bl 
 31, 153). 
 
 Aluminium is a distinctly metallic element; 
 no allotropic forms of it are known. According 
 to the investigations of Wheatstone (/. 1855. 22), 
 in KOHAq Al is electropositive to Cd, Sn, Pb, 
 Fe, Cu, and Pt, and negative to Zn ; in HClAq 
 Al is positive to Sn and Pb, and negative to Zn 
 and Cd. Al decomposes Hfi at 100°. It reacts 
 with acids to form definite salts, but at the same 
 time hydrated ALO3 dissolves in alkalis to form 
 unstable salts in which the Al forms a part of 
 the negative, or acid, radicle (v. ALniiiNAiEs). 
 
 The thermal value of the action of acids on 
 AI2O3.3H2O is a large positive number approxi- 
 mately equal to the value for CdO.^Hj and FeO^H,, 
 although considerably less than the values of the 
 corresponding actions with CaO^Hj, SrO-^Hj, and 
 BaOjHj thus (Thomsen) : — 
 
 M (M, 2HClAq] M [M, 2HClAq.] 
 
 CaOjHj 30,490 4i^s5s 18,640 
 
 SrO^Hj 27,630 
 BaO^Hj 40,042 
 
 FeO^Hj 
 
 20,290 
 21,390 
 
 The difference between the heat of formation 
 of a metallic chloride and hydroxide has 
 usually a positive value ; in the case of a non- 
 metallic chloride and oxide the difference is 
 usually a negative quantity (Thomsen, Th. 
 3, 531) ; in the case of Al the difference in 
 question has a large negative value, thus 
 [AP, 01']— IM', 0»,3H -O] = - 22, 320. Al shows 
 several analogies ■with Be ; they both very 
 readily form basic and double salts ; Al^O, is 
 less basic than BeO ; both metals readily alloy 
 with Si ; neither seems to be easily acted on by 
 S. For fuller discussion of the chemical rela- 
 tions of Al V. Earths, Metals or the. 
 
 Reactions. — 1. Pure Al is unacted on by 
 ordinary air; impure specimens of the metal 
 become covered with a film of oxide. — 2. Water 
 is decomposed by Al at 100° with evolution of 
 H. — 3. Con. or dilute nitric acid has no action 
 on Al. — 4. The metal is easily dissolved by 
 hydrochloric acid. — 5. Dilute sulphuric acid 
 evolves H, forming Al2.3SOj ; hot con. H^SO, 
 evolves SOj.— 6. Most carbon acids, e.g. acetic, 
 tartaric, have little or no action on Al ; but in 
 presence of NaClAq the action becomes marked, 
 Al^Clj being formed. — 7. Sulphuretted hydrogen 
 has no action even at high temperatures. — 8 
 Aqueous potash or soda dissolves Al, evolving 
 H, and forming an aluminate {v. Cavazzi, G. 
 15, 202) ; molten KOH or NaOH does not act 
 on Al. — 9. Sulphates, carbonates, borates, and 
 silicates, of the alkali metals are decomposed by 
 Al at high temperatures. — 10. Potassium nitrate 
 oxidises Al when the two react at a whit« heat. 
 11. Alkali sulphides are without action even 
 st high temperatures; silver sulphide when 
 
ALUMINIUM. 
 
 143 
 
 heated with Al is partly reduced with formation 
 of a Ag-Al alloy. — 12. Many metallic oxides are 
 deoxidised by Al at high temperatures, e.g. oxides 
 of Pb, Cu, Fe ; oxides of Zn and Mn are not 
 noted on. — 13. Alkaline, but not neutral or 
 slightly acid, solutions of lead, silver, and tin, 
 are reduced by Al with ppn. of the metals ; 
 Cu is ppd. from CuSOjAq. — 14. Most metallie 
 chlorides in solution are reduced by Al (KClAq, 
 NaClAq are exceptions ; Cossa, Z. [2] 6, 380, 
 4i3). Fused zinc chloride, but not MgCLj, is 
 reduced by Al (Flavitsky, B. 6, 195). 
 
 Combinations. — 1. With oxygen to form 
 AljOj ; only at high temperatures, and then 
 superficially. — 2. With sulplvwr to form an 
 unstable compound (v. Aluminium, Sulphide or) 
 only at very high temperatures. — 3. Wohler 
 (P. 11, 160) states that Al combines with 
 phosphorus, selenion, tellurium, and arsenic, 
 when heated in the vapours of these elements ; 
 but little is known of the compounds. — 4. With 
 boron Al forms at least two compounds (v. 
 Aluminium, bokides or). — 5. With chlorine, bro- 
 mine, and iodine, Al combines to iform 
 AI2CI5, AljBru, and Al^Ij (g. v.). — 6. Al forms 
 alloys with most of the metals ; these alloys are 
 usually formed by heating the metals together ; 
 or sometimes by heating AI2O3 and carbon with 
 the other metal. The properties of many metals 
 are considerably changed by alloying with small 
 quantities of Al. The alloys of Al with Cu, Ag, 
 and Su are much used because of their colour, 
 hardness, and stability, and the ease with which 
 they are worked. The alloys of Al have been 
 chiefly studied by Calvert a. Johnson (P. M. [4] 
 10, 240) ; Tissier (0. B. 43, 885 ; 49, 54) ; Debray 
 (0. B. 44, 925) ; Wohler {A. 106, 118 ; 113, 248 ; 
 138, 253 ; P. 11, 161) ; Michel {A. 115, 102). 
 The alloys with copper containing from 6 to 10 
 per cent. Al are yellow, hard, unacted on by 
 moist air, water, or salt solutions, and are easily 
 worked. The alloys with silver are also very 
 stable, have a fine colour and may be highly 
 polished. When a little Al is alloyed with tin 
 the products are very hard and elastic. (These 
 alloys will be more fully described under Coppek, 
 SiLVEB, and Tm.) Alloys of Al with the follow- 
 ing metals have been prepared: — Bi (a very 
 little Bi makes Al extremely brittle) ; Ca (by 
 heating Al, Na, and much CaCl^, Wohler) ; Cu, 
 Cr (by heating Al with Cr^Cl„.KCl, Wohler) ; Au, 
 Fe, Mg, Mn (by heating MnCl^, KCl, NaCl, and 
 Al) ; Hg (Cailletet, C. B. 44, 1250) ; Mo, Ni, Pt, 
 Ag, Na (this alloy easily decomposes H^O) ; Sn, 
 Ti, W (by heating WO3 with Al, cryolite, and 
 KCl, and NaCl) ; and Zn. 
 
 Detection. — Many Al compounds are soluble 
 in water ; most are dissolved by HClAq. Strongly 
 heated AJjOj is nearly insoluble in acids ; it, and 
 also the insoluble Al-coutaining minerals, may 
 be dissolved by fusion with KHSOj and treat- 
 ment with water (H. Eose, P. 1, 275). 
 
 Estimation. — 1. Usually as AljOj : a fairly 
 eo7i, solution is ppd. by a small excess of 
 NHjAq (if Mg salts are present a good deal of 
 NHjClAq is added), the free NH, is removed by 
 warming, the pp. is washed, thoroughly dried, 
 and strongly heated for some time. — 2. ALflJig 
 may also be ppd. by Na^S^OjAq. This method 
 is specially applicable in presence of Fe salts ; 
 the two metals are ppd. as hydrates, the pp. 
 
 is dissolved in HClAq, the solution is nearly 
 neutralised by Na^COsAq and diluted so that 
 50 c.c. do not contain more than -1 gram AljO, 
 a sUght excess of Na^S.^OsAq is added, and after 
 a little the liquid is boiled so long as SOj comes 
 oft, the pp. of AljOeHs mixed with S is filtered 
 hot, washed with hot water, and strongly 
 heated until all S is burnt off ; 
 (Al.,ClaAq + BNa^S ,0,Aq + BH^O = 
 
 Ai^OjHs + 6NaClAq + 3S + 8SO1 ; 
 FejCljAq + 2Na2S20sAq = 
 
 Fe2CljAq + 2NaClAq + Na2SjO„Aq) {v. Chancel, 
 0. B. 46, 987). — 8. Al is also sometimes estimated 
 as a basic acetate (v. Atkinson, Fr. 3, 329 ; also 
 Schulze, J. pr. 47, 313) ; or as basic formate 
 (Schulze, G. C. 1861. 3). For methods of sepa- 
 rating Al from alkaline earths v. Deville, A. Ch. 
 [3] 38, 5; from Co, Ni, and Zn v. Haidlen a. 
 Fresenius, A. 43, 129 ; from iron v. Macivor, 
 0. N. 29, 199 ; from iron and phosphoric acid 
 V. Fhght, O. J. [2] 13, 592 ; also Esilraan, C. N. 
 28, 208 ; from chromium v. Dexter, P. 89,142. 
 
 Aluminium, Alloys of, v. Aluminium ; Com- 
 binations, No. 6. 
 
 Aluminium, Arsenide of. According to Wohler 
 (P. 11, 160) Al combines with As when the 
 elements are heated together ; the product is a 
 grey metal-like mass, decomposed by water with 
 evolution of ASH3. No analyses are given. 
 
 Aluminium, Borides of. Al seems to form 
 two definite compounds with boron, AlBj and 
 AlBjj. They may be obtained by packing a 
 rod of Al in amorphous B in a carbon crucible, 
 placing this in a Hessian crucible with powdered 
 charcoal between the crucibles, covering, and 
 heating to redness for 1^ or 2 hours ; B^Oj may 
 be used in place of B (10 parts B^Oj to 8 parts 
 Al). On cooling, the fused mass is treated with 
 HClAq, whereby Al dissolves and crystals of the 
 borides remain, which may be separated by hand 
 (Hampe, A. 183, 75). Both borides were ob- 
 tained by Wohler and Deville and regarded by 
 them as crystallised boron {A. 101, 113, and 347 ; 
 141, 268) ; the compositions represented by the 
 formulae AlB^ and AlBi^ are assigned by Hampe 
 {I. c). AIB2 crystallises in thin, lustrous, pale 
 copper-coloured, six sided, plates ; unchanged by 
 heating in air ; slowly dissolved by hot con. HClAq 
 and NaOHAq, easily soluble in warm HN0,,.4.q. 
 This compound may be prepared by the action 
 of BClj vapour on hot Al ; or by heating 
 BF3.KP with KCl, NaCl, and Al. AlB.j forms 
 black, monoclinic crystals, transparent in very 
 thin plates ; harder than corundum, softer than 
 diamond. S.G. = 2-534. These crystals are un- 
 acted on by con. HClAq or KOHAq, and very 
 slowly by hot con. H^SO^Aq ; they are soluble in 
 hot con. HNOjAq. They are oxidised by molten 
 KOH and PbCrOj ; also by molten KHSO^ ; but 
 are not acted on by molten KNO3. Heated 
 with Pt an easily fusible alloy is formed. 
 
 Aluminium, Borocarbide of. AljC^Bj,. Ori- 
 ginally obtained by Wohler and Deville, and 
 supposed to be crystallised boron ; examined 
 more fully by Hampe {A. 183, 90). Prepared by 
 long-continued heating at a very high tempera- 
 ture of B^Oj and Al in a graphite crucible (for 
 details, v. Hampe, ^c). The compound crystal- 
 lises in yellowish, sparkling, crystals of the 
 dimetrio system. S G. = 2-615 ; hardness between 
 that of diamond and corundum. The orystala 
 
144 
 
 ALUMINIUM. 
 
 are slowly dissolved by hot ccm. HNOjAq, but 
 not by HClAq, H^SOjAq, or KOHlq; they 
 behave towards molten KOH, PbCrOj, and 
 KHSO4 similarly to AlB,^ (q.v.). 
 
 Aluminium, Bromide of. AlBr^ or Al.Br.; 
 not certain, [abt. 90°] (Weber, P. 103, 254). 
 (263°-3) at 747 mm. (Mallet, T. 18S0. 1003). 
 S.G. 2-54. V.D. 266-8 (Deville a. Troost, A. Gh. 
 [3J 58, 257). H J. [Al^Br*] = 239,440 {Th. 3, 240). 
 
 Formation. — By passing Br vapour over a 
 heated mixture of alumina and charcoal. 
 
 Preparation. — By the action of Br on excess 
 of powdered Al, and subsequent repeated distil- 
 lation from Al, and finally in atmosphere of N. 
 (Mallet, l.c.) 
 
 Properties. — White, lustrous, plates ; fumes 
 in air ; melts to a mobile liquid ; soluble in CS^, 
 alcohol, and water, in latter with production of 
 much heat [Al^Br", Aq] = 170, 600 (Th. 3, 240). 
 
 Beactions and Combinations. — Aqueous so- 
 lution on evaporation in vacuo yields crystals of 
 AljBrg, I2H2O ; this solution is decomposed on 
 heating into Al^OjHj and HBr. AljBrg is decom- 
 posed into AI2O3 and HBr when heated in air ; 
 it combines with the bromides of the alkali 
 metals to form double salts, e.g. 2KBr.Al.,Br5 
 (Weber, P. 103, 259) ; it absorbs NHj, also H^S, 
 forming compounds which are decomposed by 
 heat (Weber, I.e.). 
 
 Aluminium, Chloride of. AICI3. Mol. w. 
 133-13 (800°-1500°) (Nilsona.Pettersson, Z.P.C. 
 
 4, 206). V.D. 66-5 (N. a. P. l.c.). H.P. [Al,crn 
 = 160, 980 {Th. 3, 240). 
 
 Formation. — 1. By heating powdered Al to 
 redness in dry CI.- 2. By passing HCl mixed 
 with CS2 vapour over crude alumina or clay 
 heated to redness ; AI2S3 is formed but is at 
 once decomposed by the HCl (Curie, C. N. 28, 
 307). — 3. By heating Al with various metallic 
 chlorides, e.g. ZnCl^ (Flavitsky, B. 6, 195).— 4. 
 By heating Al^O^ with NH^CI (Eose, P. 74, 569), 
 or with PCI5, BCI3, or SiClj (Troost a. Haute- 
 feuille, C.E. 75, 1710 and 1819). 
 
 Preparation. — 100 parts Al^Oj are made into 
 a thick paste with 40 parts carbon by the help 
 of starch paste, or oil ; the paste is kneaded to a 
 cylinder, which is dried, heated in a covered 
 crucible, and removed while hot to a porcelain 
 tube connected with a CI apparatus ; as soon as 
 the apparatus is fuU of CI, the cylinder is heated 
 to redness ; AI2CI1, distils over into a receiver. 
 It is purified by sublimation from Al in a closed 
 tube bent to an obtuse angle. 
 
 Properties. — Transparent, deliquescent, hexa- 
 gonal plates ; colourless when pure, but usually 
 yellowish because of presence of chlorides of Fe, 
 
 5, cfec. Fusible in large masses but volatilises 
 without fusion if heated in small quantities. 
 Soluble in water with production of much heat 
 [APCl«,Aq] = 153,690 {Th. 3, 240); soluble in 
 alcohol, and ether; insoluble in benzene; unacted 
 on by HClAq. 
 
 Beactions. — 1. Fumes in moist air absorbing 
 H^O and giving off HCl. — 2. Easily decomposed 
 (to AljOjand HCl) by steam (Kuhnheim, /. 1861. 
 149). — 3. Partly decomposed by oxygen at a red 
 heat with evolution of CI (Berthelot, C. B. 86, 
 787). — i. Heated to redness with Zima, corundum 
 (AliOj) is formed ; with magnesia, spineUe 
 (AljO^Mg) is produced (Daubree, C. B. 39, 135).— 
 B. Decomposed belo-w red heat by potassium or 
 
 sodium, with production of Al, and KCl, or NiiCI. 
 — 6. Molten AL^Cl^ is electrolysed to Al and CI 
 (Buff, A. 110, 257). — 7. Sulphuric anhydride 
 forms Ala.SSOj, SO^, and CI. — 8. Solution in 
 water is decomposed by heat into AL^Oj and HCl. 
 
 Combinations. — 1. Dissolves in water ; solu- 
 tion when slowly evaporated gives deliquescent 
 crystals of AI2CI8.I2H2O (Bonsdorff, P. 27, 279). 
 — 2. Absorbs dry ammonia to form yellow- 
 AljOlj.eNHj ; when this is heated in a stream of 
 dry H, AI2CIJ.2NH3 is obtained (Persoz, A.Ch. 
 44, 319). — 3. Combines with phosphoretted hy- 
 drogen to form a yellow powder 3AI2CIJ.2PH3, 
 decomposed by H^O giving off PH, (Eose, P. 24, 
 295). — 4. Phosphoric chloride at 180° forms 
 AI2CI5.2PCI5 ; crystalline, easily fusible, easily 
 decomposed by H^O (Weber, P. 107, 375).— 5. 
 Combines with some other non-metallic chlo- 
 rides ; chief combinations are AI2CI1J.2POCI, 
 (Casselmann, A. 98, 220) ; Al2Cls.2NaCl (Weber, 
 P. 118, 471); Al2Cle.SCl,, Al^d.-SeCl,, and 
 AljCl^.TeClj (Weber, P. 104, 421). Forms a com- 
 pound with HjS which is decomposed by H^O 
 (Wohler, P. 11, 160).' — 6. Combines with 
 chlorides of alkali metals to form AI2CIJ.2MCI 
 (Degen, A. 18, 332 ; DeviUe, A. Ch. [3] 43, 30) ; 
 the most important is Al2Clj.2NaCl, white 
 crystals, melting at about 185°, volatile at a red 
 heat without decomposition; deliquescent, but 
 much less so than AIjClj. This salt is prepared 
 on the large scale, as from it the metal Al is 
 obtained {v. Aluminium, Preparation of). — 
 7. By evaporating solutions of the mixed chlo- 
 rides the compounds Al2OlB.2PdCl2.20H2O and 
 Al2Cls.2PtClj.30H2O were obtained (Welkow, B. 7, 
 304 and 802). — 8. With suVph/wrcms anhydride 
 forms AI2CI5.2SO2, a heavy liquid, solidifying at 
 - 10° (Andrianowsky, Bl. [2] 31, 495). 
 
 Aluminium, Fluoride Of. AIP3. Mol. w. un- 
 certain, as V.D. not determined. S.G. 3-1. 
 
 Occurrence.— la combination with NaP as 
 cryolite Al2Pj.6NaF ; also with sihcates in 
 topaz, (&c. 
 
 Formation. — 1. By action of HF on Al^Oj. — 
 2. By fusing cryohte with A12.3S04, and digest- 
 ing in water whereby Na^SOj is dissolved and 
 AljFe remains (Deville, C.B. 42, 49). 
 
 Preparation. — A mixture of fluorspar and 
 alumina, in a boat of graphite, is heated to 
 fusion in a tube of graphite, in dry HCl ; crystals 
 of AljFj sublime and CaClj remains (Deville, 0. B. 
 43, 971). 
 
 Properties and Beactions. — White, and very 
 obtuse rhombohedra; unacted on by air, by 
 acids, or by aqueous alkalis (Deville, C B. 43, 
 970). Volatile at bright red heat. 
 
 Combiiiations. — 1. With hydrofluoric acid and 
 water : by dissolving Al^Oj in HjSiF^Aq, digest- 
 ing with AljjOj till SiOj is ppd. and solution ia 
 neutral, and evaporating, crystals of AI2F5.7H2O 
 are obtained ; if digestion with AI2O3 is stopped 
 while liquid is distinctly acid but SiOj is ppd., 
 and alcohol is added, 3AI2F5.4HF.IOH2O is 
 formed ; if, instead of adding alcohol, the acid 
 liquid is evaporated AljFj.HF.SHjO is produced 
 (Deville, A. Ch. [3] 61, 327)'.— 2. With alkali 
 fluorides compounds of the form AI2F5.6MF are 
 formed, the most important of these are 
 the K and the Na compounds. AljFj.eKF ia 
 obtained as a gelatinous pp. by adding a solution 
 of AljO, in HFAq to an excess of KFAq.Al;^, 
 
ALUMINIUM. 
 
 145 
 
 4KF is produced by adding KFAq to excess of 
 AljF, in HFAq; if the pp. is boiled in the 
 liquid AljPj.eKP is formed. Both pps. form white 
 powders when dry, and are decomposed with loss 
 of all their ¥ by heating with con. 'K.SOtAq. 
 AljPj.eNal" occurs native as cryolite on the west 
 coast of Greenland. S.G. = 2-96. It may be pre- 
 pared by the action of HFAq on AljOj and 
 Na^COj, mixed in ratio ALjOaiSNajCOs, drying, 
 ani heating to fusion. Forms colourless, trans- 
 parent, dimetric crystals ; softer than felspar ; 
 melts below red heat, forming a colourless glass 
 on cooling. Decomposed to CaFj and a solution 
 of AljOj in NaOHAq, by boiling with milk of 
 lime, or fusing with CaCOa and boiling in HjO. 
 Heated with H2S04Aq loses HP, and produces 
 A12.3S04 and Na^SO,. 
 
 Aluminium, Hydrated Oxide of, v. Aluminium, 
 Hcteoxides op. 
 
 Aluminium, Hydroxides of. Three com- 
 pounds of Al, H, and are known; they re- 
 act rather as hydrated oxides, AlJO^.xBfi where 
 a; = 1, 2, and 3, than as hydroxides. Al^O, which 
 has not been strongly heated takes up HjO ; but 
 the definite compounds are obtained by indirect 
 methods ; Al^O, which has been strongly heated 
 has no action on Kfi. The hydrates of Alfi, 
 lose their water at a red heat. When freshly 
 ppd. they dissolve easily in acids, forming the 
 same salts Al^Xj where X = aoid radicle {v. 
 Aluminium, Salts of). Thomseu gives the 
 following thermal values [AV, 0', 3ffO] = 388,920 ; 
 
 [Al, 0», H»] = 297,000 ; r^i!2!5!, H^SO^Aql = 
 
 20,990; ^^~' 
 
 240). The hydrates also dissolve in KOHAq and 
 NaOHAq with formation of easily decomposed 
 aluminates (j. v.). The hydrates, especially 
 ALjOg.SHjO, form a class of bodies called lakes 
 by their action on vegetable colouring matters ; 
 they pp. these colouring matters from solutions, 
 hence these hydrates are used as mordants. 
 
 I. MoNOHYDKATB. Al^Oj.H^O ( = AljOiHj). Oc- 
 curs native as diaspore, in transparent, trimetrio 
 crystals, S.G. 3'43, which crumble to powder 
 when heated but lose all HjO only at about 360° ; 
 insoluble in water and in boiUng HClAq. By 
 heating amorphous AljOj in a closed tube with 
 HjO to 240°-250° Mitscherlioh obtained hydrated 
 AljO, nearly agreeing in composition with 
 formula AljO,.HjO (J. pr. 83, 468). According 
 toBecquerel (/. 1868. 87; /. 1874. 182) crystalline 
 AJLjOj.HjO is produced when a tube containing 
 CijOljAq and covered with parchment paper is 
 suspended in a solution of Al^Oj in KOHAq. 
 
 II. DiHYDEATE. AljOs.2H,0 { = A1,0^B.,). 
 Occurs native as amorphous bauxite (Berthier, 
 S. 35, 154). Prepared by the action of NH^ClAq 
 on ALjOs in KOHAq, washing, and drying at 100° 
 (Lowe, Z. 3, 247) ; also by ppg. hot solutions of 
 Al salts by NHjAq, digesting the pp. in the 
 warm liquid, washing, and drying at 100° (St. 
 GiUes, A. Oh. [3] 46, 58). A dihydrate is also 
 obtained by the slow decomposition of basic 
 aluminium acetate, and subsequent evaporation 
 to dryness at 100° (v.i.). The dihydrate is said 
 to be nearly insoluble in acids and aqueous 
 alkalis. Two varieties of A1203.2H20 in aqueous 
 solutions were obtained by Crum Ifi. J. 6, 225), 
 
 Vol. I 
 
 ?-.2HClAq'l = 18,640 {Th. 3, 
 
 and Graham {T. 1861. 183), respectively. Crum 
 prepared basic Al acetate 
 
 (2A1,(C,H,0,)«.A1,0.H,.3H,0), 
 dissolved this by heating with much water, 
 heated this solution to 100° in a closed tube for 
 ten days, whereby the salt was decomposed into 
 acetic acid and ALjOj.xHjO, then diluted, and 
 boiled in an open vessel until all acetic acid was 
 removed. The solution of Alfi^xE^O thus 
 obtained was colourless, tasteless, and neutral to 
 litmus ; it was easily coagulated by small 
 quantities of sulphuric, citric, tartaric, and many 
 other acids, and by various salts, not by acetic, 
 formic, boric, and one or two other acids. This 
 solution does not act as a mordant ; evaporated 
 at 100° AI2O3.2H2O insoluble in acids is oobtined ; 
 the coagulated hydrate dissolves in con. acids. 
 Graham dissolved Al^Oa-ccH^O in Al.jCljAq or in 
 Al acetate solution, and dialysed; the aqueous 
 solution of AljOj.ojHjO thus obtained was very 
 easily coagulated by acids, alkalis, and salts ; it 
 acted as a mordant ; the coagulated hydrate 
 dissolved easily in dilute acids. 
 
 III. Tkihydkate. AI2O3.3HJO ( = Al20|iH„). 
 Occurs native, in hexagonal, fibrous, crystals, 
 as gibhsite, and hydra/rgyllite. Prepared by 
 ppg. cold solution of Al salts by NHjAq, or 
 (NHJjCOjAq, washing, dissolving in HGlAq, 
 reppg., washing, and drying at 100°. A soft, 
 friable, white powder; easily soluble in acids 
 and fixed aqueous alkalis ; insoluble in water. 
 When freshly ppd. it forms a gelatinous mass, 
 soluble to some extent in NHaAq, but reppd. 
 on standing in air. Heated to redness it loses 
 all its H2O, and contracts considerably. A 
 crystalline trihydrate is formed by the action 
 of air on a saturated solution of AI2O3 in 
 KOHAq (Bonsdorff, P. 27, 275) ; it is insoluble 
 in cold acids, slowly dissolved by boiling HClAq, 
 more rapidly by H^SOiAq. AI2O3.3H2O is also 
 said to be formed by the action of H2O on Al 
 amalgam (Cossa, Z. 13, 448). 
 
 Aluminium, Iodide of. AII3 or AIJb ; not 
 certain, [abt. 185°] (abt. 360°) (Weber,'P. 101, 
 465; 103, 259). S.G. 2'63. V.D. 387-4 (DeviUe 
 a. Troost, A. Ch. [8J 58, 257). H.F. [A1-,I»] = 140, 
 780 {Th. 8, 240). 
 
 Preparation. — ^Al in small pieces is placed in 
 a retort, about ^ to 1 p.o. of the calculated 
 quantity of I is added, CO2 is led in, and the< 
 retort is heated until combination occurs ; rather 
 less than the quantity of I needed to convert- 
 all the Al into Al^I^ is then added, and heating, 
 in a steam of CO2, is continued until Al2la sub-- 
 limes (Gustavson, A. 172, 173). 
 
 Properties, (&c. — White, deliquescent, plates ; 
 soluble in alcohol, and CSj! soluble in water 
 with production of much heat [Al^P.Aq] = 178,000. 
 {Th. 3, 240). Solution in HjO on standing over 
 H2SO4 gives AI2IS.I2H2O. Decomposed by heat- 
 ing in O (Schulze, J. pr. [2] 21, 40). Forms 
 double salts with alkali iodides ; absorbs NH3 ; 
 apparently does not combine with H,S (Weber, 
 P. 101, 465 ; 103, 259). 
 
 Aluminium, Nitride of. Al heated in N 
 increases in weight, and heated with molten 
 NaOH evolves NH3 (Briegleb a. Geuther, A. 123, 
 288). The compound AljNj was obtained by 
 MaUet (0. J. [2] 15, 349) by heating Al with 
 NajCOs to the highest temperature of a wind 
 furnace for some hours in a graphite crucible, 
 
14S 
 
 ALUMINIUM. 
 
 ind treating tlie residual mass with HClAci. 
 The oompound is pale-yellow when' amorphous, 
 bright honey-yellow and very lustrous when 
 crystallised ; brittle, not hard enough to scratch 
 glass ; in moist air it slowly crumbles down to 
 AljOj with evolution of NHj ; it is dissolved by 
 aqueous alkalis with evolution of NH3 and solu- 
 tion of Al; fused with KOH or NaOH, an 
 aluminate is formed and NHj is given off ; heated 
 in air, NH3 is evolved and Al^Oj remains. 
 
 Aluminium, Ozide of. [There are some in- 
 dications of the existence of an oxide contain- 
 ing more than Alfi, (v. Gibson a. Morrison 
 P.B.S.E. 119, 146, 152).] AlA {Alumma) 
 Mol. w. unknown. S.Gt. (amorphous) 3*725 to 
 4-152 (Eose, P. 74, 429); (crystalline) 3-928. 
 S.H. (corundum, 9°-98°) -19762; (sapphire, 
 8°-97°) -21733 (Eegnault, A. Ch. [3] 1, 129). 
 
 Occwrrenee. — Native, nearly pure as corun- 
 dum, sapphire, topaz, (vmethyst, &o.; also in 
 opaque variety as emery. 
 
 Formation. — I. Amorphous. — 1. By 
 burning powdered Al in oxygen. — 2. By ppg. boil- 
 ing solution of potash-alum by (NHJ^COjAq, 
 washing, and strongly heating. — 3. By strongly 
 heating ammonia-alum. — 4. By digesting clays, 
 felspathio rocks, &o., with con. KOHAq under 
 pressure, and ppg. by OOj. — 5. By heating a 
 mixture of cryolite and lime in steam, lixiviating, 
 and ppg. by CO^. — II. Crystalline. — 1. By 
 fusing the amorphous AI2O3 in the oxyhydrogen 
 flame (Gaudin, O. JB. 49, 1342).— 2. By heating 
 equal parts of potash alum and E^SO, with 
 charcoal (Gaodin, A. 103, 92).— 3. By fusing 
 together Al phosphate with three or four parts of 
 KjSOi or Na^SOj (Debray, O. R. 52, 895).— 4. 
 Along with AI2O3.H2O, by heating a solution of 
 AI2O3 in HCIAq to 350° in a closed tube 
 (S^narmont, O. iJ. 32, 762).— 5. By heating to 
 bright redness equal parts of amorphous AljOj 
 and PbO (Deville a. Caron, A. Ch. [4] 5, 104). 
 
 Prepa/ration. — The amorphotis variety may 
 be prepared by heating dry potash-alum for two 
 or three hours to redness, finely powdering the 
 residue, washing with water, mixing with 
 NaOHAq containing ^ as much NaOH as the 
 potash-alum used, drying, strongly heating, and 
 washing with water (Wohler, A. 53, 422 ; Brun- 
 ner, P. 98, 488). Crystalline Alfi, may be pre- 
 pared by heating to whiteness a mixture of one 
 part amorphous AI2O3 with four parts fused 
 borax (Ebelmen, A. Ch. [3] 33, 34). Large 
 crystals 1 cm. long were obtained by Deville a. 
 Caron (A. Ch. [4] 5, 104) by the action of Al^P^ 
 on boric acid at a high temperature. The Al^Fj 
 was placed in a graphite crucible, the boric acid 
 being contained in a small Pt basin fixed above 
 the AljPj ; the whole was placed in a Hessian 
 crucible and heated in a wind furnace for some 
 time ; BP3 was volatilised and crystals of ALfl, 
 remained. 
 
 Properties. — Known in two forms, amorphous 
 and crystalline. The amorphous variety is a 
 white, soft, powder ; cakes together when strongly 
 heated, and becomes nearly as hard as corun- 
 dum ; infusible except in oxyhydrogen blowpipe ; 
 insoluble in water ; soluble in acids and aqueous 
 alkalis, but after strongly heating becomes in- 
 soluble in acids except con. HjSOjAq and con. 
 HCIAq. The crystalline variety forms colourless 
 rhumbohedra; insoluble in all acids; nearly as 
 
 hard as diamond. Both forms are undecomposed 
 by heat, and are unacted on by CI. 
 
 Reactions. — 1. With acids amorphous Al^O, 
 reacts to form Al salts — e.g. AI2.3SO4. — 2. Fused 
 with potash or NaOH, or KHSO4, both amor- 
 phous and crystalline AI2O3 form aluminates (3. v.) 
 which are soluble in water. — 3. Amorphous AljO, 
 heated to whiteness with potassiv/m is partly de- 
 oxidised with formation of an alloy of E and Al. 
 4. Heated with sal ammoniac, MjOlg is formed ; 
 the same compound is produced by the action of 
 hot BCI3, or SiClj. — 5. Al^S, is said to be formed 
 by the action of carbon disuVphMe vapour on 
 hot AI2O3. — 6. Water is taken up by slightly 
 heated amorphous Al^O,, but no definite hydrates 
 have been thus obtained (v. Aluminium, Hydbox- 
 
 IDES OP). 
 
 Aluminium, Oxychlorides of. A series of 
 these compounds seems to exist ; they may be 
 obtained by the action of a mixture of AljClj 
 vapour and on Al ; the higher the tem- 
 perature the more is there in the product ; 
 they are soluble in dilute acids and alkalis, and 
 are decomposed by water (HautefeuiUe a. Perrey, 
 C. R. 100, 1219). Tommasi {Bl. [2] 37, 443), 
 describes three compounds of AJLjOgHj with 
 AljClj obtained by the action of Al on CuCljAq 
 under different conditions. 
 
 Aluminium, Phosphide of. Described by 
 Wohler (P. 11, 160) as a dark grey mass, which 
 decomposes H^O evolving PH, ; produced by 
 heating powdered Al to redness in vapour of P. 
 
 Aluminium, Salts of. Salts obtained by 
 replacing H of acids by Al. These salts 
 belong to the form Al^Xj, or AIX3, where X = 
 
 PO, CO3 SOj, 
 3 ' 2 ' 2 
 
 NO3, 
 
 ! &0. ; besides these, many 
 
 basic salts (compounds of normal salts with 
 AljOj.xHjO) are known. Very many Al salts 
 also form double salts ; the most characteristic 
 of which are the alums Al2.3S04.MjS04.24H20, 
 where M= an alkali metal, Ag, or Tl («. Alums). 
 The haloid salts, the normal nitrate, sulphate, 
 and acetate, are soluble in water ; most of the 
 other normal salts, and almost aU the basic 
 salts, are insoluble in water. The soluble salts 
 possess a sweetish, astringent taste. Aqueous 
 solutions of Al salts generally contain more 01 
 less free acid, which is not, however, to ba 
 detected by the ordinary tests ; Erlenmeyer a. 
 Lewinstein {Z. 3, 572) add freshly ppd, 
 Mg.NH4.PO4, which pps. Al2(P04)2, and forma 
 MgSO, and (NH4)2S04, the acid can then be 
 detected by litmus &c. The number of Al salts is 
 not very large ; with some acids, e.g. sulphurous, 
 carbonic, &a., it forms no salts or very unstable 
 ones which can hardly be obtained pure. The 
 chief salts — described under Borates, Phos- 
 phates, &o. — are the borates, nitrates, phos- 
 phates, silicates, and sulphates: v. also Cabbo- 
 NATES, Sulphites, Selenatbs, &o. 
 
 Aluminium, Seleuide of. According to 
 Wohler, Al when heated in Se vapour com- 
 bines vrith the latter to form a black powder 
 which' is decomposed by HjO into AljO^-xB^O 
 and HjSe (P. 11, 160). 
 
 Aluminium, Silicides of. Al and Si react 
 in almost aU proportions ; the products seem 
 to be of the nature of alloys. When Al ia 
 heated with silicates in presence of a flnx, a 
 
ALUMINIUM ETHIDE. 
 
 147 
 
 lji;Ttion of the silica is reduced and combines 
 with part of the Al. An alloy containing 10'3 p.o. 
 Si, called cast aluminium, is grey and very 
 brittle; an alloy with 70 p.o. Si stiU exhibits 
 metallio properties. The aUoys of Si and Al are 
 much more easily acted on by reagents than 
 either of the elements which form them. 
 
 AluminiTim, Sulphide of. Al^Sj. 
 
 If Al is heated to glowing and S is then 
 thrown on to it, a black mass is produced which 
 is decomposed by HoO with evolution of H^S. A 
 mixture of AljSs and AljOjis obtained by passing 
 CSj vapour over red-hot AijOa. When AL.SSO^ 
 is heated in H, Al^O, remains and HjSO, is 
 volatUised (Wohler, P. 11, 160). The best 
 method of preparing AI2S3 seems to be to pass 
 S vapour over hot Al in a carbon boat placed in 
 a porcelain tube kept full of H. It is described 
 as yellow crystals, with a bitter taste, which melt 
 with difficulty, and are rapidly acted on by water 
 with formation of H^S and MjOs-noSfi pPremy, 
 A. Oh. [3] 38, 322 ; Sabatier, A. Ch. [5] 22, 88 ; 
 Eeichel, J. pr. [2] 12, 55). Spring (Bl. [2] 
 39, 64) obtained a sulphide of Al by very strongly 
 compressing an intimate mixture of Al and S. 
 
 Alnmi-ninni, Telluride of. Described by 
 Wohler as a black powder produced by heating 
 together Al and Te (P. 11, 160). 
 
 M. M. P. M. 
 
 AirMINIUM AMTLATE v. Aim, alcohoi,. 
 
 ALTnaiNITJU BBOMISE, Action of, on Or- 
 ganic Bodies. — Aluminium bromide assists the 
 bromination of aromatic hydrocarbons. The 
 action appears to be preceded by the formation 
 of a compound AlBrgBCnHj^.j (Gustavson, J. 
 1877, 400 ; 1878, 380 ; B. 18, Eef. 208). AlBrj 
 also combines with butylene; thus, when HBr 
 mixed with CjH, is passed into ALBrj at 60°, the 
 compound AlBrjCjHj is formed ; the same com- 
 pound is formed from AlBra and C^HjBr, and by 
 passing HBr into American or Caucasian petro- 
 leum containing AlBr, at 70° (Gustavson, /. B. 
 16, 95 ; B. 17, Bef. 163). 
 
 The compound AlBrjCjHj is an oil, insol. in 
 light petroleum or CS2; it is decomposed by 
 water with formation of unsaturated hydro- 
 carbons and by alkyl bromides at 70° with 
 formation of paraffins (Gustavson, J. jgr. [2] 
 34, 161). 
 
 Aluminium bromide converts alkyl chlorides 
 into bromides. 
 
 AlUMINITTM ISO-BTJTYIi OijHjjAl i.e. 
 A1(C<H,),. From Al and B.s(fi^)i. Fuming 
 liquid (Cahours, J., 1873, 522). 
 
 AIUMINXUM ISO-BUTYLATE v. mo-Bdttil 
 
 hLDOUOL. 
 
 ALUMINITTM CHLORIDE, Action on Organic 
 Bodies. — Aluminium chloride is converted by 
 CJE, and HCl at 100° into the compound 
 AiClaC^H, (G.). 
 
 Aluminium chloride added to a mixture of 
 an aromatic hydrocarbon and an alkyl or alkoyl 
 chloride, bromide or iodide, promotes the evolu- 
 tion of HCl, HBr, or HI and is therefore a most 
 powerful agent in organic synthesis as a means 
 of introducing alkyl or alkoyl groups into an 
 aromatic nucleus (Friedel a. Crafts, C. B. 84, 
 1392, 1450; 85, 74, 672; 86, 1368). Thus 
 methyl-benzenes may be formed by this means 
 from benzene and methyl chloride; acetophenone 
 
 from benzene and acetyl chloride. The opera- 
 tion is performed by dissolving the aromatio 
 hydrocarbon and the haloid derivative in CSj or 
 light petroleum, and adding AlCl, in successive 
 small portions. The reaction is completed by 
 heating on a water-bath. Condensation is also 
 brought about by AlCl, by the removal of water; 
 thus benzene and AcjO form acetophenone ; 
 while benzene and phthalio anhydride form 
 benzoyl-benzoic acid. Under the influence of 
 AICI3 other reactions also occur ; thus benzenu 
 is converted by oxygen, sulphur, sulphurous acid, 
 and carbonic acid into phenol, phenyl -meroaptan, 
 benzene sulphinic acid, and benzoic acid, respec- 
 tively. 
 
 These reactions are perhaps due to the 
 formation of such compounds as AICI33CJH5 in 
 which the benzene may be supposed to be more 
 unstable than when in the free state ; thus, we 
 might imagine the compound to be AlHgClgPh,. 
 Molecular changes may, however, take place in 
 the alkyls ; thus both n- and iso-propyl bro- 
 mides are converted by AlBr, into the same iso- 
 propyl-benzene ; this is because n- propyl bro- 
 mide is changed by AlBrg, into its isomeride 
 (Gustavson, J. 1878, 380 ; P. 16, 958). 
 
 In the above cases AlCl, induces the building 
 up of more complicated compounds, but this 
 reaction may be reversed and alkyl groups 
 removed instead of introduced. Thus ethyl- 
 benzene, heated with AICI3 in a stream of HCl, 
 evolves ethyl chloride and is reduced to benzene 
 (Jacobsen, B. 18, 388). When the alkyl chloride 
 is not carried ofi by a stream of HCl it may act 
 by substitution upon another portion of the 
 hydrocarbon. Thus toluene is converted by 
 boiling with AICI3 into benzene and xylene 
 (Ansohiitz a. Immendorff, B. 17, 2816). Some- 
 what similar reductions occur in other cases, 
 the hydrogen being derived from another portion 
 of the hydrocarbon. Thus naphthalene gives 
 naphthalene dihydride, by reduction, and iso-di- 
 naphthyl, by abstraction of hydrogen ; benzene 
 gives toluene and ethyl-benzene together with 
 di-tolyl ; di-phenyl-methane is reduced to ben- 
 zene and toluene (Friedel a. Crafts, B. A. 1884, 
 468; C. iJ. 100, 692). 
 
 AICI3 acting upon n-propyl iodide gives pro- 
 pylene and HI, which then react, producing 
 propane (Kohnlein, B. 16, 560). Aluminium 
 bromide or iodide acting on propyl chloride or 
 iodide at 130° form propylene but no propane 
 (Kerez, A. 231, 286). AICl, acting upon alcohols 
 and phenols eliminates HCl ; thus phenol gives 
 (PhO)3Al2Cls ; resorcin gives (0^fi'i)^\^\ ; and 
 di-chlorhydrin gives CsHjCljO.AlClj, which 
 crystaUises from CS2. These compounds are at 
 once decomposed by water into the alcohol, 
 A1(0H)3, and HCl (Claus a.Mereklin, B. 18,2932). 
 Acetyl chloride in CSj is converted by AlClj 
 into a white solid, CijHuOsAljClj, whence water 
 produces a liquid O5HSO2 (137°) which may be 
 aoetyl-acetone (Combes, C. R. 103, 814). 
 
 ALUMINIITM ETHIDE AlC^His i.e. AlEt, 
 (194°). V.D. 4-5 (for 3-9) at 234°. From mer- 
 curic ethide and aluminium heated at 100° for 
 some hours (Buckton a. OdUng, Fr. 14, 20). 
 Liquid ; fumes violently in air, soon taking fire. 
 Decomposed by water. Iodine forms EtI. 
 
 Aluminium iodo-ethlde AljCgHijI, i.e. 
 AljEtjIj, (340°-350°), is a fuming liquid formed 
 
 L 2 
 
148 
 
 ALUMINIUM ETHYLATE. 
 
 by action of EtI on Al at 130° (Cahours, A. Ch. 
 [3] 58, 5 ; A. 114, 242). 
 
 ALUMINIUM ETHYIATE v. Alcohol. 
 
 ALUMINIUM IODISE, Action on Organic 
 Bodies. Allj turns out CI displacing it by I, e.g. 
 3CCl4 + 4AU3=3Cl4 + 4AJCl3 (Gustavson, A. 
 172, 173). Aluminium iodide and aluminium 
 are singly without action on alcohol, but to- 
 gether they react, forming Al2l3(OEt)3 and 
 Al2(0Et)B. One molecule of aluminium iodide 
 may convert very many molecules of aluminium 
 into aluminium ethylate {v. Alcohol). Other 
 alcohols act similarly (v. Pkoptl, Butyl, and 
 Amtl, alcohols, Ckbsol, Phenol, Naphthol 
 Thymol), but methyl and iso-propyl alco- 
 hols, glycol, and glycerin do not ; the latter 
 forms allyl alcohol (Gladstone a. Tribe, Pr. 
 30, 546, C. J. 39, 2 ; 41, 5 ; 49, 25 ; Hodgkinson, 
 C. N. 1877, 237). Aluminium behaves in a 
 similar way towards water and ether; it does 
 not attack these bodies until after iodine has 
 been added, when it reacts with water thus : 
 3H20 + A1 = A1(0H)3 + H3, with which may be 
 compared its action on alcohol: 3H0Bt + Al = 
 Al(0Et)s + H3, while with ether it forms alu- 
 minium iodo-ethylate and EtI. 
 
 ALUMINIUM METHIDE AlCaHj i.e. AlMCj 
 L'c. 0°]. (130°). V.D. 2-8 (for 2-5) at 220° ; 4 at 
 1C0°. From HgHe^ and Al at 100° (Buokton 
 a. Odling, Pr. 14, 19). Takes fire in air. Be- 
 sembles AlEtj. Just above its boiling-point the 
 compound seems to be Al^Me^. 
 
 ALUMINIUM PROPYL 
 AIO3H2, i.e. A1(C3H,)3. (240°- 245°). 
 Prom HgPr^ and Al (Oahours, X 1873, 518). 
 
 ALUMS. — Double sulphates or selenates 
 having the composition expressed iy the gene- 
 ral formula M^S{orSe)Oi.N^8{orSe)0,.'iiB.,0, 
 where M= Al, Cr, Mn, Fe, In, or Oa; and N= Na, 
 K,Bb, Cs, NS„ Ag, or Tl. These salts crystallise 
 in forms belonging to the regular system, usually 
 in octahedra or cubes. The following are the 
 best-known alums: — I. Sulphates: (1) M = A1, 
 and N = Na, K, Bb, Cs, NH,, NH3(C2H5), Ag, or 
 Tl; (2)M = Cr, andN = Na,K, orNH^; (3) M = 
 Mn, andN = K, or NH^; (4) M = Fe, and N = K, 
 or NH^; (5) M = Ga or In, and N = NHj; (6) 
 Mj = CrAl, and N = K, or NHj. II. Selenates : 
 
 (1) M=A1, and N = Na, K, or NH<; (2) M = Cr, 
 and N = K, or NH4. III. Mixed Selenates and 
 Sulphates, M23SeO,.N2SO,.24H20 : (1) M=A1, 
 andN = K; (2)M = Cr, and N = K; (3) M = Fe, 
 and N = K. IV. Mixed Sulphates and Selenates, 
 Mj3S0<.Nj,Se04.24H20 : (1) M = A1, and N = K; 
 
 (2) M = Cr, and N = K; (3) M = Mn, and 
 N = K; (4) M = Fe, and N = K. Besides these, 
 there are certain double salts which resemble, 
 but are not isomorphous with, the alums ; of 
 these pseudo-alums the most important are 
 the following : — I. Compounds of AljSSOj with 
 (1) MnSO^, (2) FeSO„ (3) MgSO^ ; each with 
 24HjO. II. Compounds of Fe2.3S04 with (1) 
 MgSO^, (2) CuSO,, (3) ZnSO, ; each with 24H2O. 
 m. Mn23SO,.MgS04.24H20. 
 
 In naming the alums, if no prefix is used, a 
 double sulphate of aluminium and one of the 
 metals represented by N in the formula is under- 
 stood ; thus potassium alum is 
 
 ld^^m^M^m^.U^B.fi. 
 The sulphates containing no aluminium are 
 tpoken of as chromium-sodium alum, iron-am- 
 
 monium alum, iSio. Similarly, the names 
 ammonium selenio-alum, and chromium-potas- 
 sium selenio-alum are used for the members of 
 Group II. The salts belonging to Groups HI. 
 and IV. may be called selenio-sulphuric alums ; 
 the individual bodies are best distinguished by 
 their formulae. 
 
 The alums are all soluble in water, their 
 solubility in hot, being considerably greater than 
 in cold, water; (potash alum, S. 3'29 at 0°; 
 S. 22 at 30° ; S. 31 at 60°; S. 357 at 100°). The 
 solutions have a styptic taste and an acid re- 
 action. Some of the alums are separated by 
 water into their constituent salts, e.g. silver 
 alum, and manganese-ammonium and potassium 
 alums. Others are partially separated ; indeed 
 it appears very probable that every alum is to 
 some extent separated into its constituents when 
 dissolved in a considerable quantity of water. 
 Thus, Favre and Valson (0. B. 74, 1165) find 
 the heats of solution of one equivalent of alumi- 
 nium sulphate (1) in water, (2) in a solution of 
 KjSOj, and (3) in a solution of (NHJjSO,, to be 
 the same (about — 8,000) ; hence no combination 
 occurs between the two sulphates in the presence 
 of water. Further the heats of solution in 
 water of the alums .have large negative values, 
 and in some cases — e.g. iron-ammonium alum — 
 this value increases considerably as temperature 
 rises (Favre and Valson, O. B. 74, 1016). 
 G. Wiedemann (P. 126, 1 ; 135, 177), by deter- 
 mining the specific magnetism (that is, magnetic 
 moment developed by unit magnetising force -=- 
 mass of salt in unit volume) of various salts in 
 solution, has shown that an aqueous solution of 
 ferric sulphate is partly separated into sulphuric 
 acid and colloidal ferric oxide, and that the 
 amount of this separation increases the larger 
 the quantity of water added ; he has also shown 
 that an aqueous solution of iron-ammonium 
 alum behaves almost exactly in the same way as 
 ferric sulphate ; hence the separation of the ferric 
 sulphate by the water is independent of the 
 alkaline sulphate ; and hence a dilute aqueous 
 solution of this alum is to a large extent sepa- 
 rated into its constituent salts. When an 
 aqueous solution of potassium alum saturated at 
 12° is heated to 100° a precipitate is slowly formed 
 containing varying quantities of AljO,, K^O, SO3, 
 and HjO ; even after 30 days the precipitate con- 
 tinues to be produced. The decomposition of 
 the alum is hastened by adding K2SO4 to the 
 solution (A. Naumann, B. 8, 1630). Chromium- 
 potassium alum exists in two forms ; as violet 
 crystals, and as a green non-crystallisable salt. 
 When a solution of the former salt in water is 
 heated to 70°-80° the colour changes to green, 
 and this change is attended with a gradual in- 
 crease of the volume of the solution; as the 
 green solution cools the colour slowly changes to 
 violet-blue, and the volume of the liquid slowly 
 decreases (Boisbaudran, C. B. 79, 1491). The 
 violet crystals change at 300°-350° to the green 
 salt with loss of all their water of crystallisa- 
 tion; this green dehydrated alum is wholly 
 soluble in hot water, but when heated somewhat 
 above 350° it suddenly changes to greenish- 
 yellow and becomes quite insoluble in water 
 (Lowel, A. Oh. [3] 44,313 ; Siewert, A. 126, 
 86). When a quantity of barium chloride 
 sufScient to precipitate all the acid in a given 
 
AMARINE. 
 
 149 
 
 maBB of obromium-potassium alum is added in 
 four equal portions to an aqueous solution of the 
 green form of this alum, the first and second 
 fourths of the barium are at once precipitated, 
 but the rest only very slowly ; moreover, the 
 quantity of heat produced during the precipitation 
 of the first and second fourths is much greater 
 than that produced during the subsequent pre- 
 cipitations (Favre and Valson, C. B. 74, 1165). 
 Thus, 
 
 Qram-units of heat prodicced. 
 ExoesaofBaOl,. 1st fourth. 2iid fourth. 3ra& 4th fourths. 
 
 8251 4104 4102 146 
 
 These results taken together show that solution 
 in water of the commoner (probably of all) alums 
 is accompanied by partial separation of these 
 compounds into their constituent salts, and also 
 by partial decomposition of these constituents, 
 certainly at least of the sulphate of the heavy 
 metal ; and that the amount of this separation 
 and decomposition is increased by increasing the 
 quantity of water, or by raising the temperature. 
 
 The alums are dehydrated by the action of 
 heat ; at a higher temperature a portion of the 
 acid radicle is usually volatilised, and a double 
 basic sulphate remains , such as native alum stone 
 Alj3S04.KjSOi.2AlA-8H20 ; at a still higher 
 temperature more acid is removed and a mixture 
 of alkaline sulphate and oxide of Al, Cr, Mn, or 
 Fe remains ; the ammonium alums leave a 
 residue of oxide only. For descriptions of the 
 properties of the individual alums v. Sulphates. 
 
 M. M. P. M. 
 
 DI-AITIEIC ACID v. DiiiuKic acid. 
 
 AMALGAMS. Alloys of Mercury {v. AiAjOys). 
 Amalgams are formed (1) by direct union of 
 mercury with other metals; e.g. amalgams 
 of alkali metals, of Zn, Fb, Sn, Au: (2) by 
 precipitation of other metals from solutions of 
 their salts on mercury j this is often done by 
 placing sodium-amalgam in the solution of a 
 metallic salt, sometimes by electrolysing a me- 
 tallic solution in presence of mercury ; e.g. amal- 
 gams of Ag, Fe, Co, Ni, Mn, Ba : (3) by precipi- 
 tation of mercury on another metal, sometimes 
 it is necessary to electrolyse the mercurial solu- 
 tion, making the other metal one of the elec- 
 trodes ; e.g. amalgams of Cu, Ag, Au, Pt : (4) by 
 placing the other metal in contact with mercury 
 and a dilute acid ; e.g. Zn amalgam. The form- 
 ation of amalgams is not usually attended with 
 any marked thermal change, but in the produc- 
 tion of amalgams of the alkali metals much heat 
 is produced. Thus, [Na, Hg] = 10,300 ; [Na, Hg=] 
 
 = 21,600; [K, Hg^ = 20,300; [K, Hg'^ = 34,200 
 (Berthelot, O. B. 88, 1110, 1335). In the forma- 
 tion of amalgams of Sn, Pb, and Bi, heat is ab- 
 sorbed. Little or no contraction of volume 
 accompanies the formation of amalgams, except 
 in the oases of Cu, Ag, Sn, Pb, and a few other 
 metals. The relative conductivity for heat of 
 some solid amalgams is considerablygreater than 
 that of either of the metals composing them ; 
 e.g. amalgams of Sn, Zu, and Bi. Many solid 
 amalgams seem to be chemicalcompounds in defi- 
 nite proportions ; thus when various amalgams 
 containing excess of mercury were subjected to a 
 pressure of about 70 tons on the square inch 
 mercury was removed, and definite bodies re- 
 mained, containing mercury and metal approxi- 
 
 mately in the ratios expressed by the formula) 
 CuHg, AgHg, FeHg, Zn,Hg, Pb^Hg, PtHg, 
 (Joule, 0. J. 16, 378). Again, when amal- 
 gams of Au, Ag, Cu, Pb,K, and Na, were heated 
 near to, to, or above, the boUing-point of mer- 
 cury (860°), the following definite amalgams were 
 obtained (De Souza, B. 8, 1616 ; 9, 1050) :— 
 At 310° AusHg Ag.Hg Cu„Hg 
 „ 360° Au,Hg Ag„Hg Cu„Hg Pb.Hg 
 ,, 440° Au,Hg Ag.jHg Cu,„Hg K,Hg NajHg. 
 Some of the liquid amalgams may be regarded 
 as solutions of definite compounds in excess of 
 mercury, e.jr. liquid Na and K amalgams ; others 
 as solutions of metals in mercury, e.g. some of 
 the iron amalgams. For descriptions of indi- 
 vidual amalgams see the articles on the different 
 metals, also MEEcniiT. M. M. P. M. 
 
 AMALGrAMAIION'. The process of forming 
 Amalgams, q. v. 
 
 AMAIIC ACID O.jHuNjO, 
 i.e. CjHjMe^NjOj. Tetva-methyl-alloxanUn. 
 
 Formation. — 1. On mixing a solution of di- 
 methyl-aUoxan with one of di-methyl-dialuric 
 acid, amaUc acid is ppd. (Maly a. Andreasch, M. 
 3, 103). — 2. A product in the oxidation of 
 caffeine by chlorine or nitric acid (Eoohleder, 
 A. 71, 1). — 3. By reducing di-methyl-aUoxan by 
 HjS (B. Fischer, B. 14, 1912). 
 
 Properties. — Transparent colourless crystals. 
 Stains the skin red. V. si. sol. cold water or 
 alcohol, si. sol. hot water. Eeduces silver salts. 
 It forms deep violet compounds with baryta, 
 KOH, or NaOH. 
 
 Beactions. — 1. Oxidised by nitric acid to 
 di-methyl-aUoxan, or, better, by passing chh' 
 rine into water in which it is suspended.— 
 
 2. Amalic acid may be distilled without 
 leaving a residue, but it is decomposed and 
 in the distillate there is a crystalline acid, 
 CijHijNjOj, 'desoxy amalic' acid [260°]^ 
 This acid is v. sol. chloroform or glacial acetic 
 acid, sparingly so in cold alcohol, water or ether. 
 Soluble in alkalis but reppd. by HCl. Is partly 
 decomposed when distilled. Eeduces boiling 
 ammoniaoal AgNOj. Evaporated with HNO, 
 it forms dimethyl-alloxan. Chromic mixture 
 converts it into cholestrophane. Hence it is 
 possibly (Fischer a. Eeese, A. 221, 339) : 
 
 Me.N - CO CO.NMe 
 
 COHC - CHCO 
 
 MeN - CO CO.NMe 
 
 3. Hydrogen sulphide forms di - methyl - di - 
 aluric acid (M. a. A.). — 4. By hailing with 
 water in an open vessel di-methyl-oxamide is 
 produced : 
 
 C.^Hi.N.Os H- HjO + O3 = 2C,H8NjOj + 400^. 
 5. Ammonia gas turns it violet, forming 
 murexo'in, a crystaUine body resembling 
 murexide. — 6. From the solution made by heat- 
 ing amalic acid (4 pts.) with cyanamide (2 pts.) 
 and water (100 pts.) there separates out, on 
 cooling, crystalline cyamido-amalic acid 
 C,sH,jNjO,. Long prisms, si. sol. cold water, v. 
 sol. hot water, insol. alcohol or ether ; reduces 
 silver salts, and yields methylamiue and an 
 oxalate when boiled with alkalis. It gives oil 
 purple vapours when heated, and forms a subli- 
 mate (Andreasch, M. 3, 433). 
 
 AMANITINE V. Nbubine. 
 
 AMABINE V. Benzoic aldeetde. 
 
150 
 
 AMBER. 
 
 AMBER. A fossil resin from Pinites suc- 
 cinifer. S.G. 1-05 to I-IO. It contains from 
 3 to 8 p.c. sucoinio acid, also a resin [146°] 
 soluble in ether but not in alooliol, a resin 
 '105°] soluble in alcohol and. other bodies. 
 There is about 1 p.c. ash (0. Helm, P. [3] 11, 
 229). When amber is distilled, succinic acid 
 and oil of amber are got. The latter (110°-260°) 
 is a mixture of terpenes (Pelletier a. Walter, 
 A. Ch. [3] 9, 89). 
 
 AMBEEIN. [25°-30°]. Extracted from am- 
 bergris by hot alcohol. Ambergris is found in 
 the intestines of the spermaceti whale in tropical 
 climates, and also floating in the sea. Ambrein 
 is insol. water, v. sol. alcohol or ether, neutral to 
 litmus. It cannot be saponified. It greatly resem- 
 bles oholesterin (Pelletier, A. 6, 24 ; /. Ph. 5, 49). 
 
 AMENYL GLYCERIN v. Tbi-oxt-mntane. 
 
 AMENTL-VALERIC ACID v. Decenoio acie. 
 
 AMETHENIC ACID 0,H,A (185°-230°). By 
 oxidation of diamylene with chromic mixture 
 (Schneider, A. 167, 209). 
 
 Properties. — A light oil. 
 
 Salts. — SrA'j, 8aq : needles. — Zn A'^ : warts ; 
 aqueous solution forms a gelatinous pp. on 
 heating. — ^AgA': difficultly soluble pulverulentpp. 
 
 AMIC ACIDS. Bodies represented by the 
 formula X"(C02H).CO.NH2, being at once amide 
 and acid, e.g. oxamio acid. 
 
 AMIDES. Bodies derived from ammonia by 
 displacing one-third of its hydrogen by a mono- 
 valent acid radicle (Gerhardt a. Chiozza, A. Ch. 
 [3] 46, 129). When two-thirds of the hydrogen 
 is displaced by a divalent radicle the product is 
 called an imide, but if the same amount of 
 hydrogen is displaced by two monovalent 
 radicles the product is still called an amide. If 
 the whole of the hydrogen is displaced the pro- 
 duct is also called an amide unless it is displaced 
 by one trivalent radicle, when it is called a nitrile. 
 
 Amides derived from ammonia by displacing 
 one-third of the hydrogen by an acid radicle, e.g. 
 NH2.CO.X, may also be looked upon as derived 
 from mono-basic acids, X.CO.OH, by displace- 
 ment of OH by NHj. 
 
 Di-basic acids, T"(C0.0H)2, form, in a 
 similar way , first amio acids,Y"(CO.OH) (CO.NH^) , 
 then di-amides, Y"(CO.NHj)j. Thus a di-amide 
 may be considered to be derived from two mole- 
 cules of ammonia by displacing one-third of the 
 hydrogen by a di-valent acid radicle. 
 
 Formation. — 1. By action of ammonia on 
 ethers : X.CO.OEt + NH, = X.CO.NHj + HOEt.— 
 
 2. By the action of ammonia on acid chlorides ; 
 
 X.CO.Cl -I- 2NH3 = X.CO.NHj -I- NH,C1. 
 
 3. By the dehydration of ammonium salts : 
 X.CO.ONH,-HjO = X.CO.NHj. The rate at 
 which this decomposition is brought about by 
 heat has been studied by Mensohutkin (C. B. 
 98, 1049) 4. By action of NH3 on anhydrides : 
 
 (X.C0)20 -t- 2NH3 = X.CONH2 + X.CO.ONH,. 
 The anhydrides of di-basic acids are converted by 
 this reaction into amic acids or imides. — 5. From 
 nitriles and cold cone, hydrochloric acid 
 XC3N-i-H,0 = X.C0.NHj.— 6. Prom nitriles, hy- 
 drogen peroxide, and very dilute KOH (Ead- 
 ziszewski, B. 18, 355). — 7. Prepared by heating 
 acids with ammonic sulphoeyanide for three or 
 fcnir Q81VS & o * 
 
 NH^SNC +'2H0Ac = 2AcNHj + COS + H.,0 
 (J. Schulze, J.ffr. [2] 27, 512). 
 
 Properties. — The amides are usually solid, and 
 their melting-points serve to identify the several 
 acids. They are neutral to litmus, but form 
 compounds with acids ; their typical hydrogen 
 can in many cases be displaced by metals (Ag or 
 Hg). The typical hydrogen can be displaced by 
 alkoyls, by treatment with acid chlorides, but 
 heating with alkyl iodides does not result in the 
 introduction of alkyls unless sodium has been 
 previously introduced. Alkylated amides can be 
 formed by the action of alkylamines upon acid 
 chlorides or ethers. 
 
 Peactions. — 1. Converted by dehydration (e.g. 
 with P2O5) into nitriles : X.CO.NHj = X.C:N + H^O. 
 
 2. Converted into acids by boiUng' potash, 
 boiling dilute HCl, fuming HNO3, or rdtrous acid : 
 
 X.CO.NH2 -I- HNO3 = X.CO.OH + HjO H- N^O 
 (Eranchimont, B. 2, 343). 
 
 X.CO.NH2 + HNO2 = X.CO.OH -I- H^O -1- Nj. 
 
 3. One of the typical atoms of hydrogen may 
 be displaced by halogens; when bromine and 
 alkalis are both present, compounds of the form 
 X.CO.NEBr and X.CO.NKBr, are produced? 
 these readily split up into KBr and cyanic 
 ethers XNCO (Hofmann, B. 17, 1406; 18, 2734). 
 
 4. Phosphorus pentachloride reacts thus : 
 
 X.CO.NH2 + PCI5 = X.CCly.NH, + POCI3. 
 The resulting compound splits ofi HCl giving 
 X.CCl2NH2 = HCl + XCCl:NH a chloro-imide 
 and X.CCl:NH = HCl-hXC:N.— 5. PCI5 acts 
 upon alkylated amides, forming compounds 
 with twice as many carbon atoms in the mole- 
 cule. Thus CHj.CONHEt gives CHjCChNEt 
 which then acts thus : 
 
 2CH3CCl:NEt = NEt:CCl.CH,.CMe:NEt + HCl. 
 CHj-CONHPh acts similarly, while PhCO.NHPh 
 and CCljCONHEt form only chloro-imides. 
 Formanilide, HCONPhH does not produce 
 NPh:CCl.CH:NPh but NPh:CH.NPhH, di- 
 phenyl-formamidine (WaUach, A. 184, 1 ; 214, 
 193). 
 
 The HCl liberated in the decomposition 
 X.CCI2.NHY = HCl + XCCl :N Y 
 may often convert Undeeomposed amide into 
 amidine 2X.C0.NHY + HCl = 
 
 XCO2H + XC(NY)(NHY)HC1. 
 Amidines may also be formed thus : 
 XCONHY -1- XCCljNHY = 
 XC{NY)(NHY)HC1 + XCOCl. 
 6. Heated with alcohol they form alkyl-am- 
 monium salts : 
 
 X.CO.NH2 + HOEt = X.C0.0.NH3Et 
 
 X.CO.NHEt + HOEt = X.C0.0.NH,Etj 
 
 X.CO.NEtj, + H0Et=X.C0.0.NHEt3 
 
 (Baubigny, C. B. 95, 646).— 7. ZnEtj acts thus : 
 
 X.CO.NH2 + ZnEt2= X.CO.NZn + 2HEt 
 Y".(C0.NH,)2 -I- ZnEt^ = Y'-.C^O^NaH^Zn -1- 2HEt. 
 These compounds are decomposed by water, 
 with reproduction of the amide (H. Gal, C. B. 
 96, 1315). — 8. Phenyl-hydrazine reacts thus: 
 PhNH.KH, + NH,.CO.X = PhNH.NH.CO.X + NH, 
 (P. Just, B. 19, 1201).— 9. Dry HCl converts 
 primary into secondary amides : 
 
 2NACH2 + HCl = NA02H + NHjCl 
 AMIDINES. The name is applied to com- 
 pounds that contain amidogen and imidogen 
 attached to the same atom of carbon. Thus, 
 CH3.C(NH).NH2 is called acetamidine, that is 
 to say, an imide derived from acetamide, while 
 CjH5C(NH)NHj is called benz-amidine, the 
 imide of benzamide. Other names for these 
 
AMIDO ACIDS. 
 
 Ml 
 
 'bodies are etheuyl amidine, benzenyl amidine, 
 ethenyl imid-amide, benzenyl imid-amide, acet- 
 imid-amide, benz-imid-amide. The advantage 
 of the imido-amide nomenolature is chiefly seen 
 in naming derivatives, thus CH3.C(NEt).NH2 and 
 CH3.C(NH).NEtH may be called aoet-ethyl- 
 imido-amide, and aoet-imido-ethyl-amide, re- 
 spectively. But the advantage so gained is lost 
 in the great lengthening of the names, and both 
 bodies will therefore be called ethyl-aoetamidine 
 in this dictionary. They might be distinguished 
 as tertiary and secondary ethyl-acetamidine 
 respectively. 
 
 Dibasic acids can give rise to a variety of 
 amide-imides, for which Wallaeh {A. 214, 256) 
 proposes the following nomenclature : — 
 
 ^<cSnH^NH, a«»id-amidine. 
 
 kBS ^^^^- 
 
 ^CO 
 
 E<'p,-jT™ ^NH imid-imidine. 
 K<^i^S>NH imidine. 
 
 Formation. — 1. Amidines are formed by the 
 action of amines on thio-amides or nitriles : 
 Ph.CN + NPhjH = Ph.C{NH).NPhj (Bernthsen, 
 A. 184, 290, 321).— 2. By the action of amines 
 on the compounds (X.CC1:NH or X.CC1:NY) 
 formed by the action of PCI5 on amides (Wal- 
 laeh, B. 8, 1575). 
 
 Beactions. — 1. SjS forms thio-amides : 
 Ph.C(NPh).NPhH + H^S = Ph.CS.NPhH + HjNPh 
 Ph.C(NH).NPhH + H^S = Ph.CS.NPhH + NH,. 
 Another reaction also takes place : 
 
 Ph.O(NH).NPhH + HjS = Ph.CS.NH^ + NPhH^. 
 This may be explained by supposing an inter- 
 mediate compound, Ph.C.(SH)(NH2).NPhH, to 
 be formed by addition of HjS. 
 
 2. CSz acts thus : 
 
 Ph.C(NH).NPhH + CSj= Ph.CS.NPhH + HNCS 
 
 Ph.C(NH).NPhj + CS2 = Ph.CS.NPh2 + HNCS 
 Ph.C(NPh).NPhH + CS^ = Ph.CS.NPhH + PhNCS 
 
 3. Action of aceio-acetic ether, v. p. 19. 
 
 The reactions of the amidines are further 
 described in such articles as Fokmamidinb, 
 AcETAMiDrNS, Benzamidine, Makdel-amtthne, 
 PhenyIi-aoetamidine, and Phenil-benzamidine. 
 
 AMIDO-AG£TANILIDE v. Aoetyl-PHENYLENE- 
 
 DI-AMINE. 
 
 AMIDO-ACETIC ACID v. GlycocolIi. 
 Acetyl derivative V. AoETVBio Acm. 
 Benzoyl derivative ii. Hippueio acid. 
 AMIDO-ACETO-ACETIC ACID v. Aceto- 
 
 ACBTIC AOID. 
 
 AMIDO-ACETO-NAPHTHALIDE v. Acetyl- 
 
 NAPHTHYLENE DI-AMINE. 
 
 AMIDO-ACETOPHENONES CsH|,NO i.e. 
 CsHj(NH2).CO.CH3 Amidophenyl methyl ketone. 
 
 o-Amido-acetophenone (c. 249°). 
 
 Formation. — 1. By reduction of o-nitro- 
 acetophenone (Gevekoht, B. 15, 2086 ; A. 221, 
 326). — 2. By action of cone. H^SO^ on a solu- 
 tion of o-amido-phenyl-acetylene (Baeyer a. 
 Bloem, B. 15, 2154).— 3. By boiling o-amido- 
 phenyl-propiolic acid with water (B. a. B.). 
 
 Pr^aration. — o-Amido - phenyl - acetylene 
 (50 g.) is slowly dropped into cone. H2SO4 
 (600 0.0.) diluted with water (200 o.c). After 
 
 half an hour, the mixture is poured upon ice ; 
 neutralised with NajCO, ; distilled with steam ; 
 and the distillate extracted with ether. 50 p.o. 
 of the theoretical yield is got (Baeyer a. Bloem, 
 B. 17, 964). Properties. — Thick volatile oil. 
 
 Oxim [148°] (Munchmeyer, B. 20, 512). 
 
 Salts. — B'H^SO^ : needles. — B'HClSnClj: 
 needles, sol. alcohol. — B'jHjPtCl,; : yellow pp. 
 
 Reaction. — By boiling with alcoholic aceto- 
 
 phenone and some NaOHAq it is converted into 
 
 flavolin or phenyl-methyl-quinoline (0. Fischer, 
 
 £.19, 1036): CsHj(NH2).C0.Me-HPh.C0.0H,= 
 
 „„ „„ ^CMe:CH 
 
 H^O + O.H<^ : fcph 
 
 Acetyl derivati/oe CjHj(NHAc).CO.CH,. 
 [77°]. Silky needles (from benzoline). Sol. 
 alcohol, ether, and hot water, si. sol. cold water. 
 
 TO-AJoido-acetophenone [93°]. Formed by 
 reducing the nitro compound by Sn and HCl 
 (Buchka, B. 10, 1714; Hunnius, B. 10, 2009; 
 JEngler, B. 11, 932). Short yellow pyramids, sol. 
 alcohol, and ether. 
 
 Salt. — B'HCl : long pointed crystals. 
 
 j^-Amido-acetophenone [106°]. 
 
 Formation. — From the nitro compound (j. v.) 
 by Sn and HCl (Drewsou, A. 212, 162). 
 
 Preparation.— Aajlme (2 pts.), ZnCl^ (3pts.), 
 and AOjO (5 pts.) are boiled together foj; 5 
 hours ; the resulting acetyl derivative is saponi- 
 fied. Yield 55 p.c. of the theoretical (Elingel, 
 B. 18, 2687). 
 
 Properties. — Long fan-like crystals (from 
 water). V. sol. alcohol, ether and hot water, 
 si. sol. cold water, benzene, and benzoline. 
 
 SaZfe.— B'HCl : needles.— B'jHjjPtCl,: slender 
 yellow needles. — B'jH^SO, : needles. — W^iJOJOi : 
 crystals, v. sol. alcohol. 
 
 Acetyl derivative C8H,(NHAc).OO.OH3. 
 [167°]. Small needles, v. sol. alcohol, and hot 
 water, si. sol. cold water. 
 
 Ethyl derivative v. Ethyl-amido-aoeto- 
 
 PHENONE. 
 
 Benzyl derivative v. Benzyl - amido- 
 
 ACETOPHENONE. 
 
 AMIDO ACIDS. — Amidogen, when attached 
 to carbon in an acid, behaves as it does in 
 amides (g^.v.) or as in amines (g,.v.) according as 
 that carbon does or does not belong to carbonyl; 
 in the former case the compound is classed as 
 an amio acid (g^.v.), the term ' amido acid' is 
 usually restricted to the latter class of bodies. 
 
 Formation. — 1. From the halogen derivatives 
 of fatty acids, or their ethers, by the action of 
 ammonia. — 2. From the nitro-derivatives of 
 (aromatic) acids by reduction. — 3. From alde- 
 hydes, by action of hydric cyanide and NH, : 
 
 X.CHO + HON + NH3 = X.CH(NHJCN + H^O. 
 The nitrile is then converted into amide by 
 cone. HCl, and this is saponified by hot dilute 
 HCl. In this way o-amido acids may be pre- 
 pared ; alkylamido acids can be formed by using 
 alkylamines instead of ammonia (Tiemann, B. 
 14, 1982 ; Stephan, O. 0. 1886, 470). 
 
 Properties. — Neutral bodies which combine 
 both with acids and bases. Their neutrality 
 is probably due to self-saturation, as may be 
 represented by a doubled formula : 
 R.CH.NH,.O.CO 
 
 CO.O.NHs.CH.E. 
 Reactions,— 1. Converted by nitroiis aeid 
 
163 
 
 AMIDO ACIDS. 
 
 into oxy-aoids {v. p. 57, I. 6) ; di-Azo deriva- 
 tiyes (q. v.) are first formed, and this formation 
 may be utilised as a test for amido-aoida 
 (Curtius, B. 17, 959).— 2. When heated with 
 lime or baryta, they split off COj forming 
 amines. This separation of CO^ sometimes 
 occurs in formation 2 : thus C,H3(N02)Br(C02H) 
 [4:2:1] reduces to m-bromo-aniline (Soheufelen, 
 A. 231, 176) ; CeH3(N02)jC02H [4:1:2] reduces to 
 »i-phenylene diamine (Wurster, B. 7, 149 ; 
 Oriess, B. 7, 1225); while C,H3(NOj)(002H)2 
 [4:1:2] becomes m-amido-benzoio acid. In all 
 these cases the GOj is split off from the position 
 para to NOj. — 3. AcCl forms acetyl-amido acids. 
 4. Excess of methyl iodide, in presence of KOH, 
 converts (fatty) amido acids into ammonium 
 iodides : 
 
 CH2(NH2).C02H + 3MeI + 3E0H = 
 
 CHj(NMe3l).C02K + 2KI + 3H,0 
 
 (Korner a. Menozzi, (?. 13, 350). p-Amido- 
 
 benzoio acid is converted by Mel and EOH into 
 
 the betame OsH4<^^qq»>, while EtI only forms 
 
 di-ethyl-amido-benzoio acid (Michael a. Wing, 
 Am. 7, 195). — 5. Saturated with cuprio hydroxide, 
 suspended in hot water, they form blue solutions 
 from which on cooling the copper salt separates. 
 This occurs vrith leucine, glutamic acid, and 
 aspartio acid. In the case of leucine, a portion 
 remains dissolved, forming a blue mother liquor. 
 In the case of mixtures of amido-acids, the 
 copper salts are not so readily ppd., for they 
 seem to render one another soluble (Sohulze a. 
 Barbieri, J. pr. [2] 27, 351).— 6. The methods of 
 displacing amidogen by halogens in aromatic 
 bodies are mentioned under Amines. 
 
 AMIDO-ACEYLIC ACID CjHjNOj i.e. 
 CH(NH2):CH.C02H, is formed by the action of 
 alcoholic ammonia on i3-chloracrylic acid at 
 100° (Pinner a. Bischoff, A. 179, 97). H. W. 
 
 AMIDO-ALCOHOLS or Alkamines (q. v) are 
 formed by action of bases on ohlorhydrins or on 
 alkylene oxides, e.g. : 
 
 CHjOLCHjOH + NH3 = CH2(NH,HCl).CHj.0H, 
 and 
 
 I \o + NMe, + HjO = CHj(NMe30H).OHjOH. 
 
 V. OXT-ETHTL-AMINE, NBUEINE, &0. 
 
 AUISO-ALIZABIN v. OxY-AMIDO-ANTHRi- 
 
 QUINONBS. 
 
 DI-AMIDO-AMAEINE v. Amarine under 
 Benzoic aidbhtdb. 
 
 AMIDO- AMYLAICOHOI v. Oxy-amttl-amine. 
 
 AMIDO-AMYL-BENZENE C„H„N i.e. 
 C,H,(C5H„)NH2. (258°) (0.) ; (260°-265°) (H.). 
 An oil. Formed by heating amyl-aniline 
 hydrochloride at 320° (Hofmann, B. 7, 529), or 
 by heating aniline with amyl alcohol and ZnOL 
 at 270° (Calm, B. 15, 1643). 
 
 Salts.— B'jHjSO^: silky needles.— 
 B'jH2PtCl|j : slender orange-yellow needles. 
 
 Benzoyl derivative OaH,(C5H„)NHBz. 
 [0. 149°]. Pearly plates ; sol. alcohol, ether, 
 benzene. 
 
 AMIDO-ANISIC ACID v. Methyl-oxY-AMiDo- 
 
 BENZOIO ACID. 
 
 AHIDO-ANISOL v. Methyl-AMWo-VBETjOh. 
 AMIDO-AIirTHEACENE v. Anthkamine. 
 AMIDO-ANTHEAQUINONES C„H,NOj. M.w. 
 223. Three have been described, but theory 
 
 indicates only two ; (a) and m - are perhapi 
 identical. 
 
 o-Amldo-anthraqiiiiione 
 
 ^«^<Co!6!>^«^-^^^ (2). [241°]. 
 
 Formation. — 1. By reducing o-nitro-anthra- 
 quinone (Boemer, B. 15, 1790). 
 
 Properties. — ^Buby-red iridescent needles ; 
 may be sublimed. Sol. alcohol, ether, benzene 
 and HOAo, forming orange liquids, v. si. sol. 
 water. It is a weak base, dissolving in cone. 
 HCl. Converted by nitrous acid into erythro- 
 oxy-anthraquinone. 
 
 Salt. — ^B'HCl: unstable white needles. 
 
 Acetyl derivative CnH,O.^NAcH [202°]. 
 Orange-red needles, sol. alcohol and cold HClAq. 
 
 (a)-Amido-anthraqainone [254°]. 
 
 Formation. — 1. Prom bromo-nitro-anthra- 
 quinone (Glaus a. Hertel, B. 14, 980) or from 
 di-bromo-nitro-anthraquinone (Claus a. Dieren- 
 fellner, B. 14, 1334) by sodium-amalgam. — 2. 
 From (a)-nitro-anthraquinone and sodium- 
 amalgam (Bottger a. Petersen, A. 166, 149). 
 
 Properties. — Bed needles, may be sublimed. 
 Sol. benzene and chloroform, si. sol. alcohol, 
 and ether. Differs from the preceding by in- 
 solubility even in fuming HClAq. 
 
 m- Amido -anthraquinone 
 
 ^«^<C0 i6J>06H3NH, (3). [302»]. 
 
 Formation. — 1. From anthraquinone m- 
 sulphonio acid and NH3Aq at 200° (Perger, B, 
 12, 1566 ; according to Bouchardat, Bl. 33, 264, 
 this reaction produces amido-oxy-anthraquinone) 
 2. From its acetyl derivative, which is got by 
 oxidising acetyl-anthramine by CrOs in glacial 
 HOAo (Liebermann, A. 212, 61). 
 
 Properties. — Bed needles. Sol. aqueous HCl, 
 insoluble in alkalis. By the action of HNO, 
 and boiling alcohol it is converted into anthra- 
 quinone. 
 
 Acetyl derivative OhHiO^NAcH. [257°] 
 (P.) ; [263°] (L.) ; colourless needles. 
 
 Di-amido-anthraquinones 
 
 C„H,„N,02 i.e. C^HaOj (Ntt,),. 
 
 (a)-Di-amido-authraquinone [236°]. 
 
 Formation. — 1. From (a)- di-nitro-anthraqui- 
 none either {a) by ammonic sulphide, (6) by 
 aqueous NHj at 200°, nitrogen coming off 
 (J. Fischer, J. pr. [2] 19, 209), or (c) by SnClj 
 and NaOHAq (Bottger a. Petersen, A. 160, 148). 
 2. By reduction of tetra-bromo-di-nitro-anthra • 
 quinone (Claus a. Hertel, B. 14, 981). 
 
 Properties. — Bed needles (from ether), with 
 greenish reflex (when sublimed). V. si. sol 
 water, m. sol. alcohol, ether or acetone, v. sol. 
 benzene. The solutions are purple. Hardly 
 soluble in dilute acids ; does not form salts. 
 
 Reactions. — 1. Nitrous add passed into ita 
 alcoholic solution forms anthraquinone (B.a.P.). 
 2. Nitrous acid passed into its ethereal solution 
 forms a brownish-violet powder, OuHjNiOj, 
 which detonates atabout 68° (B.a.P.). — 3. Potash- 
 fusion produces alizarin (Bottger a. Petersen, 
 B. 4, 778), or some similar body (Liebermann, 
 B. 4, 231, 779). 
 
 (/3)-Dl-aimdo-anthraquinone [above 300°]. 
 
 Formation. — 1. By boiling (j3)-di-nitro-an- 
 thraquinone vrith SnClj and NaOHAq (Schmidt, 
 J.pr. [2] 9,266). 
 
 ProperHes. — Beddish-brown powder ; sub- 
 
AMIDO-BENZENE. 
 
 163 
 
 limes in dark red needles. 81. sol. water, y. sol. 
 alcohol, ether, and benzene, forming red solu- 
 tions. Sol. cono. acids, but re-ppd. unaltered by 
 •water. 
 
 (7)-I)i-amido-aiithraqTiinone, 
 
 Preparation. — Alizarin (20 grms.) is heated 
 for 7 hours at 170° with ammonia solution (200 
 CO., S.G. '916). Alcohol extracts the greater por- 
 tion(6'2 grms.) of the insoluble residue (7'3 grms.). 
 Water is added to the alcohol, and the pp. is 
 dried in vacuo and washed with ether (H. v. 
 Perger,J".i)r. [2]18, 135). 
 
 Prc^erties. — Indigo-blue powder, which ac- 
 quires a coppery lustre when rubbed. When 
 HCl is added to its blue alcoholic solution (at 0°), 
 the liquid turns cherry-red and deposits brown- 
 red needles of a hydrochloride, which, however, 
 is so unstable as to be reconverted into the 
 amorphous blue base by merely washing with 
 water. It does not dye mordanted goods. 
 
 Beactions. — 1. Boiled with potash it is con- 
 verted into oxy-amido-anthraquinone (g. v.) : 
 0„HA(NHj,)j + KOH= C„HeOj(OK)NHj + NH,. 
 2. Similar reaction by boiling HCl. — 3. Fused 
 ioith potash, or heated with HCl at 250°, forms 
 alizarin. — i. By passing N^Oj into its alcoholic 
 solution until the blue colour is changed to pure 
 yellow, it is converted into erythro-oxy-anthra- 
 quinone, which is thrown down when water is 
 added. Yield 95 p.c. 
 
 (5)-Di-aiiiido-anthraquiiioiie 
 
 (3) NH,.C,H.<gg [^j>C.H,.NH, (6). 
 
 [above 300°]. 
 
 Formation. — By reducing the corresponding 
 di-nitro-anthraquinone, [above 300°] (Koemer, 
 H. 16, 366). 
 
 Properties. — Splendid red metallic needles 
 (by sublimation). SI. sol. alcohol, ether, acetone, 
 and chloroform, with orange colour; v. si. sol. 
 water. Very weak base. 
 
 Beactions. — 1. Boiling potash has no action. 
 2. Diazotisation followed by boiling with water 
 converts it into anthrarufin {p. Di-oxt-anihra- 
 quinone). 
 
 Di-acetyl derivative Ci^fiJ^'B.kc)^. 
 
 Eeddish yellow needles, v. sol. alcohol, and ether. 
 
 AUISO-ANTHBAQUINONi; SULPHONIC ACIDS 
 
 C„H,NS05 i.e. C,.HA(NH2).S03H 
 
 o-Amido-anthraquinone sulphonic acid 
 
 C.H<C0(2! >CA(NH,)(SO,H) [1:6:2:4). 
 Formed by reducing nitro-anthraquinone sul- 
 phonic acid (Lifschutz, B. 17, 899). Silvery 
 needles. 
 
 (a)-Aiuido-antliraquinone Bulphonic acid. — 
 Prepared by reducing (o) -nitro-anthraquinone 
 sulphonic acid (Claus, B. 15, 1519). Sol. dilute 
 acids, and in hot water, si. sol. cold water, 
 alcohol, and ether. 
 
 Salts. — NaA' l^aq : small red needles. — 
 CaA'jSaq: red needles. — ^BaA'j3Jaq: slender 
 red needles. — CuA'2 7aq: yellowish-red needles. 
 
 (;3)-amido-anthraqiunone sulphonic acid. — 
 Formed by reducing the lead salt of ()3)-nitro- 
 anthraquinone sulphonic acid with HjS (Claus, 
 B. 15, 1520). Bed powder; v. sol. water forming 
 a red solution, si. sol. alcohol, insol. ether. A 
 weak acid. 
 
 (a)-I)i-amido-antIiraquiuone sul- 
 phonic acid 
 
 C„H,^,SOi i.e. C,.H,0,(NH,),SO,H. 
 Obtained from (o)-di-amido-anthraquinone by 
 means of HjSO, containing dissolved SO3 
 (30 p.cj ; ppd. by water. The solution is a 
 splendid red. It may be crystallised from 
 alcohol. Sol. glacial HOAc, and in acetic ether. 
 Insol. ether, benzene or benzoline. On passing 
 nitrous gas into its alcoholic solution anthra- 
 quinone (o)-sulphonio acid is formed. Potash- 
 fusion forms alizarin. 
 
 Salt. — BaA'ji: insol. cold water (v. Perger, 
 J'.i)?-. [2]19, 209). 
 
 AMIDO-ABACHIC ACID 
 
 CjoH^NOj i.e. 0,„H,,(NH2)02. [59°]. 
 From nitro-arachio acid and SnOlj (Tassinari, 
 B. 11, 2031). SI. sol. ether, m. sol. alcohol. 
 Combines with neither acids nor bases. 
 
 AMIDO-AZO-COSIFODNDS v. Azo com- 
 pounds. 
 
 AUIDO-BENZALDEHTDE v. Amido-benzoic 
 
 AliSEHVDE. 
 
 AMIDO-BENZAMIDE v. Amido-benzoic acid. 
 AMIDO-BENZ-ANILIDE v. AmiDo-BENzoia 
 
 ACID. 
 
 AMIDO-BEITZENE v. Aniline. 
 
 Di-amido-benzene v. Peenylene di-amine. 
 
 cow-Xri-amido-benzene C^^,i.e. 05H8(NHj), 
 [1:2:3]. [103°]. (336° cor.). Obtained by dis- 
 tilling tri-amido-benzoic acid with pounded glass 
 (Salkowsky, A. 163, 23). Crystalline; v. sol. 
 water, alcohol, and ether. Its aqueous solution 
 is alkaline and gives with Fe^Cls first a violet, 
 then a brown pp. ; hypochlorites and nitrites 
 give brown pps. Eeduces cold ammoniacal 
 AgNOjAq. HjSOi containing a little HNOj 
 forms a blue colour. 
 
 Salts.— B'SHCl: si. sol. cone, hydric 
 chloride B".— H^SOj 2aq. 
 
 i-Iri-amido-benzene CsH3(NH2),. [1:2:4]. 
 [below 100°]. (c. 340°). 
 
 Formation. — 1. From (o)-di-nitro-aniline, Sn, 
 and HCl (Salkowsky, A. 174, 265).— 2. From di- 
 amido-azo-benzene ^j-sulphonic acid by Sn and 
 HCl (Griess, B. 15, 2196).— 3. Prom chrysoidin 
 by reduction (Witt, B. 10, 658).— 4. From di- 
 nitro-benzene-azo-benzeue sulphonic acid by 
 reduction (Janovsky, M. 5, 159). 
 
 Properties. — Colourless plates. V. sol. water, 
 and alcohol, si. sol. ether. Gives a red (G.) or 
 green (J.) colour with FejClsAq. 
 
 Salts.— B"H2S04. Needles or prisms ; si. sol. 
 cold water, v. si. sol. alcohol.— B"2HC1 [133°] : 
 needles (Hinsberg, B. 19, 1253). 
 
 s-Tri-amido-beuzene C„H3(NH.,)3 [1:3:5] (?) 
 The tin double salt, CeH3(NHj)3(HCl)3SnCl„, of 
 this base may be got from tri-nitro-benzene (god 
 by nitration of di-nitro-benzene) by Sn and 
 HCl (Hepp, A. 215, 348). But after removing 
 the tin by H^S, the hydrochloride of the base 
 resinifies, NH^Cl being formed, although by 
 evaporation in vacuo over H2SO4 a very soluble 
 white hydrochloride may be got. It gives no 
 colour with Fe^Clj. 
 
 Tetra-amido-benzene CsH2(NH2)4 [1:2:4:5], 
 Formed by reduction of di-nitro-TO-phenylene dia- 
 mine with tin and SnClj. The base, is extremely 
 oxidisable. An aqueous solution of the hydro- 
 chloride when treated with Fe^Clj gives a pp. 
 of brown needles of CeHj(NHj)j(NH),HjCl3. 
 
 Salts. — B'^HjCli: v. sol. water, si. sol. cone, 
 aqueous HCl. — ^B"2(HjS04)s ; sparingly soluble 
 
164 
 
 AMIDO-BENZENE. 
 
 large plates.— B''H2S04 : long sparingly soluble 
 needles (Nietzki a. Hagenbaoh, B. 20, 334). 
 
 AMIOO-BENZENE SULFHONIC ACIDS 
 CsHjNSO, i.e. OeBii('SB^).SOsBi. AmUne sul- 
 phomc acids. In the bromination of these acids 
 Br never takes a position m to NH^ (Limprioht, 
 A. 191, 252). 
 
 o-Ainido-benzene sulphonic acid 
 
 C,H,(NHj)SO,H [1:2]. S. 1 at 7°. 
 
 FormaUon. — 1. From o-nitro-benzene sul- 
 phonic acid (Berndsen a. Limprioht, A. 177, 98). 
 2. From m-bromo-benzene sulphonic acid by 
 nitration and reduction (Thomas, A. 186, 128). 
 
 Properties. — Dull white crystals like rhom- 
 bohedra. Also, as HA'|aq, in transparent 
 shining prisms with many faces. Bromine 
 added to a very dilute solution of the barium 
 salt produces H2SO4, tri-bromo-aniline and 
 (1, 4, 5)- bromo-amido-benzene sulphonic acid. 
 
 Salts (Bahhnann. A. 186, 308).— Ki'Jaq: 
 prisms. — AgA': needles. — BaA'j (L. a. B.). — 
 BaA'j 2aq (T.).— PbA'j iaq. S. 3-4 at 6°. 
 
 m-Amido-benzene sulphonic acid 
 CjH,(NHj)S03H [1:3]. S. 1-2 at 7° ; 1-6 at 15°. 
 
 From OT-nitro-benzene sulphonic acid by 
 reduction (Laurent, C. B. 31, 538 ; Schmitt, A. 
 120, 164 ; Berndsen, A. 177, 82). Also from 
 (1, 2, 4)- bromo-amido-benzene sulphonic acid 
 and HIAq at 120° (Goslich, A. 180, 102). 
 
 Long slender radiating needles. Also, with 
 l|aq in monoclinic prisms. SI. sol. cold water, 
 T. sol. hot water, insol. alcohol, and ether. 
 Aqueous solution turns red in air. When heated 
 it decomposes without fusion. 
 
 BeacUons. — 1. Bromine added to an aqueous 
 solution produces no tri-bromo-aniline, but 
 (1, 3, 4, 6)- di-bromo-amido-benzene sulphonic 
 acid, (1, 3, 5, 4, 6)- tri-bromo-amido-benzene 
 sulphonic acid, and bromanil. Chlorine acts 
 sitmlarly (Beckurts, A. 181, 211). — 2. Does not 
 produce quinone when oxidised (ilejer a. Stiiber, 
 A. 165, 168). 
 
 Salts: BaA'j 6aq.— PbAV 
 
 Amide C^B.t(^B^).SO^T!iB.^. [142°]. From 
 jji-nitro-benzene sulphamide, cone. NHjAq, and 
 H,S (Limprioht a. Hybbeneth, A. 221, 204). 
 White plates or long needles (from water). 
 
 Hydro-chloride.— CeH4(NH3Cl)S02NHj. 
 [235°]. Needles. 
 
 Nitrous acid, passed into a cold mixture of 
 the amide with a little HNOj, produces a di-azo 
 nitrate, C|,Hj(N2N03).S02N]li, benzene sulph- 
 amide, and a diazo-amido compound 
 
 C,H,(SOjNH2).N2.NH.C,H4.SOjNH2 ; 
 the latter, [183°], is insol. water, and is split up 
 by HClAq into CjH,(SO2NH2)01, Nj, and 
 NH;,.C5H,.S02NHj. 
 
 p-Amido-benzene sulphonic acid 
 CeH4(NH2)S03H [1:4]. SulphaniUc acid. 8. •& 
 at 6°. 
 
 Formation. — 1. By heating oxanilide or ani- 
 line with HjSOj (Gerhardt, J. Ph. [3] 10, 5).— 
 2. By heating aniline with fuming H2SO4 at 
 190° (Buckton a. Hofmann, C. J. 9, 259 ; E. 
 Schmitt, A. 120, 129).— 3. From aniline and 
 p-phenoi sulphonic acid (Pratesi, B. 4, 970 ; 
 Kopp, B. 4, 978). — 4. By reducing ^-nitro- 
 benzene sulphonic acid. — 5. By heating aniline 
 ethyl-sulphate (Limprioht, A. 177, 80). 
 
 Preparation. — Aniline (93 g.) is slowly poured 
 into HjSOi (60 g.) diluted with water. The 
 
 solution is evaporated and the dried sulphate is 
 mixed with H^SO^ (50 g.) and sand, and heated 
 in a dish, with constant stirring, until it becomes 
 solid. Crystallised from water. 
 
 Properties. — Plates or trimetrio prisms (with 
 aq) ; monoclinic (with 2 aq). 
 
 Reactions. — 1. Bromine-water giyea tri-bromo- 
 aniline and (l,3,2,5)-di-bromo-amido-benzene 
 sulphonic acid. — 2. Oxidised to quinone by 
 KjOr^O, and H^SO^Aq (Meyer a. Ador, A. 159, 7) 
 or by MnOj and H^SO^ (Sohrader, B. 8, 759).— 
 3. EMnO, converts its potassium salt into the 
 azo derivative 0,H4(S03K).Nj.O,H4.SOsK (Laar, 
 J. pr. [2] 20, 264), the corresponding azoxy- 
 compound being also formed (Limprioht, B. 18, 
 1420).— 4. PClj forms CsH4(S02Cl).NH.P0Cl., 
 [158°], which is converted by alcohol into 
 05H4(S03Et).NH.PO(OEt)j [102°], and by methyl 
 alcohol into C8H,(S03Me).NH.PO(OMe)j [114°]. 
 The former is split up by boiling into alcohol, 
 Bulphanilic acid, and hydro-di-ethylic phosphate. 
 
 V. also Dl-BBOMO-AMIDO-BENZENE SULPHONIC AOID. 
 
 Salts. — NaA'2aq. — KA'ljaq: triclinio 
 prisms. — NHjA'l^aq. — BaA'2 35aq. — CuA'2 4aq. 
 — AniUne sulphanilate C8H,N2HA'. Gives ofl 
 all its aniline at 100°. 
 
 Acetyl derivative CjH4(NHAc)(S03H)— 
 obtained as the sodium salt by boiling sodium 
 sulphanilate with acetic anhydride. The free 
 acid has not been isolated, as it readily splits oif 
 acetic acid on evaporation of its solution. The 
 sodium salt (A'Na) forms small colourless prisms 
 very soluble in water, but less in alcohol 
 (Nietzki a. Benokiser, B. 17, 707). 
 
 Amido-benzene di-snlphonic acids. 
 
 L C^H^NSA, »•«• C^NH,)(S03H),. [1:3:4?] 
 From m-amido-benzene sulphonic acid and 
 fuming H2SO4 at 180° (Drebes, B. 9, 552; 
 Zander, A. 198, 21). — Bhombio octahedra, v. e. 
 sol. water or alcohol. 
 
 Salts.— (NH,)jA" aq.— KjA" aq.-KHA".— 
 BaA"liaq.— BaH2A"j; S. 2-9 at 8°.— PbA" aq.— 
 PbHjA'^j. 
 
 II. CeH3(NHj)(S03H)j2aq. [1:3:5]. From the 
 corresponding nitro acid by reduction (Hein- 
 zelmann, A. 188, 167). Four or six sided 
 columns, v. sol. water, and alcohol, insol. ether. 
 Bromine water gives a pp. of bromanil. 
 
 Salts. — (NH4)2A"aq. — HNH4A"a;aq. — 
 KjA" 3aq.— KjA" 4aq.- KHA" aq.— BaA" 3Jaq. 
 — BaHjA"j 5aq. — PbA" 3iaq. — PbHjA"j 6aq. — 
 Ag^"- 
 
 III. C5H3(NH2)(SO^H)^ [1:2:4]. Di-sulph. 
 anilic acid. 
 
 Formation. — 1. By heating sulphanilic acid 
 with fuming H^SO, at 170° for 6 hours (Buck- 
 ton a. Hofmaun, A. 100, 164). — 2. By heating 
 o-amido-benzene sulphonic acid with fuming 
 H2SO4 at 180° (Zander, A. 198, 17).— 3. By 
 reducing the corresponding nitro acid (Heinzel- 
 mann, A. 188, 170). 
 
 Properties.— Minute (red) clumps (from water). 
 V. sol. alcohol, insol. ether. Bromine water 
 gives tri-bromo-aniline, bromo-amido-benzene 
 di-sulphonic acid, and di-bromo-amido-benzene 
 sulphonic acid. 
 
 Salts. — The acid salts are less soluble in 
 water than the neutral ones.— (NH J jA" aq: small 
 
amido-benzoio acids. 
 
 165 
 
 hexagonal prisms. — NH^HA"2aq: clumps.— 
 KjA"aq.— KHA"aq: silky needles.— BaA" 3aq : 
 four-sided plates. — BaHjA" ^aq. — OaA" 2aq : 
 minute -white needles. — CaH2A"2: slender 
 needles. — ^PbA"2aq. — PbH2A"2aq: small prisms. 
 — PbH2A"2 6aq. — Ag^A": prisms. — AgHA": 
 needles or plates. 
 
 Si-amido-benzene sulphonlc acids 
 CjHjNjSOs. Phenylme-di-amine sulphonic acids. 
 
 I. CeH3(NH5)j{S03H) [1 : 2 or 5 : 3]. S. 1 at 
 10°. From the corresponding nitro acid (Saohse, 
 A. 188, 148).— Bhombic tablets. V. si. sol. alcohol, 
 insol. ether. Turns brown in air. Metallic 
 salts crystaUise with difSoulty. 
 
 Salts.— HA'HCl : needles.-HA'HOlSnClj. 
 -HA'HBr.— BLA'jHjSO, aq.— HA'H^SO, ^aq. 
 
 II. CeH3(NBL,)^S0, [1:2:4]. 
 Small colourless needles. 
 
 Preparation. — 1 By sulphonation of o-pheny- 
 lene-diamine. — 2. By reduction of (1:2:4) nitro- 
 amido-benzene sulphonic acid. 
 
 Salts A'jBa + SJHjO: easily soluble thin 
 
 tables or needles. — A'^Ca + SH^O : soluble tables 
 or needles (Post and Hardtung, B. 13, 39; A. 
 205, 98). 
 
 m. 0eH3(NHj)jHS03 [1:3:4]. 
 
 Preparation. — 1. By sulphonation of m- 
 phenylene-diamine. — 2. By reduction of nitro- 
 amido-benzene sulphonic acid [1:3:4]. 
 
 Dimorphous: monoclinic tables, a:b:c = 
 1-31 : 1 : 1-36, or triclinio prisms, a:b:c = 
 ■424 : 1 : -928. 
 
 Salts. — A'jBaSaq: long soluble prisms. 
 A'jCaSaq: soluble prisms or tables (Post a. 
 Hardtung, B. 13, 40 ; A. 205, 104). 
 
 Si-amido-benzene di-sulphonic acid 
 CsHjNjSaOs aq i.e. CjH2(NH2)j(S03H)j aq. From 
 the nitro acid by reduction (Limpricht, B. 
 8, 290). V. sol. water. 
 
 Salt. — SnA"aq: needles. 
 
 AUIOO-BENZENE FHOSFHONIO ACID 
 CeH3NP03 i.e. CsH,(NHj)PO(OH)j,. From the 
 nitro acid, tin, and HCl. Slender needles (from 
 water) ; v. si. sol. water, v. sol. HClAq ; insol. 
 alcohol and ether. Salt s.— Na^A" 3aq.— PbA". 
 CuA". — AgjA" (Michaelis a. Benzinger, A. 188, 
 282). 
 
 SI-ASIISO-BENZETSBOL v. Di-amxdo-di- 
 
 PHENTIi-CAEBINOIi. 
 
 AMIDO-BENZOIC ACIDS CjHjNOj i.e. 
 C^B.,{Nn.,).CO^. M. w. 137. The foUowing 
 derivatives are described in special articles : 
 
 NlTBO-AMmO-BENZOIO ACID, ChLOBO-AMIDO-BENZOIC 
 ACID, ChIiOKO - METHYL - AMIDO - BENZOIC ACID, 
 
 Methyl - amido - benzoic acid, Ethyl - amido- 
 benzoio ACID, Phenyl-amido-benzoio acid. 
 
 o-Amido-benzoic acid C„Hj(NH2).C0jH [1:2]. 
 
 A nthraniUc acid. [144°-145°] . 
 
 Formation. — 1. By reducing o-nitro-benzoio 
 acid (Beilstein a. Kuhlberg, A. 163, 138).— 2. 
 By boiling indigo with KOHAq (Fritzsche, A. 
 39, 83).— 3. From (1, 2, 3), or (1, 4, 5)-bromo- 
 amido-benzoic acid by sodium-amalgam (Hiibner 
 a. Petermann, A. 149, 133). — i. From its acetyl 
 derivative and boihng cone. HCl. — 5. From 
 isatoic acid {q. v.) and boiling cone. HCl. 
 
 Properties. — Plates, or rhombic crystals 
 (Haushofer, A. 193, 233). May be sublimed. 
 
 v. sol. water, and alcohol. Converted by nitrous 
 acid into salicylic acid ; and by sodium-amal- 
 gam into NH3 and benzoic acid. HCl and KCIO3 
 form chloranil (Hofmann, A, 52, 65). Its 
 anhydr ide is described as Antheanil. 
 
 Salts.— HA'HCl: [191°]; needles (Kubel, 
 A. 102, 236).— HA'HNOs.- (HA'),H2SO,2aq: 
 needles [188°].- (HAOjH^SO^aq.- (HA^HjC^O,. 
 — BaA'2: V. e. sol. water, si. sol. alcohol. — 
 PbA'^.- CuAV— AgA'. 
 
 Ethyl ether EtA'. (260°). Liquid; its 
 hydrochloride, BtA'HCl, [170°], forms needles, 
 insol. ether, and may be sublimed. 
 
 Reactions. — 1. Nitrous acid produces sali- 
 cylic acid (Gerland, A. 86, 143) or diazobenzoio 
 acid (v. Di-Azo compounds). — 2. KCNO converts 
 the hydrochloride of o-amido-benzoic acid into 
 uramido-benzoic acid (g. v.) ; Potassium sulpho- 
 cyanide forms, similarly, thio-uramido-benzoic 
 acid (q. v.). — 3. Phenyl cya/nate (q. v.) forms 
 NH2.CjH,.C0.NPh.C0.NPhH. — 4. Cyanogen 
 passed into an aqueous solution forms C9H3N3O 
 (Griess, B. 11, 1986), while in an alcoholic 
 solution it forms CuHuNjOj, [173°] (Griess, B. 
 2, 415). The latter is converted by boiling HCl 
 into CgHjNjOj, [above 350°], which is probably 
 .NH.CO 
 
 since it can be formed by heating 
 
 
 NH, 
 
 o-amido-beuzoio acid with urea. It forms 
 crystalline nitro- and amido-derivatives. 
 
 The compound C,„H,„Nj02 ' ethoxyl oyan- 
 amidobenzoyl ' is converted by alcoholic NH3 at 
 100° into benzcreatinine (q. v.). 
 
 The compound CgH^NjO ' di-cyano-amido- 
 benzoyl,' may be represented thus : 
 
 .CO.N 
 C6H,< II (Griess, B. 18, 2417). This 
 
 \nh.c.cn 
 
 body gives the foUowing reactions. — a. Strong 
 
 >CO.N 
 NH3Aq converts it into O^A^ \\ 
 
 \NH.C.CO.NHj, 
 ' carboxamido-cyano-amido-benzoyl.' — 6. Aque- 
 ous ammonium sulphide forms the corresponding 
 CO.N 
 
 0,H,^ 
 
 0,H,< 
 
 '\nH.C.CS.NHj. 
 ^CO.N 
 
 Baryta water forms 
 
 ' carboxy-oyano-amido-ben- 
 
 i\ II 
 NNH.C.CO^H, 
 zoyl ' ; which is converted by dry distillation 
 
 r/ 
 
 CO.N 
 
 into CjH,^ 11 ' carbimido-amido-benzoyl.' 
 
 \nh.ch 
 
 — d. m-amido-benzoio acid produces the anhy- 
 dride of di-phenyl-guanidiue dicarboxylic acid, 
 CO.N 
 
 C,H,< 
 
 /" 
 
 — e. jp-phenylene- 
 
 '\nH.C.NH.CsH<.002K 
 diamine produces the anhydride of amido-di- 
 phenyl-guanidine carboxylic acid 
 
 .CO.N 
 GS.jC II Allthese bodies may 
 
 \NH.C.NH.CeH,.NHj. 
 
 .CH = N 
 be looked upon as derivatives of CjH,^ | 
 
 \n=ch 
 
 which may be called Q^tAna^oline. 
 
 Formyl derivative CjHj(NHCH0)C0jH4aq. 
 [168°]. Formed by heating isatoic or o-amido- 
 
166 
 
 A5ITD0-BMNZ0IC ACIDS. 
 
 benzoic acid with formic acid (E. v. Meyer a. 
 Bellmann, J.m. [2] 33, 24). Hair-like needles ; 
 sol. alcohol, si. sol. benzene. 
 
 Acetyl derivative CbH^INHAojOOjH. 
 [180°]. Formed by boiling anthranil (g.t).) with 
 A.O2O and treating the product with water (Fried- 
 lander a. Henriques, B. 15, 2105). Also by oxi- 
 dation of {Py. 3)- methyl -quinoline by KMnO, 
 (Doebuer a. Miller, B. 15, 3075). 
 
 PrepwraUon. — Aoetyl-o-toluidine (1 g.) is 
 oxidised by KMnO, (2 g.) dissolved in water 
 (200 c.c), the liquid being kept neutral by acetic 
 acid (Bedson a. King, C. J. 37, 752). 
 
 Prcygerties.' — Lustrous leaflets (from water). 
 Prisms (from HOAo). Trimetric, a:b:c = 
 •982 : 1 : 2-803 (Fletcher). 
 
 Salts. — PbA'2 : flocculent pp. — AgA' : needles. 
 
 Tests. — Solution of sodium salt gives with 
 lead acetate a pp. sol. in acetic acid, with CaOlj 
 a pp. only on adding alcohol. 
 
 Di-acetyl derivative C8H.(NAc2)C02H. 
 [220°].— AgA'. 
 
 Ghloro -acetyl derivative 
 CaH,(NH.CO.CH2Cl).C02H. From acetyl deri- 
 vative and PCI5 (Jackson, B. 14, 888). Clumps. 
 
 Di-chloro-acetyl derivative 
 q.H,(NH.C0.CHCy.C02H. [c. 173°]. Prepared 
 like the preceding. Yellowish needles (from 
 water). 
 
 Salt.— AgA'. 
 
 Benzoyl derivative C,H4(NHBz).C02H. 
 [182°]. By BzCl ; or by acting on benzoyl-o- 
 toluidine with EMnOfAq (Bruckner, A. 205, 
 130). Long needles (from alcohol) ; insol. water. 
 
 Salts. — NaA' 4aq. — MgA'^ 4aq. — CaA'j 3aq. 
 — BaA'2 3aq. 
 
 Oxaloxyl derivative v. Casboxt-phektl- 
 
 OZAMIC ACrD. 
 
 Amide C5H,(NH2)C0.NH2. Amido-bem- 
 amide. [108°]. (300°). From NH3 and isatoio 
 acid (g.o.). White plates (from chloroform). SI. 
 sol. benzene and ether. Aqueous solution of 
 (1 mol.) of its hydrochloride gives with NaNOj 
 needles of CHjNjO, [213°]. This compound 
 forms salts, e.g. CjHjNaNsO, and a methyl ether, 
 CjHjMeNjO, The methyl ether, [123°], is also 
 formed from the methylamide of o-amido-benzoio 
 acid. The new substance is probably 
 ^CO.NH 
 
 (Weddige a. Finger, /. pr. [2] 35, 
 
 I 
 
 N = N 
 
 Aoetyl-amido-benzamide- 
 C,H,(NHAc)C0NH2. [171°]. ByAo^O. Needles. 
 Forms salts with acids. If kept melted for some 
 time it becomes solid, changing to the anhydro- 
 
 .NH.C.CH3 
 compound, CgRX || Oxy-methyl-quin- 
 
 \C0.N 
 asoUne [228°]. Yellow silky needles (from alco- 
 hol). Soluble in hot water. Forms salts with 
 acids. 
 
 Formyl-amido-benz amide 
 CeHi(NH.CHO)CONHj. [123°]. From dry formic 
 acid and o-amido-benzamide. When heated 
 this gives H^O and an anhydro-oompound 
 
 /NH.C.H 
 CA^ II Oxy-guinaeoUne (A. Weddige, 
 
 /. pr. [2] 31, 124). 
 
 Anilide OeH.(NHj)CO.NHPh. [130°]. Prom 
 aniline and isatoic acid. Needles (from benzene). 
 
 Phenyl-hydraiide 
 C.H4(NHj)CO.NPh.NH2. [170°]. From isatoio 
 acid and phenyl hydrazine ia alcoholic solution 
 at 70°. YeL:,w needles; sol. alcohol and chloro- 
 form, V. si. sol. ether (E. v. Meyer a. Bellmann, 
 /.i)r. [2]33, 21). 
 
 Hydroxylamide C5H^(NHj)C0.NH.0H. 
 [82°]. From isatoic acid {g,.v.) and hydroxylamine 
 solution (M. a. B.). Yellowish plates, sol. 
 alcohol, ether, and chloroform. 
 
 o-Oxy-phenyl ether 
 CeH,(NHJ.COj.C.H<OH. [136°]. From isatoio 
 acid and pyrocatechin at 130° (M. a. B.). Needles 
 (from water). Sol. alcohol and ether, si. soL 
 water. 
 
 m-Amido-benzoic acid CeH,(NHj).C02H [1:3J. 
 [173°-174°]. S.G.l-61at4°; S. 2 in cold water, 
 4 in boiling water or alcohol. 
 
 Formation. — 1. From w-nitro-benzoic acid 
 by reduction (Zinin, J. pr. 36, 103 ; Gerland, 
 
 A. 86, 143 ; 91, 185 ; Schiff, A. 101, 94 ; Beil- 
 stein a. Wilbrand, A. 128, 265).— 2. From nitro- 
 phthalio acid, Sn, and HCl (Faust, Z. [2] 5, 
 335).— 8. From CeH3Br(NHj)C02H [4:3:1] by 
 sodium-amalgam (BaveiU, A. 222, 180). 
 
 Properties. — Crystalline clumps ; sweet taste ; 
 may be sublimed. Aqueous solutions are browned 
 by air. 
 
 Beactions.—l. HCl and KCIO3 form chloraniL 
 
 2. Bromine forms tri-bromo-amido-benzoio 
 acid. 
 
 3. Nitrotts acid forms m-di-Azo-benzoio acid. 
 i. The solution containing m-diazo-benzoic 
 
 acid gives TO-oxy-benzoio acid on heating. 
 
 5. Fusion with ti/rea produces uramido-ben- 
 zoic acid (q. v.). 
 
 6. Boiling with CSj and alcohol produces 
 thio-oarbonyl-di-amido-di-benzoio acid, 
 CS(NH.C„H4.C0jH)s (Merz a. Weith, B. 3, 
 812). This body is also formed by heating 
 m-amido-benzoic acid with thio-urea; and, 
 together with thio-carbimido-benzoio acid, by 
 heating m - amido - benzoic acid with CSCl, 
 (Eathke a. Schafer, A. 169, 101). Thio-oarbonyl- 
 di-amido-di-benzoic acid does not melt below 
 300°; it is v. si. sol. water, m. sol. alcohol or 
 ether ; converted by HgO, in presence of KOH 
 (Griess, A. 172, 169), into carbonyl-di-amido-di- 
 benzoic acid. 
 
 7. CSCI2 produces the last-mentioned body 
 and also thio - carbimido - benzoic acid 
 SCN.CjHi.COjH. This may also be prepared 
 by boiling thio - oarbonyl - di - amido - benzoic 
 acid with HCl. It is an amorphous insolu- 
 ble powder, v. si. sol. alcohol. Decomposes 
 above 310°. It unites with aniline forming 
 di-phenyl-thio-nrea carboxylic acid, 
 PhNH.CS.NH.cX.CO2H [191°]. This body ia 
 also formed by heating phenyl-thio-carbimide 
 with jre-amido-benzoio acid at 100' (Merz a. 
 Weith, B. 3, 244). It forms slender needles 
 (from water). V. sol. alcohol, and ether, si. 
 sol. benzene, and benzoline. AgNO, added to 
 its alkaUne solution gives a black pp. of Ag„S ; 
 FojCljAq gives a yellow pp. ; Pb(0Ac)2 a white 
 pp. ; and CuSO< a green pp. (Asohan, B. 17, 430). 
 
 8. i'Aosjrene produces carbonyl-di-amido- 
 di-benzoic acidCO(NH.CaH4.C02H)j (Sarauw, 
 
 B. 15, 44). This body is also formed by heat- 
 
AMIDO-BENZOIO ACIDS. 
 
 157 
 
 ing m-nramido-benzoio aoid {q. v.) at 200° 
 (Tranbe, B. 15, 2124). White powder; insol. 
 water, alcohol, and benzene, sol. alkalis. — 
 BaA"3aq. — AgjA".— PbA". Its ether Et^A", 
 [161°-162''], is formed by heating m-uramido- 
 benzoio ether (Griess, J. pr. [2] 4, 294) : needles 
 (from dUute alcohol). 
 
 9. Phenyl cyanate forms on heating, 
 phenyl-nramido-benzoio aoid, 
 NPhH.CO.NH.C„H,.COjH. [270°]. Concentric 
 prisms, sol. alcohol, si. sol. ether, insol. water 
 (Kiihn, B. 17, 2882). 
 
 10. Aqueous KCNO evaporated with m-amido- 
 benzoio acid forms thio-uramido-bemoic 
 aoid NH2.CS.NH.CsH1.CO2H (Arzruni, B. i, 406). 
 
 11. Phenyl cyanate (g.*.) forms di-phenyl- 
 nrea carboxylio acid CO2H.CsH1.NH.CO.NPhH. 
 
 12. PCI5 converts amido-benzoic acid into a 
 white powder which, when extracted with water, 
 yields a solution greatly resembling solutions 
 of albuminous substances. Thus if a httle 
 lime-water, NaCl, or MgSOi, be added the liquid 
 may be coagulated by heat, more especially if 
 CO2 be passed through the solution before heat 
 is applied (Grimaux, C.B. 98, 231, 1336). 
 
 13. Cyanogen gas passed into an aqueous solu- 
 tion forms a dicyanide of amido-benzoic acid, 
 and oyan-Oarbimid-amido-benzoic aoid. Cyano- 
 gen passed into an alcoholic solution forms the 
 dicyanide, guanido-di-benzoio acid, and ethoxy- 
 carbimid-amido-benzoic aoid. 
 
 The di-cyanide (CWj^B.i.C^i.GO^B., is 
 a yellow, crystalline powder, insol. water, v. si. 
 sol. alcohol or ether. It does not form metallic 
 salts (Griess, B. 11, 1985 ; Griess a. Leibius, A. 
 113, 332). On distillation it forms m-amido- 
 benzonitrile (Griess, B. 1, 191 ; Hofmann, B. 
 1, 194). Boiling KOHiAq or HCl converts it 
 into benz-creatine (g. v.) (Griess, B. 3, 703). 
 
 Gyano-carhimidamido-henzoic acid 
 C02H.CsHi.NH.C(NH).CN. forms eUiptic platei. 
 V. si. sol. cold water, sol. acids and alkalis. It 
 reacts as follows : — a. Nitrous aoid converts it 
 into oyano - carboxamido - benzoic acid, 
 CO2H.OjH1.NH.GO.CN. (Griess, B. 18, 2415), 
 which forms white plates, insol. cold water, with 
 sweetish taste ; boiling water converts it into 
 HON, CO2, and carboxy-amido-benzoic acid ; 
 dilute NHjAq forms uramido-benzoio acid. — 6. 
 Cold dilute HCl forms small prisms of carbox- 
 amido - carb i midamido - benzoic aoid 
 C02H.C,Hi.NH.C(NH).CO.NH2; v. sol. hot water ; 
 its auroohloride, HA'HAuOli IJaq, crystallises 
 in needles (G.). — c. Cold aqueous di-methyl- 
 amineformsC02H.C<,Hi.NH.C(NH).C(NH).NMe2; 
 six-sided plates, v. sol. hot water, si. sol. cold 
 water, converted by hot NajCOsaq into m- 
 carboxy-phenyl-oxamide NH, and NMOjH. 
 
 Guanido-di-henzoic acid 
 NH:C(NH.C|iHi.C02H)2 is also formed from thio- 
 carbonyl-di-amido-di-benzoic acid, HgO, and 
 NH, (Griess, A. 172, 172). It is crystaUine. 
 Salts.-BaA".-H2A"HCl.-(H2A"HCl)2PtCl,. 
 
 Ethoxy - carbimidamido - benzoic 
 acid, Et0.0(NH).NH.C,Hi.C02Hl|aq forms 
 needles (from water), sol. alcohol, and ether; 
 converted by alkaUs into alcohol and uramido- 
 benzoio acid ; nitrous acid converts it into 
 
 Oarboxy-amido-benzoic aoid mono- 
 ethyl ether COjEt.NH.C.Hi.OOjH [189°]. 
 This acid is also formed from amido-benzoic 
 
 acid and Cl.COjEt. It crystallises in platea 
 (from water). Salts. — BaA'2 2aq. — AgA' 
 (Griess, B. 9, 796; Wachendorff, B. 11, 701). 
 Ether EtA' [101°] ; plates (from water). Amide 
 0,„H,„N03NH2. [158°] (W.). 
 
 Salts.— HA'HCl: prisms (Caliours, A. Ch. 
 [3] 53, 322).— (HA'HCl)2PtCli.— HA'HClSnCL.— 
 HA'HBr. — HA'HNOa — (HA')2H2S04 aq. [225°]. 
 HA'HjPOi (Harbordt, 4. 123, 290).— BaA',4aq. 
 — CaA'jSaq. — CuA', — PbA'j. Needles. -- 
 MgA'2 7aq.— AgA'— NaA' (at 100°) (Voit, A. 99, 
 100).— SrA'2 2aq.— ZnA'2 (when dried at 100°). 
 
 Methyl ether.— ^LeM. Oil (Chancel, 0. iJ. 
 30, 751). 
 
 Ethyl ether.— EtA.'. (294°). Liquid, sol. 
 water; from ?)i-nitro-benzoic ether. Salts: 
 EtA'HCl. [185°]. (MMler, B. 19, 1493). — 
 (EtA'HCl)2PtCli.— EtA'HNO, : prisms. 
 
 Acetyl derivative C5Hi(NHAc).C02H. 
 [245°]. Formation.—!. By AoCl or by HOAo 
 at 140° (G. C. Foster, C. J. 13, 235).— 2. From 
 amido-benzoic acid (10 g.) and aoetio ether (25 
 C.C.) at 150°. (PeUizzari, A. 232, 148).— 3. Prom 
 amido-benzoic aoid *nd aoetamide (P.), or AojO 
 (Kaiser, B. 18, 2946). Properties. — White powder, 
 V. sol. hot alcohol, si. sol. hot water, v. si. sol. 
 cold water and ether. Dissolves in NajHPOiAq, 
 but re-ppd. by HO Ac. May be sublimed. Salts. 
 —BaA'jSaq: needles.— CaA'23aq.—NaA'(at 120°). 
 
 Formyl derivative 
 C,Hi(NH.CH0).C02H. [225°] (PeUizzari, Q. 15, 
 555). 
 
 Septoyl derivative 
 CsH,(NH.C,H,30).C02H. [202»] (P.) 
 
 Glycollyl derivative 
 CeH,(NH.C0.CH20H).C02H. [212°]. Gives at 
 
 220° the anhydride <^Q^>N.CsH,.C02H, [248°]. 
 
 Acetyl derivative. [198°]. 
 
 Lactyl derivative 
 CH3.CH(0H).C0.NH.0sHi.C02H. [162°]. Its 
 anhydride melts at [243°] (P.). 
 
 Benzoyl -derivative C5Hj(NHBz)0OjH. 
 [248°]. 1. From amido-benzoic acid and benz- 
 amide at 180° for 2 hours. — 2. By boiling amido- 
 benzoic aoid (2 g.) with benzoic ether (4 0.0.) for 
 6hours (Pellizzari,4.232,150).— 3. From amido- 
 benzoic acid and benzanUide at 230° (P.). Mi- 
 nute prisms (from alcohol). Soluble with ease 
 in alcohol, less so in ether or water. Its Oa 
 and Ba salts are soluble. Eesolved by hot KOH 
 into benzoic and amido-benzoic acids. AndUde. 
 — CsHi(NHBz)CONPhH. [225°]. By heatmg 
 CsH4(NBzH)C02H with aniline for some hours. 
 
 Oxaloxyl derivative v. Caeboxy-phenyii^ 
 
 OXAMIC ACID. 
 
 Succinyl-derivative Ci,H,NOi or 
 CH2.C=N.C„Hi.C02H. 
 
 I \ (?). [235°]. Formed by 
 
 CHj.CO.O 
 
 melting suocinoxyl-amido-benzoic acid, or by 
 fusing succinic and amido-benzoic acids together 
 (Muretow, J. B. i, 295 ; PeUizzari, B. 18, 215). 
 Needles (from alcohol). SI. sol. cold water. 
 Salt s. — ^BaA'2 2aq. — ^AgA'. 
 
 Succinoxyl derivative 0„H„NO, i.t. 
 C0,H.CH2.CH2.C0.NH.0jjHi.COjH. [230°]. From 
 the preceding by boUing with water, baryta or 
 ammonia (M.). Plates ; m. sol. water. 
 BaA" IJaq. 
 
 Succiny I -di-atnido-di -benzoic acii 
 
168 
 
 AMIDO-BENZOIO AOIDS 
 
 C,3H,A0. »■«• C,H,(CO.NH.O.H,.CO,H),. (?) 
 fo. 300°]. Formed together with 
 C02Et.CH2.CH2.CO.NH.OeH,.C02H by heating 
 alcoholic succinic ether with amido-benzoic acid 
 (M. ; P.). Also from succinyl-amido-benzoic 
 acid, alcohol, and HCl (M.). White crystalline 
 powder. Soluble in KOHAq. Salts : CaA"7aq. 
 S. ■2. — BaA" 5aq : needles. 
 
 Phthalyl derivative CijHjNO, i.e. 
 C„H^:C20,:N.CeH,.C0jH. [282°]. Formed to- 
 gether with its ether by heating amido-benzoic 
 acid with phthalic ether (PeUizzari, B. 18, 216). 
 Ethyl ether: A'Et. [152°] : radiating needles. 
 
 Sebacyl derivative CjjHjjNjOj i.e. 
 C8H,e(CO.NH.C„Hj.C02H)j. [275°]. Formed 
 together with CO2Et.CsH,s.CO.NH.0,Hi.CO2H by 
 heating sebacic ether with amido-benzoic acid in 
 alcoholic solution (P.). White powder, si. sol. in 
 most menstrua. 
 
 Amide G^'RfQS'B^.CO.Tii'H.^ci. Amido-henz- 
 andde. [75°] ; when dry [above 100°]. From 
 m-nitrobenzamide by ammonium sulphide (H. 
 Schiff, A. 218, 185 ; Chancel, A. 72, 274). 
 
 Prc^erties. — ^Large, yellow crystals. Unites 
 with acids forming compounds : — C,HjNj,OHCl : 
 needles.— 0,H8N20HN03.— (0,H8N20HCl)jPtCl4. 
 — C^HjNjOAgNOa : needles. 
 
 BeacUons. — 1. Aqueous solutions (even when 
 very dilute) give with fatty aldehydes crystalline 
 pps. of the form E.CH(NH.C5H4.C0.NHj)2. 
 These are soluble in alcohol, but give with 
 HNO3 containing CrOj a violet colour. They 
 differ from original amido-benzamides in being 
 no longer basic and in giving no coloured com- 
 pounds with furfurol solution. — 2. Aqueous 
 salicylic aldehyde gives yellowish needles of 
 C,H,(OH).CH:N.C,H,NHj. [186°]. V. e. sol. 
 alcohol or warm water. This compound, o-oxy- 
 benzylideue-amido-benzamide, boiled with ben- 
 zoic aldehyde forms a product CssH^sNiOa, in- 
 soluble in water, alcohol, ether, toluene, chloro- 
 form or OS2, but maybe crystallised from phenol 
 (2 vols.) and alcohol (1 vol.). It may be con- 
 sidered to be an anhydride of 
 
 CA.CH(NH.CO.C5H^.N:CH.C,H,.OH)2. 
 Boiled with AC2O it takes up 1 molecule of Ac^O 
 forming small needles. Dilute aqueous NH3 
 reproduces the compound C35H25N40j. — 3. 
 Selicin (2 pts.), TO-amido-benzamide (1 pt.), and 
 water (10 pts.) form yellowish plates of a gluoo- 
 side of o-oxy-benzylidene-amido-benzamide 
 [113°] : NH2.CO.C5H,.N:CH.CeH4.0.C,H„05 2aq. 
 4. Boiled with an alcoholic solution of isatin 
 it forms a crystalline powder [c. 280°] of isat- 
 amido-benzamide : 
 
 NH<'^Q*>C:N.CsH,.C0.NH2. The compounds 
 
 NH2.CO.C5H4.N:X derived from aldehydes and 
 amido-benzamide are decomposed by heating 
 with aniline into amido-benzamide and PhN:X 
 (Schiff, G. 13, 113; A. 218, 185). 
 
 Phthalyl -amido-henzamide 
 NH2.C0.CA.N:C.C,H, 
 
 O.CO 
 
 [240°-241°]. Got by 
 
 fusing m-amido-benzamide with phthalic anhy- 
 dride. Bundles of slender needles (from alcohol). 
 V. si. sol. water. Heated with aniliue gives 
 phenyl-phthalim'ide and amido-benzamide (H. 
 Sohiff, A. 218, 194). 
 
 m-Amido-henzamidoxim 
 CeH,(NH2).C(NH2):NOH. A crystalline solid ; 
 formed by reduction of m-nitro-benz-amidoxiin 
 with SnCl^. Salt.— B'HCl; prisms (Schopff, 
 B. 18, 2472). 
 
 Anilide NH2.CjH4.CO.NPhH. Amido- 
 benzaniUde. [129°]. (P.); [114°] (E. a. V.). 
 Formed by heating w-amido-benzoic acid with 
 aniline (Piutti, B. 16, 1321) or by reducing m- 
 nitro-benzanilide (Engler a. Volkhausen, B. 8, 
 35). — Silvery scales (P.) or long needles (from 
 water, E. a. V.). Heated with aniline at 200° 
 it forms two isomerides, (C,H5N0)„, one soluble 
 in alcohol, [225°], called ' amido-benzoide,' and 
 the other an insoluble powder (Piutti, 0. 13, 339). 
 Salts: CisHiaNjOHCl.— (C,3H,2N20)2H2S04 
 
 p - Amido - benzoic acid CuH4(NH2)C02H. 
 [186°-187°]. Amido-dracylic acid. 
 
 Formation. — 1. By reducing p-nitro-benzoio 
 acid (G. Fischer, A. 127, 142; Wilbrand a. 
 Beilstein, A. 128, 264). — 2. By boiling its 
 succinoxyl-derivative with HCl (Michael, B. 10, 
 576). 
 
 Preparation. — 50 pts. of acetyl-^-toluidine is 
 suspended in about 2000 pts. of boUing water 
 and oxidised by slowly adding 200 pts. of finely 
 powdered KMnO^. The solution is filtered from 
 Mn02, the acetamido-benzoio acid ppd. by HCl, 
 and saponified by boiling for an hour with strong 
 HCl (Kaiser, B. 18, 2942). 
 
 Properties. — Long white needles, not coloured 
 by moist air. When heated with urea it forms 
 C0(NH.CsH,.C02H)2 (Griess, J. pr. [2] 5, 370). 
 
 Salts. — BaA'j: shining laminae, sol. water. 
 — A'.Pb.OAc, ppd. by Pb(0Ac)2Aq (Ladenburg, 
 B. 6, 130). — (HA^HjSOi. — The copper-salt 
 is a dark-green pp. (Geitner a. Beilstein, A. 
 139, 1). 
 
 Acetyl derivative CbH4(NHAc).C02H. 
 [250°]. Formed from acetyl-^-toluidine by 
 KMnOj (Hofmann, B. 9, 1302). Needles, si. 
 sol. water. Salt:AgA'. 
 
 Benzoyl derivative CsH,(NHBz)C02H. 
 [278°]. From benzoyl-j)-toluidine, CrOj, and 
 HOAo (Briickner, A. 205, 127).— Small needles 
 (from alcohol) . Salts . — BaA'2. — CaA'j. 
 
 Succinoxyl-derivative ' 
 CO2H.CH2.CH2.CO.NH.CjH4.CO2H. [226°]. From 
 ^J-tolyl-succinimide and dilute KMnO, (Michael, 
 B. 8, 577). Yellowish needles, si. sol. cold 
 water. Salt.— C„H„N05Ag. 
 
 Amide CjH4(NH2).CO.NH2. [179°]. Formed 
 by reducing ^-nitro-benzamide (Beilstein a. 
 Eeichenbach, A. 132, 144). Yellow crystals, si. 
 sol. water. 
 
 Si-amido-benzoic acids CjHsNjOj (Griess, 
 A. 154, 325; B. 2, 47, 434; 5, 192; 7, 1227; 
 17, 603 ; Pr. 20, 168 ; Wurster a. Ambiihl, B. 
 7, 213 ; V. Meyer a. Wurster, B. 6, 635 ; A. 
 171, 62). These acids can be formed by 
 reducing the corresponding di-nitro-, or nitro- 
 amido-, benzoic acids. They are soluble in water, 
 combine both with acids and bases, and split 
 up, when distilled with baryta, into CO, and 
 phenylene-diamine. 
 
 Nitrous acid converts the (a) acid into amido- 
 
 COv 
 
 di-azo-benzoio acid, C5H3(NH2)<'jj^^O; the 
 
 (/3) and (7) acids are converted by it into 
 azimido-benzoio acids, HN8:C|jHj.C02H, while 
 the symmetrical acid becomes tri-amido-azo-ben- 
 
AMIDO-BENZOPHENONES. 
 
 loti 
 
 Eoio acid C.H,(NH2)(CO,H).N2.C.Hj(NH2)jCOjH 
 V. Azo compounds. 
 
 s-di-amido-bemoic acid 
 C.H3(C02H)(NH,),aq [1:3:5]. [228°]. S. 1-1 at 8° 
 (Voit, A. 99, 106 ; Hubner, A. 222, 85). Colour- 
 less needles, neutral to litmus ; loses aq at 110°. 
 Very dilute solutions are turned yellow by HNOj. 
 
 Salts.— HA'2HC1: needles.-HA'H^SO,.— 
 B. 1-05 at 11°.— BaA'^l^aq.— AgA'2aq. 
 
 Amide C„H3(CONH2)(NHj)2 di-amido-benz- 
 amide. [177°] (V.); [183°] (M.). Needles 
 (Mnretow, Z. [2] 6, 642). Salt.— 
 CjHjNaO 2HC1 : silky needles. Di-acetyl-deriva- 
 tive CsHs(CONA02)(NH2)2 2aq. [Above 270°]. 
 Thin needles, si. sol. cold water (M.). 
 
 (a)-di-amido-benzoic acid 
 CjH3(COjH)(NH2)j. [1:2:5]. Formed also from 
 nitro-isatoio acid by Sn and HCl (Eolbe, J. pr. 
 [2] 30, 480). Very small prisms (from water). 
 V. si. sol. alcohol, ether, and boiling water (Or.). 
 The free acid turns blue in air. 
 
 Salts. — HA'HjSO^: needles, v. b1. sol. 
 water.— HA'2HC1 (E.). 
 
 {ff)-di-amido-benzoic acid 
 C,H3(C02H)(NHj), [1:3:4]. [211°] (Salkowski, 
 4. 173, 67 ; Griess, B. 5, 856). Plates. SI. sol. 
 cold water. 
 
 Salts.— HA'H^SO^: plates; v. si. sol. hot 
 water.— HA'HCl liaq. 
 
 (y)-di-am,ido-benzoic acid 
 C5H,(00jH)(NHj)2 [1:2:3]. Long needles. 
 
 Salt.— (HA')jH,SO, H&q : six-sided tables or 
 columns, v. si. sol. water ; FcjOlj colours its solu- 
 tion brownish-red. 
 
 Iri-amido-benzoic acids CjHgNgOj. 
 
 I. 0eHj{C0jH)(NHj)3iaq [1:3:4:5]. From di- 
 nitro-amido-benzoic (or chrysanisic) acid 
 (Salkowski, A. 163, 12). 
 
 Needles (from water). SI. sol. cold water, 
 T. si. sol. alcohol, and ether ; solution is acid. 
 Heat splits it up into CO^ and tri-amido-benzene. 
 Its solutions give a brown pp. with FcjClj. 
 
 Salts. — HA'2HC1: silver-grey needles. — 
 HA'(HCl)2SnCl2 3iaq:monoolinic.— HA'H^SO, aq: 
 b1. sol. hot water. — HA'2HN03. — CaA'^. — 
 ZnA'j 6aq. 
 
 II. 0^3:^(00 ja)(NH2), [1:2:3:5]. Formed by 
 reduction of jo-sulpho-benzene-azo-s-di-amido- 
 benzoic acid (Griess, B. 15, 2200). 
 
 Colourless crystals ; v. sol. hot water ; si. 
 Bol. alcohol, insol. ether. Very readily oxidised. 
 
 Salt. — HA'H^SOj; small white needles, v. 
 si. sol. water, insol. alcohol. 
 
 Beferences. — Cklobo-, Bkomo-, Iodo-, Niibo-, 
 and Methyl-, amido-benzoic acids and amido- 
 bulpho-benzoio acid. 
 
 AMIDO-BENZOIC ALDEHYDES C,H,NO. 
 
 o-Amido-benzoic aldehyde CeH4(NH2).CHO 
 [1:2]. [40°]. Formed by oxidising its oxim 
 with Fe^Cl, (Gabriel, B. 15, 2004). 
 
 Prepa/ration. — o-nitro-benzaldehyde (3 g.) is 
 digested with FeS04 (50 g.) and NH3 at 100° 
 (Priedlander a. Gohring, B. 17, 456). 
 
 Properties. — Silvery plates ; volatile with 
 steam ; may be distiUed. V. sol. alcohol, ether, 
 and benzene, si. sol. water, insol. light petro- 
 leum. 
 
 Salt. — B'-HaPtCl. : large yellow prisms (from 
 HClAq). 
 
 Reactions. — Very stable towards alkalis, bu» 
 condensed by acids to C,,H,2N20, which ig 
 probably C3Hi(NHJ.CH:N.C„H,.CH0 ; this forms 
 small colourless needles [189°], is not volatiln 
 with steam, and possesses only weak basic pro- 
 perties; NHjAq, cone. HClAq, and hot dilute 
 HClAq reconvert it into amido-benzaldehyde. 
 
 Acetyl derivative CeH,(NHAo).CHO. 
 [71°]. White needles (Friedlander, B. 15, 2 572). 
 
 Oicijra CeH4(NHj)CH:N0H. [133°]. Formed 
 by reducing o-nitro-benzaldoxim (Gabriel, B. 
 14, 2338; 15, 3057; 16, 517). Needles; may 
 be sublimed. Sol. alcohol and ether, si. sol. 
 water and benzene. Its methyl derivative 
 CsH,(NHJCH:NOMe melts at [58°] (E. Meyer, 
 C. O. 1885, 516). Its aoetyl-methyl deriva- 
 tive C5H,(NHAo)CH:NOMe [109°], and its di- 
 acetyl derivative CsH,(NHAo)CH:NOAc 
 [128°] are crystalline, insol. acids and alkalis. 
 
 m-Amido-beuzoic aldehyde, 
 
 Oxim CsH4(NH2).CH:NOH. [88°]. Formed 
 by reducing m-nitro-benzaldoxim with FeSO, 
 and NH3 (Gabriel, B. 16, 1997). White felted 
 needles. Sol. alcohol, ether, and hot benzene, 
 si. sol. cold benzene, and benzoline. Dissolves 
 in acids and alkaUs. Salt: B'jHjPtCls; orange 
 yellow tables. 
 
 p-Amido-benzoic aldehyde CeHj(NH2).CH0 
 [1:4]. [71°]. Formed by action of acids on 
 its oxim. Flat plates, sol. water. With acids 
 it forms red salts. 
 
 Acetyl derivative CjH,(NHAc).CHO. 
 [155°]. Long white needles. 
 
 Oxim. — CbH,(NHj).CH:NOH. [124°]. 
 Formed by reducing the oxim of p-nitro-benzoio 
 aldehyde by ammonium sulphide (Gabriel a. 
 Herzberg, B. 16, 2000). Flat yellow crystals, 
 sol. water, alcohol, ether, acids, and alkalis. Its 
 acid solution is resolved, even in the cold, into 
 hydroxylamine and ^-amido-benzoio-aldehyde. 
 Acetyl derivative OeHj(NHAc).CH:NOH. 
 [206°]. White plates. 
 
 AMIDO-BENZONITRILES C,H„N2. 
 
 o-Amido-benzonitrile NH2.Cj,H,.CN [1:3]. 
 [103°]. By reduction of o-nitro-benzonitrile 
 (Baerthlein, B. 10, 1714). Needles ; v. sol. water, 
 alcohol, and ether, 
 
 m-Amido-benzonitrlle NH^CjH^.CN [1:3]. 
 [52°]; (290°). 
 
 Formation. — 1. By reducing m-nitro-benzo- 
 nitrUe (Hofmann, Z. [2] 4, 726; Fricke, B. 
 7, 1321).— 2. By distilling the dioyanide of 
 »»-amido-benzoic acid (v. p. 157, 1. 32) (Griess, B. 
 1, 191). — 3. By heating ?>i-uramido-benzoic acid 
 (2. V.) with P2O5 (Griess, B. 8, 861). 
 
 Properties. — Needles or prisms, si. sol. water, 
 ▼. e. sol. alcohol. 
 
 Salts. — B'HCl. — W^ytG\ : four-sided 
 tables. — B'AgNOj : white laminse. 
 
 p-Amido-benzonitrile NH^.CjH^.CN [1:4]. 
 [110°] (F.) ; [74°] (E.). Formed by reducing 
 p-nitro-benzonitrile (Engler, A. 149, 302), or by 
 distilling ^-uramido-benzoic acid (F.). — Needles, 
 V. sol. alcohol, ether, and boiling water. — 
 B'HCl.— B'^H^PtCle : needles. 
 
 AMIDO - BENZOPHENONES C,3H„N0. 
 
 Amido-di-phervyl-hetones . 
 
 o-Amido-benzophenone Bz.OjH^.NHj [1:2]. 
 [106°]. Formed by reducing o-nitro-benzo- 
 phenone with Sn and HCl (Geigy a. Eoenigs, .B. 
 
leo 
 
 AMIDO-BENZOPHENONES. 
 
 18, 2403). Tellow plates, or thick crystals, t. 
 Bol. dilute acids, alcohol, and ether. 
 
 m-Amido-benzopheaoue Bz.CsHj.NHj [1:3]. 
 [89°]. Prom m-nitro-benzophenone and SnOl^ 
 (G. a. K.). — ^Yellow felted needles, sol. alcohol, 
 and ether, si. sol. water.— B'HCl : [187°] ; long 
 needles. 
 
 2)-Amido-benzoplienone Bz.CjHj.NH^ [1:4]. 
 [124°]. Bm,zo-aniUne. Prepared by boiling its 
 phthalyl derivative with alcoholic KOH (Doebner, 
 B. 13, 1011; Doebner a. Weiss, B. 14, 1836). 
 Colourless plates, v. sol. alcohol, ether, and 
 glacial HOAc, si. sol. cold water. Nitrous acid 
 converts it into jp-oxy-benzophenone. On fusion 
 with ZnClj it loses H^O forming a compound of 
 the formula CijHjN. The latter is a very stable 
 indifferent substance, crystallising in glistening 
 plates [118°], and distils undecomposed at a high 
 temperature ; it is soluble in alcohol, ether, &c., 
 sparingly in hot water, insoluble in cold. 
 
 Salts. — ^B'jHjSOj: long sparingly soluble 
 needles.— B'HOl, B'^HAOj, and B'HNOs are 
 more soluble. — (B'HCljjPtClj : yellow needles ; 
 ri. sol. cold water. 
 
 Acetyl derivative CjHj.CO.CjH^.NHAc. 
 [153°]. Long needles. Sol. alcohol, ether, 
 acetic acid and benzene ; insol. water. 
 
 Benzoyl derivative CsH5.CO.C5H4.NHBz. 
 [152°]. Plates, sol. hot alcohol, si. sol. cold 
 alcohol, insol. water. 
 
 Phthalyl derivative C^'S.^^O, i.e. 
 CJS.,.CO.C^B.^:^(Cfifi^B.^). [183->']. Prepared 
 by the action of BzCl on phthalanil in presence 
 of ZnClj. Large needles or plates, insol. water, 
 b1. sol. alcohol or ether. 
 
 (o)-Di-ainido-benzophenone Ci,H80(NH2)2. 
 [172°]. Prepared by reducing (a)-di-nitro-benzo- 
 phenone, [190°] itself got from di-nitro-di-phenyl- 
 methane. [183°] (Staedel a. Sauer, B. 11, 1747; 
 A. 218, 344). White needles. 
 
 B"2HC1: large tables. —B"2HClSnCl2.— 
 B'-H^SOi. 
 
 (j3)-Di-amido-benzoplienone C^Hi^N^O. [165°]. 
 Mavine. — From di-nitro-benzophenone [149°] 
 by reduction (Chancel a. Laurent, A. 72, 281 ; 
 Prtetorius, B. 11, 744). — Slender yellow needles 
 (from water). 
 
 Salts: B"H2SnjCls; plates.— B"H2PtCls. 
 
 Acetyl derivative C,sHgO(NHAc)2 : 
 needles, [227°]. 
 
 Oaim (C5H,.NH,)2C:NOH: [178°]; crystal- 
 line. 
 
 Phenyl-hydraside (OeH4.NH2)2C:NjHPh: 
 ri83°] ; yellowish needles (from hot alcohol). 
 (Miinchmeyer, B. 20, 511). 
 
 (7)-Di-amido-benzopheiione, C,sH;0(NH2)2 
 [131°]. From the di-nitro-benzophenone [190°] 
 obtained from benzophenone (Staedel, A. 218, 
 849).— Glittering tablets. 
 
 Salt.— B"2HC1. 
 
 Acetyl derivative. — C,jHsO(NAcH)2. 
 [167°]. Tables ; insol. water ; v. sol. alcohol. 
 
 AMIDO-BENZOYL-CABBAMIDE v. Ubea. 
 
 AMIDO-BENZOYL-FOEMIC ACID v. Amido- 
 
 PHENYL-GLyOXTIilC ACID. 
 
 AMIDO-BENZOYL-GLYOXYLIC ACID ». 
 
 Qdinisatic aoid. 
 
 AMIDO-BENZOYL-UEEA v. Ukea. 
 
 DI-AMIDO-DI-BENZYL C.jH.sN^ i.e, 
 NH2.C„H,.CH2.CH2.C„H,.NH2. [182°]. From 
 tho (jp) nitro-compound (j. v.) by reduction. — 
 
 Colourless scales (fi-om hot water), v. si. sol. ooJd 
 water, v. sol. alcohol ; may be sublimed. 
 
 Salts : B"2HC1. — B-'H^PtCl,. — B'H,SO,. 
 — B'-HjCjO,.- B"(H2C20,)j3aq (Fittig a. Stell- 
 ing, A. 137, 262). 
 
 AMIDO-BENZYI ALCOHOL C,HNO i.e. 
 NH2.CsH,.CH,0H. [1:2]. [82°]. Prepared by the 
 action of zinc dust and HCl upon o-nitro-benzyl- 
 alcohol, o-nitro-benzoio aldehyde, or anthranil 
 (Friedlauder a. Henriques, B. 15, 2109). White 
 needles, insol. light petroleum ; slightly volatile 
 with steam. 
 
 AMIDO-BENZYL-AMINE C,H„Nj i.e. 
 NH2.C„H^.CH2NH2 [1:4]. (269°). S.G.^ai-od. 
 Benzylene diamine. From acetyl-j3-nitro-benzyl- 
 amine, Sn, and HCl : the Ac being split off in 
 the operation (Amsel a. Hofmann, B. 19, 1287). — 
 Colourless liquid, v. sol. water and alcohol, insol. 
 ether ; alkaline, absorbing CO^ from the air. 
 
 Salts.— B"2HC1: needles, v. sol. water.— 
 B"2(HCl)4PtCl< : flat needles. The nitrate and 
 oxalate crystallise in long white needles. AgNO, 
 forms a double salt in large plates. 
 
 Si-amido-di-benzyl-amine C„H,,N3 i.e. 
 (NH2.CbH4.CHj)2.NH. [106°]. From the nitro 
 compound (Strakosoh, B. 6, 1060). Needles or 
 plates ; may be distilled, but not volatile with 
 steam. Salt s.— B"'3HC1.— B"'(HCl)sPtCl4. 
 
 Tri-amido-tri-benzyl-amine CjjHjjN, i.e. 
 (NH2.CsH4.CH2)sN. [136°]. From the nitro 
 compound (S.). — Octahedra (from alcohol) ; not 
 volatile with steam. Insol. water, v. sol. hot 
 alcohol. Beduced by Sn and HCl to p-toluidine 
 and the preceding body. 
 
 AMIDO-BENZYL-ANILINE C^HnNj i.e. 
 NHj.CsH1.CH2.NPhH. [88°]. From the nitro- 
 compound by NH, and HjS at 100° (Strakosch, 
 B, 6, 1063). — Scales, v. sol. alcohol, ether, and 
 benzene, not volatile with steam. Salt. — 
 B"2HC1 ; V. sol. water, less so in HClAq. 
 
 AMIDO-BENZYL-BEHZENE v. AMmo-ra. 
 
 PHENYL-METHANE. 
 
 AMIDO-BENZYL CYANIDE v. nubile of 
 Amido-phentl-aoeiio acid. 
 
 DI - n - AMIDO - DI ■ BENZYL - UALONIC - 
 
 (4) (1) 
 
 ETHYL - ETHEK (OeH,(NH2).CH2)j:C(C02Et). 
 Obtained by reduction of di-nitro-di-benzyl- 
 malonic ether with SuClj. 
 
 Salts:— (A"Et2)H2Cl2: [230°], easily soluble 
 needles.— (A"Et2)H2SOi:soales.—(A"Et2)H2C204: 
 glistening yellow scales. — (A"Et2)H2Cl2PtCli : 
 reddish-brown plates (Lellmann a. Schleich, 
 B. 20, 436). 
 
 AMIDO-BENZYL-PHENOL CuHisNO i.e. 
 C„H5.CH2.C5H3(NHi,)(OH). [1:3:4]. From the 
 nitro-oompound. Scales (Eennie, 0. J. 41, 221). 
 
 DI-AMIDO-BENZYL-TOLUENE C„H,5Nj. A 
 orystaUine powder, obtained by reducing di- 
 nitro-2>-benzyl-toluene (?.«.) (Zincke, B. 5, 684). 
 
 Salt s.— B"2HC1.— B"H2S04. 
 
 AMIDO-EBOMO-COnFOXTNDS v. Bboho- 
 
 AMIDO-COMPOUNDS. 
 
 AMIDO-BBUCINE v. Bktjoine. 
 AMIDO-BXrXYL-BENZENE v. Amido-phentl- 
 
 BUIANE. 
 
 AMIDO- BUTYRIC ACIDS C,Hs,NOj. 
 
 o-Amido-re-butyrio acid CHs.CH2.0H(NH2).C02H. 
 S. 3 at 15° ; S. (alcohol) -18 at 80°. From 
 a-bromo-butyric aoid and NHjAq (E. Schneider, 
 A. Su^l. 2, 71). — Stellate groups of small 
 
AMIDO-CINNAMIO ACIDS. 
 
 Ibl 
 
 lamincB or needles (from alcohol) ; neutral ; 
 Bweet taste ; insol. ether. 
 
 Salts.— HA'HCl ; v. sol. water.— HA'HNOs ; 
 fern-like groups of silky needles. — IKA').,H.,&0,. — 
 HOPb.A'.— AgA'. 
 
 /3-Amido-n-butyrlc acid 
 
 CH3.CH(NH,).CHj.C0jH. 
 
 Amide CHs.CH(NH2).CH2.CO.NHj. An amor- 
 phous mass, obtained by the action of alcoholic 
 NHj on /3-chloro-n-butyrio ether (Balbiano, 
 G. 10,137; B. 13, 312). Its platino-chloride 
 crystallises in orange tables, si. sol. alcohol. 
 
 a-Amido-iso-butyrio acid CMe.^(NHj).C02H. 
 
 Formation. — From aoetonyl-urea and fuming 
 HCl at 160° (Urech, A. 164, 268).— 2. From di- 
 acetonamine (Heintz, A. 192, 343 ; 198, 46). 
 
 Prepa/ration. — The acetone cyanhydrin, ob- 
 tained by the action of dilute HON on acetone, is 
 heated with alcoholic NH, at 60°, and the pro- 
 duct saponified (Tiemann a. Friedlander, R. 14, 
 1971). 
 
 Properties. — Plates or tables, v. sol. water, si. 
 sol. alcohol, insol. ether ; sublimes at about 220°. 
 
 Salt s. — BaA'2 2aq : needles. — MgA'j : thick 
 prisms. — OuA'j : plates, giving a violet solution. 
 —AgA' : needies, sol. water. — HA'HCl 2aq. — 
 HA'HCl. 
 
 Nitrile.—C^e.^B^.C'S. The product of 
 the action of alcoholic NHj on acetone-cyan- 
 hydrin (vid. sup.). 
 
 AMIOO-CAMFHOB v. Camfhob. 
 
 AUIDO-GAAIFHOBIC ACIB v. Camfhobic acid. 
 
 AUIDO-CAFBOIO ACID 1;. Leucine, and 
 
 AUIDO-HEXOIC ACID. 
 
 AMIDO-CAPKYL- BENZENE v. Amxdo- 
 phenyl-ootaue. 
 
 AMIDO-CAPEYLICACIDii.Amldo-ootoioacid. 
 AMIDO-CAEBOSTYBIL CsH.N^O i.e. 
 
 CaH^<|^^^^>CO. [127°]. Anhydride of 
 
 hydrazido-cinnamicacid; Oxy-amido-quinoline ; 
 Amido-pseudo-carbostyril. Prepared by convert- 
 ing diazo-cinnamio acid by NajSOj into 
 S03Na.N2.CBH4.CH:CH.C02H, then reducing this 
 substance by acetic acid and zinc dust to 
 S03Na.NH.NH.C„H,.CH:CH.C0,H, boiling this 
 with HCl and then adding KOH (Fischer a. 
 Kuzel, A. 221, 278). 
 
 Properties. — Slender needles ; may be sub- 
 limed ; sol. alcohol, ether, and hot water. It 
 forms salts with acids. 
 
 Beaclions.—l. Does not reduce alkaline 
 copper or silver solutions. — 2. Nitrous acid con- 
 verts it, even in the cold, into carbostyril. 
 
 7-Amido-oarbostyril. From carbostyril by 
 nitration and reduction (Friedlander a. Lazarus, 
 A. 229, 246). YeUowplates (from glacial HOAo). 
 Does not melt below 320°. 
 
 Methyl derivative C5H5N(NH2)(0Me). 
 [103°], amido-(Py.S)-methoxy-quinoline. Formed 
 from the nitro-compound by SnClz (Feer a. 
 Koenigs, B. 18, 2397).— Silvery plates ; v. sol. 
 alcohol and ether ; m. sol. warm water. Its 
 ethereal solution has a bluish fluorescence. 
 EMnO^ oxidises it to methoxy-quinolinic acid 
 [140°]. Dilute HCl at 120° forms (7)-amido 
 carbostyril. 
 
 See also Orx-Auino-QuiNOLiNE. 
 AmSO-CHBOUATE OF FOTASSIVU v. 
 ilmi<2o -cA70ffta<«j. under CaBouiuu,Aoii>s or. 
 Vol. L 
 
 AMIOO-CHBYSANISIG ACID v. Niibo-m. 
 
 AMIDO-BENZOIO ACID. 
 
 AMIDO-GINNAMIC ACIDS Cs,H|,NO,. 
 
 a-Amido-cinnamio acid 
 C5Hs.CH:C(NH J .CO^H. Obtained by saponifying, 
 its benzoyl derivative. — Silvery plates, decom- 
 posing at 240°-250° (Plochl, B. 17, 1619). 
 
 Salts. — CuA'2 2aq: small blue prisms. — 
 (HA')2HC1 : flat needles, si. sol. cold water and^ 
 alcohol. 
 
 Benzoyl derivative 
 C,H5.CH:C{NHBz).C02H [131°]. Formed by heat- 
 ing an acetic acid solution of benzoyl-di-amido- 
 ,, ;, . . , , C.H4.CH.CH(NHBz). 
 
 nydrocmnamic lactam 1 1 
 
 NH.CO 
 Needles or prisms ; sol. alcohol, ether, and hot 
 water. 
 
 o-Amido-cinnamic acid 
 NH2.C,H,.CH:CH.C02H [1:2]. [159°]. 
 
 Preparation. —From o-nitro-cinnamic acid 
 (150 g.), crystallised baryta (2100 g.), water (30 
 litres), and ferrous sulphate (1400 g.), by heating 
 two hours at 100° (Fischer a. Kuzel, A. 221, 
 266; Tiemann a. Opermann, B. 13, 2061). 
 Ammonia may be used in place of baryta 
 (Gabriel, B. 15, 2294; Friedlander, 4.229,241). 
 
 Properties. — Yellow needles; sol. alcohol, 
 ether, and hot water, si. sol. cold water. Dis- 
 solves in aqueous alkalis and acids. 
 
 Salts.— HA'HCl; prisms. — BaA'2; prisms. 
 
 Ether.— Eik' 119,°]. May be distilled. Yel- 
 low needles, with yellowish-green fluorescence. 
 Its hydrochloride is sparingly soluble in excesa 
 of cone. HCl; its acetyl derivative, [137°]» 
 forms white needles, which may be distilled, 
 (Friedlander a. Weinberg, B. 15, 1422). 
 
 Ethyl derivative 
 C,H,(NHEt).CH:CH.C02H. From the acid (60g.), 
 KOH (96 c.c. of 20 p.c. solution), alcohol (240 g.)\ 
 and EtI (60g.), by boiling (F. a. K.). 
 
 Reactions. — 1. Long boiling with HClAq 
 forms carbostyril. — 2. ZnSOjAq gives a crystal- 
 line pp. — 3. AgNOjAq gives a white pp. — 4. 
 CuS04Aq gives a light green pp.— 5. Pb(OAo)2Aq' 
 gives a yellow pp. 
 
 m-Amido-cinnamic acid 
 C„H,(NH2).CH:CH.C02H [1:3]. [181°]. The 
 preparation is similar to that of the o-compouud. 
 
 Properties. — Long yellow needles ; sol. alco- 
 hol, ether, and hot water. Dissolves in aqueous 
 acids and alkalis. 
 
 Reactions. — 1. CuSO.,Aq gives a duU green 
 pp. — 2, 3, same as above. — 4. Pb(0Ac)2Aq gives 
 a white pp. sol. hot water (T. a. 0.). 
 
 S alt s.— HA'HCl : plates.— (HA'HC^jPtCl^. 
 — HA'HNOj: slender needles. — BaA'22aq: plates. 
 
 ^-Amido-cinnamic acid 
 C„H^(NH2).CH:CH.C02H[1:4]. [176°]. Prepared 
 by reducing p-uitro-cinnamic ether in alooholia 
 solution with tin and HCl ; yield : 75 p.c. 
 (Miller a. Kinkelin, B. 18, 3234). Slender yel- 
 low needles, sol. water, alcohol, and ether. Dis- 
 solves in aqueous alkalis and acids. 
 
 Reactions.— X. CuSOiAq a brown pp. — 2, 3, 
 and 4, the same as for the m-compound. 
 
 Salt s.— HA'HCl.— (HA'HCl)2PtCl,. 
 Acetyl derivative [260°]. Long needles, 
 sol. hot alcohol, si. sol. water, v. si. sol. ether and 
 benzene (Gabriel a. Herzberg, B. 16, 2041). 
 
 M 
 
163 
 
 AMJDO-OINNAMIO AOIDS. 
 
 Oi-amido-clnnamic acid 
 C,H3(NHJ,.CH:CH.C02H. [168"]. Formed by 
 reducing (3:4:l)-nitro-amido-cinnamic acid 
 (Gabriel a. Herzberg, B. 16, 2042). Yellow 
 needles, sol. hot alcohol, and water, iusol. ether, 
 benzene, and benzoline. 
 
 AHIBO-COUENIC ACID v. Comenic acid. 
 
 AMIDO-COITlttAEIN CjHjNOj. [168°-170'=]. 
 From nitro-coumarin (j. v.). — Needles, v. si. sol. 
 cold water, v. sol. hot water. S al t.— (B'HO^jPtCl, 
 (FrapoUi a. Chiozza, A. 95, 253). 
 
 AMIDO-CSESOL 0,H,NO. Mol. w. 142. 
 Ten amido-cresoU are indicated by theory : 
 four derived from ortho-, four from meta-, and 
 two from para-cresol. The amido-cresols are 
 readily soluble in alcohol and in ether, sparingly 
 so in water. They dissolve in acids and in 
 alkalis. They are formed by reducing nitro- 
 cresols, or from nitro-toluidines by the diazo 
 reaction. 
 
 Amido-o-cresols CsH3Me(0H)(NHJ [l:2:a!]. 
 
 Amido-o-cresol x = 'd. From nitro-o-cresol 
 [69°] (Hof mann a. Miller, B. 14, 570 ; Zincke a. 
 Hebebrand, A. 226, 72). 
 
 Beaction, — 1. When heated with quinone, it 
 forms a red crystalline Base,C2jH2jN404, [285'^], 
 V. si. sol. alcohol, sol. acids ; its acetyl derivative, 
 CjjHjjAcjNjO,, forms orange needles (from dry 
 HOAc).— 2. Heated with formic acid it forms a 
 
 methenyl compound : C,H3Me<^Q^CH, [39°], 
 
 (200^). 
 
 Methyl ether C,H3Me(OMe)(NH2). (223°). 
 
 Amido-o-cresol a; = 4. [161°]. From nitro-o- 
 cresol [108°] (Noltiug a. CoUin, B. 17, 270). 
 Also from acetyl-tolylene-di-amine, 
 C,H,Me(NHj)(NHAo) [1:2:4] (Wallach, B. 15, 
 2831). Colourless plates or needles. Salt. — 
 BTSCl : glittering plates, which sublime as needles. 
 
 Acetyl derivatives 
 OsH,Me(OH)(NHAc). [225°] ; sol. KOHAq.— 
 0,H3Me(0Ac)(NAcH). [133°] (Maassen, B. 
 17, 608 ; Wallach, A. 235, 250). 
 
 Amido-o-cresoI X = 5. [175°]. 
 
 Formation. — 1. From nitro-o-cresol [85°] 
 (Hirsoh, B. 18, 1514). — 2. From nitroso-o-cresol. 
 3. From sulpho-benzeue-azo-o-oresol by re- 
 ducing with Sn and HCl (Nolting a. Kohn, B. 
 17, 365). — White plates or needles ; may be sub- 
 limed.^ — CrOj gives toluquinone. Salt . — B'HCl. 
 
 Amido-o-cresol a; = 6. [124°-128°]. From 
 nitro-cresol [143°]. Stellate groups of needles 
 (Ullmann, B. 17, 1962). Salt.— B'HCl. 
 
 Undeterviined derivatvoes of amido-o-cresols. 
 
 Methyl ether CeH3Me(0Me)(NH2) [1:2:5?]. 
 [53°] (Hofmann a. Miller, B. 14, 571). 
 
 Ethyl ether C„H3Me(OEt)(NH2) [l:2:a;]. 
 From ethyl nitro-o-cresol [71°] (Staedel a. 
 Eayser, A. 217, 217; B. 15, 1134). Salts.— 
 B'HCl l^aq.— B'jH^SOi.- B'jHjPtCls. Acetyl 
 derivative CeH3Me(0Et)(NHAc). [108°]. Tri- 
 metric plates (from water) ; tables (from ether) ; 
 cubes (from benzene). 
 
 Amido-m-cresols CjH,Me(0H)(NH2) [l:3:a!]. 
 
 Amido-m-cresoIa; = 6. [151°]. From sulpho- 
 t)enzene-azo-m-cresol by reduction (Nolting a. 
 Kohn, B. 17, 367). White warts. On oxidation 
 with CrOj it gives toluquinone. 
 
 Undeterminedderivativeo/anamido-m-cresol. 
 
 Ethyl ether CsH3Me(0Et)(NH2) [l:3:x]. 
 An oil formed by reducing ethyl-nitro-m-cresol 
 
 [54°] (Staedel, A. 217, 219). Salt.— B'.H^C.O,. 
 Acetyl derivative. [114°]. Mass of needles 
 (from water). 
 
 Amido-ivcresols C„H3Me(0H)(NHj) [l:4:a;]. 
 
 Amido-jp-cresol K = 2. [144°]. 
 
 Formation. — 1. From nitro-^J-oresol [78°] 
 (Knecht, A. 215, 91). — 2. From nitro-toluidine 
 CsH3Me.(NH2)(NOJ [1:4:2] (WaUach, B. 15,2833). 
 
 Properties. — Colourless plates by sublimation. 
 
 Acetyl derivatives 
 C,H3Me(0H)(NHAc) [178°] ; sol. KOHAq. — 
 C„H3Me(0Ac)(NHAc) [129°] (Maassen, B. 17, 008). 
 
 Methyl ether C„H3Me(0Me)(NH,). [47°]. 
 From the nitro-compound (K.) ; needles, volatile 
 with steam. 
 
 Amido-p-cresol a = 3. [135°]. 
 
 Formation. — 1. From nitro-ji-cresol [33°] 
 (Wagner, B. 7, 1270; Hofmann a. Miller, B. U, 
 572).— 2. By reducing benzene-azo-^-cresol or 
 sulpho-benzene-azo-^-cresol (Nolting a. Kohn, 
 B. 17, 360). 
 
 Properties. — White plates or needles; gives 
 a red colour with Fc^Clj. Salt .—B'HCl. 
 
 Reactions. — 1. Gives a methenyl derivative 
 whenheated with formic acid (H.a. M.). — 2. Gives, 
 when heated with Ao^O and NaOAc, an ethenyl 
 derivative which is converted by boiling dilute 
 HjSOj into an acetyl derivative. 
 
 Acetyl derivative [160°]. Long needles. 
 
 Methyl ether C,H3Me(0Me)(NH.,) [38°]. 
 
 Ethyl ether C,H3Me(OEt)(NH2). [41°]. 
 From the nitro-compound (Staedel a. Kayser, 
 B. 15, 1134). Needles (from water) or plates 
 (from other solvents). Salts. — B'HCl l|aq. — 
 B'^H2SOj2aq. Acetyl derivative [107°]. 
 
 Si-amido-^-cresol. 
 
 Ethyl ether C„H2Me(OEt)(NH,)2 [1:4:3:5]. 
 From the nitro-compound (Staedel a. Kayser, 
 A. 217, 221). Pleasant-smelling oil— B'HCl: 
 
 Rl1 kV TlGfiCllfiS 
 
 Di-amido-cresol C„H2Me(OH)(NH2)3 [l-.x-.l-.i]. 
 From amido-toluene-azo-amido-cresol (Graefi, 
 A. 229, 349) ; decomposes when liberated from 
 its salts. — B"H2S04aq; slender grey needles 
 (from alcohol-ether). 
 
 AMIDO-CEESYL- v. Amido-toltl-. 
 
 AMIDO-CBOTONIC ETHER. A name applied 
 to the imide of aceto-acetic ether (u. p. 19). 
 
 AMIDO-CUMENE v. Cumidine. 
 
 Di-amido-cumene OjHi^Nj i.e. ¥x.G^.J^'H..^.^ 
 [47°]. From the nitro-compound (Hofmann, /. 
 1862, 354). 
 
 Di - amido - pseudo - cumeue C„HMe3(NH2), 
 [1:3:4:5:6]. [92°]. Formation.— 1. By reducing 
 nitro-pseudo-cumidiue [47°] (Edler, B. 18, 630). 
 2. By reducing amido-azo-cumene (Nolting a. 
 Baumauu, B. 18, 1147). Properties. — Needles 
 or plates ; gives with Fe^Clj a brownish-red 
 colour and a quinone-like smell; also gives 
 Ladeuburg's aldehydine reaction. 
 
 AMIDO-^/'-CUmENOI. OgHijNO i.e. 
 C„HMe3(OH)(NH2) [1:3:4:6:2] [167°]. Amido. 
 pseudo-cumenol ; Oxy-cutmMne. Obtained by 
 reducing benzene-azo-if'-oumenol (Liebermann a. 
 Kostanecki, B. 17, 886) ; or nitro-i)'-oumenyl 
 nitrate (Auwers, B. 17, 2980). White needles 
 (by sublimation) ; sol. KOHAq. Fe2Cl5 gives a 
 red colouration. Di-acetyl derivativt 
 C,HMe3(OAo)(NHAo), [186°] : needles. 
 
 AMIDO-CTJMINIC ACID C,|^„NO, 
 
AMIDO-FURFUR-BUTYLENE OXIDE. 
 
 lea 
 
 m-Amido-ctmiiiiic acid 
 Pr.C.H3(NH,)C0,H [1:2:4]. [129°]. Amido-iso- 
 propyl-bemoio acid. Prepared by reducing m- 
 nitro-ouminic aoid [158°] (Paterno a. Pileti, O. 
 5, 383; Lippmann a. Lange, B. 13, 1661).— 
 Tables; some of it oooasionally crystallises 
 from water in thin plates [104°] (Pileti, O. 10, 
 12). Fe-jClj give a violet-blue colouration with 
 the hydrochloride. EtI at 100° gives a syrupy 
 ethyl-amido-cuminic acid. 
 
 Salts. — AgA': white pp. — ZnA'jSaq: needles. 
 HA'HCl.— (HA'HCl).,PtCl,.— (HA')2H,S0,. 
 
 Acetyl derivative. [248°-250°]. Slender 
 needles, si. sol. boiling alcohol, saponified by 
 water at 230°. 
 
 Ethyl ether 'EtA'. Heavy oil. 
 
 mtrile Pr.C„Hs(NH2).CN. [45°]. (805°). 
 -Fromnitro-cumino-nitrile. — Needles (from water) 
 (Czumpelik, B. 2, 183). Salt.— (B'HCl)2PtCli. 
 
 o-Amido-cuminic acid 
 Pr.C„H3(NH,).C0„H. [1:3:4]. [115°]. Prepared 
 by reducing o-ni'tro-cuminio acid with FeSO^ 
 and NHj (Widmau, B. 19, 270).— Plates or tables. 
 
 Acetyl derivative C,„H,2AoNO.,. [246°]. 
 Slender needles, si. sol. alcohol, and ether ; may 
 be sublimed (Widman, B. 16, 2579). 
 
 Di-amido-cuminic acid C,„H„Ni02 i.e. 
 *r.C,Hj(NH,),CO,H. [192°]. Formed by re- 
 ducing di-uitro-cuminic acid (Boullet, 0. B. 43, 
 399; Lippmann, U. 15,2144). — Yellowish plates, 
 sol. hot water, alcohol, ether, alkaUs and acids. 
 Crystallises from water with aq. 
 
 Salts. — AgA'aq. — HA'HOl aq: large prisms. 
 
 AMIDO-CUMYL-ACEYIIC ACIDS C.^Hi^NOj 
 
 I. Pr.CsH3(NH.J.CH:CH.C0,H [1:3:4]. [165°]. 
 From the nitro-aoid, FeSOj, and NH3 (Widman, 
 B. 19, 262).— Flat yellow prisms (from alcohol). 
 Salt. — HA'HC13aq : very slender needles, v. si. 
 sol. water ; converted by boiling water into oumo- 
 Btyril or (B. 3)-iso-propyl-(Py. 3)-oxy-quinoline 
 [169°]. Acetyl derivative 
 PrC„H3(NHAo).CH:CH.C02H, [220°] : very thin 
 needles (from alcohol). 
 
 n. i'rC3H3(NH2).0H:CH.CO2H [1:2:4]. [165°]. 
 From the nitro-aoid (Widman, B. 19, 415). Six- 
 sided tables (from ether). Warm HjSOj gives a 
 magenta colour. Salts. — HA'HOl: flat needles. 
 — (HA'HCl)2PtClj 2aq.— (HA%H,SO^ 5aq. Ace- 
 tyl derivatives Cj^HuAcNOj, [240°]: needles 
 (from alcohol).- CijHisAc^NOj. [236°]. 
 AMISO-ij'-CUMYLE NE-AGETAMIDINE 
 
 CH.A *.«. CsMe3(NH,)<^g^CMe [1:3:4:2:=]. 
 
 Ethenyl - tri - amido - tri ■ methyl - henzene. 
 [215°-218°]. From acetyl-di-nitro-pseudo-oumi- 
 dine by reduction with Sn and HOI (Auwers, B. 
 
 18, 2663). — Eosettes of plates or yellowish 
 prisms (from water) containing 2aq. 
 
 Salts. — B"2H01aq. — B"H01 2aq. — 
 B'S^PtOlj aq. 
 
 AMIDO-CUMYI PHENYL KETONE v. Phenyl 
 
 AMTDO-CUMYL KETONE. 
 
 m-AMIDO-CTTMYI-PEOPIONIC ACID 
 
 C.^H.jNOj i.e.VxC^i^^.CE^.G-E^.Q,0^ [1:3]. 
 [103°-105°]. From m-amido-oumyl-acrylio aoid, 
 NaOHAq, and sodium-amalgam (Widman, B. 
 
 19, 418). Acetyl derivative CjjHijAcNOj, 
 [168°] ; prisms (from alcohol). 
 
 AMIDO-DI-CYANIC ACID C^HjNsO i.e. 
 NH,.0O.NH.0N or HN:C<^^>00. Allo- 
 phano-nitrile; carbonyl giMnidine; carbimido- 
 
 KETONE e 
 
 Formation. — 1. From di-eyano-di-amide and 
 baryta-water.— 2. From potassio oyanate and 
 cold aqueous eyanamide (Hallwacha, A. 153, 239 ; 
 Wunderlich, B. 19, 448). 
 
 Properties. — Needles. It decomposes car- 
 bonates and behaves as a strong aoid. Produces 
 biuret when warmed with HaSO, (1 vol.) and 
 water (2 vols.) at 70° (Baumann, B. 8, 708). 
 
 Salts. — NaOjH.,NsO. — KA'. — BaA'j 3aq.- - 
 OuA'2 4aq.— OuO^HNjO 2aq.— AgA'. 
 
 AMIDO-CYANUSIC ACID v. Ammelide. 
 
 Di-amido-cyauuric aoid v. Ammeline. 
 
 AMIDO-CYMENE v. Ctmidine. 
 
 Diamido-eymene OBH2MePr(NH2)2[l:4:3:6]. 
 Hydrochloride. Formed by reducing the 
 di-oxim of thymoquinone (Liebermann a. Ilinski, 
 B. 18, 3200). 
 
 AMIDO-DRACYLIC ACID =^-AMiDO-EENZoia 
 
 AOID. 
 
 DI-AMIDO-DUEYLIC ACID v. Di-amido-tm- 
 methyl-eenzoio aoid. 
 
 AMIDO-EIHANE v. Ethylamine. 
 Di-amido-etliane v. Ethylene di-amine. 
 AMIDO-DI-ETHYL-ACETIC ACID 1;. Amido- 
 
 HEXOIO AOID. 
 
 AMIDO . ETHYL ALCOHOL v. Oxyethyl- 
 
 AltllNE. 
 
 AMIDO-EIHYL-BENZENEij.Amido-phenyl. 
 
 ETHANE. 
 
 amido-ethyl methyl 
 
 Methyl amido-ethyl ketone. 
 
 DI-AMIDO-DI-ETHYL OXIDE " C,H,,N,0 i.e. 
 (CH3.C(NH,)H),0. 
 
 Di-amido-ether. The very unstable hydro- 
 chloride (B'2H01) of this body is formed by 
 passing NH, into an ethereal solution of 
 (0Hs.0HCl)2O (Hanriot, A. Ch. [5] 25, 224). 
 
 DI-AMIDO-DI-ETHYL-DIPHENYL C,„H,„N, 
 i.e. [4:3:1] NH2.C„H3Et.O,H3Et.NH2 [1:3:4] (?). 
 Formed by the action of SuOlj and HCl or H^SOj 
 on an alcoholic solution of o-azo-ethyl-benzene. 
 — B"H2S04 : needles, si. sol. water, m. sol. alcohol. 
 
 Acetyl derivative C,^'H.,gQiiB.A.o).^. [307°]. 
 White needles (by sublimation), si. sol. alcohol, 
 sol. HOAc. 
 
 An isomeric di-amido-di-ethyl-diphenyl is 
 formed similarly from jp-azo-ethyl-benzene. Its 
 sulphate is a white amorphous powder (G. 
 Schultz, B. 17, 474). 
 
 AMIDO-ETHYL-TOLTJEHE v. Amido-Tolyl- 
 
 ETHANE. 
 
 AMIDO-ETHYL-TOLUIDINE v. Ethyl-toly- 
 
 LENE DIAMINE. 
 
 AMIDO-ETHYL-m-TJKAMIDO-BENZOIGACID 
 C,„H,3N303 i.e. NHj.OjH^.NH.OO.NH.OjH,.CO,H. 
 Formed by the action of ethylene diamine upon 
 cyano-carboxamido-benzoio acid (v. Amido jjen- 
 ZOIC acid). White prisms, si. sol. cold walar. 
 Salt. -HA'HOl 2iaq (Griess, B. 18, 2416). 
 
 AMIDO-FLAVOLINE v. Flavaniline. 
 
 AMIDO-ELTJORENE v. Fluobenb. 
 
 AMIDO-FOBMIC ACID v. Oaeeamio acid. 
 
 AMIDO-FUBrUR-BUTYLENE OXIDE 
 
 > CMe,. 
 CAiNO,*.*. C,H30.C(NH2)<: I 
 
 \o 
 
 u2 
 
164 
 
 AMIDO-rURFUR-BUTYLENE OXIDE. 
 
 (215°-220°). Obtained by reducing CsH.oN^O,, the 
 product of addition of HJO, to furf ur-butylene. 
 
 Properties. — Colourless liquid, volatile with 
 Bteam, sol. water. 
 
 Salts. — B'HClaq: crystals, v. sol. water. — 
 B'jHaPtCl, : sol. hot. water. 
 
 Acetyl derivative CgHjO^.NHAo [153°]; 
 (305°-310°) : needles, v. sol. HClAq. 
 
 Anhydride CaHjNO. [142°]. (300°-310°). 
 V.D. 4-77. Formed from amido-furfur-butyleue 
 oxide on distilling, or even on keeping. It forms 
 large colourless crystals, and is volatile with 
 steam. It is a tertiary base (Tonnies a. Staub, 
 B. 17, 854). 
 
 AMIDOGEN. The group NHj; v. Amides, 
 Amido-acids, and Amines. 
 
 AMIDO-GLTJTASIC ACID v. Glutamic Acid. 
 
 AMIDO-OLYCOLLIC ACID v. Oxy-amido- 
 
 ICBIIO-AOID. 
 
 AMIDO-HEMIPIC ACID v. Hemipio acid. 
 
 AMIDO-HEPTOIC ACID CjHjsNOj i.e. 
 C5H,,.CH(NH2).C02H. a-Amido-coiiantMc acid. 
 Prom bromo-heptoio acid and alcoholic NHj at 
 100° (Helms, B. 8, 1168). Six-sided tables or 
 plates, V. si. sol. cold water, insol. alcohol. 
 
 Salt s.— CuA'2 : insoluble powder.— HA'HCl : 
 prisms, v. sol. water or alcohol. 
 
 AMIDO-HEXOIC ACID CjHijNOj. 
 
 a-Amido-7i-liezoic acid v. Leucine. 
 
 Amido-di-ethyl-acetic acid CEt2(NH2).COjH. 
 
 Preparation. — Di-ethyl ketone cyanhydrin, 
 CEt2(0H).CN, obtained by the action of dilute 
 HON on di-ethyl ketone, is heated with alcoholic 
 NHj, and the product is saponified by HCl. 
 
 Properties. — Thick tables or prisms (from 
 water), v. sol. water, m. sol. alcohol, insol. ether; 
 may be sublimed. 
 
 Salts. — AgA': white plates. — CuA'^ : violet 
 plates. — HA'HCl : thick white prisms (Tiemann 
 a. Friedlander, B. 14, 1975). 
 
 a-Amido-iso-butyl-acetic acid 
 Pr.CH,.CH(NH2).C02H. S. -85 at 12°. Prom 
 iso-valerio aldehyde-ammonia, HCN and HClAq 
 (Limpricht, A. 94, 243 ; Hiifner, J.pr. [2] 1, 10). 
 
 Properties. — Eesembles leucine, but is opti- 
 cally inactive (Mauthner, H. 7, 223). 
 
 AMIDO-HEXYL ALCOHOL v. di-Acetone- 
 
 AI/CAMINE. 
 
 AMIDO-HIPPUEIC ACID 0,B.,„'i{fi, i.e. 
 C„H^(NH2).CO.NH.CH,.C02H. 
 
 m-Amido-bensoyl-glycocoH. [194°] (Conrad, 
 J.pr. [2] 15, 258). S. -3 at 20°; S. (alcohol) 
 •08 at 15°. Prom m-nitro-hippuric acid, ammo- 
 nium sulphide and HjS (Schwanert, 4. 112, 70). 
 
 Properties. — Plates or needles. Soluble in 
 alkalis and in acids. S a It. — B'HCl. 
 
 Reactions. — 1. Boiling HCl forms m-amido- 
 benzoic acid and glycocoU. — 2. Urea forms 
 nramido-hippuric acid C|„H„K30, and a 
 small quantity of carboxamido-hippurio 
 aoidC,„H„N,0, (Griess, J.pr. [2] 1, 135). 
 
 DI-AMIDO-HYDEO-ACBIDINE KETONE, so 
 called, CijHiiNjO. [223°]. Pormed by reducing 
 the o-carboxylic acid of di-nitro-di-phenyl-amine 
 with Sn and HCl. Plat needles or thick prisms, 
 V. sol. hot alcohol, v. si. sol. ether, benzene, cold 
 water, and light petroleum. Pe^Cl, gives a deep 
 yellow colour, passing into greenish-black; 
 KjCr^Oj gives a red pp. 
 
 Sal t. — B'HCl : thin colourless needles, si. sol. 
 eold water. 
 
 Chloro-derivative 0„'H,fiWfi. [0.2301. 
 Formed by reducing ohloro-di-nitro-di-phenyl- 
 amine o-carboxylic acid. Colourless crystals, 
 sol. hot water, v. si. sol. cold water, ether, and 
 benzene (Jourdan, B. 18, 1450). 
 
 AKIDO-HYDBATBOPIC ACID v. Amido- 
 
 PHENYL-PKOPIONIO ACID. 
 
 DI-AMIDO-HYDBAZO-BENZENE 
 
 v. Hydkazines. 
 
 AMIDO-HYDBO-CAEBOSTYBIL 0,H„N,O. 
 
 Oxy-amido-di-hydro-quinoline. 
 [B. 3)-amido-hydro-carbostyril 
 
 C„H3(NH,/ I l3:°J 
 
 Di-amido-phenyl-propiome anhydride. Di- 
 amido-hydro-cinnamic anhydride. [211°]. Pre- 
 pared by reducing di-nitro-phenyl-propionic acid 
 with tin and HCl. It forms colourless needles 
 or prisms, v. sol. hot water, alcohol, and HOAc, 
 insol. CSj. 
 
 Salt s.— B'HCl : needles.— B'^H^PtCle: yellow 
 leaflets. Bromine forms a mono-bromo-deriva- 
 tive, [210°] and a di-bromo-derivative, [179°], 
 both crystallising in needles (Gabriel a. Zimmer- 
 mann, B. 12, 601). 
 
 (Py. 4)-Amido-li7dio-carbostynl 
 
 C,H,< 
 
 
 ■CS2 CH2 
 
 I 
 
 [143°]. 
 
 ■N(NH2).C0 
 
 Prom C(,H,(NH.NH.SOsNa)OH2.CH2.COjH (». 
 HYDKAZiDO-PHENYii-PKOPioNio acid) by addition 
 of HCl (Fischer a. Kuzel, A. 221, 282). Crystal- 
 lised from water. Sol. water, v. si. sol. alcohol. 
 Does not reduce boiling Pehling's solution, but 
 reduces hot Ag^O. S alt. -CjHijN^OHCl. 
 
 Reactions. — 1. An acid solution is converted 
 by NaNOj into hydro-carbostyril. — 2. With EtI 
 and alcohol at 100° it gives an ethyl derivative 
 
 CA<S^^t)^^d>- [74°J- T^i^ ei^«« « 
 
 nitrosamine with NaNOj and HCl. 
 
 AMIDO-HYDBO-CINNAMIC ACID v. kmj>o- 
 
 PHENYl-PEOPIONIO ACID. 
 
 DI - AMIDO- DI - HYDEO - TEBE - PHTHALIC 
 ACID NH2.C.CH(C02H).CH 
 
 II II (?) Di-imido-hexa- 
 
 H.C,CH(C0^).C.NH2 
 hydro-terephthalic acid or siMcino-succirmc-acid- 
 di-imide. 
 
 Ethyl ether A"Et2 [181°]. Obtained by 
 fusing di-oxy-di-hydro-terephthalic ether (suc- 
 cino-succinio ether) with ammonium acetate. 
 Yellow needles ; si. sol. alcohol and ether with a 
 green fluorescence, v. sol. chloroform. By 
 treatment with bromine in HjSOj solution it is 
 converted into di-amido-terephthalic ether. The 
 hydrochloride and sulphate are colourless 
 sparingly soluble salts (Baeyer, B. 19, 429). 
 
 AMIDO-TETEA-HYDBO-CmiNOLINE 
 ^Clig — CH2 
 CjH.^Nj i.e. C5HX I 
 
 \N(NH2).CHj. 
 [56°]. (c. 255°). Prepared by reducing the nitros- 
 amine of tetra-hydro-quinoline with zinc dust 
 and HOAc. White crystals. 
 
 Salts. — B'2H2S0i 2aq; yellow plates, si. sol. 
 cold water. — The hydrochloride is v. sol. water. 
 
 Reactions. — Eeduces salts of Au and Pt, and 
 Pehling's solution. Ppd. HgO forms an azo- 
 quinolme (Hoffmann a. Eonigs, B. 16, 730). 
 
AMIDO-IMIDO-DI-PHENYL SULPHIDE. 
 
 166 
 
 AMIDO HYOBO-QniNONE CsH,NO, i.e. 
 NH2.CsH,(0H)j. 
 
 Di-methyl derivative NH2.CBHj{OMe)2. 
 [82°]. (270°). Formed by reducing the di- 
 methyl-derivative of nitro-hydroquinone. Pearly 
 plates, sol. hot water, alcohol, benzene, light 
 petroleum and CS^. Very readily oxidised. 
 
 Reactions. — 1. CuSO^Aq gives a greenish- 
 blaok colour. — FejClj pps. lustrous greenish 
 plates, which form a red solution in water. — 
 AgNOa gives a silver mirror. Salts. — "B'HCl: 
 white needles.— "B'jHjPtClu : brown pp. 
 
 Acetyl derivativ e.— CsH3{NHAc) (OMe)^. 
 [91°]. Silvery scales ; sol. water, alcohol, ben- 
 zene, light petroleum and CSj (Magatti, B. 14, 
 70 ; G. 1881, 352 ; Mulhauser, A. 207, 254 ; 
 Baessler, B. 17, 2119). 
 
 Ethyl derivative 0eH3(NH2)(0Et)(0H). 
 From the nitro-compound (Weselsky a. Benedikt, 
 Jf.2,370).— B'HCl. 
 
 Di-amido-hydroqninone C^(0B.).J1i(K^^. 
 Formed by reduction of di-nitro-hydroquinone 
 or its di-aoetyl derivative with tin and HCl. 
 Owing to its easy oxidisability the base was not 
 isolated in the free state. B"HjCl2. — Colourless 
 needles, v. e. sol. water, si. sol. cone. HCl. 
 
 Di-acetyl derivative C|jH2(0H)2{NHAc)2. 
 [c. 240°]. Colourless needles. Is oxidised to 
 di-acetyl-di-amido-quinone C|,H202(NHAo)2. 
 
 Tetra-acetyl derivative C|iH2(OAo)2(NHAo)2. 
 [216°] ; colourless needles or plates ; v. sol. alco- 
 hol and acetic acid, si. sol. water and ether. Dis- 
 solves in dilute alkalis, the solution becomes 
 oxidised on exposure to the air and deposits 
 yellow needles of the above-mentioned di-acetyl- 
 di-amido-quinone (Nietzki a. Preusser, B. 19, 
 2247). 
 
 Di-methyl-derivative'Cg'H.2('!!iB.^)2{0M6)2. The 
 hydrochloride of this body is formed by reducing 
 the corresponding nitro compound. It crystal- 
 lises in needles, [169°] (Kariof, B. 13, 1676). _ 
 
 Di-methyl-di-amido-hydroquinone (g. v.) is 
 isomeric with this body. 
 
 SI-AMIDO-DI-IMII)0-BENZ£X£ 
 CeH2(NHj2(NH)2 [1:2:4:5]. Small brown 
 needles. Formed by oxidation of solutions of 
 salts of tetra-amido-benzene with FcjClj, &c. 
 
 Salts. — ^B"H2Cl2: glittering brown needles, 
 sparingly soluble in water with a bluish-violet 
 colour. — B"(HN0s)2 : small green needles 
 fNietzki a. Hagenbach, B. 20, 335). 
 
 AMIDO-IMIDO-METHANE v. Fobmamidine. 
 
 AMIDO-DI-IMIDO-(o)-NAPHTHOL 
 ,NH 
 C„H,N30 i.e. C,.H,(NH,)(OH)<; | (?). Pre- 
 
 pared by the reduction of tri-nitro-(a)-naphthol 
 with tin and HCl. Brown scales, insol. water 
 and ether. Salts. — B'HCl: lustrous green 
 scales, si. sol. cold water. — B'jHjPtCl,, (Diehl a. 
 Merz, B. 11, 1663). 
 
 AMIDO-DI-IMIDO-ORCIN C^HsNaOj 2aq i.e. 
 >NH 
 CMe(NB^){OB.)X | (?). Prepared by re- 
 
 \nh 
 
 ducing tri-nitro-orcin with sodium-amalgam 
 (Stenhouse, 4. 167,167). Lustrous green needles, 
 V. si. sol. water, insol. alcohol, ether, and benzene. 
 NaOHAq forms a deep blue solution. Eeduced 
 by further action of sodium-amalgam U> tri- 
 
 amido-orcin. Salts. — B'HCl aq: brownish -reel 
 needles ; sol. water but ppd. by HCl. — 
 B'jHjSO, 2aq : purple laminae. 
 
 AMISO-SI-IUIDO-FHENOL, so called. 
 
 C,H,N30 i.e. C,H,(NH,) / | [2 : 6 : ^ . 
 
 Di-amido-quinone-imide (Hepp, A. 215, 351). 
 The hydrochloride, B'HCl, separates as brown 
 needles with blue reflex when Fe^Clj is added to 
 a cone, aqueous solution of the hydrochloride of 
 tri-amido-pheuol (Heintzel, Z. 1867, 342). It is 
 decomposed by alkalis and by hot water; hot 
 dilute HCl changes it into colourless needles of 
 the hydrochloride of oxy-amido-quinone-imide 
 (or di-amido-quinone) CjHjNjOaHCl, while HjSO, 
 forms a corresponding sulphate crystallising in 
 plates. 
 
 AMIDO-IMIDO-DI-PHENYL SULPHIDE 
 
 di-phenyl-vmide ; Amido-sulphido-di-phenyl- 
 imide. 
 
 Formation. — 1. By reduction of nitro-imido- 
 
 di-phenyl-sulphoxide, HN<;^p«g«,j^jj >> SO. — 
 
 2. By heating ^-amido-di-phenyl-amine with 
 sulphur (Bernthsen, B. 17, 2858 ; A. 230, 101). 
 White satiny plates (from water) ; m. sol. hot 
 water, v. sol. alcohol and ether. Turns grey in 
 moist air. Fe^Ole converts it into the following 
 body : 
 
 Imido-imido-di-phenyl sulphide C,2H3N2S i.e. 
 
 NH 
 
 hoi, si. sol. water and ether. Its salts dye silk 
 greyish-violet. It is easily reduced to the pre- 
 ceding body. Salt s.— B'HCl Jaq.— B'^H^ZnCl^ : 
 brown needles or prisms. 
 
 Di-amido-imido-di-phenyl sulphide 
 
 C.^H.iNjS i.e. HN<;^»^^(^g^|>S. Formed by 
 
 reducing (a)-di-nitro-imido-di-phenyl sulphoxide 
 with tin and HCl, or Lauth's violet with ammo- 
 nium sulphide (Bernthsen, B. 17, 614). Yellow 
 needles or plates ; si. sol. water and ether. The 
 sulphate is si. sol. water. 
 
 Amido-imido-imido-di-phenyl-sulphide 
 
 Small brown crystals, v. sol. aloo- 
 
 C.2H,N3S i.e. N<gg(N^^)>S. 
 
 / 
 
 NH 
 
 Lauth's Violet. 
 
 Formation. — 1. By treating a solution of p- 
 phenylene diamine hydrochloride with HjS and 
 Fe^Clj successively (Lauth, O. B. 82, 1441 ; Koch, 
 B. 12, 592, 2069).— 2. By action of Fe^ Cl^ on the 
 preceding body (B.). Its alcoholic solution has a 
 violet colour with reddish-brown fluorescence. 
 Its solution in excess of HCl is blue ; in HjSOj, 
 green changing to blue and then to violet. Long 
 heating with Mel converts it into the methylo- 
 iodide of penta-methyl-di-amido-imido-di-phenyl 
 sulphide identical with that formed in the same 
 way from methylene blue. Salt. — B'HCl: green 
 crystals, si. sol. cold water. 
 
 An isomeride {Bemthsen's Violet) is formed 
 by reducing (;3)-di- nitro -imido-di- phenyl sul- 
 phoxide and then oxidising the leuco-base with 
 FftjOle. Its hydrochloride B'2HC1, forms dark 
 
166 
 
 AMIDO-IMIDO-DI-PHENYL SULPHIDE. 
 
 needles, which dye reddish-violet. HjSO, forms 
 a violet solution. 
 
 AMIDO DI-IMIDO BESOKCIN C^H^NsOj aq 
 >NH 
 or CjH(0H)2(NH2)< | {?). From tri-amido- 
 
 resoroin hydrochloride and Fefi\, Lustrous 
 green needles, v. si. sol. water, insol. alcohol or 
 ether: KOHAq forma a blue solution. Dilute 
 HCl at 170° forms tri-oxy-quinone. 
 
 Salt.— B'HCl: red needles, ppd. by HCl 
 (Schreder, A. 158, 250 ; Diehl a. Merz, B. 11, 
 1229). 
 
 AMIDO-INDIGO C^H.jN.O^ i.e. 
 C,5Hg(NH2)2Nj02. Prepared by reducing nitro- 
 indigo with acetic acid and powdered zinc 
 (Baeyer, B. 12, 1317). Dark violet pp., v. si. sol. 
 alcohol, ether and chloroform. Forms blue 
 solutions in dilute acids. 
 
 AMISO-ISATIN^, so called, v. Isatinimide. 
 
 AMIDO-LACTIC ACID v. Oxy-amido-propionio 
 
 AOID. 
 
 AMIDO-MALEiC ACID CjH,NOj i.e. 
 C02H.CH:C(NHJ.C02H. [182°]. Easily soluble 
 crystals. Prepared by saponification of the 
 amides. — A"Ag2 ; voluminous pp., explosive. 
 
 Di- ethyl ether Et^A". [100°]. Colour- 
 less prisms. Sol. alcohol and ether, insol. water. 
 Prepared by the action of alcoholic NHj (2 mols.) 
 on chloro-malei'c ether (1 mol.). 
 
 Amido-maleamic-ethyl ether 
 
 GJB.{N-K,)<:^^'^-^. [62°]. Long white prisms. 
 
 V. sol. alcohol and ether, insol. cold water. 
 Prepared by the action of alcoholic NHj (3 mols.) 
 on chloro-maleic ether (1 mol.). 
 
 Diamide C2H(NH,)<^^-^^^ [122°]. 
 
 Colourless plates. Sol. alcohol, ether, and hot 
 water. Prepared by the action of an excess of 
 strong alcoholic NHj on chloro-maleio ether 
 (Claus a. Voeller, B. 14, 150). 
 
 AMIDO-MALONIC ACID CsH^NO, i.e. 
 CH(NH2)(C02H)2. Obtained fromnitroso-malonic 
 acid by reducing with sodium-amalgam (Baeyer, 
 
 A. 131, 295). Prisms (from water) or needles 
 (by ppg. with alcohol). When heated alone, or 
 in aqueous solution, it splits up into CO2 and 
 glycocoll. Iodine oxidises it, in aqueous solu- 
 tion, forming mesoxalic acid. 
 
 Salt.— Pb(C3HjNOj)2: crystalline pp. 
 
 Amide CH(NH2)(C0.NH2)2. [182°]. Formed 
 by heating chloro-malonic ether with alcoholic 
 NHj. Prisms, sol. hot water (Conrad a. Guthzeit, 
 
 B. 15, 607). 
 AMIDO-MESITOL C^H^NO i.e. 
 
 C,HMe3(NH2)(OH) [1:3:6:2:4]. A very oxidisable 
 body formed by reduction of nitro-mesitol. — 
 B'HCl : needles (Knecht, B. 15, 1376). 
 
 AMIDO-MESITYLENE «. Mesidinb. 
 
 Di-amido-mesitylene CgHuN^ i.e. 
 CeHMe3(NH2)j. [90°]. From di- or tri-nitro- 
 mesitylene with tin and HCl. Long slender 
 needles (from water), or large monoclinic crystals 
 (from ether). Sublimes in needles. V. sol. 
 alcohol or ether, m. sol. hot water. CrOj oxi- 
 dises it to oxy-iso-xyloquinone, G„HMe2(OH)02. 
 
 Salts. — B"2HC1: square tables (from water), 
 ppd. by HCl.— B"H2C20, : hard grains (from 
 water). — B"H2S04 : broad lamina (from water). 
 
 Di-acetyl derivative, [above 360°]; 
 
 V. si. sol. water or cold alcohol (Fittig, A. 141, 
 134 ; 180, 27 ; Ladenburg, A. 179, 176). 
 
 AMIDO-MESITYLENIC ACID CjH„NO, 
 
 o-Amido-mesitylenic acid 
 C,H2Me2(NH2).C02H [1:3:4:5]. [187°] (Schmitz, 
 
 A. 193, 171). [190°] (Jacobsen, B. 11, 2055). 
 From the nitro acid with tin and HCl. Long 
 needles (from alcohol). Splits up when heated 
 with lime into CO2 and (1, 3, 4)-xylidine. 
 
 ^-Amido-mesitylenlc acid C|iH2Me2(NH2)C02H 
 [1:3:2:5]. [235°]. From the nitro acid. Long 
 needles (from alcohol). SI. sol. water, v. sol. 
 hot alcohol. Gives (1, 3, 2)-xylidine when 
 heated with lime. 
 
 Salt.— B'HCl: long needles (Fittig a. Bruck- 
 ner, A. 147, 50 ; Jacobsen, B. 12, 608). 
 
 AMIDO - MEXHENYL - AMIDO - PHENYL 
 
 MEKCAPTAN C^HsNjS i.e. C„Hj<|^C.NHj. 
 
 [129°]. Prepared by heating chloro-methenyl- 
 amido-phenyl meroaptan with alcoholic NH3 at 
 160°. Nacreous laminse. Fusion with potash 
 produces amido-phenyl mercaptan. 
 
 Salt. — It is a weak base, and has a crys- 
 talline platinochloride, B'2H2PtCl5 (Hofmann, 
 
 B. 12, 1129 ; 13, 11). 
 AMIDO-METHOXY COMPOUNDS v. Methyl 
 
 derivatives of Oxt-amido compounds. 
 
 AMIDO-DI-METHYL-ACETIC ACID v. Amido- 
 
 isO-BniYKIO ACID. 
 
 DI - AMIDO - TETB A - METHYL - DI - AMIDO - 
 DIFHENYL v. Tetra - Methyl - tetra - amido- 
 DiPHENYL. And, in general, amido-methyl-amido 
 compounds are described as methyl- (di)-amido 
 compounds. 
 
 AMIDO - DI - METHYL - ANILINE v. Di- 
 
 METHYL-PHENYLENE DIAMINE. 
 
 AMIDO - METHYL - ANTHRACENE DI- 
 HYDBIDE CisHisN i.e. C„H,„Me.NH2. [79°]. 
 Prepared by heating amido-methyl-anthraqui- 
 none with HI and P at 150°. Glistening laminse, 
 which begin to sublime at 130° and are sol. 
 alcohol, ether, chloroform, benzene, glacial 
 acetic acid, and CSj, but v. si. sol. water. 
 
 Reactions. — 1. Nitrous acid gives a green 
 colour, and on adding NHj, a red pp. — 2. 
 Arsenic acid gives a brownish-red mass after 
 fusion. S alt .—B'HCl [245°] : glistening needles. 
 
 Acetyl derivative C,5H„AcN. [198°]. 
 White needles, sol. alcohol and ether (Eoemer, 
 B. 16, 1631). 
 
 AMIDO-METHYL-ANTHBANOL 
 
 ^C.OH 
 C„H,3N0 i.e. C,2H,Me(NH2)|' | . [183°]. 
 
 ^CH 
 Prepared by heating amido-methyl-anthraqui- 
 none with HI (S.G. 1-96) and P. Crystallises in 
 nearly white needles, but sublimes in red needles. 
 Sol. alcohol, ether, benzene, and glacial acetic 
 acid, V. si. sol. water. 
 
 Reactions. — 1. H2SO4 gives a yellow solu- 
 tion, becoming purple-red on warming. — 2. 
 HNO3 gives a violet colour, turning red. — 3. Air 
 reconverts it, jn alkaline solution, into amido- 
 methyl-anthraquinone. 
 
 Di-acetyl derivative 0,5H,,Ac2NO. [170°]. 
 Thick white needles ; its alcoholic solution ex- 
 hibits blue fluorescence (Eoemer a. Link, 16, 703). 
 
 AMIDO-METHYL-ANTHEAQTJINONE 
 C„H„N02 i.e. 0„H.02(CH3)(NH2). [202°]. Pre- 
 pared by reduction of nitro-methyl-anthraqoi- 
 
AMIUO-NAPHTHOIO ACID. 
 
 167 
 
 none. Long dark red needles. V. sol. alcohol, 
 ether, benzene, acetic acid, and chloroform, v. 
 al. sol. water. 
 
 Acetyl derivative CuH„02(CH3)NHAc. 
 [177°]. Small light-red needles, sol. alcohol and 
 glacial acetic acid (Eomer a. Link, B. 16, 698). 
 
 AMIDO-METHYL BENZENE v. Toluidine 
 and Benztlamine. 
 
 Amido-di-methyl-benzene v. Xilidine. 
 
 Amido-tri-metliyl-beiizene v. Mesidinb and 
 
 ifl-CnMIDINE. 
 
 Amido-tetra-metliyl-benzene v. Duridine. 
 Amido - penta - methyl - benzene u. Penta- 
 
 METHYL-PHENYL-AMINE. 
 
 DI - AMIDO - TETRA - METHYL - BENZIDINE 
 V. reiro-METHTL-^eira-AMiDO-di-PHENTL. 
 
 AMIDO-METHYL-BENZOIC ACID v. Amido- 
 
 lOLUIO ACID. 
 
 Amido - di - methyl • benzoic acid v. Amido- 
 
 MESITYLENIO ACID. 
 
 Di-amido-tri-methyl-benzoic acid CioHnN^Oj 
 i.e. Gj:>le,(SB..,)fiOM [6:4:3:5:2:1]. Bi-amido- 
 durylic acid. [221°]. Formed by reducing the 
 di-nitro compound with zino dust and dilute 
 HOAc. Colourless silky needles, sol. hot water 
 and hot alcohol, v. si. sol. ether. FejGla oxidises 
 it to pseudo-cumo-quinone carboxylio acid (Nef, 
 B. 18, 3496 ; A. 237, 1). 
 
 Acetyl-derivative [275°]. 
 
 AMIDO-TRI-METHYL-BUTYL-LACTtCACID 
 
 V. OXT-AMIDO-HEPTOIC ACID. 
 
 m-AMIDO-a-METHYL-CINNAMIC ALDE- 
 HYDE C,„H„NO i.e. C„H4(NHJ.CH:CMe.CH0 
 [60°]. Got by reducing the nitro compound with 
 FeSOj and NH^. Yellowish crystals ; dissolves 
 in aqueous acids, and reduces ammoniacal AgNOj. 
 
 Phenyl hydrazide 
 C,H,(NH,).CH:CMe.CH:N2HPh; [157°]: needles. 
 
 Acetyl derivative 
 C,H,(NHAe).CH:CMe.GHO ; [120°] : short thick 
 prisms (Miller a. Kinkerlin, B. 19, 1248). 
 
 AMIDO - {B. 2-Py.2) - DI-METHYL - {Py. 3)- 
 ETHYL-aUINOLINE C.sH.sN^ i.e. 
 C5H3N(NEL,)Me2Et. [149°]. Plates, monoclinic 
 tables, prisms or flat needles. Formed by reduc- 
 tion of the nitro-derivative with SnCl^. Salts. — 
 B'HGl ; very soluble colourless crystals. The 
 nitrate and sulphate are also easily soluble in 
 water (Harz, B. 18, 3392). 
 
 AMIDO - {Py. 4)-METHYL-HYDE0-QUIN0. 
 LINE "" "" 
 
 ^/ 
 
 Gxl2'C-^l2 
 
 0„H„N,i.«.C„H3(NH,)(r I 
 
 NNMe.CH, 
 Amido-kairoline. Yellowish oxidisable oil. 
 Formed by reduction of nitro-kairoline [94°] 
 with SnClj. By nitrous acid it is converted 
 into a compound C,„H,3NsO, [144°] when dry, 
 which crystallises with 5aq in splendid red 
 needles, and dissolves in dilute acids with a 
 deep red colour. 
 
 Salts. — The acid tartrate forms sparingly 
 soluble crystals. B"HjCljPtClj (Feer a. Koenigs, 
 p. 18, 2391). 
 
 AMIDO DI-METHYL-HYDBOQUINONE v. 
 ii-me<%Z-Aifn)0-HyDK0QniN0NE. 
 
 AMIDO-TRI-METHYL-PHENYL-ACETAMI - 
 SINE V. Amido-i^-cdmylene-acetamidine. 
 
 AMIDO-DI-METHYL-PHENYL-ACETIC AN- 
 HYDRIDE V. ZW-Meibtl-oxindole. 
 
 AMIDO-METHYL-PROPYL-BENZENE v. 
 Cymidine. 
 
 {B. 4)-AMID0-(P!/. 3)-METHYL.aTJIN0LINE 
 C,„H,„N2 i.e. C„Hs(CH3)(NH2)N. o-Amido-quin- 
 aldine. [56°]. Formed by reduction of (B. 4)- 
 nitro-(P2/. 3)-methyl-quinoline. Long prisms. 
 V. sol. alcohol, ether, and hot ligroine, sparingly 
 in water. — B'HGl : yellow needles (Doebner a. 
 Miller, B. 17, 1701). 
 
 (B. 1 or 3) -Amido - (Py. 3)-methyl - quinoline 
 CjuHioNjaq i.e. C„H5(CH3)(NH2)N m-Amido-quin- 
 aldine [105°] when dry. Formed by reduction of 
 (B. 1 or3)-nitro-(P2/- 3)-methyl-quinoline. Colour- 
 less crystals ( + H^O). V. sol. hot water, alcohol, 
 and benzene, sparingly in ether. B'HCl : red 
 needles (Doebner a. Miller, B. 17, 1702). 
 
 Amido - (S. 2, i-Py. 3) - tri - methyl - quinoline 
 C,2H|2N(NH2). Formed by reducing nitro-tri- 
 methyl-quinoline with SnCl^. Yellowish plates 
 (from alcohol) (Panajotow, B. 20, 36). 
 
 Sulphonic acid C,2H„(S0sH)(NH2).N. 
 Small yellow needles. BaA'j 3aq : silky needles, 
 si. sol. cold water. 
 
 AMIDO-METHYL-TOLTJIDINE v. Methyl- 
 
 TOLYLENE DIAMINE. 
 
 AMIDO-iS-METHYL TIMBELLIFERON 
 /CMe:GH 
 
 C^oH^NO, i.e. C,H2(NH,)(0H)<' 
 
 [247°]. 
 . CO 
 
 From nitro-i8-methyl-umbelliferon. Needles, 
 sparingly soluble in the usual menstrua. FCjCl, 
 gives an intense green colouration with the alco- 
 holic solution. 
 
 Salt.— B'2H2SO,2aq: sparingly soluble pp. 
 (Pechmann a. Gohen, B. 17, 2137). 
 
 AMIDO-METHYL-UBACIL v. Ubamido-oko- 
 
 lONIO acid. 
 
 AMIDO-NAPHTHALENE v. Naphthylamine. 
 
 Di - amido - naphthalene v. Naphthylenb 
 diamine. 
 
 Tri-amido-naphthalene G,„H„N3 i.e. 
 G,„H,(NH2)3. The hydriodide, B"'3HI, is 
 formed from (j3)-tri-nitro-naphthalene [218°], by 
 reducing it (1 g.) with I (20 g.), P (4 g.) and 
 water ; it forms white needles ; at 70° it becomes 
 B"'2HI. The sulphate, ^'"3.^80^ forms silky 
 needles. The free base is very unstable. 
 
 Benzoyl derivative C„H|5N30 i.e. 
 C,oH5(NH,)2(NHBz)[2:4':l]. From benzoyl-di- 
 nitro-naphthylamine. 
 
 Salts. — B"'HG1 : needles. — B"'HjS04 : 
 needles (Lautemann a. Aguiar, Bl. [2] 8, 263 ; 
 Hubuer a. Ebell, A. 208, 324). 
 
 Tetra-amido-naphthalene C,„H|2N, i.e. 
 C,oH,(NH2)j. The hydriodide B""4HI, formed 
 by reducing (S)-tetra-nitro-naphthalene [200°] 
 with P, I, and water, crystallises in yellowish 
 laminse, sol. water and alcohol (L. a. A.). 
 
 AMIDO-NAPHTHALENE SULPHONIC ACID 
 V. Naphthylamine sulphonic acid. 
 
 AMID0-(i8)-NAPHTH0-HYDB0ftTJIN0NE 
 G.oHsNOj i.e. C,„H5(NH2)(OH)2. Amido-di-oxy- 
 naphthalene. The hy drochlor id ej'R'B.Ci, is 
 got by reducing nitro- (/3)-naphthohydroquinone 
 with tin and HCl (Groves, C. /. 45, 300). It is 
 rapidly oxidised by air. 
 
 AMIDO-NAPHXHOIC ACID CuHaNOj i.e. 
 C,„H,(NH2).G02H. 
 
 Amido-(a)-naphthoic acid. [212^]. From 
 nitro-(a)-naphthoic acid, [230°], by reducing with 
 FeSO^ and NHj. Colourless needles ; may be 
 sublimed ; sol. alcohol, v. si. sol. ether (Ekstrand, 
 B. 18, 78). 
 
108 
 
 AMIDO-NAPHTHOIC AOID. 
 
 A.mido-(/3) -naphthoic acid. [211°]. Formed 
 by reducing nitro-(/3)-naphthoio acid [269°], with 
 PeSOj and NHj. Slender colourless needles 
 (Elcstrand, B. 18, 1206). 
 
 Amido-(;S)-naphthoio acid. [219']. From 
 nitro - (;8) - naphthoic acid [289°]. Slender 
 needles. Salts. — "HA'HCl: small prisms, v. sol. 
 water. — "HA'HNO^ : large thin laminae. — 
 " (HA')2H2S04 : small prismatic needles (E.). 
 
 Amido-(3)-naphthoic acid. [232°]. From 
 mtro-(j3)-naphthoioaoid [293°]. Small trimetric 
 tables ; sol. alcohol and boiling water. Salts.— 
 CaA'j 4aq : long violet needles. — HA'HNOj : 
 large needles. — (HA'jjH^SOj : needles (E.). 
 
 pari-Amido-naphthoio acid C,„H (NH^JCO^H 
 
 Preparation. — The crude product of the 
 nitration of (o)-naphthoio acid is reduced with 
 FeSOj. The solution is boiled with HCl and, on 
 cooling, the lactam of the peri-acid, [178°], 
 crystallises out in yellow needles, whilst the 
 hydrochloride of the isomeric acid remains in 
 solution. 
 
 By diazotisation, treatment with cuprous 
 cyanide, and saponification of the nitrile, naph- 
 thalio acid is formed (Bamberger a. Philip, B. 
 20, 242). , This experiment determines the con- 
 stitution ot acenajjhthene (g.«.) which may be 
 oxidised to naphthalic acid. 
 
 Lactam C„H,NO 
 
 t.e. C,„H,<g^>. [179°]. 
 
 Formed by reducing nitro-(a)-naphthoio acid 
 [215°]. Needles (by sublimation) ; sol. hot 
 alcohol, si. sol. water and ether. It is an 
 indifferent substance insoluble in alkaline 
 carbonates, but soluble in hot aqueous NaOH 
 with formation of the acid (Ekstrand, B. 18, 
 75 ; 19, 1137 ; compare Eakowsky, B. 5, 1020). 
 
 Acetyl derivative C^HjAcNO. [125°]. 
 Long hair-like needles (from alcohol). 
 
 AMIDO-NAPHTHOl G,„H,NO. 
 
 (a).Amido-(a)-naplithoI C,„H,(OH)(NHJ [1:4]. 
 Formed by reducing nitro-(a)-naphthol [164°] 
 {Liebermann, A. 183, 247) or p-sulpho-benzene- 
 azo-(a)-naphthol (Liebermann, B. 14, 1796). 
 
 The free base is unstable ; its salts produce 
 (o) -naphthoquinone when oxidised. 
 
 B'HCl : white needles ; converted by bleach- 
 ing powder into C,„H,„N3C1 or C2„H|„N,C1 which 
 separates from HOAcAq in needles [85°], and 
 explodes at 130° (Hirsch, B. 13, 1910). 
 
 (;8)-Amido-(a) -naphthol C,„Hs(OH) (NHj,) [1:2]. 
 Formed by reducing nitro-(ci)-naphthol [128°], or 
 nitroso-(o)-naphthol (L.). 
 
 The free base is unstable ; in presence of 
 alkalis, air forms violet naphthoquinone-imide, 
 
 ,NH 
 CioH„C I • Its salts give (/3)-naphthoquinone 
 
 
 when oxidised. B'HCl : white laminiB. — 
 B'C,Hj(N02),0H. 
 
 (o) - Amido - (;3) - naphthol C,„H„(OH)(NHJ. 
 Formed by reducing nitro-(/3)-naphthol [103°] 
 (Jaeobsen, B. 14, 806 ; A. 211, 48) or nitroso-(/3)- 
 naphthol (Groves, C. J. 45, 296). 
 
 Preparation. — (^)-naphthol orange is heated 
 with HClAq and SnCl, in slight excess over that 
 required by the equation : 
 
 HO.C,„H..N2.C,H4.SO,Na -i- 2SnClj -t- 6H01 - 
 HO.C,oH„.NH.,HCl + NH,,.C.H4.S03H + 
 2SnCl4 + NaCl, 
 Amido-(fl) -naphthol hydrochloride crystallises 
 on cooling, and is freed from sulp^anilic acid 
 by washing with NaOHAq (Groves, 0. J. 
 45, 291). 
 
 Properties. — Colourless scales, v. si. sol. 
 water, readily oxidised by air. Its ethereal 
 solution fluoresces violet. Chromic mixture 
 oxidises it to (fi) -naphthoquinone. 
 
 Salt.— B'HCl: white needles. 
 
 Benzoyl derivative. — C,„H5(NHBz)0H. 
 [245°]. Small colourless plates, soluble in 
 alkalis. Formed by reduction of the ben2oyl- 
 derivative of (a)-nitro-(;8)-naphfchol, the benzoyl 
 group wandering from the hydroxyl to the 
 amidogen ; this probably takes place by the 
 intermediate formation of benzenyl-amido- 
 
 naphthol C,„Hj<^q^C.C^H5 since this body 
 
 occurs in the reduction product. 
 
 Acetyl derivative. — C,„H^(NHAc)OH. 
 [225°]. Plates. Formed by reduction of the 
 acetyl derivative of (a)-nitro-(j8)-naphthol, the 
 same isomeric change taking place as in the 
 preceding case (Bottoher, B. 16, 1935). 
 
 Di-amido-(a)-naphthol C,„H,„N20 i.e. 
 C,„H5(OH)(NH2),,. From di-nitro-(a)-naphthol 
 [138°] (Griess a. Martius, A. 134, 876). Its 
 aqueous solution is turned red by Fe^Clj, amido- 
 naphthoquinone imide (g. v.) being formed. 
 
 Salts. (Graebe a. Ludwig, 4. 154, 307). — 
 B"H,SnClj : monoclinio prisms, a:b:c = 
 1-184 : 1 : 1-487, ,8 - 72° 33'. — B"H,SnCl4 4aq.— 
 B"H,SOj 2aq. 
 
 Tri-amido-(a)-naphtliol CuHiiNjO i.e. 
 C,„H,(0H)(NH,)3. From tri-nitro-(a)-naphthol 
 (Diehl a. Merz, B. 11, 1665 ; Ekstrand, B. 11, 
 161). 
 
 B"'H,SOjaq: scales.— B"'3HC1 aq : needles. 
 
 AMID0-(/3)-NAPHTH0L SULPHONIC ACID. 
 C,„H5(0H)(NH,).S03H. From nitroso-(i8)-naph- 
 thol sulphonic acid (j. ■;;.) with tin and HCl 
 (Meldola, C. J. 39, 47). Long white needles, 
 V. sol. water, turned brown by air. Gives phthalio 
 acid with HNOjAq. The acid obtained by 
 reducing ?»-carboxy-benzene - azo - sulpho - (fl)- 
 naphthol appears to be an isomeride (Griess, B. 
 14, 2032). 
 
 Di-Amido-(a)-naphthol-sulphonic acid 
 C,„H,(OH)(NH,),SO.,H [1:2:4:;8']. Prepared by 
 reducing naphthol yellow S. Laminae ; gives 
 di-imido-(a)-naphthol sulphonic acid when 
 oxidised (Lauterbach, B.14, 2029). 
 
 Amido-(3)-naphtliol di-sulphonie acid 
 C,„H|(OH)(NH,)(S03H),3aq. From m-carboxy- 
 benzene-azo-sulpho-(;8)-naphthol by reduction. 
 Laminae, v. sol. water (Griess, B. 14, 2042). 
 
 AMIDO-NAPHTHOQUINONE C,„H,N02 i.e. 
 C,„Hj(NH2)02. Oxy - naphtha - quinone imide. 
 Oximido - naphthol. Orange needles, formed 
 by boiling amido-naphthoquinone imide with 
 water (Martius a. Griess, A. 134, 377 ; Graebe a. 
 Ludwig, A. 154, 307). SI. sol. boiling water, v. 
 sol. alcohol, insol. ether. Converted by boiling 
 acids or alkalis into oxy-naphthoquinone. Ani- 
 line, when heated with it in acetic acid solution, 
 forms naphthoquinone di-anilide. 
 
 Its dihydride is described as Auido-maphtho- 
 
 BYDBOqCINONE. 
 
AMIDO-OXALOXYL-ACETIO ACID. 
 
 IGS 
 
 AlfTIDO ITA.FHTHOQiriirOKK.imDE 
 
 , C,.H,(NH,)<' I 
 
 \o. 
 
 Di-imido-naphthol. From di-amido-(o)-naphthol 
 and FejCljAq (Graebe a. Ludwig, A. 154, 307). 
 Minute needles, v. si. sol. cold water, v. sol. 
 alcohol. Boiling alkalis and dilute acids at 120° 
 convert it into oxy-naphthoquinone. Beduoing 
 agents produce di-amido-(o)-naphtliol. Aniline 
 heated with its hydrochloride forms naphtho- 
 quinone di-anilide. Salt.— B'HCl: dark red 
 monoclinio prisms with green lustre a : 6 : c = 
 2-967 : 1 : 2-396 $ = 74° 28' — B'^H^PtOls. — 
 B'aCrO^ : S. -13 at 12°.— B'HjSO,. 
 
 Bromine-water added to an aqueous solution 
 of amido-naphthoquinone imide produces two 
 derivatives (Kronfeld, B. 17, 715) : 
 
 1. CjH^Br^Oa [173°] : white plates, sol. 
 alcohol, benzene, HNO3 (S.G. 1-4), and CHCI3. 
 
 2. C,„H„-Br3N03 i.e. CBr,.C0.C,H^.C(NH).C02H 
 [213°] : white needles, sol. alcohol, benzene and 
 HNO3 (S.G. 1-4), insol. chloroform. It is split 
 up by cold alkalis into phthalimide and bromo- 
 form. When heated alone or better with H^SOj 
 at 140° it gives CO.^, Br^ and an acid CsHnBrjNO 
 [237°]. This loses HBr when boiled for a long 
 time with alkalis. When heated with HjjSO, it 
 gives phthalic acid. 
 
 AMIDO - NAPHTHOQUINONE SULPHONIC 
 ACID CijHgNjSOj. Minute coppery needles, 
 formed by oxidising di-amido-naphthol sulphonio 
 acid. 
 
 DI- AMIDO -DINAPHTHYL CjoH.jNj. Di- 
 naphthyline. C,„Hs(NHj).C,„Hs(NH2). [273°]. 
 Colourless plates (from benzene). Formed 
 together with a smaller quantity of the isomeric 
 naphthidine by warming (aa) -hydrazonaphthalene 
 with two mols. of dilute HCl at 70°-80° ; a clear 
 solution is formed from which the naphthidine 
 is ppd. as its sparingly soluble hydrochloride by 
 adding an excess of HCl, the easily soluble 
 hydrochloride of dinaphthyline remaining in 
 solution. 
 
 Reactions. — By diazotising and boiling with 
 alcohol it is converted into (aa)-dinaphthyl 
 [154°]. By boiling with acids NH3 is easily split 
 
 off, giving imido-dinaphthyl | \NH. By 
 
 CrO, it is oxidised to phthalic acid. 
 
 Salts. — B"H2Cl2'': easily soluble. — 
 B"H,Cl2PtCl4 : sparingly soluble yellow plates 
 (Nietzki a. GoU, B. 18, 5254). 
 
 Di-amido-dinaphthyl (naphthidine). Probably 
 [4:1] C,A(NH,).C,„H,(NH,) [1:4]. [198°]. 
 Silvery plates or colourless tables. Soluble in 
 alcohol and benzene. Formed, together with its 
 isomeride dinaphthyline, in small quantity by 
 heating (oa) -hydrazonaphthalene with HCl, and 
 in large quantity by reduction of (aa)-azonaph- 
 thalene with SnClj and HCl. 
 
 Preparation. — One pt. of azonaphthalene is 
 dissolved in 45 pts. of hot acetic acid, and a 
 solution of SnClj (1 pt.) in 2 pts. of HCl and 2-3 
 pts. of water is added in sufficient quantity to 
 decolourise it ; on adding an excess of HCl the 
 sparingly soluble hydrochloride of naphthidine 
 is ppd. 
 
 B(!ac<io«s.— Fe^Cl,, CrOj, Clj, Ac, produce a 
 oarmine red oolouration or pp. with solutions of 
 
 naphthidine salts. By heating with CrO, it is 
 oxidised to (a) -naphthoquinone and finally to 
 phthalic acid. Its diazo-compound yields violet 
 colouring-matters with the sulphonio acids of 
 (3)-naphthol. By boiling the diazo-oompound 
 with alcohol it yields (ao)-dinaphthyl [154°]. 
 
 S alts. — B'SjClj : sparingly soluble colourless 
 silvery plates.— B"H2Cl2PtClj.—B"H2SO, : very 
 sparingly soluble glistening plates. 
 
 Di- acetyl -derivative C2jH,j(NHAo)j 
 [over 300°] ; nearly insoluble in ordinary sol- 
 vents (Nietzki a. GoU, B. 18, 3254). 
 
 Di - amido - (aa) - dinaphthyl 02„H,2(NHj)2. 
 Obtained by reduction of di-nitro-diuaphthyl 
 with zinc dust and HCl. It is readily oxidised 
 
 .NH 
 
 to the di-imido-compound C-H.jC^ I , so that 
 
 \nh 
 
 it cannot be diazotised. B''H2Cl2 : easily soluble 
 colourless needles. The bichromate pps. in brown 
 crystals. 
 
 Di-acety I -derivative C2i,H,j(NHAo)2. 
 [Above 300°]. Colourless needles ; insoluble in 
 all solvents (Julius, B. 19, 2551). 
 
 Twenty-eight di-amido-(ao)-di-naphthyls are 
 indicated by theory. 
 
 Tetra - amido -iso - di -naphthyl C2„H,„(NH2)4. 
 [164°-167°]. From tetra-nitro-iso-di-naphthyl. 
 Grey powder, si. sol. alcohol, m. sol. toluene 
 (Staub a. Watson Smith, 0. J. 47, 104). 
 
 AMIDO-NITRO- v. Nitro-amido-. 
 
 AMIDO -NITBO-BBOMO- v. Bbomo-nitbo- 
 
 AMIDO-. 
 
 AMIDO -NITRO-CHLOBO- v. Chlobo-nitbo- 
 
 AMIDO-. 
 
 AMIDO-NITRO-IODO- v. Iodo-nitro-amido-. 
 
 AMIDO-OCTOIC ACID CsH^NO^ i.e. 
 CjH,3.CH(NH2).C02H. Amido - caprilic acid. 
 From heptoic aldehyde-ammonia (oenanthol- 
 ammonia) and HON (Erlenmeyer a. Sigel, A. 
 176, 341). Pearly white laminsB, v. si. sol. 
 alcohol, ether, and cold water. Neutral. Vola- 
 tilises before fusing. Salts. — HA'HCl. — 
 HA'HNOj: slender needles. — (HAOaH^SOi. — 
 CuA'j. 
 
 Nitrile CsH,3.CH(NH2).CN. [0°].FromHCN 
 and cenanthol-ammonia (B. a. S.). Oil, miscible 
 with alcohol and ether. Salts . — CjH, jNjHCl : 
 satiny, six-sided plates. — (CsH,sN2)2H2PtCl5. 
 
 Amide OaH,3.CH(NH2).CONH2. From the 
 nitrile and cone. HCl. Salts. — 
 (C8H,8N20)2H2PtClj.— CgHisNjOHCl. Converted 
 by aqueous NaHC03 into an acid, CgHigNjOj (?). 
 
 AMIDO-OCTYL-BENZENE v. Amido-phentl- 
 
 OOTANE. 
 
 AMIDO-OCTYL-TOLUENE v. Amibo-tolyl- 
 
 OOTANE. 
 
 AMIDO - (ENANTHYLIC ACID v. Amido- 
 
 HEFTOIC ACID. 
 
 AMIDO-OPIANIC ACID v. Opianio acid. 
 
 TRI-AMIDO-ORCIN CjHnNsOy i.e. 
 CsMe(OH)2(NH2),. From tri - nitro - orcin by 
 sodium-amalgam or by Sn and HCl. Its solu- 
 tions readily oxidise in air, forming amido-di- 
 imido-orcin (j. v.) (Stenhouse, Pr. 21, 125). 
 
 AMIDO-OXALOXYL-ACETIC ACID 
 C02H.CH(NH2).CO.C02H. Phenyl h/ydrazide 
 C02H.CH(NH2).0(N2HPh).C02H. Obtained by 
 reduction of an alkaline solution of the di- 
 phenyl - hydrazide of di - oxy - tartaric acid 
 Oj(N,HPh),(OOjH)a with Bodinm amalgam. 
 
170 
 
 AMIDO-OXALOXYL-ACETIO AOID. 
 
 Wliite pp., very oxidisable, its alkaline solution 
 quickly becoming reddish- violet on contact with 
 the air. By warming with H^SO., it is converted 
 into the anhydride OuHgNsO, which is probably 
 oxy-amido-quinizine-oarboxylic acid (q^. v.). By 
 further reduction of the alkaline solution with 
 sodium-amalgam di-amido-succinic acid [125°] 
 is formed (Tafel, B. 20, 244). 
 
 AMIDO-OXINDOLE v. Oxindole. 
 
 AMIDO-OXY- V. Ox^-AMiDO-. 
 
 AMIDO-PHENAMTHEENEu. Phenanthbene. 
 
 AMIDO-DI-PHENIC ACID C„H,,N04 i.e. 
 [1:2] COjH.C.Hj.CjHjfNHJ.COoH [1:5:2]. The 
 hydrochloride, 'S^'ii.Cl, obtained from nitro- 
 di-phenio acid, forms silvery laminsB. When 
 distilled with lime it produces ^-amido-fluorene, 
 C.sHjNHj [123'] (Stasburger, B. 16, 2347). 
 
 o-Di-amido-di-phenio acid CjjHijNjO^ i.e. 
 [3:2:1] (CO,H)(NH,).C,H3.C,H3(NH,)(CO,H) 
 
 [1:2:3]. Formed, by intramolecular change, 
 when o-hydrazo-benzoic acid is boiled with HCl 
 (Griess, B. 7, 1609). 
 
 TO-Di-amido-di-phenic acid C,4H,,N20,l|aq 
 i.e. [2:4:1] (CO,H)(NH,).C.H3.C,H3{NH,)(CO,H) 
 [1:4:2]. Benzidine di-carboxylic acid. 
 
 Formation. — 1. Prom the corresponding di- 
 nitro-oompound (Hummel, A. 193, 128 ; Struve, 
 B. 10, 75; Schultz, B. 12, 235).— 2. From 
 »»-hydrazo-benzoic acid by boiling with HCl (G.). 
 
 Properties.— Short needles (from water) ; v. si. 
 sol. water, alcohol, and ether. It gives benzidine 
 and di-amido-fluorene when distilled with lime. 
 
 Salts. — Ag2A"aq. — H2A"2HC1. — 
 H2A"2HN03.— H.,A"H2PtCls 2aq. 
 
 AMIBO-FHENOL. 
 
 o-Amido-phenol CeH,NO i.e. CsHj(NH2)(0H) 
 [1:2]. [170°]. S 1-7 at 0° (Korner). 
 
 Formation. — 1. By reducing o-nitro-phenol 
 (Hofmann, A. 103, 351 ; Fritzsohe, A. 110, 166 ; 
 Schmitt a. Cook, K. 3, 62). 
 
 Properties. — Scales ; may be sublimed. 
 
 Salts.— B'HCl; S. -8 at 0°.— B'oH^SO^. 
 
 Beaciions. — 1. Oxidised by KjFeCyj forming 
 a dye (CjjHjNjOj ?) which sublimes as pink 
 needles (G. Fischer, J. pr. [2] 19, 319).— 2. 
 Nitroiis acid forms o-diazo-phenol. — 8. Con- 
 verted into oxy-quinoline by heating with 
 glycerin, o-nitro-plunol, and HjSOj (Skraup, B. 
 15, 893). — 4. Lactic acid, o-nitro-phenol and 
 HjSOj give oxy-methyl-quinoline (oxy-quinal- 
 dine). — 5. CH2CI.CO2H gives oxy-phenyl-amido- 
 acetic acid, COjH.CHj.NH.GsHi.OH (Vater, 
 J. pr. [2] 29, 286). — 6. Cl.COjEt gives oxy- 
 phenyl - carbamic ether, HO.CgHj.NH.COjEt, 
 [85°], which is converted by distillation into 
 alcohol and oxy - methenyl - amido - phenol 
 
 C.H,<Q^C.OH, [138°] (Gronvick, Bl. [2] 25, 
 
 178).— 7. Potassic xanthate converts the hydro- 
 chloride of amido-phenol into sulpho-carbanil 
 
 CeHj-^^^Q^CSH, called also thio-carbamido- 
 
 phenol and ' oxy-phenyl-thio-carbimide' (Kalck- 
 hofi, B. 16, 1825 ; Zincke a. Hebebrand, A. 226, 
 60). — 8. Amido-phenol (30 g.) heated with alco- 
 holic guimone (48 g.) forms hydroquinone ; and, 
 on cooling, violet needles of a base G^Jita^fit 
 [250°] separate. This base is soluble in aniline, 
 sparingly soluble in alcohol, benzene, and chloro- 
 form. In dilute acids it forms deep red solu- 
 tions. Boiled with NaOH, ammonia comes off 
 
 and o-amido-phenol and other products ar« 
 formed. The salts of the base have green 
 metallic lustre and are easily soluble in alcohol 
 but sparingly soluble in water ; much water 
 decomposes them into acid and base. — ^B"2HC1. 
 — B"2HClPtCl4.— B"jH3S0,. Acetyl deriva- 
 tive C^jHisAcjiNjOj. [285°]. Oxidised in glacial 
 acetic acid solution by HNO3, this gives C25H15N5O, 
 L275°-280°]. Benzoyl derivative 
 CajHuBz^NjOj. [265°]. Beactions. — Nitrous 
 acid converts the base into C^jHuNjOj, which 
 forms small red needles, [above 290°]. HNO, 
 oxidises it in acetic acid solution to a body which 
 crystallises in yellow needles [260°] (Zincke a. 
 Hebebrand, A. 226, 60). 
 
 Acetyl derivative CgH4(OH)(NHAo). 
 [201°]. From its anhydro-derivative by boiling 
 with dilute H^SO^ (Ladenburg, B. 9, 1525). Ac- 
 cording to Morse {B. 11, 232) it can be formed by 
 reducing o-nitro-phenol with Sn and HOAo (cf. 
 Zincke a. Hebebrand, A. 226, 69). Glittering 
 white plates, v. sol. alcohol and hot water ; sol. 
 EOHAq. Not affected by quinone. 
 
 Anhydro derivative C|iH,<^-jj^C.CH3. 
 
 Ethenyl-o-amido-phenol. [201°]. S.G. s 1-1365. 
 Formed by heating o-amido-phenol with Ac^O, 
 or its acetyl derivative with P2O5 (L.). 
 
 Benzoyl derivative C5H4(NHBz)(OH). 
 [167°]. From the anhydro-compound by boiling 
 with aqueous acids, or from the di-benzoyl deri- 
 vative by boiling with water and BaCOj (Hiibner, 
 
 A. 210, 887 ; Bottcher, B. 16, 629). Laminse, 
 si. sol. cold water, v. sol. hot water, sol. alcohol, 
 ether, and benzene. 
 
 Anhydro derivative OsHj^c^-kr^CPh. 
 
 Bemenyl - - amido - phenol. [103°]. (314°). 
 Formed by heating o-amido-phenol with BzCl, 
 HOBz, or phthalic anhydride, and distilling the 
 product (L.) ; or by reducing o-nitro-phenyl 
 benzoate, with Sn and HCl. It is insol. water, 
 V. sol. alcohol. Its salts are unstable, but 
 B'jHjPtClj may be crystallised from alcohol. 
 
 Di- benzoyl derivative 
 C5H4(NHBz)(OBz). [176°]. From o-amido- 
 phenol hydrochloride and BzCl (Hiibner, A. 
 210, 887). 
 
 Formyl derivative. Only known in its 
 
 Anhydro-derivative CjH,^^^CH. 
 
 Methenyl-amido-phenol. [31°]. (183°). Formed 
 by heating o-amido-phenol with formic acid. 
 
 Phthalyl derivative 
 CjH,: (CjOj) :N.CsH,.OH. Oxy-phenyl-pUhali- 
 mide. [220°]. From o-amido-phenol and phthalic 
 anhydride at 220°. Yellowish prisms ; converted 
 by heat into COj and anhydro-benzoyl-o-amido- 
 phenol, and by boiling Na^COjAq into phthaloxyl- 
 amido-phenol, C02H.C„H4.CO.NH.Cj[,OH, 
 [223°] (Ladenburg, B. 9, 1528). 
 
 Methyl derivative CjH.,(NHj).OMe. 
 o-Anisidine (228°). From o-nitro-anisol by 
 reduction (Brunck, Z. 1867, 205 ; Miihlhauser, 
 
 B. 13, 919, A. 207, 235; Herold, B. 15, 1684). 
 Liquid. It acts upon quinone thus : 
 8C„HA + 2C„H4(OMe)NH2 = 
 
 2C,H,(0H), + C AO,(C8H3(OMe).NH,),. 
 The product forms reddish-violet needles (from 
 glacial HOAc and benzene), [230°], and gives 
 a fine blue solution in cone. H^SO, (Zincke. A. 
 
AMIDO-PHENOL. 
 
 17J 
 
 226,68). Salts.— B'HCl: needles (from alco- 
 hol) ; may be sublimed.— B'HBr.—B'HjSO,. — 
 B'jHjPtOls.- Chloroaoetate (Vater, J. pr. [2] 29, 
 988). Acetyl derivative.— C„H^(NHAc).OMe. 
 [84°] (204°). Pearly crystals. Sol. hot water. 
 Benzoyl derivative. — OsHiNHBzj.OMe 
 [59°]. 
 
 Ethyl derivative CsHj(NH2).0Et. 
 o-Amido-phenetol. (229°). A liquid prepared by 
 reducing o-nitro-phenetol (M. Forster, /. pr. 
 129, 344). Eeactions. — 1. Bromine forms a 
 di- and a tri-bromo-derivative. — 2. Cyanogen 
 chloride passed into an ethereal solution forms 
 ethoxy-phenyl cyanamide, [94°], o- 
 amido-phenetol hydrochloride being ppd. : 
 2Cja,(NH.).0Et + CNCl = 
 C,H,(NH5,)0EtHCl + C,H^(NH.CN).OEt 
 (Berlinerblau, J. pr. [2] 30, 98). Chloro- 
 ac elate .—C^,{^B.^ (OEt) CH.Cl.CO^H (Vater, 
 J. pr. [2] 29, 288). 
 
 Ethylene derivative C^i{O.O^i.'ii^^i. 
 [128°]. By reducing the ethylene ether of 
 nitro-phenol with Sn and HCl. Properties. — Tri- 
 metric plates (from alcohol or water). Feels 
 greasy. Insoluble in cold water, soluble in alco- 
 hol, ether, chloroform and benzene. Forms a 
 bluish-black solution with H^SO^. FCjClj gives 
 a sepia-brown colour. K^Cr^O, and HCl give a 
 brownish-red colour (E.Wagner, J. ^. [2] 27, 201). 
 Salts. — B"2HC12aq. Silver-grey glittering 
 flat needles grouped in tufts (from water). The 
 acetate is extremely soluble. The sulphate is the 
 least soluble salt, it crystallises in pearly plates 
 but, like the oxalate, it readily becomes oxidised. 
 Diacetyl derivative. — [226°]. Needles. 
 
 Oxethyl derivative. — 
 H0.C2H^.0.C„Hj.NH2. [90°]. Got by reducing 
 BzO.CjHj.O.CbH^.NOj {v. o-Nitbo-phenol) by Sn 
 and HCl (Weddige, J.pr. 132, 252). Properties.— 
 Colourless plates, slightly soluble in water, readily 
 soluble in alcohol, ether and boiling benzene. 
 A feeble base. Benzoyl derivative 
 BzO.CjH,.O.CsH^.NH2 [c. 100°]. Got by re- 
 ducing the benzoyl derivative of the oxethyl 
 ether of o-Nitro-phenol (g. v.). 
 
 Amido -ethyl derivative 
 
 NH,.C2H,.0.C,H,.NH2 
 
 Anhydro-benzoyl derivative 
 /NH. C^C,H, 
 
 OaH.C ^N [151°] V. O-NlTBO-PHENOIi. 
 
 \o.c,h/ 
 
 m-Amido-phenol CeH^(NHj,)(OH) [1:3]. 
 
 From TO-nitro-phenol by reducing with Sn 
 and HCl (Bantlin, B. 11, 2106). The free base 
 is extremely unstable. Its hydrochloride, B'HCl, 
 is formed by reducing bromo-m-nitro-phenol 
 (Pfaff, B. 16, 613). 
 
 Methyl derivative CjHj(NH.J(OMe) 
 m-Armidine (251°). Salt.— B'HCl (Pfaff). 
 
 Ethyl derivative C,H,(NH2)(0Et). (180°- 
 205°) at 100 mm. From the nitro compound 
 by Sn and HCl (P.Wagner, J.pr. [2] 32, 71). 
 A yellowish liquid, turning red in air. Salts. — 
 B'^H^SnCl^: plates.- B'HCl : silky grey needles ; 
 insol. ether, sol. water and alcohol. — 
 B'jH..S04 liaq.— xB'aH-.C^O, : brownish plates.— 
 »B'HBr (Staedel, B. 16, 29). Acetyl deriva- 
 tive C„H,(NHAc)(OEt). [97°]. GUttering white 
 plates (from water). 
 
 Ethylene derivative 0^^(O.C^^'E.^i. 
 [135°]. Obtained by reducing the corresponding 
 
 nitro-compound. Short prisms (from alcohol). 
 SI. sol. hot water, sol. hot alcohol and benzene, 
 si. sol. ether. Forms crystalline salts. 
 
 p-Aimdo-phenolC|,H.,(NH„)(OH) [1:4]. [170°] 
 (S. a. C). [c. 184°] (L.).' S. 1-1 at 0°. S. 
 (alcohol) 4-5 at 0°. 
 
 Preparation. — 1. From 2'-^^it''o-phenol by 
 reducing with iron and acetic acid (Fritzsche, 
 A. 110, 166) or Sn and HCl (Schmitt a. Cook, 
 K. 3, 61). — 2. From amido-saHcylic acid by 
 distillation (Schmitt, B.l, 67).— 3. From nitroso- 
 phenol (Baeyer a. Caro, B. 7, 965). 
 
 Properties.— Crystalline, but very unstable. 
 May be sublimed (S. a. C). In capillary tubes 
 it turns brown at 140° and melts at 184° with 
 decomposition (Lessen, A. 175, 296). 
 
 Salts.— B'HCl. S. 71at0°. S. (alcohol) 
 10. Turns brown in air.— B'HOAc. [183°]. 
 S. 11 at 0°. S. (alcohol) 8-3 at 0°. 
 
 Beactions.—l. Bleaching powder solution 
 added to a cold solution of ^-amido-phenol 
 hydrochloride forms quinone chloro-imide, but 
 if added to a hot concentrated solution of the 
 salt it forms a mixture of tri- and tetra-chloro- 
 quinones. — 2. Bleaching powder added to a solu- 
 tion of p-amido-phenol in fuming HCl at 0° 
 forms pure tri-chloro-quinone. — 3. Chlorine ga» 
 passed in excess into a solution of j3-amido- 
 pbenol in f umingHCl forms pure tri-chloro-ami do- 
 phenol (Schmitta.Andresen,J'.^.131,435). The 
 observation that chlorine converts ^-amido- 
 phenol hydrochloride in aqueous solution into 
 quinone-chloro-imide, while in presence of cone. 
 HCl chlorine converts _p-amido-phenol into tri- 
 chloro-amido-phenol, is explained by the fact 
 that quinone-chloro-imide is changed by cone. 
 HCl into ohloro-jp-amido-phenols. In this de- 
 composition the first reaction is : 
 
 C.H,<g^l + 4HCl = C,H,<0H j^^l4 2C1,. 
 
 This reaction is similar to that betweeo 
 chloride of nitrogen and HCl : 
 
 NCI3 + 4HC1 = NH.Cl + 3Clj. 
 
 Hence both ammonia and amidogen are pro- 
 tected by cone. HCl from the action of chlorine. 
 4. Acts on quinone as follows : 
 
 3CjHj02+ 2NH2.C,H^OH = 
 2CeHj(0H)j + C„B.^{NB.^.G„ia,.OB.)fi^. It is best 
 to use the hydrochloride of ^'-amido-phenol in 
 hot aqueous solution ; the product, which sepa- 
 rates on cooling, is sparingly' soluble in the 
 usual menstrua, and does not melt below 290° 
 (Zincke a. Hebebrand, A. 226, 70).— 5. HCl, 
 NaNOj, and KjSOj produce ^-diazo-phenol 
 sulphite, H0.CeH,.N,.S03H (Reisenegger,^. 221, 
 316). — 6. Cl.COjEt forms p-oxy-phenyl-carbamio 
 ether, H0.C5Hj.NH.C0,Et [120°].— 7. A mixture 
 of HCl and potassium cyanate produces p-oxy- 
 phenyl-urea, HO.CjHj.NH.OO.NHj [168°]. — 8. 
 HCl axiA. potassium sulphocyanide produce, when 
 the solution is evaporated, ^'-oxy-phenyl-thio- 
 urea, HO.C.H^.NH.CS.NH^ [214°].— 9. CSj pro- 
 duces di-oxy-di-phenyl-thio-urea, 
 CS(NH.CbH4.0H)2. 
 
 Acetyl derivative CsHj(NHAo)(OH). 
 [179°]. Large white prisms; obtained by re- 
 ducing ^-nitro-phenol with tin and glacial acetio 
 acid (Morse, B. 11, 232). 
 
 Benzoyl derivative CsH,(NHBz)(OH). 
 [227°]. From ji-amido-phenol and BzOI 
 
172 
 
 AMIDO-PHENOL. 
 
 ^iibnei, A. 210, 378). Needles, insol. water, 
 alcohol, and petroleum, si. sol. hot alcohol. 
 
 Amido-phenyl bemoateCgK^(N'S2){OBz). 
 [164°]. Obtained by reducing p-nitro-phenyl 
 benzoate. Plates ; sol. boiling alcohol, and water, 
 V. e. sol. glacial acetic acid. 
 
 Di-acetyl derivative C5H4(NHAc)(OAc) 
 tl51°]. From ^-amido-phenol and Ac^O. 
 
 Di-benzoyl derivativeC^iiiJSSBz)^^^?). 
 [231°]. From2>-amido-phenol and BzCl. 
 
 Methyl derivative C6H4{NH2)(01iIe). 
 j^-Anisidine. [56°]. (246°). From jp-nitro-anisol 
 <Brunk, Z. 1867, 205 ; Salkowski, B. 7, 1009). 
 Formed also, together with COj, when anisoyl- 
 hydroxylamine is distilled (Lossen, A. 175, 296). 
 Tables (from water). B'HCl : long needles. 
 S'^H^PtCle. 
 
 Ethyl derivative Cfiii^B^.OKt (253°). 
 Obtained by reducing ^-nitro-phenetol 
 <Halloch, B. 14, 37). 
 
 Ethylene derivative C2H,(O.CsH4NH2)2 
 [o. 170°]. By reducing the ethylene ether of 
 ^-nitro-phenol (g. v.). Properties. — Needles, 
 which turn brown in the air. Crystallises from 
 alcohol or from water. Very soluble in hot ben- 
 zene, less soluble in CHClj or ether. Forms a 
 ■deep blue colour with KjCrjO, and HCl. FCjClj 
 ^ives a cherry red (E. Wagner, J. pr. [2] 27, 206). 
 Salt.— B"2HC1: long thin needles grouped con- 
 •centrically. The acetate is deliquescent. The 
 sulphate is the least soluble salt. The oxalate 
 is but slightly soluble. 
 
 (o) Di-amido-phenol CeH3(OH)(NHj)2 [1:2:4]. 
 Trom (a) di-nitro-phenol (Gauhe, A. 147, 66 ; 
 .Stuokenberg, B. 10, 885 ; Post a. Stuckenberg, 
 A. 205, S6). The free base is extremely unstable. 
 
 Salts.— B"2HC1. Precipitated by adding 
 ■cone. HCl to its aqueous solution. Small prisms 
 insoluble in cone. HCl, and in absolute alcohol. 
 Dilute solutions are turned violet-red by FejCl,, 
 or bleaching powder (H. Kohler, J. pr. [2] 29, 
 -270).— B"2HI.— B"H2S0,2aq : tables. 
 
 Di-benzoyl derivative 
 •C„H3(NHBz)jOH (?). [187°]. From the hydro- 
 chloride and BzCl. Pale red leaflets ; sol. alcohol, 
 •chloroform, and aniline, si. sol. ether, insol. 
 water. Forms a nitro derivative [c. 169°]. 
 
 Tri-benzoyl derivative 
 <3eH3(NHBz)2(OBz)(?). [283°]. Ehombohedra, 
 insol. alcohol, chloroform, and ether ; sol. 
 aniline. 
 
 (;8) Di-amido-phenol OsHa(NH2)20H [2:6:1]. 
 The free base is very unstable ; its hydrochloride 
 is got by reducing the corresponding di-nitro- 
 iphenol (Post a. Stuckenberg, A. 206, 79). 
 
 Salts.— B"2HC1: thick pointed prisms, v. 
 iBol. water, si. sol. alcohol. B"H2S04: yellow 
 ■needles. 
 
 Di-benzoyl derivative CeH3(NHBz)20H. 
 [209°-218°]. Minute crystals, sol. alcohol, si. 
 •sol. benzene. 
 
 Tri-benzoyl derivative 
 €sH3(NHBz)(NBz2)(OH). [184°]. Sol. warm 
 Na^COjAq, insol. chloroform. 
 
 Tetra-benzoyl derivative 
 €„H3(NBz2)(NBZj,)dH. [182°]. Leaflets; insol. 
 water, sol. warm Na,COjAq, alcohol, benzene, 
 and ether. 
 
 Di-amido-phenol C,Hs(OH)(NH2)2. [1:3:4]. 
 
 Hydrochloride B''2H01i — Formed by 
 fceating ethoxy-^i-amido-phenyl carbamio ether, 
 
 CsHs(OH)(NHj)NH.COjEt with fuming HCl 
 (H. Kohler, J. pr. [2] 29, 269). Oblong plates. 
 Very soluble in cone. HCl and in absolute alcohol. 
 Dilute solutions are turned blood-red by Fe^Cl, 
 or bleaching powder. 
 
 Tri-amido-phenol C5H2(NHj)jOH. [2:4:6:1]. 
 
 Formation. — 1. From picric acid by reduction 
 (Heintzel, Z. 1867, 388 ; B. 1, 111 ; Bamberger, 
 B. 16, 2400).- 2. From pioramide, Sn and HCl 
 (Hepp, A. 215, 350). The free base is unstable. 
 The salts give a blue colour with a large quantity 
 of water containing air. In cone, solution Fe^Cl, 
 gives deep blue glittering crystals of amido-di- 
 imido-phenol (Heintzel). 
 
 Salts. — B'>'3HC1.— B"'28H2SO,.— B"'H3SnCl, 
 liaq. — B"'HI H^SO, 2aq. — B"'HIH3P04 2aq. — 
 B"'j,H4FeCye. If the hydrochloride is boiled 
 with HCl di-amido-dioxy-benzene is got 
 (Salkowski, A. 174, 260). 
 
 Tri-acetyl derivative C3H2(NHAo)30H. 
 [268°]. From the hydrochloride of tri-amido- 
 phenol by heating with NaOAo and Aofi. White 
 plates, soluble in acetic acid, hot alcohol, water, 
 aqueous acids and alkalis, very sparingly in 
 benzene and acetone ; by HNO,, CrOj or Fe^Cl, 
 it is oxidised to the tetra-aoetyl derivative of 
 tetra-amido-di-oxy-diphenyl-quinone 
 C5H(NHAc)2(OH).0 
 
 I I (Bamberger, B. 16, 2400). 
 
 CsH(NHAc)2(0H).O 
 
 Beaciion. — Tri-amido-phenol hydrochloride 
 is converted by bromine water into ' b r o m o- 
 dichromazin' CigHjNjBrnO,. This body 
 separates from alcohol in yellow needles with 
 feeble violet dichroism. Boiling dilute HjSO, 
 converts it into 'bromo-diohroic acid' 
 C,BH,Br,,0„ and ammonia. Bromine converts 
 bromodichromazin into hexa-bromo-acetone 
 (Wedel a. Gruber, B. 10, 1187). 
 
 Tetra-amido-phenol 
 
 Ethyl-ether, hydrochoride 
 CjH(NH2)4(OEt),2HCl. By reducing the product 
 of the action of HCl upon tri-nitro-ethoxy-phenyl- 
 urethane.— (l).C5H(NOj)3(OEt)(NH.C02Et) -I- HCl 
 = COj + EtCl -f 0,H(NO j3(0Et)NHj. 
 
 (2.) C5H(N02)3(OEt)NH,-f9H2 = 
 
 Properties. — Crystallises from dilute alcohol. 
 Insoluble in absolute alcohol, very soluble in 
 water. Does not melt at 360°- Eeduoes solu- 
 tions of Au and Pt. A feebly acid solution gives 
 with Fe^Clg or bleaching-powder the following 
 succession of colours : dark-green, violet-red, red- 
 dish-brown, yellowish-brown, yellow, colourless. 
 
 AMIDO-FHENOL SULPHONIC ACID 
 CbHjNSO, i.e. C3H3(NH2)(0H)HS03. [2:1:4]. 
 S. 1 at 14°. Prepared by reduction of o-nitro- 
 phenol-sulphonic acid or by sulphonation of 
 o-amido-phenol. Large colourless crystals like 
 oalc-spar. Does not form salts. 
 
 Anilide C,H3(NHj)(0H)(S02.NHPh). [205f]. 
 Colourless needles ; soluble in alcohol, acetic acid, 
 and benzene insoluble in ether. 
 
 Benzoyl derivative CeH,(NHBz)(0H)(S0aH). 
 Salts. — NaA'45aq : colourless needles, soluble 
 in water a. alcohol. — BaA'j ; colourless spangles, 
 sparingly soluble. — CaA'24|aq : sparingly soluble 
 colourless scales (Post a. Hoist, B. 13, 617 : A. 
 206, 49). 
 
 ^-Amido-phenol sulphonle acid 
 0.H,(0H)(NH2)803H [1:4:2]. S. -07 at W. 
 
AMIDO-DIPHENYL. 
 
 irs 
 
 Formation. — 1. Fromp-amido-phenol hydro- 
 ehloride and fuming HjSO, (Post, B. 6, 397).— 
 2. From p-nitro-phenol sulphonio acid (Post a. 
 Hoist, B. 13, 617).— 3. Together with azoreso- 
 rufin by heating a mixture of resoroin and nitro- 
 benzene with H-iSOj (Brunner a. Kramer, B. 17, 
 1867). — 4. From quinone ohloro-imide andcono. 
 NajSO, (Sohmitt a. Bennewitz, J. pr. [2] 8, 7). 
 
 . ProperUes. — White glistening needles ; si. sol. 
 cold water, v. si. sol. alcohol, insol. ether. Does 
 not combine with acids, but forms metallic salts, 
 e.5r. Ba(O.CeH3(NH2)S03). Beduoes cold am- 
 moniacal AgKOj. Turned violet by FejCl,. Not 
 ppd. by lead acetate. 
 
 Amlide C,ia,{0B.){ll<iB^)80^^¥hS.. [98°]. 
 Small colourless crystals ; v. sol. alcohol, acetic 
 acid, and benzene ; insol. ether. 
 
 jj-Amido-phenoi di-sulphonic acid 
 CeHj(OH)(NH2)(S03H)j [1:4:2:6] (?). From ben- 
 zene-azo-phenol tri-sulphonio acid (q. v.) by 
 ammonium sulphide (Wilsing, A. 215, 236 ; Lim- 
 pricht, B. 15, 1293). White silky needles. Deli- 
 quescent ; si. sol. alcohol, insol. ether. Solution 
 gives with Fe^Clj a deep violet colour. Its 
 alkaline solutions show blue fluorescence for a 
 short time. Salts. — KHA"aq : slightly sol. cold 
 water.— NH,HA"aq.—PbA" aq. 
 
 o-AMIDO-DIPHENYL C,2H„N i.e. 
 CeH5.CeH,.NHj [1:2]. [45°]. From o-nitro- 
 diphenyl with tin and glacial acetic acid (Hiib- 
 ner a. Liiddens, A. 209, 351). 
 
 Salts.— B'HCl: needles.— B'2H2PtCle4aq. : 
 orange leaflets. 
 
 ^-Amido-diphenyl CsH5.O5H4.NH2 [1:4]. 
 Xenylamine ; Martylamine. [49°]. (320°). 
 Occurs in the high-boiling fractions in the pre- 
 paration of aniline (Hofmann, Pr. 12, 389 ; O. 
 Schultz, A. 174, 212 ; Osten, B. 7, 171). Pre- 
 pared by reducing ^-nitro-diphenyl with tin and 
 HCl (Hubner a. Osten, A. 209, 339). Colourless 
 leaflets, sol. hot water, alcohol, and chloro- 
 form. 
 
 Salt s.— B'HCl : leaflets.— B'^H^PtClj 2aq ; 
 yeUow leaflets, si. sol. alcohol. — B'HNOa : pearly 
 leaflets. — B'^H^SOi : leaflets, v. si. sol. water, si. 
 sol. alcohol. — B'jHjCjOj: long needles, sol. water 
 and alcohol. 
 
 Acetyl derivative CjHj.CjHj.NAcH. 
 [167°]. Long needles ; v. si. sol. water. 
 
 Benzoyl derivative CuHj.CbHj.NBzH. 
 [230'']. Leaflets ; insol. water, v. si. sol. alcohol. 
 
 Formyl derivative CsH5.CsH4.NH.CHO. 
 [172°]. Prepared by heating ^-amido-diphenyl 
 with ethyl formate at 100°- Minute needles; 
 sol. ether, si. sol. alcohol, v. si. sol. water (Zim- 
 mermann, B. 13, 1967). 
 
 ^-Amido-diphenyl sulphonic acid 
 C,2H8(NH2)S03H. [above 300°]. Formed by 
 Bulphonation of jJ-amido-diphenyl (Carnelley a. 
 Schlevehnan, G. J. 49, 380). Insol. water. 
 
 Salts. — NaA'2aq: colourless needles, m. sol. 
 water. — BaA'2 4aq ; v. si. sol. water. 
 
 o-^J-Di-amido-diphenyl Ci^Hi^Nj i.e. 
 
 [1:2] NH2.CsH4.CsH4.NHj [1:4]. Iso- benzidine. 
 (ffl- or (5)-I)i-amido-di-phenyl. JOiphenyline. 
 [45°]. (368°) (Schultz, A. 207, 348). 
 
 Formation. — 1. From o-nitro-^-amido-di- 
 phenyl (Schultz, B. 9, 548 ; 14, 612).— 2. From 
 di-amido-diphenyl carboxylio acid (Strasser a. 
 Schultz, A. 210, 193). 
 
 Preparation. — An alcoholic solution of azo- 
 
 benzene (100 g.) is heated with a solution of SuCl,, 
 in cono. HCl ; the liquid is evaporated to dryness, 
 the residue dissolved in water and benzidine is 
 ppd. as sulphate (100 g.) while o-^-di-amido- 
 diphenyl sulphate (30 g.) remains in solution 
 (Schmidt a. Schultz, B. 12, 482). 
 
 Properties. — Long needles, v. si. sol. water. 
 
 Salts.— B"HC1: laminse.- B"2HC1 : needles. 
 — B"HjS04: prisms.- B"2H2S04. 
 
 Di-acetyl derivative OijHu^AojNa. [202°]. 
 
 m-m-Bi-amido-dlphenyl 
 [1:3] NH2.CsH4.OsH4.NH2 [1:8]. From the nitro 
 compound (Brunner a. Witt, B. 20, 1028). Crys- 
 tals, si. sol. water.— B"H2S04.—B"H2Pt01s. 
 
 Di-acetyl derivative. [258°]. Long 
 needles. 
 
 ^-p-di-Amido-diphenyl, Benzidine. 
 [1:4] NH2.CsH4.CsH4.NHj [1:4]. XenyUne-di- 
 amine. [122°]. (above 360°). 
 
 Formation. — 1. By the reduction of azo- 
 benzene or of azoxybenzene in alcoholic 
 solution by SOj (Zinin, A. 85, 328).— 2. From 
 azobeuzene by SnCLj and HCl (v. stip.). — 3. By 
 heating azobenzene with fuming HCl (Zinin, 
 A. 137, 376), HBr (Werigo, A. 166, 202), or 
 HI (Senziuk, Z. 1870, 267) in sealed tubes.— 
 
 4. By reducing nitro-benzene with sodium-amal- 
 gam in presence of acetic acid, the product 
 being treated with H2SO4 (Werigo, ji. 135, 176). — 
 
 5. From nitro-benzene, alcoholic NaOH, and 
 zinc dust and subsequent treatment with acid 
 (Alexejeff, Z. 1867, 497).— 6. From di-amido-di- 
 phenic acid by distilling with BaO (Schultz, A. 
 196, 29). — 7. From ^-amido-^-nitro-diphenyl by 
 Sn and HCl (Fittig, A. 124, 276).— 8. From 
 p-p-di-nitro-phenyl by tin and HCl (Schultz, A. 
 174, 227). — 9. From hydrazo-benzene by treat- 
 ment with mineral acids : 
 
 OsH5.NH.NH.CsH5 = NH2.OsH4.CsH4.NH2. 
 
 Preparation. — V. o-p-di-AMiDO-niesENYL. 
 
 Properties. — Silvery scales ; may be sublimed. 
 Sol. hot water, v. si. sol. cold water, v. e. sol. 
 alcohol and ether. 
 
 Salts. — ^B"H2S04: small scales, v. si. sol. 
 water and alcohol. — B"2HC1: laxamse, v. sol. 
 water and alcohol. — B"HC1 : long needles, si. 
 sol. water ; ppd. when a large excess of water is 
 added to the preceding salt. — B"2HN03: four- 
 sided lamina, sol. hot water. — B"2H2C204: 
 groups of sUby needles, m. sol. water and 
 alcohol. — B"C4HsOs : laminte ; sol. water. 
 
 Reactions. — 1. Even very dilute solutions 
 give with potassic bichromate a deep blue pp. 
 (Julius, M. 4, 193).— 2. KjFeCys gives a blue 
 pp. — 3. Chlorine-water gives a blue colour soon 
 becoming red. — 4. Exhaustive chlorination with 
 SbClj gives per-chloro-diphenyl and per-chloro- 
 benzene (Merz a. Weith, B. 16, 2874).— 5. If very 
 dilute bromine-water be poured upon a solution 
 of benzidine in CS2 the upper layer becomes 
 blue, excess of bromine destroys this colour, the 
 lower layer then turning red (Glaus a. Eisler, B. 
 14, 83). 
 
 Acetyl derivative NHj.CsHj.CjHj.NAcH, 
 [199°]. Needles, si. sol. water. 
 
 Diacetyl derivative 
 NHA0.CsH4.CsH4.NAcH. [317°]. Nearly insoluble 
 in all solvents. 
 
 Di-formyl derivative C,2Hs(NH.COH)2: 
 crystalline powder, sublimable, insoluble in all 
 ordinary solvents except nitrobenzene. Formed 
 
174 
 
 AMIDO-DIPHENYL. 
 
 by heating hydrazobenzene or benzidine with 
 formic acid. 
 
 Di-henzoyl derivative C,,Hs(NHBz)2 : 
 colourless needles or pearly plates ; insol. 
 alcohol, ether, and aniline ; sol. nitrobenzene. 
 Formed by heating hydrazobenzene or benzidine 
 with BzCl (Stern, B. 17, 379). 
 
 Di-phthalyl derivative C2sH,||N204 
 fabove 860°] : silky yellow needles, sol. hot 
 nitro-benzene ; insol. most other solvents. 
 Formed by heating benzidine or hydrazobenzene 
 with phthalic anhydride (Bj,ndrowski, B. 
 17, 1181). 
 
 Oxalyl derivative' (Ci^B.^.'^Tl).fi.fl2- An 
 insoluble powder, obtained by heating benzidine 
 oxalate at 200°. 
 
 Benzidine-v-sulphonic acid 
 H2N.C„H,.C5Hj.NH.S03H. Formed by heating 
 an alcoholic solution of'azobeuzene with hydrio 
 ammonium sulphite (Spiegel, B. 18, 1481). 
 
 Gelatinous pp. It gives colourless crystaBine 
 Halts. 
 
 The HSO3 is readily split off with production 
 of benzidine by dissolving the acid in strong 
 H,SO,. 
 
 Benzidine snlphonic acid (?) 
 C.H,(NH2).CsH3(NHJ(SOjH) (?). Hydrazo-hen- 
 zene sulphonic acid C^Hs.NH.NH.CsHj.SOjH (?). 
 Ppd. by adding HCl to the product of the action 
 of HjS on an ammoniacal solution of azo-benzene 
 sulphonic acid (Griess, A. 154, 213). — Yellow 
 needles or plates (from water).— BaA'^: plates. 
 The free acid is decomposed by solution in 
 aqueous NHj into benzidine and H^SOj. The 
 above azobenzene sulphonic acid is converted 
 by potash-fusion into j)-oxy-azobenzene, and 
 ■would therefore appear to be a ^-sulphonic acid ; 
 in which case it is not clear how the conversion 
 into a benzidine derivative could be effected. If, 
 however, the acid is hydrazo-benzene sulphonic 
 acid, we must assume that the benzidine trans- 
 formation here takes place in alkaline solution, 
 by displacement of SOjH. In any case the 
 lemoval of SO3H by ammonia is peculiar. 
 
 Benzidine sulphonic acid 
 C,,H,,Nj(S03H) 2|aq. Obtained by heating (a)- 
 benzidine disulphonic acid with water at 210° 
 (Limpricht, B. 11, 1048). Yellow needles (from 
 alcohol) ; v. sol. water. — ELA'4aq. — BaA'24aq. — 
 PbA'jSaq. 
 
 Chloride C,jH„N2(S02CI) [above 240°]. 
 
 Benzidine disnlphonlc acid 
 [4:3:1]C,H3(NH2)(S03H).C,H3(S03H)(NH,)[1:3:4] 
 S. '08 at 22°. From azo-, or azoxy-, benzene 
 disulphonic acid by reduction with SnCL, sodium- 
 amalgam, or NaOH and zinc dust, followed by 
 treatment with a mineral acid (Miihrenholtz a. 
 Gilbert, A. 202, 337 ; Bruunemann, A. 202, 344 ; 
 Limpricht, B. 14, 1359). MonocUnic prisms 
 (with 3aq). Dilute HCl at 230° gives benzidine 
 and H.iSOj. Nitrous acid diazotises this acid. — 
 Na^"3iaq.— KjA"liaq.— CaA"4aq.— BaA"4aq. 
 — PbA"4aq. 
 
 Benzidine di-sulphonic acid 
 C|2Hj(NH._)j(S03H)2. From benzidine andfuming 
 H2SO4 at 170°. Small white plates ; v. si. sol. 
 water, insol. alcohol and ether (Griess, B. 14, 
 300). Salts. — BaA"5aq: white plates.— 
 BaA"2aq: needles. — "AgjA"; white crystalline 
 pp. 
 
 Benzidine (a)-di-sulphonic acid 
 C,2H,„N2(SOaH)j. Hydrazo-hemene di-sulphordc 
 acid (?). Prepared by reducing potassium azo- 
 benzene (a)-di-sulphonate with SnClj (Limpricht, 
 B. 14, 1357). Tables (containing 2aq) ; si. sol. 
 cold water, v. si. sol. alcohol. — K^A" 3aq. — 
 BaA"aq.— "AgjA": white pp.— PbA": needles, 
 si. sol. cold, V. sol. hot, water. 
 
 Benzidine tetrasulphonic acid 
 C|2H5N2(SOsH)j. Prepared by sulphonation of 
 the preceding with fuming HjSO^ — Ba2A""14aq : 
 large prisms, v. sol. hot water, si. sol. alcohol. — 
 "KjA"" (Limpricht, B. 14, 1543). 
 
 Other sulphonic acids of benzidine 
 Benzidine heated with a large excess of fuming 
 HjSOj above 170° forms a mixture of di-, tri-, 
 and tetra-, sulphonic acids, and di-amido-di- 
 phenylene sulphone sulphonic acids (Griess, B. 
 18, Eef. 88). 
 
 Benzidine dl-carbozylic acid v. di-A.tiU)0-T)i- 
 
 PHENIO ACID. 
 
 Benzidine tetra-carboxylic anhydride 
 
 [above 360°]. Formed by the action of an HCl 
 solution of SnCl^ on azo-benzene tetra-carboxylio 
 acid (azo-phthalic acid). Light-yellow tasteless 
 powder. Insol.water, alcohol, ether.or dilute acids. 
 
 With alkalis it gives anhydride salts : — 
 
 C,2HgN2(C.^O,)(C02K)2 5aq : large prisms. 
 
 C,2HsN2(C203)(C02Na)2aq: small needles. 
 
 C,2HjN2(0203)(C02Ag)2 : fine powder. 
 
 C,2HaN2(C20s)(C02)2Pb : amorphous powder. 
 
 C,2H8N2(C203)(C02NHJ(C02H) : transparent 
 prisms (Clans a. Hemmann, B. 16, 1759). 
 
 Di-amido-diphenyl C,2H,2N2. Iso-bemidine. 
 [125°]. Occurs among the products obtained by 
 passing aniline through a red-hot tube (Bernth- 
 sen, B. 19, 420). White iridescent plates, si. sol. 
 water. Its aqueous solution gives no colouration 
 with potassic ferricyanide, and a greyish-brown 
 pp. with chlorine water. The solid base is 
 turned greenish-blaok by strong HNO3. The 
 sulphate is sparingly soluble. 
 
 letra-amido-diphenyl 
 [3:4:1] (NH2)2CjH3.C,H3(NH2)2 [1:3:4]. Obtained 
 by reducing di-nitro-^J-^-di-amido-diphenyl 
 (Brunner a. Witt, B. 20, 1025). Silvery plates. 
 
 o-AMIDO-PHENYL-ACETIC ACID CgHsNO,, 
 i.e. GsH3.CH(NH2).C02H. Phenyl-amido-acetio 
 acid. [256°]. Formed by heating a-bromo- 
 phenyl-acetic acid with NHjAq (S.G. -9) at 100° 
 (Stockenius, B. 11, 2002) ; or by saponifying its 
 nitrile, obtained by the action of alcoholic NH3 
 on the cyanhydrin of benzoic aldehyde (Tiemann 
 a. Friedlander, B. 14, 1967). White leaflets or 
 prisms ; may be sublimed. SI. sol. cold water, 
 m. sol. hot water. It forms unstable salts with 
 bases, but more stable salts with acids, though 
 these are decomposed by water. Distilled with 
 Ume, it gives benzylamine (Tiemann, B. 13, 383). 
 
 Salts.— B'HCl: trimetric prisms.— B'HNO,,. 
 — B'H^SOj.— B'H2C204.— AgA': prisms, v. si. sol. 
 water. — BaA'j : small white plates ; v. sol. hot 
 water. — MgA'^^aq : plates, si. sol. water. 
 
 Amide. The hydrochloride forms thick 
 prisms, si. sol. alcohol. 
 
 Nitrile C,Hj.CH(NH2).CN. YeUow oU 
 {v. sup.). 
 
 m-Sulphonic acid 
 C»Hj(S03H).CH(NH2).C0aH. Minute needles j bL 
 
AMIDO-PHENYL-BUTINENE. 
 
 1?5 
 
 (ol. eold water, insol. ether (PlocU a. Lou, B. 
 18, 1182). 
 
 0- Amido-phenyl-aoetio acid. When o-nitro- 
 phenyl-acetio acid is reduced the product is not 
 o-amido-phenyl-acetic acid but its anhydride, 
 oxindol (2- v.) (Baeyer, B. 11, 583). 
 
 m-Amido-phenyl-acetic acid 
 CeH^(NHj).CH2.C02H [1:3]. [148°]. Formed 
 by reducing ?7i-nitro-phenyl-acetic acid (Gabriel 
 a. Bergmann, B. 16, 2065). 
 
 Nitrile C„Hj(NH2).CH2.CN. m- Amido- 
 bernyl cyanide. A liquid obtained by reducing 
 m-nitro - phenyl - aoetonitrile (Salkowski, B. 
 17, 506). 
 
 ^-Amido-phenyl-acetic acid 
 CjH^(NH,,).CHj.C02H [1:4]. [200°]. From p- 
 nitro - phenyl - acetic acid (Radziszewski, B. 
 2, 209; Bedson, C.J. 37,92). White needles 
 (from water) ; v. si. sol. cold water. 
 
 Nitrile C,B.i(^n^).CB.^.(M. p-Amido- 
 benayl cyanide. [46°]. (312°). V.D.4-78(for4-56). 
 Formation. — 1. From ^-nitro-benzyl cyanide 
 (Szumpelik, B. 3, 474 ; Gabriel, B. 15, 834).— 
 2. As one of the products of the reduction of o- 
 p-di-nitro-oinnamio ether {q. v.) by tin and HCl 
 (Friedlander a. Mahly, A. 229, 229). The yield 
 is 15 p.c. of the substance used. Properties. — 
 Satiny plates (from water). Sol. acids. Gives 
 a di-bromo-derivative. HCl at 130° converts 
 it into amide - phenyl - acetic acid. Salts. — 
 B'^HaPtClB.— B'jHjSOj. Acetyl derivative 
 NHAc.C,Hj.CHj.CN. [97°]. Slender needles; 
 V. sol. alcohol and ether. Di-acetyl deri- 
 vative NA02.C„H,.CH2CN. [153°]. Glistening 
 needles. Sol. boiling water, benzene, and CSo ; 
 si. sol. alcohol. 
 
 Di-amido-phenyl-acetic acid 
 C,H3(NH2)2.CH2C02H [4:3:1]. Formed by re- 
 dr.cLag (3, 4, l)-nitro-amido-phenyl-acetic acid 
 (Gabriel, B. 15, 1996). Short flat crystals (with 
 aq). SI. sol. hot alcohol, insol. ether, CSj, chloro- 
 form, and benzene. Sol. acids and alkalis. 
 
 a-TO-Si-amido-phenyl-acetic acid 
 [1:3] C„H,(NHJ.CH(NHJ.COjH. [214°]. Formed 
 by reducing m-nitro-phenyl-a-amido-acetic acid 
 with tin and HCl (Plochl a. Loe, B. 18, 1181). 
 Flat silvery needles. 
 
 Salt. — "CuA'j : bluish-green crystalline pp. 
 
 o-AMIDO-PHENTL-ACETYLENE CsHjN i.e. 
 CsHj(NH2).C:CH. Yellowish oil. Prepared by 
 reduction of o-nitro-phenyl-acetylene with zinc- 
 dust and NH3. It forms yellow pps. with am- 
 moniacal AgNOj and CujClj. 
 
 B'HCl : soluble yeUow crystals. 
 
 Reaction. — Converted by H^SOj (12pts.) and 
 H.,0 (4 pts.) into o-amido-acetophenone (Baeyer 
 a.Bloem, B. 17,964). 
 
 Acetyl derivative. [75°]. Colourless 
 needles (Baeyer a. Landsberg, B. 15, 60). 
 
 Di-o-amido-di-phenyl-diaoetylene 
 C,H,(NH,).C:C.C:C.C^,(NHJ. [128°]. Pre- 
 pared by the action of a solution of potassium 
 f erricyanide on the cuprous compound of o-amido- 
 phenyl-aoetylene. Long yellowish needles. Sol. 
 alcohol, ether and acids, insol. water. 
 
 B"HjCl2 : colourless soluble crystals. 
 
 Di-acetyl derivative. [231°]. Long 
 needles (Baeyer a. Landsberg, B. 15, 60). 
 
 (B. 2)-AMID0-(4)-PHENYI,-ACaiDIIfE 
 
 C„H„N, i.e. C,H / I >C„H,(NH,). 
 NCPh'^ 
 Formed by heating phenyl-^-phenylene-diamine 
 C„Hj(NHJ.NHC,H5 with benzoic acid and ZnOij 
 (Hess a. Bernthsen, B. 18, 692). Amorphous 
 solid. Easily soluble in ordinary solvents. The 
 solutions of the base are yellow, the benzene 
 and ethereal solution having a splendid green 
 fluorescence. It dyes silk a brownish yellow. 
 The solutions of its salts are red. 
 
 Si-amido-phenyl-acridine v. Cheysaniline. 
 
 AMIDO-PHENYL-ALANINE v. Di-amido- 
 
 PHENYL-PKOPIONIO ACID. 
 
 AMIDO - PHENYL - AMIDO- v. Di-amido- 
 
 PHENYL- 01 PhENYL-DI-AMIDO-. 
 
 AMIDO-DI-PHENYL-AMINE C.^H.^N^ i.e. 
 NH2.CaHj.NH.CjH5. [61°]. Prepared by the 
 reduction of nitro-di-phenyl-amine or of phenyl- 
 amido-benzene-azo-benzene, or its sulphonic acid 
 {TropcBolin 0.) (Nietzki a. Witt, B. 12, 1399). 
 
 Thin laminse. Gives quinone on oxidation. 
 
 Salt. B'zHjSOj : silvery laminse, si. sol. water. 
 
 Acetyl derivative CijHuAcNj. [158°]. 
 
 p-^-Di-amido-di-phenyl-amine 
 NH,.C„H4.NH.C„H,.NH2. [158°]. Formed by 
 reduction of aniline black. Prepared by re- 
 ducing (a)-di-nitro-di-phenyl-amine (N. a. W.). 
 
 Acetyl derivative. [239°]. 
 
 Di-amido-di-phenyl-amine. Prepared by re- 
 ducing (/8)-di-nitro-di-phenyl-amine. Liquid. 
 
 Salts.— B"H,Cl2; si. sol. water.-B"H2PtCl„. 
 
 Acetyl derivative. [203°]. 
 
 Tri - amide - tri - phenyl - amine (C^Hj.NHJjN. 
 [230°]. Formed by the reduction of tri-nitro- 
 tri-phenyl-amine by SnCl^ (Heydrick, B. 18, 
 2157 • 19 759.) 
 
 Salts'.— B"'3HC1 : needles. Its solution 
 exhibits the following colour reactions : blue, 
 taming violet with FejClj; bluish-green with ppd. 
 MnOj ; blue with KjCr^O, ; red with chloranil 
 in acetic acid (but if in this case the free base is 
 used the colour is bluish-green). — B"'23H2PtCl,. 
 -B"'(C,H,(NO,)30H)3. 
 
 Tri-acetyl derivative N(C,jH,.NHAc)j: 
 needles which do not melt below 240°. 
 
 AMIDO-PHENYL-BENZGLYCOCYAMINE v. 
 Amido-m-phenyl guanidine caeboxylio acid. 
 
 ^-AMIDO-PHENYL-iso-BUTAlTE Ci^H.^N i.e. 
 OjHg.CsHjNHj. Butyl -phenylamine. Amido - 
 butyl-benzene. (230°). S.G. 22-937. Prom anihue 
 hydrochloride (10 g.) and iso-butyl alcohol (8 g.) 
 by heating for 6 hours at 230° (A. Studer, A. 
 211, 237 ; B. 14, 1472, 2186 ; Pahl, B. 17, 1232). 
 Colourless oil; v. si. sol. water, volatile with 
 steam. Miscible with alcohol or ether. Nitrous 
 acid converts it into butyl-phenol. 
 
 Salt s.— B'HCL— B'HBr.—B'HI. 
 
 Acetyl derivative [170°]: laminae. 
 
 Formyl derivative C,„H|3.NH.CH0 
 [59°] : laminaj (Gasiorowski a. Merz,B.18,1009). 
 
 AMIDO - PHENYL BUTINENE C,„H„N 
 (3) (1) /CH 
 probably 0„H,(NHJ.CH,.CH< || . [93° j. 
 
 \CH 
 (272° at 718 mm.). V.D. = 4-95 (for 5-02). 
 Formed by reduction of w-nitro-a-methyl-oiu- 
 namic aldehyde in alcoholic solution with tin 
 and HCl. Colourless glistening plates. Sublimes 
 at 100°. Eeduces ammoniacal AgNOj. The 
 
176 
 
 AraDO-PHENYL-BUTINENE. 
 
 hydrooUoride, snlphate and nitrate are easily 
 soluble in water. The hydrooUoride forms 
 colourless glistening plates. B'2H2Cl2PtCl4 2act: 
 slender needles. 
 
 Acetyl derivative C,„H,„NAo [140"]: 
 colourless ooneentrio prisms. 
 
 Benzylidene derivative C,„HjN:CHPh 
 [73°] : concentric light-yellow needles. Formed 
 by heating the base with benzaldehyde (Miller 
 a. Kinkelin, B. 19, 1249). 
 
 o-AHIDO-FHEITTI-CARBAIIIC ETHER 
 CaH.jNA i.e. H2N.C5H^.NH.C02Et. o-Amido- 
 phemyl-urethane. [86°]. Formed by reducing 
 o-nitro-phenyl-carbamic ether (Eudolph, B. 12, 
 1295). Long colourless needles ; sol. water. 
 
 Salt .— B'HCl : large tables. 
 
 jp-Amido-phenyl-carbamic ether. Amido- 
 earbaniUc acid. [74°]. Formed by reducing 
 p-nitro-phenyl-carbamio ether (Hager, B. 17, 
 2626; Behrend, A. 233, 10). Needles (from 
 dilute alcohol) ; insol. water. 
 
 Salts.— B'HCl: long needles.— B'H^SO^.— 
 B'H2C204 : needles, sol. hot water, si. sol. cold 
 water.— B'jHjPtCls : brown pp.-(B'HCl)3SnCL. 
 B'jSnClj aq.— (B'HCy^HgCIj. 
 
 Benzoyl derivative CeH,(NHBz).NH.C02Et, 
 [230°] : needles ; si. sol. alcohol, insol. water. 
 
 Di-^-amido-di-pIienyl-earbamic ether 
 (C5H,.NH2)2N.C02Et. Di-p-amido-di-phenyl- 
 amine urethane. [101°]. Formed by reduction 
 of di-^-nitro-di-phenyl-carbamio-ether. Violet 
 needles ( + aq). Soluble in water. 
 
 Di-henzoyl derivative 
 (CjH,.NHBz)2N.C02Et [235°] : nearly colourless 
 amorphous solid (Hager, B. 18, 2576). 
 
 DI-AMIDO-JOI-PHEITYI-CAHBINOI 
 C,sH„N20 i.e. C,B.,(WB^).C■R{0B.).G^U^1SB.^. 
 {P)-Di-amido-bemhydrol. [128°-129°]. From 
 (;3)-di-amido-benzophenone [149°] and sodium 
 amalgam (W. Staedel, A. 218, 850). Glittering 
 plates. S al t s.— B"2HC12aq.— B"H2S0, 2aq. 
 
 Acetyl-derivative. [220°]. 
 
 Di-amido-tri-phenyl-carbinol 0|9H,8N20 i.e. 
 C„H5C(0H)(C5H4NH2)2 [below 100°]. 
 
 Formation. — By the action of aniline 
 in presence of H^SO, upon the chloride 
 C^5.CC1.C5H,.NH. 
 
 Preparation. — From aniline hydrochloride 
 (40 pts.), nitrobenzene (45 pts.), benzo-trichloride 
 (40 pts.), and Fe at 180°. O.H5CCI3 + 2CeH3NH2 = 
 C„H5CCl(C8HjNH2)2+2HCl. The mass is ex- 
 tracted with dilute HCl (which leaves some 
 blue colouring matters undissolved) and the 
 nitro-benzene is distilled ofE by steam (Doebner, 
 B. 15, 234 ; A. 217, 242). 
 
 Properties. — Small crystals (from dilute 
 alcohol). Insol. in cold water ; v. sol. alcohol 
 or benzene. On heating with Mel it gives 
 malachite green. 
 
 Salts. — Dilute acids dissolve it in the cold, 
 forming nearly colourless solutions which on boil- 
 ing (split off water and) change to deep reddish- 
 violet. The salts dye violet, but the shades are 
 not fast. The coloured salts are probably of the 
 
 lorm i^6Ji5^<sCeH,NH2. This salt forms dark 
 
 I ^/--Cl 
 
 blue needles with coppery lustre. 
 
 Bea^tion. — Zinc dust and HCl reduce it to 
 dl-omido-tri-phenyl-methane (q. v.). 
 
 Tri-amido-tri-phenyl-carbinols v. Bosanilink. 
 
 DI - AMIDO - TBI - PHENYL - CARBIXOL 
 CARBOXYLIC ANHYDRIDE OjoH.sNaOj i.e. 
 (C.H4NH2)jC.C,H4.C0.0. [265°_266°]. SmaU 
 I I 
 
 colourless needles. Is prepared by heating 
 phenolphthale'in with aqueous NHg. Gives a 
 tetra-bromo-derivative [280°], and a tetra-acetyl- 
 tetra-bromo-derivative [241°] (Baeyer a. Burk- 
 hardt, B. 11, 1297). 
 
 AMIDO-DIPHENYL CARBOXYLIC ACID Vr 
 Amido-diphenio acid. 
 
 DI - AMIDO - DI - PHENYLENE KETONE 
 OXIDE (so called) C.sH.oN^Oj i.e. C„H,(NH2)202. 
 Lactoneofoxy-di-armdo-diphenylcarboxylicacid.. 
 From the nitro compound by Sn and HCl (A. G. 
 Perkin, C. J. 43, 190). Orange needles (from 
 xylene). Very slightly soluble in boiling water. 
 Euby prisms (from dilute alcohol). 
 
 Salts. — Forms two hydrochlorides. — 
 (B"HCl),PtCl,.— B"(2HCl)PtCl,. 
 
 AMIDO-PHENYLENE OXIDE OeHsNO i.e. 
 CjHs(NH2)0 (?). Di-amido-di-phenylene di- 
 oxide. From nitro-phenylene oxide by alcoholio 
 ammonium sulphide (Marker, A. 124, 251). Yel- 
 low needles, si. sol. water, v. sol. hot alcohol. — 
 B',H2PtCl,. 
 
 DI-AMIDO-DIPHENYLENE-QUINOXALINE 
 .N.C.CsH, 
 Oe'B.^CH'S,^)^ I II I . Formed by the action 
 
 ^N.O.CeH^ 
 of phenanthraquinone upon tetra-amido-benzene 
 [1:2:4:5]. Orange-yellow needles. Nearly insol. 
 acetic acid. Weak base. Dissolves in cone. 
 H2SO4 with a greenish-blue colour, passing 
 through violet into red on dilution (Nietzki a. 
 Hagenbach, B. 20, 338). 
 
 AMIDO-PHENYIENE-TIREA OjHjNjO i.e. 
 
 00<^2>CbH3(NH2) [1:2:4]. Formed by re- 
 ducing di-nitro-phenyl-urethane with tin and 
 HCl (Hager, B. 17, 2631). 
 
 Salts. — B"H2SnOl4 : long needles. — 
 B"CsH2(N02)30H: greenish-yellow needles. 
 
 o- AMIDO -PHENYL -ETHANE CgHuN i.e. 
 C„H,(NH2).CH2.CH, [1:2]. o-Ethyl-phenyl- 
 
 amine. - Amido - ethyl - benzene. (211°). 
 S.G. — "983. From o-nitro-phenyl-ethane, tin, 
 and HCl (Beilstein a. Kuhlberg, A. 156, 206). 
 Liquid at -10°. Salt.— B'HNO,. 
 
 Acetyl derivative CgHuAcN. [112°]. 
 (305°). 
 
 Benzoyl derivative CaH,jBzN. [147°]: 
 small glittering plates (Paucksch, B. 17, 2800). 
 
 o-Amido-phenyl-ethane sulphonic acid 
 CjH3Et(NH2).S03H. Formed by sulphonation of 
 the acetyl derivative. White needles (P.). 
 
 ^-Amido-phenyl-ethane C„H,(NH2).CH2.CHa 
 [1:4]. p-Ethyl-phenyl-amine. ' Phenethyla/mine.' 
 [-5°]. (214°). S.G. 22 -975. From jj-nitro- 
 phenyl-ethane by reduction (B. a. K.) or from 
 aniline by heating with ethyl alcohol and 
 ZnClj (Benz, B. 15, 1647). Formed also when 
 ethyl-aniline hydrochloride is heated at 300° 
 (Hofmanu, B. 7, 526). Colourless oil ; volatile 
 with steam. Salts. — "B'HNOj: small needles 
 or prisms, si. Bol. cold, v. sol. hot, water. — 
 B'jHjSOj : large white plates, si. sol. cold water, 
 m. sol. dilute HjSO^.— B'HCl.— B'^PtClj. 
 
 Acetyl derivative C,H4(NHAo).C9H, 
 [95°]. (316°). 
 
AailDO-PHENYL-MERCAPTAN. 
 
 irr 
 
 Bemoyl derivative CjHjfNHBzjOjH,. 
 [151°] : long needles (P.). 
 
 w-Amido-phenyl-ethane OeHs.CHj.CHj.NKj. 
 [198°]. Phenylethyl-atnine. 
 
 Formation. — 1. By dry distillation of a-amido- 
 phenyl-propionio acid (g. v.) (Schulze a. Barbieri, 
 /. pr. [2] 27, 346 ; Erlenmeyer a. Lipp, A. 219, 
 202). — 2. By action of zinc and ECl upon the 
 cyanhydrin of benzoic aldehyde, or upon 
 amygdalin fPileti, JS. 12, 297, 1700).— 3. By 
 action of bromine on an alkaline solution of 
 phenyl-propionamide (Hofmann, B. 18 2740). 
 
 Preparation. — By reducing an alcoholic 
 solution of benzyl cyanide with zinc and HCl 
 (Bernthsen, A. 184, 290), di-phenylethyl-amino 
 (C5H5.CH2.CH2)2NH, and tri-phenylethyl-amine 
 (CjHsCH^CHj),]^^, being also formed (Spica, O. 
 1875, 124 ; 1879, 566). 
 
 Properties. — Liquid ; si. sol. water. Absorbs 
 COj from the air, being converted into a solid 
 carbonate [105°], out of which, on heating, 
 another carbonate, [88°], sublimes. Oxidised to 
 benzoic acid by chromic mixture. 
 
 S a 1 1 s.— B'HCl, [217°] : trimetric tablets (from 
 cold alcohol) or satiny plates (from alcohol-ether) : 
 V. sol. alcohol or water, insol. ether. — B'^H^PtClj; 
 more soluble in hot water than in hot alcohol. 
 
 Di-amido-di-phenyl-ethaue v. Di-amido-di- 
 
 BENZYL. 
 
 co-AMIDO-TEI-PHENYL-ETHANE CjoH^N 
 i.e. CPh3.OH2.NH2. [116°]. Promtri-phenyl-aceto- 
 nitrile by reduction with zinc and HOI. Crystals ; 
 V. sol. ether, si. sol. cold alcohol. The hydro- 
 chloride forms needles, [247°],v. si. sol. water, 
 V. sol. alcohol (Elbs, jB. 17, 700). 
 
 AKIDO-FHEinrL-EIHYLENE v. Amido- 
 
 STYEENE. 
 
 Di.^-ainido-di-pheny!-etliylene 0„H,4N2 i.e. 
 C2H2(CsH^.NH2)2. Di-anUdo-stilbene. [227°]. 
 
 WormaUon. — 1. By reduction of di-jj-nitro- 
 di-phenyl-ethylene with tin and HOI. — 2. By 
 reduction with SnCl2 of the brownish-red pro- 
 duct of condensation (azoxy-di-phenyl-ethylene ?) 
 obtained by the action of sodium methylate or 
 alcoholic NaOH upon ^-nitro-toluene. 
 
 Reactions. — By nitrous acid it is converted 
 into a tetrazo-compound which by combination 
 with the sulphonio acids of amines and phenols 
 yields a series of colouring-matters which dye 
 cotton from a soap bath. Thus (a)-naphthol- 
 sulphonio acid gives a bluish-violet,(;8)-naphthol- 
 (B)-di-sulphonic acid a blue,(a)-naphthylamine- 
 Bulphonio acid a red, and salicylic acid a 
 yellow, colouring-matter. 
 
 Di-acetyl derivative 02H2(08Hi.NHAc)j ; 
 [312°] (Bender a. Sohultz, B. 19, 3234). 
 
 Si-n-amido-di-phenyl-ethylene - di-carbozylic 
 C„Hj(NH2).C.0O 
 anhydride 1| >0. [280°]. Formed 
 
 C8H4(NH2).0.0O 
 by reduction of the nitro compound (Beimer, 
 B. 14, 1802). Small plates. Insol. most solvents. 
 
 Di-p-amido-di-phenyl-ethylene-di-snlphonio 
 acid C2H2(0eH3(NHj)S03H)2. Di-amido-stilbene- 
 di-sulphonic-acid. Obtained by reduction with 
 zinc-dust of the brown product (azoxy- or azo- 
 di-phenyl-ethylene-di-sulphonio acid ?) which is 
 formed by boiling ^-nitro-toluene-o-sulphonic 
 acid 08H3Me(NH2)S0sH [1:4:2:] with aqueous 
 KaOH. Microscopic needles. Nearly insol. 
 
 water. Its salts are easily soluble. By nitrous 
 acid it is converted into a tetrazo-compound 
 which by combination with amines or phenols 
 gives colouring-matters which have the property 
 of dyeing cotton from a soap bath (Bender a^ 
 Schultz, J3. 19, 3234). 
 
 o-AMIDO-PHENYI-GLYOXYlIC ACID v. 
 
 ISATIO ACID. 
 
 m-Amido-phenyl-glyozylic acid CgHjNOj i.e 
 CbHj(NH2)CO.C02H [1:3]. Colourless prisms or 
 needles. [270°-280° with decomposition]. Pre- 
 pared by reduction of m-nitro-phenyl-glyoxylic 
 acid with alkaline FeSOj. 
 
 Salts. — A'Ag: sparingly soluble crystalline- 
 powder. — OjHjNOs.HCl : soluble flat prisma 
 (Claisen a. Thompson, B. 12, 1946). 
 
 p - AMIDO -3-m- PHENYL - GUiNIDINE 
 OT-CAEBOXYLIC ACID CnHnN^Oj i.e. 
 [l:4]NH2.C„H^.NH.C(NH).NH.O„H^.CO,H. 
 Amido-phenyl-bemzglycocyarmne. Prepared by 
 heating cyano-carbimido-amido-benzoic acid 
 (v. p. 157) with ^-phenylene-diamine (Griess, B. 
 16,338). Small prisms. Salt.— B"H20l2. 
 
 ^-amido-s-di-phenyl - guanidine o-carboxylic 
 
 acid. Anhych-ide H2N.C„H^.NH.C<^^^»^*> 
 
 Amido-phenyl-hemglycocyamidine. Formed by 
 boiling di-cyano-amido-benzoyl (v. p. 155) with 
 an aqueous solution of p-phenylene-diamine 
 (Griess, B. 18, 2421). Very small white needles ; 
 T. sol. hot water, m. sol. alcohol. 
 
 AMIDO-PHENYL-HYDBOXIDE v. Amiso. 
 
 PHENOL. 
 
 m-AMIDO-PHENYL-HYDRAZINE O3H5N, i.e. 
 CjHi(NH2).NH.NH2 Formed by saponification 
 of the oxamic acid OeHj(NH.0202.0H).NH.NH2 
 which is obtained by reduction of m-diazo- 
 phenyl-oxamio acid OeH^(NH.C202.0H).N2Cl 
 with SnOl2 (Griess, B. 18, 964). V. sol. alco- 
 hol and ether, si. sol. water. Very oxidisable. 
 
 Amido-phenyl-hydrazine sulphonic acid 
 CsH3(NH2)(N2Hs)(S03H) [3:1:6]. Formed by 
 reduction of nitro-phenyl-hydrazine sulphonio 
 acid with NH^HS or SnOl2 (Limpricht, B. 18, 
 2194). Very soluble in water. Salts:— A'H.HCl 
 easily soluble fine white needles. — A'HHjSO^; 
 microscopic needles. — "A'H.HNOj: prisms. 
 
 AMIDO-DI-PHENYL-KETONE v. Amibo- 
 
 BENZOPHENONE. 
 
 o-AMIDO-PHENYL-MERCAPTAN 
 C,H,NS i.e. CA(NH2)(SH). Amido-phenyl- 
 sulphydrate. [26°]. (234°). 
 
 Formation. — 1. By fusing benzenyl-amido- 
 phenyl-mercaptan (g. v.) with potash (Hofmann, 
 B. 12, 2363).— 2. Anhydro-oxalyl-amido-phenyl- 
 mercaptan (easily prepared from acetanilide and 
 sulphur) is fused with potash (3 pts.). The yield 
 is nearly theoretical (Hofmann, B. 13, 1230). 
 Colourless needles, very easily oxidised. It 
 forms products of condensation with acids, 
 aldehydes, and nitriles ; thus acetic acid, acetyl 
 chloride, acetonitrile, and aldehyde each pro- 
 duce ethenyl-amido-phenyl mercaptan (q. v.) 
 
 0,H,<^>0.CH3. 
 
 ^-Amido-diphenyl-mercaptan 
 [1:4] H2N.OeH4.O3H4.SH [1:4]. Prepared by re- 
 ducing j)-nitro-diphenyl sulphochloride with tin 
 and HOI (Gabriel a. Bamberger, B. 13, 1410). 
 
 Salt. — B'HCl: small glittering prisms. 
 
 N 
 
178 
 
 AMIDO-PHEITYL-METHANE. 
 
 AMIDO-PHEITTL-METHANE v. Toluidinb. 
 
 m-Amido-di-phenyl-methane CijHuN i.e. 
 C.HJ.OHJ.C5H4.NHJ. [46°]. Formed by reducing 
 •t-nitro-dj-phenyl-methane (Becker, B. 15, 2092). 
 
 Acetyl derivative. [91°]: pearly plates. 
 
 p-Amido-di-phenyl-methane. [35°]. Formed 
 bj reducing ^'-nitro-di-phenyl methane with tin 
 und HOI (Easier, B. 16, 2718). The sulphate is 
 b1. sol. cold water. 
 
 di-amido-di-phenyl-methane CisH,„(NH2)2. 
 ![85 "]. Formed by reducing (o)-di-nitro-di-phenyl- 
 methane (Doer, B. 5, 795). Pearly plates ; si. 
 sol. water fPraetorius, A. 194, 348). The 
 sulphate is v. si. sol. water. 
 
 Tetra-amido-di-plienyl-methane C,3Hg(NHj),. 
 [161°]. By reduction of the nitro compound 
 [172°] (Staedel, A. 218, 341). White needles 
 (from benzene). M. sol. water, si. sol. benzene. 
 
 Acetyl derivative CijHg(NHAo)4. Crys- 
 talline powder. V. si. sol. water ; m. sol. alcohol. 
 
 Amido-tri-phenyl-metbane CigH|,N i.e. 
 CHPhj.C,Hj.NH2. [84°]. Prepared by heating 
 aniline hydrochloride with di-phenyl-carbinol 
 and ZnClj at 180° (Fischer a. Eoser, B. 13, 674 ; 
 
 A. 206, 155). Prisms or plates. la a weak 
 base. The benzene compound (C,jH„NOjHb) 
 forms long colourless needles. Salt s. — ^B'HGl : 
 needles, si. sol. water. — B'HjPtOl,. 
 
 Di-amido-tri-phenyl-methane C„H„N2 i.e. 
 C«H,.CH(C,H,NH,),. [139°]. 
 
 Formation. — 1. From benzylidene chloride, 
 aniline, and zinc dust (Bottinger, B. 12, 976). — 
 2. From di-amido-tri-phenyl-oarbinol by re- 
 ducing with zinc dust (Doebner, A. 217, 246 ; B. 
 15, 236).— 3. By heating aniline hydrochloride 
 with benzoic aldehyde and fuming HCl (Maz- 
 zara, 0. 14, 510). 
 
 Preparation. — A mixture of benzaldehyde 
 (10 pts.), aniline sulphate (28 pts.), ZnCl^ (20 
 pts.) and a little water, is heated on a water 
 bath for several hours, the fused mass is boiled 
 with dilute HjSOj, diluted, filtered, and the 
 base precipitated with NH3 ; yield 80 p.o. of the 
 theoretical (Fischer, B. 15, 676). 
 
 Properties. — Colourless crystals (from ether) 
 [139°]. Prisms containing benzene of crystal- 
 lisation (from benzene) [106°]; at 120° the 
 benzene goes off. V. si. sol. water, sol. alcohol 
 or ether. 
 
 Additional References. — C. Bottinger, B. 11, 
 276, 840 ; 13, 958 ; 0. Fischer, A. 206, 147, 153; 
 
 B. 13, 665. 
 Tri-amido-tri-phenyl-methane C„H,gN, i.e. 
 
 CH(C5Hj.NH:j [1 : 4]),. Para-leucamline. [148°]. 
 
 Formation. — 1. By reducing tri-nitro-tri- 
 phenyl-methane with zinc dust and glacial 
 acetic acid (0. a. E. Fischer, A. 194, 272).— 2. 
 By reducing para-rosaniline (Hofmann, Pr. 12, 
 9). — 3. By reducing nitro-di-amido-tri-phenyl- 
 methane, prepared from aniline hydrochloride, 
 p-nitro-benzoic aldehyde and ZnClz (Fischer a. 
 Greiff, B. 13, 670 ; Fischer, B. 15, 678). 
 
 Properties. — Colourless plates. Eeadily con- 
 Tcrted by oxidation into para-BosANiLiNE {q.v.). 
 
 Salts. — B"'H3Cl,aq : short prisms, si. sol. 
 *lcohol, ether, and HClAq. — The sulphate 
 forms needles, v. sol. water, si. sol. alcohol, 
 insol. ether. — The oxalate forms prisms, v. 
 sol. _ water.— The platinochlotide forms 
 sparingly soluble short needles. 
 
 Tri-atetyl derivative [177^. Thin 
 
 tables; when oxidised by K^CrjO, and aootia 
 acid it gives tetra-aoetyl-para-rosaniline. 
 
 Tri-henzoyl derivative [149°]. Colour- 
 less needles ; sol. alcohol, v. si. sol. water, ether, 
 and benzene (Eenouf, B. 16, 1301). 
 
 ?n-p-p-Trl-amido-tri-phenyl-methaiie 
 [1:3] H,N.CeH,.CH(OgH4.NH2[l:4])2. Pseudo- 
 leucaniUne. [150°]. Obtained by reducing «t- 
 nitro-di-^-amido-tri-phenyl-methane (Fischer, B. 
 13, 673). Colourless crystals ; sol. alcohol, si. 
 sol. ether or benzoline. Crystallises with benzene 
 in white needles of C,sH,„N3C„H;5 [145°]. Gives, 
 on oxidation, a violet colouring-matter. 
 
 S a 1 1 s.— B2"'3H2PtCl8 : yellow crystalline pp., 
 V. sol. water, m. sol. alcohol. 
 
 o-jp-p-tri-amido-tri-phenyl-methane 
 [1:2] H2N.C„H,.CH(OgH,NH,[l:4]),. [165°]. 
 
 Formed by reduction of the o-nitro-di-p-amido- 
 tri-phenyl-methane obtained by heating o-nitro- 
 benzoio aldehyde with aniline sulphate and 
 ZnClj. SmaU crystals. On oxidation it gives a 
 brown colouring matter. 
 
 Salts. — ^B"'H3Cl3: colourless easily soluble 
 needles. The sulphate forms small quad- 
 ratic tables, V. sol. water, si. sol. alcohol. The 
 oxalate forms small soluble needles (Eenouf, 
 B. 16, 1304). 
 
 AMISO-FHENYL METHTL KETONE «. 
 Amido-aoetophenonb. 
 
 p-AMIDO-DI-PHENYl-METHYI-PYBAZOL. 
 CABBOXYLIC ACID C^HisNjOj i.e. 
 N NPh 
 
 II I 
 
 C„H4(NH,).C.C(C02H):CMe [251°]. Formed by 
 reduction of p-nitro-di-phenyl-methyl-pyrazol- 
 carboxylic acid with SnCl^ (Knorr a. Jodioke, 
 B. 18, 2259). Crystalline powder. Sol. alcohol, 
 ether, acids, and alkalis, insol. water. It evolves 
 CO2 at its melting-point. 
 
 AMIDO-(P2/.3)-PHENYI-(P2/.2)-METHYL 
 
 ftUINOLINE 
 
 C,5H,A»-«-CaH4^ 
 
 / 
 
 CH:CMe 
 
 I 
 
 '\n : C.C«H4(NH2) 
 [115]. Obtained by reduction of m-nitro -phenyl- 
 methyl-quinoliue with tin and HCl (Miller a. 
 Kinkelin, B. 19, 533). Prisms. Very soluble in 
 alcohol and benzene, tolerably in ether. Has no 
 dyeing power, although it is isomeric with 
 flavaniline. By further reduction with tin and 
 HCl it yields a tetrahydride. 
 
 Salts. — The mono-acid salts are yellow, the 
 di-acid colourless. — B"H2Cl2 2aq: easily soluble 
 glistening prisms. B"H2Cl2PtCl4 2aq : orange 
 tables. — ^B"H2Cl2PtCl4 : concentric yellow plates. 
 
 jn-Amido - (P^. 3)- phenyl -(P^. 2)-methyl- 
 >OH,.CHMe 
 tetrabydro-qninoliue C^A \ 
 
 \nH.CH.C„H4(NH2). 
 Formed by reduction of amido-phenyl-methyl- 
 quinoline with tin and HCl. 
 
 Di-acetyl derivative CuHuNjAoj. [178°]. 
 Thin colourless prisms ; sol. hot alcohol. 
 
 ^Amido - (Py. 3) - phenyl - (Py. 1) - methyl- 
 qninoline v. FiiAvaniline. 
 
 AUISO- PHENYL -HYDBO-QTTINOLINE v. 
 
 AMIDO-PHENyL-QUINOIiINB. 
 
 ^-AMIDO-PHENYL-OCTANE C^HaN i.e. 
 
 HjN.CaHj.CgH,,. Capryl-phenyl-andne, Phen- 
 
 ^capryl-amine. (291° oorr.). Formed by heating a 
 
 mixture of aniline, oapryl alcohol, and ZnCl2 at 
 
 280°. Or by heating aniline hydrochloride and 
 
AMIDO-PHENYL-PROPIONIO ACID. 
 
 179 
 
 napryl alcohol at 200°-290° (Beran, B. 18, 139). 
 Fluid at -20°. Colourless oil. 
 
 Salts. — B'jHjSO,: v.sol.hot water, v. si. sol. 
 cold. — B'jHjjCjO, : small plates, v. sol. alcohol and 
 hot water, si. sol. cold water. 
 
 Benzoyl derivative C„Hj,.NHBz. [109°]. 
 Slender felted needles, v. sol. alcohol and ether 
 when hot, si. sol. when cold. 
 
 o-Amido-phenyl-octane. Prom the nitro- 
 compound (Ahrens, B. 19, 2725).— B'^H^SnClj. 
 
 f-Amido-oi-pheuyl-n-octane. [19"5°]. (311° 
 eor.). From n-ootyl alcohol, aniline, and 
 ZnCl,(B.).— B'HCl.— B'ASO,.— B'jHjCjO,. 
 
 Formyl derivative. [56°]. 
 
 Acetyl derivative. [93°]. 
 
 Benzoyl derivative. [117°]. 
 
 AMIDO-OPIANIC ACID C„H„N05 i.e. 
 CeH(0Me)j(NHj)(CH0)(C02H) [6:5:3:2:1]. Di- 
 methoxy-amido-aldehydo-benzoic acid. From 
 nitroso-opianio acid, SnClj, and HCl. Crystalline. 
 Salt.— HA'HCl: needles, decomposed by water. 
 
 Beactions. — 1. Barj/to-«;aiergive ablue-violet 
 colour. — 2. FcjCIb gives a green colour in solu- 
 tions of NH,A'. — 3. Hot AojO gives granules of 
 C24H2<N20„ [233°] (Kleemann, B. 20, 876). 
 
 DI-AMIDO-DI-PHENYL OXIDE C.JEjjNjO 
 i.e. (CsHi.NH2)i,0. [185°]. From the nitro 
 compound (Hoffmeister, A. 159, 208). The 
 sulphate forms slender needles. 
 
 AMIDO-PHENYL-PENTAKE v. Amido-amyl- 
 
 BENZENE. 
 
 TRI - AMIDO - TBI - PHENYL - PHOSPHINE 
 OXIDE C,8H,8N3PO i.e. OF{Gfi^.l!\B^),. [259°]. 
 Obtained by reduction of tri-nitro-tri-phenyl- 
 phosphine-oxide (Michaelis a. Soden, B.17,928). 
 \Vhite prisms. Soluble in hot water, hot alcohol, 
 and acetone, sparingly in cold water, cold alcohol, 
 and ether. Its salts are very soluble in water. 
 
 Tri-acetyl derivative 
 0P(CjH,.NHAc)3aq. [188°], colourless crystals. 
 
 Tri-ienzoyl derivative 0P(0|iH4.NHBz), 
 [o. 180°], orystaUine powder. 
 
 DI ■ AIIIDO ■ DIPHENYL . PHTHAIIDE 
 /C^(O.H,NH,),. 
 Oa,H„NjO, i.e. CsH^< >0 
 
 \cdo 
 
 Lactone of di-amido-tri-phenyl-carbinol carbo- 
 xylio acid. [180°]. Tables. Prepared by 
 reduction of dinitro-diphenyl-phthalide. By the 
 action of HNOj it gives phenol-phthalem (Baeyer, 
 B. 12, 642 ; A. 202, 66). 
 
 AMIDO-PHENYL-PIPEEIDINE C„H„N2 i.e. 
 C5NH,„.CsH4.NH2. [40°]. Formed by reduction 
 of the corresponding nitro-compound [105°] with 
 SnClj and HCl. — B"H2CLjaq : large colourless 
 crystals (Lellmann, B. 20, 681). 
 
 ^-AMID0-(8-PHENYL-PK0PANE C,H,3N i.e. 
 H2N.CjH4.CH,.CHj.CH3. Amido-propyl-benzene. 
 Propyl-phenyl-amine. Phenpropylamine. (225°). 
 From anUine, ZnClj, and propyl alcohol at 270° 
 (Louis, B. 16, 105 ; Francksen, B. 17, 1220). 
 Iiiquid, volatile with steam ; v. si. sol. water. 
 Salts : B'HCl : lamins, [204°].— "B'^H^PtCle.— 
 B'HBr. [213°].— B'HI.— B'jH^SO, : laminre, si. 
 Bol. cold water. — B'jHjCjOj: si. sol. cold water. 
 
 Acetyl derivative CgEgjAoN. [87°]. 
 
 Benzoyl derivative OjHjjBzN. [115°]. 
 
 Ij-Amido-a-nhenyl-propane 
 HjN.CeH4.CH(CH3).CH3. Armdo • isopropyl- 
 benzene (217°). Similarly prepared from iao- 
 
 propyl alcohol (L.). Liquid, si. aol. water. 
 Salts: B'jHjSO,: al. sol. cold water.— B'^HAO,. 
 
 Benzoyl derivative [115°]: laminae. 
 
 See also Cdmidiiie and Phenxl-pbopyl- 
 
 AMINE. 
 
 - AMIDO - PHENYL - PEOPIOLIC ACID 
 
 CjHjNO^ i.e. C„H<(NHj).C:C.C02H. 
 
 Preparation. — An ammoniacal solution of 
 o-nitro-phenyl-propiolio acid is slowly added to 
 a cold solution of FeSO, (11 pts.) saturated with 
 NH3 ; after 1 or 2 hours' standing the mixture is 
 filtered and the amido-acid ppd. from the filtrate 
 by adding HCl in slight excess ; yield : 65 p.c. 
 of the nitro-aoid used (Eiohter, B. 16, 679). 
 
 Pj-qperiies.— Microscopic needles. Soluble 
 in alcohol, sparingly in ether, nearly insoluble 
 in water, benzene, chloroform, and Ugroine. 
 Dissolves in aqueous acids. Decomposes on 
 heating to about 125° and on boiling with water, 
 in the latter case forming o-amido-acetophenone 
 and CO2. By boiling with NaOH and then 
 adding HCl a splendid red colour is produced. 
 
 Salt. — A'Ag" : insoluble pp. 
 
 Ethyl ei/ier A'Et— [55°] needles (Baeyer a. 
 Bloem, B. 15, 2147). 
 
 a - AMIDO - o - PHENYL - PROPIONIC ACID 
 CgHnNOji-e. CH3.C(CsH5)(NH2).C02H. Amido- 
 hydro-atropic acid. From the nitrile by treat- 
 ment with HCl (Tiemann a. Kohler, B. 14, 1981). 
 Feather-liie, satiny, needles. Sublimes about 
 260°. V. e. sol. water, insol. alcohol and ether. 
 Converted by nitrous acid into atrolaotio acid. 
 
 Nitrile CH3.CPh.(NHj).CN. Yellow oil. 
 
 /3-Amido-a-phenyl-propiomc acid 
 CH2(NH2).CH(CbHJ.C03H. [169-5°]. A product 
 of action of cone. NHjAq on )3-bromo-o-phenyl- 
 propionic acid (Fittig a. Wurster, A. 195, 158 ; 
 Merling, A. 209, 11). Plates (from water). SI. 
 sol. cold water. 
 
 o-Amido-a-phenyl-propionic acid. Anhydride 
 
 or lactam C«Hj<^gjy.g^CO. [119°]. Atroxindol. 
 
 Formed, instead of the acid, by reducing 
 CsH4(NOj).CHMe.C02H. Needles (from dUute 
 HCl). SI. sol. cold water, forming a, neutral 
 solution ; sol. alcohol and ether. When quite pure 
 it has a pleasant smell. Slightly volatile with 
 steam. It dissolves in alkalis but is reppd. by 
 COj (Trinius, A. 227, 274). 
 
 p-Amido-a-phenyl-propionic acid 
 CH,.CH(CaH4NHj).C02H. [128°]. From nitro- 
 hydro-atropic acid, Sn and HOI (Trinius, A. 
 227,267). Salt.— HA'HCl; needles; v. sol. water. 
 
 a-Amido-;3-pIieiiyl-propiouic acid CgH„N02 
 i.e. CaH5.CH2.CH(NH2)C02H. 
 
 Amido-hydro-cinnamic acid, 
 
 Occti/rrence. — In the radicles of germinating 
 lupin seeds, together with other amido-acids. 
 Forms about 1 p.c. of the dry seed. The mixture 
 is heated with cupric hydrate and filtered, the 
 acid is isolated from the residue by treatment 
 with HjS and subsequent evaporation (Schulze 
 a. Barbieri, J.pr. [2] 27, 342 ; B. 14, 1785). 
 
 Formation. — From its nitrile by HCl (Erlen- 
 meyer a. Lipp, A. 219, 194). The acid formed 
 in this way is perhaps not identical with that 
 in lupin seeds. An amido-phenyl-propionic acid 
 identical with that in lupin seeds occurs among 
 the products of the decomposition of proteids by 
 HCl. It melts at [275°-280°] and is optically 
 active, while the acid from phenyl-acetic alda- 
 
 2ll3 
 
180 
 
 AMIDO-PHENYL-PROPIONIC ACID. 
 
 hyde melts at [263°-26f!°] and is inactive (Schulze 
 a, NageU, S. 11, 201). 
 
 Properties. — Glittering, anhydrous, plates 
 (from hot saturated solutions) ; groups of slender 
 needles, containing aq (from dilute solutions) 
 (S. a. B.). Satiny plates (from alcohol) ; short 
 anhydrous prisms or stars (from water) (B. a. L.). 
 Sweet taste. Neutral reaction. M. sol. water, 
 V. si. sol. alcohol, insol. ether. Small quantities 
 may be sublimed. Gives no colour with Millon's 
 reagent. 
 
 Salts. — CuA'j: insol. water (S. a. B.). — 
 OuA'2 2aq: rosettes of small blue prisms (E. a. 
 L.). — AgA.'. — HA'HCl : prisms or stars ; v. sol. 
 alcohol or water, insol. cone. HCl. — 
 (HA'HCl)jPtCl^.— HA'HN03.-(HA')AS0^. 
 
 Beactions. — 1. With EjCr^O, and HjSOj gives 
 off odour of benzoic aldehyde, and ultimately 
 forms benzoic acid. — 2. When heated it cakes 
 together and at about 270° it melts giving o& 
 COj, HjO, and exo-amido-phenyl-ethane (q. v.) ; 
 the residue may be crystallised from alcohol, it 
 melts at [280°] and has the formula OaHjNO. 
 From the behaviour of the analogous amido- 
 propionio acid, we may suppose this body to be 
 phenyl-lactimide.— 3. By putrefaction it gives 
 phenyl acetic acid. 
 
 Nitrile CjH,.CH2.CH(NH2).CN. From the 
 compound of HON with phenyl-acetio aldehyde 
 by heating with alcoholic NH, at 100° (Erlen- 
 meyer a. Lipp, A. 219, 189). Small crystals. 
 
 Salts. — B'HCl : trimetric prisms; v. sol. 
 alcohol, insol. ether, v. e. sol. water. 
 
 Anhydride or lactam CgHjNO or 
 
 0„H,8NA i-e. Ph.CH2.CH<^^> or 
 
 Ph.CHj.CH<^^^2>CH.CH2Ph. 
 
 Phenyl-lactimide. [291°]. A by-product in 
 the conversion of the acid into amido-phenyl- 
 ethane by the action of heat. Very slender 
 silky needles (from alcohol) forming an electric 
 powder. May be sublimed as woolly needles. 
 V. si. sol. water, HCl, or KOHAq ; insol. ether ; 
 si. sol. glacial acetic acid. 
 
 ;8-Amido-j3-phenyl-propiouic acid 
 CjHs.CH(NHJ.CH2.C02H. 
 
 P-Armdo-hydro-ciMnamic acid. [121°]. Prom 
 j8-bromo-;3-phenyl-propionic acid and cone, 
 aqueous NH, at 0° (Posen, A. 195, 144; 200, 
 97). Large monocliuic crystals (from water) ; 
 m. sol. cold water, v. sol. alcohol, v. si. sol. ether. 
 Boiling HClAq splits it up into NH, and oinnamic 
 acid. Salt. — B'HCl; prisms, v. sol. water. 
 
 Anhydride or lactam 
 
 CsH5.CH<^22>C0. Phenyl-lactimide. [147°]. 
 
 Formed, instead of a sulphate, when the acid is 
 added to H^SO, (1 vol.) diluted with water (1 
 vol.). Needles, insol. cold water, m. sol. hot 
 water, alcohol, or ether. Is not reconverted 
 into the amido acid by prolonged boiling with 
 water. 
 
 o-Amido-i8-phenyl-propionic acid 
 Anhydride or Zac iam CgHgNO i.e. 
 
 °'^KcK^.GK^ °^ ^«^*<CH;ch!> 
 Sydro-carhostyril. Di - hydro - (Py. 3) - oxy - 
 quinoUne. [160°]. Formed, instead of the amido 
 acid, when o-nitro-3-phenyl-propionio acid is 
 reduced by tin and HCl (Glaser a. Buchanan, Z. 
 
 1869, 194). Prisms; v. si. Bol. watei v. sol. 
 alcohol, ether, and warm cone. HOlAq. May be 
 distilled. PCI, at 140° converts it into di-chloro- 
 quinoline. 
 
 Ethyl derivative C8HsN(0Bt). [199']. 
 Formed by reducing the ethyl derivative of 
 carbostyril with sodium amalgam (Friedlander 
 a. Ostermayer, B. 15, 335). SUvery plates. 
 
 m-Amido-;8-plienyI-propionlc acid 
 C5H,(NHj,).CH2.CH2.C02H. m - Amido - hydro - 
 cinnamic acid. [85°]. Formed by reduction of 
 m-nitro-;8-phenyl-propionic acid with tin and 
 HCl (Gabriel, B. 15, 846). Colourless crystals. 
 V. sol. water, alcohol, and ether. Salt. — A'HHCl : 
 colourless needles or scales. 
 
 p-Amido-i3-phenyI-propionic acid 
 C5H^(NH2).CH2.CH2.C02H. p - Amido ■ hydro- 
 cinnamic acid. [131°] (Glaser a. Buchanan, 
 Z. 1869, 195). Prepared by reduction of ^- 
 nitro-phenyl-propionic acid with FeSO< and 
 NH3. Salts.— B'HCl.— B'jHjSO,. 
 
 Acetyl derivative 
 C,Hj(NHAe)02H4.C02H. [143°]. Long colour- 
 less needles or short prisms. Sol. alcohol and 
 ether, insol. CS^ (Gabriel, B. 15, 848). 
 
 a-;3-di-amido-j3-phenyI-propionic acid. 
 
 Anhydride or lactam 
 
 C.H5.CH.CH(NH2).CO 
 NH -' • 
 
 a. Benzoyl derivative 
 CA.CH.CH(NHBz)^CO^ [187°]. Formed b, 
 
 heating benzoyl-imido-oinnamic acid, 
 OsH5.CH.CH.OO2H 
 
 \/ , with strong aqueous NH,. 
 
 NBz 
 Glistening needles or prisms ; sol. hot alcohol 
 and acetic acid, si. sol. ether, insol. water, dilute 
 acids and alkalis. By boiling with HCl it loses 
 NHj giving the benzoyl derivative of a-amido- 
 cinnamic acid (Plochl, B. 17, 1616). 
 
 a-^-di-aniido-j3-phenyl-propionic acid 
 OgHijNjOjaq i.e. CsH4(NH2)CH2.CH(NH2)C02Haq 
 [245°-250°]. p-Amldo-phenyl-alanine. Got by 
 reducing ^-nitro-a-amido-phenyl-propionic acid 
 (Erlenmeyer a. Lipp, A. 219, 219), or by reducing 
 a-^-di-nitro-oinnamic ether and saponifying the 
 product (Friedlander a. Mahly, B. 16, 852 ; A. 
 229, 226). Silky needles (from water), si. sol. 
 alcohol, insol. ether. Neutral ; has a sweet 
 taste. Eeduces salts of gold and silver. Does 
 not give Hoffmann's mercury reaction (A. 87, 
 124). Gives off no NHs when boiled with KOH. 
 Converted by nitrous acid into tyrosine. 
 
 Salts. — HA'2HC1. — HA'HjPtCl^. — CuA'j ; 
 small violet-blue crystals, si. sol. water. — 
 HA'HjSGj : small needles. 
 
 (4,2,1) - di - amido - $ - phenyl - propionic acid 
 (4:2:1), CbH3(NH2)2.CH2.CH2.C02H. 
 
 Anhydride or lactam CjHioNjO ».«. 
 
 H2N.CbH3<^^^2"-'^^>. Amido - hydro - 
 
 carbostyril. (Py. 3)-oxy-{B. S)-amido-di-hydro- 
 gwi/noUne. [211°]. Formed by reducing (4,2,1)- 
 di-mtro-/3-phenyl-propionic acid (Gabriel a. 
 Zimmermann, B. 12, 602). Needles or prisms. 
 Not affected by boiling alkalis. Salt .—B'HCl. 
 
 (4:3:1) -Si-amido-yS-phenyl-propionic acid. 
 [4:3:1] C3H3(NH2)2.CH2.CH2.C02H. Di-anUdo- 
 hydro-cinnamic acid. [144°, dry]. Formed by 
 reduction of m-nitro^-amido-phenyl-propionio 
 
AMIDO-PHENYL SULPHYDRATE. 
 
 181. 
 
 Mid with tin and HGl (Gabriel, B. 15, 2291). 
 Thick crystals containing aq. Sol. alcohol and 
 acetic acid, v. el. sol. ether, chloroform, benzene, 
 and CS,. Dissolves in aqueous acids and alkalis. 
 
 m-iLMlDO-iPy. 3)-PHENTL-(lTriN0LINE 
 .OH:OH 
 C„H„N, t.«. C^h/ I . [120°]. 
 
 \N : C.C„H,(NH2) 
 Formed by reduction of m-nitro-phenyl-quino- 
 line with tin and HCl (MiUer a. Kinkelin, B. 
 18, 1904). Long glistening needles. Distils at 
 a high temperature undecomposed. Sol. ether, 
 benzene, and hot water, v. si. sol. cold water. 
 
 Salts. — B"H2Cl2: easily soluble colourless 
 needles. — ^B"H2Cl^PtCl4 : yeUow orystaUine pow- 
 der. — B"jH2Cl2PtCl4 : long fine needles. — 
 B"H2S042aq : thick colourless prisms. 
 
 (a) - Amido - {Py. 1) - phenyl - qninoline 
 .C(0.H,.NH2):CH 
 ■ /^ I 
 
 C„H,»N, i.e. CA 
 
 \i 
 
 'N= 
 
 =0H 
 
 [150°]. 
 
 Obtained by reduction of the corresponding nitro- 
 compound [187°] with SnCLj. Colourless glisten- 
 ing plates (from alcohol). Y. e. sol. alcohol, 
 benzene, and chloroform, v. si. sol. ether with a 
 bluish-violet fluorescence. Volatilises undecom- 
 posed. Its mono-acid salts have a deep yellow 
 colour and dye wool yellow, the di-acid salts are 
 colourless. — >'B"HI : soluble yellow needles. — 
 ''B"jHjOLiPtCaj : yellow prismatic needles. The 
 ohromateis a sparingly soluble brown pp. 
 (Koenigs a. Nef, B. 20, 627). 
 
 [P) - Amido - {Py. 1) - phenyl - quinoliM 
 .C(C,H4.NHj):CH 
 
 VN= 
 
 I 
 
 =CH 
 
 [198°]. 
 
 Obtained by reduction of the corresponding nitro- 
 compound [118°] with SnClj. Four-sided prisms. 
 SI. sol. alcohol and benzene, v. sol. chloroform, 
 V. si. sol. ether. The ethereal solution has a 
 bluish-violet fluorescence. It volatilises unde- 
 composed. Its mono-acid salts have a yellow 
 colour and dye wool yellow, the di-acid salts are 
 colourless. — ''B"H2Cl2PtCl4 : yellow prisms, sol. 
 HCl, nearly insol. water (Koenigs a. Nef, B. 20, 
 628). 
 
 Amido-phenyl-qninoline. [136-5°]. V.D. 7-67 
 (for 7'62). Obtained by heating quinoline hydro- 
 chloride with aniline (Jelliuck, M. 7, 351). 
 Yellowish white needles ; insol. cold water, sol. 
 benzene, alcohol, and chloroform. 
 
 Salts .— B"2HC1.— B"H2PtCl„. 
 
 Methylo-iodide. B"MeI. [220°]. 
 
 m-Amido-(P^. 3)-phenyl-hydroqainoliue 
 
 yCHo.CH- 
 
 c,nj 
 
 < 
 
 NH.CH.C5H,(NH2) 
 
 Thick syrup. 
 
 Formed by reduction of rn-amido-phenyl-quino- 
 line or of m-nitro-phenyl-hydroquinoUne with 
 tin and HCl (MiUer a. Kinkelin, B. 18, 1907).— 
 B"H2Cl2 : monoclinio tables. 
 
 {Py. l:2)-AMID0-PHEN?L-IS0CniIN0LINE 
 
 0„H,2Njt.e.C,H,< 
 
 / 
 
 ,C(NH2):CPh 
 
 [0. 100°]. 
 
 *\CH:N 
 
 Formed by reduction of {Py. 4:l:2)-ohloro-nitro- 
 phenyl-isoquinoline by heating with HI and P 
 (Gabriel, B. 19, 834). Yellowish plates or 
 needles. Easily soluble in ordinary solvents, 
 moderately in ether and ligroine. Dissolves 
 
 readily in acids. Salts. — ^B'HI: yellow crys- 
 tals. — B'jHjOljPtClj : long orange-red needles. 
 — B'HCl" : flat needles. 
 
 BI-AMIDO-SI-FHENTL SULPHIDE 
 C.jHijN^S i.e. (CeH4NH2)2S. Thioaniline. [105°]. 
 Mol. w. 216. Obtained by heating aniline 
 (6 pts.) with sulphur (1 pt.) at 160°, with 
 gradual addition of PbO (Merz a. Weith, B. i, 
 384) ; or from di-phenyl sulphide by nitration 
 and reduction (Krafft, B. 7, 384). A small 
 quantity is got by the action of SjClj on aniline 
 (Schmidt, B. 11, 1168). Long thin needles 
 (from water). V. si. sol. cold water, si. sol. hot 
 water, v. sol. alcohol, ether, and hot benzene. 
 Not attacked by hot cone. HCl, by hot alcoholic 
 EOH, or by sodium-amalgam. Its solutions 
 give a blue colour when warmed vsdth Fe^Cl,. 
 Cone. HjSOj dissolves it vrith violet colour. 
 
 Salts. — ^B"H2Cl2 2aq: prisms, v. sol. water, 
 si. sol. alcohol or cold cone. HCL— B"HC12aq. — 
 B"H2PtCle. — B"H2S04aq. — B"2HjS0,aq. — 
 
 B"H2C204. 
 
 Diacetyl derivative (CaH4NAcH)jS. 
 [215°]. Needles. 
 
 Si-o-amido-di-phenyl di-snlphide Oj^Hi^N.^S, 
 i.e. (CeH^NHjjaSj. [93°]. Prepared by oxidising 
 o-amido-phenyl meroaptau with Fe^Clj (Hof- 
 mann, B. 12, 2363). Plates ; insol. water, sol. 
 alcohol. BeadUy reduced back to the mer- 
 captan. The hydrochloride forms laminee, si. 
 sol. HClAq. 
 
 Si-p-amido-di-phenyl di-snlphide 
 (CjHjNHJjSj. [79°]. Formed by saponifying 
 its acetyl derivative with dilute H^SO,. Long 
 greenish needles (from water) ; v. si. sol. water, 
 V. sol. alcohol. 
 
 Salts. — B"H2S042aq: small needles. 
 
 Di-acetyl derivative (05H4NAcH)2S2. 
 [c. 217°]. Formed, together with the diacetyl 
 derivative of di-amido-di-phenyl tri-snlphide, 
 by heating acetanilide with SjOlj at 100° 
 (Schmidt, B. 11, 1171). 
 
 Si - amido - di - phenyl tri - sulphide. Di- 
 acetyl derivative (CbH^NAcH^jSj. [214°]. 
 Prepared as described above ; forms lamiuce 
 (from glacial acetic acid). 
 
 AMIDO-DI-PHENYL SXILPHONE 
 C,2H„NS02 i.e. C8H5.S02.C8H,.NH2. Amido- 
 sulphobemide. From nitro-di-phenyl sulphone 
 by alcoholic ammonium sulphide (Gerioke, A. 
 100, 209). Minute prisms, si. sol. cold water. 
 
 Salts.— B'HCl: [c. 90] ; reddish four-sided 
 prisms.— B'jHjPtClo. 
 
 Di-amido-di-phenyl sulphone C,2H,2N2S02 i.e. 
 (C8H4NH2)2S02. [168°] (Schmid a. Nolting, B. 
 9, 80). Obtained in the same way from di-nitro- 
 di-phenyl sulphone. Four-sided prisms, si. sol. 
 cold water. 
 
 Salts .— B"H2Cl2 : long prisms.— B"H2PtCl5. 
 
 Di - amido - di - phenyl-sulphone di-carbozylio 
 acid ChHjjNjSO. i.e. S02(CeHs(NH2)C02H)2, 
 [above 350°]. Obtained from jp-amido-benzoio 
 acid and fuming H2SO4 at 180° (Michael a. 
 Norton, B. 10, 580). Eose-red tufts of crystals 
 (from water), si. sol. alcohol. 
 
 Salt. — AgjA": small white laminse. 
 
 AMIDO-DI-PHEHYL SULPHONIC ACIDS e. 
 
 AMIDO-DIPHENYIi. 
 
 AMIDO-PHENYL SULPHYDEATE v. Amido- 
 
183 
 
 AMIDO-DIPHENYL DI-SULPHYDRATE. 
 
 AMIDO-BIFEENTL SI-STTLFETDBATS 
 
 C,jH„NSj i.e. 0;jH,(NHJ(SH)j. [153°]. Pre- 
 pared by reducing nitro-diphenyl di-sulpho- 
 chloride with tin and HCl (G-abriel a. Sambergia, 
 B. 13, 1411). Long needles. 
 
 p - AMIDO-DIPHENYL- ij -THIO-GLTCOLLIC 
 ACID C„H„NSOj i.e. 
 
 HjN.C„H,.cX-S.CH,.C02H. [Over 200°]. Formed 
 by action of a chloro-aoetate upon ^-amido- 
 diphenyl p-sulphydrate (Gabriel a. Dambergis, 
 B. 13, 1410). Platea; si. sol. -water. 
 
 o-AMIDO-s-DI-PHENTL-THIO-TJREA 
 CjjH.jNjS i.e. C<,H5NH.CS.NH.CA.NH2. From 
 o-phenylene-diamine and phenyl thio-oarbi- 
 mide in benzene (Lellmann a. Wlirthner, A. 228, 
 212). Glittering prisms, y. sol. alcohol and 
 glacial acetic acid, si. sol. benzene, insol. ether. 
 In a capUlary tube it cakes together at 141° ; at 
 185° aniline distUs out of it ; but at 250° it is 
 still solid : o-phenylene-thio-urea being left : 
 PhHN.CS.NH.C„H,NH2 = 
 
 CS<|^C,H, + PhNH,. 
 
 TO-Amido-di-phenyl-tliio-urea. [148°]. From 
 w-phenylene-diamine and phenyl thio-carbi- 
 mide in benzene (L. a. W.). Amorphous yeUow 
 powder or colourless prisms (from alcohol). V. 
 Bol. glacial acetic acid, m. sol. alcohol, insol. 
 ether and benzene. May be melted without de- 
 composition. Decomposed by long boiling with 
 alcohol, as follows : 2CS(NPhH)(NH.C„HjNH2) = 
 (PhHN.CS.NH),CeH4 + C5H<(NH2)2. The o and p 
 isomerides behave similarly. 
 
 ^-Amido-s-di-phenyl-thio-urea. Prom p- 
 phenylene diamine and PhNCS dissolved in 
 benzene (L. a. W.). Eeddish prisms (from 
 alcohol). Sol. glacial acetic acid, insol. ether or 
 benzene. Begins to decompose at 168°, form- 
 ing j)-phenylene-thio-urea and aniline. 
 
 AMIDO-p-PHENYL-TOLUENE G,,n,,T!^ i.e. 
 0,3H„.NH2. [93°-97°]. Amido-tolyl-phenyl. Ob- 
 tained from ^-phenyl-toluene, CsH5.C5H4.CH3, by 
 nitration and reduction (Carnelley, O. /. 29, 21). 
 
 Salt.— B'HCl. [c. 283°]. 
 
 DI AMIDQ-PHENYL-TOLTL-KETONE 
 C.^H^N^O Le. H2N.CsHj.CO.C,H3(CH3).NH2. 
 [about 220°]. Colourless needles. Formed 
 together with oxy-amido-phenyl-tolyl-ketone and 
 di-oxy-benzophenone by heating commercial 
 rosaniline with water at 270°. 
 
 Di-bensoyl derivative C|.,Hi„0(NHBz).,. 
 [226°] , colourless needles (Liebermann, B. 16, 
 1927). 
 
 DI-AMIDO-PHENYL-TOLYL-METHANE v. 
 
 Dl-AMmO-BENZYL-IOLUENE. 
 
 Di-amido-phenyl-di-tolyl-methane 
 C2,'B^^'^^i.e.G^B.fiS{G,'H,T!lB^)^. [185°] . Formed 
 by heating a mixture of ^-toluidine, y-toluidine 
 hydrochloride, and benzoic aldehyde for several 
 hours at 120° (Ullmann, B. 18, 2094). It forms 
 a compound with benzene, crystaUising in 
 glistening needles. 
 
 Tri-amido-di-phenyl-tolyl-methane 
 C3„H,,N3 i.e. (H2N.CsH,),CH.C,H,.NHj. Lcuc- 
 aniUne. [100°]. Obtained by reducing rosani- 
 line (q. V.) (Hofmann, Pr. 12, 9 ; Eosenstiehl a. 
 Gerber, A. Ch. [6] 2, 341). Small crystals (from 
 boiling water). Sl.,sol. hot water, or ether, v. sol. 
 alcohol. Converted into rosaniline by oxida- 
 tion. Salts. — B"'H3C1, aq. — B"' SHjPtCl..— 
 4J"'3HNO,. 
 
 Tri-acetyl derivative [168'^. Needles, 
 Gives tetra-aeetyl-rosaniline when oxidised with 
 KjCrjOjand acetic acid (Eenouf, B. 16, 1303). 
 
 Tri-jp-amido-phenyl-di-tolyl-methane 
 C2,H3sN3i.e. (H2N.C,H5),CH.0jHj.NH2. Prepared 
 by reduction of nitro-di-amido-phenyl-di-tolyl- 
 methane with zinc dust and HCl (Fischer, B. 15, 
 680). SmaU colourless prisms or long needles. 
 On oxidation it gives a rosaniline which dyes a 
 bluer shade than ordinary rosaniline. 
 
 o-AMID0-s-DI-PHENYL-TIEEAC,3H„NsOi.e. 
 NH2.0eH,.NH.CO.NH05H5. From phenyl cyan- 
 ate and o-phenylene diamine in benzene solu- 
 tion (Lellmann a. Wiirthner, A. 228, 220). 
 Slender silky needles (from alcohol). Y. sol. 
 glacial acetic acid, m. sol. alcohol, v. si. sol. ben- 
 zene, insol. ether. In capillary tubes it cakes 
 together and partially melts at 182°, splitting 
 up into aniline and phenylene-urea, [305°]. 
 
 m-Amido-s-di-phenyl-urea. From m-phenyl- 
 ene diamine and PhNCO in benzene (L. a. W.). 
 Grey needles (from dilute alcohol). V. sol. 
 alcohol, and glacial acetic acid, si. sol. ether 
 and benzene. In capillary tubes it decomposes 
 at 185° into aniline and w-phenylene-urea, 
 [above 300=]. 
 
 p-Amido-s-di-phenyl-urea.Fromp-phenylene- 
 diamine and PhNCO in benzene (L.a. W.). Slender 
 white needles (from alcohol). Sol. glacial 
 acetic acid, v. si. sol. benzene, insol. ether. 
 Decomposes about 210°-220° into aniline and 
 p-phenylene-urea [above 320°]. 
 
 Di-amido-di-phenyl-urea CuHuNjO i.e. 
 CO(NH.CsH,.NH2)2. From tetra-nitro-di-phenyl- 
 urea, (C(iH3(N02)2.NH)2CO by reducing with tin 
 and HCl (Fleischer a. Nemes, B. 10, 1296). 
 LaminiB (from alcohol) ; si. sol. cold water. — 
 
 B'jHjPtCle. 
 
 AMIDO- PHENYL -UEETHANE v. Amido- 
 
 PHENTL-OABBAMIO ETHEK. 
 
 0-AMIDO-PHENYL-VALEEIC ACID 
 
 [1:2] C,H,(NHJ.CH2.CH3.CH2.CH2.C03H. [62^. 
 White needles. Formed by boiling an alcohoUo 
 solution of eso-di-bromo-amido-phenyl-valerio 
 acid with sodium-amalgam. It could not be con- 
 verted into an inner-anhydride even by dehy- 
 drating-agents. Acetyl derivative: [151°] 
 (Diehl a. Einhorn, B. 20, 385). 
 
 AMIDO-PHOSPHENYLIC ACID v. Phos- 
 
 PHINES. 
 
 AMIDO-PHTHALIC ACID CjHjNO^ t.«. 
 
 C,H3(NH3)(C0,H)2 [1:2:3]. 
 
 Salt. — H2A"HSnClj 2aq : needles, got from 
 nitro-phthalic acid by tin and HCl. The 
 hydrochloride gives off CO2 on evaporation, 
 becoming m-amido-benzoic acid (Miller,* A. 
 208, 245). 
 
 Ethyl ether EtjA". Oil ; got by reducing 
 ethyl core-nitro-phthalate. - 
 
 Amido - phthalic acid CeH3(NH2)(C02H)j 
 [1:3:4]. Its hydrochloride splits up, like that 
 of the preceding acid, into COj and »t-amido- 
 benzoic acid (M.). 
 
 Ether -Etji." [95°] (M.). Got by reducing 
 u-nitro-phthalic ether (M. ; Eoenigs, B. 10, 125). 
 Monoclinic prisms (from alcohol). Ethereal 
 solutions show faint blue fluorescence. 
 
 Acetyl derivative [122°]. Minute 
 laminae. 
 
 Amido - iso - phthalic acid OgHiKO, 2aq. 
 [above 300°]. S. -104 at 15°; -92 at 99». 
 
AMIDO-PYROOATECIIIN. 
 
 ISS 
 
 Formed by reducing nitro-iso-phthalio acid, 
 [949°] (Storrs a. Fittig, A. 153, 285 ; Beyer, /. 
 pr. [2] 25, 491). Prisms (from alcoliol) or plates 
 (from water). Solutions give a deep reddish- 
 brown colour with FejClj. 
 
 Salts: EjA."; gives no pps. with salts of 
 Oa or Ba, but pps. with salts of Zn, Cd, Cu, Ag, 
 I'b, and Hg.— NajA".— MgA"4^aq : S. 20 at 
 15°. — OaA"3iaq: S. 7-4 at 15°.— SrA"aq: S. 
 
 8-6 at 15°. — BaA"liaq: S. 5-43 at 15° 
 
 ZnA". — OdA". — AgHA". — HjA"HCl aq. — 
 {HjA"HCl)jPtCl4Biaq : crystals grouped in stars. 
 — H2A"HBr.— HjA"HNO, l^aq. 
 
 Methyl ether Me^A" [176°]; solidifies 
 at 164'. 
 
 Ethyl ether Bt^A" [118°]; solidifies 
 at 113°. Prepared by treating a mixture of 
 nitro-iso-phthalio ether (50 g.), alcohol (300 g.), 
 and cone. HCl (500 g.), with zinc dust at 0°. 
 Tufts of thin plates (from alcohol) or slender 
 needles arranged in crosses (from water). V. 
 gl. sol. water. Solutions fluoresce violet-red. 
 
 Amido-tere-phthalic acid CgH^XOj i.e. 
 C,H3(NH2)(COjH)2 [2:1:4]. Obtained by reducing 
 nitro-terephthalic acid with tin and HCl (Warren 
 de la Rue a. Hugo Miiller, Pr. 11, 112). Thin 
 lemon -yellow prisms ; v. si. sol. cold water, alco- 
 , hoi, ether, or chloroform. Decomposed by heat 
 without previous fusion. Its solution fluoresces 
 blue. 
 
 Di-methyl ether McjA." [126=]. Salts: 
 MejA"HCl : white needles, saponified by water. 
 — (Me2A"HCl)JPtCl, (Ahrens, B. 19, 1636). 
 
 Si-amido-terephtaalic acid GgHgN^O, t.e. 
 C,H2(NH,)2(COjH)2 [3:6:1:4]. 
 
 Ether E\A" [168°]. Formed by the action 
 of bromine upon di-amido-di-hydro-terephthalio 
 ether (di-imide of succino-succinic ether) dis- 
 solved in strong HjSOj. Glistening orange 
 needles. Sparingly soluble in alcohol and ether 
 with a yellow fluorescence. By diazotisation 
 and treatment with Cn-fil^ it is converted into 
 di-chloro-terephthalic ether, which is reduced by 
 sodium-amalgam to terephthalio ether. The 
 sulphate forms very sparingly soluble colourless 
 needles (Baeyer, B. 19, 430). 
 
 AMIDO . PHTHALIDE OjHjNOj i.e. 
 
 C,H3(NH,)<^^p>0 [4:^]. [178°]. Formed by 
 
 reducing nitro-phthalide [141°] (Hoenig, B. 18, 
 3448). Short prisms; sol. chloroform, si. sol. 
 alcohol, q^her, and benzene, v. si. sol. cold 
 water. Salts: B'HCl: needles.— B'^H^PtCls. 
 
 DI - AMIDO - ISO - PHTHALOPHEMONE 
 CjdHjjNjOj. Two isomeric compounds of this 
 formula are obtained by reducing the two 
 di - nitro - phthalopheuones that are got by 
 nitrating iso-phthalophenone 0,H4(CO.CjH5)2 
 [1:8] (Ador, Bl. [2] 33, 56). 
 
 AMIDO-PODOCAEPIC ACID v. Podooabpic 
 
 AOID. 
 
 DI - AMIDO - FSOP AXE v. Tbimethylenb- 
 BUMTNE and Pbopylene-diasiine. 
 
 (3:4:l)-AMIDO-PEOPENYL-BENZ0IC ACID 
 C,„H„NO,i.e.C,H3(NH2)(C3HJCO,H [3:4:1] [94°]. 
 Formation: — ^1. By reduction of nitro-pro- 
 penyl-benzoic acid with FeSO, and NHj. — 
 i. By boiling amido-oxypropyl-benzoio acid 
 with HCl (Widman, B. 16, 2572). Long 
 white needles. Easily soluble in alcohol, ether, 
 
 and benzene, sparingly in water and ligroine. 
 Tolerably marked basic properties. 
 
 Salts: A'HjHCl; long colourless easily 
 soluble prisms. — (A'H.HC^^PtClj ; easily 
 soluble yellow needles. — A'H, AcOH : colourless 
 prisms, [o. 160°]. 
 
 Acetyl derivative 
 C5H3(NHAo)(C3Hj)CO,H— [212°], long white 
 needles, si. sol. hot water. By the action of 
 nitrous acid it is converted into methyl-cinno- 
 
 line oarboxylic acid COjH.CsH,<^'^^:^^>, di- 
 azo-propenyl-benzoio acid, 
 C0,H.C.H3<^^^;^^S probably being the in- 
 termediate product (Widman, B. 17, 722). 
 
 Amido-propenyl-benzoic acid 
 C,H3(NHJ(03HJCO.,H [2:4:1]. [165°]. Formed by 
 heating amido-oxypropyl-benzoic acid with dilute 
 HCl (Widman, B. 19, 272). YeUow plates. 
 
 Acetyl derivative: [122°] ; white prisms. 
 
 a-AMIDO-PEOPIONAMIDE C3H8N,0 i.e. 
 CH3.CH(NH,).C0.NHj. [above 250°]. Occurs in 
 urine (Baumstark, A. 173, 342). Small columns, 
 si. sol. cold water, m. sol. hot water, insol. ether 
 insol. alcohol (difference from urea). Converted 
 by nitrous acid into sarco-lactic acid, and by 
 baryta-water at 150° into CO^i NH,, and 
 ethylamine. 
 
 o-AMIUO-PROPIONIC ACID v. Alanine. 
 
 /3-Amido-propionic acid CsH,N02 i.e. 
 CH,(NHJ.CHi.C0.,H. [180°]. Mol. w. 89. 
 
 Formation. — 1. Together with /3-imido-pro- 
 pionio acid, by the action of NH, upon i8-iodo- 
 propionio acid (Heintz, A. 156, 36; Mulder, B. 
 9, 1903). — 2. From cyano-acetic acid by reduc- 
 tion with Zn and H^SO^ (Engel, B. 8, 1597). 
 
 Properties. — Prisms ; v. e. sol. water, si. sol. 
 alcohol. Sweet taste. Split Dp by distUlatiou 
 into KH3 and acrylic acid. 
 
 Sal t. — CuA'2 5aq : dark-blue prisms. 
 
 (o)-AMIDO-PKOPIONITEILE OsH^N, i.e. 
 CH3.CH(NH2).CN. A mixture of aldehyde- 
 ammonia and prussic acid (30 p.c. solution) is 
 acidified vrith H^SOjAq (1:3) (Eriemneyer a. 
 Passavant, A. 200, 121). Liquid; quickly 
 changes to imido-propionitrile, giving oS NH3. 
 —B'HCl.— B'^H^PtCle. 
 
 AMIDO-PEOPYL-ALCOHOL v. Oxt-fbofyi.- 
 
 AMINE. 
 
 AUIDO-ISOPEOFTL-BEKZOIC ACID «. 
 
 Amido-cominio acid. 
 
 AMIDO-n-FEOFYI-CINNAMIC ACID 
 C.jH.jNO^i-e. C,H3(C3H,)(NHj).C2Hj.CO^ [4:2:1] 
 [155°]. Formed by reduction of nitro-M-propyl- 
 cinnamic acid with FeSO, and NH, (Widman, B. 
 19, 277). Glistening yellow needles. Easily 
 soluble in hot alcohol. By heating with dilute 
 HCl for a long time it is converted into n- 
 propyl-carbo-styril [162°]. 
 
 o-AMIDO -p - PBOPYL - PHENYI - ACETIC 
 ACID 0„H,5N0j i.e. C3H,.C,Hj.CH(NH,).C0jH. 
 [197°]. Prepared by saponifying the product of 
 the action of HCN upon cumin-hydramide 
 (Ploohl, B. 14, 1816). SI. sol. cold water, iiisoL 
 alcohol and ether. 
 
 AMIDO-PYEENE v. Pyeene. 
 
 AMIDO-PYEOCATECHIN "CjHjNO, U. 
 ''CbH3(NH,)(0H),. By reducing the nitro-oon»- 
 pound by Sn and HCl. 
 
 Salt: B'HCl: dark needles. Sodic car- 
 
184 
 
 AMIDO-PYROOATECIIIN. 
 
 bonate liberates the free base which, however, is 
 rapidly oxidised by air forming a violet solution 
 (Benedikt, J.^. [2] 18, 457; B. 11, 363). 
 
 Methylene derivative CjHjNOj i.e. 
 
 H,N.CjH3<^^>CHj. Obtained by reducing 
 
 methylene nitro - pyrocatechin or nitro- 
 piperonylic acid (Hesse, j4. 199, 341). Brownish 
 oil. Salt:B'HCl. 
 
 AMIDO-PYEOGAILOL CjHjNOj i.e. 
 C5H2(NH.2)(OH)3. Amido-jpyrogallic acid. From 
 the nitro-compound. Its alkaUne solution turns 
 blue in air. 
 
 Salt.— B'HCl : needles (Barth, M. 1, 884). 
 
 AMIDO-PYRO-MECOHIC ACID C5H5NO3 i.e. 
 C5H3(NH2)03. From nitro-pyro-meconio acid, 
 tin and HCl (Ost, /. pr. [2] 19, 194). Needles 
 (from water). Fe^Clij gives a blue colour, changed 
 to red by excess. — B'HCl aq. 
 
 Di-amido-pyro-mellitic ether 
 0B(NH2)2(C02Et)4 [134°]. From the nitro com- 
 pound (Nef, A. 237,24). Diacetyl deriva- 
 tive [149=]. 
 
 (a)-AM;iDO-PYIlKYL METHYL KETONE 
 CsHjN^Oi.e. C,H3(NHJN.CO.CH3. Formed by 
 reduction of (o)-nitro-pyrryl methyl ketone with 
 tin and HCl (Ciamician a. Silber,B. 18, 1460).— 
 B'jHjPtClj : long yellow needles. 
 
 (B.4)-AMlD0-ftUIN0LINEC,NHs.NHj.[67°]. 
 
 Preparation. — 1. By reducing nitro -quinoline, 
 [89°] (Koenigs, B. 12, 451).— 2. By heating 
 oxy-quinoline with zinc - chloride - ammonia 
 (Bedall a. Fischer, B. 14, 2573). Plates. Dis- 
 solves in acids. CrOj gives a blood-red colour. 
 
 (B. 2)-Ainido-quinoline C,H,N2 [114°]. Pre- 
 pared by reduction of nitro-quinoline from p- 
 nitraniline (La Coste, B. 16, 670). Colourless 
 plates or flat needles (containing 2aq). Sublim- 
 able. V. sol. alcohol and ether, less in water 
 and ligroin. Salts: B"HC1: large colourless 
 prisms. — B"2H2Cl2PtCl4 2 aq. : crystalline pp. 
 
 Picrate B"(C5H2(N02)aOH)2 : needles. 
 
 (B. 3)-Amido-qalnoline 
 ,CH:CH 
 
 C.H3(NH3) 
 
 ,/ 
 
 [110°]. Prepared by 
 
 heating (B. 3) -oxy-quinoline with ammoniacal 
 ZnClj (Biemerschmied, B. 16, 725). Yellow 
 plates. Sublimable. Sol. alcohol, ether, and 
 hot water; si. sol. cold watef. The picrate 
 forms long red needles, v. si. sol. ether. 
 
 (a)-Di-amido-quinoline C„HjN3 i.e. 
 
 C,B.^(^B.^)^. [156° uncorr.]. Formed by re- 
 duction of (a)-di-mtro-quinoline [183°] with 
 SnClj (Glaus a. Kramer, B. 18, 1247). Thick 
 yellowish needles. — B"H2Cl2PtCl4 : red needles. 
 
 (fl)-ri - amide - quinoline. [163° uncorr.]. 
 FormeJ by reduction of (/3)-di-nitro-quinoline 
 [134"] with SnClj (C. a. K.). Small yellow 
 needles or plates. Is not sublimable or volatile 
 with steam. V. sol. water and alcohol, si. sol. 
 ether, benzene, and ligroin. — ^BaHjCl^PtCli : 
 yellow crystalline powder. 
 
 DI-AMID0-aUIN0NEC„H2(NHj2O2[6:2:4:l]. 
 
 Diacetyl derivative CbHj(NHAc).20j : 
 [265°-270°]. Formed by oxidation of tetra-ace- 
 tyl-di-amido-hydroquinone CbH2(NHAo)2(OAc)j 
 or tri-acetyl-tri-amido-phenol CeH.^(NHAc)30H 
 (from picric acid). By heating with SnCl^ dis- 
 solved in cone. HCl it yields di-amido-hydro- 
 "luinone (Nietzki a. Preusser, B. 19, 2247; 20, 797). 
 
 SI-AMIDO-QTTINONE-IMIDE v. Amido-dx- 
 
 IMIDO-PHENOL. 
 
 (B. 2)-AMID0-ftUIN0XAIINE C,H,N, t.«. 
 .N:CH 
 
 C3H3(NHj)<^ I [159°]. Formed by oonden. 
 
 \N:.CH 
 sation of glyoxal with (l:2:4)-tri-amido-ben- 
 zene (Hinsberg, B. 19, 1254). Yellow needles 
 or large crystals. Sublimable. V. sol. water, 
 alcohol, and chloroform, m. sol. ether and 
 benzene. The ethereal and chloroform solu- 
 tions have a yellowish - green fluorescence. 
 The aqueous solution gives yellow pps. with 
 AgNOj and HgClj. Its solution in HCl is deep 
 violet. 
 
 Salts.— B'HCl: brown plates with green 
 reflection.- B'^H^SOj.- B'2H,Gl2PtCl4. 
 
 AMIDO-EESOECIN C„H,N02 i.e. [1:2:4] 
 C„H3(NH2)(0H)j. Formed by reducing nitro- 
 resorcin with tin and HCl (Weselsky, A. 164, 6). 
 —B'HCl 2aq : gives brown colour with FCjClj. 
 The free base is unstable. 
 
 Ethers: C,H3(NH.J(OEt)2 : [32°]; (251°). 
 From benzene-azo-di-ethyl-resoroin (Will a. Pu- 
 kall,B.20,1124).— C,H3(NH3)(OH)(OBt). [148°]. 
 
 Amido-resorcin. Ethyl ether 
 C5H3(NH2)(OEt)2 [1:2:6]. [124°]. Frombenzene- 
 o-azo-di-ethyl-resorcin (Pukall, B. 20, 1148). 
 
 Di-amido-resoroin C^HgNaOj i.e. 
 C„H3(NHJ2(0H)2. [1:3:4:6]. The hydrochlo- 
 ride is obtained by reducing dinitroso-resorcin 
 (Fitz, B. 8, 633) or benzene-disazo-resorcin 
 (Liebermann a. Kostaneoki, B. 17, 881). It gives 
 a blue colour with Fe^Clj. The free base is un- 
 stable. If the hydrochloride is suspended in 
 chloroform, a little aqueous NaOH added, and 
 then a large quantity of water, a beautiful blue 
 colour is produced. — B"H.^S04 IJaq. 
 
 Di-amido-resorein. Formed by reduction of 
 di-nitro-resorcin with tin and HCl (Typke, B. 
 16, 555). The hydrochloride (B"H,Cl2) forms 
 easily soluble flat needles. Fe^Clj produces a 
 ppn. of steel-blue prisms of di-imido-resorcin. 
 
 ASIID0-8ALICYLIC v. Oxy-amido-benzoio. 
 
 DI - AMIDO - STILBENE v. Di-Amido-m - 
 
 PHENYL-ETHYLENE. 
 
 AMIDO-STEYCHNINE C2,H23N302 i.e. 
 C2,H2,(NH2)N202. [275°]. (c. 280°) at 5 mm. 
 From nitro-strychnine and SnClj (Loebisch a. 
 Schoop, ilf. 6, 848). Cubes (from alcohol). Insol. 
 water, si. sol. benzoline, m. sol. alcohol, v. e. 
 sol. ether and chloroform. Its salts are very much 
 more soluble than those of strychnine ; they 
 turn reddish-violet in moist air. They give the 
 general reactions for alkaloids. Give no colour 
 with cone. H^SO., and K^Cr^O,. A dilute acid 
 solution is turned blue by aqueous KjCr^O, or 
 by Fe^Cl^. Salt s.— B"2HC1 : prisms.— B"H2PtCl3. 
 
 Acetyl derivative C2|H2|(NAcH)Nj02aq 
 [205°] (L. a. S. M. 7, 77). 
 
 Di - amido - strychnine C2|H2„(NH2)2N202. 
 [263°]. From di-nitro-strychnine, tin, and HCl 
 (Hanriot, 0. B. 96, 586; Bl. [2] 41, 236). Prisms 
 (from chloroform) ; v. si. sol. water and ether, 
 m. sol. alcohol, v. sol. chloroform. Gives no 
 colour with cone. H2S0i and K^CrjO,. A dilute 
 acid solution is turned violet-blue by oxidising 
 agents such as E2Cr20,Aq or NaOCL 
 
 p-AMIDO-STYEENE CjHjN i.e. 
 C„H,(NH,).CH:CH2. [76°-81°]. A body of this 
 composition ig formed by reducing p-nitro- 
 
AMIDO-THYMOL. 
 
 186 
 
 oinnamio aoid with Un and HCl (Bender, B. 14, 
 2359), and by heating ^-amido-oinnamio aoid 
 (Bernthsen a. Bender, B. 15, 1982).— B'^H^PtCl.. 
 
 o-AMIDO-STYEYL-ACBYIIC ACID 0„H„NO. 
 U. 0eH4(NH2).CH:0H.CH:OH.CO2H. o-Amido- 
 emnamenyl-acrylic acid. [177°]. Formed by 
 reduction of o-nitro-styryl-aorylio aoid with 
 ferrous sulphate and ammonia. Yellow needles. 
 V. sol. chloroform, ether, alcohol, and acetic 
 acid, si. sol. CS^ and hot water, v. si. sol. cold 
 water. Its ethereal solution has a green fluores- 
 cence. It forms salts with acids and with 
 bases. The hydrochloride is easily soluble, 
 the sulphate sparingly soluble. The salts with 
 bases are deep yellow. 
 
 Acetyl derivative 
 C.H,(NHAc).C,Hj.C02H: [253°]. Small white 
 tables, sol. hot alcohol, si. sol. cold alcohol and 
 ether, insol. water (Diehl a. Einhorn, B. 18, 2832). 
 
 o-AMIDO-STYRYL-PEOFIONIC ACID 
 C8Hj(NH,).CH:CH.CH2.CH2.C0,^. o - Amido - 
 cinnamyl-acetic acid. [59° hydrated]. Crystals 
 { + H2O). Easily soluble in ordinary solvents. 
 Formed by reduction of o-amido-styryl-acrylio 
 aoid with sodium-amalgam (Diehl a. Einhorn, 
 B. 20, 378). 
 
 AMIDO-STJCCINAMIC ACID v. Aspakaginb. 
 
 AMIDO-STICCINIC ACID v. Aspabtio aoid. 
 
 Di-amido-succinic acid CjHjNjO, i.e. 
 C0.,H.CH(NHj).CH(NH2).C0jH. [125°]. 
 
 Formation. — 1. From di-bromo-suocinic acid 
 and NH3 (Lehrfeld, B. 14, 1817).— 2. By redu- 
 cing the di-phenylhydrazide of di-oxy-tartario 
 acid, C02H.C(N2HPh).C(N2HPh).CO,H, in alka- 
 line solution with sodium amalgam. The yield 
 is 35 p.o. of the theoretical (Tafel,B. 20, 247). 
 
 Properties. — Prisms ; v. si. sol. water, alcohol, 
 ether, acetone, acetic acid, chloroform, aniline, 
 phenol, and CSj. Sol. aqueous acids and alkalis. 
 
 Di-amido-succinic acid OjHsN^O,. [151° 
 uncorr.]. White needles or prisms. Sol. water, 
 alcohol, and ether. The acid is isomeric with 
 the preceding. The ether is formed by the 
 action of NHj on di-ohloro-suocinic ether. 
 
 Diethyl-ether A"Et2. [122° uncorr.] 
 Colourless needles or trimetrio prisms. Sol. 
 alcohol and ether, t. si. sol. water. 
 
 Salts. — ^A"Ag2 and A"Pb : insol. pps. — 
 A"Cu : green pp. 
 
 Di-amide G.^n^'S^iCO.TiiH^)^. [160° uncorr.]. 
 Long slender needles. Insol. water and ether 
 (Glaus a. Helpenstein, B. 14, 624 ; 15, 1850). 
 
 AMIDO - SUCCINURIC ACID v. Ubamido- 
 
 SUCOINIO ACID. 
 
 AMIDO - SULFHOB£NZID£ 
 
 V. Amido-di- 
 
 PHENYL SULPHONE. 
 
 AMIDO-STJLPHO-BENZOIC ACID 0,H,NS05 
 i.e. C,H3(NHJ(S0sH)(C0;H) [1:3:5]. From 
 nilro-ro-sulpho-benzoic acid and aqueous am- 
 monium sulphide (Limpricht a. Uslar, A. 106, 29). 
 Needles, v. sol. hot water, m. sol. alcohol, v. si. 
 sol. ether. Blackened by heat. Combines with 
 bases but not with acids. 
 
 (a)-amido-salpho-benzoic acid C^H^NSOsaq 
 i.e. C,B.^{SH^){SO,B.){COja.) [l:x:S]. Obtained, 
 together with the following acid, by sulphona- 
 tion of TO-amido-benzoio acid (Griess, J. pr. [2] 
 6, 244). Four-sided laminsB> m. sol. hot water. — 
 Salt :— BaA"2aq : v. si. soL water. 
 
 (/3)-amidD-salpho-benzoio acid 0,H,NSO. 
 ».«. C„H3(NH2)(S0,H){C0^ [l:a!:53. Six-sided 
 
 lamince; v. sL sol, hot water. — Salt: BaA''8aq: 
 m. sol. water. 
 
 Amido-sulptao-benzoic acid 
 CeHj(NHj,)(S03H)(C02H) [1:3:6]. Ehombio 
 plates, sol. hot water. Dilute solutions show 
 blue fluorescence (Hart, Am. 1, 363). 
 
 Amido-sulpho-benzoic acid ' 
 O.H3(NH,)(S03H)(CO,H) [1:2:4]. 
 
 Imide C<,H,(NHj)<;^^2\.NH. [285°]. From 
 
 the amide of ^-nitro-toluene sulphonio aoid by 
 oxidation and reduction (Noyes, Am. 8, 167). 
 Colourless crystals, v. si. sol. water. Its solution 
 shows dark blue fluorescence. 
 
 AMIDO-SULPHO-BENZOLIC ACID. An old 
 name for amido-benzene sulphonio aoid v. 
 Amido-benzene. 
 
 AMIDO-STJLPHO-PHENOLIC ACID. An old 
 name for amido-phenol sulphonio acid v. Amido- 
 
 PHENOL. 
 
 a-AMID0-2)-STILPH0 - PHENYL - PROPIONIC 
 
 ACIDC,H„NS05i.e. 
 
 S03H.C,H,.CHj.CH(NH,).C0,H. 
 From o-amido-phenyl propionic aoid (20 g.), cono. 
 H2SO4 (30 g.) and Nordhausen aoid (25 g.) (Erlen- 
 meyer a. Lipp, A. 219, 209). Groups of short 
 prisms (from water). M. sol. water, v. si. sol. 
 alcohol, insol. ether. Does not combine with 
 HCl. Fused with KOH gives ^-oxy-benzoio aoid. 
 — Salts: BaA'2 4aq: flat prisms. 
 
 AMIDO-TEBEfHIHALIC ACID v. Auino- 
 
 PHIHALIC ACID. 
 
 m-AMIDO-THIO-BENZAMIDE CiHgN^S i.e. 
 CsH,(NH2).CS.NH2. Obtained by boiling m-nitro- 
 benzonitrile with aqueous ammonium sulphide 
 fHofmann, Pr. 10, 598; B. 1, 197). Needles 
 (from water). Weak base. Decomposed by 
 heat into HjS and amido-benzonitrile. Alcoholic 
 solution of iodine converts it into C^Hi^N^S, 
 crystallising from water in slender needles 
 [129°]. Forms u platino - chloride 
 CnHijN^SHjPtCl, (Wanstrat, B. 6, 332). 
 
 p - Amido - thio - benzamide [170°]. From 
 p-nitro-benzonitrile and cone. H^SO, (Bngler, A. 
 149, 299). Crystals ; m. sol. alcohol. 
 
 AUIDO - THIO • CRESOL v. Amido-iolyl 
 
 MERCAPTAN. 
 
 AMIDO-THIOPHENE C,SH3(NH2). Pre- 
 pared by reducing nitro-thiophene with tin and 
 alcoholic HCl (Stadler, B. 18, 1490, 2316). YeUow 
 oil. Very unstable ; being changed in 12 hours 
 into a brittle resin. The hydrochloride reacts 
 with diazo salts forming stable azo compounds. 
 Salts .— B'HCL— B'jHjSnCl,. 
 
 a-AMISO-IHIENYL-ACETIC ACID 
 CsH,SN02 i.e. C4SH3.CH(NH2).C02H. Formed 
 by reducing the oxim of thienyl-glyoxylic aoid 
 C,SH3.C(N0H).C02H with tin and HCl (Bradley, 
 B. 19, 2115). Plates or grains ; decomposes at 
 235°-240°. Salts.— The aoid gives pps. with 
 salts of Cu, Hg, Bi, and Zn, but no pps. with 
 salts of Fe, Mg, Mn, Ur, Ni, Ba, Ca, Sn, or Pb. — 
 CuA'^aq.- HA'HCl. 
 
 AMIDO - THIOFHENOL v. Auido -phenyl 
 
 MERCAPTAN. 
 
 AMIDO - THYMOL C,„H,5N0 t.«. 
 
 C3H2Pr(NHJ(CH3)(OH) [1:3?:4:6]. Nitroso- 
 thymol, prepared from sodium-thymol, KNOj and 
 H,SO, (SchifE, B. 8, 1500), is reduced by 
 Sn and HCl to the well-crystalUsed tin salt of 
 f-amido-thymol. This is dissolved in water and 
 
186 
 
 AMIDO-THYMOL. 
 
 decomposed by H^S (Andresen, J. pr. 181, 169). — 
 Salt: B'HCl: decomposes at 210°-215°. 
 
 Beacticms. — 1. Bleaching powder solution 
 converts it into thymo-quinone-chloro-imide 
 (g.D.). — 2. A solution of bromine in NaOH 
 oxidises it to thymo-quinone. — 3. Bromine water 
 has the same effect. 
 
 Amido-thymol sulphonic acid C,oHn(S03H)NO 
 IB among the products of the action of cone. 
 NaHSOsAq upon thymoquinone-ohloro-imide 
 (A.). Needles or prisms. 
 
 Di-amido-thymoquinone CuHnNjOj i.e. 
 C^PrMe(NH2)20j or Oxy-amido-thymo-quinon- 
 
 imide 0,PrMe(NH2)(0H)<f 
 
 NH 
 
 Formed by 
 
 heating phenylamido-oxy-thymoquiuone with 
 alcoholic NHaat 100° (Anschiitz a. Leather, O.J. 
 49, 725). Dart blue crystals, insol. water, ether, 
 benzene, chloroform, and CS^ ; v. si. sol. alcohol ; 
 sol. glacial HOAo (crystallising with JHOAo); 
 V. sol. HClAq, forming a red solution. 
 
 AMIDO-TOLTIENE v. Toluidine and Benztl- 
 
 AMINE. 
 
 Si-amido-tolnene v. Tolylenb-diamine and 
 Amido-benzylamine. 
 
 TBI - AMIDO - TOLUENE C,Hi,Nj i.e. 
 CjH,Me(NHJ, [1:3:4:5]. 
 
 p-Acetyi derivativ eCsTEL.Jde{'^'RAo){'!^B.2)2 
 [1:4:3:5] [o. 264°] ; pearly rods (containing aq) ; 
 sol. acetic acid and hot alcohol, insol. water, 
 ether, and benzene. Formed by reduction of 
 aoetyl-di-nitro-j)-toluidiue (1 pt.) with tin (3 pts.) 
 and cone. HCl (8 pts.). The hydrochloride 
 (B'HCl I aq) forms white concentric easily 
 soluble needles (Niemeutowski, B. 19, 716). 
 
 Benzoyl derivative 
 C,H2Me(NHBz)(NHj,)2 [1:4:3:5] [c. 185°]. 
 Formed by reducing benzoyl-di-nitro-^-toluidine 
 (Hiibner, A, 208, 318). Insol. water, sol. alcohol 
 and ether. Salts.— B"2HGl.—B"H2SOj. 
 
 Tri-amido-toluene CjH2(CH3)(NH2)3 [1:2:4:?]. 
 Very oxidisable crystalline solid. Tri-acid base. 
 Prepared by reduction of nitro - tolylene - m - 
 diamine. B"'(HC1)3 and B"'5,(H2SOj)3 are white 
 crystalline solids (Euhemann, B. 14, 2657). 
 
 AMIDO-TOLTTEJSE STJIPHINIC ACIDS 
 CiHjNSOj. 
 
 o-Amido-toInene eulphinic acid 
 C„H3Me(NH2)S02H [1:2:4]. o-ToluidinesulpMnic 
 acid. S. '148. From o-amido-toluene thio- 
 sulphonic acid and sodium amalgam (Paysan, 
 A. 221, 361). Bectangular tables, si. sol. water 
 or alcohol, insol. ether or benzene. At 160° it 
 decomposes without melting. 
 
 BeacHons. — 1. With yellow ammonic sulph- 
 ide forms amido-toluene thiosulphonio acid. — 
 2. KMnOt forms amido - toluene sulphonic 
 acid. — 3. Boiling HCl forms the isomeric toluene 
 sulphamine. — 4. Nitrous acid forms a diazo com- 
 pound which when warmed with alcohol forms 
 the ethyl derivative of cresol sulphonic acid. 
 
 Salts .— KA'.— BaA'j 2aq.— AgA'. 
 
 Toluene sulphamine CjHjNSOj. [175°]. Got 
 by heating o-amido-toluene sulphinic acid with 
 HCl and ppn. by NHj. Needles in stars (from 
 alcohol). — B'HCl : groups of slender needles. 
 
 jp-Amido-toluene sulphinic acid CrHjNSOj 
 i.e. OBH,(NK,)Me.SOjH [1:4:5]. From 
 C„H3(NH2)Me(SO,SH) by boiling with HCl but 
 linoe much then chanjjea to toluene sulph- 
 
 smine it is better to reduce it with sodinni 
 amalgam (Heffter, A. 221, 347). Hard prisms. 
 Does not melt below 240°. Insol. alcohol, gL 
 Bol. cold water, v. sol. hot water. 
 
 Reactions. — 1. Warmed with a solution of 
 sulphur in ammonic sulphide it changes to the 
 thiosulphonio acid, C5H3tNH2)Me.(S02SH).— 2. 
 Bromine converts it into amido-toluene sulphonic 
 acid. — 3. Not reduced by Sn and HCl. 
 
 Salts . — KA'. — BaA'2 icaq. 
 
 Toluene sulphamine (isomeric with the 
 above). [132°]. Got by heating ^-amido-toluene 
 sulphinic acid with cone. HCl. It is a base. 
 Microscopic prisms (got by adding NH3 to its 
 solution in HCl). V. sol. alcohol and ether, but 
 separates from them in a resinous form ; si. sol. 
 water. Dissolved by treatment with water and 
 sodium amalgam (not NaOH alone) forming 
 sodic amido-toluene sulphinate. 
 
 Salts.— B'HCl: si. sol. HCl, v. sol. water or 
 alcohol. — B'jHjSO^. — B'HBr: changes readily 
 into amido-toluene sulphonic acid. — B'HNO, ; 
 warmed with HNO3 forms amido - toluene 
 sulphonic acid. 
 
 Si-amido-toluene sulphinic acid C,H,,N2S0, 
 i.e. C5H2Me(NH2)2S02H. Tolylene-di- amine 
 sulphinic acid. S. '047 at 20°. From 
 C<,Hi,Me(NHj2S0,SH by boiling with HCl (Perl, 
 B. 18, 70). Silky needles (containing aq). V. 3I. 
 sol. water, insol. alcohol, ether, and glacial 
 HOAc. — PbA'2 2aq : minute needles. 
 
 AMIDO-TOLUENE SULPHONIC ACIDS 
 CjHsNSOs (Limpricht, B. 18, 2172). 
 
 o-Amido-toluene sulphonic acid 
 C„H3Me(NH2)S0sHaq [1:2:5]. o-Tolwidine sul 
 phonic acid. S. 2'76 at 12° (H. Hasse). 
 
 Preparation. — 1. By heating the acid sul- 
 phate of o-toluidine at 220°-230°, or in a metal 
 dish till solid (Nevile a. Winther, C. J. 37, 626 ; 
 B. 13, 1941; Gerver, A. 169, 374; Pagel, A. 
 176, 292). — 2. By reducing the corresponding 
 nitro acid (Foth, A. 230, 306). 
 
 Salts. — KA'aq : tables and prisms. — 
 NaA'4aq: tables.— BaA'jTaq : tables and prisms. 
 — AgA' : prisms. 
 
 Reactions. — 1. Bromine water forma first 
 CH3.CsH2Br(NHJS03H [1:3:2:5] then di-bromo- 
 toluidine 0„H2(CH3)(NHJBr2[l:2:3:5][46°] is ppd. 
 2. Fused with alkalis or heated with water or 
 aqueous HCl to 190° it forms o-toluidine. — 3, 
 Nitrous acid and alcohol give m-toluene sul- 
 phonic acid.— 4. With o-toluidine at 235° it 
 forms a red dye. 
 
 o-Amido-toluene sulphonic acid 
 C5H3Me(NH2)(S03H) [1:2:3]. Obtained by re- 
 ducing the corresponding nitro acid (Pechmann, 
 A. 173, 215). Minute needles; si. sol. cold 
 water. Gives o-toluidine when fused with KOH. 
 
 o-Amido-toluene sulphonic acid 
 CsH3Me(NH2)(SOaH)aq [1:2:4]. From the nitro 
 acid (Bek, Z. 1869, 211 ; Beilstein a. Kuhlberg, 
 A. 155, 21; Weckwarth, A. 172, 193; Hayduck, 
 A. 172, 204 ; 174, 343 ; Herzfield, B. 17, 904). 
 Long needles or four-sided prisms. S. "974 at 11° ; 
 insol. alcohol. The aqueous solution is turned 
 violet by FcjClj. Potash-fusion gives o-amido- 
 benzoic acid. Bromine gives di-bromo-toluidine 
 sulphonic acid. Salts. — NaA'4aq.— KA'aq. — 
 BaA'j2iaq.— PbA'j. 
 
 Amide. — C„H3Me(NHj)S02NHj. [175°]. 
 S. -22 at 23°. From C,H3Me(NOj>S03NH, 
 
AMIDO-TOLUENE SULPHONIO ACIDS. 
 
 187 
 
 [128°],NH3, andKjS (Paysan, A. 221, 210). Four- 
 sided columns. 
 
 S al t.— O^H3Me(NH3Cl).SO,NH,. [240°]. 
 
 m-Amido-toluene salphonlc acid 
 0,HaMe(NH2)S0,,H [1:3:2]. m-Tolwdim sul- 
 phonic add [275°]. By sulphonation of m- 
 toluidiue (Lorenz, A. 172, 185). Tables or 
 plates; al. sol. water. Bromine-water produces 
 tri-bromo-toluidine. 
 
 Salts.— BaA'j9aq.—PbA'23laq. 
 
 m-Amido-tolueue sulphonic acid 
 C.H,Me(NK,)S03Haq. S. (dry) -14 at 19°. From 
 bromo-toluene sulphonic acid CuHsMeBrSOaH 
 [1:2:4] by nitration and reduction (Hayduek, A. 
 174, 350). Minute needles. 
 
 ^-Amido-toluene exo-snlpbouic acid 
 C„H^(NH2).CH.^.S03H [1:4]. p-Amido-benzyl-sul- 
 phonic acid. S. "097 at 10°. Formed by reducing 
 the nitro acid by NH3 and H^S (Mohr, A. 221, 
 219). Prisms, insol. alcohol, si. sol. cold water. 
 
 S al t s.— KA'2iaq.— BaA'jjSaq. 
 
 The diazo derivative, 03Hj<[^Q.nr %q ^ 
 
 is converted into CsH4(OEt).CH2.S03H by heating 
 with alcohol under 1100 mm. pressure. 
 
 p-Amido-toluene sulphonic acid 
 C„H3Me(NH2)S03Haq [1:4:2]. p-Toluidine sul- 
 phonic acid. S. "45 at 20°. A product of sul- 
 phonation of ^-toluidine (Sell, A, 126, 155 ; 
 Malycheff, Z. 1869, 212); formed also by re- 
 ducing ^-nitro-toluene sulphonic acid (Beilstein 
 a. Kuhlberg, A. 172, 280). Bhombohedra (con- 
 taining aq). Beduces warm ammoniacal 
 AgN03. Its aqueous solution is turned red by 
 FcjCl, (Herzfeld, B. 17, 904). 
 
 Salt s.— KA'.— BaA'^aq.-PbAV 
 
 Amide.— CeH,Me(NH2)S0.,NHj. [164°]. 
 From CsHsMe(NOJ.S02NH2 [186°] by reducing 
 with NH3, and H.,S (Heftter, A. 221, 209). Salt : 
 CaH3Me(NH3Cl)S0jNH2; converted by cone. HCl 
 and nitrous acid into CsHsMeCl.SOaNHj [138°]. 
 
 ^-Amido-toluene sulphonic acid 
 C„H3Me(NHJS03H[l:4:3]. S. 10. 
 
 Preparation. — 1. By sulphonating j)-tolui- 
 dine at 180° ; the preceding acid is also formed, 
 especially if the operation is protracted (Pech- 
 mann, A. 173, 195). — 2. By heating ^-toluidine 
 acid sulphate at 220°-240° (Nevile a. Winther, 
 C. J. 37, 632). 
 
 Properties. — Yellowish crystals. Less soluble 
 in cold water than the o-compound. 
 
 Beacticms. — 1. Bromine forms much di- 
 bromo-toluidine, C.H,(CH3)(NH2)BrBr [1:4:3:5], 
 [73°] and also a bromo-toluidine sulphonic acid. 
 
 2. Water at 180° forms jj-toluidine and H^SOj.— 
 
 3. Potash-fusion gives j)-oxy-benzoio acid. — 
 
 4. Nitrous ether gives wi-toluene sulphonic acid. 
 
 S alts.— BaA'j 3aq.— PbA',2aq.— AgA'.— The 
 K salt is insol. in cold KOHAq (difference from 
 preceding acid ; Schneider, Am. 8, 274). 
 
 Amido-toluene-o-sniplianic acid 
 C„H3Me(NH,)(S03H) [l:a!:2]. S. -34 at 22°. 
 From the (1, 4, 2) acid by nitration, removal of 
 NH2, and reduction (Pagel, A. 176, 305).— 
 BaA'22laq.— PbA'^aq. 
 
 Amido-tolnene sulphonic acid. Obtained by 
 reducing the product of successive sulphonation 
 and nitration of toluene (Hayduck, A. 177, 57).— 
 Minute crystals (containing aq). — BaA'j. 
 
 o-Amido-toluene di-sulphonic acid 
 C,E,NS30, t.0. C.H,Me(NH,)(S03H), [1:2:3:5]. 
 
 o-Toluidine di-sulphonic acid. Formed from 
 C5HsMe(NH,)S03H [1:2:5] and fuming H,SO, by 
 heating an hour at 160° (Nevile a. Winther, C. /. 
 41, 421). Needles, grouped in stars ; sol. water 
 and alcohol. 
 
 Salts (H.Hasse,^. 230, 287).— BaA"3aq.— 
 BaH,A"2 3^aq. — K2A"2aq. — Na2A"6aq. — 
 CaA" 5aq.— PbA" 2aq.— PbH,A"2 6|aq. 
 
 Reactions. — 1. By conversion into tha 
 diazo compound and subsequently boiling with 
 HNOj it is converted into cG-nitro-o-cresol 
 C,H,Me(OH)(N02)2 [1:2:3:5].— 2. At about 240° 
 it splits up into SO3 and OjH3Me(NH2)(S03H) 
 [1:2:5].— 3. By CI.SO3H at 230° it is changed 
 into an isomeric acid with a salt K^A" 6aq. 
 
 o-Amido-toluene disulphonic acid 
 C,H.,Me(NH2)(S03H)j2aq [l:2:4:a!]. From 
 
 C,H3Me(NHJ(S03H) [1:2:4] and CISO3H at 170° 
 (Saworowicz, B. 18, 2181). Minute prisms. 
 At 300° it decomposes into SOj and 
 C„H3Me(NH„)S03H[l:2:4]. Salts.— BaA"2aq.— 
 CaA"2aq. 
 
 m-Amido-toluene disulphonic acid 
 C,H2Me(NH2)(S03H)2 [l:3:2:a;]. By sulphona- 
 tion of OT-toluidine (Lorenz, .4. 172, 188). Easily 
 splits up into SO3 and the mono-sulphonio acid. 
 
 Salts.— BaH^",(?12i)aq.— PbA" 2aq. 
 
 ^-Amido-toluene-disulphonic acid 
 CsH2Me(NH2)(SOsH)2 [1:4:2:3]. From ^j-tolui 
 dine and fuming HjSOj at 200° (Peohmann, A. 
 173, 217). Nodules ; v. e. sol. water and alcohol. 
 
 Salt. — BaA"3aq: lamina. 
 
 _p-Amido-tolueue-disulphanic acid 
 C,H2Me(NH,)(S03H)22iaq[l:4:2:a;]. Formedfrom 
 C.H3Me(NHJ(S03H) [1:4:2] by CISO3H at 150° 
 or fuming H^SO, at 180° (L. Eichter, A. 230, 
 331). Long silky needles, v. sol. water, sol. 
 alcohol. At 290' it splits up into SO3 antl 
 C,H3Me(NH2)(S03H) [1:4:2]. 
 
 Salts. — BaA"aq. — BaH,A"2llaq. — 
 BaH^A''^ ^aq.— EjA" 2aq.— PbA" l^aq. 
 
 ^-Amido-toluene-disulphouic acid 
 C3H2Me(NHJ(S03H)22aq [l:4:3:x]. Formed from 
 C,H3Me(NHJ(S03H) [1:4:3] and H^SO, or 
 CISO3H (L. Eichter, A. 230, 314). Mass of 
 minute needles (from water). With water at 140 ' 
 (or dry at 200°) it splits up into SO3 and 
 C„H3Me(NH2)(S03H) [1:4:3] . This acid is perhaps 
 identical with that of Fechmann. 
 
 Salts.— BaA"3aq.—BaHjA"j3aq.—KjA"2aq. 
 — PbA".— PbA"2aq. 
 
 Diazo derivative ''0sH2Me(N2S03)"S03H. 
 V. sol. water,insol. alcohol. KA'. — BaA'j. — PbA'.^. 
 
 Hydrazine derivative, — From the diazo 
 acid by SnClj. 
 
 (C„H,Me(N,H3)(S03H)S03)^a2Jaq. 
 Eeduces HgO, ammoniacal AgNO,, FcjCl, and 
 Fehling solution. 
 
 Amido-toluene di-snlphonic acid 
 OsH2(NH,,)Me(S03H)j(?2)aq. Fromp-bromo-tolu- 
 ene disulphonic acid by nitration, and reduction 
 of the resulting nitro-toluene disulphonic acid 
 (Kornatzki, A. 221, 198). 
 
 Si-amido-toluene exo-sulphonic acid 
 C,H,„N2S0ai.e. CsH3(NHj)3CH2S03H. Di-amido- 
 bemyl-sulphonic-acid. Formed by reducing 
 C„H3(N02)2CH,S03H with NH3 and HjS (Mohr, 
 A. 221, 228). Silky needles. 
 
 Di-amido- toluene sulphonic acid 
 C3H,Me(NHJ2S03H [1:2:4:5]. Formed from 
 C„H,Me(NOj)(NHj)S0,H and SnClj (Foth, A. 
 
188 
 
 AMIDO-TOLUENE SUI.PHONIO AOIDS. 
 
 230, 809). Small brownigh prisms, thombohedra 
 ^from water). Salts.— HA'HOl aq: prisms, de- 
 composed by boiling water. — ELA.'HBr aq. — 
 BaA'j 5^aq. — KA' aq. 
 
 o-AMIDO - TOLTJENE - THIO - S0LPHONIC 
 ACID C,HgKS,Oji.e. C.H3Me(NH2)S02SH [1:2:4]. 
 From CjHa{N02)MeS02Cl and ammonic sulphide 
 "(Limprieht a. Paysan, A. 221, 360). Four-sided 
 prisms. Decomposes without melting at 115°. 
 SI. sol. cold water, insol. alcohol. Warmed with 
 HCl forms S and toluene sulphamine. Salt. — 
 AgA'. 
 
 ^-Amido-tolneue thio-sulphonlc acid 
 •CeH3(NH2)Me.SO,SH [1:4:5]. Formed from 
 •C„H3(N02}MeSO.,Cl [44°] and ammonic sul- 
 phide (Limprioht a. Heffter, 4.221, 345). Hard 
 jellowish prisms (from water). Decomposed at 
 120° without melting. Insol. alcohol or ether, 
 si. sol. water. Decomposed by HCl with deposi- 
 tion of S and formation of CjH3(NHj)MeS02H. 
 Salts: BaA'2 2aq.— AgA'. 
 Sl-amido-toluene thiosulphonic acid 
 <!,H,.N2S,02i.e.C,H,(OH3)(NHJ,.SO,SH. [152°]. 
 Formation. — 1. By reduction of di-nitro- 
 toluene-sulphonic chloride with NHjHS. — 2. By 
 reduction of di-nitro-toluene sulphinic acid with 
 NHjHS. Small silky prisms. V. si. sol. water, 
 insol. alcohol and ether. 
 
 Salts. — AAg: white insol. pp. — A'Na: large 
 -tables— A'jPb : easily soluble (Perl, B. 18, 67). 
 
 AMIDO-TOLUIC ACIDS CsHsNOj. Amido- 
 -toluylic acids. 
 
 (a)-amido-o-taluic acid CBH3Me(NH2)C02H 
 [1:4:2]. [196°]. Formed by reducing (a)-nitro- 
 'O-toluic acid (Jacobsen, B. 17, 164). Small 
 prisms, v. sol. hot alcohol, and hot water, si. sol. 
 ■cold water. Converted by nitrous acid into 
 -oxy-toluic acid [172°]. 
 
 (^)-amido-o-toluic acid C,H3Me(NHj)C02H 
 [1:6:2] [191°]. Formed by reducing (;8)-nitro- 
 ,0-toluic-acid (Jacobsen, B. 16, 1959; 17, 164). 
 Small needles, v. sol. cold water. Converted by 
 nitrous acid into oxy-toluic acid [183°]. 
 
 (7)-ainido-o-toluic acid CjH3Me(NH2)C02H 
 £1:5:2]. [153°] (Hoenig, B. 18, 3449); [c. 
 165°] (J.). 
 
 Formation. — 1. By reducing (7)-nitro-o- 
 toluic acid. — 2. Byheating nitro-phthalide [141°] 
 with HI and P at 205°. Colourless needles; 
 may be sublimed, but at 200° it splits ofi COj 
 forming m-toluidine. V. sol. hot alcohol, m. 
 sol. hot water and ether, si. sol. chloroform, 
 benzene, and cold water. Nitrous acid produces 
 ■oxy-toluic acid [179°]. 
 
 Salts: HA'HCl: slender needles.— "CuA'j. 
 — HA'HjPO,: plates. 
 
 Amldo-OT-toluic acid 08H3Me(NHj)C02H 
 ■i:i:4:3] or [1:4:5]. 
 
 Formation. — 1. The hydrochloride is ob- 
 tained by warming methyl-isatoio acid with 
 HClAq (Panaotovid, J. pr. [2] 33, 61).-2. The 
 same acid is got from m-toluie acid by nitration 
 and reduction (Jacobsen, B. 14, 2354 ; compare 
 Panaotovid, loc. cit.). 
 
 Properties. — Trimetric, thread-like rods (from 
 •water). SI. sol. water, v. sol. alcohol and ether. 
 :Salt: HA'HCl. [207°]. Colourless trimetric 
 prisms ; m. sol. water and alcohol, si. sol. ether. 
 Methyl ether C,B.,Ue(lHni)COM^. [62°]. 
 From methyl-isatoio acid and MeOH at 180°. 
 Ji lender columns; b1. boI. water. 
 
 .4mi(ZeC^3Me(NH2)CO.NH,. [178°]. From 
 methyl-isatoic acid and NHjAq. Small columns 
 (from water) ; t. sol. alcohol. 
 
 Anilide CsH3Me(NH3)CONPhH. [240°]. 
 Pearly tablets (from alcohol) ; v. A. sol water. 
 
 Phenyl-hydraeide CsH3Me(NH2).CO.NjHjPh. 
 [198°]. From methyl-isatoic acid and phenyl- 
 hydrazine. Pearly crystals (from alcohol) ; v. 
 si. sol. water. Forms a violet solution with 
 cone. H3S04. 
 
 (3)-Amido-toluic acid C5H3(CH3) (NH^) (CO^H) 
 [1:2:3]. [132°]. Obtained by nitration and 
 reduction of m-toluio acid (Jacobsen, B. 14, 
 2354 ; compare Panaotovid, J. pr. [2] 33, 61). 
 Small flat prisms ; m. sol. water. 
 
 Amido-m-toluic acid. Benzoyl deriva- 
 tive C8Hs(NHBz)MeC02H[5or6:l:3]. Formed 
 by oxidation of benzoyl iso-cymidine (Kelbe a. 
 Warth, A. 221, 168). SmaU yeUowish needles 
 (from alcohol). 
 
 DI-AMIDO-DITOLTL 0„H,jNj. 
 
 Di-amido-ditolyl 
 [4:3:1] (NH3)MeC„H3.CeH3Me(NHj) [1:8:4]. o- 
 ToVidme. [112°]. 
 
 Formation. — 1. By passing CL,0 into an 
 ethereal solution of o-hydrazotoluene (Petrieff, 
 B. 6, 557). — 2. By heating o-hydrazo-toluene 
 (PetriefE, B. 6, 557).— 3. By heating o-hydrazo- 
 toluene with HCl (Schultz, B. 17, 467).— 4. By 
 warming an alcoholic solution of o-azo-toluene 
 vrith SnClj and HCl (S.). 
 
 Pearly plates ; v. sol. alcohol and ether, si. 
 sol. water. Converted by diazo reaction into m- 
 ditolyl. Converted by boiling its diazo-perbro- 
 mide with alcohol, into a di-bromo-ditolyl, which 
 oxidises to bromo-OT-toluio acid [1:2:4], [205°]. 
 Salts. — The sulphate and hydrochloride are 
 sparingly soluble in water. 
 
 Acetyl derivative C,2^sMe2(NAcH)2. 
 [315° cor.] 
 
 Di-amido-ditolyl. m-ToUdine. 
 
 The sulphate, B"H2S04, separates slowly 
 when a few drops of HjSO^ are added to an 
 alcoholic solution of w-hydrazotoluene (Gold- 
 schmidt, B. 11, 1626). The free base has a low 
 melting-point. Gives a blue colour with FejCl^. 
 
 ' Di-amido-ditolyl.' [107°]. Formed by the 
 action of SOj or of SnCl^ and HCl upon an 
 alcoholic solution of jp-azo-toluene (Mehns, B. 
 3, 554; Schultz, B. 17, 472). Silvery plates. 
 Gives a blue colour with Fe^Clj. Fischer (B. 
 25, 1019) has shown this body to be tolylene- 
 tolyl-diamine. 
 
 Di-amido-u-ditolyl 
 [4:3:1]. (NH,)MeCeH3.CeH3Me(NHj) [1:2:4]? 
 
 o-m-Tolidine. Formed by the action of 
 SnCl2 and HCl on an alcoholic solution of 
 o-m-azo-toluene. By diazotisation in alcoholic 
 solution it is converted into a ditolyl of boiUng 
 point 270° which on oxidation gives isophthalic 
 acid. 
 
 Salts . — B"H2Cl2 : easily soluble silky needles. 
 — B"HjS04'' : very sparingly soluble plates 
 (Schultz, B. 17, 471). 
 
 AMIDO-TOIYL-BENZAmiDINE C„B.i^, ix. 
 NHj.CjH3Me.NH.C(NH).C,Hi [212°]. From ben- 
 zonitrile and (l:2,4)-tolylene-diamine hydro- 
 chloride (Bernthsen a Trompetter, S. 11, 1758). 
 White needles. — B'HCl : prismatic tables. 
 
 AMIDO-TOIYL-ISO-BUTAITE C„H„N i.* 
 C.HsMe(0»E[,)NH, [ld!:2]. (243°). From o- 
 
AMIDO-VALERIO ACIDS. 
 
 189 
 
 toluictine and isobutyl alcohol (Effront, B. 17, 
 2320). Salt s.— B'HCl.— B'HBr.— B'XSO,.— 
 
 B'^CA- 
 
 Acetyl derivative [162°]. Plates. 
 
 Benzoyl derivative [168°]. Needles. 
 
 Amido-tolyl-isoliutane C„H3Me(CiHg)NH2 
 [1:3:2]. {24J;°). From o-toluidine, isobutyl alco- 
 hol, and ZnCl^ (Erhardt, B. 17, 419 ; BfEront, 
 B. 17, 2340). Formyl derivative [105°]. 
 
 Acetyl derivative [142°]. 
 
 o-AMIDO-TOLYX-ETHANE CgH,sN i.e. 
 OBH3Me(NH2)Et (230°). Methyl-ethyl-phenyl- 
 amine. Amido-ethyl-toltiene. From o-toluidine, 
 alcohol, and ZuClj at 270° (Benz, B. 15, 1650). 
 S a 1 1 B.— B'jHjSOi.- B'^HoCOj. 
 
 Acetyl derivative [106°]. (314°). 
 
 DI-AMIDO-DI-TOLYL- ETHYLENE DIA- 
 
 UINE V. DI-TOLYLENE-ETHYLENE-TEIBA-AlVrTWE. 
 
 AMIDO-TOLYL MERCAPTANS 0,HaNS. 
 Amido-thio-cresols. Amido-tolyl suVphydrate. 
 Prepared by reducing the chlorides of the cor- 
 responding nitro-toluene sulphonic acids (Hess, 
 B. 14, 488). 
 
 Amldo-o-tolyl mercaptan CeH,Me(NH2).SH 
 [1:4:2]. [42°]. Sol. alcohol, ether, alkalis, 
 and acids ; oxidised by air. 
 
 Salt. — B'HCl : prisms or tables. 
 Acetyl derivative [195°]: slender needles; 
 insol. HCl. 
 
 Amido-m-tolyl mercaptan CgH,Me(NE2)SH 
 [1:4:3]. Oil ; oxidised in air gives with HgClu a 
 white orystaUine pp.; with Pb(0Ac)2 a yellow 
 amorphous pp. Gives anhydro compounds with 
 formic acid, acetic anhydride, and benzoyl 
 chloride. 
 
 Amido-p-tolyl mercaptan CsH3Me(NH2)SH 
 [1:2:4]. OU. Oxidised by air to the disulphide. 
 Salt.— B'HCl: short needles. 
 Acetyl derivative [240°]. 
 Amido-tolyl mercaptan CsH3Me(NH2)SH 
 [1:2: ?] From o-nitro-toluene sulphochloride 
 [36°]. Oil. 
 
 Salt. — B'HCl aq: six-sided tables. Gives 
 with FcjClii a pp. of the disulphide. HgClj 
 gives glistening plates, and alkaline lead acetate 
 gives a yellow pp. 
 
 AUIDO-IOLYL METHYL KETONE CjHnNO 
 i.e. [1:2:5] CeH3(CH3)(NH,).CO.CH3 [102°]. 
 (280°-284°). Prepared by heating a mixture 
 of o-toluidine (1 pt.), ZnCl^ (2 pts.), and acetic 
 anhydride (3 or 4 pts.), for 8 or 9 hours (KUngel, 
 B. 18, 2696). Flat white needles. V. sol. 
 alcohol, ether, and hot water, v. si. sol. benzene 
 and petroleum-ether. Salts. — B'HCl: flat 
 white soluble prisms.— B'jHjCl^PtCl, : yellow 
 needles, v. sol. alcohol, si. sol. hot water, in- 
 soluble ether.— B'jH^SO, : white needles. 
 
 Acetyl derivative 
 0„H3Me(C0.Me)(NHAc), [144°] ; white crystals; 
 V. sol. alcohol and warm water. 
 
 AMIDO-TOLYL-(oa)-DIMETHYL-PYKKOL 
 C^NHjMeAHsNHj. [73°]. (322°). Obtained 
 by heating its dicarboxyUc acid (v. infra). 
 
 m - AMIDO - TOLYL - (oo) - DI-METHYL-PYB- 
 EOL (/3;8)-DICAKBOXYLIC ACID CuH^NA «•«• 
 C4NMe2(0,H3NHJ(C0jH)2. From m-tolylene 
 diamine and diacetyl-suceinio ether (Knorr, A. 
 236, 313). Yellow plates (containing 2aq). At 
 203° it gives COj and m-amido-tolyl-(oo)-di- 
 methyl-pyrrol. Ether Et^" [134°]. 
 
 C5H3Me(NH5)C,H„. [325°]. From n-oetyl aloo- 
 hoi, o-toluidine, and ZnClj at 280° (Beran, B. 18, 
 145). Salt s.— B'HCl.— B'ASO,.- ■ B'^H^C^O,. 
 
 Acetyl derivative [81°]. 
 
 DI-AMIDO-DI-TOLYL-OXAMIDE v. Oxalyl- 
 
 DI-ToLYLENE-lETKA-AMINE. 
 
 AMIDO-TOLYL STILPHYDBATE v. Amido- 
 tolyl MEBCAPTAH. 
 
 DI-AMIDO-DI-TOLYL SULPHIDE 
 OnH.eNjS i.e. {0^n,UeTS.B.^)S [1:4:2]. Tlm- 
 toluidine. [103'^]. Prepared by heating ^-tolu- 
 idine, sulphur, and litharge together at 150° 
 (Merz a. Weith, B. 4, 893). Laminss (from alco- 
 hol) ; si. sol. water. 
 
 Salts . — Decomposed by water. — B" 2HC1 si. 
 sol. cone. HClAq. — B"HjPtCl3.— B"H„S04.— 
 B"HjS04 2aq. — WUJSi^. — B"HJj. — 
 B"(C3H2(N02)30H)2 [179°]: silky yeUow needles 
 (from benzene) ; v. si. sol. ether and cold water. 
 
 Diacetyl derivative [211°]. 
 
 Dihenzoyl derivative [186°] (Truhlar,B, 
 20, 664). 
 
 Di-amido-di-^-tolyl sulphide v-carbozylic 
 ether S(C8H3MB.NH.C02Et)2. TUo-p-toVyl 
 urethane [113°]. From the preceding and 
 ClCOjEt. Crystals; v. sol. alcohol, ether, and 
 benzene (T.). 
 
 AMIDO-TOLYL-TJEEA CsH„N30 i.e. 
 
 NH2.CO.NH.CjH3Me.NHj. Formed, in small 
 quantity, by the action of tolylene diamine 
 sulphate on potassium oyanate (Strauss, A. 
 148,159). V. sol. alcohol. 
 
 Di-amido-di-2)-tolyl-urea C0(NH.C,Hs.NH2)j. 
 Formed by reducing the corresponding nitro- 
 compound (A. G. Perkin, C. J. 37, 700). Minute 
 satiny needles ; gl. sol. alcohol. — B" 2HC1. 
 
 AMIDO-TYROSINE C,-E.,^T<{fi, i.e. 
 C,H3(0H)(NH2).C2H3(NH2).C02H. From nitro- 
 tyrosine (Beyer, Bl. 1867, ii. 369). Crystalline 
 powder ; v. sol. water, si. sol. alcohol. 
 
 Salts.- B"H2Cl2aq.— B"HjS0<.— B"2HjS0^. 
 — (B"H2S04)2ZnS04. 
 
 AMIDO-irBAMIDO-BENZOIU ACIDS 
 0,H„N303 i.e. NH2.CO.NH.C„H3(NHj).C03H. 
 Prepared by reducing the two nitro-uramido- 
 benzoic acids (Griess, B. 5, 195). 
 
 (a)-Aoid. Plates ; si. sol. water, v. si. sol. 
 alcohol. Salts.— HA'HCl.—AgA'. 
 
 (i8)-Acid. Plates ; m. sol. hot water. Forms 
 no hydrochloride. BoUing aqueous baryta or 
 HCl forms NH3 and amido-carboxamido- 
 benzoic acid, of which the barium salt, 
 Ba(CsH5N203)2 4aq crystallises in needles. 
 
 (a) - AMIDO - UVITIC ACID CjHjNO, i.e. 
 OeH2(NH2)(CH3)(C02H)2 [2:1:3:5] (?). Colourless 
 soUd. SI. sol. water. Prepared by reduction of 
 (a)-nitro-uvitic acid (Bottinger, B. 13, 1933). 
 
 (/3)-Amido-'aTitic acid [c. 255°] (Bottinger, 
 B. 9, 807). 
 
 AMIDO-VALEEIC ACIDS OjHi.NOj. 
 a-Amido-n-valeric acid 
 CH3.CH2.CHj.CH(NH2).C02H. 
 
 Formation. — 1. From »i-butyric aldehyde- 
 anmionia and aqueous HON (Lipp, A. 211, 359). 
 2. From its benzoyl derivative which occurs 
 among the products of oxidation of benzoyl- 
 coniine (Baum, B. 19, 506). — 3. From bromo- 
 valeric acid and NH,Aq at 130° (Juslin, Bl. [2] 
 37, 3). 
 
190 
 
 AMIDO-VALERIO ACIDS. 
 
 Properties.— White glistening plates ; v. sol. 
 crater, gl. sol. alcoliol, insol. ether ; may be 
 sublimed. Has a sweet taste. Is optically in- 
 active. Neutral to litmus. 
 
 Salts. — HA'HCl: needles or groups of 
 prisms ; only deliquescent in very moist air. 
 — HA'HNOs.— (HA'HO^jPtCl^. — CuA'^: small 
 blue plates, si. sol. water, insol. alcohol. — AgA' : 
 crystalline pp., si. sol. water. 
 
 7-Ainida-valeric acid 
 CH3.CH(NH2).CH2.CHi,.C02H. [193° unoorr.]. 
 Obtained by reduction of the phenyl-hydrazide 
 of ;8-aceto-propionic acid — 
 CH3.C(N2HPh).CH2.CH2.COjH in alcoholic solu- 
 tion with sodium amalgam and acetic acid (Tafel, 
 B.19,2415; 20,249). Whiteplates. V.sol. water, 
 nearly insol. alcohol, insol. benzene and ether. 
 On heating it splits off HjO and the anhydride 
 distils. The hydrochloride forms glistenin 
 plates, easily soluble in alcohol. 
 
 NH , 
 
 Anhydride i _ _ i Oxy- 
 
 " CH3.CH.CH2.CH2.CO. " 
 
 methyl-pyrrol di-hydride. (248° i.V.) at 743 mm. 
 colourless liquid which solidifies in a freezing 
 mixture. V. sol. water, alcohol, ether, and ben- 
 zene. Its nitrosamine is a yellow oil. 
 
 a-Amido-iso-valeric acid 
 (CH,)3CH.CH(NH2).C02H. 
 
 Formation. — 1. Prom NH3 and o-bromo-iso- 
 valerio acid (Cahours, A. Suppl. 2, 83 ; Fittig a. 
 Clark, A. 139, 199 ; Schmidt a. Sachtleben, A. 
 193, 105) or a-chloro-iso-valeric acid (Schle- 
 busch, A. 141, 326).^2. From its nitrUe (Lipp, 
 A. 205, 18 ; B. 13, 905). 
 
 Properties. — Colourless laminsB, composed of 
 minute monoclinio prisms ; v. sol. water,, v. si. 
 sol. cold alcohol or ether. Neutral. May be 
 sublimed. 
 
 Salts. — HA'HCl: large tables, not deli- 
 quescent in moist air. — HA'HNOj. — CuA'j : 
 scales, si. sol. hot water. — AgA' : spherical 
 ^oups of crystals, v. si. sol. water. 
 
 Amide Me2CH.CH(NH3).CO.NHj. The hy- 
 drochloride, got by action of fuming HCl on 
 the nitrile, forms monoclinio plates, v. sol. water. 
 — (B'HCl)2PtCl,: prisms. 
 
 Nitrile Me,CH.CH(NHj).ON. From iso- 
 Ijutyric aldehyde - ammonia and HCN (L.). 
 TeUow oil; m. sol. water, v. sol. alcohol and 
 ether; gradually changes to imido-di-valero- 
 nitrile, NH(CH¥r.0N)2, giving off NH3. Salts.— 
 B'HCl : insol. ether.— (B'HCljjPtCl,. 
 
 i3-Amido-iso-Taleric acid 
 <CH3),C(NH,).CHj.C02Haq [0. 215°]. 
 
 Formation. — 1. Amongtheproduotsof oxida- 
 tion of the sulphate of diacetonamine (Heintz, 
 A. 198, 51).— 2. By reduction of /3-nitro-iso- 
 valeric acid (Bredt, B. 15, 2321). 
 
 Prqper-iies. — Crystalline powder; begins to 
 sublime at 180°. V. e. sol. water, si. sol. alcohol, 
 insol. ether. 
 
 Salts.— HA'HClaq : needles, [c. 120°].— 
 <HA'HCl)2PtCl4.— CuA's2aq: large crystals.— 
 AgA'.— (AgA')3AgN03aq. 
 
 Amido-valeric acid C5H5(NHj)02. Found 
 in the radicles of the sprouting lupin seeds. It 
 occurs along with amido-phenyl-propionio acid, 
 from which it may be separated by virtue of the 
 greater solubility of its copper salt (Schulze a. 
 Barbieri, J. ■pr. [2] 27, 352). 
 
 Properties. — Glittering plates, resembling 
 leucine (from alcohol). When heated, a woolly 
 substance sublimes out of it. Gives no pp. 
 with cupric hydrate or acetate (difference from 
 leucine). Salt . — HA'HCl : deliquescent prisms. 
 
 Constitution. — Probably identical with 
 Lipp's a-amido-jt-valerio. acid (A. 211, 354). 
 
 Amido-valeric acid. Occurs in the pancreas 
 of oxen (Gorup-Besanez, A. 98, 15). Prisms; 
 V. si. sol. alcohol (difference from leucine). The 
 hydrochloride forms slender deliquescent 
 needles. An amido-valeric acid was found by 
 Schutzenberger (A. Ch. [5] 16, 283) among the 
 products of the decomposition of albumen by 
 baryta -water. 
 
 AMIDO-VEEATBIC ACID v. di-methyl-di- 
 
 OXY-AMIDO-BENZOIO ACID. 
 
 AMISOXIMS. Oxy-amidines. Oxy-imid- 
 gamides. The oxims of amides, the general 
 formula being B.C(N0H).NH2. 
 
 Formation. — 1. By action of hydroxylamiue 
 uponnitriles : B.CN + N(0H)H2 = E.C(NOH).NHj. 
 2. By heating the thio-amides with alcoholic 
 solution of hydroxy lamine (Tiemann, B. 19, 1668) : 
 B.CS.NH2 -I- H,.NOH = E.C(N0H).NH3 + H^S. _ 
 
 Properties. — The amidoxims combine with 
 acids ; they also contain hydrogen displaceable 
 by metals. The acid salts of the alkaline 
 metals, EC(N0K).NH3,EC(N0H).NHj crystallise 
 well. The stability is increased by the presence 
 of electro-negative substituents ; thus, nitro- 
 benz-amidoxim can be reduced to amido-benz- 
 amidoxim without destruction of the amidoxim 
 group. 
 
 JJi/iers.- E.C(N0Et).NH2. These are formed 
 by the action of iodide of ethyl (or of other alky Is) 
 upon the alkaline salts, such as B.C(N0K).NH3. 
 They are bases. 
 
 Reactions. — 1. Split up by treatment with 
 acids or alkalis into NHg, hydroxylamine, and 
 the corresponding acid : B.C(N0H).NH2 + 2HjO =■ 
 B.CO.OH + HjNOH + NH3. This reaction takes 
 place most readily with methenyl-amidoxim 
 (isuretine) and ethenyl-amidoxim, while benzenyl- 
 amidoxim requires long boiling with HCl before 
 it is decomposed. In this saponification of 
 amidoxims the amide seems to be first formed : 
 E.C(N0H).NH3 -I- HjO = B.CO.NH^ -1- H^NOH.— 2. 
 The hydrochlorides are converted by sodium ni- 
 trite into amides : E.C(NOH).NHjHCl + NaNOj = 
 B-CCNHj + NaCl-hNjO-KHjO.- 3. They com- 
 bine with phenyl cyanate forming bodies called 
 uramidoxims; e.g.: Ph.C(N0H).NH2 + PhNC0 = 
 Ph.C(NOH).NH.CO.NHPh.— 4. Chlorides of acid 
 radicles, E'.CO.Cl, form alkoyl derivatives, 
 B.C(N.0.C0.E').NH2, which can split oft water 
 
 forming azoxims E.C<^^'^^OE. These 
 
 azoxims, although of high boiling point, are 
 extremely volatile in the vapour of other 
 liquids, even ether. — 5. Dibasic organic 
 anhydrides give rise to carboxylio acids of 
 
 azoxims, e.j. : B'.C(NOH).NHj + E"<;^>0- 
 
 E'.C<^°>0.E".C0jH-fHjO.— 6. Chlorofontm 
 
 ether produces bodies of the composition 
 B.C(NHJ:N.O.CO^t.— 7. Ca/rbonyl chloride 
 gives carbonyl-di-oximB, (E.C(NHj):N.0)2C0.-» 
 8. Chloral forms crystalline addition-products. 
 iie/erence«.— Tiemann, B. 18, 1060, 2466; 
 
AMINES. 
 
 191 
 
 19, 1475. The Amidoxima are described as 
 
 FOBMAMIBOXIM, EthENTL-AMIDOXIM, HeXOAMID- 
 
 oxiM, Bbnzamidoxim, Cinnamidoxim, Toluamid- 
 oxiM, Benzamidoxim cabboxyuo aoid, Niiko-benz- 
 
 AUIDOXIU, &0. 
 
 AMIDO-XYLENE v. XtIiIDINb. 
 
 jBa;o-Amido-xylene CHj.OjH^.OHj.NHj [1:3?]. 
 (196°). From CH3.C,Hj.CHjCl and alcoholic 
 NH, (Pieper, A. 151, 120). OU. Salts.— 
 B'HCl [185°].— B'jHjPtClj. 
 
 Exo - Amido -p - xylene CHj.CbH^.CHj.NHj 
 [1:4]. From CHj.C^H^.CS.NHj, tin, and HCl 
 (Paterno a. Spica, B. 8, 441). 
 
 di-Amido-xylene v. Xylyibne diamine. 
 
 tri-Amido-xylene CgHiaNs i.e. C^BMe^Qm.,), 
 [1:3:4:6:2]. Formed by reducing tri-nitro-w-xylene 
 [177°] (Greving, B. 17, 2427). White needles 
 which may be sublimed. 
 
 AMIDO-XYLENE-SULPHONIC ACID 
 OaHnNSO,. 
 
 Amido-xylene snlphonio acid 
 OeH,(NHj)Me,SO,H [4:1:3:6]. S. -276 at 0°; 
 •735 at 100°. From (l,3,4)-xylidine and H^SO, 
 or from nitro-m-xylene sulphonio acid (Jacob- 
 sen a. Ledderboge,B. 16, 193). Salts.— NaA'aq 
 and KA' aq form large trimet ric tables. — Ba A'^ aq : 
 minute needles, v. sol. water.— BaA'2 2aq (Sartig, 
 A. 230, 334; Nolting a. Kohn, B. 19, 137). 
 Diazo compound CsHjMejNjSOj : plates. 
 
 Amido-^-xylene sulphonio acid 
 0,H2Me,(NH2)(S0,H) [1:4:6:2]. From p-xylene 
 sulphonio acid by nitration and reduction (Nol- 
 ting a. Kohn, B. 19, 143). Needles (with aq) : 
 si. sol. cold water. Its salts are easily soluble. 
 Does not give xyloquinoue on oxidation. 
 
 Amido-p-xylene sulphonic acid 
 CsH:2Me2(NH2)S0aH [1:4:2:5]. From amido-^j- 
 xylene and fuming HjSO, or by heating its aoid 
 sulphate at 230°. Beadily oxidised by CrOj to 
 xyloquinone. Salts. — NaA': plates, v. sol. 
 water.— BaA'j7aq (Nolting, B. 18, 2664 ; 19, 141). 
 
 Si-amido-xylene sulphonio acid 
 C5HMej(NHj)2S0sH [1:3:6:?:4]. From nitro- 
 xylidine sulphonic acid and ammonium sulphide 
 (Limpricht, B. 18, 2190 ; Sartig, A. 230, 343). 
 Fawn-coloured prisms, si. sol. water, insol. alco- 
 hol. FejClgColours the solution wine-red. Salts: 
 BaA'j3iaq.— KA'aq.— PbA'j.- HA'HClaq. 
 
 AMIDO-»i-XYLEirOL CaH„NO i.e. 
 CjHjMej(NHj)(OH) ll:d:x:y]. [161°]. Got by 
 reducing nitro-xylenol(Pfafi, B. 16, 1137). White 
 glistening crystals. Salt: B'HCl: plates. 
 
 Aniido.5)-xylenol 05H2(0H3)2(NHj)(0H) 
 [1:4:3:6]. [242°]. White scales. Formed by 
 reduction of nitroso-^-xylenol (phlorone-oxim) 
 with tin and HCl (Goldschmidt a. Schmid, B. 
 18, 570 ; Sutkowski, B. 20, 979). CrOj oxidises 
 it nearly quantitatively to phlorone. 
 
 Salt: B'HCl: white crystals. 
 
 AUIKES. An amine is a body obtained by 
 displacing hydrogen in ammonia by one or more 
 alcohol radicles. They may be divided into 
 mono-, di-, tri-, and tetra- amines according as 
 it is considered that their molecule is derived 
 from one, two, three, or four molecules of 
 ammonia. Monamines are spoken of as primary, 
 secondary, or tertiary, according as one, two, or 
 three of the atoms of hydrogen in the molecule 
 of ammonia is held to have been displaced by 
 one or more alkyls. If part of the hydrogen 
 bfts been displaced by an aoid radicle (alkoyl) 
 
 and part by an alooholio radicle (alkyl) the 
 product may be viewed either as an amide or aa 
 an amine, thus NMeAoH may be called methyl- 
 aoetamide or acetyl-methylamine. In this 
 dictionary the latter name will be used, such 
 derivatives being described under the amines 
 from which they may be held to be derived. 
 Fatty amines are amines in which the nitro- 
 gen is attached to carbon that does not form 
 part of a ring; aromatic amines are bases in 
 which the nitrogen is attached to carbon in a 
 benzene nucleus. In addition to these there are 
 amines, such as pyridine and quinoline, in which 
 the nitrogen itself forms part of a ring, and also 
 others in which the nitrogen is united to carbon 
 in rings other than that peculiar to benzene. 
 
 Formation. — 1. By the action of ammonia 
 on the ethers of inorganic acids. The iodides, 
 bromides, and chlorides' of fatty, but not of 
 aromatic, alkyls, combine with ammonia and 
 with the amines (Hofmann, T, 1850, i. 93 ; 
 1851, ii. 357) : 
 
 NH5-HEtI = NEtH3l 
 NEtH2-hEtI = NEt2H2l 
 NEt2H + EtI = NEt3HI 
 NEt3 + EtI = NEtJ. 
 
 The fatty alkyl iodides also act upon the 
 hydriodides of the amines, in presence of 
 ammonia : 
 
 NH3 + NEtHjI + EtI = NEt^HJ + NH^I 
 
 NH3 + NEt^HjI + EtI = NEtjHI + NH,I 
 NH3 -I- NEtjHI -v EtI = NEtjI + NH J. 
 
 It is therefore impossible to prepare a pure 
 base by this method; methyl iodide gives 
 chiefly NMeJ, while ethyl iodide gives chiefly 
 NEtHjI, but in the case of primary iodides, 
 whatever proportions are taken, the entire series 
 of salts is formed. Isobutyl iodide does not 
 form the quaternary iodide, secondary butyl 
 iodide forms hardly any tri-butylamine, but only 
 mono-, and di-butylamine, while tertiary butyl 
 iodide is split up by NH, into isobutylene and 
 HI. NEt3 at 100° splits up isopropyl iodide and 
 tertiary butyl iodide forming NEt3HI and define 
 (Hofmann, B. 7, 513; Eeboul, O. B. 93, 69). 
 Secondary propyl, hexyl, and octyl iodides form 
 only mono-amines when heated with ammonia 
 (Jahn, M. 3, 165). In the action of alkyl chlo- 
 rides upon aqueous NH3, the higher the molecular 
 weight, the less primary amine is formed (Mal- 
 bot, C. B. 104, 998). 
 
 Ammonium iodide can be separated by its 
 insolubility in alcohol. The compounds NE3HI, 
 NE2H2I, and NEH3I are decomposed by KOHAq 
 with formation of KI and NE3, NB^H, or NEHj 
 respectively, while tetra-alkylated ammonium 
 iodides are not affected. The following method 
 may be employed in the preparation of fatty 
 amines (Hofmann, B. 3, 776). The alkyl iodide, 
 EI, is heated with alcoholic NH, at 100° ; the 
 product is filtered from NHjI, evaporated, and 
 distUled with potash. NE^I remains behind. 
 The distillate, dried by means of solid KOH, is 
 cooled and treated with oxalic ether which is 
 slowly added. The following reactions then 
 occur : 
 
 EtO.CO.CO.OEt + 2NEH2 = 
 
 HEN.CO.CO.NEH + 2H0Et 
 
 EtO.CO.CO.OEt + NEjH = 
 
 EtO.CO.CO.NBj-FHOBt. 
 
 The reaction is completed by heat, and the 
 
192 
 
 AMINES. 
 
 tertiary baBe, NK3, which does not react with 
 oxalic ether, is distilled ofi. The residue is well 
 cooled and the solid di-alkyl oxamide separated 
 from the liquid di-alkyl-oxamio ether by pressure. 
 The latter is purified by washing with water. 
 Boiling potash liberates the alkylamine from 
 the di-alkyl oxamide and the di-alkyl-amine 
 from the di-alkyl-oxamio ether. 
 
 When the halogen is situated in a benzene 
 nucleus ammonia cannot effect its displacement 
 by amidogen unless other chlorous groups are 
 also present in the nucleus. Thus 0- and p- 
 chloro-nitro-benzene (but not m-chloro-nitro- 
 benzene) are converted into nitro-anilines by 
 alcoholic NH, at 100°. 
 
 Primary monamines may be prepared by 
 acting with KOH on the alkyl ammonium sul- 
 phates (Morrison, Pr. E. 28, 693) : 
 MeNH.SO, + 2K0H = K,SO< -I- MeNH^ -I- SH^O. 
 
 2. By boiling alkyl oyanates with potash 
 (Wurtz, C. B. 28, 223), thus: EtNC0-hH20 = 
 EtNH^ + COj. The primary bases prepared by 
 this reaction may be contaminated with secondary 
 and tertiary bases. This occurs when the potas- 
 sic cyanate used to prepare the alkyl oyanates 
 contains cyanide (Silva, C. B. 64, 299). 
 
 3. Similarly, from thiocarbimides and H^SO. : 
 EtNCS + nfi = EtNHj -f COS. 
 
 4. By the reduction of nitro compounds : 
 ENOJ-^3H2=ENH2-^2H^O. This reaction is 
 chiefly used in the aromatic series, inasmuch as 
 it is easy to prepare nitro derivatives of com- 
 pounds containing a benzene nucleus. 
 
 The following reducing agents may be used : 
 
 (a.) Alcoholic ammonium sulphide. The 
 compound is dissolved in alcohol, saturated with 
 NH3 and H^S is then passed in. The solution 
 is boiled, filtered from S,acidified,and evaporated ; 
 a salt of the base is then left : CjHjNOj + SH^S = 
 C ANHj + 2B.fi + Sj (Zinin, A. 44, 283). This 
 method is especially useful in reducing nitro- 
 azo compounds which would give hydrazo com- 
 pounds if reduced in acid solution. 
 
 Substances containing several nitroxyls 
 usually have only one of them reduced when 
 treated in this way. 
 
 (6.) Zinc dust may be used either alone, by 
 mixing the substance with it and distilling, or 
 it may be used in conjunction with water or 
 aqueous potash : Zn + 2K0H = K^ZnOj -f B.^. 
 
 (c.) Ferrous sulphate and aqueous ammonia 
 are used in reducing unsaturated and unstable 
 compounds. 
 
 (d.) Arsenious acid and NaOHAq. 
 
 (e.) An acid and a metal. For the acid, 
 HClAq or HOAc is used; for the metal, zinc, 
 tin, or iron, is taken. Tin and HClAq give, as 
 a rule, the best results. A mixture of zinc and 
 tin is as effective as pure tin, for the zinc pps. 
 the tin as fast as it dissolves. The amount of 
 acid used may sometimes be very small ; thus, 
 in the preparation of aniline, the action seems 
 to be : 
 iCjHjNO, -I- iBfi + 9Fe = 4C,H,NH2 -I- 3Fe30,. 
 
 (/.) Stannous Chloride. In reducing with 
 SnClj and HCl the resulting SnClj sometimes 
 chlorinates the product ; thus o-nitro-toluene 
 gives chloro-o-toluidiue. The nitroxyls of poly- 
 nitro derivatives may be reduced one by one by 
 adding to their cold alcoholic solution the cal- 
 culated quantity of SuCl^ dissolved in alcohol 
 
 saturated with HCl. In the case of diuitro-toluena 
 CsHjMe(N02)2 [1:2:4] the nitroxyl in the posi- 
 tion is first reduced, forming 0„H3Me(NH2)(N02) 
 [1:2:4] ; whilst alcoholic ammonium sulphide' 
 reduces the nitroxyl in the p position, forming 
 C,H3Me(N02)(NH2) [1:2:4] (Auschiitz a. Heusler, 
 B. 19, 2161). 
 
 (g.) Hydric iodide solution, alone, or with 
 addition of phosphorus. 
 
 5. By the reduction of nitriles (Mendiua^ 
 
 A. 121, 229) : 0H3CNh-2H2 = CH3.GH2.NH2. 
 The reduction is effected by Zn and dilute- 
 
 H2SO4 but it is slow, and a great deal of uitrile- 
 is saponified : OH3.CN + 2Bifi = CH3.CO2NH,. 
 
 6. Primary bases are instantly formed whea 
 oarbamines are treated with acids : 
 
 CH3NC -I- 2HjO = CH3NHj -I- HCOjH. 
 
 7. By boiling bromo-amides with aqneoui 
 NaOH. If bromine and potash be simultaneously 
 supplied to an amide, a potassium bromo-amide,. 
 X.CO.NKBr, is formed. If this compound be 
 treated with silver carbonate, an alkyl cyanate i^i 
 produced : X.CO.NKBr = KBr + X.N.CO. 
 
 When this cyanate is boiled with potash an 
 alkylamine is formed (by Formation 2). The 
 two last stages may be performed simultaneously 
 by boiling the potassium bromo-amide with, 
 aqueous NaOH. 
 
 The operation is conducted as follows : 
 
 Bromine is mixed with its equivalent of 
 amide, and a 10 p.c. solutign of potash is added 
 till the colour of the bromine has nearly 
 disappeared. 
 
 X.CO.NHj + Brj + 2KH0 = 
 X.CO.NKBr + KBr + 2HjO. 
 
 Three equivalents of potash dissolved so as 
 to form a 30 p.c. solution are now heated to 70° 
 in a retort, and the first solution is added 
 gradually through the tubulus. Finally the 
 whole is distilled, and the base collected in a 
 receiver containing hydric chloride. A mixture 
 of ammonium chloride and the hydro-chloride 
 of the base is thus got ; they may be separated 
 by alcohol, which does not dissolve the former 
 (Hofmann, B.15, 765). 
 
 8. Amides can be converted into amines 
 by heating with alcohols : thus acetamide 
 and ethyl alcohol give ethylamine acetate 
 CH3.CO.NH2 + HOEt = CH3.CO.ONEtH3, while 
 ethyl-acetamide and ethyl alcohol give diethyl- 
 amine acetate (Baubigny, C. B. 95, 646). 
 
 CH3.CO.NEtH + HOEt = CHjCO.ONEt^Hj. 
 Sodium alooholates act similarly (Seifert, B. 
 18, 1355) : 
 
 X.NH.CO.T + NaOE = X.NH.R -t- NaO.CO.Y. 
 
 9. From amido-acids by heating alone or with 
 baryta : CeH,(NHJCO.,H = C3H3NH2 -h CO^. 
 
 10. From alcohols or phenols by displacing 
 hydroxyl by amidogen. Ethyl and methyl 
 alcohols give a little ethyl- and methyl-amine 
 when heated with NH,C1 at 300° (Weith, B. 8, 
 459). Similarly, phenols produce small quanti- 
 ,ties of amines when heated with NH, ; this re- 
 action takes place very readily in the naphtha- 
 lene' and anthracene series. Ortho- and pa/ra-, 
 but not meta-, nitro-phenols are converted by 
 aqueous ammonia into nitranilines (Merz a. Biz, 
 
 B. 19, 1749). The reaction takes place more 
 readily when the alcohols are heated at 260° 
 with the compound ZnCljNHj or CaCLiNH, 
 (Merz a. Weith, B. 13, 1300 ; 14, 2343 ; Merz a. 
 
AMINES. 
 
 193 
 
 Gasior-owski, B. 17, 623 ; Merz a. Buoh, B. 17, 
 2634). Ammonia-zinc-chloride converts phenol 
 into aniline; anUine-zinc-chloride acting upon 
 phenol gives di-phenylamino. )3-naphthol is 
 converted by heating with NH, into naphthyl- 
 amine, but by ammonia-zinc-chloride into di-|3- 
 naphthyl-amine. Fatty alcohols act differently 
 upon aromatic bases in presence of ZnClj, the 
 alkyl entering the nucleus; thus aniline-zino- 
 ohloride and alcohol produce amido-phenyl- 
 ethane : 
 
 O^HjNH^ + HOEt = CeH^EtNHj + H,,0. 
 
 11. By reduction of the phenyl-hydrazides 
 of the aldehydes and ketones in alcoholic solu- 
 tion by sodium-amalgam and acetic acid (Tafel, 
 B. 19, 1924) : 
 
 EB'C:NjHPh + 2Hj = EB'CH.NHj + PhNH^. 
 
 12. By reduction of aldoxims and ketoxims 
 in alcoholic solution by sodium amalgam and 
 acetic aoid (Goldschmidt, B. 19, 3232) : 
 
 BE'C:NOH + 2H2 = EE'CH.NHj -^ H^O. 
 
 13. From sulphonates by heating with sod- 
 amide (Jackson a. Wing, B. 19, 902) : 
 
 E.SO3K + NaNHj = E.NHj + NaKSOj. 
 
 Properties. — Most amines are volatile or can be 
 distilled alone or with the aid of steam. Primary 
 bases in which amidogen is not united to carbon 
 in a benzene nucleus turn red litmus paper blue 
 and combine with carbonic acid ; aniline and its 
 homologues are neutral to litmus, and do not 
 combine with carbonic acid. Ammonia pps. the 
 amines from cold aqueous solutions of their 
 salts ; but at high temperatures the amines expel 
 NH3 from its salts. The relative saponifying 
 power of amines has been studied by Ostwald 
 {J. pr. [2] 35, 112). If a mixture of aromatic 
 bases is dissolved in an excess of glacial acetic 
 acid, and the solution is diluted with three times 
 its volume of water and then boiled, the primary 
 amines remain in solution while the acetates of 
 Boooudary and tertiary amines are decomposed 
 and the bases are found on the filter (Michael, 
 B. 19, 1391). To determine whether a given base 
 is primary, secondary, or tertiary, it is heated 
 with methyl iodide until a quaternary iodide is 
 formed; this iodide is known by its stability 
 towards potash. The original base and the am- 
 monium iodide are both analysed. If the am- 
 monium iodide differs in composition by con- 
 taining CH3I more than the base, then the base 
 was tertiary. If it differ by C^HjI, this shows 
 that the original base was secondary, and had to 
 exchange hydrogen for methyl before it could 
 become tertiary. If the iodide contains CjH,! 
 more than the base, then the latter was primary. 
 
 Eeactions 1, 2, 3, 4, 5, 6, 11, 12, 15, 20, 27, 28, 
 may also be used to distinguish between primary, 
 secondary, and tertiary bases. 
 
 When a quaternary ammonium base is 
 distilled, if it contains ethyl it splits up thus : 
 NBE'E"C2H,(0H) = NEE'E" f O^H, + Kfi ; 
 (Hofmann, B. 14, 494). 
 
 Quaternary ammonium chlorides containing 
 methyl split off MeOl on distillation : 
 
 NEE'E"MeCl = NEE'E" + MeCl ; 
 (Lossen, A. 181, 377). 
 
 Eeactions 3, 5, 6, 12, 13, 26, and 28, serve to 
 distinguish o-diamines from m- and p- diamines. 
 
 Reactions. — 1. If a primary base be boiled 
 with alcoholic potash and chloroform II10 dis- 
 
 VoL. L 
 
 gusting odour of the corresponding oarbamlne 
 will be noticed (Hofmann, B. 3, 707) : 
 EtNHg -^ CHCI3 + 3EH0 = EtNC -1- 3KC1 -i- 3H,0. 
 2. If a primary fatty base be dissolved in 
 alcohol mixed with an equal volume of CSj, and 
 the liquid be boiled down to half its volume, a 
 thiooarbamate will be formed : 
 
 2ENH2-i-CS2=ENH.CS.S.NEH3. 
 If the liquid be now boiled with a little aqueous 
 mercuric or ferric chloride a pungent odour of 
 an alkyl mustard oil (or thiocarbimide) vrill 
 be perceived, thus: ENH.CS.SNEH3-HHg0l2 = 
 HgS + ENCS -I- NEH3CI + HCl. In the aromatic 
 series the product of the action of alcoholic CSj 
 is usually a thio-urea which requires to be treated 
 with P2O5 in order to get the thiocarbimide (Hof- 
 mann, B. 3, 768 ; 8, 107 ; Weith, B. 8, 461). 
 Mesidine and amido-penta-methyl-benzene give 
 thio-carbimides in addition to smaller quantities 
 of the thio-ureas (Hofmann, B. 18, 1827). — 3. 
 Nitrous acid converts primary fatty amines into 
 alcohols: ENH2 + HNO^=EOH^-N2-^H20. It 
 converts primary aromatic amines into diazo- 
 oompounds: ENH2 + HN02 = EN20H + H20. II 
 converts all secondary bases into nitrosamines, 
 which are neutral substances, volatile with 
 steam : EE'NH + HNOj = EE'N.NO -h H^O. It 
 cannot act upon tertiary fatty bases, except 
 with elimination of an alkyl. It converts most 
 tertiary aromatic bases into nitroso derivatives, 
 which still possess basic properties : 
 
 CjHsNMe^ + HNO2 = C,H^(N0)NMe2 H- H,0. 
 
 Aromatic nitrosamines are converted into 
 p-nitroso derivatives under the influence of 
 acids. OsHsNMe(NO) = CsHj(NO).NMeH. By 
 means of the preceding reactions, nitrous aoid 
 may be used to separate secondary from primary 
 and tertiary bases, for the nitrosamines do not 
 combine with acids, and may therefore be ex- 
 tracted from the aoid solution by ether, or by 
 distilling with steam : and on reduction they 
 give the secondary base. If the diazo com- 
 pounds are boiled with water phenols are formed : 
 ENjCl + HjOsEOH-hN^ + HCl, while if they 
 are boiled with alcohol, the amidogen is usually 
 displaced by hydrogen: EN^Cl -F CjHjO = 
 EH-fHOl+CaHjO. Frequently, however, boil- 
 ing with alcohol displaces amidogen by ethoxyl ; 
 C,Me,H.N2Cl -I- HOEt = C^MejH.OEt ^■ HCl -1- N, 
 (Hofmann, B. 17, 1917). Aiaidogen may also 
 be displaced by hydrogen by reducing the diazo 
 compound to a hydrazine and boiling the latter 
 with aqueous OuSO^ (Haller, B. 18, 90). In 
 order to displace amidogen by chlorine we may 
 distU the platinochloride of the diazo derivative ; 
 to displace amidogen by bromine we may boil 
 the perbromide of the diazo derivative with 
 alcohol ; to displace it by iodine we may boil 
 the diazo salt with aqueous HI or KI. These 
 operations may be more conveniently performed 
 by the method of Sandmeyer (B. 17, 1633, 
 2650). This method consists in boiling the 
 diazo compounds with cuprous chloride, bromide, 
 iodide, or cyanide. 
 
 Examples. — (a) 4 g. m-nitro-aniline, 7 g. HCl 
 (S.G. 1-17), 100 g. water, and 20 g. of a 10 p.c. 
 solution of cuprous chloride in HClAq are heated 
 to near boUing and 2-5 g. sodic nitrite dissolved 
 in 20 g. water are slowly added, the mixture 
 being well shaken. 4 g. pure »»-ohloro-Diirc- 
 bcnzeno is obtained, 
 
 
 
194 
 
 AMINES. 
 
 (6) 12-6 g. oryBtalllsed ouprio sulphate, 36 g. 
 KBr, 80 g water, 11 g. HjSO^ (S.G. 1-8), and 20 g. 
 copper turnings are boiled until the dark colour 
 has nearly disappeared. Aniline (9-3 g.) is now 
 added, and the boiling liquid treated as before 
 with NaNOj (7 g.) dissolved in water (40 g.). 
 Bromo-benzene passes over on subsequent dis- 
 tillation. 
 
 (o.) 25 g. crystallised CuSOj, 150 g. water 
 and 28 g. EON (96 p.c.) are dissolved in hot 
 water. A solution of diazobenzene chloride is 
 run in, this is prepared from 7 g. NaNOj dissolved 
 in 20 g. water added to a solution of 9"3 g. 
 anihne in 20-6 g. HCl (S.G. 1-17) and 80 g. 
 water. The yield of benzonitrUe is 63 p.c. of 
 the theoretical. 
 
 In these reactions a double compound be- 
 tween the cuprous salt and the diazo salt is 
 perhaps an intermediate body. Such a double 
 compound has been isolated in the case of 
 8-naphthylamine, OijHjN^BrCujBrj (Lellmann 
 a. Bemy, B. 19, 810). Substitution of amidogen 
 by halogens may also be effected by gradually 
 adding HNO., to a hot solution of the amine in 
 HCI, HBr, or HI (Losanitsch, B. 18, 39). 
 
 Amidogen may be changed into SH by heat- 
 ing the diazotised base with warm alcoholic 
 potassium sulphide. By oxidising the resulting 
 mercaptan with KMnO, a sulphonio acid is got 
 (Klason, B. 20, 349). 
 
 Nitrous acid serves to distinguish o-, m-, and 
 p- diamines {v. di-Azo-compounds). 
 
 4. Bemsoyl chloride acts on primary and 
 secondary amines : 
 
 BNHj -H BzCl = ENBzH + HCl, 
 BB'NH + BzCl = EE'NBz + HCl 
 
 (Hofmann, B. 5, 716; Hallmann, B. 9, 846). 
 
 Tertiary aromatic amines heated with it at 200° 
 
 may exchange alkyl for benzoyl : 
 
 NPhEtj + BzCl = NPhEtBz + EtCl 
 
 (Hess, B. 18, 685). 
 
 5. Acetyl chloride converts primary and 
 secondary amines into acetyl derivatives. 
 
 The di-alkylated tertiary aromatic amines 
 readily allow one of the alkyl groups to be re- 
 placed by acetyl when treated with acetyl bro- 
 mide, the alkyl bromide formed converting 
 another portion into quaternary ammonium 
 bromide: 2XNBj + AoBr = XNEAc + XNB3Br. 
 
 The reaction sets in spontaneously, and is 
 completed on gentle warming (Staedel, B. 19, 
 1947). 
 
 Primary aromatic amines may be converted 
 into acetyl derivatives by boiling not only with 
 AoCl or AcjO but even with glacial HOAc. 
 
 The alkoyl derivatives of o but not of m and 
 ■p aromatic diamines give rise to anhydro com- 
 pounds : 
 
 C,H<NH.C0.CH3^H,0. O.H,<NH^O.CH, 
 
 (Hiibner, /. 208, 278). 
 
 6. Aldehydes form products of condensation 
 ^ith amines. (Enanthol is recommended by 
 Sohifi (A. 159, 158) as a means of distinguishing 
 between the different classes of amines. Primary 
 amines require one equivalent of oenanthol : 
 
 0,H„0 + PhNHj = PhN(0,H,j) + H^O, 
 while secondary amines require only half as 
 much aldehyde : 
 
 CjH,.0 + 2Me,NH = (Me,K),(O,H,0 + H^O. 
 The base is dissolved in benzene and a stEmdard 
 
 solution of cenanthol in benzene is run in as 
 long as it produces further separation of drops 
 of water. 
 
 Tertiary aromatic amines can aJso condense 
 with aldehydes : 2PhNEt J + [1:2] C5H^(N0J.CH0 
 = N02.C8H<.CH(0(,H4NEtj)j + H^O. Aromatio 
 amines heated with aldehydes and ZnOlj give 
 tri-substituted methanes (Fischer, B. 15, 676). 
 
 In order to distinguish whether an aromatio 
 diamine is an ortho compound, Ladenburg (B. 
 11, 600) heats its hydrochloride with benzoic 
 aldehyde ; if the compound is ortho an aldehydine 
 (g. V.) is formed and HCl is evolved, while no 
 HCl is evolved in the case of m or ^J compounds. 
 E"(NH2HCl)j + 2PhCH0 = 
 B"(N,C,H2Phj)HCl + 2H2O + HCl. 
 
 7. Bromine and aqueous potash convert 
 primary amines into di-bromamines : 
 
 MeNHj -H 2Br2 + 2K0H = MeNBr^ + 2KBr + 2H2O. 
 Secondary amines, containing one divalent alkyl, 
 behave similarly : 
 
 CsHnKH + Br^ + KOH = CsH^NBr + KBr + H^O 
 but secondary amines containing two monovalent 
 alkyls are split up into an alkylene bromide and 
 a primary alkylamine (Hofmann, B. 16, 559). 
 
 The di-bromo-amines containing hex^ and 
 its higher homologues are split up by aqueous 
 NaOH into HBr and nitrHes : 
 
 CjH.sCHjNBr^ + 2NaOH = 
 
 C,H,5CN + 2NaBr + 2H20. 
 
 Hence amides may be converted first into amines 
 
 and then into nitriles by treatment with bromine 
 
 and NaOHAq, the first reaction being : 
 
 G,H,,CH2.C0.NH2 + Br^ + 4NaOH = 
 CjHijCHj.NHj + 2NaBr + Na^COa -^ 2H2O 
 (Hofmann, B. 17, 1920). 
 
 8. Sulphuric oxide combines with primary 
 and secondary fatty amines, forming small 
 quantities of sulphamio acids : 
 
 NEt^H + SO3 = NEtj-SOsH. 
 It also combines with tertiary fatty amines : 
 
 NEtj + SOs =Et3N<;^Q ^> (Beilstein a. Wiegand, 
 
 B. 16, 1264). 
 
 It combines with aromatic amines forming 
 sulphonic acids : 
 
 C5H5NHj+ S03 = CsH,(SOsH)NH2. 
 Aromatio amines may also be sulphonated by 
 HaSO, and by ClSOaH. 
 
 -9. Sulphuryl chloride acts upon secondary 
 fatty amines thus, forming tetra-alkyl sulph- 
 amides : SO^Cl^ + 2HNEt2 = S02(NEt2)2 + 2HC1. 
 With the hydrochlorides of these bases the re- 
 action stops half way: SOjClj + HCl.NHBtj^ 
 Cl.S02.NEt2 + 2HCl (E. Behrend, A. 222, 116). 
 
 10. Zinc ethide does not attack tertiary 
 amines, but acts upon primary and secondary 
 amines in the following ways : 
 
 2ENHj -h ZnEt J = E^N^H^Zn + 2HEt, 
 2EE'NH + ZnEtj = BJB'jNjZn + 2HEt 
 (Frankland, Pr. 8, 504 ; Gal, 0. B. 96, 578). 
 
 11. Cyanic ethers unite with primary and 
 secondary bases forming alkyl-nreas : 
 
 ENH^ + B'NCO = ENH.OO.NE'H, 
 EB"NH + E'NCO = EB"N.OO.NE'H. 
 Cyanic acid acts similarly : 
 
 BNH,HC1 + KNCO =BHN.OO.NHj + KCl 
 
 12. TMo-carbimides unite with primary and 
 secondary amines forming thio-ureas : 
 
 ENHj + E'NCS =BNH.OS.NB'H. 
 When the solid product obtained by boiling an 
 
AMMELIDE. 
 
 195 
 
 aromatic di-amine with alcohol and oil of 
 mustard (C3H5NCS) is gradually heated, then if 
 the diamine were o it would solidify above its 
 melting-point ; if it were to it would melt with- 
 out further change and would therefore soUdify on 
 cooling ; if it were p it would melt and undergo 
 decomposition and on cooling would remain 
 liquid (Lelhnann,4. 221, 1 ; 228, 248 ; B. 19, 808). 
 In all cases di-thio-ureas, ^"(NH.CS.NHGaHs)^ 
 are first formed ; those from m-diamines are not 
 affected by heat, while the and p derivatives 
 split up on melting thus : 
 
 B"(NH.CS.NHC3H5)j= 
 
 13. The di-sulphocyanides of the o-diamines 
 are changed at 120°-130° into thio-ureas, 
 
 OxHy<^-j^-rr^CS, which are not desulphurised 
 
 by hot solution of PbO in NaOHAq. The m and 
 p diamines give compounds of the form 
 CxHy(NH.CS.NH2)2 which ai-e desulphurised by 
 this reagent (Lelhnann, A. 228, 8, 248). 
 
 14. SmaU quantities of orthodiamines are 
 readily detected by adding a few drops of a hot 
 acetic acid solution of phenanthraquinone to an 
 alcoholic solution of the substance ; if an ortho- 
 diamine is present a yellow crystalline pp. of 
 the corresponding quinoxaline is formed on boil- 
 ing the solution ; this pp. in the case of pheny- 
 lene and tolylene o-diamines is coloured deep- 
 red by HCl (Hinsberg, B. 18, 1228). 
 
 15. If a mixture of bases is treated with 
 sufficient citraconic acid to form the acid salts 
 and the aqueous solution is boiled the primary 
 amines will be ppd. in the form of alkyl-oitraco- 
 namio acids, while the secondary and tertiary 
 amines can be obtained by distilling the filtrate 
 with steam (Michael, B. 19, 1390). 
 
 16. Oxidising agentscoTiveitaroraatio amines 
 into azo or azoxy compounds. Hence the nitra- 
 tion of such amines by the usual methods re- 
 quires previous introduction of acetyl into the 
 amidogen. But by treating the nitrates with 
 cold cone. H2SO4 nitro-amines may be prepared, 
 the nitroxyl taldng a m position with regard to 
 amidogen (Levinstein, D, P. J. 256, 471). 
 
 17. Amines form condensation products with 
 quinones, e.g. 
 
 CaH202(NHPh)2; OAO(NPh)(NHPh)r 
 
 18. Aromatic amines when boiled -with fatty 
 amides produce ammonia and alkyl-amides, e.g. 
 
 CH3.CO.NHj + NPhHj --= CH3.CO.NPhH + NH3. 
 
 19. Silver salts form additive compounds 
 with amines (Mixter, A. C. J. 1, 239). 
 
 20. The ferrocyanides are obtained by adding 
 the amines to a mixture of aqueous K^FeCyj and 
 hydrochloric acid ; a crystalline pp. of the acid 
 ferrooyanide B'^HiFeCy, a;aq, is usually formed 
 (Fischer, A. 190, 184 ; Eisenberg, A. 205, 265). 
 The ferrocyanides of tertiary amines are par- 
 ticularly insoluble in water and may be used 
 as a means of isolating those amines. To re- 
 cover the amine, the pp. is suspended in water 
 and decomposed by CuSO^, and the excess of 
 CuSO, removed from the filtrate by baryta. 
 
 21. Chloral hydrate heated with tertiary 
 aromatic amines and ZnClj forms a condensation 
 product which, when decomposed by aqueous 
 EOH gives an aldehydo derivative, Ojg. 
 
 C0l3CH( OH) J + CjHjNMej = 
 
 CCLCH(OH).CaH,NMe, + HoO 
 CCl3CH(0H).0ANMe2= 
 
 CCl3H + HC0.03HjNMe, 
 (Boessneck, B. 18, 1516; 19,365). 
 
 22. Primary aromatic amines in alcoholic 
 solution absorb cyanogen; and the product when 
 boiled with glacial HOAo becomes a di-alkyl- 
 oxamide : 
 
 2PhNH2 + C2N2 = PhNH.O(NH).C(NH).NPhH 
 PhNH.C(NH).C(NH).NPhH + 2Hj0 = 
 
 PhNH.CO.CO.NPhH + 2NH3. 
 Aromatic o-diamines act similarly ; the result- 
 ing oxalyl-o-diamine may be viewed as a di-oxy- 
 quinoxaline (Bladin, Bl. [2] 42, 104). 
 
 23. Primary aromatic amines heated with 
 glycerin (or acrolein), H^SOj, and nitrobenzene 
 (as oxidising agent) produce bases of the quino- 
 line series. A similar reaction occurs when 
 glycol (or paraldehyde) is substituted for 
 glycerin. 
 
 24. Nitric oxide passed into an alcoholio 
 solution of tertiary aromatic bases produces azo- 
 oompounds of the form BK'N.CeHj.N^.CsHj.NEE'. 
 
 25. For the action of aceto-acetia ether, 
 V. p. 19. 
 
 26. Orthodiamines form crystalline com- 
 pounds with glucose (Griess a. Harrow, B. 20, 
 281). 
 
 27. Diazobemene chloride reacts with primary 
 and with secondary amines, forming diazo-amides 
 (v. di-AZO-compouuds). In the case of the 
 secondary amines the compounds C5H5.N2.NEB', 
 being easily crystallised and si. sol. water, may 
 be conveniently used in separation of these bases 
 from tertiary and in some oases from primary 
 bases (Wallaoh, A. 235, 235). 
 
 28. A solution of potassium croconate gives 
 with salts of o-diamines dark-coloured ppg. con- 
 sisting of the corresponding azines (Nietzki, B. 
 19, 2727). 
 
 29. Tertiary aromatic amines form condensa- 
 tion products when heated with aromatic acids 
 or alcohols in presence of ZnCl^ or Pfis > water 
 being eliminated at expense of H para to N 
 (Fischer, A. 206, 85). 
 
 OTHEB BEACTIONS of the amines are 
 described in articles on the several bases, e.g. 
 Methylamine, EthyiiAmine, Aniline, Pheny- 
 LENE-niAMiNE. See also Amides, Auido Acids, 
 Amidlnes, and Amidoxims. 
 
 AMISATIN v. Isatin. 
 
 AMMELIDE 03H4N,0j or OoHsNaO, i.e. 
 CjNs(NH2)(OH)2(?). Melanu/renic acid. 'Amido^ 
 cyanuric acid.' Mono-a/mide of cyanwric acid. 
 Ijiebig made a distinction between ammelide 
 and melanurenio acid, but his ammelide was a 
 mixture of ammeline and his melanurenic acid, 
 hence it seems best to transferthe name ammelide 
 to melanurenic acid (Klason, J.pr. [2] 33, 295). 
 
 Formation. — 1. From melam and cone. 
 H2SO4 (Liebig, A. 10, 30; Gabriel, B. 8, 1165; 
 Jager, B. 9, 1554). — 2. From melam and boiling 
 cone. KOHAq or cone. H2SO4 at 150° (K.).— 
 8. From ammeline and cone. HjSOj at 160° or 
 by beating ammeline nitrate (Enapp, A. 21, 
 244) ; the change is incomplete. — 4. A product 
 of the dry distillation of urea (Liebig a. W6hler, 
 A. 54, 371 ; Laurent a. Gerhardt, A. Oh. [2] 19, 
 93; Dreohsel, J. pr. [2] 11, 289).— 5. Among 
 products got by boiling mellon-potassium with 
 
 o2 
 
100 
 
 AMMELIDE. 
 
 aqueous KOH (Hennesberg, A. 73, 246 ; Liebig, 
 A. 95, 269). — 6. From its ethers or their thio- 
 derivatives by gentle heat (K.). — 7. From thio- 
 ammelide and KMnOj (E.). — 8. From cyanogen 
 bromide and cyanamide at 100° (Cech a. 
 Dehmel, B. 11, 25). — 9. From urea and cyano- 
 gen iodide at 150° (Poensgen, A. 128, 339 ; 
 Hallwaohs, A. 153, 294 ; Schmidt, J. pr. [2] 5, 
 36). — 10. In small quantity by action of COClj 
 on NH3 (Bouchardat, A. 154, 355).— 11. In 
 small quantity from di-cyan-di-amide by heat- 
 ing with water at 160° or with aqueous ammonic 
 carbonate at 120° (Bamberger, B. 16, 1078, 
 1703). 
 
 Preparation. — Cono. H^SO, (300 g.) is slowly 
 poured upon melam (100 g.) and the solution 
 ieated for a few minutes to 190°. When cold 
 it is poured into a litre of water, when ammelide 
 sulphate slowly crystallises (Striegler, J. pr. [2] 
 33, 163). 
 
 Properties. — White crystalline powder ; v. si. 
 Eol. water, insol. usual menstrua, sol. mineral 
 acids, insol. acetic acid, v. sol. ammonia. It 
 does not separate when its solution in warm 
 aqueous NaOH is cooled (difference from amme- 
 line). May be crystallised from boiling water. 
 Not attacked by CI, Br, HI, or AcCl. 
 
 Beactions. — 1. Boiling dilute acids or alkalis 
 form NHj and oyanurio acid. Baryta-water 
 does not effect this change. — 2. Phosphorus 
 pentachloride forms CyjCls. — 3. KMn04 in acid 
 solution forms oyanuric acid. — 4. Water at 170° 
 forms CO2 and NHj. — 5. Heated in a current of 
 moist CO2 it forms cyanamide. 
 
 Salts.— (H2A" = CeHsN80J.— 
 HjA"HjS043aq.— HjA" 2HKOs.— H^A" 2HC1.— 
 Na^A" 6aq. — NaHA"5aq. — KjA". — EHA". — 
 (NH,).,A"5aq. — (NH,)HA"liaq. — CaA"a;aq. — 
 BaA"2iaq. — CuA". — NiA"2aq. — Ag,A". — 
 AgHA'liaq (Striegler; Volhard, B. 7, 92). 
 
 Di-methyl ether CsHgN402 i.e. 
 C3N3(NH2)(OMe)2. [212°]. Formed by action 
 of ammonia on trimethyl cyanurate, and occurs 
 as a by-product in the preparation of that body 
 (Hofmann a. Olshausen, B. 3, 273). Plates, si. 
 sol. cold alcohol, v. si. sol. ether, si. sol. cold 
 water. — CjHjN^OjAgNOa : needles. 
 
 Di-ethyl ether C,'H.^^fi^ i.e. 
 C3Ns(NH2)(OEt)2. [97°]. By-product in the 
 action of CyCl on NaOEt, and formed by 
 heating cyanetholin with aqueous NH, at 100° 
 (H.a.O.). Prisms.— CjHijNiOjAgNOa : needles. 
 — (C,H,„N402)2AgN03 : needles. 
 
 AMMELINE C3H,N50 i.e. C3N3(NH2)j(OH). 
 ' Di-amido-cyamt/ric acid,' Diamide of cyanuric 
 acid. 
 
 Formation. — 1. By boiling melam for a long 
 time with KOHAq or HClAq or by heating it 
 with cone. HjSO, at 100° (Liebig, A. 30, 24 ; 
 lOason, ■7'. pr. [2] 33, 286). — 2. From 
 Cy3(NH2)jCl by alkalis (Lament a. Gerhardt, 
 A. Ch. [3] 19, 92). — 3. From thio-ammeline and 
 EMnO.|. — 4. From its ether or its thio derivative 
 by HCl. — 5. Formed by boiling the hydro- 
 chloride of ' di-amido-tri-chloro-methyl cyani- 
 dine ' {v. 2Vi-CHLOKo-A0ET0NiTErLE) with NHjAq : 
 
 Cy3(NH2)2(CCl3)HCl + NH3 + H^O = 
 Cy3(NH2)2(OH) + NH,C1 + HCGI3. Also by heat- 
 ing tri-ohloro-acetonitrile with NHjAq at 120°, 
 or with alcoholic NH, at 170° (Weddige, J. pr. 
 [2] 33, 85). 
 
 Properties. — Minute needles in dendritic 
 groups (when ppd. from a warm solution). Insol. 
 water, alcohol, ether, and benzene ; sol. mineral 
 acids; insol. acetic acid; sol. NHjAq. Sepa- 
 rates when its solution in warm NaOHAq is 
 cooled. 
 
 Beactions. — 1. SpUt np by heat into NH, 
 and meUon. — 2. Warm H2SO4 forms NHj and 
 ammelide. — 3. Boiling dilute nitric acid forms 
 first ammelide, then cyanurio acid (Knapp, A. 
 21, 255). 
 
 Salts. — Its compounds with acids are de- 
 composed by water. — B'HOl : prisms. — B'HNO,. 
 -BAgNO,. 
 
 Ethyl ether Cya(NH2)20Et. [190°-200°]. 
 From cyanetholine and NH, (Hofmann a. 
 Olshausen, B. 3, 275). V. si. sol. alcohol. 
 
 Chloride Cy^iTfi'S.^)!'^^- ' Ohloro-cyanamide.' 
 From Cjfil, and NHjAq (Liebig, A. 10, 43; 
 Laurent a. Gerhardt, A. Ch. [2] 19, 90 ; 20, 98 ; 
 Bineau, A. Ch. [2] 70, 254). Powder, insol. 
 water. Decomposed by heating with HCl into 
 mellon and NH3. Dilute EOHAq converts it 
 into ammeline. NHj at 100° forms melamine. 
 EHS forms thio-armneline. 
 
 AMMONIA NH3. {Volatile AlkaU. Alkaline 
 air.) Mol. w. 17-01. [-75°. Faraday, Q. J. S. 
 19, 16]. (-38-5°; pressure less than 760 mm. 
 Eegnault.) S.G. °-° (liquid) -6234 (Jolly, A. 117, 
 181: compare also Andreef, ibid. 110, 1). V.D. 8-5. 
 
 5. 0°, 1050; 10°, 813; 15°, 727; 20°, 654; 
 (Bunsen, Gasometry, Engl. ed. 169). S. 0°, 
 1148 (Eoscoe a. Dittmar, A. 110, 140) ; S. 0°, 
 1270 (Berthelot, C.B. 76, 1041). C.E. (liquid-ll° 
 to 0°) -00155 (JoUy, A. 117, 181). Eefractive 
 power (gas) compared with air = l, 1'309. 
 [N,HS] = 11,890; [N, H^ Aq] = 20,320; [NH», Aq] = 
 8,430 {Th. 2, 68). 
 
 Occwrrence. — Ammonia salts occur in the 
 atmosphere and in rain water ; in many mineral 
 waters ; in sea water ; near volcanoes ; in many 
 soils ; in almost all plants ; in the excrements 
 of many animals ; among the products of the 
 decay of nitrogenous organic bodies. Free 
 ammonia is not known to occur in nature. 
 Ammonia was distinguished from ammonium 
 carbonate by Black in 1756 ; Priestley obtained 
 it approximately pure and named it alkaline 
 air; Scheele showed it to contain nitrogen; 
 Berthollet demonstrated its composition in 
 1785. The word ammonia comes from sal 
 annnoniacum, the name given in the middle 
 ages to ammonium chloride. 
 
 Formation. — 1. By the action of the in- 
 duction spark, or the silent discharge (Donkin, 
 Pr. 21, 281), on a mixture of N and H in the ratio 
 NrHj a small quantity of NHj is produced 
 (Morren, C.B. 48, 432; Perrot, C.B. i9, 204; 
 Chabrier,C.i?.75,484). — 2. According to Eamsay 
 a. Young (C. J. 45, 93) a trace of NHj is formed 
 when a mixture of moist N and H is passed 
 through a red-hot tube containing iron filings ; 
 3. Ammonium nitrite is formed, a. when 
 hydrogen is burnt in air (ZoUer a. Grete, B. 
 10,2145; but againstthis«. Wright, C.J^.38,240); 
 
 6. by the action of a strong induction-spark on 
 a mixture of N and H.O (Thenard, C. B. 76, 983 ; 
 Johnson, C.N. 48, 253 a. 264). Ammonium 
 chloride is produced when electric sparks are 
 passed for 8 to 10 hours through a mixture of 
 HCl gas, N, and H, the elements being in th« 
 
AMMONIA. 
 
 197 
 
 ratio N:H3 (Deville, O. B. 60, 317) ; or by passing 
 (he same gases through a red-hot porcelain 
 tube containing a metal tube cooled by a 
 stream of cold water (Deville, A. 135, 104). — 
 4. By the action of a porous body — e.g. spongy 
 platinum, pumice, ferric oxide— aided by heat, 
 on a mixture of H with an oxide of nitrogen or 
 HNOj, NHj is produced. — 5. By decomposing a 
 compound of H and one of N together, NH, is 
 formed : e.g. by the action of water on nitride 
 of Si, B, Mg &c., SiOj, Bfi,, or MgO is produced, 
 and the N and H combine to form NH, : again 
 moist NO passed over hot iron filings yields NH^. 
 6. By strongly heating easily oxidised bodies — e.g. 
 As, Zn, K, &o. — with alkaline oxides, in presence 
 of air. — 7. By strongly heating metallic nitrates 
 or nitrites with hydroxides of the alkali or 
 alkaline earth metals and iron filings or zinc. — 
 8. By heating metaUio cyanides vrith steam 
 {v. Marguerite and Sourdeval, D. 'P. J. 157, 73 
 and 316). — 9. By heating solutions of nitrates or 
 nitrites with KOHAq and Zn or Fe, or with a 
 Cu-Zn couple. Ammonium sulphate is formed 
 when nitric acid is dropped into a vessel con- 
 taining Zn and dilute H2S04Aq (Kuhlmann, A. 
 64, 233). — 10. By the action of water on chloride, 
 iodide, or phosphide, of nitrogen, or on the 
 amides; in the last cases it is often neces- 
 sary to use solutions of KOH or NaOH. — 11. 
 By the dry distillation of many nitrogenous 
 organic bodies — e.g. horn,bones, blood, coal, &o. 
 Ammonia is produced, according to Johnson, 
 when N and H are passed over spongy Pt 
 (C. J. 39, 128) ; but this is denied by Wright 
 (C. X 89, 359), whose experiments seem to prove 
 that the NHj obtained by Johnson was the pro- 
 duct of the mutual action of a trace of NO (in 
 what was supposed to be pure N) and H, in 
 presence of the spongy Pt (but v. also Johnson's 
 pamphlet Elementary Nitrogen, and on the 
 Synthesis of Ammonia [ChurohiU, 1885]). 
 
 Preparation. — 1. By gently heating a mix- 
 tiure of 1 part chloride or sulphate of ammonium 
 with 2 parts finally powdered slaked lime ; 
 the mixture is covered with a layer of lime to 
 absorb water, and the gas is dried by passage 
 through a cylinder containing lime in small 
 pieces.— 2. By gently heating a solution of 
 CaCL, in NHjAq previously saturated with NH3 ; 
 this mixture may be kept unchanged for long. — 
 3. Pure ammonia is prepared by Stas {Fr. 6, 
 423) by one of the foUovring methods : — (i.) 
 From pure NHjCl and KOHAq ; 10 litres of a 
 boiling cone, solution of NH4CI are mixed with 
 1 litre HNOaAq, S.G. 1-4 ; the boiUng is con- 
 tinued so long as 01 comes off, the NH4CI which 
 separates on cooling is dissolved in hot water, 
 and again boiled with ^ volume of HNO3 till 
 CI ceases to come ofi, water is then added, 
 and NH3 is obtained by decomposing by KOHAq. 
 (ii.) From pure (NHJ^SO, and KOHAq ; 2 kilos, 
 of (NHJjSOj are heated with IJ kilos, cone. 
 H2SO4 to the temperature whereat the sulphate 
 begins to decompose with effervescence, small 
 quantities of nitric acid are then added until the 
 liquid becomes quite colourless ; the salt which 
 crystallises on cooling is dissolved in warm 
 water and decomposed by KOHAq. [The 
 object of these treatments is to remove the 
 small quantities of substituted ammonias — 
 KH,CH„ NH^CjH, &o.— which are present in 
 
 ammonium chloride and sulphate.] (iiL) From 
 pure KNOj by the action of Zn and Fe in 
 presence of KOHAq : the KNOj is prepared 
 by heating Ikilo KNO, with metallic copper, and 
 dissolving" out the KNOj in water ; this solution 
 is digested with 15 litres KOHAq— S.G. 1-25— 3^ 
 kilos, granulated zinc free from carbon (Zn 
 obtained by fusing commercial Zn with 5 p.o. 
 PbO may be used), and \ kilo, iron wire pre- 
 viously strongly heated in air and then reduced 
 by hydrogen ; the liquid is poured off and 
 distilled with gentle ebulhtion. 
 
 Properties. — A colourless, strongly-smelling, 
 gas, which turns red litmus paper blue, and 
 turmeric paper brown. Taste, hot and strongly 
 alkaline ; poisonous when breathed ; it destroys 
 the mucous membrane. Kasily liquefied to a lim- 
 pid, colourless, highly refractive, liquid ; best by 
 heating solid 2AgG1.3NH3 in one end of a strong 
 glass tube, closed at both ends, and bent to an 
 obtuse angle, the other end being surrounded 
 by snow and salt (Faraday, Q. J. S. 19, 16). 
 The silver compound begins to melt at 38°, it is 
 quite liquid at 90°, begins to boil at 100°, and 
 the change is complete at 112°. Liquefied at 
 —40° to —50°; this may be effected by passing 
 the weU-dried gas through a U tube surrounded 
 by a mixture of crystallised CaClj and snow, or 
 by liquid SO^ which is rapidly evaporated by a 
 current of air (Loir and Drion, J. 1860. 41). 
 If liquid ammonia is cooled by solid CO^ and 
 ether in vacuo (Faraday), or by rapid evapora- 
 tion over H2SO4 (Loir and Drion), white trans- 
 parent crystals of solid ammonia are obtained, 
 which melt at —75° (Faraday). Liquid 
 ammonia vaporises in a closed vessel, the 
 vapour-pressures according to Eegnault (/. 
 1863. 66) being as foUows :— 
 -30° 866-09 mm. +40° 11,595-30 mm. 
 
 -20 1392-13 „ 60 15,158-33 „ 
 
 -10 2144-62 „ 60 19,482-10 „ 
 
 3183-34 „ 70 24,675-55 „ 
 
 ■hlO 4575-03 „ 80 30,843-09 „ 
 
 20 6387-78 „ SO 38,109-22 „ 
 
 30 8700-97 „ 100 46,608-24 „ 
 
 Ammonia gas is very soluble in water («. 
 Combinations No. 1), alcohol, and ether; it is 
 largely absorbed by charcoal {v. Hunter, 
 O. J. [2] 9, 76 ; 10, 649) and other porous sub- 
 stances ; it is absorbed by many saline solutions, 
 the quantity of NHj absorbed being, as a rule, 
 the less the more concentrated is the solution 
 {v. Eaoult, C. B. 77, 1078). Ammonia solution 
 is a strongly smelling, caustic, alkaline, liquid ; 
 at —40° it forms long needle-shaped crystals; 
 at —49° it solidifies to an inodorous mass; the 
 B.P. and S.G. increase the less is the quantity 
 of NH3 present. Many metallic oxides insoluble 
 in water are dissolved by NHjAq, e.g, 
 CuO, AgjO, &c. ; aqueous NH3 also dissolves 
 many fats and resins. Ammonia resembles 
 PH3 in its properties and reactions ; it is, how- 
 ever, much more stable and less easUy oxidised 
 than that compound; an aqueous solution of 
 NHj, which doubtless contains NH^OH, is 
 characterised by the properties expressed by the 
 word alkali {v. Ammonium Compounds ; 
 comp. also the arts. Hydrides, Hydbox- 
 IDES, and Nitrogen Gboup of Elements.) 
 
 Beactions. — I. Liquid ammonia does not 
 react withH^SOjat-GS"; dissolves alkali metals 
 
198 
 
 AMMONIA. 
 
 at first with red, then blue, colour ; the metals 
 crystallise out unchanged (Gore, Pr. 21, 140) ; 
 alkaline earth metals and heavy metals do 
 not dissolve (Seeley, 0. N. 23, 169; concern- 
 ing solubilities of other elements andsaltsu. Gore 
 I.e.). — II. Ammonia gas. 1. Heat decomposes 
 NHj partially into N and H; when the gas is 
 passed through an iron or porcelain tube, de- 
 composition begins at about 500° ; the nature of 
 the hot surface exerts a, most marked influence 
 on the extent of decomposition ; the decompo- 
 sition is, however, never quite complete (Eamsay 
 a. I Young, C.J.ih, 88). A spiral of Pt heated 
 by an electric current also decomposes NH, 
 (Grove, A. 63, 1). — 2. The electric discharge 
 decomposes NHj slowly,but MK^Mciitm spares from 
 a large Euhmkorff's coil more quickly ; the de- 
 composition is not quite complete (Deville, A. 135, 
 104; Buff a. Hofmann, ibid. 113, 132).— 3. 
 NHj is decomposed, into N and H, by passage 
 over several metals at 700° or so, e.g. Au, Pt, Ag, 
 Fe, Cu, &o. ; some metals, e.g. Ti, combine with 
 the N ; the alkali metals set free J of the H pro- 
 ducing compounds of the form NHjM : the com- 
 pound NHjK is decomposed at a red heat giving 
 NKj and NH, ; water acts on it to produce KOH 
 and NH, (v. Potassium). — 4. Mixed with oxygen 
 and submitted to the electric discharge, NHjNO^ 
 andNHjNOj are formed (Carius, A. 174, 81).— 5. 
 Mixed with oxygen and heated, NHj burns to H2O, 
 H, and N, if the NH3 is in excess ; and to H^O, 
 N, and NH^NOj, if the is in excess (v. Hofmann, 
 A. 115, 283 ; Heintz, ibid. 130, 102). The flame 
 examined speotrosoopically shows characteristic 
 lines, especially one near D (Dibbits, P. 122, 521). 
 6. Osone oxidises NHj chiefly to NH4NO3 and 
 NHjNOj (Carius, A. 174, 31).— 7. A platinum 
 mre heated in NH3 mixed with air produces 
 NHjNOj, if oxygen is passed into the NH3 red 
 fumes of N oxides are also produced. — 8. Am- 
 monia reacts with N^O, and CI2O3 to form HjO, 
 N, NHjNOj or NH^NOs, and C1.-9. Metallic 
 oxides reducible by H are usually also reduced 
 by NH3 with formation of metal, N, and H^O, 
 sometimes with formation of metallic nitrides. — 
 
 10. NH3 reacts with many metallic oxides and 
 haloid salts to form compounds, either of NHj 
 with the metallic salt — e.g. PtCl2.4NH3, 
 CUSO4.2NH3 — or compounds in which part of 
 the H of NHj is replaced, e.g. NHjHgCl {v. 
 Ammonium Compounds; also the several metals). 
 
 11. Chlorine, bromine, and iodine react ener- 
 getically with NHj to produce NH4X(X = CI, Br, 
 or I), and N. NHj combines with cooled I to 
 form a brown liquid which is decomposed 
 by water with production of NHJAq and explo- 
 sive iodide of nitrogen [? NI3] {v. Nitkoqen). — 
 
 12. Sulphur absorbs NHj ; on heating N is set 
 free and ammonium sulphide formed (Brunner, 
 D.P.J. 150, 371). — 13. Carbon heated in a stream 
 of NHj forms NHjCN and H, sometimes also 
 CHj. — 14. Boron heated in a stream of NH3 
 form BN (v. Bokon), and H. — 15. NHj combines 
 with acids (H^SO^, HCl, &c. &o.) to form am- 
 monium salts ( (NH4)2S04, NHjCl, &c. &a., q.v. ; 
 V. also Combinations, No. 4). — 16. With many 
 organic anhydrides NHj combines to form the 
 ammonium salts of amio acids, q.v. NHj also 
 acts on several inorganic anhydrides and acid 
 chlopdea to form bodies more or less analogous 
 to the amio aoids ; thus with SOgOH.d am- 
 
 monia forms NH(S02.0NH4)2— the NH, salt oJ 
 imido -sulphuric acid NH(S020H)2— from the 
 salts of this acid are obtained salts of amido 
 sulphuric, or sulphamio, acid — NH2(S020H). 
 Again by the action of NHj on the acid chloride 
 SOjClj it is probable that the amide of sulphuric 
 acid— (NH2)2S02— is produced. So also NH, 
 reacts with CO^ to produce NH2(C0.0Nnj— 
 the ammonium salt of amidooarbonio, or car- 
 bamio, acid. These compounds will be de- 
 scribed under the various acids {v. Cakbamio 
 acid; Sulphamio acid ; Sulphur oxyaoids, nitbo- 
 oen debivatrves oe ; &c.). 
 
 III. Ammonia solution. 1. Heat decom- 
 poses NHjAq, the whole of the NHj being re- 
 moved as gas. — 2. Chlorine, bromine, and iodine 
 react as with NHj gas ; chlorine produces a little 
 NHjClOj (Fresenius, Fr. 2, 59).— 3. Eeaots with 
 acids to form ammonium salts {v. Combinations, 
 No. 4, also Ammonium compounds). — 4. With 
 many metallic salt solutions it reacts (similarly 
 to KOHAq) to form an ammonium salt and 
 an oxide or hydroxide of the metal. — 5. Heated 
 with sulphur in a closed tube ammonium poly- 
 sulphides are slowly formed (Fliickiger, J. Ph. 
 [3] 45, 453). — 6. Heated with selenionia a closed 
 tube, ammonium selenide and selenite are 
 formed ; with tellurium ammonium tellurite is 
 produced (Fliickiger, l.c.). 
 
 Combinations. — 1. Ammonia gas dissolves 
 very freely in water, the action is attended 
 with production of heat ; [NH',Aq] = 8,430 {Th. 2, 
 68) ; a concentrated solution of NHjAq diluted 
 
 1270 
 with n HjO develops — !-: units of heat (Berthe- 
 
 n 
 lot, A. Ch. [5] 1, 209). Thomsen (Th. 3, 86) 
 gives the following data 
 
 NHHiK'O.mWO 
 n + m 15 25 50 
 
 n = 3-2 319 350 372 
 
 „15 — 31 53 
 
 „25 — — 22 
 
 The mass of NHj absorbed by water at 0° is 
 not directly proportional to the pressure ; for 
 pressures varying from 50 to aboufl.OOO mm. 
 the mass of NHj is less, and for higher pres- 
 sures it is greater, than that calculated by 
 Dalton and Henry's law (for data v. Eoscoe a. 
 Dittmar, A. 112, 349). As temperature in- 
 creases the mass of NH, becomes more nearly 
 directly proportional to the pressure, until at 100° 
 the proportion is established (for data v. Sims, A, 
 118, 345). The S.G. of an aqueous solution of NH, 
 varies from -8844 at 14°, corresponding to 36 p.c. 
 NHj, to -9991 (at 14°) corresponding to -2 p.c. 
 NHj (Carius, A. 99, 164). Carius gives the 
 annexed table. Determinations made at 14° C. 
 A solution containing 32 p.c. NHj corresponds 
 with the quantity calculated on the assumption 
 that the liquid consists of the compound 
 NH4OH.H2O {v. Ammonium Compounds). — 2. 
 Dry ammonium nitrate absorbs NHj at all tem- 
 peratures from —13° to -t-25° with liquefaction 
 of the salt ; heated over 25°, NH, is evolved and 
 the substance becomes solid ; the liquid at — 10° 
 and 760 mm. contains 42-5 grams NH, and 100 
 grams NH^NOj, these numbers agree with those 
 calculated from the formula NH4NO3.2NH3 ; the 
 solid at 28°-6 contains NH^NOj and NK, in tha 
 proportion NH,Na,:NH, (Divers, Pr. 21, 109; 
 
AMMONIA. 
 
 xoo 
 
 Bpeclfic 
 
 P. 0. 
 
 Speolflo 
 
 P. C. 
 
 Speoiflo 
 
 P. C. 
 
 gravity 
 
 NH. 
 
 gravity 
 
 NH. 
 
 gravity 
 
 NH, 
 
 0-8844 
 
 86-0 
 
 0-9188 
 
 24-0 
 
 0-9520 
 
 120 
 
 0-8848 
 
 85-8 
 
 0-9189 
 
 23-8 
 
 0-9527 
 
 11-8 
 
 0-8852 
 
 35-6 
 
 0-9145 
 
 23-6 
 
 0-9534 
 
 11-6 
 
 0-8856 
 
 35-4 
 
 0-9150 
 
 23-4 
 
 0-9542 
 
 11-4 
 
 0-8860 
 
 35-2 
 
 0-9156 
 
 23-2 
 
 0-9549 
 
 11-2 
 
 0-8864 
 
 35-0 
 
 0-9162 
 
 23-0 
 
 0-9556 
 
 11-0 
 
 0-8868 
 
 34-8 
 
 0-9168 
 
 22-8 
 
 0-9563 
 
 10-8 
 
 0-8872 
 
 34-6 
 
 0-9174 
 
 22-6 
 
 0-9571 
 
 10-6 
 
 0-8877 
 
 34-4 
 
 0-9180 
 
 22-4 
 
 0-9578 
 
 10-4 
 
 0-8881 
 
 34-2 
 
 0-9185 
 
 22-2 
 
 0-9586 
 
 10-2 
 
 0-8885 
 
 34-0 
 
 0-9191 
 
 220 
 
 0-9598 
 
 10-0 
 
 0-8889 
 
 33-8 
 
 0-9197 
 
 21-8 
 
 0-9601 
 
 9-8 
 
 0-8894 
 
 33-6 
 
 0-9203 
 
 21-6 
 
 0-9608 
 
 9-6 
 
 0-8898 
 
 83-4 
 
 0-9209 
 
 21-4 
 
 0-9616 
 
 9-4 
 
 0-8903 
 
 33-2 
 
 0-9215 
 
 21-2 
 
 0-9628 
 
 9-2 
 
 0-8907 
 
 830 
 
 0-9221 
 
 21-0 
 
 0-9631 
 
 9-0 
 
 0-8911 
 
 32-8 
 
 0-9227 
 
 20-8 
 
 0-9639 
 
 8-8 
 
 0-8916 
 
 82-6 
 
 0-9233 
 
 20-6 
 
 0-9647 
 
 8-6 
 
 0-8920 
 
 32-4 
 
 0-92B9 
 
 20-4 
 
 0-9654 
 
 8-4 
 
 0-8925 
 
 32-2 
 
 0-9245 
 
 20-2 
 
 0-9662 
 
 8-2 
 
 0-8929 
 
 820 
 
 0-9251 
 
 200 
 
 0-9670 
 
 8-0 
 
 0-8934 
 
 31-8 
 
 0-9257 
 
 19-8 
 
 0-9677 
 
 7-8 
 
 0-8938 
 
 81-6 
 
 0-9264 
 
 19-6 
 
 0-9685 
 
 7-6 
 
 0-8943 
 
 81-4 
 
 0-9271 
 
 19-4 
 
 0-9693 
 
 7-4 
 
 0-8948 
 
 31-2 
 
 0-9277 
 
 19-2 
 
 0-9701 
 
 7-2 
 
 0-8953 
 
 31-0 
 
 0-9283 
 
 19-0 
 
 0-9709 
 
 7-0 
 
 0-8957 
 
 30-8 
 
 0-9289 
 
 18-8 
 
 0-9717 
 
 6-8 
 
 0-8962 
 
 30-6 
 
 0-9296 
 
 18-6 
 
 0-9725 
 
 6-6 
 
 0-8967 
 
 30-4 
 
 0-9302 
 
 18-4 
 
 0-9733 
 
 6-4 
 
 0-8971 
 
 30-2 
 
 0-9308 
 
 18-2 
 
 0-9741 
 
 6-2 
 
 0-8976 
 
 30-0 
 
 0-9314 
 
 180 
 
 0-9749 
 
 60 
 
 0-8981 
 
 29-8 
 
 0-9321 
 
 17-8 
 
 0-9757 
 
 6-8 
 
 0-8986 
 
 29-6 
 
 0-9327 
 
 17-6 
 
 0-9765 
 
 5-6 
 
 0-8991 
 
 29-4 
 
 0-9333 
 
 17-4 
 
 0-9778 
 
 5-4 
 
 0-8996 
 
 29-2 
 
 0-9340 
 
 17-2 
 
 0-9781 
 
 5-2 
 
 0-9001 
 
 29-0 
 
 0-9347 
 
 17-0 
 
 0-9790 
 
 50 
 
 0-9006 
 
 28-8 
 
 0-9353 
 
 16-8 
 
 0-9799 
 
 4-8 
 
 0-9011 
 
 28-6 
 
 0-9360 
 
 16-6 
 
 0-9807 
 
 4-6 
 
 0-9016 
 
 28-4 
 
 0-9366 
 
 16-4 
 
 0-9815 
 
 4-4 
 
 0-9021 
 
 28-2 
 
 0-9373 
 
 16-2 
 
 0-9823 
 
 4-2 
 
 0-9026 
 
 280 
 
 0-9380 
 
 160 
 
 0-9831 
 
 4-0 
 
 0-9031 
 
 27-8 
 
 0-9386 
 
 15-8 
 
 0-9839 
 
 3-8 
 
 0-9036 
 
 27-6 
 
 0-9398 
 
 15-6 
 
 0-9847 
 
 3-6 
 
 0-9041 
 
 27-4 
 
 0-9400 
 
 15-4 
 
 0-9855 
 
 3-4 
 
 0-9047 
 
 27-2 
 
 0-9407 
 
 15-2 
 
 0-9863 
 
 3-2 
 
 0-9052 
 
 27-0 
 
 0-9414 
 
 15-0 
 
 0-9873 
 
 30 
 
 0-9057 
 
 26-8 
 
 0-9420 
 
 14-8 
 
 0-9882 
 
 2-8 
 
 0-9063 
 
 26-6 
 
 0-9427 
 
 14-6 
 
 0-9890 
 
 2-6 
 
 0-9068 
 
 26-4 
 
 0-9434 
 
 14-4 
 
 0-9899 
 
 2-4 
 
 0-9073 
 
 26-2 
 
 0-9441 
 
 14-2 
 
 0-9907 
 
 2-2 
 
 0-9078 
 
 26-0 
 
 0-9449 
 
 140 
 
 0-9915 
 
 2-0 
 
 0-9083 
 
 25-8 
 
 0-9456 
 
 13-8 
 
 0-9924 
 
 1-8 
 
 0-9089 
 
 25-6 
 
 0-9463 
 
 13-6 
 
 0-9932 
 
 1-6 
 
 0-9094 
 
 25-4 
 
 0-9470 
 
 13-4 
 
 0-9941 
 
 1-4 
 
 0-9100 
 
 25-2 
 
 0-9477 
 
 13-2 
 
 0-9950 
 
 1-2 
 
 0-9106 
 
 250 
 
 0-9484 
 
 13-0 
 
 0-9959 
 
 1-0 
 
 0-9111 
 
 24-8 
 
 0-9491 
 
 12-8 
 
 0-9967 
 
 0-8 
 
 0-9116 
 
 24-6 
 
 0-9498 
 
 12-6 
 
 0-9975 
 
 0-6 
 
 0-9122 
 
 24-4 
 
 0-9505 
 
 12-4 
 
 0-9983 
 
 0-4 
 
 0-9127 
 
 24-2 
 
 0-9512 
 
 12-2 
 
 0-9991 
 
 0-2 
 
 Eaonlt, C. B. 76, 1261.— 3. Ammonia gas com- 
 bines with a great many metallic chlorides, sul- 
 phates, &o., to form either double compounds or 
 compounds which are best regarded as substi- 
 tuted ammonium salts. (For a slight general 
 sketch V. Ammonium Oompoottds. The several com- 
 
 pounds are described in the arts, on the different 
 metals). — 4. Ammonia gas or solution combines 
 with acids to form well-marked salts isomorphous 
 with the corresponding salts of the alkali metals. 
 The value of the heat of neutralisation of an 
 acid by NHjAq is always rather smaller than 
 the value when KOHAq or NaOHAq is used; 
 thus Thomson (Th. 1, 412-421) gives these 
 numbers : 
 
 BAq [H^SO'Aq.BAq] [H^CPAq, BAq] 
 2E0HAq 31,288 27,504 
 
 2NaOHAq 81,378 27,488 
 
 2NHsAq 28,152 24,544 
 
 [H-'N'O'Aq, BAq] 
 
 27,544 
 
 27,364 
 
 27,644 
 These results are quite in accordance with the 
 view that an aqueous solution of NHj contains 
 the compound (NHJOH, analogous in composi- 
 tion and properties to the hydroxides of the 
 alkali metals {v. Ammonium Compounds). 
 
 Detection. — Free ammonia is detected : 1. by 
 its smell ; 2. by its action on HOI whereby white 
 clouds of NHjCl are produced; 8. by its 
 action on paper, a. moistened with neutral 
 HgNOjAq, whereby a black stain (Hg.^O) is 
 formed, 6. moistened with CuSO^Aq whereby 
 a sky-blue colour (CuSOj.4NH3) is produced, c. 
 moistened with MnSO^Aq, whereby brown spots 
 (Mn^Oj) are formed, d. steeped in an ethereal 
 solution of alkanna root (Enz, J. 1870. 935), 
 whereby a blue colour is produced (Bottger, J.pr. 
 107, 146). The presence of ammonia or am- 
 monium salts can be ascertained by various 
 tests ; the following may be mentioned.— 4. 
 Sodium picrate precipitates yellow ammonium 
 picrate. — 5. A solution of sodium molybdate con- 
 taining phosphoric and nitric acids forms a citron 
 yellow pp. (Sonnenschein, J. pr. 56, 302). — 
 6. Nessler's solution — a strongly alkaline solu- 
 tion of Hglj in KIAq — forms a brown pp., or 
 brown colour in extremely dilute solution, of 
 ,NHg2l.H20 (Nessler, 0. 0. 1856. 529). All am- 
 monium salts are at least partly volatilised when 
 heated ; some give sublimates of the original 
 salt, e.g. NHjCl; others are decomposed, e.g. 
 NH^NOa and NH^NO^. 
 
 Estimation. — 1. Ammonium salts are some- 
 times estimated in a mixture, all the other con- 
 stituents of which are non-volatile, by heating a 
 specified quantity and determining the loss of 
 weight. — 2. AH ammonium salts are decomposed 
 by heating with KOHAq (or NaOHAq) with evo- 
 lution of NHj: if organic N-oontaining coni- 
 pounds which evolve NH, by the action of 
 alkalis are absent, it is only necessary to add a 
 weighed quantity of the ammonium compound 
 to an excess of KOHAq, or KaOHAq, which has 
 been boiled and cooled, in a flask connected 
 with 3, condenser and receiver, and to warm on 
 a sand-bath ; NHj passes over and is received in 
 dilute HClAq; the NH4CI is then transformed 
 into 2NHjGl.PtCl4(i;. No. 3) , or the NH, is received 
 in a measured quantity — excess — of standardised 
 HCLAq, HjSO^Aq, or HjCjO^Aq, and the re- 
 sidual acid is determined by titration with 
 standard alkali. [A special apparatus is de- 
 scribed by Haroourt {Fr. 2, 14).] If N-coa- 
 taining organic compounds are present which 
 evolve NHj by the action of alkalis, Schlossins 
 
200 
 
 AMMONIA. 
 
 (A. Ch. [3] 31, 153) recommends to place the 
 Bubatance witli excess of milk of lime over a 
 measured quantity of standard HsSOjAq, under 
 a bell jar, for 48 hours, and then to determine 
 the residual acid by standard alkali. — 3. Am- 
 monium salts the acids of which are soluble in 
 alcohol may be estimated by conversion into 
 2NH401.PtClj ; an excess of nearly neutral 
 PtCl^Aqjfree fromHN03,is added to the solution, 
 the liquid is evaporated at 100°, the residue is 
 washed with alcohol, dried at 100°, and weighed, 
 or it is strongly heated and the residual platinum 
 is weighed. This method is applicable in the 
 presence of salts which form double compounds 
 with Pt soluble in alcohol ; it is best that such 
 salts should be chlorides, to insure this the 
 mixture is evaporated with excess of cone. 
 HClAq (it is best to remove sulphuric acid by 
 Ba(0H)2, excess of Ba{0H)2 being afterwards 
 removed by CO.J. In the case of KCI, which 
 forms a salt SKCLPtClj insoluble in alcohol, the 
 mixed Pt salts are weighed, then strongly heated 
 and again weighed, the KCI is dissolved out in 
 water, and the residual Pt is weighed. — 4. Am- 
 monium salts are decomposed by alkaline hypo- 
 chlorites or hypobromites giving off all their N, 
 which may be collected and measured. 
 
 (2NH,ClAq + BNaClOAq = 
 N, + SNaClAq + 3H,0 + 2HC1 Aq). 
 Wohler employed calcium hypochlorite for the 
 purpose ; Knop (Fr. 9, 225) used barium or sodium 
 hypobromite (prepared by the action of Br on 
 Ba(0H)2Aq or on NaOHAq) ; Schifi has described 
 a special apparatus {Fr. 7, 480) ; Erocker a. 
 Dietrich (Fr. 3, 64 ; 5, 40) decompose by excess of 
 brominatedNaOClAq, and determine the residual 
 hypochlorite by titrating with an alkaline solu- 
 tion of arsenious oxide. (Comp. also Foster, 0. J. 
 33, 470.)— 5. Minute quantities of NH3 are de- 
 termined by the colorimetric process of Nessler- 
 ising ; a measured quantity of Nessler's reagent 
 — Hglj in EIAq made strongly alkaline by 
 KOHAq — is added, and the colour is compared 
 with that produced by an equal quantity of 
 Nessler's solution in an equal volume of water 
 containing a known quantity of ammonia. 
 
 M. M. P. M. 
 
 AMMONIA, ACTION ON ORGANIC BODIES. 
 1. Ammonia converts alkyl salts of inorganic 
 acids into amines (g. v.). — 2. It converts alkyl 
 salts of carboxylic acids into amides (q. v.). — 
 3. It converts the oxides of acid radicles into 
 amide and ammonium salt: Ac20 + 2NH3 = 
 AcNHj + AcONHj. — 4. It converts chlorides of 
 acid radicles into amides of the correspond- 
 ing acids : AoCl + 2NH3 = AcNH^ + NH,C1.— 5. It 
 unites with cyanic ethers forming ureas. — 6. 
 It unites with thio-carbimides forming thio- 
 ureas. — 7. It unites with aldehydes, but in 
 the case of the higher fatty aldehydes and the 
 aromatic aldehydes water is simultaneously split 
 oft. — 8. It unites with ketones and quinones. — 
 t. Alcoholic NH3 sometimes removes HCl ; thus, 
 it converts isobutyUdene chloride MejCH.CHCl^, 
 chloro-iso-butylene Me2C:CHCl, and di-chloro- 
 IH^opane CH3.CCI2.CH,, into chloro-propylene 
 OH3CCl:CH2(Oeoonomides, 0. B. 92, 1236).— 10. 
 For its action on oxy compounds see Amines, 
 Formation 10.— 11. Ammonia can displace O 
 byNH. 
 
 AMMONIAC GUM v. Gum. 
 
 AMMONIUM COMPOUNDS. Compoauds 
 produced by the action of ammonia on acids. 
 The conditions of occurrence in nature, and also 
 of the artificial syntheses, of these salts are re- 
 ferred to in the article Ammonia, q. v. In that 
 article some data are given regarding the ab- 
 sorption of ammonia by water {Combinations, 
 No. 1), and regarding the thermal values of the 
 neutralisation of acids by NHjAq {Combina- 
 tions, No. 4). The products of the mutual 
 actions of NHjAq, and HGLAq, H.2S04Aq, and 
 other acids — the ammonium salts — are for the 
 most part white crystalline bodies, easily soluble 
 in water, and many of them soluble also in alco- 
 hol; they exhibit marked analogies with the 
 salts of potassium. Corresponding ammonium 
 and potassium salts are isomorphous, hence they 
 probably have similar compositions. The am- 
 monium salts are distinguished by their com- 
 paratively great volatility ; heated, as solids, 
 they are completely volatilised, if the acid of the 
 salt is volatile ; if the acid is non-volatile (e.g. 
 borate or phosphate), ammonia is evolved. They 
 do not exist as gases ; when volatilised they are 
 either decomposed e.g. NH4NO3, or dissociated 
 e.g. NH4CI, 2. V. {v. also Dissociation). When 
 gaseous NH3 acts on gaseous HCl, HBr, or HI, 
 combination occurs with production of much 
 heat and formation of solid compounds NH,HX, 
 thus (Th. 2, 75) : 
 
 X (NH', HX) 
 01 41,900 
 
 Br 45,020 
 I 43,4G0 
 
 If the solid products of these actions, NHjHX, 
 are heated to about 450°, a vapour is obtained 
 containing NH3 and HX ; on cooling this vapour 
 the compound NH3HX is re-formed. Gaseous 
 NH3 does not combine with HCl, HBr, or HI, at 
 temperatures above about 450°. These facts 
 establish a difference between the ammonium 
 and potassium compounds. This difference is 
 further exhibited in the reactions of the two 
 classes of compounds ; the ammonium salts are 
 easily decomposed, e.g. by alkalis and alkaline 
 earths, with production of NH3. On the other 
 hand the properties of NHjAq {v. Ammonia, Pro- 
 perties of) are so similar to those of KOHAq, 
 and the reacl;ions of acids with these solutions, 
 whether considered thermally or chemically, are 
 so analogous, that there can be little doubt that 
 the composition of ammonium salts is similar 
 to that of potassium salts. This similarity is at 
 once rendered apparent by formulating the 
 former class of salts as compounds of the hy- 
 pothetical group of atoms NHj, ammonium. 
 Thus we have : 
 
 NHj.Cl isomorphous with and chemically analo- 
 gous to K.Cl, 
 NHj.NOj isomorphous with and chemically 
 
 analogous to K.NO3, 
 (NHJj.SOj isomorphous with and chemically 
 
 analogous to K2.S04, 
 (NHJj.CjOj isomorphous with and chemically 
 
 analogous to K^.C^O^, 
 NHi.C^HjOj isomorphous with and chemically 
 analogous to K.CjHjOj. 
 If this analogy of properties is in all oases 
 supposed to accompany analogy of composition, 
 then NHjAq must be formulated as NH^.OHAq. 
 The compound NH^OH has not been separated 
 
AMMONIUM COMPOUNDS. 
 
 201 
 
 trom the solation of NH3 in water ; but this does 
 not prove the non-existenee of the compound in 
 this solution. A chemical compound may, and 
 sometimes almost certainly does, exist as a 
 member of a system, and yet it may be incapable 
 of existence apart from the other members of 
 the system. The existence of every compound 
 is conditioned by other factors than the 
 elements which compose it ; among these 
 factors, temperature, and the presence or absence 
 of other compounds, are very important. Com- 
 pounds closely resembling NHjOH, and un- 
 doubtedly derived from NH4OH, are known as 
 definite solid bodies ; they are obtained by re- 
 placing the four hydrogen atoms in the com- 
 plex NHjOH by alcoholic radicles C^Hj^^., or 
 C.Hj..,; thus N(CH,),.OH, N{OjHJ^.OH, and 
 N[(C2H5)2(CjH5)J0H, have been prepared. These 
 bodies closely resemble NaOH and KOH in their 
 properties; their existence and properties are 
 strong arguments in favour of the existence 
 of the compound NHjOH in aqueous solutions 
 of NHj. The formula NH,.OH, NH,.C1, (NHJ^SO, 
 &c., then better summarise the properties 
 and reactions, and suggest the analogies, of the 
 ammonium compounds, than the alternative 
 formula NHj-H^O, NH3.HGI, (NH3).,.H2S04 &a. 
 The name ammomimi is given to the compound 
 radicle, or group of atoms, NH^. We do not 
 know that the composition of the molecule of 
 ammonium chloride is represented by the 
 formula NH,C1 ; indeed we do not even know 
 the molecular weight of this, or of any other, 
 ammonium compound. These compounds seem 
 to exist only as solids, or in solution. We are 
 scarcely justified in applying the term molecule to 
 the chemically reacting small particles of solids 
 or liquids, unless the term is used in a wider 
 and vaguer sense than is given to it when we 
 speak of the molecule of a gas {v. Atomic and 
 MOLEOULAB WEioHTs). But in Saying that the 
 complex or collocation of atoms which forms 
 the reacting weight of ammonium chloride is a 
 combination of an atom of chlorine with the 
 radicle, or group of atoms, ammonium, we 
 mean to imply that, when this complex of 
 atoms reacts with various other kinds of matter, 
 it behaves as if the four atoms of hydrogen were, 
 in some way, more directly and closely related 
 to the atom of nitrogen than to the atom of 
 chlorine. The fact that when the same complex 
 of atoms is heated it separates into two distinct 
 molecules, HCl and NH,, neither proves nor dis- 
 proves the correctness of the formula NH,,.C1, 
 and the conception which that formula em- 
 bodies. Neither does the fact, that no gaseous 
 molecule is known containing a single atom of 
 nitrogen combined with more than three mono- 
 valent atoms, disprove the formula NH^.Cl ; for 
 the solid compound ammonium chloride presents 
 us with phenomena to which the conceptions 
 regarding the valencies of atoms, which have 
 been gained by the study of gaseous molecules, 
 are not strictly applicable. 
 
 In connection with the constitution of am- 
 monium compounds it is of interest to observe 
 that the compound produced by the union of 
 N(CH3)2CjH5 vrith C^jl appears to be identical 
 with the compound produced by the union of 
 N(C2H5)2CH3 with CH3I; it seems as if this 
 compound N[(0Hs)j{CbH5)JI belonged to the 
 
 same form or type as NH^.l, NH,.C1,NH,.0H, &<s. 
 (V. Meyer and Lecco, B. 8, 233 a. 936). 
 
 The group of atoms, NH„ is evidently chemi- 
 cally comparable with the atoms K, Na, Li, Os, or 
 Eb ; but these are the atoms of strongly positive 
 metals ; hence if the group NHj could be isolated 
 it might be expected to exhibit properties similar 
 to those of the alkali metals. Experiments have 
 demonstrated the impossibility of the existence 
 of NH, unoombined with other atoms ; but 
 certain reactions are known which suggest the 
 existence of an alloy of this hypothetical metallic 
 radicle with mercury. 
 
 Ammonium Amaiqam. If an electric current 
 is passedthroughconc. NHjAq, or NH.,ClAq, the 
 negative electrode consisting of mercury and the 
 positive of a platinum wire, the mercury swells up, 
 sometimes to 20 times its original volume, and 
 becomes pasty so that it may be lifted by the 
 hand, while nitrogen is evolved at the positive 
 electrode. The same result is obtained as 
 regards the mercury, if a piece of solid NH^Cl 
 is used; also if sodium-amalgam, containing 
 about 1 p.c. Na, is placed in cone. NH^OlAq — 
 in this case NaClAq is produced. The peculiar, 
 pasty, lustrous, metal-like, substance formed in 
 these experiments is called ammonium-amal- 
 gam ; at a very low temperature, obtained by 
 solid CO2 and ether, it is a dark-grey, solid, 
 crystalline, mass ; even at —29° it begins to 
 evolve NH3 and H, and this change proceeds 
 rapidly at moderate temperatures ; the two gases 
 always come ofi in the ratio NH3 : H. 
 
 An amalgam of K with Hg is produced by 
 electrolysis under conditions very similar to 
 those which attend the production of ammonium- 
 amalgam; the analogy between ammonium 
 and potassium is thus carried out here also. 
 Ammonium-amalgam, it is said, does not 
 reduce salts of Ag, Cu, or Pe, as K amalgam does 
 (Landolt, A. Swppl. 6, 346). When the amalgam 
 is subjected to increased pressure its volume 
 is found to change almost inversely as the 
 pressure; in this respect then it behaves like 
 a gas rather than a semi-solid compound. 
 The following data are given by Eoutledge 
 (O. N. 26, 210) :— 
 
 c.c. of Hg 
 
 in 
 
 0.0. of 
 
 amalgam, 
 
 Inoreased 
 pressure 
 
 C.C. of 
 
 amalgam 
 
 nnrlpr in- 
 
 0.0. of 
 
 amalgam 
 calculated 
 
 amalgam. 
 
 pressure 
 762 mm. 
 
 Dim. of Hg. 
 
 creased 
 
 pressure. 
 
 by Boyle's 
 law. 
 
 14-5 
 
 21-0 
 
 1524 
 
 18-0 
 
 17-9 
 
 24-4 
 
 36-2 
 
 1524 
 
 31-6 
 
 80-9 
 
 10-4 
 
 18-0 
 
 1863 
 
 14-7 
 
 13-7 
 
 23-8 
 
 42-2 
 
 1026 
 
 38-8 
 
 38-5 
 
 23-8 
 
 42-0 
 
 2015 
 
 32-2 
 
 31-6 
 
 23-8 
 
 36-2 
 
 1495 
 
 32-6 
 
 30-6 
 
 29-2 
 
 39-5 
 
 1989 
 
 34-4 
 
 35-4 
 
 As the pressure increases, the surface of the 
 amalgam becomes brighter, untU under largepres- 
 sures it has the appearance and liquidity of 
 mercury (Seeley, G. N. 21, 265). These results 
 point to the existence of gaseous NH3 or H, 
 or, it may be, gaseous NH„ in the Hg; but 
 they do not disprove the existence of the 
 atomic group NHj in some kind of loose com- 
 bination with Hg. An alloy of Fe and NH^ 
 
202 
 
 AMMONIUM COMPOUNDS. 
 
 is said by Meidlnger (C, C. 1862. 78) to be formed 
 when PeSOiAq or FeCljAq, to which a con- 
 Biderable quantity of NH.,ClAq has been added, 
 ■is electrolysed by a strong current, the negative 
 electrode consisting of a copper wire. 
 
 By electrolysing aqueous solutions of ammo- 
 nium salts using carbon electrodes, Bartoli a. 
 Papasogli ((?. 13, 281) obtained benzeneoarboxylio 
 acids and a compound of C, H, 0, and H, re- 
 sembling mellogen. 
 
 Of the ammonium compounds we have here 
 to consider the bromide, chloride, fluorides, 
 iodides, selenides, telluride, and sulpliides ; the 
 others will be considered under the headings 
 Carbonates, Nitbates, Sulphates, &o. The hy- 
 droxide, known only in aqueous solution, has 
 been already treated of in the art. Ammonia. 
 
 Ammonium bromide. NHjBr. Mol. w. un- 
 known ; does not exist as a gas, but is disso- 
 ciated by heat into HBr + NHj. S.G. i° 2-379 
 (Schroder, P. 106, 242). S. G. Ls° 2-327 (Eder, 
 SiU. W. 82 (2), 1284). V. D. at 440° to 860° 24-4 
 (Deville and Troost, O. B. 49, 239 ; 56, 881). 
 S. (10°) 66-2; (16°) 72; (30°) 81-1; (50°) 94-1; 
 (100°) 128-2. S. (alcohol, S.G. -806, 15°) 3-1 ; 
 (75°) 10-5. S. (ether S. G. •729)-12 (Eder, Z.c). 
 [NH', HBr]= 45,020; [N, H*, Br] = 65,348 
 (Th. 2, 75). [NH<Br,Aq] = - 4380 (Th. 3, 197). 
 S.V.S. 41-7. 
 
 Formation. — 1. By adding HBr or HBrAq to 
 NHj or NHjAq. 2. By the action of Br on 
 NHjAq; 4NH3Aq + 8Br = 3NHjBrAq -^ N : on 
 evaporation, crystals are obtained. 
 
 Properties and Beactions.— 'White crystals ; 
 soluble in water ; the act of solution is attended 
 with absorption of much heat. Exposed to moist 
 air turns yellow, and acquires an acid reaction. 
 An aqueous solution gives off ammonia at mode- 
 rately low temperatures. 
 
 Troost (C. B. 92, 715) describes three com- 
 pounds, NHjBr.ENHj, !!; = 1, 3, and 6, obtained 
 by the action of excess of NH3 on warm NH,iBr ; 
 the dissociation-phenomena of these compounds 
 have been studied by Eoozeboom (B.T.0. 4, 361). 
 
 Ammonium chloride. NH^Cl. (Sal ammo- 
 niac.) Mol. w. unknown; does not exist as 
 gas, but is dissociated by heat into NHj-nHCl. 
 S.G. 1-52 (Schroder, P. 106, 242). V.D. at 350° = 
 14-4, at 1040°= 14-5 (Deville a. Troost, C. B. 49, 
 289 ; 56, 891) ; but vapour consists of equal 
 volumes of NH, and HCl [v. Beactions, No. 1). 
 S.H. (15° to 45°) -373 (Kopp, T. 155, 71). S.H. 
 (23° to 100°) -3908 (Neumann, P. 126, 123). O.E. 
 (cubical, 0° to 40°) -00018764 (Fizeau, 0. B. 64, 
 314). S.V.S. 35-2. S. (0°) 28-4 ; (10°) 32-8 ; (110°) 
 77-2; S. increases approximately 4-4 parts for 
 each 10° (AUuard, 0. B. 59, 500). S. (alcohol 
 S.G. -939, 8°) 12-6 ; (56°) 30-1 (Gerardin, A. Ch. 
 [4] 5, 129). [NH», HCl] = 41,900 ; [NH'Aq, 
 EClAq] = 12,270; [N, H', CI] =75,790 (Th. 2, 
 75). [NH'Cl,Aq] = - 3,880 (Th. 3, 197). 
 [NH^Cl.wH^CmH'O] {Th. 3, 109). 
 n + m = 25 60 100 200 
 
 n= 10 -87 -121 -129 -129 
 
 „ 25 — _ 34 - 42 - 42 
 
 „ 50 — _ 8 - 8 
 
 „ 100 — _ 
 
 Occurrence, — In small quantities, in the 
 
 neighbourhood of voloanoes, and in fumaroles ; 
 
 in some animal secretions, e^, saliva. 
 
 Formation. — 1. By mixing HCl and NH, in 
 
 equal volumes. 2. By the action of HCl on N 
 and H, under the influence of the electric dis- 
 charge, or when heated and quickly cooled (for 
 details v. Ammonia, Formation, Nos. 1, 2, and 
 3). — B. By the decay, or destructive distillation, 
 of various N-containing organic matters. 
 
 The name Sal ammoniacum seems to have 
 been given by the earlier chemists to rock-salt ; 
 Geber, probably latter part of 8th century, pro- 
 pared ammonium chloride from urine and com- 
 mon salt ; towards the end of the seventeenth 
 century the name Sal ammoniacum came to be 
 applied to ammonium chloride. The salt was 
 prepared in Egypt by subhmation from the 
 sooty deposit obtained by burning camel's dung. 
 The first manufactory of sal ammoniac in 
 this country was established at Edinburgh in 
 1756. 
 
 Preparation. — Crude ammonium carbonate 
 obtained by the dry distillation of bones, horn, 
 blood, &o., or gas coal, is decomposed by hot 
 milk of lime, and the NH3 produced is led into 
 HClAq, the liquid is boiled down, and the crude 
 NHjCl is purified by solution, filtration through 
 animal charcoal, re-erystallisation, and sublima- 
 tion. For details of preparation of pure NH,C1 
 V. Ammonia, Preparation No. 3. 
 
 Properties. — Pure ammonium chloride is a 
 white, inodorous, salt, with a pungent taste ; it 
 crystallises from aqueous solutions in small oubss 
 or octahedra which gather together into f eathary 
 masses {v. further, Naumann, J. pr. 60, 11 and 
 310). By sublimation and rapid cooling it is 
 obtained as a loosely cohering powder consisting 
 of minute octahedra ; the ordinary sublimed salt 
 has been partially fused and appears as a semi- 
 translucent mass of fibrous crystals. It is very 
 tough, and cannot be powdered ; sal ammoniac 
 is best obtained in fine powder by evaporating a 
 solution to dryness with constant stirring. It is 
 easily soluble in water (v. data at beginning of 
 article) ; a cone, aqueous solution boils at 115-8° at 
 768 mm. (Alluard, 0. B. 59, 500) ; S.G. i£° of cone. 
 NH^ClAq containing 26 p.c. NH^Cl is 1-0752 
 (Michel a. Krafft, A. Ch. [3] 41, 471). Tables of 
 S.G. of NHjClAq are given by Geriaoh {J. 1859. 
 42), and Sohiff {A. 110, 74). On heating NH^ClAq 
 of 10-6 p.c. to 37° NHjis given off in the 
 water-vapour (Leeds, Am. S. [3] 7, 197) ; aa 
 temperature increases the decomposition of NH4CI 
 probably increases also (v. Fittig, A. 128, 189 ; 
 Dibbits, B. 5, 820; Brucke, J.pr. 104, 481). 
 
 Beactions. — 1. When NH^Cl is heated it 
 vaporises, but the vapour is found to consist of 
 HCl and NH3 {v. Pebal, A. 123, 199 ; Than, A. 
 131, 129 ; Wanklyn, P.M. [4], 29, 112 ; Wurtz, 
 /. 1859. 30 ; Deville a. Troost, 0. B. 49, 239 ; 56, 
 891 ; Tommasi, B. 14, 353). The density of the 
 vapour is 12-9 according to Bineau {A. Ch. [2] 
 68, 416) ; 14-4 at 350°, and the same at 1040°, 
 according to Deville and Troost (C. B. 49, 239 ; 
 56, 891). Than (i.e.) has shown that HCl does 
 not combine with NHj at 350° or higher 
 temperatures. — 2. NH^ClAq is decomposed by 
 chlorine with formation of HCl and nitrogen 
 chloride (q. v.).^-S. Heated with iron, zinc, or 
 better with potassium, NH4CI is decomposed 
 with production of metallic chloride, NH,, and H; 
 in presence of air and moisture the reaction pro- 
 ceeds rapidly with formation of metallid chloride 
 
AMMONIUM COMPOUNDS. 
 
 20S 
 
 or oxyohloride and NH,. — 4. Many metallic 
 oxides decompose NHjCl with formation of chlo- 
 rides, and NHj ; in some cases — e.g. oxides of 
 Hg, Pt, Au &o. — the chloride combines mth a 
 portion of the NH^Cl to form a double compound. 
 
 5. Alkaline carbonates decompose NHjCl when 
 heated with volatilisation of ammonium car- 
 bonate. Calcium carbonate, especially when 
 freshly precipitated, dissolves readily in NHjClAq ; 
 on heating, ammonium carbonate is evolved. — 
 
 6. Crystallised sodium sulphate partially 
 decomposes NH^Cl when the two are mixed 
 together by rubbing, NaCl and (NH4)2SOj being 
 formed and partly dissolving in the water which 
 comes from the sodium sulphate crystals. — 
 
 7. Sulphuric anhydride vapour is absorbed by 
 powdered NH,C1, on warming HCl is evolved 
 and SO2NH2ONH4 is formed ; if water is added 
 (NHJ2SO4 is produced. — 8. The reaction between 
 acids and NH,C1 follows the ordinary course of 
 the interaction of acids with salts of other acids. 
 
 Combinations. — 1. NH^Cl combines with 
 many metallic chlorides to form double com- 
 pounds ; e.g. PtCl4.2NH4Cl ; HgOl2.2NH,Cl ; 
 CuCl2.2NH,Cl &o. (v. the several Metals).— 2. 
 With an aqueous solution of IC1.„ the compound 
 NHjCl.IClj is produced (v. Ammonium iodide; 
 Beactions, No. 2).— 3. According to Troost (O.B. 
 88, 578) when NH^Cl is heated with a large excess 
 of pure dry ammonia, at least two compounds 
 are formed: HCI.4NH3, melting at 7°; and 
 HCI.7NH3, formed at - 31° and 750 mm., melting 
 at -18°. 
 
 Ammonium fluorides (Marignac, Ann, M. [5] 
 15, 221). 
 
 I. Necteaii Salt. , NH^F. Mol. w. unknown. 
 [NH'Aq, HPAq] = 15,200 pSfH», HE] = 30,100 
 (Guntz, O. B. 97, 1483). Formation.— 1. By 
 mixing HF and NH3. — 2. By heating KP or 
 NaP with NH4CI. Preparation. — 1. By gently 
 heating a dry finely powdered mixture of 1 part 
 NHjCl with 3J parts EF in a platinmn crucible 
 covered with a lid, which is kept cold by drop- 
 ping water on to it ; the NH4F sublimes on to 
 the lid. — 2. Ordinary HFAq is saturated with 
 NHjAq, a little (NHJjCOaAq is added, the clear 
 liquid is decanted and evaporated in a platinum 
 dish with repeated additions of small pieces of 
 solid ammonium carbonate. Properties. — Hexa- 
 gonal prisms with strong saline taste ; unchanged 
 in dry air, but deliquescent in moist air ; easily 
 soluble in water, less soluble in alcohol; an 
 aqueous solution gives ofE NH, and acquires au 
 acid reaction; the dry salt absorbs NH, but gives 
 it off again on heating; sublimes readily with 
 previous fusion ; etches glass, and must be kept 
 in platinum, silver, orgutta percha, vessels. Be- 
 actions. — 1. When moist, or in solution in 
 water, NHjF decomposes siZicaJes with formation 
 of SiF, ; the same decomposition is effected by 
 the dry salt by heating it with silicates. — 2. An 
 aqueous solution is decomposed by heat, with 
 formation of the acid salt NH^F.HF and evolution 
 of NH3 {v. infra). 
 
 II. Acid Salt. NH,F.HF. MoI. w. un- 
 known. S.G. 1'21. Formation. — 1. By evapora- 
 ting an aqueous solution of NH^F at 36° to 40° 
 in a platinum dish. — 2. By adding excess of 
 NHjAq to a solution of fluosilioic aeid, and 
 e\-aporating • as thus obtained the salt is mixed 
 with silica. Properties. — OoloodeBS prisms; 
 
 easily soluble in water; slightly deliquescent} 
 easily volatilised, vapour being very acrid. 
 Ammonium iodides. 
 
 I. NHjI, Mol. w. unknown ; does not exist 
 as gas, but is dissociated by heat into NH, + HI. 
 S.G.ii° 2-498. S.V.S. 58. V.D. (440° to 860°) 
 38-8, but vapour consists of equal volumes of 
 HI and NH3. [NH', HI] =43,462; [N,HM] = 
 49,313 {Th.2,75). [NH%Aq] = - 3,550 (Th. 3, 
 197). Formation. — 1. By mixing equal volumes 
 of HI and NH3, or by acting on HIAq with 
 NHjAq. — 2. By decomposing FejI.Aq by 
 (NH4)jC03Aq, or Bal^Aq by (NHJ.SOAq. Pre- 
 paration.—\. Hot saturated solutions of (NHJjSO, 
 and EI, equal equivalents, are mixed ; aftsr 
 cooling, alcohol equal to 15 p.c. of the water 
 used is added ; " the liquid is filtered after 12 
 hours, and evaporated with addition of a little 
 NHjAq from time to time (Jacobsen, C. 0. 1864. 
 192).— 2. A solution of 27| parts KI in 48 parts 
 H2O is mixed with a solution of 22 parts tartaric 
 acid in 48 parts water, the mixture is placed in a 
 freezing mixture to separate KHC.,H40j, the 
 filtrate is evaporated at 100° with addition of 
 a little (NH,)2C03 (Beyer, D. P. J. 171, 467). 
 Properties. — Colourless cakes, very soluble in 
 water and alcohol ; deliquesces in moist air, and 
 becomes yellow through separation of I, and loss 
 of NHj ; may be sublimed unchanged in absence 
 of air. Beactions. — 1. NHjIAq is easily decom- 
 posed by dilute acids ; the soUd compound is 
 decomposed by dry HCl gas at high temperatures, 
 at 360° about ith, at 440° about Jth, at a dark 
 red heat about gths, of the NH4I being decom- 
 posed (Hautefeuille, C. B. 64, 704).— 2. Chlorine 
 led into saturated NHjIAq produces long, golden- 
 yeUow, needles of NH4CI.ICI3 (Filhol, J. Ph. 
 25, 441) ; this compound is decomposed by 
 gentle heating into ICI3 and NH4CI. — 3. By heat- 
 ing in ammonia, the compounds NHjI.aiNHj 
 9; = 1, 8, and 6, are obtained according to 
 Troost (0. B. 92, 715). 
 
 II. According to Guthrie (C. J. [2] 1, 239) a 
 compound of NH4I with I — NH4I.I — is obtained, 
 as a brownish-black liquid, soluble in alcohol, 
 ether, CS2, and KIAq, less soluble in CHCI3, when 
 I is added in small quantities to a cone, solution 
 of NH4NO3 with which J equivalent of KOH has 
 been mixed. NH4I.I easily separates in dry air 
 into NH3 and I ; water or dUute alkali produces 
 iodide of nitrogen, NH4I, and HI; mercury acts 
 on it to form Hgl^ and NH, ; aqueous solutions 
 of acids produce NH, salts and separate I. 
 
 Johnson (0. /. 33, 397) describes a compound 
 of NH4I and I the composition of which agrees 
 with the formula NHjIj. It is produced by 
 adding I to NH4I in presence of a little water 
 until no more I dissolves. It forms dark-blue, 
 somewhat deUquescent, prisms ; S.G. 3-749 ; 
 soluble in a little water, decomposed on dilution 
 with precipitation of I. This compound seems 
 to form a double salt with EI, viz. 5NH4IJ.EI, 
 obtained by passing NH3 into the mother liquor 
 from which EI, has separated. 
 
 Ammonium selenides (NH4)2Se, and (NHj)SeH 
 (Bineau, A. Ch. [2] 67, 229). Neither has been 
 gasified and therefore mol. ws. are unknown. 
 NH3 has no action on Se, but readily combines 
 with HjSe ; when excess of NH3 is used 2 vols, 
 combine with 1 vol. HjSe and produce (NHXSe, 
 when excess of E,Se is used equal vols, oif the 
 
204 
 
 AAIMONIUM COJIPOUNBS. 
 
 gases combine and form NHj.HSe. These com- 
 pounds are white solids which soon turn red hj 
 exposure to air or when dissolved in air-contaiu- 
 ing water ; both smell of NHj and H^Se and appear 
 «asily to undergo change; their aqueous solu- 
 tions probably contain polyselenides although 
 none of these has been isolated ; the products 
 of the distillation of KiSe with NHjCl probably 
 also contain ammonium polyselenides. 
 
 Ammonium telluride NHj.HTe. White leaf- 
 shaped crystals; easily soluble in water, vola- 
 tilised at 80°. Formed by the direct union of 
 NH3 and HjTe (Bineau, A. Ch. [2] 67, 229). 
 
 Ammouium sulphides, and Sulphydrate or 
 Hydrosulphide. Five solid sulphides, and a 
 hydrosulphide, of ammonium are known ; their 
 compositions are expressed by the formulte 
 NH.HS, (NHJ.S, (NHJ,S„ (NHJA, (NH,),S„ 
 (NHJj S, ; none of these exists in the gaseous 
 state ; the first and second, which have been more 
 studied than the others, are dissociated by heat, 
 into NH3 + H2S, and 2NH3 + H2S, respectively. 
 All the ammonium sulphides are soluble in water, 
 ■they very easily undergo change at ordinary tem- 
 peratures, usually giving off NH3, and HjS which 
 is often partly decomposed with precipitation of 
 S. They are all decomposed by dilute acids 
 with precipitation of white amorphous S, evolu- 
 tion of HjS, and formation of an ammonium salt 
 of the reacting acid. These sulphides act as 
 salt-forming or basic compounds towards such 
 acidic sulphides as As^Sj, ASjSj, Sb2S3 &c. {v. 
 infra: also Aesenio, and Antimony, thio-acids). 
 According to Berzelius any one of the ammo- 
 nium sulphides, except (NHJ^S,, can be pre- 
 pared by gently heating the corresponding sul- 
 phide of potassium with sal ammoniac ; in every 
 case except that of K^S^ the NHjCl must be in 
 excess, else part of the ammonium sulphide 
 formed is decomposed with production of S (NHj 
 and H) which combines with the potassium sul- 
 phide to form K2S5. Little or nothing is known 
 of the physical constants of these compounds ; 
 the following thermal data are given, but, by 
 reason of the instability of the sulphides and 
 the indirect methods by which the numbers have 
 been obtained, they must be accepted with cau- 
 tion : — 
 
 H.F. of solids from gaseous N audH, and solid S. 
 
 (NHJ, S, = 69,000 ho.wipr P R qi «^ 
 (NH,), S, = 69,600 p^abatier, O. M. 91, 56) 
 
 <NH J2 Sj = 69,400 (Sabatier, A. Ch. [5] 22, 73). 
 
 The tetra- and penta-sulphide dissolve in 
 water vrith absorption of about 8,000 gram-units 
 of heat per formula- weight of the sulphide. 
 
 The sulphides of ammonium have been 
 studied chiefly by Fritzsche {/. pr. 24, 460 ; 
 82, 313). 
 
 Preparation. — NHjHS is prepared by the 
 reaction of equal volumes of NH, and HuS at the 
 ordinary temperature, or at temperatures not 
 lower than — 10°. An aqueous solution of NH^HS 
 is obtained by saturating NHaAq with B^S in 
 absence of air. 
 
 (NHj)2S is prepared by cooling a mixture of 
 2 vols. NH3 and 1 vol. H^S to -18° ; or by dis- 
 tilling K2S with excess of NH^Cl and cooling the 
 distillate to - 18°. 
 
 (NHj)2S2 is obtained by passing vapour of S 
 and of NHjCl through a hot porcelain tube and 
 
 then into a well cooled receiver. An aqueous 
 solution may be prepared by dissolving S in 
 (NHJ2S Aq in the proportion (NHJ2S:S. 
 
 (NHjjjSs: when NH^HSAq (v. supra) is di- 
 gested with S, the solution saturated with NH3, 
 and then with H^S, more S added, and saturation 
 with NH3 and then with H^S repeated, the whole 
 liquid sets to a crystalline mass ; if this is heated 
 to 40°-50° a clear liquid is produced from which, 
 on gradual cooling, large crystals of (NHJjSj 
 separate out. 
 
 (NHJjSj : if the mother liquor from the 
 crystals of (NHJ2S5 is surrounded by a freezing 
 mixture, and treated first with NHj and then 
 with H2S a crystalline magma is formed ; on 
 warming a clear liquid is produced from which 
 crystals of (NHJ2S4 are deposited. 
 
 (NHJjSj is obtained by the gradual decom- 
 position of (NH4)2S5 in dry, slightly warm, air ; 
 it is also formed when a solution of (NHJ2S5 in 
 its mother liquor (v. supra) is placed under a 
 large bell jar for some time. 
 
 Properties and Reactions. — NH^SH : hard, 
 white, plates or needles ; very soluble in water, 
 and easily volatilised. V.D. at 56° 12-8, which 
 corresponds with equal vols, of H^S and NH, 
 (Deville a. Troost, 0. B. 56, 891). Aqueous solu- 
 tion is colourless, but soon changes in air from 
 absorption of 0, which decomposes a p.art of 
 the NHjHS with formation of H^O, NH3, and S ; 
 some of the S acts on the remaining NH^HS to 
 form (NHj)2S2, another part of the S is oxidised 
 to H2S2O3, and a portion of it is usually de- 
 posited. This process proceeds if exposure to 
 air is prolonged ; the (NH,|)2S2 is slowly decom- 
 posed, until finally a solution of (NHj)2S203 in 
 NH,Aq, mixed with solid S, is the result. 
 NH.|HSAq reacts with most metallic salts in 
 solution to form sulphides of the metals ; it also 
 reacts with acidic metallic sulphides to form 
 ammonium thio-salts, with evolution of H.,S, 
 e.g. AS2SS -I- 2NH,SHAq = 2NHiAsS2Aq + H^S 
 {v. Aesenic, thio-aoids op). 
 
 (NHJ2S: white,lu3trous,crystals; easily soluble 
 in water, forming a colourless Kquid which easily 
 decomposes with evolution of NHj and formation 
 of NHjHS. V.D. 18-2 (calculated for 2 vols. 
 NH, + 1 vol. HjS = 17-0) (Deville a. Troost, 
 0. B. 56, 891). Eeacts as a strongly marked 
 base towards acidic sulphides to form ammonium 
 thio-salts. 
 
 (NHJjSj: sulphur-yellow crystals, easily 
 soluble in water and alcohol. Stable only in an 
 atmosphere saturated with NH3 and HjS ; easily 
 decomposed in air with evolution of NH3 and 
 HjS. A saturated aqueous solution is fairly 
 stable ; more dilute solutions, and solutions in 
 alcohol, soon precipitate S. When heated, 
 NH4HS and S are formed. 
 
 (NHJjSj : orange-red prismatic crystals, 
 easily soluble in water and alcohol. These 
 solutions are very unstable, decomposing into 
 (NHJ2S2, S, H2S, and NH3, and after some time 
 also (NHJjSjOj. In dry air the crystals give off 
 NH3 and NH4HS and are changed into (NH4)2S,. 
 
 (NHJjS, : ruby-red crystals, much more 
 stable than any of the lower sulphides ; <iecom- 
 posed at about 300° ; soluble in water forming a 
 fairly stable liquid which is only slowly decom- 
 posed by HOlAq. 
 
 The liquid known as fwm/mg Uguor of Boyle, 
 
AMYI* 
 
 20& 
 
 or volatile liver of sulphur, chiefly consists of a 
 mixture of various ammonium polysnlphides ; 
 obtained by distilling a mixture of 1 part S, 
 2 jiarts NH^Cl, and 3 parts CaO. It is a dark 
 yellow, strongly smelling, and strongly fuming, 
 liquid. It dissolves sulphur and then no longer 
 fumes in air. 
 
 Ammonia reacts with many metallic salts 
 to form compounds, several of which behave as 
 if they were derivatives of ammonium chloride, 
 sulphate, &c., rather than double compounds of 
 ammonia with the metallic salts in question. 
 Thus NHs and PtCl^ form the crystalline com- 
 pound PtClj.iNH, ; by the action of H^SO., on 
 this, HCl is evolved, and there is produced 
 PtS04.4NH3; decomposed by BafOHj^Aq this 
 compound yields Pt(OH)2.4NH3, which loses H^O 
 when heated, with production of PtO.iNHj. The 
 compound Pt(OH)2.4NHj is a markedly alkaline 
 body, resembling NaOH or KOH; it neutral- 
 ises 2 equivalents of a monobasic acid. The 
 compounds PtCL.4NH3, PtS04.4NH3, and 
 Pt(OH)2.4NHj, can scarcely be regarded as double 
 compounds of ammonia and platinum salts ; 
 their reactions are better suggested by supposing 
 them to be derivatives of ammonium compounds, 
 obtained by replacing part of the hydrogen by 
 platinum. Thd nameplatinammonium has 
 been given to the hypotheticalradicle 
 
 N,H.Pt 
 
 (^kS:)- 
 
 The chloride of this radicle would be N2H3PtCl2 ; 
 if two hydrogen atoms in the group N^HjPt are 
 supposed to be replaced by two ammonium 
 groups (NHJ we get the hypothetical radicle am- 
 monium-platinammonium N2H^(NHj2Pt. 
 The compounds PtCl2.4NH3, PtS04.4NH3, 
 and Pt(OH)2.4NH3 may be regarded as com- 
 pounds of this radicle; thus N2H4(NH,)2Pt.Cl2, 
 N2H,(NHj2Pt.S04, N2H,(NHj2Pt.(OH)2. 
 
 Compomids are obtained by the action of 
 NHgAq on Hg^Clj and HgClj, respectively, which 
 have the composition HgjNH^Cl and HgNHjCl ; 
 these react as derivatives of NHjCl in which H2 
 is replaced by Hgj and by Hg, respectively. The 
 name mercuro-ammonium is sometimes 
 given to the hypothetical radicle NH2Hg2, and 
 the name merouri-ammonium to the hypo- 
 thetical radicle NHjHg. 
 
 A great many bodies are known the reactions 
 and relations of which can be gathered together 
 into one point of view by considering them as 
 compounds of various hypothetical radicles de- 
 rived from NHj, NjHg, NjHij, &c., by replace- 
 ment of part of the hydrogen by various metals. 
 These compounds wfll be described under the 
 headings of the various metals {v. more par- 
 ticularly the CHEOM-AMMONIUM-jCOBAlT-AMMONIUllI-, 
 COPPEK-AMMONIUM-, MEEOnRT-AMMONlnM-, and PLA- 
 
 IINDM-AMMONIUM-, COMPOUNDS ; in the articles 
 Chkomium, CoBAiiT, CoppBE, Mebcury, and Pla- 
 liNirM respectively). 
 
 Ammonium salts, i.e. derivatives of acids 
 obtained by replacing H by the group NHj, 
 are described under the various headings 
 
 CARBONATES, NITRATES, SULPHATES, &C. &0. The 
 
 principal salts are the following : — Anti- 
 vionate; arsenate, arsenite; borate; bromate, 
 (£c.; carbamate; carbonates; chlorates, chlorite, 
 £c.; ehromates ; eyanates ; cyanide ; iodate,per- 
 
 iodate, do. ; molybdates ; nitrate, nitrite, &c. ; 
 phosphates ; selenite, do. ; silicates ; sulphamate, 
 dc; sulphates, sulphites, dc; tantalate; tellu- 
 rates ; thioarsenates, thiocya/nates, thiosulphateSy 
 dc. For an account of the general properties oi 
 these salts v. beginning of present article. 
 
 M. M. P. M, 
 AMOXY-. Contraction for amyl derivative 
 
 of OXY-. 
 
 AMYDECYLENIC ACID v. Deoenoio acid. 
 
 AMYGDAIIC ACID G^^fi,^ or C2PH28O,,, 
 Formed by boiling amygdalin with baryta. Deli- 
 quescent crystalline mass, iusol. alcohol, and 
 ether. By boiling with H.^SOj and MnOj it 
 yields formic acid, CO2, and benzoic aldehyde 
 (Liebig a. Wohler, ^.22, 11 ; 66, 240 ; Schiff, A. 
 154, 348). 
 
 Acetyl derivatives C2nH2.Ao,0,. and 
 C2,H2,Ac,0,3 (S.). 
 
 AMYGDALIN C2,H,,N0„ 3aq. [200°J; after 
 solidifying it melts at 125°-130° (Wohler, A. 41, 
 155). Mol. w. 611. S. 8-5 at 12°. [a] =35-5°. 
 
 Occurrence. — In bitter almonds (Eobiquet a. 
 Boutron, A. Ch. [2] 44, 352) ; to a small extent 
 in sweet almonds ; in laurel leaves {Cerasus 
 lauro-cerasus) ; in the leaves, blossoms, and 
 bark of the birdcherry (Prunuspadv^) ; in young 
 shoots of the apple tree ; and in the kernels of 
 apples, pears, and peaches (Riegel, A. 48, 361 % 
 Wicke, A. 79, 79 ; 81, 241 ; Lehmann, N. B. P. 
 23, 449). 
 
 Preparation. — The almond-cake from which 
 the fatty oil of almonds has been removed by 
 pressure is extracted with boiling alcohol ; the 
 filtrate is concentrated and the amygdalin ppd, 
 by ether. 
 
 Properties. — White pearly scales or thin 
 prisms (from water). Insol. ether. 
 
 Reactions. — 1. Under the influence of emul- 
 sin or of boiling dilute H2SO4 it is split up 
 into benzoic aldehyde, prussic acid, and glucose 
 (Liebig a. Wohler, A. 22, 17) : 
 C2„H2,NO„ -H 2H2O = C,H,0 -h CNH + iG^B.,fi^.— 
 
 2. KMnOj forms cyanic and benzoic acids. — 
 
 3. Potash or baryta form amygdalio acid. — 4. 
 Cone. HGl gives mandelio acid, glucose, and 
 NHj. — 5. PCI5 gives CyCl and benzylidene 
 chloride. — 6. Zn and dilute hydrochloric acid 
 give CjH5.CH2.OH2.NH2 (Fileti, B. 12, 297). 
 
 Acetyl derivative C2„H2„Ac,N0,,. Long 
 needles (from alcohol) ; insol. water (Schiff, A. 
 154, 338). 
 
 Amorphous amygdalin has been described 
 by Winckler (B. J. 20, 428), Neumann (B. J. 23, 
 503), Simon (A. 31, 263), andLehmann [loc. cit.). 
 
 AMYL CjH,,. Pentyl. A monovalent basyl- 
 ous radicle which can occur in eight forms : 
 w-amyl, CH3.CH2.CH,.CH2.CH2 ; 
 iso-butyl-carbinyl (CH3)2CH.CH2.CH2 ; 
 sec-butyl carbinyl, (CH3)CH(C2HJ.CH2 ; 
 tert-butyl-oarbinyl (CH.)3C.CH2 ; 
 methyl-TC-propyl-carbinyl,CH3.CH2.CH2C(CH3)Hj 
 methyl-isopropyl-oarbinyl, (CH3)2CH.C(CH3)H ; 
 di-ethyl-carbinyl (C2H5)20H ; 
 and di-methyl-ethyl-oarbinyl (CH3)2(C2H5)C. 
 Ordinary amyl alcohol is a mixture of iso-butyl- 
 carbinol and sec-butyl carbinol, and it is from 
 this mixture that most of the amyl compounds 
 have been prepared. The term 'iso-amyl' com- 
 pounds will, for the sake of brevity, be used in 
 this dictionary to denote the mixture of amy} 
 
908 
 
 ATMYL. 
 
 ooiuponnds prepared from this aonrce. Inasmuch 
 as the proportion of the two constituents oi 
 'isoamyl' alcohol varies mth its source, 'iso- 
 amyl ' compounds prepared by different chemists 
 can hardly be expected to possess identical 
 physical characters. Amyl derivatives of hy- 
 droxylio carbon compounds are described under 
 the compounds of which they are the ethers. 
 
 Si-amyl (CsH,,)^ or CuHj, v. Deoam:. 
 
 AMYL-ACETYLENE v. Heptinene. 
 
 AMYL ALDEHYDE v. Valekio aidehtde. 
 
 AMYL ACETATES OjHjA- Fentyl acetates. 
 Mol. w. 130. 
 
 Preparation. — Similar to that of ethyl 
 acetate, p. 14. 
 
 «-Amyl acetate. (147'6°) (Garteumeister, 
 A. 233, 260) ; (148-4°) at 737 mm. (Lieben a. 
 Eossi, A. 159, 74). S.G. g -8948 ; §§ -8774 (G.). 
 C.B. (0°-10°) -00106 (G.). S.V. 173-8 (G.). 
 Prepared from »i-amyl iodide and silver acetate. 
 
 iBO-amyl acetate. (137-6°) at 745 mm. ; 
 (138-9°) (E. Schiff, A. 220, 110). S.G. « -8762 
 (MendelSeff, J. 1860, 7); =i° -8561 (Briihl). 
 /i^ 1-4088 (B.). Eoo 59-7 (B.) S.V. 174-6 (S.). 
 Is largely used as a flavouring agent to imitate 
 jargonelle pears. 
 
 Methyl-propyl-carbinyl acetate. (133°-135°) 
 (Wurtz, A. 148, 132) ; (1340-137°) (Schorlem- 
 mer, A. 161, 269). S.G. 2 -922 (W.). 
 
 fflethyl-isopropyl-carbinyl acetate. (125°) 
 (Wurtz, A. 129, 367). 
 
 Di-ethyl-carbinyl acetate. (132°) at 741mm. 
 S.G. 2 -909 (Wagner a. SaytzeH, A. 175, 306). 
 
 Tert-amyl acetate. (124°) at 750 mm. 
 S.G. 2 -891 (Ha-svitzky, A. 179, 348). Decom- 
 posed by heat into amylene and acetic acid 
 (Mensohutkin, C. B. 95, 648). 
 
 AMYL ALCOHOLS CsH.jO. Mol. w. 88. 
 Theory indicates 8 amyl alcohols {v. Amyl), viz. : 
 4 primary, 3 secondary, and 1 tertiary. One of 
 these, tert-butyl carbinol, is unknown. 
 
 m-Amyl alcohol CHa.CHj.CHj.CH^.CHj.OH. 
 (137°) at 740 mm. (Lieben a. Eossi, G. B. 71, 
 370) ; (137-9° i. V.) (Zander, A. 224, 81). 
 S.G. g -8282 (Z.). C.E. (0°-10°) -00091 (Z.) 
 S.V. 123-4 (Z.). 
 
 Occurrence. — In fusel oil (Wysohnegradsky, 
 A. 190, 350). 
 
 Formation. — 1. From n-valeric aldehyde and 
 sodium amalgam (L. a. E.). — 2. From Ji-amyl 
 chloride (Schorlemmer, A. 161, 268). 
 
 Inactive amyl alcohol 
 [CB.,)fiB..CB.^.CB.fiB.. (130-5°-131-2°) (Laoho- 
 wicz, A. 220, 171); (131-5° cor.) (Perkin). 
 S.G. if -8135 ; fj -8078 (P.). M.M. 5-959 at 
 18-6° (P.). Fusel oil is a mixture of active and 
 inactive amyl alcohol ; they can be more or 
 less separated either by passing HCl into the 
 boiling alcohol, when the inactive alcohol is 
 converted into amyl chloride more readily than 
 itsisomeride (LeBel.O. iJ.77, 1021) ; or by means 
 ■of the barium salts of the two amyl-sulphuric 
 acids, OjHiiSOjH, the active salt being the 
 more soluble in water (Pasteur, C. B. 41, 296). 
 The simplest way to obtain an inactive amyl 
 alcohol is carefully to fractionate fusel oil (L.). 
 The same alcohol can be prepared from iso- 
 butyl alcohol by converting it first into valeric 
 acid (Balbiano, G. 6, 229). 
 
 Iso-amyl alooho). 
 A mixture of (OHJjCH.OH,.OHjOH and 
 
 (CH,)CH(C2H5).CH20H. Fermentation, amyl 
 alcohol. Fvsel oil. [o. — 134°] (Olszewski, 
 M. 5, 128). (130-5°-131°) (E. Schiff, A. 220, 
 102). S.G. f -8104 (Bruhl, A. 203, 23). S.H. 
 •679 (DiaconoS, Bl. [2] 38, 172). Latent heat 
 of vaporisation 123-8 (D.). S. 2-5 at 16°. 
 H.F.p. 74,890 (Thomsen). H.F.v. 71,700 (T.). 
 Mfl 1-4124. Eoo 43-08. S.V. 122-7 (S.). Critical 
 temperature 307° (Pawlewski, B. 16, 2634). 
 
 Occurreruie. — Formed in small quantity in 
 the alcoholic fermentation of saccharine liquids. 
 Isoamyl angelate and isoamyl tiglate occur in 
 Eoman oil of chamomile (Kobig, A. 195 99). 
 
 Properties. — Poisonous liquid with powerful 
 odour. Its detection in alcohol is described on 
 p. 96. It burns with smoky flame. 
 
 Decorryposition. — 1. Its vapour led through a 
 red-hot tube produces acetylene, ethylene, propy- 
 lene, and butyleue (Wurtz, A. 104, 242).— 2. 
 S2CI2 gives amyl chloride and amyl sulphite 
 (Carius a. Fries, A. 109, 1).— 3. PCI3 and PCI5 
 form amyl chloride. — 4. Potash-lime at 220° 
 gives hydrogen and potassic valerate. — 5. ZnClj 
 produces amylene (3. v.). Hot HjSOj and PjOj 
 act similarly. — 6. Poured upon bleachingpowder, 
 it reacts in less than an hour; the distillate 
 decomposes with evolution of 01^ and HCl, and 
 then contains amyl alcohol, valeric aldehyde, 
 and amyl valerate (Goldberg, J.pr. [2] 24, 116). 
 
 Compoumds. — (05H,20)2SnCl4. Deliquescent 
 crystalline plates, decomposed by water (Bauer 
 a. Klein, A. 147, 249).— C5H,jO,SbCl5.— Crystal- 
 line.— (C5H,20)3CaCl2 (Heindl, M. 2, 209). 
 
 Sodic amylate, C5H„NaO,2C5H,20 (Froh- 
 lich, A. 202, 295). At 165° it combines with 
 CO forming sodic isovalerate and the sodium 
 salt of an acid OuHisOu. CO passed over a mix- 
 ture of NaOCsH,, and NaOAo at 180° produces 
 sodic formate and the sodium salts of a variety 
 of acids, the principal being iso-heptoio acid 
 {q. V.) formed by substitution of H of acetic acid 
 by C5H1,. Another product is oxy-vinyl-heptoio 
 oroxy-ennenoic acid (?.«.). An acid crystallising 
 in needles OuHuG, [139°] is also formed ; its 
 empirical formula is that of di-acetyl-heptoio 
 acid (Poetsch, A. 218, 56). 
 
 Potassium, amylate C|jH,,OK. White 
 silky crystals (de Forcrand, 0. B. 104, 68). 
 
 Thallium amylate C,B.,fiT\. S.G. 2-5. 
 An oil obtained by heating thallium ethylate 
 with amyl alcohol. 
 
 Aluminium amylate AHOCi'H.j,)^. [70°]. 
 S.G. 4 -9804. Formed by action of All, and 
 iodine (Gladstone a. Tribe, 0. J. 39, 7; v. 
 AiiUMDinjM Iodide, p. 148). 
 
 Active amyl alcohol CBtMeH.CH^OH. (128°) 
 (Pedler, A. 147, 243) ; (127°-128°) (Just, A. 220, 
 149). Od -2-3° (J.); -4-4° (LeBel; Pierre a. 
 Puchot). 
 
 Occurrence. — In fermentation amyl alcohol, 
 which is thus rendered more or less Isvorotatory. 
 
 Preparation. — Described under inactive amyl 
 alcohol. 
 
 Properties. — In a sample for which a was 
 only - 1-14°. Perkin (0. /. 45, 470) found S.G. 
 i| -8150 ; If -8091 ; and M.M. 5-94 at 20°. A rota- 
 tion of more than 4-4° to the left (in a tube 100 
 mm. long) has been observed by Ley ( — H'5°), 
 and by Pedler (-8-6°). 
 
 Beactions. — 1. A dilute solution mixed with 
 yeast, pmidlVmn glcmcwm, and a little H,SO| 
 
AMYLAMIKES. 
 
 307 
 
 beoomea dextrorotatory. The new dextro- I 
 rotatory amyl alcohol forms a Isevorotatory 
 iodide (Le Bel, Bl. 31, 104). — 2. On oxidation it 
 yields a dextrorotatory valerio acid, boiling at 
 170° (Pedler).— 3. Hot NaOHTenders it inactive. 
 
 References.— Paateuv, G. B. 41, 296 ; A. 96, 
 255; Popoff.B. 6,560; Ley.JB. 6, 1362; Erlen- 
 meyer a. Hell, A. 160, 257 ; Pierre a. Puchot, 
 C. B. 76, 1332 ; Bakhoven, J. pr. [2] 8, 272 ; 
 Le Bel, B. 6, 70 ; 9, 358, 732 ; C. B. 82, 562 ; 
 Bl. 25, 545 ; Pedler, A. 147, 243 ; Chapman a. 
 Smith, Pr. 17, 308. 
 
 Methyl-m-propyl-carbinol Pr.OMeH.OH 
 
 (119°). S.G.2-824. S. 13-7. 
 
 Formation. — 1. From its iodide. — 2. By re- 
 ducing methyl propyl ketone with sodium- 
 amalgam (Belohoubek, B. 9, 924). So prepared 
 it is inactive, but if it be dissolved in 20 pts. 
 water and penicillium glatccum be introduced, it 
 becomes Isavorotatory (a — 6'5°) (LeBel, 0. iJ. 89, 
 312). — 3. From acetyl chloride and zinc propyl 
 (Markownikoff, Bl. [2] 41, 259). 
 
 Reactions. — 1. Oxidation gives methyl propyl 
 ketone. — 2. Gives the iodoform reaction. 
 
 Methyl-isopropyl-earbinol. Pr.OMeH.OH. 
 (113°). S.G.2-833 (Wischnegradsky,X.190,338). 
 
 Formation. — 1. From methyl isopropyl ke- 
 tone with sodium-amalgam (Munch, A. 180, 
 339). — 2. By adding water to the product of the 
 action of zinc methide on bromo-aoetyl bromide 
 (Wiuogradoff, A. 191, 125), or chloro-acetyl 
 chloride (Bogomoletz, A. 209, 86 ; Bl. [2] 34, 330). 
 
 Beactions. — 1. Cone. HjSOj forms tri-methyl- 
 ethylene, MCjCiCMeH, which may be converted 
 by warm cone. HI into the iodide of tertiary 
 amyl alcohol. — 2. Oxidation gives methyl iso- 
 propyl ketone, acetone, acetic acid, and COj. — 
 3. PCI5 forms a chloride (87°). 
 
 Di-ethyl carbinol Et2CH.0H. (117°). S.G.2 
 •832. Formed by adding water to the product of 
 the action of zinc ethide 'on ethyl formate 
 (Wagner a. Saytzeff, A. 175, 351). The first 
 reaction may be written HCO.OEt + 2ZnEt2 = 
 HCEt(OZnEt)Et + ZuEt(OEt). Water then dis- 
 places OZnEt by OH. It gives di-ethyl ketone 
 on oxidation. 
 
 Tertiary amyl alcohol Et.CMcj.OH. 
 Di-methyl-ethyl-ca/rhinol. Amylene hydrate. 
 [-12°]. (102° cor.) (Perkin, O. /. 45, 471). 
 S.G. if -8144; M -8070 (P.). M.M. 5'99 at 
 19°. H.P.p. 84,510. H.P.V. 81,320 (Th.). 
 S.V. 121-3 (B. Schiff, A. 220, 102). 
 
 Formation. — 1. From tertiary amyl iodide 
 (g. i;.). — 2. From zinc methide and propionyl 
 chloride (Popoff, A. 145, 292; Jermolajeff, Z. 
 1871, 275 ; Wysohnegradsky, A. 190, 336). 
 
 Preparation. — Amylene (1 vol.), prepared 
 from ordinary amyl alcohol, is shaken with an 
 ice-cold mixture of water (1 vol.) and H^SO, 
 (1 vol.). 
 
 Beaations. — 1. On oxidation it gives rise to 
 acetone and acetic aoid. — 2. When introduced 
 into the stomach (of a rabbit) it is excreted as a 
 glyouronate, Oi,H2,0„ which is split up by acids 
 into the alcohol and glyouronic aoid (Thierf elder 
 a. Mering, S. 9, 515).— 3. Slowly decomposed 
 by heat at 220° into HjO and amylene ; this de- 
 composition does not take place unless traces 
 of HOI or HI are present (WolkofE a. Bougaiefl, 
 J. B. 1885, 276). 
 
 AMYIAMINES CjH„N. 
 
 Normal Amylamine 
 CH3.CH2.CHj.CHj.CH2.NH2 (103°). 
 
 Formation. — From the amide of normalhexoio 
 acid by the action of bromine and potash (Hof- 
 mann, B. 15, 770). A mixture of 1 mol. pro- 
 portion amide and 1 mol. bromine is run into 
 excess of 10 p.c. solution of potash at 60°. 
 
 Amylamines feom Amyii Alcohol of Fee- 
 mentation : — 
 
 Ordinary Amylamine 
 (0H3)2.CH.CH2.CH2.NH2 (95°_96°). S.G.ia-7503. 
 S.Y. 126-84 (Schiff). 
 
 Formation. — 1. Amyl oyanate or oyanurata 
 with potash (Wurtz, A. Ch. [3] 30, 447 ; Brazier 
 and Gossleth, A. 75, 252). — 2. Dry distillation of 
 animal substances (Anderson, A. 105, 335). — 
 3. Dry distillation of leucine (Sehwanert, A. 102, 
 225).— 4. Amylsulphate of potassium with alco- 
 holic ammonia at 250° (Berthelot, A. 87, 372). — 
 5. Distillation of horn with aqueous potash 
 (Limpricht, A. 101, 296). — 6. Caustic potash on 
 flannel (Gr. Williams, Ghem. Gas., 1858, 310).— 
 
 7. Amide of isohexoic acid (isobutylacetamide) 
 with bromine and aqueous potash (Hofmann, B, 
 15, 770). — 8. In the decomposition of yeast 
 (MuUer, J. 1857, 403). 
 
 Preparation. — ^Amyl bromide is heated to 
 100° with alcoholic ammonia in large excess, 
 the alcohol evaporated and the residual hydro- 
 bromides decomposed with potash. The oily 
 layer which consists of mono-, di-, and some 
 tri-, amylamine, is dried with caustic baryta and 
 fractionated. Or, potassium amyl sulphate is 
 distilled with potassium cyanate ; the resulting 
 amyl cyanate and cyanurate distilled with 
 strong potash ; the distillate neutralised with 
 hydrio chloride, evaporated and crystallised; 
 and the amylamine obtained by distilling the 
 hydrochloride vrith lime (Wurtz ; Silva, Bl. [2] 
 
 8, 363). 
 
 Properties. — Colourless liquid, miscible with 
 water and alcohol. 
 
 Beactions. — 1. Oxidised by chromic acid to 
 isovaleric aoid (Chapman a. Thorpe, A. 142. 
 177).— 2. With ClCOzEt yields ethyl-amyl-car- 
 bamate, CsHnNHCOjEt (amylurethane) (Custer, 
 B. 12, 1329). 
 
 Salts.— B'HCl : scales; sol. alcohol.^ 
 B'2H2PtClj : scales ; sol. hot water, insol. alcohol. 
 — Aurochloride : scales. 
 
 Combination. — With carbonic disulphide it 
 forms C"H2''N2S^(2C-'H'^N + CS') white shining 
 scales, insol. water and ether, sol. alcohol 
 (Hofmann, 0. J. 13, 60). 
 
 Active Amylamine. — The amylamines ob- 
 tained from active amyl alcohol, probably 
 (C2Hs)(CH3)CH.CH20H (Erlenmeyer; v. AioL 
 alcohols; Sauer, B. 8, 1037), are optically active, 
 and their salts are much more difficult to crys- 
 tallise than are those of the corresponding 
 inactive compounds (Plimpton, 0. J. 39, 332). 
 Amylamine from alcohol rotating 4° for 10 cm. 
 rotated 3° 30' to the left ; (96°-97°) ; S.G. 2 
 •n^S.—Sydrochloride: deliquescent; feebly 
 dextrogyrate. — Platino-chloride: scales; sol. 
 hot water. S. 2-4 atl4°. — Aurochloride : sol. 
 alcohol; separates on slow evaporation in 
 lozenge-shaped crystals with the acute anglei 
 truncated. 
 
208 
 
 AMTLAMINES. 
 
 Inactive Amylamine from inactive amyl 
 
 chloride. (96°-97°). S.G.J -7678; 
 
 •7501. 
 
 —Hydrochloride: crystallises well. — Pla- 
 tinochloride S. 1'7 at 14°: scales. — Auro- 
 chloride: sol. alcohol; lozenge-shaped crystals 
 with one acute angle truncated. 
 
 Diamylamine (05Hi,)2NH. (186°-187°). 
 S.G.fi-7825(Silva). 
 
 Formation. — 1. Prom ord. amylamine and 
 ord. amyl bromide (Hofmann, 4.79, 21). — 2. From 
 amyl cyanide and potash (Silva, Z. 1867, 457). 
 3. From amyl bromide and alcoholic ammonia 
 (Custer, B. 12, 1329 ; Plimpton, C. J. 39, 332 ; 
 BeU, B. 10, 1867).— 4. From amyl chloride and 
 aqueous NH, at 140°-165=' (MaUot, G. B. 104, 
 998).— 5. From the nitroso-oompound (Ouster, 
 B. 12, 1333). 
 
 Properties. — Oily liquid ; si. sol. water. Ee- 
 acts with Ol.OOJEt yielding diamylurethane 
 (Custer). 
 
 Salts. — B'HCl : laminsB ; crystallises well 
 from hot water.— (B'HO^jPtOl, : sol. alcohol, si. 
 sol. water. Auro-chloride: sol. alcohol, insol. 
 water. 
 
 Active Di-amylamine. (182°-184°). S.G.| 
 •7878. From active amyl bromide. {V. active 
 amylamine) (Plimpton, loc. cit.) Dextrorotatory 
 (5° 15' for 10 em.). 
 
 Hydrochloride : soluble in water, alcohol, 
 and ether. Much more soluble in cold water 
 than the inactive salt. Solution rotates to the 
 right. Platinochloride: sol. alcohol, insol. 
 water. Crystallises from dilute alcohol in 
 octahedrons. Aurochloride : insol. water, 
 sol. alcohol. 
 
 Inactive Di - amylamine. (186°-187°). 
 S.G. £ -7878 ; w -7776. From inactive amyl 
 chloride (Plimpton). 
 
 Hydrochloride: lamina; rotates when 
 thrown on the surface of water. Insol. ether. — 
 Platinochloride : sol. alcohol, insol. water. 
 Crystallises easily from dilute alcohol in 
 rectangular prisms. 
 
 Triamylamine (C5H„)3N. (237°). From 
 diamylamine and amyl bromide or from amyl 
 bromide and ammonia (Hofmann, A. 79, 22). 
 Amyl cyanate and potash (Silva, Z. 1867, 458). 
 Oily liquid, insol. water. 
 
 Salts. — B'HCl : crystalline mass with 
 lustre of mother-of-pearl. Platinochloride: 
 rhombic prisms ; insol. water, sol. alcohol. 
 
 Active Triamylamine. (280 =-237°). 
 
 S.G. j' '7964. Prepared from active amyl 
 bromide (3°) and active diamylamine (5° 15'). 
 Eotates 44° 15' to the right for 10 em. (Plimpton, 
 loc. cit.). 
 
 Hydrochloride : syrup which solidifies 
 over sulphuric acid. Solution strongly dextro- 
 gyrate. 
 
 Aurochloride: needles; insol. water, sol. 
 alcohol. 
 
 Inactive Triamylamine. (237°). S.G. ^^ '788. 
 From inactive amyl chloride and ammonia. 
 
 Hydrochloride: crystallises from water 
 in prismatic needles, from ether in pearly 
 scales. — Aurochloride: needles; sol. alcohol. 
 Inactive triamylamine may be separated from 
 inactive diamylamine by treating the hydro- 
 chlorides with ether which dissolves the triamyl- 
 amine salt. 
 
 Tetramylammonium Salts. 
 
 Iodide (C-H„)4NI. From ordinary amyl 
 iodide and triamylamine or amyl iodide and 
 ammonia (Hofmann, O. J. 4, 316). The mixture 
 of triamylamine and amyl iodide is boiled and 
 after three or four days solidifies on cooling 
 into an unctuous crystalline mass. Monoolinic 
 laminm (Lang, J. 1867, 491). Dissolves 
 sparingly in water forming an extremely bitter 
 solution from which it is ppd. in a crystalline 
 form by alkalis. Boiled with silver oxide it 
 yields a very bitter alkaUne solution of 
 Tetramylammonium hydroxide, Oa 
 mixing the liquid with potash or on concentra- 
 ting, the hydroxide separates as an oily layer, 
 which gradually solidifies. By evaporating a. 
 solution of the hydroxide in an atmosphere free- 
 from carbonic acid, crystals containing several 
 molecules of water are obtained. When heated 
 these crystals melt and give off water, tri- 
 amylamine, and a hydrocarbon which is pro- 
 bably amylene. 
 
 (C5H„)jNCl : laminae with pahn-like ramifi- 
 cations. — ((CsIIiJjNC^jPtOlj : orange - yellow 
 needles. — Sulphate: long capiUary threads. — 
 Nitrate: needles. — Omalate: large deli- 
 quescent plates. 
 
 Amylamine. Corresponding to methyl pro- 
 pyl carbinol. (CH3)(C3H,)CHNH2. (89°-91°). 
 By reduction of methyl propyl ketone phenyl 
 hydrazide in alcoholic solution with sodium 
 amalgam and acetic acid (Tafel, B. 19, 1924).. 
 MobUe liquid, smelling strongly ammoniacal, 
 misoible with water, alcohol, and ether. 
 
 Hydrochloride : silky needles. — 
 Platinochloride: yellow needles ; sol. water 
 and hot alcohol, less so in cold alcohol. — 
 Oxalate: crystallises from hot alcohol in scales. 
 
 Tertiary amylamine. (CH3)j(CaH5)CNH2. 
 (77-5°-78°). S.G. £ -7611 ; 11? -7475. Formerly 
 considered to be (CH3)2CH(CH3)CHNH2 on 
 account of its formation from the cyanate 
 corresponding to Wurtz's amylene hydriodide 
 and amylene hydrate, then regarded as iso- 
 propyl-methyl carbinol, and now shown to be di- 
 methyl-ethyl carbinol (Flavitzky, A. 179, 840). 
 
 Formation. — 1. From pseudoamylurea and 
 strong potash (Wurtz, Bl. [2] 7, 143).— 2. By 
 the action of dimethyl ethyl carbinol iodide on 
 the cyanides of potassium and mercury, and 
 treatment of the nitrile so obtained with hydrio 
 chloride (Wysohnegradsky, A. 174, 60). — 3. By 
 treating the product of the action of the same 
 iodide upon silver cyanate with strong hydrio^ 
 chloride (Eudnew). 
 
 Properties. — Odour ammoniacal; pps. copper 
 salts but does not redissolve the ppd. cuprio 
 hydrate. 
 
 Hydrochloride : efflorescent scales, or 
 octahedrons, from alcohol and ether. — 
 Platinochloride : fine crystals derived from 
 a monoolinic prism, easily soluble water and 
 alcohol. — Aurochloride : large yellow 
 crystals, monoolinic. 
 
 Reactions. — With bromine it forms brom- 
 amyl-amine CjHi^rN which can be distilled with 
 steam (Wurtz). E. T. P. 
 
 AMYI-ANILINE C„H„N i.e. C,H5.NHC,H,,. 
 (258°). Mol.w. 163. From aniline and isoamyl 
 bromide (Hofmann, G. J. 3, 297). Smells, when 
 cold, like rosea. When its hydrochloride is 
 
ISO-AMYL OARBAMIC ETHER. 
 
 S08 
 
 heated at 820* it ohanges to the hydrochloride 
 of amido-phenyl-pentane, OsHu.CjH^.NHj (Hol- 
 mann, B. 7, 529). 
 
 Isoamyl-aniline CjHs.NHCsH,, (243°) at 
 720 mm. Colourless oil. Y. sol. alcohol, ether, 
 and benzene, insol. water. Is a by-product of 
 the action of isovaleric aldehyde and HGl upon 
 aniline. Salts. — B'HOl: colourlessprisms.v.sol. 
 water. The nitrate andoxalate are sparingly 
 soluble. The picrate is a reddish-yellow oil. 
 
 Acetyl derivative CjH5.N{C5H„)Ac, 
 (278°) at 720 mm., colourless fluid, v. sol. alcohol 
 and ether ; insol. water. 
 
 Nitrosamine CjH5.N(C5H,,)N0: oil; vola- 
 tile with steam ; v. sol. alcohol and ether, insol. 
 water (Spady, B. 18, 3376). 
 
 Di - isoamyl - aniline CsH5N(C5H„)2. 
 
 (275°-280°) (Hofmann,^. 74, 156).— B'^H^PtCl^. 
 
 Iso ■ AMYL - ANTHEACEHE C.^E^ i.e. 
 ^0(CA.)\ 
 
 Nj 
 
 
 CH 
 
 / 
 
 CsH,. [59°]. From amyl- 
 
 hydro-anthranol by boiling alcoholic HCl. 
 
 Pre^araUon. — ^Ahthraquinone (30 g.), zinc 
 dust (100 g.) NaOH (50 g.), water (450 g.) are 
 boiled together for 5 hours and then amyl 
 bromide is added. The liquid is poured off, and 
 the pp. dissolved in alcohol, reppd. by water, 
 and boiled with alcoholic EGl (Liebermann, 
 A. 212, 104 ; B. 14, 796). 
 
 Properties Long sea-green needles with blue 
 
 fluorescence (from alcohol). Cone. H^SOj gives a 
 green solution. V. sol. benzene, CSj, chloroform, 
 or benzoline. Picrate forms red needles 
 [115°], CrOj in HOAc gives amyl-oxanthranol. 
 Forms a bromo compound 
 
 [76°]. Picrate [110°]. 
 
 Forms also a corresponding chloro-deriva- 
 tive [71°]. Picrate [108°]. 
 
 Zso-Amyl-anthraceue-^-hydride 
 
 0„H« i.e. C,H,<;gg<^'^")>C,H,. (350°) ; 
 
 (292°) at 570 mm. S.G. if 1-031. Prepared by 
 reduction of amyl-oxantnranol with P and HI 
 (Liebermann, B. 14, 457; 15, 1000; A. 212, 79). 
 Clear fluorescent liquid. Miscible with alcohol, 
 ether, benzene, and acetic acid, in aU proportions. 
 On oxidation with HKO3 anthraquinone is 
 formed. 
 
 7S0-AMTL AESENATE (G^U^^^ksOt (Crafts, 
 Bl. 14, 101). 
 
 iso-AMYL AESENITE (C5H„)3As03. (288°) 
 (Crafts, Bl. 14, 105). 
 
 w-AMYL-BENZENE. Phewyl-pentane. C„H,5 
 i.e. Ph.CH2.CH2.CH2.CHj.CH3. Mol. w. 148. 
 (201° uncor.) at 743 mm. S.G. ^ -8602. From 
 benzyl bromide, w-butyl bromide, and sodium 
 (Schramm, A. 218, 388). Pleasant smelling oil. 
 
 Reaction. — Bromine vapour at 150° gives 
 "Ph.CHBr.CHj.CHj.CHj.CHs (?) which on 
 distillation gives Ph.CHiCH.CHj.CH^.CHa 
 (210°-215°) which combines with Br^ forming 
 Ph.CHBr.CHBr.CH2.CH2.CH3. [54°]. 
 
 Isoamyl-benzene (193°) at 736 mm. S.G. i^ 
 ■859. From bromo-benzene, isoamyl bromide, 
 and Na (Pittig a. ToUens, A. 129, 369 ; 181, 
 313 ; Bigot a. Pittig, A. 141, 160 ; Sohranmi, 
 A. 218, 390). Also from isoamyl chloride, ben- 
 zene, and AlClj (Friedel a. Crafts, A. Ck. [6] 
 1, 454). 
 
 Vol. L 
 
 Reaction. — Bromine vapour at 150° gives 
 ''Ph.CHBr.CH2.CH(CH,)2(?) which on distillation 
 gives HBr and Ph.CH:0H.CH(CHs)2, phenyl- 
 isoamylene, which forms a dibromide [129°]. 
 
 Di-ethyl-oarbinyl-benzene Ph.CHEtj. (178°). 
 S.G. ^ •873. 
 
 Formation. — 1. From benzylidene chloride 
 and zino ethide (Lippmann a. Luginin, Z. 
 1867, 674).— 2. From benzo-trichloride, Ph.CClj, 
 and zinc ethide (Dafert, M. 4, 153, 616). 
 
 r^-f-amyl-benzene Ph.0Me2Et. (0. 187°). 
 S.G. 2 -874. From tert-amyl chloride, benzene,, 
 and AICI3 (Essner, Bl. [2] 36, 212). 
 
 Si-isoamyl-benzeue OieHjs i.e. {GiRjj)fie^,. 
 (c. 265°). S.G. 2 -887. From benzene, isoamyV- 
 chloride, and AlCl, (Austin, Bl. [2] 32, 12). 
 
 AMYl-BENZENE STOPHONIC ACIDS 
 C„H„S03 i.e. C,H„.05H,S03H. 
 
 ^ Isoamyl-benzene sulphouic acid. Deliques- 
 cent crystalline mass (Fittig a. ToUens, A. 
 131,815). Salts.— KA'aq.—BaA'j: hair-like- 
 needles. 
 
 Di-ethyl-oarbinyl-benzene snlphonlc aci* 
 CHEt2.CsH1.SO3H. Salts.— BaA'^l^aq: pearly 
 leaflets, si. sol. water and alcohol (Dafert, M. 
 4, 617). 
 
 jp-iso-AMYI-BENZOIO ACID C,^B.,fi2 i.e. 
 CsH,(C5H„).C02H [1:4] [158°]. Formed by 
 saponification of the nitrile. Sublimes in flat 
 colourless needles. Sol. alcohol, ether, and hot 
 water, si. sol. cold water. Salt: AgA': small 
 colourless needles, si. sol. cold water (Kreysler, 
 B. 18, 1710). 
 
 p-Jso-AMYI-BENZOKITRILE 
 C,Hj(C5H,i).CN (260°_268° unoorr.). Colourless 
 oil. Formed by heating tri-isoamylphenyl- 
 phosphate vrith dry KCN ; yield — 20 p.c. (Kreys- 
 ler, B. 18, 1709). 
 
 Iso - AMYL BORATE C.-Hj-BO. U. 
 (C,H„0)3B. (254°). S.G. 2 -872. 
 
 Iso-amyl borate (C5H„0)B0. S.G. a -971. Oil. 
 
 TO-AMYL BROMIDE CsH^Br i.e. 
 CH3.CH2.CH2.CH2.CH2Br. Mol. w. 151. (129°). 
 S.G. 2 1'246. From w-amyl alcohol (Lieben a, 
 Eossi, A. 159, 73). 
 
 Inactive amylbromide (CH3)2CH.CH2.CH2Br 
 (120-6° i. V.) at 734 mm. S.G. 2a 1-026 (Laoho- 
 wicz, A. 220, 171). 
 
 Isoamyl bromide (118-5°) at 756 mm. (E, 
 Sohiff, B. 19, 563). H.F.p. 34,000 (Berthelot), 
 S.V. 138-6 (S.) ; 1438 (Eamsay). For a speoi- 
 men which rotated -I- -52° in 100 mm. Perkin 
 (0. J. 45, 458) found: (120-5° cor.) ; S.G. if 
 1-2193 ; If 1-2083 ; M.M. 9-04 at 17°. 
 
 Active amyl bromide (117°-120=) ; S.G. i^ 
 1-225 (Le Bel, Bl. [2] 25,545). Dextrorotatory; 
 o=+3-75°. 
 
 ?i-Sec-amyl bromide CH3.CH2.CH2.CHBr.CH3. 
 (113°) (Wurtz, A. 125, 118). Formed when 
 isoamyl bromide is heated at 230° (Eltekow, B. 
 8, 1244). 
 
 Iso-sec-amyl bromide (CH3)„.CH.CHBr.CHs, 
 (116°) (Wyschnegradsky, A. 190^ 357). 
 
 2'eri-amylbromideCH3.CH2.CBr(CH3)2.(109°). 
 
 AMYL-BROMO- v. Beomo-amti,. 
 
 Jso-AMYL-CARBAMIC ETHER CsHjjNOji.fc 
 CsHiiNHCOjEt. Amyl-urethane. (218°). S.G. 
 -93. From isoamyl-amine and ClCOjBt (Custer, 
 B. 12, 1828). Oil ; sol. alcohol and ether. 
 
 Di-isoamyl-carbamic ether (C5Hi,)2N.C02Et. 
 (247°). From di-isoamyl-amine and C1002Et(C.). 
 
 P 
 
SIO 
 
 XSO-AMYL OAKBAMINE. 
 
 Iso-AMTt CABBAMINE 0jH„Ni.6. CsHnNC. 
 (137°). Mol. w. 97 (Hofmann, A. 146, 109). 
 
 Iso-AMYL CAKBONATE C„HjA i.e. 
 (OjEiO^CO, (229° oor.). S.G. i^ -91. 
 
 Iso-ASni CETYL OXIDE C^.H^O i.«. 
 CsHi.OCibHss. [30°]. Plates. 
 
 TC-AMYL CHLOBIDE CsH.iCl i.e. 
 CH,.CH2.CHj.CH;j.0HjC1. MoI. w. 106-5. (106°), 
 S.G. 22 -873 (Laohowioz, A. 220, 191); -883 
 (L. a. B.). Formed from n.-amyl aloohol (Lieben 
 a. Eossi, A. 159, 72 ; G. 1, 314) or by the chlori- 
 nation of w-pentane (Soborlemmer, A. 161, 268). 
 
 Inactive amyl chloride (0H5)2CH.CH2.CH2C1. 
 (99-8°-100-5°). S.G. 22-870. Prom iso-pentane 
 (Laohowitz). 
 
 Iso-amyl chloride (99-5°) (E. Schiff, B. 19, 
 562). S.V. 184-4 (S.) ; 136-5 (Eamsay). In a 
 specimen which rotated +5-8° in 100 mm. 
 Perkin (C. /. 45, 452) found: (97°-99° cor.) ; S.G. 
 ^ -8801 ; if -8716 ; M.M. 7-17 at 19-5°. 
 
 Formation. — 1. From isoamyl alcohol and 
 HCl (Balard, A. Gh. [3] 12, 294), S^CI^ (Carius a. 
 Fries, A. 109, 1), or PCI5 (Cahours, A. 37, 164). 
 
 Reactions. — 1. Conyerted into amyl alcohol 
 by water at 100° (Butlerow, A. 144, 34), or better 
 at 120° (Niederist, A. 186, 392).— 2. H^SO, 
 forms HCl and OjHuSOiH (Oppenheim, J, ipr. 
 102, 339). 
 
 Active amyl chloride 
 CH,.CHj.CH(CH3).CH201. (99°). a= + l-24°. 
 S.G. iS -886 (LeBel, Bl. [2] 25, 546). 
 
 TC-Sec-amyl chloride CHs.CHj.CHj.CHCl.CHj. 
 (104°). S.G. 21 -891. FromTC-peutane bychlori- 
 nation (Schorlemmer ; Laohowioz). From 
 CH3.CH2.CH:CH.CH8 and HCl (Wagner a. Sayt- 
 fceff, A. 179, 321). 
 
 Iso-sec-amyl chloride (CH3)jCH.CHCl.CH3. 
 (91°). S.G. 2 -88. From (CH3),CH.CH:CH5, and 
 HCl (Berthelot, G. R. 56, 700 ; Wurtz, A. 129, 
 368 ; Wyschnegradsky, A. 190, 357). 
 
 s-Sec-amyl chloride Et^CHCl. (103°-105°). 
 S.G. 51 -895. From the alcohol (W. a. S.). 
 
 Teri-amyl chloride EtCMejCl. (86°). S.G. is 
 •870. By action of PCI5 on tert-amyl alcohol 
 or on methyl-isopropyl-oarbinol (Wysohnegrad- 
 Bky,4.190,336-, 191,331). 
 
 AHYL-OHLOBO- v. Chlobo-amyl. 
 
 Iso - AMYL CYANATE OeH„NO i.e. 
 QHjjN.CO. (135°). Prepared by distilling 
 amyl-carbamio ether with P^Oj (Custer, B. 
 12, 1330), or from CjHuSOjK and potassium 
 .cyanate (Wurtz, A. Gh. [3] 42, 43). With 
 .cmimoma it yields amyl-urea, and with potash it 
 yields amylamine. 
 
 AMYL CYAITIDE v. Amiii Cabbamine and 
 nitrile of Hexoio Acid. 
 
 AMYLENE C,H„. Pentene. Mol. w. 70. 
 
 n-Propyl-ethylene CHj.CHj.CHj.CHrCH^. 
 (40°). 
 
 Formation. — 1. Together with amyl acetate 
 when KOAo and Ac^O act on w-amyl chloride at 
 200° (Schorlemmer, A. 161, 269).— 2. Together 
 with di-aUyl (principal product), pentane, and 
 other bodies, in the action of zinc ethide on allyl 
 iodide (Wurtz, A. 123, 203 ; 127, 55 ; 148, 131). 
 
 Properties. — Liquid; insol. HjSO, (2 vols.) 
 diluted with water (1 vol.). 
 
 Reactions. — 1. Gives Pr.CHI.Me with HI. — 
 2. Alkaline EMnOj gives succinic, butyric, 
 oxalic, and formic acids (Zeidler, A. 197. 2S3). 
 
 Isopropyl-ethylene (CHs)2.CH.CH:CHj,. (21°). 
 Formed together with EtCMeiCH^ by action o£ 
 alcohoUo KOH on isoamyl iodide (Wysohne- 
 gradsky, B. 10, 81 ; A. 190, 328). 
 
 Properties. — Liquid; insol. at 0° in H^SO, 
 (2 vols.) mixed with water (1 vol.). 
 
 Reactions. — Does not combine with HI at 
 - 20°, but at 20° it combines slowly forming 
 (CH3)jCH.CHI.CH,. 
 
 s-Methyl-ethyl-ethylene CH3.CH:CH.Et. 
 (36°). 
 
 Formation.— 1. From CHs.CH2.CHI.CH2.CH, 
 (Wagner a. Saytzeft, A. 176, 373; 179, 302), or 
 CH3.CHI.OH2.CH2.CH3 (Wurtz), and an alcoholio 
 solution of KOH. — 2. From ethyl-crotonio acid, 
 CH3.CH:CEt.002H, by combining it with HBr 
 and neutralising the resulting ;3-bromo-di- 
 ethyl-acetio acid: CH3.CHBr.CEtH.C02Na = 
 NaBr + COj + CHj.CHrCEtH (Fittig, A. 200, 27). 
 
 Reaction.— EI forms CHs.CHI.Ca.CHj.CH,. 
 
 M-Methyl-ethyl-ethylene Et.C(CH3):CH2. 
 (32°). S.G. 2 -670. Prom active amyl iodide 
 and alcoholic KOH (Le Bel, Bl. [2] 25, 546). 
 
 Properties. — Liquid ; dissolves in HjSO, 
 (2 vols.) diluted with water (1 vol.). 
 
 ReacUons.—BI forms CH3.CH2.CI(0H3).CH3. 
 
 Tri-methyl-ethylene {CS^)fi:GB..GB.,. (36°). 
 S.G. If -6704 ; 2| -6614. M.M. 6-121 at 13-2° 
 (Perkin, C. J. 45, 448). 
 
 Formation.— 1. From CHs.CH2.CI(CH,), 
 (Ermolajeff, Z. [2] 6,275) or CH3.CHI.CH(CHs)j 
 (Wy.) and alcoholio KOH.— 2. From ethyl 
 isoamyl oxide and P^Os (Flavitzky, A. 169, 206). 
 
 Properties. — ^Liquid ; soluble at 0° in H^SO, 
 (2 vols.) diluted with water (1 vol.) 
 
 Reaction.— Bl forms (CHs)2CI.CH2.CH,. 
 
 Iso-amylene. (36°). S.G. ^ -661; 'i -648. 
 H.F.p. 10,600 (Berthelot) ; 18,970 (Th.). H.P.v. 
 16,650 (Th.). V.D. 2-47 (for 2-42). S.V. 110 
 (E. Schiff, A. 220, 89); 110-8 (Eamsay). 
 fii3 1-3813. Eoo 39-29 (Bruhl). A mixture of tri- 
 methyl-ethylene (90 p.o.) and M-methyl-ethyl 
 ethylene (10 p.o.) with a small quantity of 
 isopropyl-ethylene (Flavitzky, A. 179, 340). 
 
 Preparation. — From isoamyl alcohol and 
 ZnClj, many other hydrocarbons being also 
 formed (Etard, 0. R. 86, 488 ; Wyschnegradsky, 
 O. R. 86, 973). 
 
 Properties. — Absorbed at 0° by H^SOj (2 vols.) 
 diluted with water (1 vol.), with production of 
 tertiary amyl alcohol. A more dilute acid (2 
 pts. H2SO4 to 1 pt. water by weight) forma 
 methyl-isopropyl-carbinol (Ossipoff, B. 8, 542, 
 1240).— NOCl forms a compound CsHjoNOCl 
 which may be reduced to amylamine (Tonnies, 
 B. 12, 169).— 3. CjHioKjPtCl^ aq is formed by 
 boiling isoamyl alcohol with PtCl4 and then 
 adding KCl (Birnbaum, A. 145, 73) ; deliquescent 
 plates. 
 
 Other References.— 'SsXaxdi, A. Gh. [3] 12, 320 ; 
 Frankland, G. J. 3, 35 ; Bauer, Sitz. B. 44 [2] 
 87 ; Z. 1866, 380, 667 ; Bauer a. Klein, Z. [2] 4, 
 386 ; Guthrie, A. 121, 108 ; Lippmann, A. 129, 
 81 ; M. 5, 559 ; Eltekoff, B. 6, 1258; Linnemanu, 
 A. 143, 350 ; Buff, A. Suppl. 4, 143 ; 148, 349 ; 
 Thorpe a. Young, A. 165, 7 ; Flavitzky, A. 165, 
 157 ; Le Bel, Bl. 17, 3 ; 18, 166 ; Berthelot, 
 A. Gh. [4] 9, 442; G.B. 44,1350; Eenard, A. Gh. 
 [6] 1, 227 ; MarkownikofE, Z. [2] 2, 502. 
 
 Oxidation of amylenes, — Examined by Zeid- 
 
AMYL-GLTOXALINE. 
 
 Sll 
 
 ler,4. 186, 245; 197, 253; Truohot, O. B. 63, 
 274 ; Berthelot, C. E. 64, 36. 
 
 Di-amyleae C^H^.. (156°). S.G. w '780. 
 Eqo 76-58 (Nasini a. Bernheimer, O. 15, 93). 
 B.V. 211'18. Ooours in the product of action of 
 ZnClj, H2SO4, or PjOj, on isoamyl alcohol; and 
 is also formed by shaking amylene with H^SOj. 
 
 Beactions. — 1. Bromine forms duH^jBrj. — 
 2. Chromic acid mixture produces amethenio 
 acid C,HnOj (Schneider, A. 157, 218; Pawlow, 
 /. B. 9, 75). 
 
 Combinations. — OmHojSjCljj ; from amylene 
 and SoClj (Guthrie, G. J. 12, 112; 13, 35 ; 14, 
 128). Distilled over KOH it forms 0,„H,8S2, 
 (112°), S.Q. iS -880. ZnEt^ gives CnHs.Sj 
 (240°-250°). 
 
 Befermces.—'Balaii, A. Ch. [8] 12, 320; 
 Bauer, Bl. 1863, 332 ; 1867, 341 ; Berthelot, 0. B. 
 56, 1242 ; Walz, Z. [2] 4, 315 ; W. v. Schneider, 
 A. 157, 185 ; Wysohnegradsky, B. 8, 434 ; Lebe- 
 deff, J. B. 7, 246 ; Tugolessoff, B. 12, 1486. 
 
 Triamylene G.^B.^^. (248°). S.Gt. -81. V.D. 7-6 
 (for 7'4). Among products of action of 
 ZnCl, on isoamyl alcohol (Bauer, Site. B. 44 
 [2J 87; A. 137, 249 ; 147, 254). Forms a bro- 
 mide, OjsHjifBrj, converted by alcoholic EOH 
 into benylene, C.sHm, (223°-228°). 
 
 Tetra-amylene C^oH^o. (390°-400°). S.G. e 
 •871. Among products of action of ZnClj on 
 isoamyl alcohol (Balard ; Bauer). 
 
 AMYLENE DI-ACETIN v. t?i-OxY-PENTAME. 
 
 AMYIENE BENZOATE v. di-OxT-PENTANE. 
 
 AMYLENE BBOMIDE v. <2i-BB0M0-FB0PANE. 
 
 AMYLENE TEI-CABBOXYLIC ACID 
 CbH,„0, i.e. CB4CE..CB^.C(C0^\.CH^.C0^. 
 
 Ether.— Kt^k!". [151°]. Obtained by intro- 
 ducing aUyl into ethane tri-carboxyUc acid 
 (Hjelt, B. 16, 388). At 160° it splits up into 
 CO2 and aUyl-succinic acid (q. v.). 
 
 AMYLENE CHLOEHYDEIN v. Chloko- 
 
 AMYL AliCOHOIi. 
 
 AMYLENE CHLOEIDE v. tZi-CHLOno-PENTANE. 
 AMYLENE ■ CHLOBO - SULPHIDE v. di- 
 Amtlene, Combinations. 
 
 AMYLENE IS-ETHIONIO ACID v. Ox:- 
 
 PENTAKE SULFHONIC ACID. 
 
 AMYLENE GLYCOL v. dj-OxY-PBNTANE. 
 
 AMYLENE GTTANAMINE CsH.sN^. [178°]. 
 Formed by heating guanidine caproate (hexoate) 
 at 225° (Bandiowski, B. 9, 243). Crystals ; v. si. 
 Bol. water, v. sol. alcohol. Salt. — B'HCl. 
 
 AMYLENE HYDEATE. Tertiary Amtl 
 ALCOHOL (q. v.). 
 
 AMYLENE HYDEIDE. Pentane (g;. v.). 
 
 AMYLENE HYDEOCHLOEIDE. Amyl 
 
 OHLOBIDE {q. v.), 
 
 AMYLENE NITEITE C^Ki^Nfi, i.e. 
 C5Hi„(NO,)2. From amylene by treatment with 
 NO2 or fuming HNO3 (Guthrie, O. J. 13, 45, 129). 
 Tables ; decomposed at 95°. 
 
 AMYLENE OXIDE C^HioO. 
 
 Isopropyl-ethylene oxide Pr.CH^ | 
 
 (82°). By action of potash on chloro-amyl alco- 
 hol, ?r.CHCl.CHjOH or ¥rCH(OH).CH,Cl 
 (Eltekoff, Bl. [2] 40, 23 ; J. B. 14, 355). Heated 
 with water for 50 hours at 100° it forms 
 Pr.CH(0H).CH20H. Does not combine with 
 NaHSO- 
 
 Trl-methyl-ethylene oxide Me,C<^ I 
 (76°). S.G. 2-829. \OHMe 
 
 Preparation.— By action of potash on the 
 chloro-amyl alcohol obtained by the union of 
 Me^CiOHMe with HCIO (E.). 
 
 Properties. — Liquid ; readily unites with 
 cold water to form di-oxy-pentane. Does not 
 combine with NaHSOj. 
 
 Methyl-ethyl-ethylene oxide MeOH^ | 
 
 \CHEt 
 (80°). Prepared by action of potash on the 
 chloro-amyl alcohol resulting from union of 
 Me.CH:CHEt with HCIO (E.). Unites at 100° 
 with water forming MeCH(OH).CHEt(OH). 
 
 Di-amylene oxide C,„H2„0. (170°- 180°). From 
 di-acetyl-di-oXY-DECANE (q. v.) (di-amylene di. 
 acetin) and solid KOH (Bauer, Sitz. B. 45, 276) 
 Oil. Beduoes ammoniacal AgNOj. 
 
 Di-amylene oxide (198°-203°). V.D. 5-3 
 (for 5-4). Obtained as an oil by the action of 
 potash on a mixture of amylene and BZjOj that 
 has been heated at 110° (Lippmann, M. 5, 562). 
 Does not reduce ammoniacal AgNO, or combine 
 with NaHSOj. 
 
 Di-amylene oxide (180°-190°). From di- 
 amylene and chromic mixture (Schneider, A. 
 157, 221). Eeduces ammoniacal AgNOj. Oxi- 
 dised to amethenic acid, C.'H.ffl^. 
 
 Di-amylene oxide (193°). From di-amyleno 
 bromide (v. di-BBOMO-DECAUE), water, and PbO 
 (Eltekoff, J. 1878, 374). 
 
 Two or more of the preceding di-amylene 
 oxides may be identical. 
 
 AMYLENE SULPHIDE CsH^S. (c. 200°). 
 S.G. la .907. Formed by boiling GuU^Sfii^ 
 {v. Diamylenb) with zino (Guthrie, O. /. 14, 
 128). Colourless oil. 
 
 Amylene sulphide (?) C^HioS. (130°-150°). 
 V.D. 3-2 (calc. 3-5). Formed by action of acids 
 or of heat upon the product of the union of 
 ZnEt^ and CS^ (Grabowsky, A. 138, 165). Alco- 
 holic HgClj forms plates of CsHijSHgSHgClj; 
 alcoholic AgNOa forms OsHioOAgjOAgNOj. 
 
 AMYL ENNONYL KETONE (?) C,.K„0 i.e. 
 Et2CH.CO.CsH,(OjH,)3 (?). (280°-300°). One 
 of the products got by passing CO over a 
 mixture of NaOEt and NaOAo at 250° (Geuther 
 a. PrbhKch, A. 202, 312). 
 
 AMYL ENNYL KETONE OnHj,0 i.e. 
 C4H5.CO.C,H,5 (?). Amyl - valerme. (209°). 
 S.G.— -845. One of the products of the passage 
 of CO over sodium iso-amylate at 100° (Geuther 
 a. Frbhlich, A. 202,301). Liquid; smells like 
 quinces. Does not combine with NaHSOj. 
 
 AMYL ETHEE v. Amyl oxide. 
 
 AMYL FLTTOEIDE xC^HnF. (72°_92°). A 
 mixture of amyl fluoride and polymerides of 
 amylene is formed by saturating amylene at 0° 
 with HF (S. Young, G. J. 39, 489). 
 
 AMYL-GLYOXALINE CsH,jN, i.e. 
 
 CH-^pCTjT^C.CsHi, (?). Glyoxal-cenanthyline. 
 
 [84°]. From cenanthol-ammonia and glyoxal 
 (Eadziszewski, B. 16, 748). Thin glistening 
 needles. Sol. alcohol, b1. boI. ether, insoL 
 water. 
 
813 
 
 AMYL^LYOXALINE. 
 
 Jso-amyl-glyozaline CgE^^^^i, i.e. 
 
 CH<^p^»^'^^CH (?). (240°-245°). 
 
 B.G. — "94. J'rom glyoxaline and amyl bromide 
 (WaUach, A. 214, 322; B. 15, 651). Liquid; 
 V. si. sol. water, sol. even in very dilute alcohol. 
 
 Salt.— B'jHjPtClj : plates (from alcoholic 
 IICl) ; V. si. sol. cold water or cold alcohol. 
 
 Iso-AMTI. HEPTYL OXIDE C,jHs,0 i.e. 
 CsHu.O.CjHis. Amyl-cmanthyl ether. (221°). 
 S.G. ^ -668. V.D. 6-57 (calc. 6-45). From 
 sodium heptylate and isoamyl iodide (Wills, 
 0. J. 6, 316). 
 
 (Py. 2:3)-AMYL-HEXYL-ftUIN0LINE 
 .CH:C(C5H„) 
 Cj„Hj.N i.e. CaH,< I . (320°-360°). 
 
 \N : C(C,H,J 
 Oily fluid. Formed by the action of oenanthic 
 aldehyde and ECl upon aniline (Doebner a. 
 MiUer, B. 17, 1719). 
 
 Salts.— B'jHjOljPtCl,: large yellow plates. 
 — B'CsH2(N02)30H : yeUow needles ; si. sol. 
 water and cold alcohol. 
 
 AMYL HYDRIDE v. Pentake. 
 
 Iso-AMYL-HYDEO-ANTHRANOL OisHj^O or 
 
 C.H,^gg '^"HO^)> C„H,. [74°]. Formed, as 
 
 a by-product in the treatment of anthraqui- 
 noue with zinc-dust and amyl bromide (Lieber- 
 mann a. Tobias, B. 14, 801; A. 212, 102). 
 Crystalline solid. Insoluble in water, extremely 
 soluble in other solvents. On boiling with 
 alcoholic HCl it gives amyl-anthracene. 
 
 Iso- AMYL -HYDEOQTJINONE. From iso- 
 amyl-arbutin and dilute HjSOj, glucose being 
 also formed (Sohiff a. Pellizzari, A. 221, 365). 
 Needles. Gives a crystalline nitro-derivative. 
 
 AMYLIDENE - ACEIO - ACETIC EIHEB 
 V. p. 24. 
 
 Iso-AMYLIDENE-TO-AMIDO-BENZOICACID 
 C„H,5N02i.e. C4H3.CH:N.C5H,.C02H. [c. 130°]. 
 From valeric aldehyde and w-amido-benzoio 
 acid (Schiff, A. 210, 119). 
 
 AMYLIDENE ANILINE C„H,5N i.e. 
 Me20H.CH2.0H:NPh. [97°]. From valeric 
 aldehyde and aniline in the cold (Lippmann 
 a. Strecker, B. 12, 74). Prisms. — B'HCl. — 
 B'jHjPtClj. Valeric aldehyde and aniline at 
 100° form di-amylidene-di-phenyl-diamine, a 
 neutral oil, Cj^Hs^N^ (Sohiff, B. 12, 298). 
 
 AMYLIDENE BIURET CjH.jNsOj. From 
 valeric aldehyde and cyanic acid (Baeyer, A, 
 114, 164). 
 
 AMYLIDENE BROMIDE v. di-BBOMO-PBNT- 
 
 ANE. 
 
 AMYLIDENE-DI-CARBAMIC ETHER 
 
 C„HjjNjO, i.e. Me,CH.0H2.CH(NH.C02Et)2. 
 Amylidene urefhane, [126°]. From carbamic 
 ether, valeric aldehyde, and cone. HCl (Bischoff, 
 B. 7, 683). Needles. Split up by hot dilute 
 acids into valeric aldehyde and carbamic ether. 
 AMYLIDENE CHLORIDE v. di-CHLOBo- 
 
 fENIANE. 
 
 AMYLIDENE GLYCOL v. ortho-ytJMmo ai.- 
 
 DEH1DE. 
 
 AMYL IODIDES CsH,,:. Mol. w. 198. 
 
 TO-Amyl iodide CE^.CS^.CB.^.GK^GRJ.. 
 (156° cor.) S.G. 2 1-544 ; 22 1-517. From the 
 chloride and HI (Lieben a. Eossi, A. 159, 74). 
 
 Iso-amyl iodide. (148°). S.G. « 1-510; 
 |S 1-498. M.M. 13-20 at 19-6° (Perkin, 0. /. 45, 
 
 462). S.V. 161-08 (E.Schiff,B. 19, 564|. From 
 isoamyl alcohol (4 pts.), iodine (5 pts.), and P 
 (Cahours, A. Ch. [2] 70, 81 ; Grimm, J. pr. 62, 
 385). From amyl-ohloride and Calj3jaq at 
 100° (VanEomburgh, B. 1, 151). Partially con- 
 verted by heating with BtOH into EtI and 
 isoamyl alcohol (Friedel a. Crafts, A. 130, 198). 
 Active amyl iodide EtCHMe.CHjI. (144°- 
 145°). S.G. U 1-5425 (Just, A. 220, 152). 
 0= 3-76° for 100 mm. at 16° (J.) ; 6-2° (Le Bel, Bl. 
 [2] 25, 542). From the alcohol by HI. Eeduced 
 in alcoholic solution by Sn and cone. HCl. to 
 inactive isopentane (J.) 
 
 u-n-Sec-amyl iodide CHj.CHj.CH^.CHI.CHj. 
 (144°-145°). S.G. a 1-539. Formed by union 
 of HI with CH3.CH2.CH2CH:CH2 (Wagner a. 
 SaytzeS, ^. 179, 313; Wyschnegradsky, ^. 190, 
 347) or CHj.CH2.CH:CH.CH3 (Wurtz, A. 148, 
 132). 
 
 2so-sec-amyl iodide (CH,)2CH.CHI.CH,. 
 (137°-139°). From (CH,)20H.CH:CH2 and HI 
 (Wy.). Water and PbO convert it into 
 (CH3)2C(OH).CHj.CH,. 
 
 s-n-8ec-a,mjl iodide CH,.CH2.CHI.CH2.CH3. 
 (145°-146°). S.G. 2 1-528 ; ^ 1-50. From di- 
 ethyl-carbinol and HI (W. a. S.). 
 
 rerf-amyl iodide (0H3)j.CI.CH3.CH3. (129°). 
 S.G. 2 1-524 ; 12 1-50. From iso-sec-amyl iodide 
 and HI (Winogradoff, A. 191, 132) ; also from 
 tert-axajl alcohol and HI (Wy.). By shaking 
 with water for IJ hours it is almost completely 
 converted into ieri-amyl alcohol (Bauer, A. 
 220, 158). With MeOH at 100° it forms Mel 
 and tert-axajl alcohol; MeOAo at 110° gives 
 amylene, Mel, and HOAo. 
 
 DI-TC-AMYL KETONE OnHj^O i.e. (C5H„)2C0. 
 Caprone. [15°]. (226° cor.). S.G. 22 -826. Pre- 
 pared by distilling calcic caproate. Does not 
 combine with NaHS03. 
 
 Reactions. — 1. Cone. HNO, forms caproio 
 nitro-valeric, and oxalic acids. — 2. CrOj forms 
 caproic and valeric acids (E. Schmidt, B. 5, 601 ; 
 Lieben a. Janecek, A. 187, 134 ; Hercz, A. 186, 
 263). 
 
 n - AMYL - MALONIC ACID CsHi.O, i.e. 
 {C5H„)CH(C02H)2. [82°]. Formed by saponify- 
 ing the product of the action of KCy upon 
 o-bromo-heptoic ether (Hell a. Schiile, B. 18, 
 626). Split up at 140° into CO^ and n-hexoic acid. 
 
 Salts.— CaA": S. -04 at 18°.— SrA": S. -09 
 at 16°.— BaA" : S. -6 at 10°.— CdA".— PbA" : 
 S. -008 at 20°.— AgjA". 
 
 TRI-Iso-AMYL-MELAMINE C^HseNj i.e. 
 C3H3 (C5H„)3N3. Formed by desulphuration of' 
 isoamyl thiocarbimide (Hofmann, B. 3, 264). 
 Thick oil.— B"H2PtCl3. 
 
 Zso-AMYL MEECAPTAN CsH^S i.e. 
 CjHiiSH. Mol. w. 104. (120° i.V.) (Beckmann) ; 
 (118°) (Nasini, Q. 1883, 302). S.G. f -8348. 
 Eoo 31-94 (N.). From isoamyl chloride and EHS 
 (Balard, A. 52, 313) or C,H,iSO,K (Krutzsoh, 
 /.^. 31, 1). 
 
 AMYL MUSTARD OIL v. Amtl ihio- 
 
 (o) -Iso-amyl -naphthalene C,„H,.C5H„ [1J» 
 Formed by heating an ethereal solution of (o)- 
 bromo-naphthalene and isoamyl bromide with 
 Na (Leone, G. 12, 209).— Picrate, [85°-90°]i 
 pale yellow needles. 
 
AMTL SULPHATEa 
 
 213 
 
 (/3) • iM-amyl - naphthalene 0„H,.C,H„ [3]. 
 (e. 290°). From naphthalene, isoamyl chloride, 
 and AlCl, (Boux, Bl. [2] 41, 379).— Piorate 
 C,.H„C,H,(NO,),OH. [lOS^-llO"]. 
 
 AJmyl-naphthalene (?). (305°). From lapaohio 
 acid, HI and P (Paterno, ff. 12, 36Q).—Fierate 
 £141°] : orange needles. 
 
 Iso-AMYL NITRATE CsHi.NO,. Mol. w. 133. 
 <147°). S.V. 153-59 (R. Sohifl, B. 19, 567). 
 From urea nitrate (10 g.), isoamyl alcohol (40 g.) 
 and HNOj (30 g.) (P. W. Hofmann, A. Ch. [3] 
 23, 374). Liquid, smelling like bugs. 
 
 Jso-AMYl NITRITE OjH.iNOj. Mol. w. 117. 
 <96°) (B.). (99°) (Guthrie, A. Ill, 82). S.G. -9. 
 H.F.p. 48,140. H.F.V. 44,660 (Th.). 
 
 Preparation. — 1. Nitrous vapours (from 
 ABjO, and HNO, of S.G. 1*52) are passed into 
 isoamyl alcohol (Balard, A. Ch. [3] 12, 318; 
 Hilger, Ar. Ph. [3] 4, 485 ; Williams a. Smith, 
 Ph. [3] 16, 409). — 2. By distilling together 
 KNO„ isoamyl alcohol, and dUute HjSO^ 
 {Bennard, Buss. Zeitschr. Pharm. 1874, 1). 
 Yellowish liquid, smelling like nitrous ether. 
 
 AUYLNITBOTJS ACID, so-called. Cja^^Nfit. 
 Obtained by action of HKO, on di-amyl ketone 
 (Chancel, C. B. 94, 399). Liquid; may be 
 reduced to n-valeric acid. 
 
 Salt. — CsHgKNjOj: greasy-looking plates. 
 
 AUYLODEXTBIN v. Dbxtbin. 
 
 AMYLOID V. SiABOH. 
 
 AUYLONITBOFHOSFHOBOUS ACID, so- 
 called. CijHjjPNOi (?). An oil, got by action of 
 P2O5 on isoamyl nitrite (Guthrie, A. Ill, 85). 
 
 AMYL OXALATE v. OxAuto acid. 
 
 Zso-AMYL OXAMIDE CH^NA i.e. 
 NH2.CO.CO.NHC5H,,. [181°]. From isobutyl- 
 isoamyl glyoxahne and HjOj (Badziszewsky a. 
 Szul, B. 17, 1296). 
 
 Di-iso-amyl oxamide C^2H^^^fi, ix. 
 0sH„.NH.C0.C0.NHC5H„. [129°] (WaUacha. 
 Sohulze, B. 13, 616). [139°] (Wurtz). Silky 
 needles ; insol. water. From isoamylamine and 
 ethyl oxalate. 
 
 AMYL-OXANTHEANOL v. Oxantheanol. 
 
 AMYL OXIDE CioHjjO. Amylether. M.w.158. 
 
 Jso-amyl oxide (CsH„)jO. (173°). S.G. Jf 
 •7807 ; H -7741. M.M. 11-168 at 15-6° (Perkin, 
 C. /. 45, 474). From potassium isoamylate and 
 amyl iodide. 
 
 iso-sac-amyl oxide (Pr.CMeH).^. (163°). 
 From Pr.CMeHI and Ag^O (Wurtz, A. 129, 366). 
 
 Jso-AMYL-PHENOL C„H,sO i.e. 
 05H„.C,H,.OHi:i:4]. [93°]. (250°). Formed by 
 heating phenol with isoamyl alcohol and ZnClj 
 at 180° (Liebmann, B. 15, 151) or by the action 
 of nitrous acid upon amido-phenyl-isopentane 
 (Calm.B. 15, 1646). Long needles ; si. sol. water. 
 
 Benzoyl derivative C,jH,50Bz. [81°]. 
 (349° cor.). Flat needles, formed by distilling 
 tri-isoamyl phosphate with NaOBz (Kreysler, B. 
 18, 1717). 
 
 AMYL-PHENYL- v. Phenyi-amyl-. 
 
 Iso-AMYL-PHENYL PHOSPHATE 
 C„H„P04 i.e. (C,H„.C,H,.0),PO. (above 400°). 
 Formed by heating isoamyl-phenol with POCI3 
 (Kreysler, B. 18, 1701). Thick oil ; v. sol. ether, 
 sol. alcohol. 
 
 Jso-AMYL-PHENYL SILICATE 0„H5„SiO, 
 i.e. (0;B.n.C^^i-0)t^i. (0. 394°) at 118 mm. 
 From isoamyl-phenol and SiOl^ (Hertkorn, B. 
 18, 1&93). 
 
 AMYL PHOSPHATES. 
 
 Jso-amyl-phosphorio aoii ^OjH,,0).PO(OH), 
 From syrupy phosphoric acid and amyl alcohol 
 at ordinary temperature (Guthrie, O. J. 9, 134). 
 Deliquescent crystalline mass ; v. sol. water, 
 and alcohol, insol. ether. Salts. — K^A". — 
 (NH,)jA.".— BaA".— PbA".— CuA".— AgjA". 
 
 Di-iso-amyl-phosphorlc acid 
 (OiH„0)jPO(OH). From amyl alcohol and 
 bromide of phosphorus (Kraut, A. 118, 102). 
 Salts.-CaA'j: S. 1-6 at 18°.— AgA'.— AgHA',. 
 
 AMYL-PHOSPHINES v. Phosfhines (Hof- 
 mann, B. 6, 297). 
 
 Zso-amyl phosphine OsHnPHj. (107°). 
 
 Di-iso-amyl phosphine (OsHiJ^PH. (0. 213°). 
 
 Tri-iso-amyl phosphine (C5H„),P. (300°). 
 
 Oxide (CsHnJsPO. [c. 65°]. 
 
 Iso-amylo-iodide (CsH,,)^?!. 
 
 Zso-AMYL PHOSPHINIC ACID C^HiaPO, 
 i.e. 05H„.P0(0H)j. Pentane phosphinic acid. 
 [160°]. From isoamyl phosphine and HNO, 
 (S.G. 1-35). Pearly plates (from water). 
 
 Salt. — AgjA": amorphous pp. (Hofmann, 
 B. 6, 305). 
 
 AMYL PHOSPHITES. 
 
 iso-amyl phosphorous acid (OjH„0)P(OH),: 
 Formed together with di-isoamyl-phosphoroua 
 acid by shaking with water the product of the 
 action of PCI3 on isoamyl alcohol. Dilute 
 Na^CO, dissolves mono- but not di-, amyl 
 phosphite (Wurtz, A. Ch. [3] 16, 227). 
 
 Chloride Ci^Hi.O.POl^. (173°). S.G. 2 1-109 
 (Menschutkin, A. 139, 348). 
 
 Di-iso-amyl-phosphorouB acid 
 (CjH„0)jP(OH). S.G. i2 .97. 
 
 Tri-iso-amyl phosphite (CsH„0)3P. (236°), in 
 hydrogen. From PCI3 and NaOCsHi, (William- 
 son a. Eailton, O. J. 7, 218). 
 
 AMYL-PIPEBIDINE C,„H3,N i.e. 
 C5H,„N(C5H„). (188°). Colourless liquid, nearly 
 insoluble in water. Formed by digesting piperi- 
 dine with amyl bromide and aqueous EOH. 
 
 Methylo-iodide. B'Mel. [195°]. Thick 
 prisms. By moist Ag^O it gives an alkaline 
 hydrate which on dry-distillation yields methyl- 
 amyl-piperidine (Sehotten, B. 15, 421). 
 
 Jso-AMYL-PYEEOL CjH.jN i.e. C,H„NC,H, 
 (0.182°). S.G. i2-879. Formed by distilling iso- 
 amylamine mucate (C. A. Bell, B. 10, 1866). 
 
 Jso-amyl-pyrrol carboxylic acid, isoamyl- 
 amide OsHn.NCiHj.CO.NHCjH,,. [77°]. Prisms. 
 Formed along with the isoamyl-pyrrol (B.). 
 
 Iso-AMYL SILICATE C2„H„SiO< i.e. 
 Si(C3H„0),. (324°). S.G. 22 -868. V.D. 15-2 
 (calo. 13-0). Prom SiCl, and isoamyl alcohol 
 (Bbelmen, A. 57, 331). Oil, very slowly decom- 
 posed by water. 
 
 AMYL SULPHATES. 
 
 Iso-amyl sulphuric acid CsHj^SO, i.e. 
 CsH.iSOjH (Cahours, A. Ch. [2] 70, 8C; 
 KekuM, A. 75, 275). 
 
 Salts. — NH^A'.— NaA'liaq. — KA' faq.— 
 MgA'j 4aq.— CaA'22aq.— SrA'j2aq. — BaA'j 2aq: 
 flat tables, S. 9-7 at 10° (Balbiano, B. 9, 1437); 
 S.G. 1-623 at 21-2° (Clarke, B. 11, 1506).— 
 ZnA'j2aq.— HgA'j2aq.— PbA'jaq.— MnA'j4aq.— 
 NiA'j 2aq.— CuA'2 4aq.— AgA'. 
 
 Zso-amyl sulphate (CjHjOjSO,. Formed by 
 passing SO, into warm amyl nitrite (Chapman, 
 B. 3, 920). 
 
214 
 
 AMYL SULPHIDES. 
 
 AMYL SULPHIDES. 
 
 Di-iso-amyl-Bulphide (C5H„)2S. Mol.w. 174. 
 (214° i.V.). S.G. «> -8431. E oo 54-2 (Nasini, 
 G. 13, 302). Amyl alcohol (131°-132°) is con- 
 verted by PCI5 into amyl chloride and this is 
 mixed with alcoholic KjS (from hali saturation 
 of alcoholic KOH with H^S) and heated in 
 closed vessels for 10 hours at 100°. Product 
 fractionated (Beckmann, J. pr. [2] 17, 440). Also 
 from potassium amyl-sulphate and K^S (Balard, 
 A. Ch. [3] 12, 303). 
 
 Dl-iso-amyl disulphide (CsHiO^S^. (250°). 
 S.Gr. — '918. Prom potassium amyl-sulphate and 
 KjSj (0. Henry, A. Oh. [3] 25, 246 ; Spring a. 
 Legros, B. 15, 1938). 
 
 Jso-AMYL SULPHITE {G,'B.,fi)SO. (230°- 
 250°). From SOCl^ or SjClj and isoamyl alcohol 
 (Carius, A. 106, 291; 111, 97). Oil; decom- 
 posed by water or KOHAq into amyl-sulphurous 
 acid and amyl alcohol. 
 
 AMYL SULPHOCYANIDE C„H„NS i.e. 
 C,H„S.CN. (197°). S.G. ^ -905. Got by 
 distilling potassium amyl-sulphate with potas- 
 sium sulphooyanide (Henry, A. Ch. [3] 25, 248 ; 
 Medlook, A. 69, 214). 
 
 Di-iso-AMYL SULPHONE (C,H„),S02. 
 [31°]. (295°). Di-iso-amyl sulphoxide (5 pts.) is 
 heated with water (20 pts.) till it melts, a solu- 
 tion of EMnOj (3 pts.) in hot water (30 pts.) is 
 added with constant agitation. The sulphone 
 is extracted with ether. The yield is that indi- 
 cated by theory (Beckmann, J. pr. [2] 17, 441). 
 
 Properties. — Long needles, grouped in tufts. 
 SI. sol. hot water ; sol. alcohol, ether, benzene, 
 CHOlj and CSj,. Soluble in H^SO^, HNO3 and 
 acetic acid, but precipitated by water from these 
 solutions. Not reduced by Zn and H2SOJ, by 
 sodium-amalgam or by HI. 
 
 AMYL-SULPHONIC ACID v. Pentane 
 
 BITLPHONIC ACID. 
 
 DI-iso-AMYL-SULPHOXIDE (C5H„)2SO. 
 [37°]. From di-amyl sulphide (1 pt.) and 
 fuming HNO3 (2 pts.). Crystallised from ether 
 (Saytzeff, A. 139, 354 ; Beckmann, J. pr. [2] 
 17, 4'41). Flexible fatty-looking crystals. 
 Chlorine acts on it in presence of water forming 
 pentane sulphonio acid, chloro-pentane sulphonio 
 acid, di-isoamyl sulphone, valeric acid, chloro- 
 valeric acid, tri- and tetra-chloro-pentanes, &c. 
 (Spring a. Winssinger, Bl. [2] 41, 807). 
 
 AMYL - SULPHUEIC ACID v. Amyl 
 
 SuiiFHATE. 
 
 Jso-AMKL TELLUEIDE Te(C,H„)5,. (c.l98°). 
 Got, in impure state, by distilling calcium 
 amyl sulphate with TeK^ (Wohler a. Dean, A- 
 97, 1). 
 
 Iso - AMYL - DI - THIO - CAEBAMIC ACID 
 CgHijNSji.e. CjHuNH.CS.SH. Isoamylamine 
 salt CjHiiNHjHA'. From isoamylamine and 
 CS2 in ethereal solution (Hofmann, /. 1859, 
 379). Laminae. 
 
 AMYL THIOCAEBIMIDES C„H„NS i.e. 
 CjH.iN.CS. Amyl mustard oils. Mol. w. 129. 
 
 Iso-amyl-thio-earbimide (183°). S.G. U -942. 
 Obtained by boiling the preceding compound wiih 
 aqueous HgClj (Hofmann, B. 1, 173 ; Buff, B. 
 1, 206). 
 
 Tert-amyl thio-carbimide EtCMe2N.CS. 
 (106°). From EtOMe2NH2by successive treatment 
 with CSj and HgCl^ (Eudneff, Bl. [2] 33, 300). 
 
 AMYL THIO-PHOSPHATES. 
 
 Iso-amyl thio-phosphate (CjH„)H2PS0j. 
 From isoamyl alcohol and PSCI3 (Chevrier, Z, 
 1869, 413). 
 
 Tri-iso-amyl thiophosphate (CjHuJjPSOs. 
 S.G.ia -85. From CsHi.ONaand PSCI3 (C). Oil. 
 
 Di-iso-amyl di-thio-phosphate 
 (OsHiJ^HPS^O^. Salt.— PbA'2 [70°]. 
 
 Tri - iso - amyl - tetra - thio - phosphate 
 (C3Hi,)3PS4. Formed, together with the pre- 
 ceding, when P2S5 acts on isoamyl alcohol (Kowa- 
 lewsky, A. 119, 310). 
 
 Jso-AMYL THIOSULPHATE. The salt 
 Na(C5H,i)S2032aq is formed by acting with 
 isoamyl iodide on sodium thiosulphate. It 
 crystallises in laminse (Spring a. Legros, B, 15, 
 1938). 
 
 Iso-AMYL THIO-UEEA C^Hi^N^S i.e. 
 C5H|,NH.CS.NH2. Monoclinic crystals (Arzruni, 
 P. 152, 284). 
 
 AMYL-TOLUENE O.^.^i.e. CHj.C.Hi.C^H,,. 
 
 Methyl-amyl-hamene 
 
 o-Iso-amyl-toluene (?). (204°). S.G. 2 -895. 
 From toluene, isoamyl chloride, and zinc dust 
 (Pabst, B. 9, 503). 
 
 m-Iso-amyl-toluene. (208°). S.G. ^ -868. 
 From toluene, isoamyl chloride, and AlClj 
 (Essner a. Gossin, Bl. [2] 42, 213). EMnOi gives 
 isophthalic acid. 
 
 ^-Iso-amyl-toluene. (213°). S.G. 2 -864. 
 From ^-bromo-toluene, isoamyl bromide, and 
 Na (Bigot a. Fittig, A. 141, 160). CrOj produces 
 terephthalie acid. 
 
 AMYLUM V. Stabch. 
 
 AMYL-UEEAC^H^NjO i.e. CsHnNH.CO.NH^. 
 
 Iso-amyl-urea [91°]. From amyl eyanate 
 and hot alcoholic NH3 (Custer, B. 12, 1330; 
 cf. Wurtz, C. E. 32, 417 ; -BL [2] 7, 141). Crystals ; 
 si. sol. water. 
 
 Is o-Hexoyl -derivative 
 C5H„NH.C0.NH.C0.CjH„. [94°]. From the 
 amide of isohexoio acid, Pr.CH2.CH2.CO2H, by 
 means of Br and NaOH (Hofmann, B. 15, 758). 
 
 Tert-amyl-nrea. [151°]. S. 1-26 at 27°. 
 From tert-amyl cyauate and NHj (Wurtz, A. 139, 
 328). 
 
 n-Hexoyl derivative. [97°]. Formed by 
 action of potash on a mixture of w-hexamide 
 and bromine (H.). Plates ; sol. alcohol, and 
 ether, insol. water. 
 
 Di - iso - amyl - urea CsHnNH.CO.NHCsH,,. 
 [39°]. (270°). Formed by boiling isoamyl 
 cyauate with isoamylamine and alcohol (C). 
 Needles ; insol. water, sol. alcohol and ether. 
 
 Di-ieri-amyl-urea. Formed by action of 
 KOH upon tert-amyl eyanate (W.). Needles; 
 may be sublimed. 
 
 Tri -iso -amyl -urea (CsHnyjN.CO.NH.OsHj,. 
 (260°). From isoamyl eyanate and di-isoamyl- 
 amine (C). Liquid. 
 
 Tetra-iso-amyl-urea (C5H„)2N.CO.N(C5H„)2, 
 (241°). Obtained by the action of Cl.COjEt 
 upon a mixture of di- and tri- isoamylamine (C.). 
 
 AMYL UEETHANE v. Amti.-baebamio etheb. 
 
 AMYL-VALEEONE v. Butyl ennyl ketone. 
 
 Iso-AMYL-XYLENE CisHj, i.e. 
 CjHsMej.CsH,,. Di - methyl - isoamyl - hemeiie. 
 (233°). S.G. a -895. From bromo-xylene, iso- 
 amyl bromide and Na (Fittig a. Bigot, A, 141, 
 168). 
 
ANALYSIS. 
 
 2lii 
 
 AMYRUT. A orystalline resin, diffioultly 
 soluble in alcohol, contained in some specimens 
 of elemi, and in arbol-a-brea resin (Buri, 
 Neues Bepert. fUr Pliarm. 25, 193 ; Hesse, A. 
 192, 179). According to Hesse its formula 
 is Cj,H,8(OH)2 and its acetyl derivative is 
 C„'B.^JiOk.c)i. Bromine forms a complicated 
 bromo-derivative. 
 
 ANACAEDIC ACID O^B.,fi^. [26°]. Occurs 
 in the fruit of Anacardium occidentale (Staede- 
 ler, A. 63, 137). Crystals ; insol. water, v. sol. 
 alcohol and ether. Salts. — CaA"aq[. — BaA". — 
 PbA".-HA"PbOAo.— A'TeOHaq.— AgHA". 
 
 ANALYSIS. To analyse a thing means to 
 resolve it (avahveiv) into its components. This 
 term, however, has a very wide meaning, which 
 Btretches far beyond the outermost limits of our 
 resources of even virtual analysis. So well is 
 this understood by all that even when we speak 
 of a complete analysis we refer only to as com- 
 plete a solution as the science affords of one or 
 other of three special problems. One of these 
 is the actual or virtual resolution of the body 
 into its component chemical species or perhaps 
 genera ; another, the determination of its ele- 
 ments ; the third, the determination of what, in 
 the sense of some imagined general mode of 
 decomposition, are its primary radicles. This 
 (the last named) problem has received a partial 
 solution in the sense that we have ready-made 
 methods for the determination of the acids and 
 bases that may be contained in a solution of 
 salts of a certain low order of complexity. These 
 methods include only a minority of the non- 
 metallic salt radicles, but they include all the 
 better-known elements as such ; and as we 
 have general methods for converting any kind 
 of substance into salts of low order of com- 
 plexity, these latter methods, conjointly with the 
 former, constitute a complete solution of the 
 ^vohlemotuUimatemmlysis. In regard to the first 
 problem, our powers are very limited. That we 
 have methods for the proximate analysis of cer- 
 tain classes of substances need not be specially 
 affirmed ; without these, vegetable and animal 
 chemistry could have no existence — but a general 
 exposition of their principles would resolve itself 
 into the retailing of commonplaces. We prefer 
 to give a brief summary of what we have of 
 means and ways for seeing whether a substance 
 presumed to be pure really is one substance or is 
 a mixture. In a sense there is only one method : 
 we subject the substance to some physical or 
 chemical process of fractionation, which, while 
 sure not to produce transmutations, gives the 
 several proximate components a chance of part- 
 ing from one another ; and we then compare the 
 several products with one another and with the 
 original substance. The form which the 
 method assumes depends largely on the state of 
 aggregation of the substance under operation. 
 
 I. Gases. The oneness of a gas can in 
 general be proved by {a) fractional dtfftision 
 through a septum of gypsum or graphite ; if 
 the gas is a mixture of, say, two species, the 
 lighter one diffuses out faster than the other ; 
 with mixtures of gases of the same specific 
 gravity, the method, of course, breaks down: 
 (6) partial absorption. This method is dis- 
 cussed fully under ' gas-analysis ' (j. ».). 
 
 II. Solids. These may be susceptible at 
 fractionation by (a) partial fusion ; (6) pa/rtial 
 solution in suitable solvents ; (c) partial freezing 
 of the liquefied body ; (d) pa/rtial crystallisation 
 out of solutions ; (e) partial volatilisation. 
 (See III.) For the comparison of the several 
 fractions, the determination of the fusing points 
 comes in as a handy, and in general sensitive, 
 test. 
 
 III. Liquids. For these the methods given 
 under (6) and (c) for solids may be available. In 
 the case of distillable liquids we generally resort 
 to fractional distillation, taking care to observe 
 the temperature of the (saturated) vapour, during 
 the progress of the operation. A mixture may 
 have a constant boiling-point, and may besides 
 remain undecomposed on distillation ; as a rule, 
 however, it is not so. The volatility of each 
 component depends chiefly on the value for it of 
 the product mp, where m is the molecular weight 
 (or vapour density), and p the vapour-pressure 
 at the prevailing temperature of ebullition. For 
 two components, the respective products m^p, 
 and m^pj have in general different values. 
 Hence it is not necessarily the lowest boiling 
 component which comes over first ; because a 
 large m may make up for a small p. As a mere 
 test for purity, the determination (at a series of 
 suitable temperatures) of the vapour-pressure by 
 the statical method goes considerably further 
 than the determination of the boiling-point 
 curve. In a pure substance, the pressure, p, at 
 t° is a function of t only ; in a mixture of (say) 
 two liquids, p depends (in a given trial) on the 
 volume of vapour produced, because the ratio of 
 the weight of the vapour to that of the un- 
 volatilised residue changes with this volume. If 
 this ratio is very small, we have an approxima- 
 tion to the vapour-pressure of the more volatile 
 component ; if the ratio is large, the pressure 
 approaches the value characteristic of the 
 mixture as such. Any of the many mixtures of 
 constant boiling-point, when subjected to this 
 test, at a suitable temperature, is sure to reveal 
 its complexity. Unfortunately the operations 
 involved are somewhat troublesome, and the 
 results are liable to be largely vitiated by the 
 presence of absorbed air in the sample. 
 
 The second and third of our three general 
 problems, qualitatively considered, form the body 
 of what is customarily being taught as 
 
 QuAIilTAirVB AKAIiTSIS. 
 
 The resources of qualitative analysis — apart 
 from mere methods of identification of named 
 species, which we leave on one side — may be 
 arranged under three heads : — 
 
 I. name Tests. A set of methods for the 
 detection of elements as such, which, being all 
 founded upon ultimate or penultimate dissocia- 
 tions at high temperatures, are in a high degree 
 independent of the constitution of the substance 
 operated upon. Another specific feature in these 
 tests is that they are easy and rapid of execution, 
 and demand only very small quantities of sub- 
 stance. 
 
 n. A set of what we will call methods of 
 chemical disintegration (each general in refer- 
 ence to a large class of bodies), by means of 
 which compounds of high chemical complexity 
 can be, so to say, opened up, and their elements 
 
316 
 
 ANALYSIS. 
 
 brought mtbin tlie range of our routine methods 
 of salt analysis (v. i/nfra). These methods might, 
 each, be indexed, by reference to a certain 
 element, generally of high valency ; as a rule it 
 is a uon-metallio element, and in the analyst's 
 sense, am generis, i.e. not susceptible of detection 
 as one of a group. 
 
 ni. The systematic methods for the radical 
 analysis of a solution of salts which were 
 referred to in the introduction. In addition to 
 these analytical methods, the analyst naturally 
 discounts all that may help him towards the 
 solution of his problem. Our three classes of 
 methods alone, it is true, if judiciously employed, 
 would enable one in general to perform an ex- 
 haustive ultimate analysis ; but a purely 
 ultimate analysis, in the majority of cases, is 
 not what we want. The ideal which we aim at 
 in all analyses made for practical purposes is (as 
 good an apology as is attainable for) a proximate 
 analysis ; a recipe, so to say, for composing the 
 substance from things of known constitution. 
 Hence, if the substance presents the aspect of 
 a mixture — mechanical or physical — we naturally 
 begin by trying to effect a separation of the 
 several things from one another : by mere pick- 
 ing out, or elutriation, in the case of an obvious 
 mixture ; by distillation in the case of a solution 
 in a volatile solvent. We will assume, however, 
 that this division of the given substance into 
 two or more substances has been effected (if 
 called for, and possible), and that the substance 
 to be analysed is a solid (which virtually includes 
 the case of a liquid) ; gases demand special 
 methods, which lie beyond our programme. In 
 this, as in any analogous case, we naturally begin 
 by a close observation of at least the general 
 properties of the body ; it may be expedient to 
 supplement this observation by the exact deter- 
 mination of certain physical properties, such as 
 hardness, specific gravity, crystalline form, 
 optical constants, &c., &a. Everything here 
 depends on the nature of the case, and — of the 
 operator. A mineralogist, for instance, by such 
 determinations, may be able virtually to analyse 
 a mineral ; but everybody cannot do this. After 
 the more purely observational stage, it is ex- 
 pedient to study the behaviour, at a graduated 
 succession of high temperatures, of (a) the sub- 
 stance itself, (b) the substance and atmospheric 
 oxygen, (c) the substance plus added reagents. 
 We therefore begin by heating a few centigrams 
 of substance in a sublimation tube over a Bunsen 
 lamp— first gently, then more and more strongly 
 — on the chance of obtaining a readily recognis- 
 able sublimate, gas or vapour, or residue. Of 
 the identifiable residues, charcoal is the most 
 important, because its formation proves the pre- 
 sence of organic matter in the sample, although 
 all organic matter does not yield charcoal. If 
 the substance presents a metallic, or semi- 
 metallic, aspect, it is expedient to roast a frag- 
 ment in a draught-tube, on the chance of 
 obtaining a sublimate of mercury, oxide of 
 cadmium, white arsenic, iodine, &o., or an 
 evolution of sulphurous acid, &o. If the sub- 
 stance proves partially volatile or partially 
 eombustible, we prepare a supply of the fire-proof 
 part (at the lowest sufficient temperature), and, 
 treating it from the first as we would a fiie-pioof 
 ■abstance, subject it to a selection of 
 
 I. Flame Tests. 
 
 By "flame-tests" we mean dry -way tests, in 
 which the substance, or substance plus reagents, 
 is heated directly in the flame. These tests 
 were introduced by Oahn, and subsequently ex- 
 tended and brought to high perfection chiefly by 
 Berzelius and Plattner. In accordance with the 
 modes of operating which these authorities 
 found it convenient to adopt, a blowpipe flame 
 used to be universally employed as a heating 
 medium. But Bunsen, some twenty years ago, 
 showed that most blowpipe tests can be done 
 more easily and conveniently in the flame of the 
 gas lamp which bears his name, and that this 
 flame can also be employed for certain new tests 
 introduced by him, which tests could not be 
 conveniently done with the blowpipe. Many 
 chemists prefer the Bunsenian modus operandi, 
 but the blowpipe has not by any means become 
 obsolete ; it will continue to be used, because it 
 offers certain specific advantages of its own. 
 For the purposes of this article it will be 
 sufficient to give the following enumeration of 
 the more important of the characteristic flame- 
 test operations : 
 
 (1.) A few mgms.of the substance are placed 
 on an asbestos-stick, and exposed to the several 
 regions of a Bunsen-flame, proceeding from 
 lower to higher temperatures, to determine 
 degrees of fusibility and volatility. 
 
 (2.) A few mgms., fixed to one end of a hair- 
 fine platinum wire, are exposed first to colder, 
 and then to the hottest, part of the flame-mantle 
 of a Bunsen, in order to see whether the flame 
 is thereby coloured. If a colour is produced, it 
 is analysed optically (by means of a spectro- 
 scope), with the view of thus effecting a 
 chemical analysis of the glowing vapour. Of 
 elements identifiable by their spectra (or flame 
 colours), the following may be named : — Tl, In, 
 Bb, Cs, E, Na, Li, Ba, Sr, Ca in most of the 
 ordinary states of combination, Cu as haloid 
 salts, B as boric acid or fluoride, P as free phos- 
 phoric acid or PHj. 
 
 Spectrum analysis, as everybody knows, was 
 invented by Bunsen and Kirchoff. Some years 
 ago Bunsen brought it into a new form, in which 
 a spark current, produced by means of an 
 induction-ooiL is used for the volatilisation of 
 the substance'; at the very high temperatures 
 thus produced, a great many elements, besides 
 those named, become identifiable by their 
 spectra. 
 
 Flame Tests with Beagents. — Of these 
 sodium carbonate is most extensively employed ; 
 either platinum wire or charcoal being used as 
 a support. 
 
 On platinum; (1) as a mere flux, it 
 identifies SiOj, given as such or as highly acid sili- 
 cate ; (2) in conjunction with oxygen used as 
 air, or introduced as nitre — it detects Cr and Mn 
 with certainty, converting the former into 
 (yellow) ohromate, the latter into (green) man- 
 ganate. 
 
 When used on charcoal; in the reducing 
 flame, it may bring to light, (1) S, Se, Te. Any 
 non-volatile form of these yields a fused mass, 
 containing Na^S &b., recognisable by the black 
 stain (AgjS <fco.) which it produces when placed 
 on a silver coin, and moistened with a drop of 
 
ANALYSIS. 
 
 817 
 
 water.— (2) Oth or more of the following metals; 
 As, Hg, Zn, Cd, Pb, Bi, Sn, Cu, Ag, Au, Pe, Ni, 
 Co, Ft. The oxides and many of the salts of 
 these metals when subjected to the operation 
 under discussion, are reduced to the elementary 
 state. The metal thus liberated may assume 
 the form of a visible fused bead, or remain con- 
 cealed in the form of fused scales or an unfused 
 powder or sponge ; these, however, can in all 
 cases be isolated and brought to light by elutria- 
 tion with water in an agate mortar. Part of 
 the metal, in general, volatilises, and in passing 
 tlirough the flame becomes oxide. If the re- 
 duction is effected in the blowpipe flame on 
 a block of charcoal (old style), part of the oxide 
 in general settles down on the charcoal as a 
 ring, and by its colour may aid in identifying 
 the metal. When operated upon as described, 
 compounds of As yield only vapour of oxide, 
 which in most cases is lost altogether. Hg ; 
 vapour of metal, which is also lost. Zn, Cd ; 
 little or no metal, but abundant oxide rings; 
 (ZnO is white, CdO brown). Pb, Bi; easily 
 fusible metal, and tangible quantities of yellow 
 oxide. Sn; easily fusible metal, and little 
 (white) oxide. Cu ; not easily — Ag ; more easily 
 — Au ; not easily — fusible metal or scales, and 
 no oxide. Fe, Ni, Co; unfused powdery, or 
 spongy, metal, which follows the magnet. No 
 oxide. Pt ; like Pe, but the metal is not mag- 
 netic and is unacted on by HNOjAq. 
 
 In Bunsen's mode of operating — which con- 
 sists in heating the mixture of substance and 
 soda on a slender stick of charcoal in the re- 
 ducing part of the ' zone of fusion,' the oxide is 
 lost, but all the respective metals fall within the 
 range of 
 
 Bunsen's Film Tests. — ^When the air- 
 holes of the Bunsen are partially closed, a 
 luminous tip forms somewhere near the apex of 
 the flame. Many oxides suffer reduction when 
 held la the centre of this tip on an asbestos stick ; 
 and the reduced elementary substance can be 
 collected on a Berlin basin (filled with water to 
 keep it cold), held over the sample across the 
 flame. The elements thus appear as films 
 resembling the stains of As and Sb produced in 
 Marsh's test. The following elements chiefly 
 yield films : As, Sb, Te, Se ; hardly attacked by 
 nitric acid of 20 p.c. Bi, Hg, Tl ; very slowly 
 dissolved by nitric acid of 20 p.c. Pb, Cd, Zn, 
 In ; instantly dissolved by nitric acid of 20 p.c. 
 By a very obvious modification of the process, 
 oxide films can be produced in lieu of metalUc 
 ones; but we cannot go any further into this 
 matter. 
 
 Borax is always used as a bead fused to 
 the end of a platinum wire. Such a bead dis- 
 solves most metallic oxides at a moderately high 
 temperature, forming glasses, the colours of 
 many of which are characteristic of the metal. 
 Often one metal gives two colours according to 
 whether the fusion is effected in the oxidising 
 or in the reducing flame ; this affords additional 
 means of discrimination. 
 
 Microcosmic salt (or rather the fused 
 NajCPjOj produced by its decomposition by 
 heat) acts on metalUc oxides pretty much as 
 borax does; but its specific function is the 
 detection of silica. If a splinter of a silicate is 
 heated in a fused meta-phosph.ite bead, the 
 
 bases dissolve out, the silica remains in the 
 characteristic form of an unfused ' skeleton ' of 
 the splinter. 
 
 Whatever the flame-tests may have brought 
 out by way of positive results, their negative 
 results count for very little. 
 
 II. Methods of Chemical Disintegration. 
 
 Substances may be divided into two classes, 
 as regards the operations required to bring them 
 within the range of our systematic methods of 
 salt-analysis. _ (1) Such as are simple salts (we 
 mean salts which can be analysed by our routine 
 methods), or can be made into solutions of such 
 by the application of the ordinary mineral sol- 
 vents, such as water, dilute mineral acids (jua 
 acids), nitric acid or aqua regia {qua oxidants). 
 This class comprises manyminerals, and ordinai7 
 chemical bodies, but unfortunately (and naturally) 
 we have no general test for the recognition ol 
 these bodies as a class. (2) Such as demand 
 special methods of disintegration. Of the more 
 commonly occurring chemical genera, the fol- 
 lowing may be named as falling within this 
 class : — (a) Fluorides ; these although perhaps 
 of the simplest constitution, demand special 
 methods because hydrofluoric acid and all 
 acid fluoride-solutions attack glass and porce- 
 lain, (b) Most silicates : siUco-fAiorides. (c) 
 Cyanides, especially metallocyanides. (3) Salts 
 of certain complex organic acids (not cyanides) ; 
 in the sense that they exhibit abnormal metal- 
 reactions, (e) Organic compounds generaMjiia 
 the sense of ultimate analysis generally. (/) 
 An-orthophosphates. (g) Certain classes of sul- 
 phur compounds. 
 
 This fist does not pretend to be complete, but 
 it includes most bodies which the practical 
 analyst is likely to come across. For the second 
 class of substances as a class, we of course have 
 not a general test any more than we have for 
 the first, but we have general tests for the several 
 genera, in this sense at least that we have 
 general methods for the detection of their cha- 
 racteristic elements. 
 
 The following section is compiled partly with 
 the view of supplying the necessary information 
 in this direction. 
 
 General methods for the detection of 
 certain elements (mostly non-metals) 
 and for the ultimate analysis of their 
 compounds. 
 
 Silicon is always isolated in its highly cha- 
 racteristic form of silica, SiOj, which is easily 
 identified by the blowpipe tests given above, and 
 by its oonvertibiUty into volatile SiP, by the ac- 
 tion of HP. Silicon andmetallic silicides, when 
 fused with caustic alkali, yield alkaline silicates 
 (q. v.). Alkaline silicates (even if so acid as 
 B20.4Si02) dissolve in water, forming alkaline 
 solutions. Mineral silicates. Slags, Glasses, (&e. 
 fall within two classes according to whether they 
 are, or are not, decomposable by hydrochlorio 
 acid. Those of the first class are finely pow- 
 dered and digested in cone, hot HClAq until 
 disintegrated, evaporated to complete dryness (to 
 convert the colloidal part of the silica into the 
 insoluble form), drenched with HClAq, allowed 
 to stand (to re-ohlorinate the AL,0, and Fe^O 
 
218 
 
 ANALYSIS. 
 
 produced), treated with water, and filtered. The 
 silica remains on the filter ; the solution contains 
 the metals as chlorides. Of those of the second 
 class, some are disintegrable by hot semi-cone. 
 HjSOjAq (ex. the clays). The general method 
 is to fuse the finely powdered silicate with 
 ENaCOj until all is dissolved, and to analyse 
 the fused residue as a silicate of the first class. 
 Alkalis must be tested for in another portion of 
 the silicate, after evaporation with NH^FAq, 
 whereby Si is removed as SiFj and the bases 
 remain as fluorides easily convertible into sul- 
 phates by HjSOiAq (comp. Fluorine). 
 
 Aluminium. — Only the forms of Al^Oj in- 
 soluble in acids need be considered here ; these 
 if finely eiiotigh divided, all dissolve at a red- 
 heat in fused EOH, becoming aluminates soluble 
 in water. 
 
 Chromium. — All non-volatile compounds, 
 when fused (in silver) with KOH and KNO3, 
 yield alkaline chromate, recognisable by its yellow 
 colour and the very intensely yellow colour of 
 its aqueous solution. This operation constitutes 
 a general method of disintegration for the forms 
 of Cr^Oj and chromites insoluble in acids ; it 
 goes a certain way even with chrome iron ore, 
 but the complete disintegration of this mineral 
 demands special methods. 
 
 Titanium. — TiOj stands between SiOj and 
 AI2O3. Unlike the former it is not volatiHsed 
 by evaporation with HPAq. Titanates are de- 
 composed by fusion with KHSO, ; the cold 
 aqueous extract after fusion includes the TiOjj 
 which is precipitated on boiling, as such. 
 
 Tin. — The forms of SnO^ (including tin- 
 stone) which are insoluble in acids yield Sn 
 when fused on charcoal with NaHCOj and EON. 
 They may be disintegrated (1) by fusion with 
 EOH; the SnO, becomes stannate soluble in 
 water : (2) by fusion with six pts. S and six pts. 
 Na2C03; the aqueous extract after fusion con- 
 tains the Sn ( also any As and W that may be 
 present) as thiosalt, and consequently falls in 
 with a certain stage of the routine method of 
 metal-analysis {v. infra). 
 
 Carbon in any state of combination is con- 
 vertible into COj, which is readily i«lentified. 
 It is distinguished from HCl and SO^ by its 
 scanty solubility in water, and inertness towards 
 oxidising agents ; from N, H, &c. by its abundant 
 solubility in solutions of basic hydrates ; with 
 CaO^HjAq and BaOjHjAq it gives a character- 
 istic white pp. of carbonate. Carbonates (almost 
 without exception) are decomposed by mineral 
 acids with evolution of CO^. Elementary carbon 
 (in all forms) burns in oxygen to CO^. 
 
 Combustible Carbon Compownds. — The 
 methods of organic analysis (2. v.) are easily 
 translated into general methods for the detection 
 of combustible carbon as COj. It is necessa/ry 
 to purify the CuO or PbCrO, immediately before 
 use by heating it to redness in air until it ceases 
 to give off COj. 
 
 All non-volatile carbon compounds can 
 be burnt by heating them with cone. HjSOjAq 
 and CrOj. Many volatile organic bodies unite 
 readily with cone. HjSO.Aq to form non- 
 volatile compounds, and thus fall within the 
 range of the method which obviously suggests 
 itself for the detection of combustible carbon 
 hcside carbonate. 
 
 Analysis of Carbon Compounds.'— 
 I. Orgarm acids proper (COOH compounds) 
 need here be considered only in regard to the 
 extent to which they interfere with the routine 
 methods for the detection of the metals in a 
 solution of salts. Some (including formic, 
 acetic, succinic, and maivy others) interfere only 
 in this sense that, in their presence, the preci- 
 pitate obtained by H^S in the presence of free 
 acid, may include Zn, Co, Ni, and perhaps 
 other metals of the iron group. This difficulty 
 is easily overcome. A large class of non- volatile 
 acids, including the ordinary fruit acids, prevent 
 the precipitation of Vefi,, KLf)„ Cxfi,, CuO, 
 and other metallic oxides by alkalis, and that of 
 Al and Cr even by sulphide of ammonium. In 
 all difficult or doubtful cases, it is best to 
 destroy the organic part of the salt, which 
 can be done in two ways : — (1) By incineration : 
 which, of course, had better be postponed until 
 after the elimination of the copper and arsenio 
 groups by sulphuretted hydrogen ; if this has 
 been effected, iZn, of all the metals left, is the 
 only one which may be lost by volatilisation. — 
 (2) By treatment (of the dry salts) with oil of 
 vitriol. The ultimate product contains the 
 metals in the form of sulphates. 
 
 II. Cyanides, a. Hydrocyanic acid; easily 
 recognised by its volatility and specific smell 
 and reactions ; regarding the latter, see 6. 
 b. The simple cyanides of the more positive 
 metals (E to Ca inclusive). These are all soluble 
 in water. The solutions are alkaline, and give 
 oH HCN with acids. AgNOjAq in excess pre- 
 cipitates AgNO, insoluble in dilute HNOaAq. 
 When mixed with (1) excess of alkali, (2) ferroso- 
 ferric salt, (3) excess of HClAq, they yield a blue 
 precipitate (or green suspension) of Prussian 
 blue. c. Cyanide of mercury, Hg(NC)2. Soluble 
 in water. Exhibits anomalous reactions both as 
 a mercuric salt and as a cyanide. But is de- 
 composed by HoS into a pp. of HgS and a solu- 
 tion of HCN. d. Heavy metallic cyanides, and 
 metallooyanides. Some give ofi part of their 
 cyanogen as HNC, when distilled with dilute 
 HClAq or H^SOjAq. Many (e.g. prussiates) re- 
 cognisable by specific tests. Solutions of metallo- 
 oyanides mostly give pps. with AgNOjAq, in- 
 soluble in dilute HNOjAq, in which the charao- 
 teristic metals of the radicles can be detected 
 (v. Halogens). 
 
 A general method for the detection of the 
 metals in cyanides, cyanates, and thiocyanates, 
 is to heat the dry substance with cone. HjSOiAq 
 until completely decomposed. The cyanogen 
 becomes ammonia-salt, and CO ; the metals 
 remain as sulphates. About the detection of 
 non-metallic elements in carbon compounds, see 
 sect, on S, P, &c. 
 
 Boron occurs chiefly in the form of borate. 
 The presence of boric acid does not interfere 
 with the routine methods of metal analysis. 
 
 Phosphorus is always isolated and identi- 
 fied as orthophosphate. I. Orthophosphates, as 
 far as not soluble in water, are mostly soluble in 
 HClAq. To search for phosphoric acid, we 
 supersaturate the solution strongly with am- 
 monia, and (after filtration, if necessary) add 
 magnesia mixture (NH,C1 and MgClu in NHjAq), 
 crystalline POjMgNHj.eH^O gradually forms, 
 insoluble in dUute NHjAq. A pp. formed by 
 
ANALYSIS. 
 
 810 
 
 NHjAq generally contains part, sometimes the 
 whole, of the phosphorio acid. To detect the 
 latter we dissolve the pp. in HNOjAq, add excess 
 of a nitric solution of molybdate of ammonia, 
 and allow to stand at 40°C. All the phosphorio 
 acid comes down gradually as a yellow powdery 
 pp. of phospho-molybdate of ammonia, insoluble 
 in excess of reagent, but soluble in excess of 
 acid phosphate ; soluble in ammonia. Both re- 
 actions are very delicate, and, in the absence of 
 arsenic acid (which in the circumstances be- 
 haves like phosphoric), highly characteristic. 
 Phosphates in any other state of combination 
 can be brought into the orthophosphate form 
 by suitable operations. II. Meta- and jayro- 
 phosphates (which besides being different in their 
 own reactions from orthophosphates, exhibit 
 anomalous metal-reactions); by long-continued 
 boiling with mineral acids, or (what is better) 
 fusion with carbonate of alkali. III. Elemen- 
 tary phosplwrus, and all oxidisable phosphorus 
 compounds ; by treatment with HNOaAq of the 
 proper strength at the proper temperature. 
 Many organic phosphorus compounds, it is 
 true, cannot be thus completely oxidised, but in 
 their case, we need only neutralise the nitric 
 liquor produced with potash, evaporate to dry- 
 ness, and fuse the residue with KOH, to convert 
 all the phosphorus into orthophosphate. 
 
 S u 1 p h u r. — Analytically speaking, sulphuric 
 acid is to sulphur what orthophosphoric acid is 
 to phosphorus. I. Sulphates, in an aqueous or 
 IICl solution, are separated out completely by 
 BaCljAq, as white, powdery, BaSOj, insoluble in 
 aqueous mineral acids, and thus distinguished 
 from all the baryta-pps., except the selenate and 
 fluosihcate. BaSeO, is decomposed by boiling 
 HClAq with formation of CI and SeOj, while 
 BaSOj is not so decomposed. The fluosilicate 
 yields no sulphide on fusion with NajCOj on 
 charcoal ; and dissolved fluosUicates give no pp. 
 with SrCljAq, while sulphates yield a pp. of 
 SrSO„ slightly soluble in dilute acids. II. Acid- 
 insoluble sulphates are disintegrated by fusion 
 with alkaline carbonate, and treatment with 
 water; a solution of alkaline sulphate, and a 
 residue of the respective carbonate, oxide, or 
 metal, are obtained. III. Metallic sulphides. — 
 Many are decomposed by HClAq with evolution 
 of HjS. IV. The salts of the lower sulphur 
 acids, when heated (in solution) with alkaline 
 permanganate are completely oxidised with ppn. 
 of manganite, Mn02.E20. The excess of oxidant 
 used is brought into the same form by addition 
 of a few drops of alcohol. The filtrate contains 
 ell the sulphur as sulphate. Only dithionio 
 acid does not yield readily to this process of 
 oxidation. All the sulphur compounds III. and 
 IV., including dithionates, and many organic 
 sulphur compounds, are oxidised completely by 
 hot, sufficiently cone. HNOsAq. Volatile com- 
 pounds (such as CSj) must be manipulated in 
 a sealed glass tube. From some organic bodies 
 only sulphonio acids are produced ; but these, 
 when fused with KOH and END, all yield up 
 their sulphur as sulphate. 
 
 All oxidisable sulphur compounds are com- 
 pletely oxidised to sulphates by the action of 
 basic reagents (likeNajCOj, CaO, &c.), and KNO3, 
 or even oxygen-gas, at a red heat. All non- 
 volatile sulphur compounds yield alkaline 
 
 sulphide when fused with NajCOs on charcoal in 
 the reducing flame (v. Flame Tests). 
 
 Selenion and Tellurium are closely 
 allied to sulphur, but must be passed over. 
 
 Nitrogen, in all states of combination, is 
 susceptible of elimination as nitrogen gas, 
 recognisable by the methods of gas-analysis. 
 Another less general, yet widely applicable and 
 more convenient, method is based upon the 
 conversion of the element into ammonia. 
 
 I. Ammonia; recognisable by its smell, its 
 great solubility in water, its ready union with 
 HCl to form soUd NHjCl, &o. The least traces 
 of NH3, or NH^ salt in water, are detected by 
 Nessler's reagent (a solution of Hgl^ and KI 
 in EOHAq) ; iodide of mercurammonium 
 separates from moderately dilute solutions, as a 
 brown pp., and even in the most dilute solutions 
 is visible as a brown or yellow colour. II. 
 Ammonia salts ; many amides (including all 
 acid-amides) when distilled with caustic alkaU, 
 yield NH, which passes into the distillate. III. 
 Nitrates and nitrites in alkaline solutions are 
 reduced by nascent hydrogen (KOHAq and Al) to 
 NH3. IV. Metallic nitrides, and all organic 
 nitrogen compounds not containing their nitrogen 
 in the form of oxygenated radicles or in the 
 diazo-form, when burnt with soda lime yield 
 their N as NHj. 
 
 Fluorine. Most metallic fluorides, when 
 treated (as powders) with cone. H^SOjAq in a 
 platinum crucible at a gentle heat, give off HP, 
 recognisable by its etching glass and even rock- 
 crystal. For the purpose of metal-detection, the 
 mass must be evaporated until a tangible quantity 
 of sulphuric acid has gone off as a heavy vapour. 
 The bases remain as sulphates. 
 
 Mixtures of fluorides and silicates, when, 
 heated with cone. H^SO^Aq give off SiF„ decom- 
 posed by water into HjSiFjAq and a gelatinous 
 pp. of SiOj, which, however, may be invisible. 
 To detect the fluorine, add excess of ammonia 
 to bring down aU the silicou as silica (which 
 filter off), and evaporate the filtrate in platinum 
 on a water-bath nearly to dryness. Besidue is 
 fluoride of ammonium. 
 
 FluosUicates. Those of the most basylous 
 metals when heated dry break iip into SiF, and 
 a residue of fluoride. FluosUicates generally 
 behave to boiling alkali solutions as if the siUcon 
 were a basylous metal. 
 
 The Halogens (01, Br, I). I. The elemen- 
 tary substances are recognised by their very 
 characteristic properties. When treated with 
 zinc and water, they all dissolve as haloid salts of 
 zinc (ZnClj, &e.). II. Haloid salts ; mostly 
 dissolve in water or in BCNOjAq. Even from 
 the latter solution, the halogen is completely 
 ppd. as haloid salt of silver, insoluble in dilute 
 mineral acid. III. The oxygen acids of the 
 halogens. (Periodic acid ignored.) Of these- 
 only bromio and iodic give silver pps. insoluble 
 (or soluble with difficulty) in cold,dilute,HNOsAq, 
 All the rest form soluble silver salts. Their 
 alkaU and alkaline-earth salts when heated dry 
 give off oxygen and become haloid salts. With 
 the only exception of perchloric acid they are 
 all reduced by SOjAq to halogen-hydride {e.g. 
 HCIO3 to HCl). Hence an obvious IV. Be- 
 Uttively general method for the detection of 
 halogen in a solution of salts. The solntios 
 
220 
 
 ANALYSIS. 
 
 (whioh we will assume to be neutral or aoid) is 
 mixed with excess of SO^Aq and AgKOjAq, the 
 pp. is allowed to form, and then treated with 
 HNOjAq, to remove foreign salts (including 
 AgjSOj whioh is not very readily dissolved). The 
 pp. contains all the halogen of the solution, 
 (except that of the perchloric acid) ; but it may 
 besides contain — if it does not oonsi st of — cyanide, 
 thio-cyanate, and metallo-cyanates, of silver, 
 (not to mention the sulphide which is easily kept 
 out). An analysis can be effected by calcining 
 the dry pp. with chemically pure soda-lime, 
 preferably in a current of moist hydrogen. The 
 nitrogen of the cyanogen radicles goes off as 
 ammonia, which is easily identified. The 
 residual product contains the metals of the 
 metallo-cyanates as oxides, the silver as metal, 
 the sulphur of the sulphocyanogen as alkaline 
 sulphide, and the halogens as alkaline haloids. 
 V. Organic halogen compounds. All these, 
 when burnt with quick-hme in a combustion 
 tube, yield up their halogen as haloid salt of 
 calcium, extractable by cold, dilute, HNO,Aq. 
 
 III. methods for the Systematic Examination of 
 a Solution of Salts for its Uetals 
 
 can be given only on the basis of restrictive 
 assumptions. We assume, in the outset at least, 
 that the solution is so constituted that it might 
 have been prepared by dissolving a set of basic 
 or acid metallic oxides in aqueous mineral acid 
 or alkali, and that certain rare oxides and 
 certain rare combinations of things are absent. 
 Some of the cases lying beyond this programme 
 are dealt with in appended notes to which refer- 
 ence is made in the context. For the sake of 
 generality, however, we assume that all the more 
 ordinary metallic radicles may be present. It 
 evidently would not do to search for them indi- 
 vidually and seriatim ; the only course one could 
 reasonably think of is to begin by splitting up 
 the given complex group of metals into a number 
 of groups, BO that each of these shall contain the 
 whole of, and nothing but, certain metals, A, S, 
 C, . . . ; to then apply the same principle to the 
 groups ; and then to the groups of the second 
 order; and so on until one arrives at last at 
 either the individual metals, or at groups of such 
 smallness that the side-by-side recognition of 
 their members offers no difficulty. This, at any 
 rate, is the course whioh is adopted by every 
 ■chemist. The table on p. 221 in its first vertical 
 .column names the generic reagents whioh are 
 customarily used for the formation of primary 
 groups, and shows how these act on solutions of 
 the groups of oxides named in the successive 
 column headings. For the separation of the 
 groups from one another it is obviously expedient 
 to begin by eliminating the silver group by 
 means of hydrochloric acid, whioh must be added 
 in instalments until the solution is decidedly 
 aoid, and, if a permanent pp. appears (which 
 with us can consist only of these three chlorides), 
 until the ppa. is completed.' The pp. contains 
 
 ' If the solution contains Tl, the metal passes for the 
 most part into the pp., where it is easily detected by 
 spectrum analysis. The characteristic solubility of its 
 chloride in Na>CO,Aq enables one to separate it from the 
 oroinary silver-group chlorides. 
 
 In an alkaline soliuim oj mils generally, HOlAq may pro- 
 duce a great variety of permanent pps. other than silver- 
 Hjronp chlorides. For the puipose of a mere metal-analysis 
 
 all the silver and mercurosum as AgOl and 
 HgjClj, but only part (if any) of the lead ; a small 
 quantity of this metal always passing into the 
 filtrate. From the filtrate the copper and arsenic 
 groups are ppd. conjointly by means of sulphu- 
 retted hydrogen. Before applying this reagent, 
 however, we must make sure of the at least 
 relative absence of nitrous, nitric, and chloric, 
 acid and other oxidising agents, which, whUa 
 not easily or completely reducible by HjS would 
 at least tend to oxidise it and impede its normal 
 action. Any of the three oxidants named can 
 be expelled by repeated evaporation to a small 
 volume with cone, hydrochloric acid.'' The 
 last residue is diluted with the proper propor- 
 tion of water, and (heedless of any insoluble 
 oxychloride that may separate out) treated with 
 sulphuretted hydrogen, first at about 70° to 
 make sure that As^O, is completely reduced 
 to ASjOg, and its metal ppd. (as As^S, + SJ, 
 and then again after cooling, or else part at 
 least of the cadmium and other copper-arsenio 
 group metals, whose sulphides are rathei 
 unstable in opposition to aqueous acids, would 
 escape ppn. 
 
 On account of the metals just referred to, 
 we must see that the quantity of free mineral 
 acid is not excessive, but is sufficient to prevent 
 the ppn. of the zinc, whioh from only feebly 
 acid solutions is liable to pass into the sul- 
 phuretted hydrogen pp. 
 
 The ppd. sulphides are collected on a 
 filter and washed with very dilute sulphuretted 
 hydrogen water, to constantly re-sulphurise 
 what may have become sulphate by the action 
 of the air ; the first instalments of wash-water 
 being acidified to the extent of the mother 
 liquor, to prevent ppn. of the zino. In order 
 now to separate the two groups, the pp. is 
 digested on a water-bath heat with undiluted 
 yellow sulphide of ammonium ; an excess of 
 sulphur in this reagent being necessary, chiefly 
 on account of the stannous sulphide, SnS, 
 which becomes soluble only through conversion 
 into stannic, SuSj. To effect a complete sepa- 
 ration, the treatment with sulphide of ammo- 
 nium may have to be repeated with the first 
 residue. The copper-group sulphides are filtered 
 off and washed with warm water mixed vrith s 
 little sulphide of ammonium. From the filtrate 
 the arsenic-group sulphides are reproduced by 
 acidification with dilute sulphuric aoid; after 
 expulsion of the dissolved sulphuretted hydrogen 
 by a gentle heat, they are filtered off, and 
 washed with plain water (sulphuretted hydrogen 
 water would dissolve sulphide of arsenic As^Sj). 
 The pp. is liable to be contaminated with 
 sulphide of copper ; this can be eliminated by 
 treatment with warm dilute caustic potash, 
 which dissolves the arsenic-group sulphides 
 
 a pretty safe rule is this. If a solution on adding HClAq 
 gives an abnormal-looking pp., repeat the experiment with 
 HNOjAq ; if no permanent pp. is produced, HClAq will 
 act normally as a chloride ; if a pp. is formed, it must be 
 filtered off and analysed for the metals that may be in it, 
 (as sulphides, e.g. As,S, ; or chlorides such as AgOl, &o., 
 &e. ), The solution, as a rule, is now flt for treatment with 
 hytirochloric acid, &o, 
 
 ' In evaporating a solution of metallic oxides with 
 HCLAq, it is as well to remember the volatility of AsOl- 
 SbOl,, SbCl„ SnC!l„ BiCl,. The evaporation is best con- 
 ducted in a retort, and these volatile chlorides are searchnl 
 for in the distillate. 
 
ANALYSIS. 
 
 331 
 
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223 
 
 ANALYSIS, 
 
 only. From the filtrate, these sulphides can be 
 recovered by acidification, in their original 
 form. After elimination of the copper and 
 arsenic groups, the barvum-group may be sepa- 
 rated out by means of sulphuric acid. The 
 barium comes down at onoe (as BaSO,), the 
 strontium gradually, on standing and keeping 
 warm. From the filtrate from these two sul- 
 phates the calcium can be ppd., after due con- 
 centration, by judicious addition of alcohol, 
 and allowing to stand for, say, 12 hours. The 
 calcium sulphate is filtered off and washed, 
 first with dilute, and lastly with strong, alcohol. 
 The filtrate, after removal of the alcohol, is 
 ready for the elimination of the iron-group, &o. 
 This method is the best that can be adopted if 
 an analysis for the barium-group metals is our 
 principal object ; it also offers certain other 
 specific advantages j yet the majority of chemists 
 prefer (after application of sulphuretted hydro- 
 gen in the presence of acid) at once to separate 
 out the iron-group, by means of sulphide of 
 ammonium. The addition of this precipitant 
 must of course be preceded by the neutrahsation 
 of the free mineral acid of the solution with 
 ammonia; if a sufSciency of sal-ammoniac is 
 not thus produced incidentally, some sal-am- 
 moniac must be added, to bring the pp. into a 
 fit condition for filtration. But we have no 
 space for these technicalities, and accordingly 
 assume the pp. to have been filtered off and 
 washed with warm water mixed with some sul- 
 phide of ammonium, so as to remove the whole 
 of the mother-liquor. This liquor, by theory, 
 contains the whole, in practice it may be as- 
 sumed in general to contain the bulk, of the 
 barium-group metals and of the magnesium, in 
 addition to the whole of the alkalis.. For its 
 analysis, the barium-group is ppd. by means 
 of carbonate of ammonia added to a warm solu- 
 tion. In the presence of ammonia-salts, of 
 which as a rule there is more than enough, 
 only the barium-group metals are ppd. as 
 carbonates ; the pp. is collected on a filter, and 
 washed with hot water. Part of the filtrate 
 serves for the detection of magnesia by means 
 of ammonium phosphate. The rest of the 
 filtrate is evaporated to dryness, and the residue 
 calcined. The ammonium-salts volatilise, or at 
 least their ammonia does, and there remains a 
 residue containing only magnesium and alkali- 
 metals, which latter can be detected without 
 elimination of the magnesium by suitable 
 methods. 
 
 In regard to the analysis of the groups, our 
 space does not permit us to do more than 
 shortly indicate how the sulphide of ammonium 
 pp. (which may be of very complex composition), 
 can be split up into minor groups. Before doing 
 so, let us state that in the presence of representa- 
 tives of a certain group of acids which includes 
 H3P04,HF,H3B03, and certain organic acids, e.g. 
 oxalic, the pp. is liable to contain part, or all that 
 there is, of barium-group metals and of magne- 
 sium, as salts of the acids named. A thoughtful 
 analyst takes care to keep these inconvenient 
 acids out of the solution ; but the introduction 
 of phosphoric acid is often unavoidable, and we 
 therefore assume it to be present. Whether this 
 acid is present or not, the cobalt and nickel 
 tan be eliminated, approximately at least, by 
 
 treatment of the pp. with cold, dilute ' HClAq, 
 and removed by filtration. The filtrate is next 
 tested for iron, best by adding a few granules 
 of chlorate of potash and boiling, when the iron 
 assumes the form of ferric salt, and becomes 
 visible by the intense yellow colour of its hot 
 hydrochloric solution, and at the same time 
 assumes the right form for the next step, which 
 aims at a separation of the metals present as 
 FcjCle, AljClj, Cr^Clj, and the phosphates, from 
 the metals (manganese, zino, &o.) present as 
 dichlorides. Of the various methods which we 
 have for their separation, the most convenient 
 for general purposes is the following : — 
 
 After having made sure of the complete 
 reduction of the manganese (Mn^Cls) to man- 
 ganous chloride by sufficient boiling with hydro- 
 chloric acid, we allow to cool, dilute pretty 
 considerably, and next add (sal-ammoniac if 
 necessary, and) ammonia, drop by drop, until 
 the mixture is alkaline. We then (without 
 losing time and giving the oxide of manganese 
 much chance to get per-oxidised), boil until 
 the vapours cease to smell of ammonia, and 
 filter. The pp. contains all the iron, alu- 
 minium, and chromium, and all the phosphoric 
 acid as lime-salt, or in other forms ; the filtrate 
 contains at least part of the zino, manganese, 
 and in general part of the rest of the protoxides. 
 If the sesquioxide-pp. is bulky, it must be re- 
 dissolved (after a few washings) and re-produced 
 by a repetition of the first operation. From the 
 pi-otoxide filtrate, the zinc, after acidification 
 with acetic acid, can be ppd. pure by fractional 
 ppn. with sulphuretted hydrogen-water in the 
 cold. The manganese, traces of nickel and 
 cobalt, and in general much lime, baryta, and 
 strontia, remain dissolved. 
 
 The sesc^moxides-^ip.'' (if chromium be pre- 
 
 ' The cohalt-nickel pp. never contains the whole of these 
 metals ; part passes into solution, and ultimately finds its 
 way into the ^protoxide filtrate* In addition to its normal 
 components it is liable to contain sulphide of zinc, and 
 perhaps traces of other iron-group metals, and any 
 cadmium, antimony, &c., that may have been allowed to 
 Blip into the filtrate from the sulphuretted hydrogen pp. 
 
 ^ If the solution contains uranium, this, in our scheme 
 of analysis, goes with the iron, and consequently has to be 
 looked for in the sesquioxide pp. ; from which it can be ex- 
 tracted by digestion with warm, concentrated, solution of 
 carbonate of ammonia. To pass now to a number of rare 
 metals, which we have so far entirely ignored: 
 
 Palladium, in our system, belongs to the copper-group. 
 It is characterised chiefly by the ntter insolubility and 
 black colour of its iodide. 
 
 Platinum and gold go into the arsenic group ; only the 
 sulphides are not easily soluble in alkaline sulphides. In 
 almost all practical cases they can be kept outside the 
 solution intended for the detection of the metals by suit- 
 able methods. If they are unavoidably present, they are 
 best separated out ; the gold by ferrous chloride (aa 
 metal); the platinum, by means of solid sal-ammoniao 
 added to the concentrated solution, as PtCl«(NH«)„ which 
 must be washed with the least possible quantity of a solu- 
 tion of the precipitant. 
 
 Titanium, as TiOg, in the analyst's sense stands 
 between SiO. and Al.O,. In our system it goes with tha 
 AlA. 
 
 Beryllium behaves to our group-reagents like AlgOs, but 
 it is far more easily soluble in sal-ammoniac than alumina 
 is. Unlike it, it dissolves in carbonate of ammonia, and 
 does not form an alum. 
 
 The rare earth me^a/^, cerium, lauthauum, &c., &c,, must 
 all be passed over here. 
 
 Lithium (easily detected by spectrum analysis) behaves 
 on the whole like E and Na, but unlike them forms an 
 insoluble phosphate producible by evaporating its solution 
 with phosphate of soda plus caustic soda {i.e. with NagFO^)* 
 to dryness, and treating the residue with water, when it 
 remains. From magnesia (if ammonia salts are absent) It 
 
ANALYSIS. 
 
 223 
 
 sent) is best analysed by fusion with caustic 
 potash and nitre in a silver dish, and treatment 
 of the fused mass with water. Should the 
 solution be green from manganate, this must be 
 reduced (to MnO^) by addition of a few drops of 
 alcohol and heating. The mixture is then 
 filtered. The filtrate contains the chromium as 
 (yellow) ohromate, the aluminium as aluminate, 
 and part, in general, of the phosphoric acid as 
 phosphate. The residue contains oxide of iron, 
 magnesia (MgO), and possibly barium-group 
 metals as phosphates. 
 
 The Determination of the Non- 
 Metallic Components. — Our systematic 
 methods for the detection of the metals con- 
 tained in a solution of salts are far less ham- 
 pered by onerous conditions than are most of 
 our methods of acid detection. Hence the 
 general rule to first complete the analysis for 
 metals before attempting the systematic and 
 exhaustive search for the non-metaUic compo- 
 nents. How far the solutions obtained in the 
 disintegrations are available for the latter 
 purpose, and the respective methods of proce- 
 dure generally, depend chiefly upon whether 
 we merely aim at the detection of the non- 
 metallic elements as such or at that of the acid 
 radicles contained in the substance. All we 
 could say in regard to the former case is antici- 
 pated in the section on the 'Detection of 
 certain elements, dc' (p. 217) and the latter 
 is not susceptible of being treated instructively 
 in general terms. In regard to it we must refer 
 to the special hand-books. 
 
 Quantitative Analysis. 
 
 The general problem of quantitative analysis 
 defines itself. Its solution, scientifically at 
 least, assumes its simplest form, if the thing to 
 be analysed is given as a free suljstance and the 
 (let us say one) component to be determined can 
 be separated out exhaustively in the form in 
 which it is meant to be reported. In such a 
 case all that is required, in addition to the 
 analysis proper, is the numerical definition of 
 the two quantities concerned. Of the several 
 direct methods which we have for this purpose, 
 only two need be mentioned ; one is to measure 
 the volume of the body under stated conditions 
 of temperature and pressure, the other is to de- 
 termine its weight. The former method is 
 confined in practice to gases and liquids; the 
 latter is applicable, and indeed is applied, to 
 bodies of all kinds, and, when we have choice, 
 applied preferably. The volume of a body is a 
 function of temperature and pressure, and its 
 numerical statement is consequently encumbered 
 with the necessary reference to — in general — 
 two corresponding standards; the weight of a 
 given body depends only on the intensity of 
 gravity, and even this variable in practice is out 
 of court, because, in chemistry we always use 
 that well-known method of relative weighing 
 which measures the weight of the body not in 
 terms of a unit-force but as a multiple of the 
 weight, at the time and place, of an adopted 
 standard mass, viz. the unit-piece of our set of 
 
 is separated by solution ol baryta in a warm liquid whicb 
 pp3. only tlie magnesium as Mg(OH)a. 
 
 BuUdium and caesium, in any soheme of analysis, follow 
 potassium to the end. 
 
 weights. The result of such a weighing is inde- 
 pendent of the prevailing force of gravity, and 
 consequently not subject to any variation ; it 
 consequently, at least, indexes the mass with 
 perfect definiteness. We, moreover, know that 
 it is independent of any chemical change within 
 the body (or set of bodies) weighed. A mass of, 
 for instance, sulphide of copper weighs precisely 
 as much as the two components did conjointly. 
 Hence for chemical purposes our method of 
 weighing might safely be viewed as a method of 
 true mass-measurement, even if Newton had not 
 proved that equal weights (chemically deter- 
 mined) correspond to equal inertias. 
 
 The method of direct quantitative analysis 
 explained is the only one which suggests itself 
 when the component to be determined is a 
 chemically indefinite mixture (such as for 
 instance the mixture of salts contained in a 
 natural water) ; it applies to a good many other 
 cases ; but of course breaks down whenever the 
 body to be determined is an imaginary radicle 
 such as SO, or CIO3, &o. In such cases (and 
 many others as a matter of expediency) we 
 determine the component by one or other of our 
 indirect methods of mass measurements ; which, 
 however, all come to this, that instead of the 
 unknown mass x, we measure some other quan- 
 tity q, which bears to a; a known fixed relation, 
 x=f(q,m), where ot is a mass which must be 
 measured directly, although the analyst does not 
 always do this at the time, or himseU at all. 
 
 Most of our determinations in analysis are 
 uncertain by at least 0-001 of their values, and 
 a higher degree of relative precision is afforded 
 by any fair ordinary balance. But the nature 
 of our methods compels us, in general, to work 
 on small quantities — we rarely care to start 
 with more than one gram of a given solid — 
 and besides the products to be weighed can in 
 most cases not be placed on the bare pan, but 
 must be shut up in apparatus weighing perhaps 
 100 or 1000 times as much as themselves. The 
 net weight then comes to us only as a small 
 difference between two large weights directly 
 determined. So it comes that even for the ordi- 
 nary routine of quantitative analysis, we need a 
 balance which to be generally useful should 
 carry about 100 grams on each side, and with 
 this charge turn distinctly with anything greater 
 than, say, 0'2 milligrams. 
 
 The Chemical Balance.' 
 In its present form the chemical balance is 
 nothing more than a refinement upon the ordi- 
 nary beam and scales to be seen in any grocer's 
 shop; it is a more perfect realisation of the 
 same ideal machine. There is an absolutely 
 rigid beam, suspended so that while it oscillates 
 freely about a certain axis, every point of which 
 is fixed in reference to the stand, it cannot per- 
 form any other motion. From two points 
 which lie in the same plane with the axis of 
 rotation — one a near the left, the other b near 
 the right, end,— the pans are suspended by 
 means of absolutely flexible linear strings, a 
 and B are equidistant from the axis of rotation. 
 The form of the (ideal) beam is arbitrary; so in 
 
 ' Partly abstracted from the writer's memoir : Veber 
 die Waage des Ohemikera (Zeitschn/t fiir ImtrumeiUeitkuttdt. 
 1881, 31.1 et «3.). 
 
?24 
 
 ANALYSIS. 
 
 ti sense is its mass, which, however, must be so 
 distributed that, supposing the line a b to be 
 horizontal, the centre of gravity of the empty 
 beam lies vertically below, though very near, 
 the axis of rotation. Let us at once add that in 
 the actual instrument the weight of the beam 
 ehould be no greater than is necessary to ensure 
 to it sufficient stability of form in all circum- 
 Btances, because the greater the weight of the 
 beam, the greater {ceet. par.) the friction in the 
 axis of rotation, and the greater the time of 
 ribration. 
 
 Of the difficulties involved in realising the 
 ideal machine, that of producing a light and yet 
 practically inflexible beam seems to have rested 
 most heavily upon the minds of the earlier 
 maters ; but there can be no doubt that many 
 of their efforts in this direction (which occasion- 
 ally resulted in what we should now call fan- 
 tastical beam forms, such as hollow ellipsoids or 
 double cones, monstrous skeleton forms, &c.) 
 must be traced bact to their inability to reach 
 a sufficient degree of precision in the geometric 
 adjustment of the three pivots, and their thus 
 charging againstthe flexibility of the beam what 
 was really owing to these defects in the adjust- 
 ment. As these difficulties were overcome, beams 
 assumedless fantastic forms. Saor6, of Brussels, 
 we believe, never uses any but plain rod-shaped 
 beams for even his finest instruments; most 
 balance-makers, however, prefer the form of a 
 largely perforated rhombus or flat isosceles 
 triangle ; and thereby attain all that is needful 
 even for the best instruments without offending 
 the eye by unduly stretching the maximum sec- 
 tion, or without using anything more rigid, 
 intrinsically, than hammered brass or some 
 kind of hard bronze.' 
 
 In all modern balances the axis of rotation 
 is sought to be realised in a straight knife-edge 
 ground to a prism of hard material, which is 
 firmly fixed to the beam traversing it cross-wise, 
 and rests — in the best balances along its entire 
 length — on a horizontal, plane, (andequally hard) 
 bearing fixed to the stand. The arrestment is so 
 contrived that, besides doing its primary duty, it 
 secures to each point of the knife-edge a fixed 
 position on its bearing whenever the balance 
 works. In former times both bearings and knives 
 used to be made of hard steel; subsequently 
 agate bearings came to be combined with steel 
 edges, and this is still the most popular com- 
 bination; although Eobinson long ago introduced 
 agate knives in conjunction with agate bearings. 
 The agate knife adds nothing to the precision 
 or mechanical durability, but for laboratory 
 balances offers the great advantage of rendering 
 the system proof against acid-vapours ; accord- 
 ingly it is gaining more and more in popularity. 
 Quite lately an American has introduced as a 
 material for both knives and bearings that very 
 hard (and acid-proof) alloy of osmium and iridium 
 which is used for the tipping of stylograph 
 pens. 
 
 The point pivots, A and b, used to bo realised 
 visibly by means of two circular knives fixed to 
 the end of the beam so that their working-edges 
 were parallel to the axis of rotation. Prom the 
 
 ' For further information regarding this question ve 
 Teia to the writer's memoir quoted in footnote to p. 228. 
 
 lowest points, the pans were suspended by means 
 of ? shaped hooks of steel wire. In this way 
 a very high degree of precision can be attained, 
 and the system when well executed is more 
 durable than one would think, but with balances 
 used for heavy charges it cannot possibly last 
 for many years. 
 
 In the better system introduced by Eobinson 
 of London half a century ago each extremity of 
 the beam is provided with a knife-edge similar 
 to the central one (except that it is turned up- 
 wards) ; on each knife-edge rests a stirrup-shaped 
 (or J-shaped) contrivance, terminating in a ring 
 below, and from this ring the pan is suspended 
 by a hook. This, of course, comes to the same 
 as if the pan were suspended from the projection 
 of the working point of the hook-and-eye arrange- 
 ment on the respective knife-edge ; so that the 
 latter need not be absolutely parallel to the axis 
 of rotation. Flat end-bearings demand a some- 
 what cumbrous and expensive appendage to the 
 arrestment to secure to each point of every edge 
 a fixed position on its bearing in the working in- 
 strument. Hence Staudinger, and many other?, 
 prefer to combine (long) end-knives with roof- 
 shaped bearings, which, in virtue of their shape, 
 fall into their prescribed positions without 
 external aid. 
 
 In now passing from fundamentally impor- 
 tant to subsidiary points, the arrestment ought 
 to be taken up first ; but we could not possibly 
 do justice to this (practically all-important) sub- 
 ject without workman-like drawings and lengthy 
 descriptions. We therefore pass on at once to 
 the needle which serves to define the position of 
 the beam in reference to the plumb-line. 
 
 In the precision-balance the needle is made 
 to point downwards towards a scale fixed to the 
 lowest convenient point of the pillar. The zero- 
 point defines the ' normal position ' of the beam, 
 i.e. that position in which its centre of gravity 
 lies vertically below the axis of rotation. The 
 scale is so divided that the radii drawn from the 
 axis of rotation through the marks divide the 
 tangent to the circle described by the oscillating 
 needle, at the zero point, into pieces of equal 
 length, which in most practical cases means 
 into degrees of equal angular value. 
 
 To avoid the use of small weights, each arm 
 of the beam, in most balances, is divided into 
 ten equal parts in the sense that the projections 
 of the marks on the line A B connecting the two 
 point-pivots divide the distance from the 
 central pivot to (say) b into ten equal parts. A 
 rider weighing ten mgms., when suspended on 
 mark 1, 2, 3, &c., acts like 1, 2, S, &c., mgms. 
 placed on the pan. In most balances, however, 
 points and 10 are inaccessible. Becker's 
 Sons, of Botterdam, avoid this inconvenience by 
 dividing each arm into twelve equal parts, and 
 providing a rider of twelve mgms. weight. Some 
 makers make the top bar of their beams straight, 
 and exactly parallel to the plane of the three 
 pivots, and let it project beyond the terminal 
 edges, besides keeping it clear of encumbrances, 
 so that the rider can move freely from one end 
 of the beam to the other. This system, besides 
 its obvious advantages, admits of the use of 
 heavier riders ; because the increase in sensibility 
 caused by the presence of the rider is the same 
 at any position which it may have; only the 
 
ANALYSIS. 
 
 225 
 
 rider in such cases must be counted part and 
 parcel of the instrument.' 
 
 In proceeding now to develop the statical 
 theory of the precision-balance we will assume, 
 for a first approximation, that the three pivots 
 are physically and geometrically perfect in 
 themselves, but, for the sake of greater gene- 
 rality, we will not assume that the knives are 
 exactly in their intended positions. Imagine a 
 system of rectangular co-ordinates fixed to the 
 beam so that, while the z-axis coincides with 
 the axis of rotation, the x-axis goes through the 
 centre of the middle knife, and runs parallel to 
 the line A B which joins the two point-pivots. 
 Let the co-ordinates of A and B, of the centre 
 of gravity s„ of the empty beam, and of a certain 
 point to be defined presently, be as follows : 
 A B s. 
 
 a= —V +1" o a!o 
 
 y= +h* +h* s„ y„ 
 
 Let p' denote the total charge from a, e" 
 that from b, and w„ the weight of the empty 
 beam ; the joint effect of these three weights is 
 the same as if they were aU concentrated in some 
 point at cB = a!|, and y = y„- For calculating 
 purposes we may assume gravity in one case I. to 
 act in the direction of the Y-axis, and in a second 
 II. in the direction of the x-axis ; we then have : 
 (CaseL) . r"l"~s'l' = {s' + s" + w,)x, . 1. 
 (Case II.) (E' + E")fc + w„s„= 
 
 (p» + p«^.^)(p' + p" + ^^)j^^ . II. 
 
 In any sensibly constructed balance things 
 are so arranged that, under all circumstances 
 that come into practical consideration, the 
 centre of gravity o of the whole system lies 
 outside and below the axis of rotation (i.e. that 
 y„>o). Assuming both x„ and y„ to have 
 positive values, and the beam to be left to 
 itself in its normal position, it will turn, and 
 tend to assume that position in which o lies 
 vertically below the axis of rotation. The radius 
 oo then describes an angle equal to that which 
 separates oc from the Y-axis, and obviously, 
 
 tan. o = — -=7 
 
 x„ r"l"—r'l' 
 
 III. 
 
 tan. a=i 
 
 Ilia. 
 
 To bring the equation into a handier form 
 lor our purposes, let us separate p' and p" into 
 parts, thus; p'=Jp'„-^y, and v"=p'„+pf' where 
 the pifi stand for the weights of the empty 
 pans, which are always so adjusted thaty„Z' = 
 p„"l" ; let us then himpp\+p^'o with the weight 
 of the beam as w = w„ +p'„ +^'0 and write 
 p"l"-^ 'l' 
 ' {p'+p") + ws ' 
 where s has an obvious meaning. We then 
 have for x„ the equation 
 
 yr -y J' = (»' -hjp" -I- w)a!„. 
 
 This equation may be said to state the theory 
 of the ordinary method of weighing. _ To find 
 the weight p' of a given body we place it on the 
 left pan, and then try heavier and lighter com- 
 binations of standards on the right, until we 
 have found out that one (representing p' 
 grams) which reduces x„ to nothing, so that the 
 balance is at rest at, or it vibrates about, its 
 
 p"l" 
 normal position. We then have p'= — jr- 
 
 ■ Por more exact Inf ormation see the writer's memoir, 
 page 322. 
 
 * + means ' below ».' 
 Von. I. 
 
 In formulating the relation between a small 
 overweight on one side and the corresponding 
 angle of derivation a, we may take V - V' (as it 
 reallyis very nearly in all well-adjusted balances), 
 and (forjfi'=^ andp''=^ + A) write 
 
 tan. (t=- 
 
 IV. 
 
 ws + 2ph 
 
 where a means the angle through which the 
 position of rest turns in consequence of the 
 addition of A units of weight to the right pan, 
 the charge before having been x=p on each 
 side. 
 
 In practice tan. a is measured in degrees of 
 the scale. Supposing a corresponds to n degrees 
 of the scale, and the index-length is J in 
 degrees, we have 
 
 ~ = —^l— . . . . V. 
 
 J ws-^2pA 
 
 The ratio — defines the sensibility of the 
 
 balance ; we have for it 
 _ w _ Z J 
 ~E ws-i-2pfc 
 
 VL 
 
 and for its reciprocal, — • , the weight-value of 
 
 1° of the scale, 
 1 _ ?is + 2ph 
 B I3 
 
 VII. 
 
 For h = Q, the term iph vanishes, and the 
 sensibility becomes independent of the charge. 
 In the actual instrument ^ is a function of the 
 charge, of the form h = h„ + Pp, where ;8 is a 
 small constant depending on the coefficient of 
 elasticity and the configuration of the beam^ 
 For a given charge, a good maker has no. 
 difficulty in bringing h down to less than ± O'OI. 
 mm. The best instruments are so adjusted that,. 
 for a certain medium charge, /i = 0, so that for 
 p = it has a. small negative, and from p = 
 maximum charge a small positive, value. The; 
 relative change in the sensibility involved in: 
 passing from p=0 to p=p, is shown by tha 
 equation 
 
 E~'— E|)~' _ 2ph 
 B^-^ ws 
 
 and consequently is the less {ccBt. par.), the 
 greater s, i.e. the less the initial sensibility, 
 B„. It (i.e. the left side of our equation) comes 
 to its minimum (assuming p to represeiit the 
 maximum charge) if the balance is so adjusted 
 that, for the .charge 0-83 p, h = 0. Supposing 
 this rule to be generally adopted, the relative 
 inconstancy of the sensibility is independent 
 of the arm-length (see the writer's memoir, 
 p. 318). 
 
 No balance is complete without a ' gravity- 
 bob,' a small button or sphere of metal attached 
 to a wire which stands vertical on the top of 
 the beam (in the Y-axis) so that it can be 
 screwed up and down into any position. Matters 
 are arranged so that when the bob is quite 
 down the sensibility is below the lo■B^est value 
 we care for, while, by screwing up the bob to its 
 highest place, we can bring into, and even a 
 little to the wrong side of, the axis of rotation. 
 Hence it would appear that, by screwing up the 
 bob sufficiently we can get our balance to turn 
 
 Q 
 
326 
 
 ANALYSIS. 
 
 visibly with say 0-001 milligram or anything 
 less that we might care to name. So indeed it 
 would be if our fundamental assumptions could 
 be — and were— realised. In practice, however, 
 the knife edges are not absolutely straight nor 
 the bearings absolutely plane, and neither are 
 absolutely rigid. Hence the three axes, instead 
 of being always at a! = A, o, D respectively, so to 
 ■say oscillate irregularly, each from a; — A to 
 a: + A, where x is the theoretical x. In going 
 more fuUy into the matter we see that as a oon- 
 Becjuence the balance at a given charge (say 
 p left ; p right) is in a state of indifferent equili- 
 brium within a small angle ± ;8, which, of course, 
 is the greater the greater is E. But the weight- 
 value e of this angle is constant, and is governed 
 by some equation like 
 
 e=.L(w + 2i,) 
 
 where ' X ' ia meant to lump the joint effect of 
 the three As previously referred to. e may 
 be called the ' inherent error ' of the balance. 
 There is obviously no use in screwing up the 
 bob any further than necessary to render this e 
 {i.e. angle j8) distinctly visible. It may be in- 
 expedient even to go so far, because, in practice, 
 we never aim at the absolutely true weight, but 
 at a value sure to differ from it by no more than 
 say ± O'l mgm. The angle corresponding to 
 this need not be more than distinctly visible. 
 To make the angle greater than necessary 
 needlessly adds to the time of vibration which 
 may already be inconveniently high. Because 
 the time of vibration {t in seconds) is governed 
 by the equation 
 
 where S denotes the length of the pendulum 
 beating seconds at the place of observation. 
 fcw„Z^ denotes the momentum inertia of the 
 empty beam in reference to the axis of rotation. 
 The denominator of eq. VIII. suggests the 
 expression given in eq. VII. for the sensibility 
 E. Combining the two we have 
 
 i^ ^ { (fcw„ + 2p„) + 2p|E . . IX. 
 
 The bob enables us to choose our own e, or our 
 own t (for a named charge), but it does not 
 enable us to choose both. We of course refer to 
 a ready-made balance ; in the hands of a me- 
 chanician who designs a balance for a stated 
 purpose, I becomes an arbitrary variable, and 
 the equation then assumes something like this 
 form : 
 
 f = l{c + kbl + 2p)B . . . . X. 
 
 Tfhere c and 6 are constants whose meaning is 
 Buffioiently apparent. In words : Whatever 
 i(reasonable) value for e may have been fixed 
 •upon we can bring down t (for say p = 0) to any 
 'desired figure by making I sufficiently small. 
 ■But where shall we stop? For high-class 
 balances intended to weigh up to 100 grams, 
 mechanicians used to draw the line at Z = 180 to 
 aOO mm. These values (perhaps more by dint of 
 iiabit than on rational grounds) were retained 
 until about twenty years ago, when P. Bunge, 
 of Hamburg, introduced a new form of the in- 
 
 strument, in which the arm-length is reduced 
 to some 60 to 65 mm. Thanks to the general 
 excellence of Bunge's work, these short beams 
 soon became very popular among both chemists 
 and mechanicians ; and it therefore is worth 
 while to inquire what their specific advantages 
 as short-beam balances amount to. 
 
 For this purpose the writer, some years ago, 
 determined the constants of eq. X. for a very 
 excellent Oertling (hectogram) balance, which 
 he has in his possession, (its Z = 184 mm.), and, 
 taking it as a general model for an imaginary 
 genus, calculated the values of t for a number 
 of charges- and sensibilities, assuming I to be 
 equal to {a) 180 mm. and (6) 60 mm. He 
 found for 
 
 I. E = 2 degrees of the scale per 1 mgm. 
 
 of over-weight.^ 
 
 if Z = 180 mm. 60 mm. 
 
 for^ = 0;«= 7"-7 3"-6 
 
 The short beam obviously vibrates too fast for 
 
 high-precision work. To set this right let us 
 
 screw up the bob on both sides, so as to double 
 
 the sensibility. We now have 
 
 II. E = 4 degrees per mgm. 
 if I = 180 mm. 60 mm. 
 
 forp= 0; «= ll"-0 5"-2 
 
 as p= 30; t= 14"-8 7"-8 
 
 asiJ=100: i= 21"-2 ll"-6 
 
 *,„„: «„= 1-93 2-23 
 
 The times of vibration no doubt assume the 
 more convenient values in the shorter beamed 
 instrument. But what does this amount to 
 practically ? In our opinion not to as much as 
 some people seem to think. We are inclined to 
 think that the short beam offers material advan- 
 tages to those who are accustomed to the dead- 
 beat method of weighing (see below). All those 
 who prefer the method of vibration will on 
 the whole, we think, fare better with the old 
 form of the instrument. But this, to be com- 
 plete, should be provided with the two following 
 auxiliary contrivances of the writer's invention : 
 
 I. An auxiliary small bob^ attached by 
 mere friction to the upper part of the needle, 
 which has the form of a triangular prism and 
 is (virtually or actually) graduated, so that one 
 is able, at a moment's notice, to give to the 
 weight-value of 1° of the scale any convenient 
 pre-determined value, to make it equal to 
 exactly 2, 1, 05, 0'2 cfeo.mgm. as he may please. 
 
 II. A microscopic arrangement ' for reading 
 the excursions of the needle. A narrow ivory 
 scale, divided into very small degrees, is fixed 
 to the needle near its lower end, so that a micro- 
 scope which is fixed slantingly to the stand but 
 passes through the central (fixed) portion of the 
 front pane enables one to read it. The micro- 
 scope has a vertical wire in its focus ; this wire 
 appears as a vertical line crossing the image 
 of the scale. Every degree of the micro-scale 
 corresponds to exactly O'l degree of the ordinary 
 scale, which latter does duty as usual. As the 
 microscope reverses the image, the apparent 
 motion of the ' wire ' on the micro-scale is in the 
 
 * I.e. tlie addition of 1 mgm. causes tlie needle to oscil- 
 late between and ± 2° ; 1° in the given instrument^ 
 1 mm, very nearly. 
 
 • Pr. B., 1876 ; C. N. 33, 167. 
 
 " ZHIaehrf/t/ar Instrumentenkunde, 1883, p. C3. 
 
ANALYSIS. 
 
 227 
 
 eame sense as the real motion of the needle in 
 reference to the ordinary scale, so that there is 
 no fear of blunders through mistaking plus for 
 minus. The writer is indebted to Mr. Oertling 
 for having executed this arrangement for him 
 in a most masterly manner. Though intended 
 originally to be reserved for special work, such 
 as weight-testing &c., it was found so convenient 
 that both the writer and his assistants use it 
 preferably for even their everyday weighings. 
 The specific advantage of the microscope ie that 
 it enables one to adjust the 'bob' so as So pro- 
 duce the most convenient time of vibration. 
 The microscope more than makes up for the 
 involved loss of sensibility. 
 
 On Weighing. 
 
 A precision-balance should stand on an un- 
 shakable table, and should not be exposed to 
 the risk of one-sided elevation of temperature. 
 Before being used for a series of weighings it 
 must of course be set in order, which includes 
 that the case be 'levelled,' so that the plane 
 including the axis of rotation and the zero of 
 the scale is a plumb-plane. The next thing to 
 do (if necessary) is to bring the ' bob ' into its 
 proper position ; i.e. to place it so that the 
 least difierence of weight we care for just be- 
 comes visible as an angle of deviation and no 
 more, because to increase the sensibility beyond 
 what is needful means needlessly to diminish 
 the range of weights determinable by vibration, 
 the constancy of the sensibility, and the rate of 
 vibration. This rate of course must not be 
 allowed to fall below a certain limiting value. 
 In the vrriter's opinion, t = 6" is about the 
 lowest permissible limit for relatively heavy 
 charges. Next, the balance must be brought 
 ' into equilibrium ' at least approximately. For 
 this purpose Oertling's balances carry a vane 
 at the top of the beam, consisting of a little 
 lever hinged to the wire of the bob, which can 
 be turned round, so as to shift the centre of 
 gravity to the right or left.' A better arrange- 
 ment is a small horizontal gravity bob at one 
 end of the beam. For simplicity's sake we 
 assume that the balance has been brought into 
 perfect equilibrium, so that the needle in the 
 vibrating instrument moves forwards and back- 
 wards between -l-n.° and —n°. To weigh an 
 object (which, to fix ideas, we will assume to be 
 a solid, and non-hygroscopic), the ordinary mode 
 is to place it on the left pan, and then coun- 
 terpoise very nearly vfith standard weights, say 
 p grams, on the right. In order now to deter- 
 min( the small additional weight which is re- 
 quired to establish perfect equilibrium, we may 
 use one or other of two methods. In the 
 
 Dead-heat method we simply continue our 
 trials, until the needle vibrates about the zero 
 as its position of potential rest. It is, however, 
 hardly possible for any thinking person to use 
 this method without at least instinctively com- 
 bining it with 
 
 The method of vibration, which in its most 
 exact form consists in this that we note down 
 (at least mentally) the successive excursions of 
 
 ' A vane with properly graduated limb Is as good as a 
 •rider' ; better in fact, inasmuch as it is not liable to drop 
 off and get lost ; this innovation was proposed by Hempel, 
 but has not met with maob &TOUr as tar as we know. 
 
 the needle, and from these calculate the posi- 
 tion of rest. Supposing we count distances 
 traced by the needle in moving, from to the 
 left as positive, and those to the right as nega- 
 tive, and the needle turns successively at n,, n„ 
 Jij, TC^, «5, degrees, we have for the position of 
 rest, 4 values, 
 
 ^(Mi + wJ; i(ra2-HWs); K'is + Wj); i(»i + «s). 
 and the mean of these four values gives the 
 reading corresponding to the position of rest. 
 But the factor ^ can be dropped, because we are 
 evidently at liberty to measure in half -degrees. 
 By taking an odd number of readings we elimi- 
 nate the error caused by what the needle loses 
 in passing through its path ; for ordinary prac- 
 tice 3 readings are sufficient. It suffices to deter- 
 mine n, = (say) + 4-2 •,n^= — 1*0 ; TOj = -^ 4-0, and 
 compute ' a ' = mean of + 3-2 and -H 3-0 = -I- 3-1. 
 In this case the right pan is too heavy by 3'1 x 
 k mgms., it /i; is the weight-value of 1° at the 
 respective charge. In a good balance Tc is almost 
 independent of the charge ; the writer's supple- 
 mentary bob of course enables one to give it a 
 pre-determined value. How h is determined 
 need not be explained. 
 
 Supposing p grams to have established exact 
 equilibrium, the object weighs 
 
 I" 
 x=py grams. 
 
 The several weights which enter the calculation 
 of an analysis need only be relatively correct. 
 Hence, if all the weighings involved are made 
 on the same balance and with the same set of 
 weights, and the objects are always in the left 
 
 7" 
 
 pan, in any such series we may adopt -=; grms. 
 
 as our unit and say x =p. 
 
 We do not consider it necessary to quote 
 
 examples of cases in which as a matter of prin- 
 
 l" 
 ciple -y- dare not be cancelled ; we rather say 
 
 that in all precision-balances worthy of the name 
 
 I" 
 
 Y is very small, not more than 0-00005 at the 
 
 most. If the empty balance was in equilibrium 
 at + Oj degrees we must add, if at — o„ degrees 
 we must subtract, %k mgms. from ji. 
 
 Absolute Weighing. 
 Absolute precision-weighing in the chemical 
 laboratory hardly occurs otherwise than in this 
 sense that we may have to determine the weight 
 of an object in terms of an arbitrary (but for 
 this occasion absolute) standard. For this we 
 have two methods. 
 
 I. The Metlwd of Substitution. The object 
 is placed in one pan of the balance, and coun- 
 terpoised exactly by some suitable tare placed 
 in the other. We then take off the object and 
 put on standard weights until equilibrium is 
 again established. If the method of vibration 
 be used, the immediate result is the proof that 
 the constant tare was balanced by (1) x grams 
 of object plus 5 grams, and (2) by ^ + 82 grams 
 of standards. Whence a; = jj + S^ — 8,. 
 
 II. The Method of Beversicm. After having 
 brought the balance very nearly into equilibrium, 
 we ascertain the number of grams which have 
 to be placed in the opposite pan to exactly 
 
 q2 
 
223 
 
 ANALYSIS. 
 
 balance the object, once with the object on the 
 left, and once with the object on the right, side. 
 Assuming, for greater generality, that the right 
 pan was from the first too heavy by S grams, we 
 have 
 
 I. a;Z'= (p"+ S) V< by the first trial. 
 II. (a; + 8) l"=p'V by the second trial. 
 
 Assuming for a moment that V = 1" (as we 
 always may if x is small), we obviously have 
 2a; + S =p' +y + S ; or a; = J (p' +p"). 
 
 We will now drop this assumption, but as- 
 sume that B is BO small that the balance cannot 
 distinguish between 8Z' and St'; then we may 
 write as 
 
 I. {x-S)V=p"l". 
 II. (a;+5)Z"=2)T. 
 Whence, by multiplication, 
 yy = (a;_S)(a! + 5) = 
 
 It is always possible to make a guess at the 
 maximum value which -- could possibly have ; 
 
 supposing 5 = ± O'OOl grm. and x (i.e. p' or p") = 
 about 10 grms. S''j-a!^ = l-=-10' and can be neg- 
 lected. In practice we tate care not to allow S 
 to assume a greater relati ve value, and compute 
 hj x^=p'p' or x='/p'p', for which expression 
 we may substitute J ip'+p"), if p' and^)" differ 
 by less than, say, p mgms. 
 
 On Sets of Weights. 
 
 A set of weights to be fully on a par with a 
 given balance must be so exactly adjusted that 
 no combination of the several pieces which can 
 ever occur is wrong by more than the inherent 
 error ' e' (v. supra) of the instrument. This 
 means that chemical weights, to be properly ad- 
 justed, require a balance of a very high order. 
 But even the most perfectly adjusted set is of 
 no permanent value unless the substance that 
 it is made of offers a sufficient guarantee for 
 constancy of mass. Of all available materials, 
 rook-crystal comes nearest perfection, but it is 
 difficult to work and bring into a handy shape. 
 Of metals, Mr. George Matthey's ten per cent, 
 iridio-platinum is the best; it is absolutely 
 proof against even acid fumes, and sufficiently 
 hard to be proof against abrasion by reasonable 
 usage. Next after it comes 'hard' platinum 
 (the slightly iridiferous metal of which crucibles 
 are generally made) ; pure platinum is too soft. 
 Brass, bronze, German silver, and other cheap 
 metals are mere apologies for what ought to be 
 used ; yet these are used (in a sense unavoid- 
 ably) for making the larger pieces in sets for 
 every-day use. Gilding affords no protection 
 against atmospheric influences, unless the noble 
 metal is laid on thickly; a good lacquer is better 
 than the film of gold which is customarily put 
 on by electrolysis. 
 
 In constructing a set of chemical weights, 
 we might choose our own unit, but whatever 
 unit we might,fct,upon, any other mode of sub- 
 division or inuiltiplication than the decimal 
 mode would Wabsurd ; and there is no reason 
 why we shbtild not adopt some legally fixed and 
 universally obtainable unit as our unit. The 
 gram is used by chemist's all over the world, 
 almost to the exclusion of any other unit. 
 
 Sets of weights exact enough for all practical 
 purposes can be had in commerce. Whoever 
 may be the maker, a set of weights should not 
 be used without having first been tested and 
 found correct, at least in a relative sense. To 
 show how the errors in a given set can be deter- 
 mined, let us assume for a while our set comprised 
 only the pieces (1)„, (1), (2), (2)„ (6), (10) grams, 
 and adopt these bracketed numbers as symbols for 
 the unknown true weights. As a unit for the 
 errors to be determined, we will adopt the 1 mil- 
 ligram as determined by a given rider of 10 mgm. 
 weight ; the (1)„ shall serve as our provisional 
 unit for the values (1) (2) (10). To determine 
 
 (1) we compare it with (1)„ by the method of 
 substitution or reversal, and note down the dif- 
 ference between the two in terms of ' the milli- 
 gram,' as determined by the method of vibra- 
 tion. We then compare (1)„ + (1) with (2) ; then 
 
 (2) with (2),, &a., &o., to establish the following 
 equations : 
 
 (1) =(l)o + 'i mgms. 
 
 (2 =(l„+(l) + 5,. 
 2 , = (2) +S',. 
 (5) =(2) +(2), + (l)„+S.. „ 
 
 Computed. 
 (l)o + A, mgs. 
 2x(l)o + A, „ 
 2x(l„ + A'j „ 
 
 1) =(1)„ + S, . . 
 
 2) =2x(l)„-^S, + S, 
 2U2m„ + S,-hS, + 8', 
 
 (5) = 5 (1)„ + 2S, + 28, + 8'j + 8^5 x (1)„ + A, 
 (10) = 10 X (1)„ + &c. . 10 X (1)„ + A,; 
 
 To know what the values n x (1)„ really are 
 in terms of an adopted gram (say the true 
 gram) we must compare one of the pieces, or 
 a combination of some or all, directly with the 
 corresponding standard weight. Supposing this 
 had been done with the 10 gram piece, and this 
 piece had been found free of error, we have 
 10 X (l)i, + A,„mg. = 10 g.(meaning 10 true grams) 
 
 TO --^^.-f^'^SB- 
 
 and by substituting this value for (!)„ in the 
 expressions n x (l), + A„ we obtain the values of 
 all the six pieces in the form 
 
 (N) = Ng.-Fa!mgm.; 
 but our ' mgm.' is strictly speaking an arbitrary 
 unit ; we have no right, for instance, to say 
 
 (5) = 5g. + i^g. 
 
 What the true gram-value of the rider is can 
 only be found by joining on to our gram set 
 a set of deci- and centi-grams comprising that 
 rider, and determining their values by establish- 
 ing the equation : 
 
 ■•Wo Tn = lg. 
 
 •Oil = (rider) + 8„ 
 
 (rider) + ('01) + Sj, &c. up to 
 !)„■ = (0-5) + (0-2) + (0-2), + (0-1) &o. 
 and thus finding out the value of the rider in 
 terms of g. But in practice the rider as a 
 rule does not differ mu?h from 'Olg., and this 
 part of the work is Uot necessary for the sake o"^ 
 the calculation of the errors, the less so as a 
 great value in any of these would simply condemn 
 that piece. 
 
 The above method is always used when we 
 test a set of weights with ihe view of seeing how 
 it falls in with the rest of the sets in the labo- 
 ratory, which in the aggregate form our set fo« 
 
ANAI.YSIS. 
 
 229 
 
 general purposes. It the set is meant to be used 
 by itself — if, for instance, we test a set from 50 
 grms. down to 1 centigr. with the view of using 
 it for our analyses — it is better not to refer to 
 any external standard at all, but to an imaginary 
 unit so chosen that the sum total of the errors 
 becomes nil, i.e., to choose as unit ^ of the 
 actual weight of all the ' 100 grams ' which the 50 
 gram set represents in toto. If one or more of 
 the pieces come out with relatively large errors, 
 the unit is re-adjusted so that it suits only the 
 good pieces, the errors are re-calculated, and 
 the two rejected pieces either replaced by new 
 ones, or re-adjusted. According to the writer's 
 experience, we must be satisfied if the errors of 
 the individual pieces are brought down to values 
 varying from very little to about ± O-Ol mgm. 
 
 Seduction to the Vacuum. 
 All weighings executed in air are liable to 
 an obvious correction. Supposing an object 
 occupying v c.c. is balanced in air by p grams 
 of standards occupying v o.o. ; if the balance 
 were transferred to a vacuum, the side of the 
 greater v (in our case the object side) would 
 become heavier than the other by (v— «) 8 grms. 
 where 8 is the weight of one c.c. of air at the 
 time and place. As p is a close approximation 
 to the true weight, the volume of the object in 
 CCS can be put down as p-i-B, that of the 
 standards of course is pH-s,, where s and s,, 
 are the respective specific gravities which prac- 
 tically need not be reduced to water at 4°. The 
 correction to be applied to p is 
 
 K^i)• 
 
 8 = 0-46464 
 
 273 + t 
 
 (mgrns.), 
 
 where b is the height of the barometer in mm. 
 reduced to 0°C., and t is the temperature ; the 
 constant is calculated from Begnault's weight 
 of 1 litre of air of 0° and 760 mm. at London. 
 
 For i = 15°, and b = 760 mms., 8=1-22615, 
 which number, at stations where b is habitually 
 near 760, if the highest precision is not aimed 
 at, may often be taken as holding for air gene- 
 rally. 
 
 Standard weights for absolute weighings (in 
 true grams) ought to be adjusted for the vacuum ; 
 hence, if the minor weights are of platinum and 
 the larger ones of brass, the brass 1 grm. should 
 appear lighter than its equivalent in platinum 
 decigrams in air. But sets of this order had 
 better be made of one metal. 
 
 For a series of relative weighings, the 
 buoyancy of the weight-standards in air may be 
 neglected, because we are at liberty to take as 
 our unit the weight of the 1 grm. piece in air of 
 the average density prevailing during the progress 
 of the experiments. That this unit is strictly 
 speaking variable is of no practical significance. 
 
 The vacuum-correction for any single weigh- 
 ing involved in an analysis amounts as a rule 
 to more than we should care to neglect ; yet it 
 may be neglected in most cases, because the 
 weight to be determined is only one term of a 
 ratio, whose other term is faulty in the same 
 sense. Suppose we have determined two 
 weights, Pt and p^t *nd we want the correct value 
 X of the ratio of which 2>, : p, is only an 
 
 approximation. If the reciprocals of the specifio 
 gravity are s,~' and Sj"' respectively, we have 
 
 p^ (1+ S.s,-') . 
 p, (1 -I- S,sr') • 
 or as a sufficient approximation 
 
 x=?i. (1 -^ 8,8,-' - S^V')- 
 Pi 
 And it a, does not differ much from Sj (as 8, 
 and Sj are always nearly the same) the bracketed 
 factor may come close to unity although neither 
 of the two terms s^'S could be neglected if it 
 stood by itself. Here, as everywhere in experi- 
 mental science, the golden rule is neither to 
 strain at the gnat nor to swallow the camel. 
 
 Weighing of Qases. 
 
 For the weighing of a gas, we have in general 
 three methods. 
 
 (1) If the gas to be weighed is a product 
 formed in a reaction between solids or liquids, 
 we may identify its weight with the loss of 
 weight suffered by the reagents during the 
 reaction. 
 
 (2) We may collect the gas in a evacuated 
 tared balloon, and weigh it like anything else. 
 In this case it is expedient to tare the flask 
 with another flask of the same displacement 
 and nearly the same weight, so that only a few 
 grams need be put on to establish equilibrium. 
 (Begnault's method). The vacuum-correction 
 is then out of court. 
 
 (3) We may measure the gas by volume at 
 a known temperature, t, and pressure, p, and 
 calculate the weight from the volume. 
 
 If the gas to be weighed is a product of a re- 
 action carried out quantitatively, one way of mea- 
 suring it is to construct the apparatus so that 
 the vessel in which the reaction goes on and the 
 gas-measurer have a common atmosphere, and 
 to measure the gas-volume as an increase in 
 the total atmosphere of the apparatus (gas- 
 volumetric method). According to Eegnault, 
 1 lit. of oxygen at 0° and 760 mm. of mercury 
 of 0°C., weighs 1-42982 grams. Hence by an 
 easy computation, based on Avogadro's law, we 
 have for the weight of 1 litre of a given species 
 of gas of the molecular weight m (o = 16) 
 
 D = 0-032089 - 
 
 -grams 
 
 (273 + t) 2 ' 
 where p means the dry pressure in mm. 
 
 If the gas is moist, the vapour-pressure ot 
 steam at t° must be deducted from the observed 
 pressure to find the d of the formula. The 
 constant, strictly speaking, holds only for places 
 where gravity is the same as it is at 45° lati- 
 tude, and sea-level. 
 In Paris, | London, | Berlin, | Glasgow, 
 it must be multiplied by 
 1-000333, I 1-000583, | 1-000663, | 1-000956. 
 
 Indirect Methods of Mass Measurement. 
 
 I. Physical Methods. 
 
 The nature of these is best explained by a 
 general example. In a given aqueous solution 
 of sulphuric acid, sugar, salt, &c., &c., the 
 specific gravity at t°, the refractive index, the 
 power of turning the plane of polarised light 
 (if any), &o., bear each a fixed relation to tha 
 
230 
 
 ANALYSIS. 
 
 percentage of substance (or the weight of 
 substance_ per litre) in the solution, which 
 relation is susceptible of translation into a 
 formula p =f (physical property), or a corre- 
 sponding curve, and by means of either of tabu- 
 lation. Hence, supposing the function to have 
 been determined by standard experiments, p in 
 a given case can be calculated (virtually or 
 actually) from the value of the respective 
 physical property. In practice we must of 
 course try to establish conditions under which 
 the change in the specific gravity, &c., &c., 
 corresponding to the passing from p to, say, 
 (I'Ol) p, assumes a sufficiently great value. 
 
 The popular method for determining the 
 strength of aqueous oil of vitriol, &o., by means 
 of a hydrometer may be referred to as an 
 example. The customary method of deducing 
 the percentage of sugar in a syrup from the 
 angle through which a column of given length 
 turns the plane of polarised light is another. 
 
 II. Chemical Methods. 
 
 These, being all founded upon our knowledge 
 of the quantitative laws of certain reactions, are 
 methods for the indirect weighing of radicles 
 rather than of substances. Scientifically one 
 might arrange them according to their degree 
 of directness. If we do so, the following two 
 claim precedence before any of the rest. 
 
 (1.) The direct gravimetric method. An un- 
 known weight of this or that radicle is deter- 
 mined by separating it out exhaustively, by itself 
 or as part of a compound of known composition, 
 and weighing the product either directly on the 
 balance, or perhaps indirectly by gasometrio 
 measurement. 
 
 (2.) The method of titration. An unknown 
 weight of radicle is deduced from the quantity 
 of reagent necessary and sufficient to cause it to 
 undergo a certain definite change of combination ; 
 the quantity of reagent being ascertained syn- 
 thetically, i.e. by direct trial. 
 
 These two methods we will designate as 
 ' direct ' methods in opposition to the following 
 'indirect ' methods. 
 
 (3.) The method of substitution. Instead of 
 determining a radicle k, we substitute for it an 
 equivalent of some other radicle (or substance) 
 b' ; we determine k' by method I. or II., and from 
 it calculate B. Thus, to determine an unknown 
 weight of free chlorine, x CI2 mgms., we substitute 
 ailjmgms.bymeans of the reaction CI2 + 2KIAq = 
 2KClAq + l2Aq, and determine the iodine. In 
 some cases we effect a serins of substitutions 
 (b' for B ; e" for b' ; e'" for b", &o.), and deter- 
 mine only the ultimate substitute. Thus, to deter- 
 mine X CrOj, we substitute first x x 3C1, then for 
 this we substitute x x 31, and by ascertaining the 
 value a; X 31 we find x x CrOj. 
 
 (4.) The residue-method. The body contain- 
 ing the radicle is subjected to a definite chemical 
 change by means of a known (excessive) weight 
 of reagent, and the excess of reagent left is 
 determined. 
 
 (5.) Methods founded upon the numerical 
 difference between formulce-values : — We pass at 
 once to examples : — 
 
 (o.) To analyse a mixture of the compounds 
 AgCl and AgBr, we expose a known weight to 
 the action of dry ohlorine until all the AgBr has 
 
 = I, grma 
 
 become AgCl, and determine the decrease ol 
 weight involved. From the obvious equation of 
 the reaction, we see that every Br-Cl gram of 
 loss of weight corresponds to Br grams of bromine, 
 or AgBr grams of bromide of silver. 
 
 (6.) To determine the weight of real sul- 
 phuric acid contained in a given quantity of an 
 aqueous acid, we evaporate with a known (ex- 
 cessive) weight of anhydrous carbonate of soda, 
 and weigh the residue (Thorpe). As 
 a; Na^CO, + NafiO, + H^SO, = 
 CO2 + H^O + Na^SO, + ffiNa^COs, every (SO, - CO^) 
 grams of increase of weight indicate SOj grama 
 of sulphur trioxide. 
 
 (c.) To analyse a mixture of the sulphates ol 
 sodium and lithium; take p grams of the 
 mixture, ppt. all its sulphuric acid with barium 
 chloride, and weigh the barium sulphate. 
 1 grm. of the sodium salt gives BaSOj _^ 
 
 Na^SO, * 
 
 1 grm. of the lithium salt gives BaSO, 
 Li^SO, 
 
 of barium sulphate. Hence if c grms of pp. 
 were obtained we have (from x grms of sodium 
 sulphate, and y of lithium sulphate) 
 xxs+yxl=c 
 x + y=p. 
 Whence x and y are easily calculated. 
 
 Many other examples might be quoted. 
 
 We will now pass to 
 
 The Operations involved in quantitative 
 determinations by chemical methods. But 
 first let us say a few words about a necessary 
 preliminary to any quantitative analysis, namely, 
 the preparation of the sample. This problem 
 assumes perhaps its most difficult form if the 
 thing to be analysed is a large mass of im- 
 perfectly homogeneous matter, say, a cargo of 
 copper ore. In this case the analysis must of 
 course be preceded by the preparation of a 
 sample, which, although it may amount to only 
 a few pounds, yet can be assumed with a suffi- 
 cient degree of probability to have the composi- 
 tion of the whole heap. And supposing even a 
 homogeneous sample to have been prepared for 
 the analyst, a mere assay (of the copper in our 
 case) would be of no use unless accompanied by 
 determinations of the moisture in, a the ore as it 
 lies, and b the small ultimate sample which goes 
 to the balance. An impure specimen of a named 
 chemical species to be rendered fit for the 
 analysis of the species must first be purified, 
 unless we prefer to determine the impurities, 
 and allow for them in the calculation. 
 
 In now passing to our subject, we will give 
 the first place to the operations involved in 
 those 
 
 I. Assays by igneous operations, 
 
 which are so extensively employed in practical 
 metallurgy. These, however, are quite a speciality 
 which is almost entirely confined to metallurgical 
 laboratories. Suffice it, therefore, to say that 
 these assays, as the name indicates, are, at least 
 by original intention, processes of metal-smelting 
 carried out tentatively on a small scale. The 
 metal is separated out as a regulus either of the 
 metal itself or of some definite arsenide, and in 
 either form is weighed directly on the balance- 
 pan. 
 
ANALYSIS. 
 
 231 
 
 H. Qtiantitativa expulsion of volatile 
 components by exposure of the 
 substance to regulated tempera- 
 tures. 
 
 Under this heading fall most of our methods 
 for the determination of water, given in com- 
 bination with non-volatile residues. Water thus 
 combined, can, as a rule, be driven out with or 
 without the help of a dry atmosphere, by pro- 
 longed exposure of the substance to a suitable 
 temperature, and, if other changes are known 
 not to take place, the weight of the water ex- 
 pelled is the loss of weight involved in the drying 
 process. 
 
 If the residue, while giving up its water, takes 
 up oxygen or suffers some other change involv- 
 ing change of weight, the water must be expelled 
 in an apparatus so constructed that the steam 
 can be purified (if necessary) and collected with- 
 out loss by absorption in a weighed U-tube 
 filled with chloride of calcium, or pumice 
 moistened with sulphuric acid, and determined 
 as an increase of weight of the absorption 
 apparatus. We have no means of discriminating 
 experimentally between water present as such 
 (moisture) and water present in chemical com- 
 bination ; ' nor can we discriminate analytically 
 between the difEerent states of combination 
 which we distinguish in our formulae. All the 
 analyst can do (after removal of what there 
 may be of palpably free water by mechanical 
 means) is to try, successively, exposure to (1) 
 ordinary ' dry ' air ; (2) artificially dried air, or a 
 dry vacuum ; (3) a graduated series of higher 
 temperatures, such as 100%- 120°, 150°, 200°, in 
 a hot air chamber ; (4) a red or perhaps a white 
 heat ; and to report the several losses of weight, 
 taking care of course to apply each temperature 
 again and again, until the weight of the residue 
 (or of the calcium chloride tube) has become 
 constant. 
 
 From hydrates undecomposable by mere 
 heating, the water must be expelled by suitable 
 reagents. Basic hydrates, like caustic potash, 
 can be dehydrated (quantitatively) by fusion with 
 excess of anhydrous bichromate of potash ; 
 many hydrated acids, by evaporation of their 
 solutions vrith a known excessive weight of oxide 
 of lead, and weighing the dried residue. The 
 writer directs attention to the applicability of 
 tri-sodio phosphate as a weighable form of Na^O 
 for the latter purpose. 
 
 IIL Combustions in glass tubes, v. 
 AsMjYSIS, Oeqahic. 
 
 IV. Carius' general method of ultimate 
 organic analysis, v. AnaiiYsis, Oeoauio. 
 
 V. Oas evolutions. 
 
 We here refer to a class of methods in which 
 the thing to be determined is measured by the 
 weight of a gas evolved in a wet- way reaction 
 of the substance to be analysed. The gas 
 evolved is weighed as loss, or after absorption 
 
 ' According to tlie current notions on dissociation, a 
 current of (originally dry) air which has passed oyer a 
 sufficient column of p^tially dehydrated salt, should take 
 away the free water from a given specimen of moUt salt of 
 the same kind at the same temperature. Hence an obvious 
 (theoretical) method for recognising free water as suoh. 
 
 by a suitable absorbent, or is measured (anij 
 thus indirectly weighed) gasometrioally {v. supra). 
 
 VI. Electrolysis, 
 
 Solutions of many heavy metallic salts, when 
 subjected to a galvanic current under suitable 
 conditions, are fully decomposed, in the sense 
 that all the metal separates out as such on the 
 negative electrode. By properly regulating the 
 strength of the current and the composition of 
 the liquid, it is possible, in many cases, to 
 cause the whole of the metallic pp. to assume 
 the form of a coherent, truly metallic, deposit, 
 so that, if a platinum electrode be used, the 
 metal can be determined as an increase of weight 
 of the latter. The method, however, is not as 
 easy as it is obvious ; and is in general use only 
 for two metals, namely copper (Luckow'a 
 method), and nickel. Classen' haa tried, not 
 without success, to extend the method to many 
 other heavy metals ; but his processes have 
 failed so far to become popular. 
 
 VII. Gravimetric Precipitation. 
 
 Our heading refers to the very large number 
 of cases in which we determine a component of 
 a solution by separating it out in an insoluble 
 form, and weighing the pp. or converting it into 
 another body and weighing that. With the pre- 
 liminary separations that may be necessary we 
 can have nothing to do here ; we assume that the 
 ppn. has been efieoted exhaustively, and that 
 the pp. is (in the sense of the method) free from 
 foreign components. In this case the next thing; 
 to be done of course is to separate the pp. com- 
 pletely from the mother-liquor. In some cases, 
 (for instance in the case of the haloid salts of' 
 silver, and of metallic gold ppd. by ferrous salt), 
 this can be done by deoantation ; but as a rule- 
 it is necessary to resort to filtration. For thia 
 operation the first requisite is a good funnel,, 
 and good filter-paper. The funnel should be a. 
 smooth cone of exactly 60° aperture, so that a. 
 filter folded in quarto fits it exactly. The best 
 filter-paper for general purposes is that Swedish 
 paper known as Muntkell's; only it filters some- 
 what slowly, and in many cases, therefore, papers 
 of looser texture are preferable. Filters, which, 
 having been washed with hydrofluoric and 
 hydrochloric acids, leave almost no ash on in- 
 cineration. In conducting a filtration, the 
 following rules should be observed : 
 
 1. Before starting the filtration, allow the 
 pp. to settle completely ; then decant ofl the 
 liquor on to the filter, allowing as little of the 
 pp. as possible to go on to the paper.— 2. The 
 same rule holds for the first stages of the wash- 
 ing process ; the bulk of the pp. should go on to 
 the filter only after almost aU the dissolved 
 matter has been washed away. — 3. The wash- 
 liquor should be employed in small instalments, 
 and each instalment be allowed to drain off, 
 before the next one comes on. — 4. The washing 
 must be continued until the purity of the last 
 runnings is proved by direct testing. No calcu- 
 lation of the attenuation reached can be rehed 
 on impHcitly, although it is valuable for pre- 
 liminary guidance, and may be the only method 
 
 ■ Classen ; Quanlilttliiie Analyte durch Electrolyse. [Sad 
 ed. Berlin, 1386.] 
 
233 
 
 ANALYSIS. 
 
 available.— 5. The filter should fit the funnel 
 closely J it should be smaller than the funnel, 
 and not much larger than is necessary for the 
 convenient aooommodation of the pp. 
 
 Many pps. run through the paper as soon 
 as the wash-water becomes nearly pure ; bi- 
 sulphide of tin exhibits this property in a marked 
 degree. Addition of some suitable salt (sal-am- 
 moniac, acetate of ammonia, &o.) to the wash- 
 water often helps one over this difficulty. 
 
 In the case of slimy or gelatinous pps. 
 {e.g. hydroxides of silicon, aluminium, and chro- 
 mium) Bunsen's method of quick filtration is 
 employed. It consists in this, that the funnel 
 is made to communicate, by its stem, with a 
 vessel in which a partial vacuum of adequate 
 strength is maintained by means of an aspi- 
 rator (a Sprengel pump wrought with water, 
 or equivalent arrangement). To protect the 
 filter from being torn by the pressure of the 
 atmosphere, its open end is supported by a small 
 cone of platinum foil, resting on the bottom of 
 the funnel. In regard to the operations subse- 
 quent to filtration and washing, pps. may be 
 classified as follows : — 
 
 A. Such as stand calcination ina plati- 
 num or porcelain crucible, and when thus treated 
 assume a definite composition. In this case the 
 general modus operandi is as follows : the pp. is 
 dried in the funnel ; it is then detached as com- 
 pletely as possible from the paper, and put into 
 the tared crucible. The filter, with adhering 
 particles of pp. is folded up into a narrow strip, 
 and this is rolled up tightly into a parcel, so 
 that the part stained with the pp. is in the core. 
 A platinum wire is then wound round two or 
 three times, and the parcel is kindled in a gas 
 flame and allowed to burn, the surplus wire 
 serving as a handle. After the combustion has 
 gone as far as it will spontaneously, the residual 
 charcoal is burned away by applying the outer 
 portion of the fiame of a Buuseu. The ash is 
 'dropped into the crucible and calcined along 
 with the pp. In some cases, as for instance in 
 that of alumina, it is better not to detach the 
 pp. from the filter, but simply to fold up the pp. 
 in the filter, and heat the whole in a platinum 
 crucible. Any deposit of charcoal formed on 
 the lid or crucible sides is easily removed by 
 heating the respective part while a shield of 
 platinum foil is stretched over the deposit. The 
 charcoal vanishes almost instantaneously. The 
 weight of the filter-ash must of course be ascer- 
 tained by a blank experiment, and allowed for. 
 The correction (cateris paribus) is proportional 
 to the superficial area of the filter ; i.e. ash- 
 weight = cr', where c is a constant which can be 
 determined once for all. 
 
 It is to be observed, however, that even with 
 the same filter-paper, c depends on the nature 
 of the liquid which passed through the filter. 
 It is less for dilute mineral acid, for instance, 
 than for pure water, or salt solutions followed 
 by water. 
 
 B. Precipitates which do not stand 
 calcination; but assume a definite composi- 
 tion when dried at a suitable lower temperature, 
 say at 100° or 120°C. Such pps. are collected 
 on filters (previously dried at the respective 
 temperatures) and weighed in the filters. As 
 filter-paper is hygroscopic, the empty filter, and 
 
 the filter with pp., must be weighed between a 
 couple of closely fitting watch-glasses held 
 together by a suitable clip. 
 
 0. Precipitates which demand some 
 supplementary chemical treatment to 
 become fit for the balance. In regard to 
 these it is difficult to make general statements ; 
 suffice it to say that certain metallic sulphides 
 assume a definite composition when strongly 
 heated (repeatedly, and until constant in weight) 
 with sulphur in hydrogen gas. The sulphides 
 of copper, manganese, zinc, lead, may be quoted 
 as examples. The resulting definite sulphides 
 are CujS, MnS, ZnS, PbS, respectively. 
 
 GAS ANALYSIS. 
 
 A large supply of homogeneous gas may be 
 dealt with, analytically, in a variety of ways. 
 With a small gas-sample given for analysis only 
 one mode of treatment could be— or at any rate 
 ever is — thought of. We must collect our gas 
 over mercury, or some other suitable liquid, and 
 learn what we can concerning it by applying 
 physical or chemical reactions, involving changes 
 of gas- volume ; we must measure the gas volumes 
 involved as the only practicable mode of defining 
 the respective masses. 
 
 Friuciples of volumetric gasometry. To 
 measure a given quantity of gas means to deter- 
 mine its volume, v, and its pressure, p, at a 
 definite temperature, t. In any fluid body of 
 known nature the three quantities conjointly 
 define the mass; yet the method is confined 
 to gases, because in these only is the evidence 
 afforded by the three numbers condensible into 
 one numerical statement by mere calculation. 
 
 Practical gasometry knows of no pressure 
 greater than two atmospheres (indeed pressures 
 above one atmosphere are exceptional) ; and of 
 no temperature below 0°C. 
 
 Within this range of conditions the law of 
 interdependence between volume, temperature, 
 and pressure, in all gases is in approximate 
 accordance — in the so-called permanent gases 
 it is in perfect accordance — with the equation 
 
 VP 
 — = 9 (1) 
 
 where t may be defined as t = 273 -^ i. q is a con- 
 stant which depends only on the nature of the 
 gas and its mass, and consequently, in reference 
 to any named species, measures the quantity. 
 
 Condensible gases and vapours deviate from 
 the law embodied in eq. (1) to a greater or less 
 extent, but always in this sense that the true 
 relations are expressible by an equation of the 
 form 
 
 T (! + ')=« (2) 
 
 where e is an inherently positive number 
 which is a function of t and p, to the 
 effect that, for any given species, e is the 
 less the further the pressure and temperature 
 remove the gas from the state of saturated vapour. 
 Gasometrically speaking e is mainly a function 
 of temperature which runs pretty much like 
 
 e = const.— ; not by any means exactly so, but 
 
 we are safe in saying that for every gas-species 
 there is a certain temperature t„ above which 
 this species is, as the phrase goes, a ' perfeot 
 
ANALYSIS. 
 
 2SS 
 
 gas,' in at least this sense that e is less than 
 the unavoidable error involved in the experi- 
 mental determination of pv-m by the customary 
 instruments. In this sense our equation (1) is 
 true for all kinds of gas or vapour -without 
 exception. 
 
 The constant q is obviously susceptible of 
 a number of definitions. One definition is to 
 call it the volume which the gas assumes when 
 T = 1° and p = 1 (say 1mm.), or rather the volume 
 which the gas would assume if it were a perfect 
 gas down to t = 1 or t=— 272°. To eliminate 
 this fiction, let us view v as a function, not of p 
 
 T 
 
 and T, but of -, thus : 
 
 '=«(i)' 
 
 and, taking ' disgregation ' as a name for this 
 ratio T : p, define q as that volume which the 
 gas assumes whenever the disgregation is unity 
 through p being equal to i numerically. If, for 
 instance, 
 
 T = l° 273° 373° 500°0. &o. 
 then p = l 278 373 500 mm. &o. 
 
 In this manner it is always easy to find for q a 
 real significance, q, however, has two denomina- 
 tions. Obviously 
 
 T 
 
 !' = «:?. 
 hence q may be called the particular pressure 
 which the gas assumes whenever t = v ; i.e. for 
 T = l° and v=l unit; t = 500° and v = 500, &c. 
 
 For the purely comparative measurement of 
 two or more gas quantities, only one of the three 
 variables need actually be measured. 
 
 Assuming the Qs for the gases i, n, ni...to 
 be q' q" q'", &o., we may (1) keep t and p at 
 constant (though perhaps unknown) values 
 and measure the volumes 
 
 y y" y"' ^c_ which are 
 
 q'x q"T q'"T 
 
 — &o. 
 
 p p p 
 
 The constant factor disappears in the ratios. 
 
 This used to be, at least by intention, the method 
 
 of comparative gasometry. 
 
 (2) We may keep T and v constant and 
 measure the pressures p' p" p'" which are 
 
 T 
 
 «"? 
 
 and consequently again measure the qs (Eeg- 
 nault's method). 
 
 (3) We may allow t and p to vary, but keep 
 their ratio, the disgregation, constant, and mea- 
 sure the volumes, i.e. substitute for the qs 
 
 T 
 
 (q' q" q'"...) X a constant - 
 
 (Doy^re's method). 
 
 But q has an important chemical significance. 
 A glance at eq. (1) shows that the specific 
 gravity of a gas, meaning the number of times 
 its weight is greater than that of the same 
 volume of some standard gas of the same dis- 
 gregation, is independent of t and p. As stated 
 by Avogadro, and since proved by numerous 
 experiments, we have for any set of gas-species 
 
 s':s":s"'... = m':m":m"' 
 
 or quite generally 
 
 s = const. M . . • • . (8) 
 
 where M is the mol. weight. 
 
 
 q"'7&c. 
 
 Hence supposing, at a given disgregation, 
 unit volume of standard gas weighs b units, then 
 unit vol. of another gas of the mol. w., u, 
 
 weighs B — , where m„ refers to the standard gas. 
 
 M„ 
 
 Hence unit-volume of any gas , if measured at that 
 disgregation, contains —xm units of weight of 
 
 Mo 
 
 its substance ; hence equal volumes of any two 
 gases, if measured at the same disgregation, 
 contain the same number of molecules, where 
 ' molecule ' may have the usual meaning given 
 to this term. Hence our constant q, or any of its 
 substitutes as given above under (1) (2) and (3), 
 in a relative sense counts the molecules of the 
 respective gas. 
 
 Eq. (1) tells us nothing about the relation 
 between the volume v of a gas-mixture, and the 
 volumes «' v" v"'...ot its components; but we 
 kuow.by direct experience, that v = «' -I- w" + 1)'". . . ; ' 
 hence Avogadro's law holds for mixed as well as 
 for homogeneous gases ; and, independently of 
 it, we have 
 
 q' + q" + q"'... = Q (4) 
 
 and at any constant value of 
 
 V-l-T 
 
 p'+p"+p"'...=-B (5) 
 
 (where the small letters refer to the components 
 and the large ones to the mixture). And so 
 quite generally 
 
 g:q = t>:v=2):p= (number of mols.inthe 
 component): (number of mols. in the mix- 
 ture) (6) 
 
 Hence our customary mode of stating the com- 
 position of a gas-mixture is susceptible of three 
 readings. Instead of saying (1) 100 volumes of 
 air contain 21 vol. of oxygen and 79 of nitrogen; 
 we may say (2) the partial pressure of the oxy- 
 gen is 21 p.c. and that of the nitrogen 79 p.c. of 
 the total pressure of the air ; or (3) every n x 100 
 mols. of air contain to x 21 mols. of oxygen and 
 M X 79 of nitrogen. 
 
 In the more easily condensible gases,' the 
 number € (which might be called the measure of 
 gaseous imperfection) assumes appreciable values 
 at the ordinary temperature ; yet in the ordinary 
 practice of gas analysis even these gases are 
 customarily being measured at, or near, the 
 temperature of the laboratory. To give an idea 
 of the possible value of the error thus neglected 
 we will take up the case of carbonic acid, 
 which, of ordinarily occurring gases, is perhaps 
 the most imperfect. 
 
 According to Amagat, carbonic acid, from 0°C. 
 upwards, expands at a greater rate than air, up 
 to about 200°, whence onward it behaves like a 
 perfect gas in reference to expansion caused by 
 changes of temperature or pressure. At 760° 
 mm. its expansion from 0° to 200° is in the ratio ^ 
 of 1 : 1-74065. Hence supposing we find for a 
 quantity of carbonic acid v = v„ for T = 273 and 
 p = 760, we have for the constant q : — 
 
 (1) By the ordinary routine mode of caloula- 
 
 tion, 4.6. by eq. (1) ; q' = — gyg — . 
 
 ' It Is worth while to note that thia all-important pr<v 
 position has never been looked into in the Begnault- 
 fashion. 
 
 " Calculated by the writer from the coefficients of ea« 
 pansion statsd by Aisagat for B0°, 100°, 180°, and 200°. 
 
334 
 
 ANALYSIS. 
 
 (2) For the true g ; 
 
 ^«„x 1-74065x760 
 
 273 
 
 Whence (3„ = 1'004:6 q'; or in -ihe sense of our 
 equation (2), for i = 273 and p = 760 mm. 
 
 AQo=^i|^(l + 0; and 6 = 00046. . (7) 
 
 This number, or Bay 0-005, might perhaps 
 be put down as the maximum value which e 
 may assume in the customary mode of measur- 
 ing gases proper, were it not for the following 
 consideration. As a rule the gas to be measured 
 is contaminated with vapour of water, and it is 
 the Q of the dry gas that is wanted. One mode 
 of obtaining it is to remove the water by chemical 
 absorbents and to measure the dry gas ; but 
 this is a tedious process ; hence we prefer, in 
 practice, to saturate the gas completely with 
 water, to measure it in this condition, and, before 
 calculating by eq. (1), to correct the observed pres- 
 sure by deducting the maximum steam-pressure 
 at the respective temperature, as determined 
 by Magnus and by Eegnault for the vacuum, as- 
 suming the corrected value p„ = p — ir to represent 
 the pressure which the gas would exhibit at the 
 same vol. and temperature if it were dry. As 
 shown by Eegnault, this is not quite exactly 
 the case, yet if ir is small, i.e. if the temperatii/re 
 is low, the error may be neglected. A low tem- 
 perature, it is true, means a relatively great c, 
 but ir certainly, and the error in tt probably, 
 increases (with t) much faster than € decreases. 
 
 Both the authorities named give their its in 
 terms of the pressure of a column of mercury of 
 0°C. whose height equals 1 mm. Hence to be 
 able to use their numbers directly we must pro- 
 vide our eudiometers and barometer with true 
 mm.-soales. And we ought to reduce all mercury 
 columns (measured as pressures) to O^C. This, 
 however, is necessary only in the case of abso- 
 lute measurements, i.e. if we measure a gas as a 
 step towards calculating its weight ; for relative 
 measurements we may choose our units for v, t, 
 and p, at pleasure,' hence the absolute magni- 
 tude of our ' mm. ' is of no consequence. Nor is 
 it necessary to reduce the ir to what our mm. is 
 at the respective temperature, because the cor- 
 rection is practically irrelevant. 
 
 Gases like hydrochloric acid, ammonia, 
 sulphur dioxide, &a., must be measured dry — 
 for an obvious reason. 
 
 Gas-Analysis. (a) Proximate. For the 
 proximate analysis of a gas-mixture we have 
 only one direct method. After having measured 
 off a convenient sample, we withdraw the several 
 components (singly or in groups), by the succes- 
 sive apphcation of appropriate chemical absor- 
 bents, as pressureless solids or liquids, and, 
 after each absorption, we measure the gas-residue 
 left. Supposing the sample measures v units at 
 T and p, and the same, minus component i, mea- 
 sures v' units at t' and p' ; we have for the sample 
 
 Q = Z£,for the residue q'=^ ; hence for the 
 T t' 
 
 percentage of i ; a= ' x 100. 
 Q 
 To show the jjossibUities of the method, we 
 
 * /.c. we may, if we choose, measure our ^s with a 
 Fahrenheit thermometer and take T ae being TK4f)9-4+/ 
 (In F. degrees). 
 
 enumerate the most important reagents and 
 state the powers of each as an absorbent. 
 
 (1) Water (as such or as Na^SO^lOHaO) 
 absorbs HCl, HBr, HI, very promptly. 
 
 (2) Solid DBY caustic potash absorbs water 
 very completely; acid gases generally more or 
 less slowly. 
 
 (3) Solid MOIST caustic potash absorbs all 
 acid gases (00^, SOj, H^S, HCl, &c.) very 
 readily. 
 
 (4) Caustic potash solution acts like (3) 
 and (1). ' 
 
 (5) Dilute sulphuric acid absorbs all alka- 
 Une gases (NH3, CH3NH2 &c.) ; besides acting as 
 
 (6) Oil of vitriol (E^SO, + ^nfi) absorbs (a) 
 water, alcohol, ether, methyl-oxide, very readily; 
 (ft) propylene and higher homologues, with a 
 fair degree of promptitude. C^H^ is absorbed 
 only on long-continued shaking (Berthelot). 
 
 (7) Sulphuric anhydride in HjSOj absorbs 
 C2H4 in addition to the gases named in (6). _ 
 
 (8) Bromine (over water in diffused daylight) 
 acts pretty much like (7) ; the excess of Br 
 vapours left is removed by means of KHOAq. 
 
 (9) Pyrogallic acid in caiistic potash ley 
 absorbs oxygen abundantly and promptly 
 (Liebig), besides acting like (4). 
 
 (10) Ouprozis chloride in hydrochloric acid 
 absorbs oxygen; also CO, CjHj, C3H, (Bertholet). 
 — Spoils the mercury. 
 
 (11) Same reagent in aqiieous ammonia acts 
 like (10), and besides absorbs certain other gases, 
 e.g. all the olefines (Berthelot). 
 
 (12) Ferrous sulphate in concentrated solu- 
 tion absorbs nitric oxide ; but hardly in the che- 
 mical sense, as the compound has a measurable 
 dissociation-pressure.' 
 
 (13) Binoxide of manganese, as compressed 
 powder, is used by Bunsen for absorbing H^S 
 and SOj.— Solution of CrOj or of KMnO, acts 
 similarly and more promptly. 
 
 (14) Ohromous sulphate in NH, and NHfil 
 solution absorbs 0,NO,C2H2,C3Hj, but does not 
 act on CO, C^Hj, or C3H5 (Berthelot). 
 
 That all gas mixtures cannot be analysed 
 by means of these 14 reagents is obvious. Un- 
 fortunately they are all group-reagents, and a 
 group when once absorbed is not susceptible 
 (practically) of further gasometrio analysis. One 
 or other of the absorbed components may be 
 determinable otherwise— thus for instance HjS 
 (absorbed in KHO) by titration with iodine— 
 but these are rare exceptions. For the analysis 
 of a gas-mixture which, with regard to chemical 
 absorbents, behaves as a whole, only two 
 methods are at our disposal ; one is to determine 
 the ultimate composition of the gas (if possible), 
 and from the results to try and arrive at the 
 proximate composition ; the other is to exa- 
 mine the gas by means of physical absorbents. 
 But to obtain definite results with these we must 
 follow the lead of Bunsen, and both contrive 
 their application and interpret the results, in 
 the light of the laws of gas-absorption. 
 
 Analysis by physical absorbents. 
 
 Imagine v volumes of a mixture of the 
 unitary gases I., II., III., . . . to be shut up 
 
 ' KO is absorbable also by the oonjoint action of an4 
 KHO solutlou, as KNO, and KNO,. 
 
ANALYSIS. 
 
 38S 
 
 in a close vessel over h volumea of water or 
 alcohol, an impervious diaphragm separating the 
 two. As soon as the diaphragm is removed, the 
 gas and liquid exchange molecules, and this goes 
 on for ever j but if a constant temperature t is 
 maintalued, a point is reached, sooner or later, 
 at which the changes of composition, exactly 
 compensate each other, so that matters are the 
 same as if the exchange had come to a stop. 
 This point of dynamical equilibrium is reached 
 almost instantaneously on violent shaking. The 
 final result is that the gas-space v is saturated 
 with the vapour of the liquid, while a quantity q 
 of each of the components of the gas is held in 
 solution by the h volumes of liquid. This quan- 
 tity qata given temperature is in (more or less 
 exact) accordance with the equation — 
 
 q^hPTT (8) 
 
 where ir means the partial pressure of the respec- 
 tive component in the residue, and jS is a con- 
 stant, which may be defined as being the value 
 which g assumes when h = l and7r= lmm.g and 
 j3 are, of course, of the same denomination ; if j 
 means mgms., ;3 means mgms. likewise. But 
 we wiU assume g to be measured by volume at 
 0° 0. (or T = 273° C.) and p = l mm., and on the 
 basis of this assumption (with Bunsen) call P 
 the ' co-efiScient of absorption.' 
 
 Our equation has been tested experimentally 
 only with water and, in a more limited sense, 
 alcohol, as a solvent ; and in reference to either, 
 it may be assumed to hold, at pressures up to 
 about 1 atm., and temperatures from 0° to 
 about 30° C, for all gases which, under the 
 circumstances, do not act chemically on, or 
 dissolve very abundantly in, the respective 
 liquid. With a given gas-species, J3, in general, 
 increases when the temperature falls, or when 
 alcohol is substituted for water. It has, in 
 general, different values for different species of 
 gas. Hence we at once see our way towards 
 distinguishing a unitary gas from a mixture. 
 Take, for instance, the case of marsh-gas CHj 
 as against a mixture of equal volumes of H^ 
 and GjHj = OH, per 1 volume. With alcohol as 
 an absorbent, the /3 of GJ3.g is far greater than 
 that for H^. Hence, if the mixture be dissolved 
 partially by alcohol, the residue will contain less 
 carbon per unit volume than ^C^ ; and similarly 
 in similar cases. 
 
 The relation between the composition of the 
 mixture operated upon and that of the un- 
 absorbed residue is easily formulated. Let m', 
 m", &o., stand for the quantities of the several 
 components present in unit volume of the 
 original gas, and let n', n", &a., have a similar 
 meaning in reference to the residue; let p stand 
 for the (dry) pressure of the original gas, and 
 p for that of the residue, then we have for any 
 one of the components g = h0{pn) ; and for the 
 vmabsorbed part of that component 
 
 and q-i-r^pn{v„ + Bh); but g-^r=PJ»^>o, hence 
 pmv„=pn{Vi, + Ph), which enables us to calculate 
 the ' n' of a named component from its ' m.' 
 For further developments we refer to Dittmar's 
 'Exercises in Quantitative Analysis,' section on 
 gas analysis (Glasgow, W. Hodge & Co.). With- 
 out mathematics it is clear that the quantity, \, 
 
 \=: 
 
 of total gas absorbed, reduced to |> ^ 1 and h = l, 
 
 M^-P) 
 hp 
 
 In the case of a unitary species \ is the cO' 
 efficient of absorption, and is consequently con- 
 stant, while, in the case of a mixture it varies 
 (in general) with h:v, i.e. with varying quantities 
 of water for the same quantity of gas started 
 with. Hence an obvious second method for 
 testing a gas for chemical oneness. 
 
 Of general methods of gas analysis, only 
 one remains to be considered. We refer to 
 the 
 
 Method of Combustion. — A method of 
 ultimate analysis which presumes that the 
 gas to be analysed is in, or by addition of 
 hydrogen or of oxygen or of either plus ful- 
 minating gas,' can be brought into, such a 
 condition, that the mixture, when fired with 
 an electric spark is resolved entirely into (in 
 general) carbonic acid, nitrogen, and water, and 
 excess of either hydrogen or oxygen as the case 
 may be. The method consists in this that a 
 measured volume of the given gas is exploded, 
 and the gas quantities involved are measured as 
 far as necessary to enable one to calculate the 
 elementary composition of the gas under opera- 
 tion, the results being regarded customarily in 
 volumes (reduced to some tacitly assumed con- 
 stant disgregation) of the respective elementary 
 substances. For uniformity's sake this system 
 is extended even to the carbon, one volume of 
 carbon being used as a phrase for the quan- 
 tity of carbon contained in two volumes of car- 
 bonic anhydride. This mode of reporting comes 
 to the same as stating the quantities of hydro- 
 gen, oxygen, &o., as multiples of the molecular 
 weights Hj, Oj, N^, and of the double atom C» 
 of carbon. In the sequel we sometimes use 
 Hj.Oa, Nj, CO2, CO, as symbols for ' 1 volume.' 
 When in a calculation we have to refer to a 
 certain (reduced) volume of carbonic acid we 
 designate it by the letter k ; in a similar sense 
 s refers to oxygen ; w to water vapour ; ^ to 
 nitrogen (' N ' is reserved for the atom) ; o to 
 contraction. The following examples explain 
 the method : 
 
 I. The gas is a mixture of hydrogen and 
 hydrocarbons ; i.e. 1 vol. = aG^t^S.^. We deter- 
 mine the following gas-quantities : 
 
 (0) The volume of the sample, as . v 
 
 (1) „ „ plus 
 added oxygen, as . . . v^ 
 
 And after firing 
 
 (2) The volume of the total product 
 
 measured cold, as . . v, 
 
 (3) The volume of the residue left after 
 
 removal of the carbonic anhy- 
 dride, as . . . . V3 _ 
 The quantity of carbonic anhydride produced 
 in the combustion is 'k' = V2— Vj, whence 
 
 The hydrogen is calculated from the ' con- 
 traction,' laeamng the difference 'o' = v, — v^, 
 thus: v, = v + s, where s stands for the added 
 oxygen. 
 
 Vj =• K -H oxygen left unburnt, which is s — k — as, 
 
 ■ The mixture H,+iO, obtained In the eleotrolysis at 
 water. 
 
2SS 
 
 ANALYSIS. 
 
 where x means the oxygen which converted the 
 hydrogen into water. Hence o = v, — V2= 
 V + 3 — [K + (s — K — a)] or = V + k; hence 
 
 a! = o-v, and i3 = H(£zl). 
 
 V 
 
 The sum a + ;3 is, of course, always greater 
 than unity unless o = 0. 
 We will assume now 
 
 II. That the gas contains (in the v units 
 taken for analysis) z volumes of free oxygen 
 and y volumes of free nitrogen beside Vj of 
 hydrocarbons ; both z and y being unknown. 
 Here we at once see that the measurements of 
 Ti, Vj, V3, do not enable us to calculate z or y. 
 But we cannot even calculate the volume x of 
 oxygen which combined with the hydrogen in the 
 'Combustion ; because from case I. we see that 
 a = c — v„, and Vj is unknown. Nor does a direct 
 'determination of the oxygen-residue Sj. in v, help 
 413, because s, is a function of c, independent of 
 a and z. We have, in fact : — 
 
 Sr = Z + S — E — k; 
 o = y — {z + y) + x; 
 
 Sr + o = a-K + v— 2/; 
 and Sr= — o + s— K + y— y. 
 
 The determination could only confirm this 
 calculation. If z is known to be = 0, or z and y 
 'Conjointly are known to be so much air, the 
 problem becomes easy of solution. 
 
 III. The gas is oC2.;8H2.702.5N2 = 1 volume ; 
 states of combination unknown. If we add to 
 "the values (for v of substance) of k and that 
 of the nitrogen in the ultimate residue (let 
 its quantity be = J|}) we have a and S at once. 
 But, (even supposing we did not care for 7), to 
 determine $ we must measure the quantity, w, 
 of steam produced in the combustion. Prom 
 
 w we have ;8=iw; and from this, and the oon- 
 
 V 
 
 traction c, we can calculate 7 thus ; let s, 
 denote the quantity of oxygen which, con- 
 jointly with the oxygen in the substance, is 
 just sufacient to burn the substance into COj, 
 H2O, and N2, and let s, be the surplus added, so 
 ■that Sr + Sj = s ; we have 
 
 T, = V'+S„ + Sr 
 V2 = j3 + g + B, 
 
 c = v-f-s„-i8-K; 
 «r, _ v,-V3 = v + s„-i3. 
 
 Now, it was obviously the oxygen sum Sj + T7 
 which produced the HjO and COj ; hence, 
 s„ + T7 = K + iw; 
 
 7 = -^(K + iw-s„). 
 
 Whenever, in a gas of unknown constitution, 
 cxygen may be present, the determination of w 
 becomes indispensable, because without it the 
 water possibly present in a gas would escape 
 us altogether ; we could not, for instance, dis- 
 'Criminate between ethylene and oxide of methyl. 
 The case which we have just been discussing 
 includes that of the analysis of any gas 7O2.8N2 
 •which is combustible by means of hydrogen. 
 Because the added hydrogen, for calculating 
 purposes, may be included in the ' v ' of our 
 formulse, to be ultimately allowed for. In 
 practice, however, the variety of proximate com- 
 positions included in the formula 7O2.8N2 is 
 very small, so that, in the case of such a gas, 
 
 we had better at once calculate the proximate 
 components (Nj, N2O, Oj &o.) directly from the 
 data of the combustion. 
 
 IV. Let us now see how far the method of 
 combustion goes as an indirect method of proxi- 
 mate analysis. Let us assume that we have to 
 deal with a gas of the nature pre-supposed in 
 case III., and that the quantities, k, c, w, jj, 
 have been determined, and none of them found 
 = 0. We also assume that we know the formula 
 
 of all the several species I., II., which can 
 
 possibly be present. To find the quantities of 
 these contained in unit-quantity of the given 
 
 gas {x' for I.; x" for II ) we might begin 
 
 by calculating the elementary composition of our 
 gas, i.e. the coefficients in the average formula 
 o02.;8H2.702.SN2 = l vol., and then express these 
 algebraically in terms of the special values a', a" 
 , p', $" &c., appertaining to the com- 
 ponents I., II , (fee, thus, 
 
 a = a'x' + a"x" + a"'x"',&a. . . I. 
 
 P^$'x' + P"x" + P"'x"',&o. . . II. 
 
 7=7'x' + 7"!b" + 7"V", &o. . . in. 
 
 8=5'a!' + S"a;"-H5"'a!"', &o. . . IV. 
 
 l = xf + x" + x"',&B. ... V. 
 
 In practice, of course, we need not calculate 
 a, /3, &o., but may at once form equations between 
 
 -K=&; io = c; -i<8 = m, &o., and the special 
 
 v V V 
 
 values k'k"..., c'c''..., n'n"..., thus — 
 
 k=k'x' + h"x",&o. . . . La. 
 
 c = c'x' + c"x", &c. ... Il.a. 
 
 w = w'x' + w"x",&o. , . . Ill.a. 
 
 n = n'x' + n"x",&o. . . . IV.o. 
 
 l = x' + x",&o. . . . V.ffl. 
 
 and solve these equations; but the former set 
 shows more clearly how far the method goes as 
 a method of proximate analysis. 
 
 From either set we at once see that if the 
 number of potential components does not exceed 
 five, we can in general calculate the quantity 
 of each in unit quantity of gas, i.e. x" x'^-.x". 
 In general we say, because obviously if one or 
 more of the co-efficients a, ;8...is==0, so many 
 equations collapse ; in the case, for instance, of 
 7 = and 5 = 0, only three equations are left. 
 And (to adhere to the example) if it should 
 happen that all the values of j8 are the same func- 
 tion of the respective values o,then equation II., 
 or, if you prefer it, equation I., is lost, and only 
 the case of two components is susceptible of a 
 solution. A similar result occurs if all the com- 
 ponents should happen to contain the same 
 number of hydrogen -atoms (or the same number 
 of carbon-atoms) per molecule. Supposing, 
 for instance, all the components were of the 
 general formula C^Hj then $ would by necessity 
 be = 3, and equation II. would be resolved into 
 3 = Sx' + Sx" + Sx"'... which is a mere repetition 
 of equation V. And similarly, if all the compo- 
 nents were di-carbon gases, equation I. would 
 become useless. 
 
 The general rule is, first of aU to find out 
 how many of the quantities k, c,n,w...in addi- 
 tion to our knowledge of the constitution of the 
 gas, we should need to calculate the oo-effioients 
 a, p... of the average formula. Supposing 4, 3, 2 
 suffice, then (in general) 3, 2, 1, (but not any 
 3, 2, 1), equations of the second set, taken along 
 with equation V..., will suffice to find the ua- 
 
ANALYSIS. 
 
 337 
 
 known (quantities a^, xf'.„ sought, piovided their 
 number does not exceed 4, 3, 2. 
 
 For examples see the writer's Tables to 
 facilitate chemical calculations (Williams & 
 Norgate). 
 
 The following table gives the values of c, k, 
 s„ w for several gases. 
 
 I. — Combustible by Oxygen, 
 
 
 e 
 
 k 
 
 
 
 '0 
 
 W 
 
 n 
 
 Hydrogen, Hj . . . . 
 
 1-5 
 
 0-5 
 
 1- 
 
 0- 
 
 Garbonio oxide, CO . . 
 
 0-5 
 
 1 
 
 0-5 
 
 0- 
 
 0- 
 
 Methyl-aldehyde, CH^O 
 
 1- 
 
 1 
 
 1- 
 
 1- 
 
 0- 
 
 Ammonia, NH3 . . . 
 
 i-as 
 
 
 
 0-75 
 
 1-5 
 
 0-5 
 
 Methylamine, OH5N . 
 
 1-75 
 
 1 
 
 2-25 
 
 2-5 
 
 0-5 
 
 Cyanogen, N^C^ . . . 
 
 0- 
 
 2 
 
 2- 
 
 0- 
 
 1- 
 
 Hydrocyanic acid, NCH 
 
 0-75 
 
 1 
 
 1-25 
 
 0-5 
 
 0-5 
 
 Marsh gas, CH4 . . . 
 
 a- 
 
 1 
 
 2- 
 
 2- 
 
 0- 
 
 Acetylene, O^Hj . . . 
 
 1-5 
 
 2 
 
 2-5 
 
 1- 
 
 0- 
 
 Ethylene, CjjH, . . . 
 
 2- 
 
 2 
 
 3- 
 
 2- 
 
 0- 
 
 Ethane, CjH, .... 
 
 a-5 
 
 2 
 
 3-5 
 
 3- 
 
 0- 
 
 Propylene, CjHj . . . 
 
 2-5 
 
 3 
 
 4-5 
 
 .S- 
 
 0- 
 
 Propane, CjH, . . . 
 
 3- 
 
 3 
 
 5- 
 
 4- 
 
 0- 
 
 Oxide of methyl, CaHjO, 
 
 2- 
 
 2 
 
 3- 
 
 3- 
 
 0- 
 
 Benzene, OJB., . . . 
 
 2-5 
 
 6 
 
 7-5 
 
 3- 
 
 0- 
 
 lvol. = C.H;j . . . . 
 
 '*! 
 
 a 
 
 "1 
 
 0-5i8 
 
 0- 
 
 n, — Combustible by Hydrogen.* 
 
 Nitrous oxide, THJO 
 Nitric oxide, NOf • 
 
 1- 
 1-5 
 
 1- 
 0-5 
 
 The Practice of Gas Analysis. 
 
 In this section we take cognisance only of 
 the chemical methods, and in regard to these 
 confine ourselves in the main to those apparatuses 
 in which mercury serves as a trapping fluid. 
 
 Taking ordinary laboratory appliances for 
 granted, all that gas analysis demands of special 
 apparatus is : a barometer, a pneumatic trough 
 vrith transparent sides, and a series of glass 
 tubes, closed at one end and open at the other, 
 and provided, virtually, with two scales, of which 
 one divides the gas capacity, and the other the 
 axis, into units of sufiioient smallness. One or 
 more of these tubes must be provided near the 
 closed end with a couple of fused-in platinum 
 wires so that a combustible gas-mixture in it 
 may be exploded by means of an electric spark. 
 The possibility of obtaining exact results by 
 means of these simple contrivances is proved 
 by the fact that all the great gasometrio work 
 of Cavendish and Gay-Lussac, which laid the 
 foundations for our present chemistry, was done 
 with apparatus like those referred to, or even 
 with apparatus of a lower order of complexity. 
 01 course to obtain exact results we must be 
 alive to all the numerous sources of error 
 involved, and eliminate them as far as possible 
 experimentally or otherwise. It is one of the 
 
 * h—hySxog&R necessary for combustion. 
 
 t Nitric oside cannot be burned with Ha alone ; it 
 requires addition of a certain proportion of N.O ; and even 
 then the combustion la irregular (Bunsen, Gat. Meth. 
 Sud Ed. pp. »6, »8). 
 
 merits of Bunsen to have done this for us, and 
 to have thus brought the old method of gas 
 analysis into a form which, on the score of pre- 
 cision at least, leaves nothing to be desired. 
 
 Bunsen's Apparatus and Methods, 
 The first requisite of exact gas analysis, Bunsen 
 says, is a special room in which the tempera- 
 ture is subject to only slight, and to no sudden, 
 variations. The ideal gas-room forms part of a 
 substantial building ; it is not warmed artifici- 
 ally nor is it contiguous to any other room thus 
 heated ; and its windows face the North, to keep 
 out the sun. In such a room the temperature 
 during a working-day remains constant as a rule 
 to within 1°C. although the variations of tem- 
 perature of the outside air may amount to as 
 much as 12°C. A characteristic of Bunsen's 
 method is that the chemical treatment of a gas 
 is effected in the tube in which it has been 
 measured ; but he uses two kinds of tubes, one 
 for the absorptions, the other (eudiometers) for 
 the combustions. Both are about 20 mm. wide 
 (inside measurement ; in narrower tubes the 
 capillarity assumes measurable values) and 
 2 mm. or so strong in the body, which strength 
 sufifices even for the eudiometers. The absorp- 
 tion tubes are about 250 mm. long, and are pro- 
 vided with spouts, so that a gas contained in one 
 can be transferred to another tube by laying 
 dovm the absorption tube in the trough. In the 
 case of the eudiometers a length of 500-600 mm. 
 suffices for all ordinary purposes. The platinum 
 wires are fused in somewhere near the closed end, 
 and are bent so that the two ends stand opposite 
 each other at a distance of about 2 mm. Every 
 gas tube is provided with an etched-in mUli- 
 metre-scale, and the gas-volimies corresponding 
 to the several marks are determined by cahbra- 
 tion, so that each tube is a laboratory, a volu- 
 meter, and a manometer, in one. The scale is 
 figured from the closed end downwards. To 
 calibrate a tube it is fixed, open end upwards, in 
 a vertical position ; successive, exactly equal, 
 quantities of mercury are introduced, each cor- 
 responding to some 20 mm. of scale, and after 
 each such addition the exact position of the top 
 of the meniscus in reference to the scale is ob- 
 served by means of a horizontal telescope stand- 
 ing at a distance of 1-2 metres, and the readings 
 are taken down, care being taken, before each 
 reading, to remove any air-bells that may be 
 imprisoned between the mercury and the sides 
 of the tube, by means of a long stick of whale- 
 bone. The measuring off of the standard volume 
 of mercury is effected by means of a short stout 
 test-tube, ground exactly flat at its lipless rim, 
 and provided with a lid of ground plate-glass. 
 It is filled from a pipette-like reservoir provided 
 with a long narrow outlet tube and a stop -cock 
 at the top end of this tube. If care be taken so 
 to operate that the mercury, while it fills the 
 measure, forms one continuous mass, the forma 
 tion of air-beUs is easily avoided. The measure, 
 while being fiUed, is held in a wooden clip (not 
 directly in the hand, which would cause the 
 mercury to expand) while the lid is slung to the 
 thumb of the same hand. The measure is filled 
 to overflowing, the excess of mercury is removed 
 by putting on the Ud, and the mercury is poured 
 into the tube. 
 
 The mercury-measure is assumed to hold 
 
23S 
 
 ANALYSIS. 
 
 ' V ' volumes of mercury, v being so chosen 
 that, for differences of capacity at least, the 
 numerical value of the volume corresponds as 
 nearly as possible with the respective scale 
 readings, bo that, for small differences, every 
 1 mm. of difference of level can be assumed to 
 correspond to unit-volume (i.e. to Av = l). 
 Supposing after addition of k measures, full of 
 mercury the meniscus stands at e mm., the 
 volume of the body of quicksilver now in the 
 tube is kv units by definition ; but the gas- 
 volume corresponding to R is greater than kv, by 
 the volume x of the 0:^( -shaped space between 
 the meniscus as it is when the gas is being 
 measured, and the meniscus as it was in the 
 calibration. To determine x, we pour some cor- 
 rosive sublimate solution on the meniscus (after 
 having read off the number b in calibration) 
 which causes the meniscus to flatten out into 
 Id, plane, and we read the position of this plane 
 which stands say at B-5 mm. Counting from 
 some horizontal reference-plane 00 upwards, the 
 volume of the mercury and the total space from 
 00 to the horizontal plane through b are constant. 
 The volume J-x has become visible as a cylinder 
 of the height 5 millimetre's, and consequently 
 of the capacity of 5 ' units.' Hence the gas 
 volume corresponding to point n is kv + 25. 
 From the values kv + 25, and the corresponding 
 readings b' b" b"' &o., it is easy (though tedious) 
 to calculate a calibration table which gives all 
 the gas-volumes from mm. to mm. directly. In 
 reading off with a good telescope one soon learns 
 to divide every individual degree into tenths by 
 the eye; the (Av)s corresponding to them are 
 found by interpolation from the tabular entries. 
 Should the tube be used for measuring over 
 water, we remove the meniscus-correction by 
 Bubtraeting 25 from the registered volume, and 
 thus obtain as good an approximation to the 
 gas-volume over water as is called for in such a 
 case. 
 
 During the course of the calibration the tem- 
 perature of the mercury must be kept as nearly 
 as possible constant, or else the values recorded 
 for the lower marks may be very appreciably 
 incorrect. It is well to record the mean tem- 
 perature <„ during the period of calibration, and 
 to determine the weight in grams of a measure- 
 full {v ' volumes ') of mercury at t°, in order to 
 be prepared for reductions of gas-volume to gas- 
 weight. One gram of mercury at 0°C. occupies 
 O-07355 c.c. (log. 2-866589), and the volume at 
 t°G. is 0-07355 (1 + 0-0001814 t) c.c. 
 
 To prepare a eudiometer for receiving a gas 
 we first make it rigorously clean, and next, if 
 the gas is meant to be measured ' moist,' attach 
 a, small drop of water to the closed end, which 
 ■during the operation of filling with mercury 
 ^ets flattened out and spread over the inside, 
 and so offers a large surface to the gas. The 
 mercury is introduced through a long funnel- 
 tube (provided with a stop-cook at the bottom 
 of the funnel) which goes to the bottom of the 
 eudiometer. By means of this arrangement it 
 is easy, after the introduction of the first thimble- 
 full of metal, to let the mercury in eudiometer 
 and funnel form one unbroken mass, and thus 
 to avoid formation of air-bells at the sides of 
 the tube.' , 
 
 * In regard to the aolleotton and preservation of g&8 
 
 Assuming the gas to have been introduced, 
 and the tube to have been fixed in a vertical 
 position, we begin by preparing for the reading 
 of the level of the trough by inserting a paper 
 screen, provided with a C^ shaped perforation, 
 between the mercury and the front (glass) wall 
 of the trough, which gives a fairly distinct image 
 of the line of intersection between scale and 
 trough-level plane ; we then suspend the ther- 
 mometer somewhere close to the tube and next 
 leave the room for a time to allow the gas to 
 assume the temperature of the air. On return- 
 ing we read off : 
 
 1. The position B of the meniscus in the 
 tube. 
 
 2. The level of the mercury in the trough, Bj. 
 
 3. The temperature, t°. 
 
 4. The barometer ; let its height be = Bmm. 
 This reading comes last because the barometer 
 requires to be tapped before being read and this 
 cannot be done from a distance. 
 
 In the vast majority of cases the tempera- 
 tures t'f't'"... for the several gases to be com- 
 pared do not differ much from their mean ; 
 hence, even if they differ considerably from the 
 temperature which prevailed in the calibration, 
 the value furnished by the calibration table for 
 B can be put down as the correct relative 
 volume of the gas measured ; and the pres- 
 sure of any mercury-column measured may be 
 identified with its nominal height in mms. as 
 read. Hence we have for the pressure of the 
 dry gas at the observed volume p = 
 B + B — (R|, + ir) where ir is the maximum pressure 
 of steam at t°, and for the gas-quantity (the 
 
 volume reduced to unit disgregation) v„=f 
 
 278-K 
 (see theoretical part). 
 
 Bunsen prefers reducing to 0°C. and 1000 
 mm. pressure by the formula 
 
 V - . •"' 
 ' I005fr+¥003fi65i) 
 which, if a table of the logarithms of all the 
 values {1 + at) is at hand, is as short a method 
 as the one recommended by us. 
 
 Corrections of tube-capacities and mercury- 
 heights for variations of temperature occur 
 only in the rare case when one of the gases 
 concerned in the analysis was measured at an 
 artificially established high temperature t. In 
 this case the value v furnished by the calibra- 
 tion table for the reading B must be corrected 
 thus : — 
 
 (True capacity down to B)=v[l + X(i — („)] 
 where \ stands for the coefficient of the cubical 
 expansion of glass, and may be put down at 
 27-6 X 10"°. And for the observed height h ot a 
 mercury column measured at a high tempera- 
 ture t we must substitute the height h„ of the 
 equivalent column of mercury of <„ degrees. i„ 
 stands in both cases for the average temperature 
 that prevailed during the determinations made 
 
 in the ordinary manner. Obviously fe, = , , 
 
 and with sufficient exactitude. 
 
 \ = h[l-k(t-t,)2 
 
 samples, and the mode of introducing a sample Into the 
 eudiometer, we refer to Bunsen's QasometrUche Methoden, 
 second edition, Braunschweig, 1877. The first edition, 
 1857, was translated into English by Roacoe, and pabliahed 
 by Walton and Maberley, London. 
 
ANALYSIS. 
 
 239 
 
 k - -OOOIS.— Stiiotly speaking the nominal value 
 L of a piece of millimetre-scale as measured at 
 t should be corrected thus : 
 
 (True length at t) =l{1 + (t-t„)Q-2 x 10-«). 
 (It is easier to remember that 1000 mm. expand 
 by 0'92 mm. per 100° of increase of tempera- 
 ture.) But our work must be very exact to be 
 worth this correction. It is more relevant to 
 state that whenever we wish to make use of 
 Eegnault'a determinations of absolute gas- 
 donsities we must measure by his unit of 
 (temperature and) pressure, and consequently 
 reduce our mercury-columns to true mm. of 
 mercury of 0°C. Begnanlt's densities d, on 
 the other hand, ought to be reduced to the 
 gravity of the place of observation ; this correc- 
 tion, however, may as a rule be neglected. 
 
 For the execution of an absorption the most 
 obvious method is to shake the gas with the 
 respective reagent in the liquid form, and to 
 measure the gas-residue as it stands over the 
 layer of liquid reagent. But this method is 
 in general attended with a number of obvious 
 grave errors, and, besides, does not readily adapt 
 itself to the successive application of different 
 reagents. To overcome these difficulties Buusen, 
 as a general rule, uses all the absorbents in the 
 form of solid or semi-solid balls, fixed each to 
 the end of a platinum vrire. Caustic potash, 
 chloride of calcium, &o., are cast in a bullet- 
 mould around the ooiled-up end of the wire. 
 To bring sulphuric acid, alkaline pyrogallate- 
 solution, and other intrinsically liquid reagents 
 into a gjtctsi-solid form, a ball of some suita- 
 ble porous material— battery charcoal for vitriol; 
 papier-mach6 for pyrogallate, &c. — is fixed to 
 the end of the wire and the ball is then soaked 
 in the respective liquid. In this manner it is 
 quite possible to accomplish an absorption even 
 with oil of vitriol, without soiling the tube or 
 the mercury to an inconvenient degree. Ee- 
 agent vapours left after an absorption, or foreign 
 vapours produced by the reagent — e.g. the SO, 
 and SO2 which are always left after an ab- 
 sorption of olefines by fuming vitriol^must of 
 course be removed by suitable reagents (SO, and 
 SO2 by a soft potash ball) before the residue 
 is measured. As small remnants of, for instance, 
 KHO, remain unavoidably in the tube, the resi- 
 dues must in general be measured dry, because 
 the pressure of water in the presence of moist 
 KHO is incalculable. 
 
 The weak point in Bunsen's method is that 
 it is tedious, and that it does not enable one to 
 see the end of an absorption otherwise than by 
 the repetition of the process with a fresh reagent 
 ball. Bunsen himself has indeed come to effect 
 carbonic acid absorption, by shaking the gas 
 with solution of caustic soda, and measuring 
 the gas-residue over the layer of reagent. To 
 be able to correct for the pressure of this layer 
 and for the vapour-pressure of the reagent, he 
 employs it in the form of a standardised solution 
 containing exactly 7 p.c. of NaOH, which has a 
 practically constant specific gravity. He has also 
 determined the course of the pressure-curve by 
 standard experiments; the results are embodied 
 in a table appended to his Oasometrische Metho- 
 den, second edition. 
 
 In this connection we must refer to an 
 ingenious method devised by Bussell (C. J. [2] 
 
 6). He introdu ees the reagents as solutions by 
 means of a graduated syringe; and after they 
 have done their work, removes them by means 
 of a ball of cotton -wool, previously rendered air- 
 free by kneading it under mercury. To remove 
 what adheres to the tube and mercury he rinses 
 the inside with some injected water and removes 
 this by a fresh cotton-wool plug. 
 
 In the analysis of a gas by combustion a 
 necessary preliminary step is to remove (and 
 determine) what there may be of SO;,, CO^, NHj, 
 and similar gases, by suitable absorbents. Part 
 of the residue is transferred to the eudiometer 
 and measured. Let its volume (reduced to, say, 
 unit disgregation) be equal to v units. The ne- 
 cessary quantity of oxygen or hydrogen is now 
 added and its quantity is determined by mea- 
 suring the mixture (let its red. volume be «'). 
 The mixture is now rendered explosive, if ne- 
 cessary, by adding the requisite proportion of 
 fulminating gas, the whole is well mixed and 
 prepared for explosion by pressing the open end 
 of the eudiometer firmly against an india-rubber 
 pad lying on the bottom of the trough. The 
 upper surface of the pad must have been rendered 
 air-free by rubbing it over with a few drops of 
 corrosive sublimate and mercury. After these 
 preliminaries the combustion is efitected by pass- 
 ing an electric spark through the mixture. After 
 the combustion, the eudiometer is carefully lifted 
 from its cushion, so that the mercury enters 
 slowly and without drawing in air. The gas, 
 after having been allowed to cool down to the 
 teinperature of the room, is measured, to deter- 
 mine its reduced volume v". From the data 
 obtained so far, we have for the contraction per 
 unit of original gas ; 
 
 After this determination comes, if necessary, 
 that of the water produced, which of course is 
 practicable only if the original gas and the 
 added oxygen were used in the state of perfect 
 dryness and any added fulminating gas measured 
 exactly. To determine the water— of which 
 part in general separates out in the liquid form 
 — the eudiometer is lifted out of the trough by 
 means of a small beaker, and with it, as its 
 temporary trough, placed within a glass cylinder 
 through which a current of steam can be passed 
 to raise the temperature of the whole to some- 
 thing like 100°C. The exact temperature V" 
 is noted down. If care be taken to arrange 
 matters so that the pressure of the gas mixture 
 produced is not more than 0'5-0-6 atmospheres 
 the steam may be practically regarded as a 
 perfect gas, so that the measurement of the 
 mixture enables one to calculate its quantity. 
 If the red. volume of the mixture be v'", we hav« 
 for the steam per unit of original gas ; 
 
 «; = - (v"'-v"). 
 
 In this measurement the corrections for the 
 expansion of the glass and mercury, which were 
 referred to above, necessarily come in. 
 
 The determination of the carbonic anhydride 
 produced is effected by caustic potash. In an 
 aliquot part of the residue, the surplus-oxygen 
 (or hydrogen if we have to deal with a gaa 
 combustible by hydrogen) is determined, if neoes- 
 
240 
 
 ANALYSIS. 
 
 Bary. Oxygen can be determined by explosion 
 witli excess of hydrogen (its quantity is 5 of 
 the contraction), or it may be determined by ab- 
 sorption with pyrogallate; hydrogen is deter- 
 mined by explosion with excess of oxygen, § of 
 the contraction is the volume of the hydrogen. 
 The nitrogen is found by difference. The method 
 of combustion — as a method of ultimate analysis 
 at least — is susceptible of a high degree of pre- 
 cision, which, however, is attained only if we 
 take care to avoid its numerous sources of error. 
 
 I. The reagents used must be absolutely 
 pure, which of course includes absence of air ; 
 hence in any case the gas-evolution apparatus 
 employed should be no larger than is absolutely 
 necessary, so that the air-space is reduced to its 
 minimum. 
 
 Pure oxygen is easily made. A few grams of 
 pure potassium chlorate are introduced into a 
 little bulb blown to the end of a glass tube, and 
 the latter is then drawn out and bent into the 
 form of a gas-delivery tube. The rest needs no 
 explanation. 
 
 Pure fulrrdruMng gas is best produced 
 electrolyticaUy from 10 per cent, pure sulphuric 
 acid. The two elements are sure to be produced 
 in the exact ratio of Hji^Oj, but whether the 
 gas as it comes off reaUy has this composition 
 depends on the observance of certain conditions 
 which cannot be formulated better than by a 
 description of Bunsen's apparatus (Fig. 1). 
 
 f Id. 1. 
 
 The decomposition-cell consists of a cylindrical 
 bottle provided with fused-in platinum electrodes 
 aa, and terminating in a funnel ; it is fiUed 
 with the acid up to about |ths of its capacity. 
 The end e of the washing-bulbs and delivery- 
 tube is ground into the neck of the funnel ; a 
 few drops of acid poured over the joint make it 
 absolutely tight. The bulbs d are charged with 
 a few drops of oil of vitriol to dry the gas 
 evolved. The bottle is suspended within a bath 
 of water c c (or alcohol to avoid its freezing in 
 winter-time). To produce a current of fulmi- 
 nating gas, the wire ends bb are connected with 
 the poles of a battery of four ' Grove ' or 
 ' Bunsen ' cells, and the gas evolved during the 
 first five minutes is allowed to escape in order 
 to expel the air, and to establish absorptio- 
 
 metrio equilibrium between the gas above, and 
 the gas held in solution by, the acid. As oxygen 
 has a greater coefficient of absorption (;3') than 
 hydrogen (|8"), the first portions of gas that come 
 off contain an excess of hydrogen. Besides, the 
 ratio P':P" varies with the temperature ; for 
 this reason, and also to avoid undue heating of 
 the conduoting-wires, the bath is used. 
 
 Imagine the apparatus to be so modified 
 that the oxygen electrode is immersed in a mass 
 of liquid zinc-amalgam, which takes up the 
 oxygen as quickly as it is liberated from water, 
 and you have Bunsen's apparatus for producing 
 pure hydrogen. But a suificiently pure gas for 
 most purposes can be obtained in the ordinary 
 manner, namely, by the action of 10 p.o. (pure) 
 sulphuric acid on pure zinc, in the presence of 
 platinum, within a small, narrow-necked, flask. 
 The hydrogen thus evolved is filtered through a 
 short narrow tube fuU of fragments of caustic 
 potash to remove traces of sulphuretted hydrogen 
 and moisture. 
 
 II. The second point to be attended to is 
 that the quantity of oxygen (or hydrogen) added 
 to the gas to be burnt must be in excess over 
 the calculated quantity (a large excess is not 
 necessary). The mixture must be perfectly 
 homogeneous before the spark is sent through 
 it. 
 
 III. The gaseous mixture must be brought 
 to a proper state of attenuation. Let us assume 
 that the gas to be burnt is a pure specimen of 
 H, CO, CH4, or some other gas, C^Hj,. A glance 
 at the formula shows how many volumes of 
 oxygen we have to add to produce what we may 
 call the respective fulminating gas. Thus the 
 equation C2H^-^302 = 2C02-^2H20, tells us that 
 every one vol. of ethylene needs 3 vols, of oxy- 
 gen. Any fulminating gas wiU explode when 
 the spark is sent through it at the ordinary 
 pressure, but the force of the explosion is in 
 general more than the best eudiometer will 
 stand. To avoid such accidents, we must 
 attenuate the gas by addition of diluents (such 
 as surplus oxygen or air), or by mere expansion, 
 or in both ways. In practice we must go even 
 beyond the safety point, because in most oases 
 nitrogen is present even in the original gas, and 
 a considerable quantity of this nitrogen may be 
 converted into nitric acid if the temperature of 
 the flame is too high. But we must take care 
 on the other hand not to attenuate too largely, 
 or else the mixture may miss flre, or, what is 
 worse, suffer only partial combustion. The effect 
 of an explosion — in the chemical, physical, and 
 mechanical, sense — is determined by many inde- 
 pendent variables, which, if arranged in the order 
 of their importance, would begin with the che- 
 mical constitution of the gas to be burnt, and end 
 with the relative narrowness of the eudiometer. 
 But given a certain eudiometer, and suppose it to 
 be charged with a certain fulminating gas which 
 contains, let us say, unit vol. of the respective 
 'fuel,' measured at the ordinary temperature 
 and the pressure of one atmosphere, the attenua- 
 tion of this gas to a certain eudiometer space, 
 equal to A units of vol., will render the explosion 
 both safe and effective. A of course has one value 
 if the attenuation be produced by mere expan- 
 sion (mere reduction of pressure), another value 
 if it be produced — at, say, 1 atm. pressure — by 
 
ANALYSIS. 
 
 211 
 
 Addition of air, a third, fourth, &o., in inter- 
 mediate oases ; each case fortunately admits of 
 a liberal toleration, ± (A a). The a for a given 
 species of fuel can of course be determined only 
 by experience ; supposing it has been ascertained 
 for H, CO, CHj, and the value for CH, is a„, we 
 might suppose that the proper A for O^H^ or 
 CjHg would be about 2a,, that for a Cj-gas about 
 3Aj, (fee. ; but unfortunately the supposition is 
 not borne out by experience; CjHj, for instance, 
 explodes far more violently than CjH,, although 
 it contains less hydrogen per molecule. But to 
 pass to experience. According to Bunsen and 
 Eolbe, the explosion of ordinary fulminating 
 gas (H2 + JO2) in admixture with air takes its 
 normal course at from 500 to 600 mm. total 
 pressure, if the percentage of the explosive gas 
 lies between 20-8 and 39-1. According to our 
 calculation from the data of the five experiments 
 recorded by Bunsen, this comes to the same as 
 saying, if the partial pressure of the fulminating 
 gas lies between 108 and 230 mm. ; or if A, re- 
 ferred to the hydrogen, is between 4-9 and 10'5. 
 If A > 10'5, the gas f aUs to burn ; if A < 4'9, 
 nitric acid is produced. In the combustion of 
 a given quantity of oxygen by added hydrogen, 
 we may use 3-10 volumes of the latter, per 1 vol. 
 of oxygen, if we start with almost pure oxygen. 
 In the analysis of ordinary air, 0'5 — 1 vol. of 
 hydrogen per 1 vol. of air works well (Bunsen). 
 Whenever hydrogen is used as a reagent, the 
 chance of nitrogen being drawn into the com- 
 bustion is relatively small, so that we have greater 
 latitude on this score, in choosing our conditions. 
 If the oxygen to be determined is accompanied 
 by an unknown proportion of nitrogen, we first 
 try two volumes of hydrogen for one of total 
 gas ; if the mixture fails to explode properly we 
 add the requisite proportion of fulminating gas, 
 i.e. so nmch of the latter that it forms about 40 
 p.o., but no more, of the whole, and explode 
 again ; this time presumably with success (Bun- 
 sen). In the case of marsh gas, Bunsen directs 
 us to add 8-12 volumes of air besides the neces- 
 sary 2 volumes of oxygen, which, assuming the 
 mixture before the explosion to be at 600 mm., 
 makes our A equal to 14 to 19. For C^Hj, his 
 directions are somewhat obscure, but in a test- 
 analysis quoted by him, the pressure of the 
 mixture as exploded was 546 mms., and it con- 
 tained 0-04868 of its vol. of CjH,. Hence a= 28-6 ; 
 and the partial pressure of the explosive gas 
 (CjHi + 3O2) was 106 mm. 
 
 The addition of large volumes of air to the 
 gas to be analysed does not of course add to the 
 precision of the work generally, and in the best 
 case will render the determination of the nitro- 
 gen in the ultimate product somewhat uncertain. 
 
 Thomas (C. J. 35, 213) was the first to sub- 
 stitute mere expansion for dilution; the (Frank- 
 land) apparatus he used enabled him to do this 
 without trouble. Lothar Meyer and Seubert (0. J. 
 45, 581) have lately taken up the same method 
 and rendered it available forBunsen's apparatus 
 by the invention of an auxiliary apparatus in 
 which a kind of mercurial air-pump, constructed 
 on the Geissler principle, serves to establish any 
 desired pressure at the same time in the eu- 
 diometer and in a moist-vacuum barometer, so 
 that the difference of level between the menis- 
 cuaes of the two at once gives the pressure of 
 
 the dry gas. By means of this apparatus, they 
 ascertained, for each of a series of gases com- 
 bustible by oxygen, the minimum pressure at 
 which the undiluted fulminating gas is exploded 
 by an electric spark, and also a range of pres- 
 sures at which the explosion is both safe and 
 effectual. The following table summarises what 
 for us are the main results. To explain the 
 headings let us give the reading of the table for 
 CH, in full. Imagine a given quantity of marsh 
 gas mixed with a little more than two volumes 
 of oxygen ; this mixture will explode normally if 
 its pressure is reduced to p = 140 mm. by mere 
 diminution of pressure, the partial pressure of the 
 CH, itself will now be at 47 mm., and its attenua- 
 tion (as defined above) at a = 16, that is to say, 
 every 16 units of vol. of the expanded mixture 
 contains 1 vol. of CH, measured at 760 mm. 
 
 Fuel in millimetres 
 
 CH, 140 47 
 
 CjHj 70-80, say 75 19 
 
 CjHj 40-50, say 45 13 
 
 C3H, 80 14-5 
 
 O3H, 80 13-3 
 
 CO 243-219 162-146 
 
 H, 176-127 117-85 
 
 {Partial Pressures.) 
 
 [Hj 176-127 117-85 4-9-10-5] 
 
 A 
 16 
 40-5 
 59-1 
 52-2 
 67-0 
 4-7-5-2 
 6-5-9 
 
 [By Bunsen and Kolbe's experiments {vide 
 swp7-a) ; air added as diluent ; total pressure in 
 the mixture as exploded, 520-590 mms.] 
 
 With Meyer and Seubert's, or some other 
 equivalent, apparatus at hand, the order of 
 operations with a gas of unknown composition 
 is as follows : — After having added a sufficient 
 volume of oxygen, we next expand so largely as 
 to be certainly on the right side of the safety 
 line, and apply the spark ; if no explosion occurs 
 we repeat the trial at successively greater 
 pressures. Should the greatest available pres- 
 sure fail to produce inflammability, we add a 
 suitable proportion of ordinary fulminating gas 
 (Hj + JO2) as above explained, &c., &o. 
 
 The Bunsenian mode of gas-analysis, while 
 perfection in regard to precision and elegance, 
 is very wasteful of time, for obvious reasons, 
 which any reader who has followed us so far 
 will easily discern. The desire to do away with 
 this evil has led to the construction of quite a 
 series of more or less complicated gas appa- 
 ratus. The more important of these are 
 described in the following paragraphs. To 
 avoid repetitions, let us state beforehand that 
 all the apparatus to be noticed agree in the 
 following points : — 
 
 1. For accelerating the absorptions the re- 
 agents are all used as Hquids, and the absorp- 
 tions are carried out in a special piece of 
 apparatus (laboratoire) ; the residual gas is then 
 transferred to the measv/rer, where it is saturated 
 with vapour of water, and measured. 
 
 2. The measurer is immersed in a water-bath 
 to bring the gas contained in it to a definite 
 constant temperature, without much loss of 
 time. 
 
 3. The mode of measurement is so contrived 
 that the calculation of the gas-quantities (the 
 Qs) becomes very easy or even unnecessary. 
 
 IX 
 
242 
 
 ANALYSIS. 
 
 Begnault and Eeiset {A. Ch. [3] 26, 333), 
 while engaged in their great research on respi- 
 ration, felt the want of a quick-working appara- 
 tus for the numerous gas-analyses involved, and 
 at last adopted the combination represented in 
 figs. 2 and 2a. The vertical tube a conjointly 
 with the moveable trough t constitutes the 
 
 V7 
 
 rio. 2. 
 
 laboratory; the measurer consists of a long 
 U-tube, the limbs of which are of glass, whUe 
 the bend consists of an iron or steel tube, ter- 
 minating in two sockets b and c (see auxiliary 
 figure 3), in which the two glass tubes B and 
 c are fixed by means of a resinous cement. A 
 two-way cock b below b (fig. 3) enables one to 
 effect the necessary connections. Tube b is 
 provided with a couple of fused-in platinum 
 wires near its top, so that it can be used for the 
 combustions as well as for the measurements of 
 the gases. Tube o conjointly with b serves as 
 an open manometer. The capillary ends of A 
 and b are cemented, each into the socket of a 
 capillary steel stop-cook, and the ends of the two 
 steel-fittings which face each other are shaped 
 BO as to constitute the two halves of a Regna/uU- 
 cov^Ung, so that the two tubes can be united 
 hermetically, or can be separated, at a moment's 
 notice. The construction of a Eegnault's coup- 
 ling is seen from fig. 4. To unite A and b, the 
 convex end of r (fig. 4) is smeared over with 
 melted india-rubber, pressed against the con- 
 cave part a' b', and the two are then bound 
 together by means of the clip a". As the conical 
 
 groove in a" has a slightly less angular 
 aperture than the sharp welt which it goes 
 over, if the two halves of a" are screwed against 
 each other, they exert a powerful pressure, and 
 make the joint absolutely tight. The volumeter, 
 B, in the original apparatus, had only one 
 mark, somewhere about the middle ; but the 
 
 Flo. 2a. 
 
 inventors subsequently added two more, one 
 close to the upper end, and one near the lower, 
 for the measurement of exceptionally small, or 
 large, quantities of gas. The manometer o is 
 not graduated, as the apparatus is intended to 
 be used with a cathetometer ; where this costly 
 
 Fia. S. 
 
 Ita. 4. 
 
 instrument is not at hand, tube a must be pro- 
 vided with a millimetre scale. 
 
 To prepare the apparatus for use it is placed 
 on a substantial support not liable to incon- 
 venient vibration, and the three levelling screws 
 of the stand are adjusted so that the tubes 
 b and stand vertical. To determine the 
 relative gas-volumes corresponding to the three 
 
ANALYSIS. 
 
 243 
 
 marks, the volumeter is filled with mei-oury, 
 through c, and after the air-bells have been 
 removed by the well-known artifices, the weights 
 of mercury w„ w,,, Wj, which the tube holds 
 from its exit-end at r (fig. 2a) to the highest, 
 middle, and lower, mark, respectively, are deter- 
 mined. For comparative measurements the 
 
 volumes are put down as — l, !I? = 1, and — ?, 
 w„ w„ w„ 
 
 respectively. In the absence of a cathetometer 
 the level points oi the three marks on the scale 
 must be determini'd with the help of an ordi- 
 nary gas-room telescope. Lastly, a drop of water 
 is introduced into e and spread over its surface. 
 To analyse, say, a mixture of carbon dioxide, 
 oxygen, and nitrogen, a sample of the gas is 
 collected over mercury in a (perhaps with the 
 help of an auxiliary -trough) ; tube A is coupled 
 on to B (which is supposed to be quite full of 
 mercury), and the gas is sucked into this tube 
 by letting mercury run out at z. B having 
 been closed by shutting the cock r, communica- 
 tion is made with o, and mercury is run out 
 until the meniscus in b stands at say exactly 
 the middle mark ; the final adjustment is made 
 with the telescope when the temperature of the 
 gas has certainly become equal to that of the 
 bath. When the final reading is made, b 
 must of course communicate with o only. The 
 reading of the height h of the mercury column 
 in c, counting from the respective mark up or 
 down as the case may be, and the reading of the 
 barometer, complete the measurements. Sup- 
 posing A to be positive, and the barometer to 
 stand at b, the gas-quantity measured is 
 
 ( T, = l)x(fe + B-7r). 
 "" 273 + < 
 
 To absorb the carbon dioxide, the laboratory 
 tube (which was left full of mercury) is charged 
 with a little caustic potash solution, and the gas 
 is blown into it from b. By letting the gas 
 travel forwards and backwards between a and a 
 a number of times, the absorption can be com- 
 pleted in a short time. The residual gas is then 
 sucked back into b, care being taken to shut the 
 cock r' as soon as the potash solution comes to 
 some mark a, in the capillary part of a. The 
 thread of gas from (r to r which is thus lost ia 
 of no consequence, as it amounts to only -g^^-^ of 
 v,. The mixture of nitrogen and oxygen is 
 measured as before. The rest requires no ex- 
 planation. If all the several gases are measured 
 at the same temperature and volume, the (dry) 
 pressure p', p", p'", of course may be taken as 
 representing their qs (red. vols.). 
 
 Frankland and Ward, in 1853, introduced an 
 ingenious modification of Begnault's apparatus, 
 which differs from the original model chiefly in 
 this, that the volumeter bears ten marks, so 
 adjusted that the respective gas-volumes are to 
 one another as 1 : 2 : 3 .... 10 exactly, and 
 that in addition to Begnault's open tube o (Figs, 
 2, 2a), there is a third tube, d, which terminates 
 above in a stoppered funnel or stop-cock. Tube 
 D stands in the same water-bath with b and o ; 
 when used it contains only mercury and a Httle 
 water, and thus assumes the character of a 
 'moist' barometer, which serves to directly 
 measure the dry pressure of the gas shut up in 
 B. Tube (in P. and W.'s apparatus) serves only 
 
 for the introduction of the mercury. The levels 
 of the ten volumeter marks, in reference to the 
 scale on the barometer, are of course determined 
 once for all, hence the measurement of a gas, 
 supposing its volume to have been adjusted to 
 one of the ten marks on the volumeter, involves 
 only one reading, namely that of the height of 
 the mercury column in the barometer, which 
 balances the (dry) pressure of the gas. Another 
 advantage of F. and W.'s apparatus is, that for 
 each gas measurement it gives one the choice 
 among at least some three of the ten standard 
 volumes, and thus enables one to reduce the 
 error by an obvious method of repetition. Un- 
 fortunately, however, the barometer rather 
 aggravates what in the original apparatus is a 
 suflScient trouble, namely, the liability of the 
 apparatus to get out of order. However care- 
 fully it may have been constructed, the joints 
 between the glass tubes and their sockets are 
 sure to become leaky, and the capillaries between 
 the laboratory and the volumeter are exaspera- 
 tingly fragile. 
 
 MoLeod [1869] (O. J. [2] 7, 314), and Thomas 
 [1879] (O. J. 35, 218) endeavoured to remedy 
 these evils, and to effect other improvements. 
 For details see the papers referred to. 
 
 Infinitely handier than Begnault's unwieldy 
 machine, though not quite equal to it in poten- 
 tial precision, is 
 
 Doyire's Appwratus. — (First notice dates 
 from 1848. Full description in A. Ch. [3] 28, 1.) 
 The essence of Doyire's system is that the 
 measurement of the gases is effected in a plain 
 graduated eudiometer, while a series of Ettling'a 
 gas pipettes serves for the chemical treatment 
 of the gases, and their transference from vessel 
 to vessel. The Ettling gas-pipette is depicted 
 in fig. 5, and a glance at the figure suffioes to 
 
 Fia. 6. 
 
 show, in a general way at least, how the instru- 
 ment is used for the transference of a gas from 
 one tube to another ; nor is it necessary to for- 
 mulate the conditions or limits of its availability. 
 The measurer (fig. 6) when in use is suspended 
 over a pneumatic trough, deep enough to admit 
 of the total immersion of the measurer, and ia 
 surrounded by a mass of water contained in a 
 cistern whose sides are of plate-glass, while the 
 mercury of the trough forms its bottom. To 
 
 b8 
 
244 
 
 ANALYSIS. 
 
 prepare the measurer for the reception of a gas, 
 it is cleaned, slightly moistened inside, trans- 
 ferred to the trough by means of the portable 
 mercury trap (fig. 7) fixted in the clip l, and 
 filled with mercury by sucking out the air, by 
 means of the U-shaped tube (fig. 8). The gas, 
 which we will suppose to be contained in a gas- 
 
 v„. The standard body of air is contained in 
 the ' BigulaUur ' (fig. 9), a kind of air-ther- 
 
 Fia, 6. 
 
 pipette, is then blown in, to be measured at a 
 certain fixed disgregation, which is kept rigor- 
 ously constant for the set of gas-quantities to 
 be compared. A glance at fig. 6 at once suggests 
 a mode of fulfilling this condition. But this 
 mode is not Doy^re's. He allows the tempera- 
 
 1 
 
 VJ-i/ 
 
 I'la. r. 
 
 71(1. & 
 
 tnre of the bath and the barometer to take care 
 of themselves, but before each measurement he 
 ao adjusts the height of the water in the bath 
 that the volume of a certain fixed quantity of 
 air, shut up over water at a place within the 
 water of the bath, assumes a certain fixed value, 
 
 Tlia. 9. 
 
 mometer which is fixed against a glasa-plate, 
 and, by it, suspended at a certain (by intention 
 constant) height over the mercury-level of the 
 trough. The water of the bath goes to some 
 point B in the ascending branch of the capillary 
 U-tube; BA is a thread of air; from a down- 
 wards there is a continuous mass of water, over 
 which the standard body of air is shut up at 
 B. Before each gas-measurement, the height 
 of the water in the trough is so regulated (by 
 means of taps) that meniscus A stands at some 
 determined point of the scale, and the air which 
 serves as regulator is consequently at some fixed 
 volume v,. This being done, the eudiometer 
 is raised or lowered, until the height of the 
 column of mercury suspended in it is at some 
 fixed value, h„. As a result, the gas is now 
 practically at least, at a fixed disgregation. 
 
 Proof, The preBsure of tlie gas exceeds that of the air 
 of the regulator by A+p,+h„ where A stands for the 
 height of B ' over ' A (we refer to the regulator), and p, for 
 the height from the level in the trough to that in B of the 
 regulal^r — both reduced to mercury. With a properly 
 chosen hn the value c^A-t-i*,— Ao. ^ not nil, is at least 
 small, and nearly constant. Now supposing we have, for 
 two successively measured quantities of gas, I. and II. : 
 
 I. n. 
 
 Por the regulator-air v„ T*; p". r,;t"; p". 
 
 For the gas . . . v';T';(p'+e) v"; T"; (p"+c). 
 
 As the regulator-air Is at the constant volume, v,, we 
 liave 
 
 "F^F^ c L 
 
 The 'reduced volumes' (the Qs) of the two gases are 
 
 , v'(p'-fc) , „ V"(P"-K!) „ 
 
 Q'= '^ ^ andQ"=— ^ — ' . . . n. 
 
 end, as e_ 
 
 Is hut small, we may write 
 
 p'orp" 
 
 As both factors in the second term with the braoket | 1 
 are very small, we have practically, 
 _S.'= ^' 
 
 As the measurer is necessarily very email, 
 the adjustment of fc„ must be made, and the 
 
ANALYSIS. 
 
 245 
 
 gas-volumea read, with more than ordinary 
 exactitude. Doy^re accordingly provides a 
 Email short-vision telescope, which has a glass 
 micrometer-scale (fig. 10) in its foous. The 
 
 Fig. 10. 
 
 telescope is attached to a three-legged stand 
 (which rests on a horizontal glass-plate fixed on 
 the table close to the trough), in such a way 
 that in all the necessary shiftings the optical 
 axis remains parallel to, or when necessary, in, 
 the same horizontal plane. To adjust h^ the 
 telescope is so focussed that it gives a distinct 
 image of the mercury meniscus in the trough, 
 which image is then made to coincide with line 
 o-o' (or bb' if the telescope is an astronomical 
 one). The eudiometer is then lifted or lowered 
 nntil the image of the top of its meniscus 
 touches the central line A-i', which assigns to 
 h„ a definite, though unknown, value. This 
 adjustment being made, the telescope is drawn 
 backwards a little on the glass-plate to afford 
 a good image of the eudiometer-scale, and to 
 enable one to read the volume of the gas. The 
 
 Fig. 11. 
 
 micrometer-scale serves to sub-divide the indi- 
 vidual divisions on the eudiometer, which it 
 does with an amply sufficient degree of precision. 
 Before reading h„ the eudiometer must be tapped 
 to bring the mercurial meniscus into its normal 
 shape. 
 
 Assuming now that a gas, measured as de- 
 scribed, contained carbon dioxide and air, and 
 that we wished to determine the carbon dioxide 
 by absorption with caustic potash. We begin 
 by charging a gas pipette with mercury to about 
 the extent shown in fig. 5. We then take the 
 pipette to an auxiliary trough, immerse its (J 
 in the well, and, after having blown out the air, 
 suck in the requisite quantity of caustic potash 
 solution from a teat-tube inverted over the 
 trough, taking care not to let any more mercury 
 follow than is necessary (practically) to trap 
 
 the contents by a thread of mercury 1 1. We 
 then transfer the pipette to the measurer con- 
 taining the gas (as indicated in fig. 6), press 
 down the measurer over the outer branch of 
 the Ui ^^i transfer the gas from the measurer 
 to the pipette, by sucking at a, until drops of 
 mercury are seen to fall into the working bulb, 
 but no longer. Things are now in the condition 
 depicted in fig. 11, and all that remains to be 
 done is to agitate the contents gently so as to 
 insure absorption of the CO2, and then to return 
 what is left of the gas to the measurer. This, 
 however, is a delicate operation, which in the 
 hands of a beginner is not unlikely to fail. The 
 first step is to replace the pipette under the 
 measurer, to lower the latter sufficiently (v. 
 infra), and to blow into the pipette so as just 
 to dislodge the mercury thread i I. Supposing 
 the pipette contains no more surplus mercury 
 over and above that which was in it at the 
 beginning, then as long as the meniscus in the 
 eudiometer is below or at a level with that of 
 the mercury in the trough, as it is underneath 
 the bath, only part of the gas will pass out of 
 the pipette into the eudiometer. The second 
 step is to hft the pipette, so that its outflow 
 end, B (fig. 6) or I (fig. 11), becomes visible 
 within the gas-space of the measurer. As long 
 as it is there, and the pipette is kept vertical, 
 whether the gas flows out of B, or in at b, or 
 remains at rest, depends mainly on the pressure 
 of the gas in the eudiometer, and consequently 
 on the altitude of the latter. But this altitude 
 we have under absolute control. Hence what 
 we have to do is carefully and slowly to lift the 
 eudiometer until the thread of liquid reagent 
 which makes its appearance as soon as the bulk 
 of the gas is out, has come to, say, 2 mm. from 
 the outflow end. We then stop sucking, put the 
 pipette down on the table (which of course at 
 once seals the end B with mercury), suck at a 
 until we see mercury dropping into the pipette, 
 take the pipette out of the mercury, and put it 
 on the table to have it at hand for a repetition 
 of the absorption. 
 
 The sequence of operations described is not 
 quite so easy in practice as it looks on 
 paper, because success depends largely on the 
 permanence of the position of the pipette in 
 reference to the plumb-line. Tilting over the 
 pipette in the direction of the [J means adding 
 to the pressure of the gas inside; and vice versd. 
 
 For the explosions, Doy^re provides a special 
 stout pipette, with fused-in platinum wires, &o. ; 
 but the method of combustion finds Uttle favour 
 in his eyes, because his apparatus does not 
 readily fall in with its requirements. 
 
 In conclusion, the writer may be permitted 
 shortly to describe an apparatus of his own 
 invention, which, thanks to the valuable assist- 
 ance of Mr. Lennox, he was enabled to con- 
 struct on his own premises, and which has 
 since done hi'in good service. 
 
 Dittmar's apparatita, Uke DoyAre's, is based 
 upon the Ettling gas-pipette. Apart from the 
 necessary two troughs, it consists of the follow- 
 ing three independent parts. 
 
 The measurer (fig. 12j is a combination of 
 a wide with a narrow glass-tube, after the 
 maimer of Gay-Lussac'a burette. The wide 
 tube communicates by its lower contracted end 
 
346 
 
 ANALYSIS. 
 
 with a long capillary tube of india-rubber, and 
 tbrougb it with a Geissler mercury-reservoir. 
 At their upper ends both tubes are provided 
 with Geissler stopcocks ; to the exit-end of the 
 wide tube is soldered the capillary [J tube, 
 
 vdlumes are counted from the point of the 
 junction, because, after the introduction of a 
 gas, the narrow canal firmly retains its thread 
 of mercury. The measurer holds a fixed posi- 
 tion on the right side of a pneumatic trough, a, 
 
 Fio. 13. 
 
 characteristic of EttHng's pipette. The wide 
 tube bears a mm. scale ; the gas-volumes cor- 
 responding to the several marks are determined 
 by gravimetric calibration, at a rigorously 
 
 Pie. u 
 
 constant temperature, maintained by means of 
 the water-bath. The narrow bit of tube between 
 the top of the measurer and its stopcock is a 
 capillary of the same bore as the (j ; it joins 
 oa quite abruptly to the wide tube, and the 
 
 Via. la. 
 
 provided with two wells, one for the U of the 
 measurer, the other for that of the exploder. 
 In regard to the exploder (fig. 13), we have 
 nothing to add to what is clearly seen from the 
 figure, except the statement that the exploder 
 in its present form is wider than the figure 
 represents it to be, so wide, indeed, as to enable 
 one to expand a gas considerably before ex- 
 ploding it. 
 
 The absorber in its original form is repre- 
 sented in fig. 14. For the interpretation of this 
 fig. it suffices to say that b is a small mercury- 
 reservoir which enables one to sweep out the 
 thread of gas left in the capillary after the 
 liquid reagent has been allowed to travel up to 
 the safe side of the point of junction between 
 the horizontal part of the capillary delivery tube 
 and the stem of the' reservoir. An improved 
 form of the absorber (devised by Mr. Lennox) is 
 represented in fig. 15. 
 
 To prepare the measurer for the reception of 
 a gas, it is completely filled with mercury from 
 the reservoir, the stopcock of the side tube is 
 turned off as soon as all the air is driven out of 
 it, and a drop of water is introduced into the 
 main tube at a suitable stage. 
 
 The gas to be measured must be contained in 
 a tube short enough to be within the range of 
 the (J : from this tube the gas is sucked into the 
 measurer with the help of the reservoir, which 
 ia then adjusted so that ^e gas-pressure inside 
 
ANALYSIS. 
 
 247 
 
 is about one atmosphere. The stopcock at the 
 side tube is then opened, and the height of 
 the reservoir is re-adjusted so that the menisci 
 in the narrow and wide tube are in the same 
 horizontal plane. A horizontal wire in the tele- 
 scope facilitates this adjustment materially, but 
 is not indispensable. The gas is now at the 
 pressure B + 6— ir, where B is the height of the 
 barometer, ir the pressure of the vapour of 
 water, and b the excess of the capillary depres- 
 sion in the narrow side tube as compared with 
 that in the wider branch. The temperature is 
 of course that of the water-bath. As both s and 
 I oscillate with a series of measurements only 
 
 Fia. M. 
 
 within small amplitudes, it is expedient to 
 reduce, not (for instance) to unit disgregation, 
 1)ut to some mean pressure and temperature 
 (if there has been any variation in either or 
 both) by means of some suitable formula, such 
 as: 
 
 v.= vj l+i±ll-^\ 
 
 i Po To > 
 
 where p,, and t„ stand for the standard values, 
 and the observed values are assumed to be 
 greater than these by (Ap) and (Ai) respec- 
 tively. If a table of the reciprocals of the 
 practically occurring ps and is is at hand, the 
 calculation becomes so very easy that it is not 
 worth while to set up a disgregation indicator. 
 
 Technical Oas-Analysis. 
 To meet the demands of chemical industry 
 there has been invented a variety of methods for 
 the rapid, though perhaps only approximate, 
 analysis of certain classes of gas-mixtures. The 
 methods all agree in this, that the use of mercury is 
 dispensed with, the gases being measured over 
 Tyater, or even perhaps over the respective ab- 
 sorbent solutions. The Bunte Gas-burette may 
 be quoted as a typical example of this class of 
 apparatus. Imagine a long cylindrical pipette 
 graduated for gas-volumes and provided with a 
 stop-cock at each end, and combinable with a 
 reservoir by means of a long india-rubber tube. 
 To analyse, say, a chimney-gas, the burette is 
 filled vrith the gas by displacement, and the 
 reservoir, after having been filled with water, is 
 attached below. By placing the reservoir at a 
 certain convenient altitude, and temporarily 
 opening the upper cock, a certain volume of the 
 gas is shut off at the pressure of one atmo- 
 sphere. In order now to determine the carbonic 
 acid, we suck out the water by an (easily ima- 
 
 gined) auxiliary apparatus, and replace it by a 
 solution of caustic potash, which is shaken with 
 the gas. The caustic potash is then sucked out, 
 water is let in, the original pressure is re-estab- 
 lished, and the residue is measured. In a similar 
 manner, the oxygen is determined by absorption 
 with alkaline pyrogallate.' 
 
 AnaiiYsis bt the Method op Titbatiom. 
 
 This branch of analysis comprises the appli- 
 cations of what was described in a previous sec- 
 tion as the titrimetric method of indirect weigh- 
 ing. The method in any of its present forms 
 is applicable only to such reactions as proceed 
 readily in aqueous solutions ; the reagents, ac- 
 cordingly, are always used in the form of standard 
 solutions {liqueurs titries), i.e. solutions the 
 strengths of which are known in reference to 
 the process under consideration. 
 
 The amount of standard solution required in 
 a titration may be measured either by weight or 
 by volume; in either case the measurement of the 
 solution is only an indirect mode of weighing 
 the active agent contained in it. The gravimetric 
 method is certainly susceptible of the higher 
 degree of precision ; yet the volumetric method 
 is universally preferred, because it is by far the 
 more handy and expeditious of the two, and, if 
 properly conducted, (with very few exceptions) 
 does ample justice to even the best titrimetric 
 processes. 
 
 The iavention of volumetric analysis must 
 be credited to Gay-Lussac. Long before him, it 
 is true, Stirling enunciated the principle of the 
 method, and Yauquelin and DescroizUle used it 
 for assaying commercial alkalis; but to Gay- 
 Lussac undoubtedly belongs the credit of bfeing 
 the first to bring the method into an exact form, 
 and to work out all its technicalities in the most 
 masterly manner. Volimietrio analysis was slow 
 in progressing. Gay-Lussao's more immediate 
 successors, misled by his success in regard to 
 silver, directed their attention almost exclusively 
 to the translation of established gravimetric 
 into volumetric methods ; failing to see (what is 
 now so obvious) that the number of reactions to 
 which both methods are applicable must neces- 
 sarily be very limited. 
 
 Very little real progress was made until 
 1856, when Bunsen, by introducing a new idea, 
 gave a fresh impetus to investigation. Starting 
 from the well-known reaction which takes place 
 when iodine solution is dropped into aqueous 
 sulphurous acid (and which Langlois had 
 already utilised for the determination of this 
 substance), he established the conditions under 
 which the process takes the precise course indi- 
 cated by the equation ; and on the basis thus 
 gained he developed exact methods, not only 
 for the direct determination of these two bodies, 
 but also for the indirect determination, by 
 means of the same two solutions, of a whole 
 
 * Professor Winkler, of Preiberg, has made a special 
 study of this branch of gas-analysis, and has written two 
 excellent books oq the subject; one of these has been 
 translated into English by Professor Lunge. To these 
 books and another we refer for further information. (1) 
 Dr. Clemens Winkler, Anleitung zur chemUchen Analyu 
 der Induitrie-Gase (Preiberg, Engelhardt, 1876). (2) An 
 abridged edition of the same by the author. Translated by 
 Lunge (Van Voorst, London). Also, Neue Uethoden tur 
 Antlyie der Giue, Ton Walter Hempel (BraunwhweiR, 
 Vieweg u. Sohn, 1880). 
 
M8 
 
 ANALYSIS. 
 
 ceriea of oxidiaing agents, for whioh an equiva- 
 lent of iodine can be substituted by the purely 
 qualitative execution of certain reactions. 
 
 By this memorable research volumetric ana- 
 lysis found its true sphere of action, as an in- 
 valuable means for the determination of generic 
 radicles, such as the active oxygen in peroxides, 
 the loosely held chlorine in perchlorides, the 
 replaceable hydrogen in acids, the oxygen or 
 chlorine-equivalent of reducing agents ; for a 
 host of determinations, in short, which prac- 
 tically lie outside the range of the gravimetric 
 method. Where the two methods compete in 
 the solution of the same problem, volumetric 
 analysis generally offers the advantages of greater 
 promptitude and facility of execution ; it, indeed, 
 stops where with gravimetric analysis the most 
 difficult part of the work would begin. This 
 advantage, however, is not an absolutely clear 
 gain. The volumetric method, so to say, does 
 not look at the body to be determined, but, in a 
 somewhat blindfolded way, only measures one 
 of its chemical properties, which in no case 
 appertains to that body only ; hence errors are 
 miore likely to be overlooked, and are far more 
 difficult of subsequent correction, in volumetric, 
 than in gravimetric, analysis; for gravimetric 
 analysis furnishes the thing to be weighed in 
 the form of a definite compound, which can be 
 examined for its purity, and, if necessary, be 
 purified before it is weighed. A small amount 
 of iron, nickel, zinc, &e., which has escaped 
 precipitation may be searched for in the filtrate 
 and recovered; any deficit or excess obtained 
 in a titration is thrown away with the rest of 
 the products. 
 
 We have no space for a full history of our 
 subject ; yet we must not forget to give credit 
 to the late F. Mohr for having contributed largely 
 to the modern development of volumetric ana- 
 lysis, by his criticisms of old, and his invention 
 of new, methods ; by the construction of useful 
 apparatus ; and last, not least, by the compila- 
 tion (for the first time) of an original and com- 
 prehensive handbook' on the subject. 
 
 In now passing to the systematic exposition 
 of our subject, we will begin with a few remarks 
 on the 
 
 Graduated Glass Keasures 
 
 which serve for the preparation of the standard 
 solutions, and the necessary measurements of 
 liquids generally. Volumetric analysis of course 
 involves only comparative measurements ; we 
 indeed never measure a standard solution other- 
 wise than in reference to itself ; hence the unit 
 of volume may not only be chosen at pleasure, 
 but need not bear any known relation to the 
 unit of weight. But the only correct mode of 
 gauging a liquid measure is to determine the 
 weight of water it holds (or delivers) ; hence for 
 those who are in the habit of using the gram as 
 their unit of weight the most convenient unit of 
 volume is the volume at (let us say) 15°0. of that 
 mass of water whose uncorrected weight in air is 
 one gram. We might herewith adopt this unit and 
 oaU it the 'fluid gram.' In doing so we should 
 not be guilty of any innovation. The customary 
 nnit with most chemists and instrument-makers, 
 
 * Mohr, Lehrbueh der chemUch-analytiMhen TitrimU' 
 Ihodt. The flrat edition dates from 18S7 ; the tomth and 
 last from 1889. 
 
 it is true, is the cubic centimetre, but it is this 
 only nominally; the actual unit in almost all 
 commercial ' cubic centimetre ' measures comes 
 nearer to our fluid gram than to the nominal 
 unit. From what we have said, the reader will 
 understand that if in the sequel we speak of 
 cubic centimetres, or litres, these terms mean 
 only unit-volume, and 1000 unit-volumes, 
 respectively, unless it is clear from the context 
 that we mean to approximately define an abso- 
 lute quantity, or to refer to the well-known 
 relation between the litre and the kilogram. 
 
 As all aqueous liquids wet glass, the mark 
 on a litre flask, &o., can be correct only in 
 reference to a specified mode of reading. The 
 best mode is this. Place the vessel so that its 
 axis is vertical, and look at the meniscus hori- 
 zontally with one eye. The meniscus then 
 appears as aflat crescent-shaped strip. The lower 
 boundary of this strip is taken as the line of 
 reference, and the real, or imaginary, mark on the 
 graduation with which it coincides (visionally) is 
 taken down as the reading of the liquid. The 
 line referred to gains in sharpness of definition 
 if it is observed in transmitted light, and a strip 
 of black paper is fixed to the back of the measure 
 about 2-3 mms. below the line. With only one 
 of the customary standard solutions, namely 
 the almost opaque solution of permanganate of 
 potash used for iron titrations, this mode of 
 reading does not work. In the case of this liquid 
 we must take the upper boundary of the meniscus 
 as our reference mark ; this upper boundary 
 assumes its maximum definition if viewed in 
 reflected light, and with a white background (a 
 piece of paper) immediately behind it. Any 
 reading made in this exceptional manner is of 
 course subject to an obvious correction, the 
 amount of which is ascertained by measuring the 
 height of the meniscus of a transparent solution 
 in the same vessel. In most cases, however, 
 the volume to be determined is the difference 
 between two consecutive readings, so that the 
 correction in question becomes unnecessary. 
 
 In a vessel which serves for measuring out a 
 certain volume, the small quantity of liquid 
 which permanently adheres to the glass must be 
 allowed for by the maker, i.e. the scale must be 
 constructed so as to include what would other- 
 wise be a necessary correction. In the case of 
 graduated pipettes this can of course be done 
 only on the basis of a conventional mode of 
 emptying out, which, when once fixed upon, 
 must be rigorously adhered to. The thermic ex- 
 pansion of glass may unhesitatingly be neglected 
 in the graduation of a titrimetrio measure. A 
 glass flask which holds 1000 c.o. at 15°C., at 
 15 ± 10° holds 1000 c.c. ± 0-27 c.o. ; i.e. only jj^th 
 more or less. The thermic expansion of the 
 solutions measured is far more considerable, and " 
 cannot in all oases be neglected. We shall 
 come back to this point in the next section. 
 
 The chemist uow-a-days has no occasion to 
 graduate his own burettes, litre-flasks, &o., but 
 he should never use a set of instruments — 
 although they come from the most famous 
 maker — ^without having first tested them. The 
 following is the method to be pursued. Passing 
 from measure to measure, and with each measure 
 from mark to mark, measure in or out the 
 several marked oS volumes of pure water of 
 
ANALYSIS. 
 
 :-i'.) 
 
 known temperature, and determine their weights 
 iu grams. In the case of apparatus with a 
 running-on scale, only every 10th or 20th mark 
 need be checked in this manner, unless there 
 are visible irregularities in the graduation. 
 After having thus gone through the whole sys- 
 tem, reduce all the water-weights to the same 
 temperature, say to 15°C. {i.e. from the observed 
 weight of water of t° calculate the weight of 
 water of 15° which fills the same space) ; divide 
 each corrected weight by the corresponding 
 nominal volume, to find the weight- value of the 
 actual unit — and draw your conclusions. Sup- 
 posing the several units agree fairly, select a 
 suitable average value (not necessarily the mean, 
 because the numbers are not all of the same 
 weight mathematically) as the unit, and calcu- 
 late the volumes corresponding to the several 
 marks in terms of this adopted unit. The results 
 ought, by theory, to agree with the respective 
 nominal values, but in practice, of course, we 
 cannot expect absolute coincidence. In a burette, 
 for instance, which gives ^ c.c.s directly, we must 
 tolerate ±0'1 c.c, and with the lower marks, 
 even a little more. Whether the actual unit is, 
 or is not, equal to the nominal is of no conse- 
 quence ; yet, if it is not, it is obviously advisable 
 to note down its value— in fluid grams or o.o.s 
 — for future reference. 
 
 To facilitate the calculations involved in 
 such work as the graduation of instruments, 
 the writer many years ago calculated the follow- 
 ing table : — 
 
 A mass of water, which, in air of t°C, and 
 760 mm. pressure, balances a brass kilogram 
 weight, at t°G. occupies (WOO -k- x) fluid grams = 
 (1000 + y) true cubic centimetres. 
 
 <o 
 
 X 
 
 y 
 
 i" 
 
 0! 
 
 y 
 
 0° 
 
 -0-64 
 
 + 1-25 
 
 + 15° 
 
 ■fO-00 
 
 + 1-89 
 
 4 
 
 0-78 
 
 1-12 
 
 16 
 
 0-15 
 
 2-04 
 
 8 
 
 0-68 
 
 1-21 
 
 17 
 
 0-30 
 
 2-20 
 
 9 
 
 0-63 
 
 1-27 
 
 18 
 
 0-47 
 
 2-37 
 
 10 
 
 0-56 
 
 1-34 
 
 19 
 
 0-66 
 
 2-65 
 
 11 
 
 0-47 
 
 1-43 
 
 20 
 
 0-85 
 
 2-74 
 
 12 
 
 0-38 
 
 1-52 
 
 21 
 
 1-06 
 
 2-95 
 
 13 
 
 0-27 
 
 1-63 
 
 22 
 
 1-28 
 
 3-17 
 
 14 
 
 0-14 
 
 1-76 
 
 23 
 
 1-51 
 
 3-39 
 
 15 
 
 0-00 
 
 1-89 
 
 24 
 
 1-75 
 
 3-63 
 
 Freparation of Standard Solutions. 
 In fixing upon the degree of concentration for 
 a specified standard solution, we may allow 
 ourselves considerable latitude. As a rule the 
 nature of the volumetric process for which the 
 solution is to be used may be left out of account ; 
 all we need look to is that the probable inherent 
 error of the method corresponds to a distinctly 
 visible difference of level in the burette ; say to 
 0-1 or 0-2 c.c. according to the size of the ' c.c' 
 With methods possessing a very high degree of 
 inherent precision this rule would lead to an 
 inconveniently dilute reagent. In such (rare) 
 cases we help ourselves by supplementing a 
 moderately dilute standard solution with a 
 decimal solution, meaning a solution prepared by 
 diluting the reagent proper with water to 10 times 
 its volume. The decimal solution serves only 
 to finish the titration which has already been 
 almost completed by means of the standard 
 solution proper. This system of course is a 
 mere delusion unloBB the stronger solution be 
 
 measured with at least 10 times the precision 
 attained with the decimal one. 
 
 The strength of any given solution should be 
 so defined as to reduce the subsequent calcu- 
 lations to their highest degree of simplicity. 
 Supposing, for instance, we have to deal with 
 a standard sulphuric acid intended for the 
 measurement of alkalis ; evidently it would not 
 be expedient to note down the number, n, of 
 grams (or mgms.) of H^SO^ or SO3 which is 
 contained in each litre (or 0.0.) of the reagent. 
 As the number when calculated into KHO, 
 NaHO, NajCOj, &o. has always to be divided by 
 SOjH,( = 98) or by ^H2SOi( = 49), it is obviously 
 
 better to calculate the value — = t (as a decimal) 
 
 and put down this t as the strength of the 
 solution. Were the solution intended exclu- 
 sively for the determination of soda, to be 
 reported as NajO, it would be still better to 
 
 calculate the value of ' = t', and note 
 
 H2SO4 
 down the weight t' (of sodium monoxide) as the 
 strength of the reagent. 
 
 For the standardisation of a specified solu- 
 tion we have in general the choice between two 
 methods ; (1) a quantitatively exact synthesis ; 
 (2) an approximate synthesis, followed by an 
 exact analysis. The first method may assume 
 one of two forms ; we either weigh out exactly 
 BO much of the pure reagent, dissolve it in 
 water, and dilute to, say, 1 litre ; or else (if the 
 pure reagent is not itself at hand) we analyse, 
 say, a strong solution of the pure or impure 
 reagent, by means of some very exact method, ' 
 and synthesise directly on the basis of thia 
 determination. In regard to the second method, 
 the first step of course is to procure an approxi- 
 mately correct solution. For example, let us 
 assume we wish to prepare a standard hydro- 
 chloric acid containing exactly HCl = 36-5 grams 
 per litre. An apology for such a solution might 
 be obtained from the ordinary (pure) labora- 
 tory acid, by determining its specific gravity, 
 deducing the percentage, and synthesising on 
 the basis thus gained. In all such cases it is 
 expedient to so allow for the uncertainty in the 
 assumed percentage that the solution obtained 
 is sure to be stronger than intended. In 
 accordance with the rule, let us assume the 
 actual strength, as found by analysis, to be 
 p, instead of the intended strength p,,, and let 
 p >p^. Obviously our ' v ' litres of reagent must 
 
 be diluted to T= — to bring the strength down 
 
 from p to p„; the liquid must not be diluted 
 
 withu (^ — l)=w litres of water, because the 
 
 Pa 
 
 two liquids when mixed would contract, and 
 a little more than w litre, say {1 + e) w litre, of 
 water would be necessary to bring up the voluma 
 to the intended value, v. In practice, however, 
 large volumes (such as we assume our v and v 
 to be) cannot be measured with adequate pre- 
 cision, so that the second (theoretically faulty) 
 method is generally the better of the two. It 
 certainly is the better if the required correction 
 
 is only small; if for instance (£. — 1) is some- 
 
 Po 
 thing like 0'03 or less. In suoh a case, if only 
 
£uO 
 
 ANALYSIS. 
 
 10 as oaloulated is measured aoouiately, the 
 ooirected Eolution 'will be as near the intended 
 strength, p„ as the given solution was near its 
 strength p. 
 
 As an example, let us take <— — 1 = 0-03 ; 
 Po 
 v = 10 litres ; 5t) = ± 0-5 litre (which is a liberal 
 allowance) ; and we have 
 
 ^ = *£± 0-0015. 
 
 Po J? 
 Even in such a case it is only prudent again 
 to analyse the corrected solution, to see that 
 no blunder has been made. Supposing (to 
 return to the example) the number p had been 
 the result of three well-agreeing analyses, the 
 intended value for p,, had been 37'00, and the 
 analysis of the corrected solution had given for 
 ^0 the value 36-84: ; the most probable value for 
 the actual strength would be (3 x 37-0 + 36-84) -=-4. 
 Turning back, let us now assume ^„ >p. In 
 this case our v litres of solution should be reduced 
 
 to S-v litres, by elimination of (1 + e) (1 —^)v = 
 
 Po Po 
 
 '(1 + f) w' litres of water. Even where evapora- 
 tion would be permissible, it is better to com- 
 pensate for the surplus water by addition of 
 the substance which served to make the solu- 
 tion. Supposing we had used s grams of sub- 
 stance for every 1 litre of reagent produced. 
 
 Clearly. Pi^ = s„ grams is what ought to have 
 
 P 
 been taken. One way then is to prepare some (say 
 ^ litre) of the solution by means of the corrected 
 method and to determine its specific gravity, 
 Tg, in order to be able to reduce to weight; 
 thus: 
 
 1 litre of solution (pj) . . . = lOOOir^grms. 
 Weight of substance in it . . la s„ 
 
 Hence weight of the water . . = 1000 »,— s,, 
 Or every gram of water requires 
 
 ' * ' ~ -innn ° grms. of substance to be 
 
 1000 T„-s„ 
 
 converted into solution of the intended strength, 
 Pn ; hence our v x(l — e)wx kilos, of water require 
 « X (1 + e) wax kilos, of substance. All that we 
 need for the calculation of (1 + «)«; is the specific 
 gravity tt of the uncorrected solution. Obviously 
 
 {l + e)w = 1000(ir—.£-ir^) grams. In practice, 
 
 Po 
 however, it is scarcely advisable to go to all this 
 trouble. It is easy by some short cut (based 
 on the above) to name a number of grams of 
 substance, which if added to one litre of solu- 
 tion would bring up the strength to a little above 
 p„. Suppose the increase of volume involved in 
 adding these grams of substance is less than, 
 say, 0-1, 0-2..., say y litre. Then, to set things 
 right, we calculate the correct mass of substance 
 
 toil + y litres, which is (1 + 2/) -^ s, weigh out 
 
 p 
 what this mass is more than the s grams 
 present, in each litre, add this to each litre of 
 solution as given, and dilute to 1 + y litre by 
 addition of water. If p differs much from jp,,, 
 it is expedient to slightly over-correct the solu- 
 tion, to determine the exact value, pf, which the 
 solution now has, and (if p'>p„ as intended) to 
 correct the strength, by dilution, as explained 
 above. If p is only a little less than the in- 
 
 tended value Po, we may safely assume the sur- 
 plus water per litre to be 1 — — litre, and add 
 
 Po 
 
 the exact weight, x, of substance, which by 
 calculation converts the smaU quantity of water 
 into correct solution. The result (in the absence 
 of blunders) -will be quite correct even if v was 
 only approximately measured, because a very 
 small volume of water added or withdrawn from 
 the total of v litres would make the solution 
 absolutely correct (apart from the error in p 
 of course). One point remains to be considered. 
 Supposing the strength of a solution at t„ degrees 
 is Pa, what is the strength p^ at t, degrees ? It 
 would not do to calculate the correction from 
 the expansion of pure water from t„ to ^„ because 
 all standard solutions expand more largely than 
 pure water does. A correct method is to deter- 
 mine the specific gravity (say the weight con- 
 tained in a narrow-necked 100 c.c. flask) of the 
 solution at t„ degrees and at t, degrees. Sup- 
 posing the weight of it is it at t, and ir, at t„ 
 
 we have jp, = —p,,- 
 
 This correction of course is indicated only in 
 the case of very exact methods. But in their case 
 it is best altogether to eliminate the uncertainties 
 of volume-measurement by effecting the final 
 standardisation by volume and by weight at the 
 same time ; by determining for instance at the 
 same time the weight in grams and the volume 
 in CCS of the quantity of standard nitrate of 
 silver which is required for the exact ppn. of 
 
 KCl 
 (say) — - grms. of pure chloride of potassium. 
 
 This need not hinder one in so adjusting the 
 solution that the quantity referred to may for 
 all ordinary purposes be assumed to be equal to 
 100 c.c. For the purpose of a highly exact deter- 
 mination, the bulk of reagent (e.g. AgNO, solu- 
 tion) required, after having been measured out, 
 is weighed into the (chloride) solution to be 
 analysed, and the small excess of substance or 
 reagent left is determined by volumetric titra- 
 tion with decimal solutions.' 
 
 The adjustment of an analytically standard- 
 ised solution to an exact pre-determined 
 strength is advisable only if the solution is 
 permanent, and is meant to be used very fre- 
 quently, otherwise it is better to note down the 
 strength as it is, and calculate from it. A solu- 
 tion known to contain 1-023 x HOI grams per 
 litre is almost as convenient as one containing 
 1 X HCl exactly. Because for one or two analyses 
 we can well afford to calculate, say, the product 
 
 1-023 X ■ ^'^' and for a very long series of such 
 
 determinations the value may be calculated once 
 for all and noted on the label. 
 
 On the Theory of Titration. 
 
 Let A and b be two chemical species, which, 
 when their solutions are mixed together, com- 
 bine with, or decompose, each other in some 
 definite manner. Is the reaction available for 
 the mutual volumetric measurement of a and b, 
 or (let us rather say) for the measurement of a 
 
 ■ Compare Dittmar's Memoir on the Composition of 
 Ocean Water. 'Challenger* Memoirs, page 4; also hia 
 Exerxises in QmmlUatite Analfili, section on Sea-waier. 
 
ANALYSIS. 
 
 251 
 
 by B ? It may be if, under easily realisable con- 
 ditions, it proceeds rapidly, and, if it is possible 
 onder these conditions to recognise the point of 
 taturation with sufficient sharpness, i.e. the 
 point from which onwards an additional drop of 
 B-solution does not produce a recognisable 
 change. In some cases the point of saturation 
 defines itself naturally by coinciding with some 
 sudden visible change, e.g. a change of colour. 
 It does so, for instance, if the reaction is a double 
 decomposition, a + 6 = c + i (where a, b, c, d, 
 stand for definite relative quantities of the re- 
 agents A or B, and the products o and d respec- 
 tively), and it a (or b) is intensely coloured, 
 while B, 0, and d (or a, o, and d) are relatively 
 colourless, or at least do not hinder the observa- 
 tion of the colour of the last remnant of a, or a 
 fiUght excess of b. 
 
 Examples : 1, Oxidation of ferrous salt (a), 
 by permanganate (b), with formation of ferric 
 salt (o), andmanganous salt (d). — 2. Decolourisa- 
 tion of the intensely blue solution of cupric- 
 ammonium salt (a), by the reducing action of 
 (standard) cyanide of potassium (b), with for- 
 mation of colourless double cyanide of copper 
 and alkali metal (c), and cyanate and other salts 
 of alkali (d). 
 
 Sometimes when such colour-changes do not 
 occur, they may be produced by addition to the 
 eolation to be titrated of a suitable indicator. 
 Thus : 1. Litmus solution may serve as an in- 
 dicator in the volumetric neutralisation of acid 
 by alkali (or vice versd). — 2. Iron-alum may 
 serve as an indicator in the determination of 
 silver (salt) by added sulphocyanide of ammo- 
 nium, the red colour of Fe(N0S)3 becomes 
 permanent only when all the silver has been 
 ppd. as AgNCS, and a slight excess of sulpho- 
 cyanide has been added. The indicator in this 
 case would evidently be of no use if it were not 
 the case that Fe(N0S)3, which is produced 
 locally from the first, is decomposed as readily 
 and in the same way by silver salt as the alka- 
 line sulphocyanide is. A similar remark applies 
 to indicators generally. If an indicator, while 
 otherwise trustworthy, fails only to fulfil the 
 condition stated above, it may still be available 
 in the sense that, instead of adding it to the 
 'A '-solution from the first, we may apply a 
 Uttle of it to drops of the mixture taken out at 
 suitable stages in the process of the reaction. 
 Thus, for instance, in the titration of phosphate 
 (a), by uranie acetate (b), prussiate of potash 
 may serve as a drop-reagent, because, al- 
 though unavailable as an indicator proper, if 
 added to a drop of the mixture it produces the 
 red-brown colour of ferrocyanide of uranium 
 only if the uranium is present as (an excess of) 
 acetate ; the uranie phosphate is not decomposed 
 by the prussiate. The action of an indicator 
 need not necessarily consist of a colour-reaction ; 
 a ppn. if sufficiently delicate, is as good in prin- 
 ciple, though not as a rule in practice because 
 the locally-formed characteristic pp. will not 
 disappear so readily on stirring up as the colour 
 of a (Ussolved product would. 
 
 If the reaction is a steadily progressing ppn. 
 of the essential radicle a in a by b, the end of 
 the reaction of course coincides with the com- 
 pletion of the ppn., i.». the point when (sup- 
 posing B to be added in successive drops) the last 
 
 remnant of a has just been thrown down by &e 
 jjth drop of B, so that the (n + l)sti drop falls to 
 give a turbidity. For such reactions we need no 
 indicator or drop-test, although such may be 
 very convenient. 
 
 As soon as we have found some means for 
 recognising the end-point in our reaction with 
 sufficient sharpness, we can decide the question 
 as to its availability by preparing standard solu- 
 tions of A and B respectively, and determining 
 the ratio a : b corresponding to the end-point 
 under a sufficient variety of conditions. In a 
 first series we work with the plain solution, 
 but take care in one set of trials to begin with A 
 and drop in B until the reaction is apparently 
 completed ; and in another set of trials we begin 
 with B, pour in a slight excess of a, and then 
 finish with b; this is done in order to see 
 whether the ratio a:bia independent of the 
 mode of mixing. In a second series, we add 
 known, but varying, proportions of water. In a 
 third series we add more or less (but always a 
 known weight (x) of this or that body x which 
 in the practical application of the method would 
 be likely (if not sure) to be present, &c. From 
 Series I. and II. we easUy calculate the small 
 excess of reagent b which must be added, per 
 F c.c. of total mixture at the end, to produce a 
 visible end-reaction. We then calculate for 
 
 each trial the value K=-Ii^£^, and see 
 
 whether there is a practically sufficient and 
 available area of experimental conditions within 
 which the ratio a : b has a constant value. Or, 
 what comes to the same thing, we take the mean 
 of all the KS (let it be = kJ, and see whether 
 the values of Vt, as calculated by the equation 
 Vi, = K„Va + i8p agree sufficiently with the di- 
 rectly observed values. Should this not be the 
 case, the process need not necessarily be given 
 up as hopeless ; it may stiU remain worth while 
 to see whether agreement between theory and 
 practice cannot be established by adding a term 
 c aj to the right side of the equation, where x 
 stands for the weight of some subsidiary com- 
 ponent X, and c is a positive or negative 
 constant, whose value must of course be ex- 
 perimentally ascertained. In such cases, how- 
 ever, it is better to leave the chemical 
 significance of k„, j8, and c, entirely on one side, 
 and to calculate them as so many empirical 
 coefficients from the sum-total of the results. A 
 formula thus obtained is of course of no prac- 
 tical value unless ;3 and c are so small that an 
 approximate determination of p and x suffices 
 for an exact calculation of the respective terms. 
 As an illustration, we may quote Liebig's method 
 for the determination of urea (a), in presence of 
 chloride of sodium (x), by means of standard 
 mercuric nitrate (b) as a pptnt. of the urea, and 
 carbonate of soda as a drop-test for excess of 
 pptnt. The exact volume vj of mercuric nitrate 
 solution (i.e. weight of HgO) to reach the end- 
 point for a given weight (a) of urea, varies with 
 the dilution, f, and the weight x of salt present ; 
 but Vi, is ' in sufficient accordance with equation 
 Yi, = ak + PF + cx, whose constants have been 
 determined (virtually) by Liebig. 
 
 Nothing said so far is based on the presumption 
 
 1 0r at least is supposed toYiOb 
 
:>ii2 
 
 ANALYSIS. 
 
 that the ezaot chemical theory for the reaction 
 between b and a is known. There are indeed 
 a number of useful volumetric processes which 
 arebased upon unezplaiued,or only half -explained, 
 chemical reactions. Fehling's method for the 
 determination of glucose affords an iUustratiou. 
 If a dilute solution of glucose is dropped into a 
 hot, strongly alkaline, solution of tartrate of 
 copper (OuO) and potash, the CuO is reduced to 
 (a pp. of) OUjO, the blue colour of the solution 
 disappears, and the sugar suffers some unknown 
 kind of oxidation. Yet the ratio between (say) 
 dextrose oxidised and copper-oxide reduced, 
 under specified conditions, is fairly constant, 
 and the reaction is accordingly available for a 
 fairly exact method for the determination of 
 dextrose. 
 
 The well-known process of Clark tor the 
 determination of the hardness of a water by 
 means of standard soap might be quoted as 
 another example. But such purely empirical 
 processes, however useful they may be for this 
 or that practical purpose, are of little import- 
 ance as auxiliaries of exact analysis, which 
 demands of a titration-process in the first 
 instance that in any given case the question of 
 its applicability can be decided a priori with 
 at least a high degree of (if not with perfect) 
 certainty. And this is possible only if the 
 process is based on a definite chemical equa- 
 tion which gives a qualitatively and quantita- 
 tively exact account of what is going on. 
 
 Prom the fact, however, that some equation, 
 a + b = c + d,ia in itself a correct theory of the 
 action of A on B as resulting in the products 
 and D, it does not follow that the equation is 
 a sufficient theory of the corresponding process 
 of titration. Because experience shows that, 
 in general, ready-made o and d when mixed 
 together produce A and B in accordance with 
 the inverse equation c + d = a + b. Hence 
 supposing we start with a parts of A and add 
 more and more of B, the end reaction is reached 
 only when a part (say qa) of A is transformed 
 at the expense of qb parts of B, while (1 — 2) 
 times {a + 6) are still present in their original 
 condition. Generally, g is a continuous 
 function of the experimental variants (state 
 of dilution, temperature, &c.), and the transla- 
 tability of the reaction into a titrimetrio process 
 depends on the possibility of finding a sulEcient 
 area of conditions within which q is, at least 
 practically, equal to unity. 
 
 If one of the products (0 and n) separates 
 out as an absolutely insoluble pp., or escapes 
 as a gas, the reverse reaction does not occur, 
 and 2 becomes equal to unity ; the apparent 
 end-point is the real end-point of the reaction. 
 Hence we should think that ppns. (we mean 
 cases where that radicle in A which is really the 
 thing to be determined, by uniting with the 
 essential radicle in B, separates out as a pp.), 
 should be pre-eminently suitable for volumetric 
 application. Experience, however, shows that 
 the reverse is true. Because in the majority of 
 cases the pp. carries down more or less of one 
 or other of the other reagents or products, and 
 80 disturbs the quantitative relations. Very 
 often also a considerable excess of pptnt. is re- 
 quired to produce complete ppn. within a reason- 
 ili.e time. Both diffiouUie.s (for example) pre- 
 
 sent themselves in the case of that reaction, 
 BaX-HS04Rj=B2X + BaS0„ which is so largely 
 used for the gravimetric determination of SO, 
 and of Ba. The irregularities referred to ' can 
 be set right (more or less easily) in the gravi- 
 metric application of the reaction ; to the 
 volumetric application they are absolutely fatal. 
 The number of ppns., indeed, which afford a 
 basis for correct volumetric processes is extremely 
 limited. 
 
 Certain classes of double decompositions and 
 oxidations, in which reverse reactions are pre- 
 vented by the great inherent stability of one of 
 the products, are admirably adapted to volu- 
 metric processes. To give examples : 
 
 Any strong acid, XH, when mixed pro- 
 gressively with a solution of some strong base 
 of the type EOH (ex. KHO,NaOH,Ba(OH)j), is 
 ultimately converted into normal salt, XB, with 
 formation of that highly stable substance water. 
 The general reaction is XH -I- EOH = EX + HHO, 
 and the end-point can in all cases be sharply 
 defined by means of a few drops of neutral 
 litmus-solution as an indicator. Hence any 
 acid (or rather the 'H' in any acid) maybe 
 accurately measured by means of a standard 
 solution of, for instance, caustic potash ; and 
 any of the bodies EOH (or rather their 'OH') 
 by means of a standard solution of (say) hydro- 
 chloric acid. The latter method applies almost 
 directly to the (soluble) carbonates, sulphides, 
 cyanides, &o., of the alkali metals. All the 
 carbonates &o. referred to can be measured 
 indirectly by the combined application of the 
 two standard solutions : we add first an excess 
 of standard acid, and heat to expel the volatile 
 acid (COj.H^S, &a.), then colour with litmus, 
 and titrate back with standard alkali, till the 
 point of neutraUty is exactly reached. By sub- 
 stituting aurime (in alcoholic solution) for 
 litmus, the method becomes available also for 
 magnesia (Torno) ; and by using nitric acid as 
 the standard XH, we can determine even oxide 
 of silver (Dittmar). 
 
 What we said of carbonates, &o., in refer- 
 ence to the metaUio radicles, E, holds for the 
 ammonium salts of our acids, XH. To determine, 
 for instance, HCl or HjSO^, in the presence of 
 ammonia (as the only base), we need only add 
 a known excess of standard alkali, expel the 
 liberated ammonia by evaporation, then add 
 litmus, super-saturate by standard acid, boil off 
 the carbonic acid, titrate back with standard 
 alkali until the point of neutrality is exactly 
 reached, and balance the equivalents of base 
 and acid used as reagents, against each other ; 
 the balance of base-equivalents measures tha 
 acid given for determination. 
 
 That this method of acidimetry applies also 
 to cases where the base can be separated out 
 by excess of standard alkali, as an acid-free 
 pp., is obvious. Oxide of copper (given aa 
 CUSO4 or other cupric salt) fulfils this condi- 
 tion in the sense at least that the acid ppd. at 
 first as part of a basic salt, can be re-extracted 
 by boiling with excess of alkali.' 
 
 * And other irregularities sucli as for instance the varia- 
 bility of the ratio of sulphur to copper in ppd. sulphide ol 
 copper. 
 
 " We will avail ourselves of this opportunity for 
 referring to the process of fractional filtration as ttseful In 
 
ANALYSIS. 
 
 s.oa 
 
 To pass to another example. There is a 
 series of reducing agents b, the solutions of 
 which, when mixed with a solution of iodine in 
 iodide of potassium, are oxidised into products 
 b', while the corresponding quantity of free 
 iodine passes into iodide. 
 
 For example : — 
 I. SOj + HjO + l2 = 2HI + SO, 1 
 
 III AbA + 2H,0 + 2I, = 4HI + AsA > «„° 
 IV. SbA + 2H20 + 2I, = 4HI + SbA 
 V. SnCl2 + 2HGl + Ij = 2HI + SnCl4 J 
 
 Each of these reactions takes its normal 
 course only under certain conditions, which, 
 however, in cases I. to IV. at least, are easily 
 established. All go on readily in the cold ; and 
 with all, starch solution is a safe and delicate 
 indicator of excess of free iodine. Hence, to 
 determine any of our reducers, B, we bring it 
 into solution in the proper manner, add starch 
 solution, and then drop in iodine solution from 
 the burette until the blue colour of iodide of 
 starch, which appears locally from the first, 
 becomes permanent on stirring. Supposing t 
 0.0. of iodine solution to have been used, and one 
 c.c. of it to contain t x 127 mgms. of free iodine, 
 the weight of B is tr (5SO2, S-fi^, JAs^Oj, 
 ■ iSboOa, iSnClj,), as the case may be. By theory, 
 any one of our reducers might serve as a reagent 
 for the measurement of free iodine ; in practice 
 sulphurous acid and alkaline thiosulphate work 
 best. 
 
 According to Bunsen, sulphurous acid acts 
 normally on iodine, if it is diffused through at 
 least 3,000 times its weight of (air-free) water. 
 JPor the determination of free iodine he uses an 
 aijueous sulphurous acid diluted to the extent 
 stated, in combination with a standardised 
 solution of iodine. The sulphurous acid is 
 measured out by means of a glass-stoppered 
 cylinder (or a narrow necked flask with one 
 mark on the neck) holding some 100-200 c.c. 
 To determine an unknown weight (x mgms.) of 
 free iodine given as solution in HI or KI solu- 
 tion, we add the least number n of measures of 
 the sulphurous acid water which suflSces to 
 decolourise the solution, then starch solution, and 
 lastly, from the burette, standard iodine, until 
 the blue colour becomes permanent after addition 
 of, let us say, t c.c. On the other hand, we 
 ascertain the number, t„, of o.c.s of standard 
 iodine required for 1 measure-full of the sulphur- 
 ous acid. Obviously, n<„T x 127 = x + trx 127 
 (mgms. of I2). Whence x = {nt„ -t) tx 127. 
 
 So far Bunsen had done no more than trans- 
 late an old process for determining SOj into a 
 precise method for determining iodine. His 
 great merit was to see that, given a method 
 for determining free iodine, we have an indirect 
 method for the determination of any of the large 
 number of oxidising agents for which a definite 
 proportion of iodine can be substituted by the 
 purely qualitative execution of suitable reactions, 
 cases like that referred to. Instead o{ filtering ofE the 
 CuO pp., we allow the mixture to cool, dilute to a known 
 volume, To.c, filter through a dry filter, and measure off a 
 Known aliquot part of the filtrate, v c.c, for the titration. 
 If V is sufficiently large, the volume of the CuO need not 
 be taken into account ; supposing for instance v=500 c.c. 
 find the pp. of CuO amounts to 1 gm., the error introduced 
 by neglecting its volume amounts certainly to no more 
 than about 0'5 o.c, or 0-001 of the whole. 
 
 Thus, for instance, we may determine Irv^^ 
 bromine, iodate £I0„ bromate EBrO,, hypo- 
 chlorite EOlO, ozone O3, by letting the respec- 
 tive substance act on excess of iodide of 
 potassium solution, acidifying with hydrochloric 
 acid, and then titrating the iodine liberated as 
 above explained. 
 
 From the respective equations, we see that 
 Br2, or CI2, or EGIO, or O3, liberates Ij ; and 
 that EIO3 or EBrOa liberates 31^. 
 
 The same principle obviously applies to all 
 those peroxides which, when distilled with excess- 
 of hydrochloric acid, liberate a definite propor- 
 tion of chlorine. As examples : MnO.O^ (when 
 distilled with HCl) yields x x CI2 of free chlorine, 
 which when passed into iodide of potassium 
 solution liberates x x I^ of iodine. Hence for every 
 
 one I mgm. obtained, there was — x (MnO.Ox) 
 
 mgms. of that peroxide of manganese. And 
 similarly (to quote another ease which is known 
 to work) every CrO^ mgm. of chromic trioxide, 
 liberating 3 x 01, ultimately yields 3x1 mgms. of 
 iodine ; or, in this case, every 1 x I mgms. cor- 
 responds to ^CrOs, or to ^ X KjCr^, if the CrOj 
 was present in this form. It is as well to men- 
 tion that what the method in any case really 
 determines is, not the respective species, but the 
 Ij-yielding radicle; the active oxygen in the 
 MnO.Ox, or the Cr^Oa.Os, or EClO; the 0, in the 
 KIO, ; the one in O3, &c. 
 
 The applicability of the general method, 
 however, goes further. As ferrous chloride ia 
 readily converted into ferric salt by free fihlorine, 
 we can determine an unknown weight oiferrosmii 
 (ferrous iron) (given as FeCl^, FeO, FeSOj, &c.) 
 by distilling the respective substance with a 
 weighed excess of potassium dichromate and 
 hydrochloric acid, and collecting the chlorine in 
 iodide of potassium, &c. Supposing we used 
 k X K2Cr20, mgms. of this salt, the chlorine 
 furnished by it is 6 x A; x CI mgms., and, if the 
 iodine obtained at the end was (nt^ — i) x t x I 
 mgms., then 6k x CI- {nta — t)T CI must have 
 been used by the FeCl^, and consequently, 
 {&k — {nt„ — t)T\x(Ee = 5Q mgms.) of ferrosum 
 must have been present in the substance 
 analysed. 
 
 Strictly speaking, all volumetric methods are 
 empirical methods, in this sense, that the funda- 
 mental chemical equation is only an approximate 
 theory of the process. Hence, unless we are 
 sure that the error in the equation, considered as 
 a theory of titration, is less than the unavoid- 
 able error involved in the operations, to attain 
 the highest possible degree of precision wc 
 must standardise our measuring reagent (il 
 possible) by means of a known weight of the 
 very thing (or radicle) to be determined, and 
 both in the standardisation and the analyses we 
 must maintain as nearly as possible the same 
 conditions. To illustrate this, let us assume we 
 had to analyse a series of alkaline carbonates by 
 means of a standard hydrochloric acid. Ppn. ot 
 a known volume of the reagent by nitrate o£ 
 silver, and weighing the pp. of AgGl (or the 
 corresponding process of titration) would no 
 doubt give the most exact result for the number 
 of mgms. of HCl contained in 1 c.c. of the reagent, 
 Tet it is better in our case to standardise thf 
 
254 
 
 ANALYSIS. 
 
 aoid by means ol a known -weight of pure 
 caifaonate of soda, although this method, as one 
 for the determination of HCl, could not for a 
 moment be compared with either silver process 
 in point of inherent precision. 
 
 In now passing from generalities to the con- 
 sideration of individual methods, we shall 
 confine ourselves in the main to those methods 
 which are applicable to whole classes of bodies. 
 Under the head of each we shall brieiiy state 
 what applies to it as a general method. For 
 special applications of these methods, as for 
 special methods generally, also in regard to 
 technicalities, we must refer to the special hand- 
 books.' 
 
 I. Methods based on double decom- 
 positions. 
 
 Theoretically these processes are founded on 
 equations of the form 
 
 a!B + by = ab + !cy 
 
 A, B, 0, D, 
 
 where a and 6 are the constant radicles charac- 
 teristic of the process. Here we have to dis- 
 tinguish between two cases : — I. o and n remain 
 dissolved. Only a very few processes fall into 
 this group. As an example, we may quote 
 Liebig's process for the titration of NCH by 
 neutral nitrate of silver. Large excess of potash 
 is added, the liquid is diluted largely, and, after 
 addition of a little NaCl as indicator, stan- 
 dard AgNOj (neutral) is dropped in until the 
 cloud of AgCl becomes permanent, showing that 
 the reaction 2KNC + AgNO, = KAg(NC)2 + KNOj, 
 has been just completed. II. The characteristic 
 product o = ab comes down as a pp. Of these 
 numerous processes, only those need now be 
 noticed in which, on account of the absence of 
 an end-reaction, and of a suitable indicator, the 
 end-point cannot be recognised otherwise than 
 by proving quite directly that the ppn. has just 
 reached its end. If the pp. settles readily, this 
 can be done with comparative ease — in an 
 obvious manner; but easily settling pps. are 
 exceptional. It is more generally practicable to 
 get the pp. to settle so far that it is possible to 
 draw ofE a few drops of the clear top-stratum, 
 and to examine them on a watch-glass by addi- 
 tion of a drop of B, or of a solution of a, or of 
 any delicate reagent for A or B. If this method 
 does not work, the only course left is, from time 
 to time, to take out a little of the mixture, filter 
 it through paper, and examine the filtrate. 
 One way of doing this is to put a drop of the 
 fluid on a small double filter-paper, and to ex- 
 amine the lower filter by means of some reagent 
 which strikes an intense colour with a or B as the 
 case maybe. But such colour-tests are not always 
 available, so that ordinary filtration must gene- 
 rally be resorted to. Each such filtration of course 
 means a loss of a, and consequently ought to be 
 done with a measured aHquot part of the whole, 
 to enable one to aUow for the loss by calculation. 
 This, however, is apt to lead to errors ; in prac- 
 tice it is better in the first trial to neglect the 
 error, and in a second and third practically 
 
 1 Mobr's Lehrbuch der chemische-analytUchen Titrirme- 
 thode; 2, Pleisoher, Die Titrirmethoie ; 3, Pleisoher, Die 
 Tilrirmethode, English edition Volumetric Analysis, trans- 
 lated by M. M. Pattison Muir ; 4, Sntton, Volumelrie 
 AncUytit; i, Vtesieaiw, QmntUatiM AMOlyits. 
 
 to avoid it by filtering only a few times near the 
 end of the process, when the amount of nn- 
 ppd. A has become very small. In any case it il 
 convenient to have a standard solution of some 
 reagent, ax!, by means of which to retrace one's 
 steps if an excess of pptnt. has been added. This 
 auxiliary solution is best adjusted so that it pps. 
 exactly its own volume of b. The method of 
 procedure then assumes this form : — We add b, 
 finally in small instalments of, say, 4 c.c. each, 
 until by the last instalment the end-point has 
 been over-stepped ; we then go back with A-solu- 
 tion, adding it in instalments of 2 c.c, until 
 this reagent is in excess ; we then again apply b 
 in portions of 1 o.c, &o., until we come to know 
 that, say, v c.c. of b is too little, while v + 0'2 o.c. 
 is an excess ; or that (v-^ 0-1 o.o.) ± O-l c.c. may 
 be adopted as the final result. 
 
 Of the vast number ot precipitaUon-analyses 
 which have been invented, only those founded 
 upon mutual decomposition of solutions of 
 Silver salts and haloids occupy the rank 
 of precise methods. If (dissolved) chloride and 
 (dissolved) silver-salt meet in a neutral or aoid 
 solution the whole of the potential chloride of 
 silver is formed, and comes down as a pp. as 
 demanded by the equation, 
 
 ECl + AgNO, = AgCl + ENO3. 
 Upon this, and the fact that the AgCl (if suffi- 
 ciently abundant) readily unites on shaking into 
 a quickly settling pp., Gay-Lnssao long ago 
 founded his famous process for the determina- 
 tion of silver by standard NaCl solution, which 
 process is directly translatable into an equally 
 exact process for the determination of chloride by 
 standard silver. The equation, however, is not 
 an absolutely correct theory of either process. 
 Gay-Lussao observed that if the silver nitrate and 
 the sodium chloride are exactly balanced against 
 each other, the clarified mixture gives a distinct 
 cloud with either reagent. Hence to exactly 
 complete the ppn. of (say) AgNO, mgms. by salt, 
 we must add, not NaCl, but a trifle more, call it 
 (1 -I- a)NaCl mgms. And similarly, the complete 
 ppn. of NaCl mgms. demands (l + i3)AgN0, 
 mgms. The exact values of o and |8 vary with 
 the experimental conditions, and are not sus- 
 ceptible of separate determination. Hence to 
 determine an unknown weight, x x Ag mgms. of 
 silver (if we do not care to neglect the correcting 
 factors), all we can do is : (1) to add standard 
 chloride solution — at last in very small instal- 
 ments, corresponding to say 0'02 mgms. of silver 
 each — until the ppn. is exactly completed by, 
 say, n x BCl mgms. as calculated from the 
 strength of the solution, and the quantity used. 
 We then (2) titrate back with (very dilute) stan- 
 dard silver until the last drop no longer gives 
 a cloud of AgOl, which will take, say, e x Ag 
 mgms. The mixture now is (practically) in the 
 same condition as if no silver had been added 
 but the chloride diminished by e x BCl mgms. 
 Obviously the truth lies between x = n and 
 
 x=n—e, and we may say x={n — _)±-l, 
 
 2 2 
 Or, to put it somewhat differently ; we have 
 
 2x = in + {fi-a)n-e I. 
 
 andO = TC(.a + ci)-e II. 
 
 If we knew that a = ;3, we should have a; = » - -L 
 exactly. 3 
 
ANALYSIS. 
 
 L"6S 
 
 According to Mulder, if the silver, calculated 
 aa metal, amounts to about 1 gram, and ia 
 diffused throughout some 120 to 150 c.o. of 
 mixture (a + ff) =0-001, about.' The explanation 
 given in regard to chlorides holds substantially 
 for bromides, iodides, cyanides (NOB) ; sulpho- 
 cyanides (perhaps also for cobaltocyanides, and 
 gome other metallo-cyanides) ; in the case of 
 bromides, however, the numbers o and P are 
 practically equal to nil (Staa), AgBr being even 
 more insoluble in HNOj and KNO3 &c. solu- 
 tions than AgCl is ; hence we may surmise that 
 the (a + ;8) for iodide is still nearer to nothing. 
 The cases of NC.B and NCS.B have not been 
 investigated in this sense. Presumably the 
 
 !a + $) for cyanide is greater than, and that for 
 NCS)E is about equal to, the value for chlo- 
 rides. 
 
 Given (let us say) an alloy for which the 
 percentage of silver is approximately known (say 
 to ± 0*5 p.c.) ; the exact determination of the 
 noble metal by titration with standard chloride 
 (e.g. NaCl) solution ofiers no difficulty ; but with 
 an alloy &c. of utterly unknown composition 
 the process even in practised hands is apt to be 
 tedious. Practical assayers, indeed, never apply 
 Gay-Lussao's method without having first made 
 a preliminary assay by the old method of oupel- 
 lation. Volhard, some years ago, invented a 
 modification of Gay-Lussac's method, which, 
 with a small number of samples at least, is 
 quicker even than cupeUation, and, in all cases, 
 is more accurate. He dissolves a known weight 
 (equal to presumably 0'5 grm. of silver) in nitric 
 acid, dilutes moderately, boils off all the NjOj, 
 adds 5 c.c. of saturated iron-alum solution, and 
 then drops in standard sulphocyanide of potas- 
 sium (or anmionium) until the red colour of 
 Fe(NCS)3 becomes permanent. (The large quan- 
 tity of indicator prescribed is necessary, or else 
 the end-reaction lacks delicacy.) For the deter- 
 mination of chlorine (given as ECl), Volhard 
 pps. the chlorine first by an excess of standard 
 silver, he then adds iron-alum, and (without re- 
 moving the AgCl") titrates back with KNCSAq 
 until the end-point is reached. 
 
 A very handy (but less exact and less widely 
 upplicable) method, introduced by Mohr, may 
 here be referred to. He brings the chloride into 
 neutral or very feebly alkaline solution, and, after 
 adding a few drops of yellow ohromate of potas- 
 sium, titrates with neutral silver nitrate until 
 the red colour of the AgoCrO, becomes perma- 
 nent. The method, if used as an empirical one, 
 gives very good results. 
 
 SiABPAKD Substances and SoIiUiions. 
 
 1. Standard silver. — Best prepared by Stas's ' 
 process (precipitation of a cupriferous am- 
 moniacal solution of nitrate by added alkaline 
 ammonium sulphite). The ppd. metal, after 
 having been washed, first with ammonia in the 
 
 ^ Our impression ia that Mulder over-estimated the 
 value. 
 
 ^ The writer finds that high precision can be reached 
 only by removing the AgOl pp. before titrating back with 
 KNCS. (See Dittmar's Report on the Composition of Ocean 
 W^(i/e;', p. 4. ['Challenger' Memoirs.] Also his ^arern'w* 
 (n Quantitative Anal/sit, section on Sea-water.') 
 
 ■ Reclierches sur lea rapports riciproques des poids aio. 
 tniques (Bruzelles, 1860) ; and Nouvelles SechercheSy &c. 
 (iJruxelles, 1865), or Oermau translation of both works 
 Axouateiu (LeipEig, 1867), 
 
 presence of air, then vfith water, is heated to red- 
 ness, when it becomes semi-compact. It is then 
 broken up in a mortar into granules, again 
 heated, and preserved in this form. There is no 
 need of going to the trouble of fusing the metal, 
 provided it is proved to be free from every trace 
 of chloride. 
 
 2. Standard chloride. — Pure chloride of 
 sodium is universally recommended. The 
 writer prefers pure KGl prepared by strongly 
 heating re-crystaUised perchlorate. The per- 
 chlorate is deoxygenated as far as convenient in 
 a platinum basin, and then fully by fusion in 
 a platinum crucible. The fused salt is quite 
 neutral ; yet for very precise work it is perhaps 
 better to dissolve the fused salt in water, add 
 hydrochloric acid, evaporate to dryness (in pla- 
 tinum), and keep the residue at a temperature 
 just short of the fusing point until the weight is 
 constant. 
 
 3. Standard solutions of 1 and 2. — ^Both can 
 be standardised synthetically, on the basis of 
 Stas' atomic weights; for general purposes 
 
 _S and -— - grmg. per litre are convenient 
 
 10 10 " 
 
 strengths. For exact work the solutions are 
 
 combined with centinormal solutions, containing 
 
 Ag J KCl ,.* 
 
 i^ 100 ^™ ■^ 
 
 4. Pure bromide of potassium, and standard 
 
 solution (-rrrr- grms. per litre) of the same for 
 
 very precise determinations of silver. Eegarding 
 the preparation of the pure salt, see Stas's 
 Memoir. 
 
 5. Standard sulphocyamde. — About A 
 NCS.NH4 grms. of the pure (chlorine-free) 
 ammonium salt is dissolved to 1 litre, and the 
 exact strength is determined empirically by 
 means of a known weight of silver dissolved as 
 nitrate. 
 
 n. Methods based on saturations, 
 that is, reactions of the type 
 
 XH -1- EOH = HOH -I- XE ; 
 regarding these, we have little to add to what 
 was given under Theory of Titration {q.v.). For 
 XH = NOsH, iSOiHj, C1H,HC10„ and other strong 
 acids (inclucung oxalic and formic) on the one 
 hand, and B = E,Na, generally, and for 
 E = i (Ba, Sr, Ca) as long as no insoluble salt is 
 produced, on the other, the equation is a strictly 
 correct theory of the process. For phosphoric 
 acid, HX must be taken as representing 
 ^^[(HPO,), EHO being an alkali, but even 
 then the results are not very constant. For 
 weaker acids, such as acetic, butyric, &c., the 
 method is purely empirical. An approximation 
 to a standard acetic acid is obtained by measuring 
 off a known volume of standard sulphuric acid, 
 and adding say two equivalents of perfectly 
 neutral acetate of soda. In determinations of 
 ammonia it is as well not to assume that NH,OH 
 is an absolutely exact equivalent for KOH or 
 NaOH. 
 
 Stakdabd Substances and Solutions. 
 
 1. Pure carbonate of sodium, as a general 
 standard alkali. Prepared from pure bicarbonate 
 (reorystaUised as such) by strongly heating in 
 platinum. The salt must not be fused for de- 
 
256 
 
 ANALYSIS. 
 
 hydration, or else it loses oarbonio acid. To 
 obtain a really pure, and especially a potasb- 
 free, salt, the best method is to add pure oxalic 
 acid to a decided excess of solution of the purest 
 obtainable carbonate of soda, to collect the pp. 
 of CjOiNaj formed, to wash it by displacerhent 
 and to reduce it to Na^CO, by heating strongly 
 (W. D.). 
 
 2. Oxalic acid, C2H20, + 2H20, recom- 
 mended by Mohr as a general standard acid. 
 Bee that the preparation is free from fixed matter 
 (e.g. potassium salts). If not, recrystallise it 
 from hot 10 p.c. HCl, repeatedly, and lastly from 
 water (Stolba). The carefully air-dried crystals 
 have the correct composition. We prefer a hydro- 
 chloric acid, standardised by silver, for general 
 purposes. 
 
 3. Solution of standard acid. — Sulphuric 
 works best for alkalis; hydrochloric is prefer- 
 able for general purposes. The latter may be 
 standardised by means of silver ; either acid 
 by means of a known weight of carbonate of 
 soda,' with standard alkali as an auxiliary re- 
 agent. Thorpe recommends for the standardisa- 
 tion of SO^Hj, to add a known (excessive) weight 
 of NajCOj, to evaporate to dryness, heat, and 
 weigh the residue. As every Na^COj grms. in 
 passinginto Na^SO,, gains (SO, - COjjgrms., every 
 
 1 grm. of gain of weight corresponds to ' 
 
 SO,-CO, 
 grms. of sulphuric anhydride. (I have tested 
 this method, and found it to give very good re- 
 sults.— W. D.) 
 
 4. Solution of standard alkali. — Caustic 
 potash or caustic soda for general purposes. 
 The reagent must be as free as possible from 
 carbonate. The preparation known as potash 
 •purified by alcohol almost fulfils this condition. 
 The best method is to causticise an almost 
 carbonic acid free (dilute) ley with a slight 
 excess of baryta in a nickel vessel ; allow to 
 settle, and preserve in a bottle provided with a 
 protection-tube filled with granulated soda-lime, 
 or baryta, Ba(0H)2. The trace of dissolved 
 BaO disposes of traces of COj that find their 
 way into the reagent while being preserved. 
 ^ROH grms. per litre is a convenient strength. 
 It is standardised empirically against measured 
 standard acid. 
 
 5. Standard baryta water containing about 
 JBa(0H)2 grms. per litre is used for special pur- 
 poses, e.g. determination of free or liberated 
 CO2. A stronger reagent is apt to deposit crys- 
 tals in cold weather. It is standardised em- 
 pirically against standard hydrochloric acid. In 
 the absence of sulphates, baryta water is the 
 best standard alkali for all purposes. 
 
 III. Methods based upon processes of 
 oxidation and reduction. 
 
 (As illustrated in Theory of Titration, by 
 reference to Bunsen's methods.) 
 
 I. Iodine (solution of I in EI) as oxidant 
 is available for the measurement of the follow- 
 ing reducers : — 
 
 1. Dissolved sulphurous acid acts normally 
 under the conditions stated under Theory of 
 Titration. 
 
 ' Ppn. with BaOl, and weighing the BaSO. is not a 
 very exact method for the standardisation o£ a sulphuric 
 acid. 
 
 2. Dissolved alkali tliiosulphate (in the 
 absence of excess of alkali; even carbonate is 
 not permissible) acts normally at any state of 
 concentration which one could reasonably 
 employ. In the presence of acid the reaction 
 takes its normal course only if the solution is 
 suificiently diluted, and the H^SjOj has no time 
 to decompose spontaneously. In practice, how- 
 ever, this spontaneous decomposition is out of 
 court, because, in all cases in which free acid is 
 present, it forms part of the iodine solution, and 
 the thiosulphate plays the part of reagent, so 
 that the SjOjHj liberated passes at once into 
 SjOjHj, which is sufficiently stable. Free sul- 
 phuric acid in any quantity must be avoided 
 (v. supra) ; free hydrochloric acid in moderate 
 quantity does no harm, if the given iodine solu- 
 tion is diluted to about J-| of the strength of 
 the customary standard solution. 
 
 3. Alkaline arsenite. The reaction proceeds 
 (not as promptly as those of 1 and 2, but) in a 
 fair degree normally, provided there is enough of 
 pure carbonate or bicarbonate of alkali to keep 
 up an alkaline reaction to the end (Mohr). The 
 best auxiliary alkali to add is sesqui-carbonate of 
 ammonia; it does not decolourise iodide of starcli, 
 to anything like the (slight) extent to which 
 Na^COj does (Mohr ; later communication). 
 
 4. Alkaline antimonite, or rather SbjO, 
 given as tartar emetic or in similar forms, is 
 oxidised by iodine just as ASjOj is (Mohr). 
 Besults fair. 
 
 5. Stannous chloride. The execution of the 
 process (SnCl^ -f 2HC1 -1- Ij = 2HI + SnClJ offers 
 no difficulty, and added starch solution defines 
 the end-point sharply ; but the results are very 
 variable and inexact. 
 
 6. Sulphuretted hydrogen H^S (in much air- 
 free water) with iodine reacts substantially 
 thus : — 12 + HjS = 2HI + S. Eesults are only 
 approximate, yet the method is of some value 
 for determining small quantities of HjS iumuch 
 water. 
 
 II. Iodine in combination with reducers 
 
 for general purposes. 
 Only the combinations 1^ and H^SO,, and I, 
 
 and Na^SjOs are used now-a-days. Discussion 
 anticipated in section on Theory of Titration. 
 
 III. Permanganate of potassium, as an 
 
 oxidant, 
 measures the following reducers directly, and in 
 all cases the intense colour of the reagent mark? 
 the end-point with great sharpness. 
 
 1. Ferrosum. A dilute, strongly acid, solution 
 of ferrous sulphate, when titrated with solution 
 of permanganate, is promptly oxidised into 
 ferric salt with formation of MnO-salt from the 
 reagent (Marguerite). 
 
 Conditions of success: — a, large dilution; 1 
 litre of solution should contain at most 1 gram 
 of metallic iron ; 6, a sufficiency of free sulphuric 
 acid, more than the equation demands, or else 
 MnOj may separate out as a pp. ; c, absence of 
 hydrochloric acid (and chlorides generally), or 
 else part of the reagent is reduced by it with 
 formation of Cl^. According to Zimmerman, 
 however, this by-reaction can be prevented by 
 addition of manganous sulphate to the ferrosum 
 solution. 4 grams of the salt MnS0,-f4H„0, 
 
ANALYSIS. 
 
 2C7 
 
 euffice per 60 o.c. of 20 p.c. HCl used for dis- 
 solving the respective iron compound. 
 
 Iron given as ferric salt may be reduced to 
 ferrous salt, by (1) treatment with HjS ; (2) pro- 
 longed treatment in a warm solution with Na^SO, 
 and HCl (works better with chloride than with 
 sulphate solution) — in either case the excess of 
 reducer must of course be expelled by ebullition 
 — (3) zinc and acid; handy, but not so trust- 
 worthy as (1) or (2). 
 
 2. Oxalic acid. A strongly sulphuric solu- 
 tion of this acid is oxidised by the reagent into 
 carbon dioxide and water (Hempel). The re- 
 action at first proceeds very sluggishly, but 
 then more and more promptly, as the quantity 
 of MnSO, produced increases. Hence the ex- 
 pediency of adding MnSO, from the first (De 
 Koninck). Whether hydrochloric acid interferes 
 with this reaction as with the preceding one 
 (whether, for instance, it is permissible to dis- 
 solve oxalate of lime given for the determina- 
 tion of its oxaUc acid in hydrochloric acid before 
 titrating) has not yet been determined. 
 
 3. Arscnious acid. Arsenious acid in strongly 
 hydrochloric solutions is oxidised by permanga- 
 nate into arsenic acid, but part of the manganese 
 separates out as MnO^ (Kessler). 
 
 4. Antimonmis acid as SbClj, in a solution 
 which contains not less than 1-2 volumes of 
 hydrochloric acid for 5 of water, is readUy and 
 completely oxidised into Sb^Oj. The reaction is 
 available quantitatively. [(3) and (4), Kessler, 
 /. 1863. 683)]. 
 
 5. Sulphwrova acid is readily oxidised into 
 sulphuric ; not investigated quantitatively, as far 
 as we know. 
 
 6. Peroxide of hydrogen. In the presence 
 of water and dilute sulphuric acid, the mutual 
 reduction 
 
 5H^0.0 -1- Mn^O, = 5a,0 + 2MnO -I- SOj 
 proceeds normally and promptly. 
 
 7. Nitrous acid (liberated from nitrite by 
 HjSOj in very dilute solutions) is oxidised by 
 permanganate to nitric acid. Eesults, under 
 certain conditions, fair. 
 
 8. OujD (ppd.) dissolved in acid iron alum, 
 ia oxidised readily, and fairly normally, to 2CuO. 
 
 rV. Combined application of permanga- 
 nate and reducing agents. 
 
 A. Ferrosum as reducer. 
 
 The higher oxides of manganese, when 
 digested with HCl or dilute HjSOj and excess of 
 ferrous salt, are readily dissolved as MnO-salt, 
 with formation of a quantity of ferricum pro- 
 portional to the loosely held oxygen in the per- 
 oxide. In the absence of atmospheric oxygen, 
 i.e. in an atmosphere of CO2, the reaction takes 
 its normal course, and becomes available for an 
 obvious remainder-method for the determination 
 of such oxygen. No doubt available for other 
 peroxides. 
 
 Upon the ready action of alkaline permanga- 
 nate on the sulphides, sulphites, thiosulphates, 
 iodides, arsenites, formates, of K or Na, with 
 formation of sulphate, iodate, arsenate, carbonate, 
 respectively (and hydrated binoxide of manga- 
 nese), P^an de St. Gilles (A. Ch. [3] 65, 374), 
 has founded a general method for the determina- 
 tion of the respective acids by means of a 
 standard solution of permanganate, and an 
 
 Vol.. I. 
 
 auxiliary solution of ferrous sulphate. After 
 having carried out the required oxidation by 
 means of excess of permanganate and a suffici- 
 ency of caustic potash, the mixture is acidified, 
 the MnOj and surplus Mn^Oj reduced by addition 
 of, first, acid, and then excess of ferrous solution, 
 and finally the surplus ferrosum is titrated by 
 addition of more of the permanganate solution. 
 
 B. Oxalic Acid as reducer. 
 Any higher oxide of manganese, MnO.Oj, 
 when digested with excess of oxalic acid and 
 sulphuric acid, is dissolved as MnSOj, with 
 formation of COj from the reagent, The oxalic 
 acid is used as a standard solution, and what 
 remains over after the oxidation is determined 
 volumetrically by permanganate. (Calcium oxa- 
 late may separate out as a pp.) 
 
 V. Chromic acid (in practice a solution 
 
 of KjCr^O,) as oxidant 
 is available for the direct titration of the follow- 
 ing reducers : 
 
 1. Ferrosum. Ferrous sulphate or chloride, 
 in the presence of free acid, is readily and com- 
 pletely oxidised by added bichromate solution. 
 The latter may be standardised synthetically (or 
 analytically by means of a known weight of dis- 
 solved ferrosum). The end point is recognised 
 by means of ferricyanide as a drop-test. The 
 results are in exact accordance with the chemi- 
 cal equation, even in the case of hydrochloric 
 solutions (Penny; Schabus). An unknown 
 weight of CrOj can be determined with equal 
 exactitude by adding a known excessive weight 
 of ferrosum (as sulphate) to the previously 
 acidified solution, and titrating back with bi- 
 chromate solution. 
 
 The combination K^Gr^O, and ferrous salt 
 is equivalent to that of MnjOjK^O and the same 
 reducer. It is available likewise for thi3 deter- 
 mination of As.^Oj and Sb^Oj in strongly hydro- 
 chloric solutions. The solution is mixed with 
 a (measured) excess of bichromate solution, and 
 the mixture allowed to stand to give the oxi- 
 dation time for completion ; a known excessive 
 quantity of ferrosum is then added, and its ex- 
 cess is titrated by means of bichromate (Kessler). 
 
 2. Sulphurous acid, Sulphuretted hydrogen. 
 Stannous chloride, in mineral acid solutions, 
 are readily oxidised by CrOa into SO3, S + HjO, 
 SnClj, respectively, and in , all cases iodide of 
 potassium and starch afford a sensitive indi- 
 cator of excess of oxidant, which sharply defines 
 the apparent end-point of the process. But, 
 unfortunately, the corresponding ratio of the re- 
 agents in no case coincides with that demanded 
 by the respective equations, nor is it even con- 
 stant in itself. It varies according to the degree 
 of dilution, the proportion of free acid, the 
 quantity of absorbed air in the reagents, &c., in 
 a manner which defies all calculation (Kessler. 
 Mohr, Casselman). 
 
 VI. Ferric chloride, in combination 
 
 with Stannous chloride. 
 The oxidation of an acid solution of SnCl^ by 
 added ferric chloride proceeds very readily when 
 the liquid is hot, and in fair accordance with 
 the equation: 
 
 SnClj -I- PejClj = SnOl, + 2FeCl4 ; 
 but the dissolved air of the reagents is drawn 
 
 S 
 
258 
 
 ANALYSIS. 
 
 into the oxidation, and the results are conse- 
 quently irregular. If however (according to Fre- 
 Bcnius) we start with a hot, strongly acid, solution 
 of ferric chloride, and at a nearly boiling tem- 
 perature drop in stannous chloride, the process 
 proceeds exactly as described by the equation, 
 and the disappearance of the last trace of the 
 yellow colour of the ferric salt defines the end- 
 point very sharply. In case of doubt, add a 
 alight excess of SnClj, allow to cool, add starch, 
 and titrate with iodine solution to determine 
 the excess of SnClj, and allow for it. According 
 to the writer's experience the whole of these 
 operations must be done in an atmosphere of 
 CO2, else the results are not exact. Fresenius 
 utilises the process for the determination of 
 nitric acid. The nitrate to be analysed is 
 allowed to react with an excess of ferrous sul- 
 phate, strongly acidified by HCl, in an atmo- 
 sphere of H or CO2 first cold, then hot ; the NO 
 is boiled off, and the ferricum produced is de- 
 termined by means of standard SnCl2. The 
 ferricum present as an impurity in the ferrous 
 salt is determined by a blank experiment,-and 
 is allowed for : 6 x Fe of ferricum produced, 
 indicate 1 x N2O5 of nitric anhydride. 
 Standard Substances and Solutions, por the 
 Processes of Oxidation eefebked to. 
 
 1. Pure iodine is best made by Stas's 
 method. Ordinary iodine is dissolved in the 
 minimum of a highly concentrated solution of 
 iodide of potassium, and re-ppd. as far as pos- 
 sible by dilution with water. The pp. is 
 washed, dried first on a porous tile, then over 
 CaNjOj. The dry product is distilled (or the 
 small quantity needed for an experiment 
 sublimed ex tempore between watch-glasses), the 
 first instalments of vapour being rejected on 
 account of possible contamination with water. 
 From such iodine 
 
 2. A standard iodine solution might easily 
 be made by exact synthesis. But it is more eco- 
 nomical and less troublesome to prepare this 
 solution by approximate synthesis from ordi- 
 nary good iodine (5 grams of Ij dissolved in 
 10 grams of IK and 10-20 c.c. of water in a 
 mortar, and diluted to 1 litre, gives a solution 
 of convenient strength) ; and to determine the 
 exact strength by comparison with a known 
 weight of pure iodine, by means of a thiosul- 
 phate solution of arbitrary strength. _ Supposing 
 p mgms. of pure iodine weighed directly, and 
 dissolved in IK solution, require f„ c.c. of thio- 
 Bulphate for their decolourisation, while n 0.0. 
 of the iodine-solution require t c.c. ; then 1 c.c. 
 of thiosulphate is equivalent on the one hand to 
 
 ?. mgms. of iodine, and on the other to - 0.0. of 
 to t 
 
 iodine-solution. Hence 1 CO. of the latter 
 
 contains! — ^ .„_ 1 xl( = 127) mgms. of pure 
 \«„w X 127/ 
 
 iodine. 
 
 3. Thiosulphate soluticm. — Made by dis- 
 solving 10 grms. of the pure salt, NaaSjOj.SHjO, 
 in water, to 1 litre. It decolourises about its 
 own volume of the above iodine-solution. The 
 strength is determined empirically by means of 
 the latter. 
 
 4. Arsenioiis add. — Pure As^O, is to be had 
 in commerce ; but the best qualities even are 
 
 liable to he contaminated with SbjOj. The 
 powder is not hygroscopic. 
 
 5. Arsenite soluUon. — 4"95 grms. = 
 
 ASgO; 
 
 40 
 
 ,o{ 
 
 powdered ASjOj along with 11 grms. of pure 
 NajCOs ( = 30 grms. of crystals, NajCOj -I- lOH^O) 
 are dissolved in a slanting litre flask in water, 
 over a water-bath ; after cooling, the liquid is 
 diluted to 1 litre. 1 0.0. = 0-1 x 'I,' '01,' &c. 
 mgms. [This solution, as a feagent, may serve 
 for the direct titration of dissolved hypo- 
 chlorite — 2EC10 -f ASjjOa = 2EC1 + AsjOj. The 
 end-point is recognised by means of iodide of 
 potassium and starch paper ; a drop of the 
 mixture when placed on the paper produces a 
 blue stain only as long as the BCIO is in excess. 
 (P6not)]. 
 
 6. Standard ferrosum. — Fine pianoforte wire 
 is sure not to contain more than 0-4 p.c. of 
 impurities, and consequently may be assumed 
 to represent 0'998±0'002 times its weight of 
 real iron. A known weight is dissolved in HCl 
 or dilute H^SOj, in the absence of air, &c. More 
 convenient is 
 
 Ferrous sulphate. — FeSOj.THjO, ppd. from 
 a pure, hot, concentrated, acid solution, by 
 alcohol. The ppd. salt is washed with alcohol, 
 dried on bibulous paper, and finally by exposure 
 to the ' dry ' air of a room. The dried salt is 
 sifted to remove lumps, again exposed to the 
 air for a while, and bottled up for use. The 
 exact percentage of iron is determined by 
 strongly heating a known weight in a platinum 
 crucible— at the end in the presence of air— 
 until the weight is constant, and weighing the 
 Fe^Oj. This old preparation of Otto, accord- 
 ing to the writer's experience, has a higher 
 degree of stability in air than Mohr's salt 
 (Fe(NH,),SA-6H,0). 
 
 7. Standard oxalic acid. — The crystallised, 
 normal, ammonium salt is the best standard 
 oxalate for processes in which it serves as a 
 reducing agent. If air-dry, it has exactly the 
 composition C204(NH,)2 -I- H^O = 142. 
 
 8. Standard permanganate of potassium. — 
 An almost pure salt is to be had in commerce. 
 Yet it is not pure enough to serve as a standard 
 substance in itself. A convenient solution is 
 obtained by dissolving a little more than 3'16 
 grms. ( = 6-6 grms. of ferrosum) in water, in a 
 mortar, and diluting to 1 litre. The solution is 
 standardised by means of a known weight of 
 ferrosum or oxalate of ammonium, according to 
 the object which it is meant to serve. 
 
 9. Bichromate of potassium. — KjCTjO,. The 
 pure salt is not difficult to obtain ; but it is not 
 easy to prove that it contains exactly 2CrOs for 
 IKjO. Besides, the uncertainty of the atomic 
 weight of chromium is a difficulty. To prepare 
 the salt for use, it is powdered and dehydra,ted 
 by keeping it near its fusing-point for a time 
 in a platinum basin. It is then fused at 
 the lowest temperature, and allowed to solidify, 
 when it breaks up spontaneously into small 
 granular fragments, and thus assumes a con- 
 venient form for weighing. 
 
 10. Standard soVutian of bichromate ofpotas- 
 
 siu/m. — A convenient concentration is ■ „ ■ ' ' = 
 
 60 
 
 4 '92 gms. per litre. It may be standardifed 
 
ANALYSIS, ORGANIC. 
 
 259 
 
 eynthetioally ; but for the reasons stated' it is 
 on the whole preferable to standardise the 
 solution analytically by means of a known 
 weight of dissolved ferrosum. 
 
 11. Standard ferric chloride. — Pure ferric 
 «xide is prepared by strongly heating ferrous 
 cxalate. It is dissolved, by prolonged digestion, 
 in fuming HCl, and the solution is diluted to 
 
 the right volume. -^--?=8 grms. per litre is a 
 
 21} 
 convenient strength. 
 
 12. Stannous chloride (for No. 11). Pure 
 granulated tin (approximately weighed) is 
 •boiled with pure HOI until a sufficiency of the 
 metal is dissolved. The residual metal is 
 weighed, to ascertain how much has passed 
 into solution. For every 3 grms. of dissolved tin, 
 the solution is diluted— with air-free water — to 1 
 litre. The solution decolorises about \ its volume 
 of the iron solution, which latter serves for its 
 standardisation. This solution is so prone to 
 oxidise in the air that it must be restandard- 
 ised expressly for each analysis. W. D. 
 
 ANALYSIS, OEGANIC. Ultimate organic 
 analysis is the determination of the elements 
 present in an organic substance. Proximate 
 organic analysis is the determination of the 
 compounds present in a mixture, or of the 
 radicles present in a compound. 
 
 UlIIMA.TE AnAIiYSIS. 
 
 Qualitative. 
 
 Carbon. If a substance blackens when it 
 is heated either alone or with sulphuric acid it 
 probably contains carbon, in which case the 
 black residue may be burnt away by heating to 
 redness in air. A substance that does not 
 blacken may nevertheless contain carbon. A 
 more general method of detecting carbon is 
 first to warm the substance gently with dilute 
 sulphuric acid, in order to expel QO2 that may 
 be present as carbonate, and then to add several 
 volumes of strong H2SO4 and some KjCrjO, ; 
 when the mixture is heated any organic sub- 
 stance will be oxidised, and the escaping COj 
 will give a pp. with lime-water. 
 
 Hydrogen. The substance is mixed in a 
 tube with dry CuO or PbCrO^ and heated to 
 redness ; water comes off and condenses in a 
 cold tube. Very small quantities of water may 
 be detected by passing the gases through a glass 
 tube lined with P^Os, which will deliquesce. In 
 these experiments carbon may be detected by 
 passing the escaping gases into lime-water. 
 
 Nitrogen. The substance is heated with 
 soda-lime and the nitrogen may then be given 
 off as NH3 and detected by its smell, action on 
 red litmus, or fumes with HCl. The soda-lime 
 must be strongly heated before use, until it no 
 longer gives off NH,. This test will not succeed 
 with compounds rich in oxygen. A more deli- 
 cate test consists in heating the substance with 
 potassium in a test-tube drawn out to a point. 
 After deflagration, the mass is dissolved in water 
 and examined for cyanide (Lassaigne, A. 48, 367). 
 This test is not applicable to diazo-compounds 
 (Graebe, B. 17, 1178). 
 
 Chlorine. The chlorine is eliminated in 
 the form of a chloride, the presence of which is 
 detected by AgNOj. The conversion into chloride 
 
 can be effected: (a) by boiling with fuming 
 HNOj ; in the case of volatile substances, the 
 operation must be performed in a scaled tube : 
 (6) by boiling with alcoholic potash : (c) by mix- 
 ing with quicklime and heating to redness : (d) 
 by heating with H^SO, and MnO^. 
 
 Bromine and iodine may be detected by 
 the same methods. 
 
 Salogens may also be detected by fixing a 
 lump of CuO to a platinum wire, dipping it into 
 the substance, and heating first in the inner and 
 then in the outer part of a Bunsen flame : a green 
 colour indicates halogens (Beilstein, B. 5, 620). 
 
 Sulphur is detected by strongly heating 
 the substance with a mixture of sodio carbonate 
 and sodic nitrate, or sodie carbonate and potassio 
 chlorate ; and testing the product for sulphate. 
 Or the substance may be fused with sodium 
 free from sulphur in a test-tube, and the pro- 
 duct examined for sulphide (Schonu, Fr. 8, 52, 
 399). Some compounds, such as albumen, give 
 a black pp. of PbS when boiled with a solution 
 of PbO in NaOHAq. Boiling HgClj or ammo- 
 niacal AgNO, often give a black pp. of metallic 
 sulphide. 
 
 Phosphorus may be detected by fusing 
 with NajCOj mixed with NaNOj, and examining 
 the product for phosphate. Or the carbonised 
 substance may be heated with magnesium pow- 
 der ; the product, containing magnesium phos- 
 phide, is luminous in the dark, and when 
 moistened with water will give off PH, (Schonn, 
 Fr. 8, 55). ^ 
 
 Quantitative. 
 
 Substances containing no elements beside 
 carbon, hydrogen, and oxygen. 
 
 The substances are subjected to Combus- 
 tion as proposed by Liebig (P. 21, 1), hydrogen 
 being weighed as HjO and carbon as 00^. The 
 operation is performed in a closed or in an open 
 tube. 
 
 Closed tube, combustion. 
 
 A tube of hard glass (diameter "5 inch) is 
 drawn out as represented, the length being about 
 18 inches. It is thoroughly cleaned by washing 
 with fuming HNOj, water, alcohol, and ether ; 
 and is then dried. Coarsely powdered oxide of 
 copper, which has been prepared by oxidising 
 the metal, not by strongly heating the nitrate, 
 and has been dried at a red heat, is poured in 
 as far as a ; a mixture of the weighed substance 
 with finely powdered dry CuO is then poured in, 
 it fills up the space from a to 6 ; the vessel 
 (mortar or glass tube) in which the mixture has 
 been effected is then rinsed with more finely 
 divided CuO, and these rinsings are poured into 
 the tube and take up the space 6 to c ; finally 
 some coarse CuO is poured in, taking the space 
 c to d. The tube is then gently tapped to ensure 
 free passage for gas from end to end. A tube 
 containing CaClj is fixed by means of a cork to 
 the open end of the combustion tube, and a 
 bulb-apparatus (Liebig's or Geissler's) contain.- 
 ing caustic potash (1 pt. KOH to 2 pts. HjO) is 
 attached to this, and in accurate experiments a 
 drying tube containing CaClj or solid KOH is 
 placed beyond the potash-bulbs. 
 
 The oxide of copper at d is first heated to 
 redness, and then the tube is heated at the other 
 end; the gas-burners of the furnace are then 
 
 s 2 
 
260 
 
 ANALYSIS. ORGANIC. 
 
 gradually turned on, at either end, so that a 
 regular stream of bubbles passes into the potash 
 bulbs. When the entire tube has reached a dull 
 red heat, the potash solution will begin to be 
 sucked back, owing to absorption of COj ; at this 
 moment the point of the tube is broken off, and 
 air is sucked through the entire apparatus in 
 order that the gases still contained in the tube 
 
 of gas. At the end of one experiment the 
 tube is quite ready for a second. 
 
 Liquids of high boiling-point are analysed 
 in the same way as solids, except that they are 
 weighed in short open tubes ; volatile liquids 
 such as ether are best put into a bulb or 
 V-tube, which is inserted between the oxygen 
 apparatus and the combustion tube ; the pro- 
 
 (E=^ 
 
 J 
 
 a 
 
 may be drawn into the weighed bulbs ; in this 
 operation a long glass tube, open at both ends, 
 may be placed over the broken point of the tube 
 to prevent furnace gases being sucked in. The 
 calcium chloride tube and potash bulbs are 
 weighed when cool : | of the increase of weight 
 of the former is hydrogen, ^ of the increase of 
 weight of the latter is carbon. 
 
 Open tube, combustion. 
 
 It is in every way better to make the com- 
 bustion in an 'open tube,' that is a tube through 
 which oxygen is continually passing. 
 
 The greater part of such a tube is filled with 
 oxide of copper, c & ; this is followed by an open 
 
 portion between oxygen and vapour of the sub- 
 stance depends upon the temperature of the 
 bulb-tube and should be so regulated that the 
 oxygen should be always in considerable excess, 
 otherwise an explosion might occur. 
 
 The potash-bulbs may be replaced by a 
 U -tube containing soda-lime ; in this case the 
 escaping gas must be allowed to bubble through 
 H2SO4 in order that the rate at which it is com- 
 ing off may be noted. 
 
 Minute quantities of carbonic acid are ab- 
 sorbed by CuO and even by PbCrO^ and retained 
 at a red heat. Hence in the determination of 
 minute quantities of carbon (as in the residue 
 from drinking water) these substances should 
 
 space of about 2 inches ; then comes a porcelain 
 or platinum boat, h, containing the weighed sub- 
 stance ; beyond (between 6 and a) it is advisa- 
 ble to have a spiral of oxidised copper. The 
 boat and its contents are not inserted until the 
 whole tube has been red hot for some time, 
 during which a current of dry oxygen, free from 
 carbonic acid, has been passing through it ; it 
 is of course necessary to allow the end as c of 
 the tube to cool down before inserting the sub- 
 stance, otherwise this would be volatilised too 
 rapidly. While the tube is cooling, the calcium 
 chloride tube A, potash bulbs b, and the drying 
 tube c are attached. The tube, which is still 
 red-hot from c to d, is now heated at a and 
 the burners are lighted one after another until 
 the whole tube is red hot. A slow current of 
 oxygen is passed in at a during the combustion. 
 The combustion is continued until oxygen 
 escaping from will rekindle a glowing match. 
 Before weighing, the oxygen in the tubes A, c, 
 but especially e, must be displaced by air ; in a 
 properly conducted experiment will not gain 
 more than -01 g., a greater increase indicates 
 spurting of the potash due to a too rapid current 
 
 be previously ignited in a current of air (Dittmar 
 a. Eobinson, C. N. 36, 26). 
 
 Minute quantities of carbon may also be esti- 
 mated by burning in an open combustion tube 
 in a current of oxygen, in the usual way, and 
 absorbing the CO2 in baryta water. The BaCOj 
 is filtered off, converted into sulphate and 
 weighed (Dupr^ a. Hake, O. J. 35, 159). Other 
 methods are described below. 
 
 Combustion with Chromic Acid. 
 
 Carbon may be determined by heating the 
 substance with CrOj and HjSOj and measuring 
 the mixture of CO and CO, given ofE (Cross a. 
 Bevan, C. Zf. 52, 207). 
 
 Suhstances containing Nitrogen. 
 
 Determination of Carbon and 
 Hydrogen. 
 If the substance contains nitrogen, nittoua 
 fumes might be evolved, and these would be ab- 
 sorbed in the weighed tubes. To prevent this, a 
 layer of metallic copper is put in the front of the 
 tube,_near d, and kept red-hot : it reduces oxides 
 of nitrogen to nitrogen. This copper is best 
 
ANALYSIS, ORGANIC. 
 
 261 
 
 obtained by heating a roll of wire gauze in a 
 Bunsen flame, and reducing the oxidised surface 
 in a current of hydrogen ; it should then be 
 allowed to cool in a current of COj, as it would 
 absorb hydrogen if left to cool in that gas. The 
 copper spiral may also be reduced by heating it 
 in the mixture of CO and CO^ obtained by 
 wanning oxalic acid with HjSOj (C. E. Groves, 
 C. J. 37, 505). 
 
 Binoxide of manganese mixed with potassic 
 chromate may be used instead of a reduced 
 copper spiral in combustion of nitrogenous sub- 
 stances. The mixture is made by stirring 
 precipitated binoxide of manganese with a 
 saturated solution of potassic chromate con- 
 taining a little bichromate; the paste is dried 
 and heated somewhat strongly. The combustion 
 is performed with plumbic chromate (or copper 
 oxide) in the usual way, about 5 inches of the 
 chromate mixture being put in the front part 
 of the tube to absorb the nitrous fumes. In per- 
 forming a combustion, the whole tube is strongly 
 heated, while pure air is passed through it, 
 then the absorbent mixture is allowed to cool to 
 200°-250° and kept at that temperature during 
 the combustion (Perkin, O. /. 37, 457). 
 
 Estimation of Nitrogen. 
 
 Will and Varrentrapp (A. 39, 257) mix 
 the substance with soda lime, that has recently 
 been strongly heated, and put the mixture into 
 a short combustion-tube drawn out to a point 
 at one end. The operation is conducted exactly 
 as in combustion in a closed tube {v. supra), 
 the escaping gases being passed into a bulb- 
 apparatus to absorb ammonia. The bulbs con- 
 tain hydrochloric acid, the NHj being weighed 
 as (NHJjPtCls ; or, better, standard hydrochloric 
 or oxalic acid, the amount of NHj being then 
 determined by subsequent titration. 
 
 If the soda-lime contain nitrate it will evolve 
 NHj even when heated with sugar (Schulze a. 
 Ereussler, Fr. 12, 362). If in preparing the 
 Boda-hme a little Na^SjOg be added before 
 evaporating and strongly heating, small quan- 
 tities of nitrates and nitrites wiU be reduced 
 and eliminated as NHj (Dittmar, priv. com.). 
 Substances rich in nitrogen should be mixed 
 with sugar after weighing. 
 
 Unfortunately many organic compounds do 
 not yield all their nitrogen in the form of am- 
 monia when ignited with soda-lime ; such are 
 nitroso-, nitro-, azo- and diazo-, compounds, 
 and even someproteids (Eitthausen, i*"?-. 17, 501; 
 Ereussler, J. 1884, 1608) ; in this case the method 
 of analysis proposed by Dumas is generally used. 
 Modifications of the soda-lime process intended 
 to overcome this difficulty have, however, been 
 proposed. Kuffle (C. J. 39, 87) mixes the sub- 
 stance (1 g.) with sulphur (-75 g.) and finely. 
 powdered wood charcoal ('75 g.). Soda-lime pre- 
 pared from NaOH (160 g.), water and CaO (56 g.) 
 is dried and mixed with Na2S203(21 g.). Two- 
 thirds of the tube is filled with this mixture, 
 containing the substance to be analysed; the 
 remaining third is ordinary soda-lime, which 
 prevents evolution of HjS. The thiosulphate 
 reduces nitro compounds. 
 
 Arnold (B. 18, 806) prefers a mixture of 
 8 5da-lime, sodium formate and Na.SjOj. 
 
 Dumas (A. Oh. [2] 53, 171i heats the sub- 
 
 stance with oxide of copper and measures the 
 escaping nitrogen. A combustion-tube closed 
 at one end has first some bicarbonate of soda, 
 or, much better, magnesite, put into it ; this is 
 followed by pure oxide of copper, a mixture of 
 oxide of copper and the weighed substance, pure 
 oxide of copper, and finally a bright copper spiral 
 — just as in an ordinary combustion ; the end of 
 the tube is closed by a cork through which passes 
 a delivery tube dipping under mercury. Before 
 beginning the combustion all the air must be 
 driven out of the tube by carbonic acid; this is 
 effected by heating the magnesite ; the combus- 
 tion is then proceeded with in the ordinary way, 
 and the gaseous products are collected in a 
 graduated tube standing over mercury and con- 
 taining 50 c.c. of a solution of caustic potash 
 (equal weights of potash and water). The pro- 
 ducts of combustion are water, carbonic acid, and 
 nitrogen ; the two former are stopped by the 
 potash, so that the gas that collects is pure 
 nitrogen ; at the end of the experiment the com- 
 bustion tube still contains nitrogen which must 
 be expelled by heating the magnesite a second 
 time. The eudiometer and its contents is then 
 transferred to a vessel containing air-free water, 
 which takes the place of the mercury and 
 potash. The volume of the nitrogen corrected 
 for pressure and temperature enables one to 
 calculate its weight. 
 
 As there is some danger that the magnesite 
 may be all used up in the preliminary expulsion 
 of air from the tube, a convenient modification 
 of this process consists in expelling the air by 
 hydrogen ; the hydrogen is got rid of by igniting 
 a little of the copper oxide in the front part of 
 the tube ; a complete vacuum is thus formed, 
 and the mercury rises in the delivery tube to the 
 height of the barometer. The combustion is 
 proceeded with in the usual way, and the 
 residual nitrogen expelled by heating the mag- 
 nesite. 
 
 Bicarbonate of soda, MnCOj, or a mixture of 
 NajCOj and Kfiijd, riLa,j be used instead of 
 magnesite as a source of COj. In order that the 
 tube may be used several times without turning 
 out all the copper oxide, 0. E. Groves (O. /. 37, 
 504) places the substance intended to evolve 
 COj in a separate tube, 7 inches long, which is 
 attached by a short glass connecting-tube to the 
 end of the combustion-tube, which is in this 
 ease open at both ends. A fresh carbonic acid 
 tube is used for each experiment. The COj may 
 also be obtained from marble and HCLAq or 
 H2SO4, but it is then liable to contain air unless 
 the apparatus be first exhausted by an air-pump 
 (Bernthsen, Fr. 21, 63) or heated to boiling 
 (Hufschmidt, B. 18, 1441). The nitrogen is 
 frequently contaminated with NO. Frankland a. 
 Armstrong (C J. 21, 77), after reading off the 
 nitrogen, pass up a little oxygen, and, when the 
 resulting NO2 has been absorbed, they remove 
 the excess of oxygen by potassium pyrogallate. 
 The mean between the volumes of gas before 
 and after this operation is the true volume of 
 nitrogen (Thudichuni a. Wanklyn, 0. J. 22, 293). 
 Apparatus for collecting and measuring the 
 nitrogen have been devised by Zulkowsky (A, 
 182, 296), Sohwarz {B. 13, 771), Ludwig, 
 (B. 13, 883), H. Schiff (B. 13, 885), C. E. 
 Groves (C. /. 37, 500), Staedel {Fr. 19, 452), 
 
202 
 
 ANALYSIS, ORGANIC. 
 
 Bchmitt (J. pr. [2] 24, 444), Gladding {Am. 4, 
 42), Hempel {Fr. 17, 409), and lUnski {B. 17, 
 1347). Prankland a. Armstrong (O. J. 21, 77) 
 connect the tube -with a Sprengel's pump, which 
 delivers the gas into a eudiometer at the end of 
 the dropping tube (see also Gibbs, Fr. 11, 206 j 
 Hempel, B». 1, 9; Pfluger.^r. 18, 296; Johnson 
 a. Jenkins, Am. 2, 27). Explosive substances 
 may be analysed under diminished pressure. 
 
 The -weight of nitrogen is calculated from its 
 volume with the aid of the annexed table. From 
 the barometric height, corrected for expansion 
 of mercury and of the scale, the vapour pressure 
 of water at the temperature of the nitrogen is 
 deducted ; from the corrected pressure and the 
 temperature the weight of nitrogen is at once 
 given by the table. 
 
 (Arnold, Ar. Ph. [2] 24, 785). Kreusler reoom. 
 mends a mixture of cono. HjSO, (9 pts.) an4 
 P2O5 (1 pt.) as a substitute for fuming HjSOi 
 {v. also Warington, 0. N. 52, 162). 
 
 Substances containing Halogens. 
 
 Determination of Carbon and 
 Hydrogen. 
 
 In the combustion of substances containing- 
 chlorine white fumes of cuprous chloride might 
 pass into the chloride of calcium tube, and eveni 
 chlorine might be given ofE by the action of the 
 oxygen (Stadeler, A. 69, 335 ; Kraut, Fr. 2, 242) ;. 
 these sources of error may be prevented by 
 placing a roll of silver foil between the copper 
 oxide and the cork into which the chloride of 
 
 Pressure of Aqueous Vapour, in mm. 
 
 Temp. I 10° I 11° I 12° I 13° I U° I IS" I 16° I 17° I 18° I 19° I 20° I 21° I S3° I 53° I 24° I 26° 
 
 Pressure | 9-2 | 9-8 | 10-6 | 11-2 | 11-9 | 12-7 | 13-6 | U-4 | 16-4 | 16-3 | 17-4 | 18-6 | 19-7 | 20-9 | 22-2 | 23-6 
 
 Bedttction of Barometric Height. 
 
 If the barometer has a glass scale, the 
 necessary reduction will be found by multi- 
 plying the following numbers by the temperature. 
 
 Keduction 
 •128 
 •129 
 •130 
 •131 
 •132 
 •133 
 
 Vapour-Pressti/re of Aqueous KOH. 
 When nitrogen is measured over aqueous 
 potash, the correction for vapour-pressure is less 
 than that given above, as is seen from the fol- 
 lowing table, which relates to a solution of 1 pt. 
 of potash in 2i pts. water (S.G. 1-258). 
 
 mm. 
 
 Eeduotion 
 
 mm. 
 
 720 
 
 •123 
 
 750 
 
 725 
 
 ■124 
 
 755 
 
 730 
 
 •125 
 
 760 
 
 735 
 
 •126 
 
 765 
 
 740 
 
 •127 
 
 770 
 
 745 
 
 •127 
 
 775 
 
 10° 
 
 6^19 
 
 18° 
 
 10-47 
 
 11° 
 
 6-58 
 
 19° 
 
 11-20 
 
 12» 
 
 7-02 
 
 20° 
 
 11-97 
 
 13° 
 
 7^48 
 
 21° 
 
 12-80 
 
 14° 
 
 7-99 
 
 22° 
 
 13-70 
 
 15° 
 
 8-53 
 
 23° 
 
 14-62 
 
 16° 
 
 9^13 
 
 24° 
 
 15-60 
 
 17° 
 
 9-77 
 
 25° 
 
 16-65 
 
 (Kreusler, Fr. 24, 445). 
 
 In the course of an elaborate discussion of the 
 various methods of estimating nitrogen, Kreusler 
 (Landvn/rthschaftliche Versuchstationen, 31, 207 ; 
 c/. Fr. 19, 92 ; 24, 438) recommends that the 
 copper oxide be mixed with asbestos. Cupric 
 sulphate (150 g.), water (400 g.), and light asbes- 
 tos (50 g.), are evaporated until almost dry ; the 
 mass is then thrown in small quantities into 
 boiling water (2500 g.) containing KOH (160 g.), 
 and finally washed, dried, and heated until red 
 hot. Kreusler also uses copper-asbestos prepared 
 by reducing this oopper-oxide-asbestos in place 
 of a copper spiral. 
 
 Kitrogen may often be converted into NHj by 
 KMnO, and boiling NaOHAq (Wanklyn, Chap- 
 man, a. Smith, C. J. 20, 445), or by KMnO, and 
 fuming HjSO^ (Kjeldahl, Fr. 22, 370). In the 
 •atter case it is better to add CuSOj (Hilfahrt, 
 C. C 16, 17), benzoic acid, sugar, and mercury - 
 
 calcium tube is inserted. This part of the tube- 
 is kept at a dull red heat throughout the com- 
 bustion ; cuprous chloride and silver form silver 
 chloride and copper. 
 
 If the substance contains nitrogen as well as- 
 halogens, a copper spiral need not precede the- 
 silver spiral. 
 
 Determination of Halogens. 
 
 This is usually effected by placing 4 c.c. 
 fuming nitric acid and about a gram of silver 
 nitrate in a strong glass tube, then sliding down 
 a little tube containing the weighed substance 
 in such a manner that it may stick to the wet 
 glass and not at once fall into the acid; tho 
 open end of the strong glass tube is then fused, 
 drawn off to a stout point and sealed. A little 
 tapping will now cause the tube containing the 
 substance to fall into the acid, after which the: 
 whole is heated at 180° for seven hours in a gun- 
 barrel. Aromatic substances require a higher 
 temperature, 250°-300°. SUver chloride (bro- 
 mide or iodide) is formed, and, after opening the 
 tube, diluting and boiling, it is collected, dried, 
 and weighed (Carius, A. 116, 1 ; 136, 129). A 
 stiU easier method is that lately proposed by 
 Plimpton and Graves (C. -J. 43, 119), in which 
 the organic substance is burnt in the flame of a 
 small Bunsen burner ; the halogen is left chiefly 
 combined with hydrogen but partly in the free 
 state. The products are sucked through aqueous 
 NaOH, which is then boiled with SOj and sub- 
 sequently mixed with HNO3. The halogen is 
 then estimated volumetrically (best by sulpho- 
 cyanide method) or gravimetrically. 
 
 Another method is to heat the substance in 
 a combustion tube through which oxygen charged 
 with nitrous fumes is passing (Klason, B. 19, 
 1910). 
 
 Halogens may in many cases be determined 
 by strongly heating -with lime ; -with a mixture of 
 Na^COa and KNO, (Volhard, A. 190, 40) ; with 
 Fe^Os (E. Kopp, B. 8, 769 ; Klobulowski, B. 10, 
 290); or -with alcoholic KOH; or by reducing 
 vrith sodium amalgam (KekuW, A. Suppl. 1, 340). 
 
 Halogens in the side-chains of aromatio 
 compounds may be estimated by boiling with 
 a saturated alooholio solution of AgNO, 
 (Sohulze, B. 17, 1676). 
 
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264 
 
 ANALYSIS, ORGANIC. 
 
 Compounds containing SuVphv/r. 
 
 Determination of Carbon and 
 Hydrogen. 
 In tlie analysis of compounds containing 
 sulphur there is danger that SO2 may be absorbed 
 in the weighed tubes. This is obviated by using 
 lead ohromate, in the form of small fused lumps, 
 instead of cuprio oxide. The PbCrO^ (10 pts.) 
 may be mixed with KjCrjO, (1 pt.). Sulphur 
 remains in the tube as PbSO,. Volatile 
 substanoes containing N as well as S must be 
 burnt slowly (V. Meyer a. Stadeler, B. 17, 1577). 
 According to Bitthausen {Fr. 22, 108), reduced 
 lead chromate can be re-oxidised by heating in a 
 current of oxygen. It is of course not necessary 
 to fill the whole tube with lead chromate, the 
 posterior half may contain CuO. A mixture 
 of CuO and PbCrO, is sometimes used. 
 
 Determination of Sulphur. 
 
 Sulphur may be estimated by the method 
 of Carius, by heating with fuming HNO3 in a 
 tube as described for halogens ; the sulphuric 
 acid is ppd. by BaClj. This method cannot 
 usually be employed in the case of organic sul- 
 phides, since these are converted into sulphonio 
 acids. 
 
 The most rapid method is that of Plimpton, 
 which consists in burning the substance in 
 the flame of a small Bunsen, sucking the pro- 
 ducts of combustion through dilute NaOHAq, 
 oxidising with 01, and ppg. as BaSO^ (Morley 
 a. Saint, 0. J. 43, 401). Or the substance may 
 be burnt in a stream of oxygen and the SO^ 
 collected in HClAq containing Br (Sauer, Fr. 
 12, 32, 178 ; Mixter, ¥r. 22, 581). In this experi- 
 ment it is better to pass the oxygen through 
 fuming nitric acid so that it may be charged 
 with nitrous fumes (Klason, B. 19, 1910). In 
 many oases sulphur may be determined by fusion 
 with a mixture of Na^COa and KNO3 or ECIO3. 
 In the case of albuminoids it is convenient to 
 evaporate with HNO3 (10 pts. of S. G. 1-4) before 
 fusing (Koohs, 0. O. 1886, 894). Oxidation may 
 also be effected by NajCOa and HgO (Bussell, 
 C. J. 7, 212). 
 
 Phospliorus. 
 
 The estimation of phosphorus resembles that 
 of S. It is weighed as Mg2P20,. 
 
 Boron. 
 
 If compounds containing boron are analysed 
 by combustion with copper oxide the hydro- 
 gen will come out too high, owing to the 
 volatilisation of boric acid. This is prevented 
 by using lead ohromate instead of oupric oxide 
 (Oouncler, J.pr. [2] 18, 375). 
 
 Silicon. 
 SiOj is left behind when non-volatile com- 
 pounds are heated. Volatile compounds are 
 heated with cone, or fuming H^SO, and KMnO^; 
 the product is poured into water. The ppd. 
 Il2Si0j is freed from traces of manganese by 
 fusion with NajOO, and END. (PoUs, B. 19, 
 
 1024). all 
 
 AlkaUs or Alkaline Earths. 
 In an ordinary combustion these would be 
 left as carbonates, the estimation of carbon thus 
 
 being too low ; but if the substance is thoroughly 
 mixed with PbOrO, (10 pts.), and KoCr^O, (1 pt.), 
 the COj will be turned out by CrO.,, the bases 
 being left as chromates. Schaller (Bl. [2] 2, 93) 
 mixes the alkaline salts of organic acids with 
 an equal weight of SiO^ and then with CuO. 
 
 The alkaline metals are determined by strongly 
 heating and analysing the inorganic residue. 
 
 Silver, Platinum, and Gold 
 Are determined by strongly heating the substance 
 and weighing the metallic residue. 
 
 Explosive Substances 
 Must be well mixed with CuO before being 
 put into a combustion tube; very explosive sub- 
 stances are analysed in vacux). 
 
 Combustion with platinum, black. 
 
 Eopfer (0. J. 29, 660) introduced the use of 
 finely divided platinum as a carrier of oxygen. 
 The anterior half of a combustion-tube is filled 
 with platinum black intimately mixed with 
 asbestos, the posterior half of the tube contains 
 the weighed substance in a boat ; air or oxygen 
 is passed through the tube, the combustion 
 being conducted in the usual way. 
 
 Additional Beferences. 
 
 Gay-Lussac a. Thenard, A.Ch.li, 47 (KCIO,) ; 
 Saussure, A. Gh. 78, 57 ; Berzelius, Thomson's 
 Annals of Philosophy, 4, 401, P. 44, 391 ; Liebig, 
 P. 21, 1; Liebig a. Wohler, A. 26, 270; Hof- 
 maun, C. J. 11, 30 ; Cloez, A. Oh. [3] 68, 394 
 (iron tube) ; Bl. [2] 1, 250 ; Fr. Sohulze, Fr. 6, 
 289 (KCIO3) ; Wheeler, Am. S. [2] 41, 33 ; Mar- 
 chand, /. pr. 41, 177 ; Gottlieb, A. 78, 241 ; Mel- 
 sens, A. 60, 115 ; Frankland, T. 147, 63 ; Thorp, 
 0. /. 19, 359; Maxwell Simpson, C. J. 6, 289; A. 
 95, 63 ; Pfliiger, Arch. ges. Phys. 1878, 117 ; H. 
 Sohili, A. 195, 293 ; Warren, Am. S. [2] 42, 156. 
 
 Determination of oxygen: Wanklyn a. 
 Frank, P. M. [4] 26, 554 ; Baumhauer, A. 90, 
 228; Ar. N. 1, 179; Ladenburg, A. 135, 1 
 (Agio,) ; A. Mitscherlich, P. 130, 536 ; B. 1, 45 ; 
 6, 1000 ; Gretier,^?-. 13, 1 ; Stromeyer.il. 117, 247. 
 
 Simultaneous determination of 0, H, 
 and N : (Schulze, Fr. 5, 269 ; Frerichs, B. 10, 
 26; Hempel, Fr. 17, 409; Jannasch a. V. 
 Meyer, B. 19, 949). 
 
 Proximate Analysis. 
 Separation of Mixtures. 
 
 A complete account of proximate organic 
 analysis would include descriptions of the pro- 
 perties of every known organic substance, since 
 the methods to be adopted vary in almost every 
 case. 
 
 The simplest method is separation by sol- 
 vents which dissolve some but not all of the 
 components of a mixture ; when solid substances 
 have been dissolved, they may usually be further 
 purified by crystallisation. 
 
 An unknown mixture is treated with water ; 
 the insoluble portion is shaken with dilute 
 H2SO4 which dissolves bases, then with dilute 
 Na2008 which dissolves acids, then with dilute 
 NaOH which dissolves phenols ; the bases are 
 ppd. by adding KOH to the H^SOjAq ; the acids 
 and phenols by acidifying the alkaline solutions 
 ooat&iniug them. 
 
ANETHOL. 
 
 266 
 
 The neutral residue is fractionally distilled 
 and the various portions are boiled with alco- 
 holic KOH which saponifies compound ethers, 
 and gives a pp. of KCl in the case of fatty 
 chloro-derivatives. The alcohol is distilled oH 
 together with volatile alcohols, &c., and the 
 residue treated with water, which dissolves salts 
 of acids that may have been formed. The in- 
 soluble residue is a hydrocarbon, high-boiling 
 alcohol, alkyl oxide, ketone, haloid aromatic 
 compound, &c. ; the hydrocarbon will usually 
 be left on treating the residue with cold H2SO4 
 If aromatic chloro-derivatives are absent. 
 
 The aqueous extract of the original sub- 
 stance is neutralised (if necessary) and distilled. 
 The distillate is treated with KjCOj which 
 separates alcohols, lactones, methyl acetate &o. 
 The residue is made alkaline by KOH and dis- 
 tilled ; bases pass over ; it is then acidified with 
 H-SO, and distilled : volatile acids pass over. 
 The residue is exactly neutralised and neutral 
 substances are extracted by ether, chloroform, 
 and benzene, the aqueous residue is acidified 
 and non-volatile acids are extracted by these 
 solvents ; the residue is now made alkaline and 
 again extracted, finally it is evaporated to dry- 
 ness, and, if any organic matter is stiU present, 
 extracted with solvents. (V. also Aikaioids, p. 
 120 ; AoiDS, p. 56.) 
 
 Many substances, even of very high boiling 
 point, distil in a current of steam. 
 
 Detection of radicles. 
 
 Hydroxyl. — Compounds containing OH 
 evolve HCl when treated with PCI3 (p. 54) ; 
 but if PCI5 is used chlorination may occur 
 e.g. OeH^OMe -t PCl^ = C„H,C1.0Me -I- PCI, -H HCl. 
 AcCl acts upon hydroxylic compounds with evo- 
 lution of HCl ; when water is added to the pro- 
 duct the acetyl derivatives of alcoholic hydroxyls 
 are not affected, but CO.OAc is converted into 
 CO.OH. AcCl acts also upon amines in the fol- 
 lowing way : 
 
 ANH, + AcCl = CeH^NAcH + HCl. 
 BzCl and ACjO also displace hydroxylic hydro- 
 gen by acid radicles. In compounds whose 
 molecules do not contain NHj or NH the number 
 of hydroxyls (other than those in carboxyls) 
 present can be determined by estimating the 
 acetic acid obtained by saponifying the pro- 
 duct after treatment with water. The groups 
 C.CO.NH and C.CO.CHj in many cases act as if 
 they contained hydroxyl and were C.C(OH):N 
 and C.C(OH):CH. 
 
 Very dilute, colourless solutions of Fe^Clj 
 give a distinct colouration with compounds con- 
 taining alcohoUo hydroxyl (Landwehr, B. 19, 
 2726). 
 
 Zinc ethide evolves ethane gas when mixed 
 with compounds containing hydroxyl or amido- 
 gen (Japp, C. J. 37, 665) ; compounds contain- 
 ing imidogen evolve gas when heated with ZnEt^ 
 at 100° (Japp, C. J. 39, 224). (V. also Alcohols 
 and AoiDS.) 
 
 Amidogen is indicated by the reactions 
 just mentioned, and also by the readiness with 
 which methyl can be introduced by heating with 
 Mel. Methyl iodide does not act upon hydroxyl 
 except in presence of an alkali. Compounds 
 containing NHj evolve nitrogen when heated 
 with nitrous acid. 
 
 The number of amidogens in the molecule of 
 a compound may be found by treating the sub- 
 stance with KNO2 and H^SO,, ; the escaping 
 nitrogen is freed from NO by FeS04 and then 
 measured (Saohsse a. Eormann, Fr. 14, 380). In 
 easily diazotised aromatic amido compounds, the 
 number of amidogens may be determined by 
 dissolving in cone. HClAq and titrating with a 
 normal solution of KNO2, until a drop of the 
 solution gives a blue colour with KI and starch 
 (Green a. Evershed, S. C. I. 5, 683). 
 . Imidogen is indicated by the production of 
 a nitrosamine when treated with nitrous acid. 
 (See also Amines, Amido-aoids, Amides.) 
 
 Carbonyl is indicated by the reaction with 
 phenyl-hydrazine and hydroxylamine (p. 107). 
 
 Carboxyl is indicated by the easy pro- 
 duction of metallic salts, and by the splitting off 
 of CO, when the substance is heated alone or 
 with lime. 
 
 Want of saturation is indicated by instant 
 bleaching of bromine. 
 
 Acetylenio hydrogen is indicated by the 
 formation of explosive pps. with ammoniacal 
 cuprous chloride or silver nitrate. 
 
 Nitroxyl. — Nitro compounds may be re- 
 duced to compounds containing amidogen. The 
 number of nitroxyls is found by reducing vrith 
 standard SnClz and titrating with iodine (Lim- 
 pricht, B. 11, 35). 
 
 Methoxyl. The number of MeO groups can 
 be found by boiling with aqueous HI (S.G. 1"68) the 
 distillate (Mel) being received in alcoholic AgNO, 
 and the resulting Agl weighed (Zeisel, M. 6, 989). 
 
 Halogens in the side chains of aromatic 
 compounds can be estimated by boiling with a 
 saturated alcoholic solution of AgNO. (Schulze, 
 B. 17, 1675). 
 
 ANAMIBTIN Ci,K,^0,„(?). Occurs m grains 
 of cocculus indicus (Anamirta cocculus) along 
 with piorotoxin {q. i;.),picrotin, and glyceryl stea- 
 rate (Earth a. Kretschy, Sits. B. [ii] 81, 7 ; 
 Pranois, A. 42, 254). Short needles (from water), 
 insol. benzene ; becomes brown at 260° Neither 
 bitter nor poisonous. 
 
 ANCHOIC ACID = AzEi,AioACiD. 
 
 ANCHTJSIN V. Alkanet. 
 
 ANDROMEDOTOXIN Cj.HsiO.o [228°]. A 
 poisonous substance in Ehododendron ponticum 
 (Zaaijer, E. 5, 318). 
 
 ANEMONE. — The plants Anemone nemo- 
 rosa, A. pratensis, and A. Pulsatilla when dis- 
 tilled with steam yield anemonin, anemone- 
 camphor, anemonic acid, and a yellowish oil, 
 which are extracted by shaking the distillate 
 with chloroform (Lowig a. Weidmann, P. 46, 45 ; 
 Schwarz, Mag. Pharm. 10, 198 ; 19, 168 ; Feh- 
 ling, A. 38, 278 ; Dobraschinsky, J. Ph. [4] 1, 
 319 ; H. Beckurts, C. C. 1885, 776). 
 
 Anemonin CisHuOj. [150°]. Trimetrio 
 crystals ; sol. CHCI3, si. sol. alcohol and water, 
 insol. ether. Eeduces AgNO,.— PbOCisHijOj. 
 
 Anemonic acid. Amorphous powder ; insol. 
 water, alcohol, and ether. 
 
 Anemone-camphor. Trimetrio prisms; un- 
 stable. 
 
 ANETHOL C,„H,jO i.e. 
 CHjO.CeH^.CHiCH.CH, [1:4]. Methyl p.pro. 
 pmyl -phenol. [213°]. (282°). S.G. 21 '987 
 Ha 1-6167 (Gladstone, C. J. 49, 623). E^ 
 77-97 (Nasini, Q. 15, 93). S.V.S. 149-34. 
 
266 
 
 ANETHOL. 
 
 Ocevrrence. — In oil of anise (from Pimpi- 
 nella anisvm) together with a terpene, in China 
 or star anise (from BUcimn anisatuin),m fennel 
 {Anethum foemcuhim), and tarragon {Artemisia 
 Dracunculus) (Laurent, Eevue Scient. 10, 6; 
 Gerhardt, A. 44, 318 ; 52, 401 ; Cahours, A. Ch. 
 [3] 2, 274). 
 
 Formation. — Together -with CO^ when 
 CH30.0„H,.CH:C(CH3).C02H is heated (Perkin, 
 C. J. 32, 669). , 
 
 Properties. — Plates ; v. si. sol. water, v. e. 
 sol. alcohol and ether. Easily polymerised. 
 
 Reactions. — 1. Oxidation produces anisic 
 aldehyde, anisic acid, and acetic acid (Hempel, 
 A. 59, 104). — 2. Alcoholic potash produces 
 CieHisOj [87°] and C„H,„02 [65°] ; the latter 
 forms an acetyl derivative [40°] (Landolph, B. 
 13, 147 ; C. B. 81, 97 ; 82, 226).— 3. Nitrosyl 
 chloride produces CjHj(0Me).CsH5N0Cl which 
 reduces to CsH,(0Me).C3H5NH2 (Tonnies, B. 12, 
 169). — 4. Nitrous acid produces two bodies : 
 C„Hj(OMe).C3H,N203 and C,H^(OMe).CsH3N202 
 [97°]. The former may be reduced to 
 C,H,(OMe).C3H3(OH)NH2HCl, the latter to 
 (CH30.C,H,.C3H3),N,0, (?) (T., B. 13, 1845).- 
 
 5. Boron fluoride produces CjH^OMe, and a 
 liquid C„H,jO (c. 227°) (L., O. B,. 86, 601).— 
 
 6. HI at 260° forms CsH,^ (150°) and C^H^, 
 (210°) (L., C. R. 82, 849). — 7. PCI, forms 
 C,„H„C10, [-3°], (229°), S.G. 22 i-igi 
 (Landolph) ; Ladenburg gives different proper- 
 ties for chloro-anethol, viz. : [6°], (258°), S.G. a 
 1-125.— 8. Br forms C,„H,jBr,0, [65°] (Laden- 
 burg, A. Suppl. 8, 87 ; Z. [2] 5, 576). 
 
 Anethol - tetrahydride C|oH„0. Anethol- 
 camphor. [190°-193°]. Has a camphor-like 
 smell. Formed together with anisic aldehyde 
 by the oxidation of anethol with HNO3 (L.). 
 Smells like camphor. On oxidation with KjCr^O, 
 it gives an acid which forms long needles of melt- 
 ing point [175°] (anisic acid ?). 
 
 Anethol - hexahydride C|„H,sO. Anethol- 
 horneol [19°]. (198°). Formed together with 
 an acid by heating anethol - tetrahydride with 
 alcoholic KOH (L.). Long slender needles. 
 Insol. EOHAq. 
 
 Anethol dihydride = Methyl-VBx>vYii-ssEsoi^. 
 
 Anethoin (C,„H,20)„. Arnsom. [140°-145°]. 
 From anethol by shaking with a little H^SO^ 
 or P-^Os (C), or by the action of SnCl^ (Gerhardt, 
 J. pr. 36, 267), I in KIAq (WiU a. Ehodius, A. 
 65, 230) or BzCl (Kraut a. XJelsmann, J. pr. 77, 
 490). Prepared by distilling oil of anise with 
 cone. H2SO4. Keedles (from ether) ; insol. 
 water and alcohol. Decomposed on distillation 
 into liquid metanethol and solid isanethol. 
 
 Metanethol (0,„H,20)„. [132°]. (above 300°). 
 Prepared by heating anethol (210 g.) with 
 ZnClj (750 g.) in a copper retort ; in a few 
 minutes white fumes appear in the receiver, 
 superheated steam is then passed into the re- 
 tort ; the metanethol then passes slowly over. 
 The yield is 5 to 10 p.c. (Perrenoud, A. 187, 63). 
 Silky needles (from ether). Not volatile with 
 steam at 100°. 
 
 Metanethol sulphonic acid 
 (C,„H„(S03H)0)„. Formed by cone. H^SO^ in the 
 cold. Salts. — CaA'^aq: laminiB.- BaA',. 
 
 Chloride 0,„H„ (80^01)0. [183°]. 
 
 Liquid metanethol (0,„H,20),. (233°). 
 S.G, iS -971. Formed by distilling auethMn 
 
 (Kraut a. Sohlun, Z. 1863, 359) ; and by dis- 
 tilling anethol with ZnCl^. Converted by cone. 
 HjSO^ into anethoiin. At 320° it partially 
 changes to isanethol. 
 
 Sulphonic acW.— (C,„H„(SOsH)0), (Ger- 
 hardt, J.^jr. 36, 275). Salt.— CaA'jaq: gummy. 
 
 Isanethol (0,„H,20)„. A viscid mass left in 
 the retort when anethoin is distilled; cone. 
 HjSOj converts it into anethoin. 
 
 ANGELICA, OIL OF. The seeds of Angelica 
 a/rchangelica yield an essential oil (S.G. 2 -872 ; 
 [a]D 13° 8') containing a terpene, C,„H,5, (175°), 
 S.G. 2 -833, [o]d = 12° 38'. The rotatory power 
 of this terpene is reduced to 4° 52' by heating 
 for 432 hours at 100° ; it is readily polymerised 
 and easily oxidised (Naudin, G. B. 93, 1146). 
 The essential oil also contains methyl-ethyl- 
 acetic and oxymyristio acids (E. Miiller, B. 14, 
 2476). The roots of Angelica g/rchangelica yield 
 an essential oil (S.G. 2 -875) containing a ter- 
 pene (166°), S.G. 2 -870, [o] = 2° 50'. This 
 terpene polymerises readily under the influence 
 of heat or sodium (Naudin, C. B. 96, 1152 ; Bl. 
 [2] 39, 406). 
 
 ANGELIC ACID CsHjOj i.e. 
 CH2:CH.CH(CH3).C02H. Pentenoic acid. Mol.w. 
 100. [45°]. (185° i. v.). 
 
 Occurrence. — In the root of Angelica 
 archangelica (Buchner, A. 42, 226). Oil of 
 chamomile (Anthemis nohilis) may be separated 
 by fractionating into isobutyl isobutyrate, iso- 
 butyl angelate, amyl angelate, and amyl tiglate ; 
 the residue contains hexyl tiglate and anthemol, 
 CijHijO (Kobig, A. 195, 95). Angelic acid is 
 formed, together with laserol by heating laser- 
 pitin with alcoholicKOH(Feldmann, .4. 135,236). 
 
 Prepa/ration. — 1. Angelica root (50 lbs.) is 
 boiled with lime (4 lbs.) and water, and the 
 filtrate acidified with H^SO, and distilled (Meyer 
 a. Zenner, A, 55, 317).^2. Oil of chamomile is 
 saponified by alcoholic KOH (Kopp, A. 195, 81 ; 
 Pagenstecher, A. 195, 108 ; Beilstein a. Wiegand, 
 B. 17, 2261). — 3. Sumbul or moschus root con- 
 tains a resin which when boiled with alcoholic 
 KOH yields angelic and methyl-crotonio acids 
 (Eeinsch, Jahrb.pr. Pharm. 7, 79 ; E. Schmidt, 
 Ar. Ph. [3] 24, 528). 
 
 Properties. — Monoclinic prisms or needles; 
 si. sol. cold water, v. sol. hot water, alcohol, and 
 ether. 
 
 Beactions. — 1. Hydriodic acid at 190° re- 
 duces it to valeric acid (Ascher, Z. [2] 6, 217). — 
 2. Poiosfe-Z^isioM produces acetate and propionate 
 (DemarQay, O. B. 80, 1400). — 3. Bromine forms 
 a dibromide [86°]. — 4. Cono. H2SO4 converts it 
 into tiglio acid. — 5. KMnOj gives CO^ and alde- 
 hyde (B. a. W.). 
 
 Salts. — BaA'24iaq: crystalline mass. — 
 CaA'2 2aq : long needles, much more soluble in 
 cold, than in hot, water. — AgA' : feathery 
 crystals, si. sol. water. — ^PbA'2 : crystals, si. sol. 
 
 Ethyl-ether.— EtA.'. (141-5°). S.G.2-935. 
 
 Isobutyl ether C^JJ. (177°). 
 
 Isoamyl ether OjHuA'. (201°). 
 
 Anhydride (C5H,0)sO. Oil (Ohiozza, 
 A. Ch. [3] 39, 210). 
 
 Hydriodide CH3.CHLCH(CH3).C02H. 
 [46°]. Todo-valerio acid. Prisms. Formed by 
 very cone. HI. 
 
 Constitution — Angelic acid is isomeric with 
 
ANHYDRIDES. 
 
 267 
 
 tUyl-aoetio acid, CH2:CH.CH2.CHj.C02H, methyl- 
 crotonio or tiglio aoid OH3.CH:C(CH3).002H, 
 iB-/3-di- methyl -acrylic aoid (CH3)2C:0H.C02H 
 (Ustinoff, J. pr. [2] 34, 484), propylidene- 
 Boetie aoid, CHs.CH2.0H:CH.C02H, and tetra- 
 methylene oarboxylic aoid. 
 
 The same valeric aoid, (ITS'-ITS" unoor.), 
 S.Q-. — •941, is formed by reducing the hydriodides 
 of angelic and of tiglio acids by Zn and H^SO,. It 
 is probably CH3.CH2.CH(CH3).CO,H (Schmidt, 
 B. 12, 252). Angelic acid changes when long 
 kept, or when treated with AgNOj, into tiglio 
 aoid, and hence the two acids have probably the 
 same carbon skeleton. The hydriodide of angelic 
 acid is, however, different from that of tiglio 
 acid, CHs.CHj.CI(OH3).C02H. This would be ex- 
 plained by assigning to angeUo acid the formula 
 CHj:CH.CH(CH3).C02H, its compound with HI 
 being CH3.CHI.CH{CH3).C02H. The latter iodo- 
 valerio acid is not CH2l.CH,.CH(CH3).C02H for 
 it gives no lactone on neutralisation with NajCOj, 
 but butylene CH3.CH:CH.CH3 (Fittig, A. 216, 
 161). An alternative formula, GH^iCEt.COjH, 
 would form with HI either CHJ.CHEt.COaH or, 
 more probably, CHs.CIEt.COjH ; sodium car- 
 bonate would convert the latter into an oxy-acid, 
 or back into angelic acid, while the former would 
 give the butylene CH^iCH.CHj.CHa. 
 
 ANGELICO-BENZOIC OXIDE C^HijOs i.e. 
 CsHjO-O-Bz. From potassium angelate and BzCl 
 (Chiozza, A. 86, 260). Oil. 
 
 ANGELICO LACTONES. G^fi^. /3-aoetyl- 
 propionic (levulic) acid splits up on distillation 
 into HjO and a mixture of these lactones, transi- 
 tion compounds being doubtless the two iso- 
 meric oxy-aoids CH3.0(0H):GH.CH2.C03H and 
 CH2:C(0H).CH2.CH2.C02H. They are dried over 
 K2CO3 and separated by fractional distillation 
 (Wolff, A. 229, 249 ; B. 20, 425). The (a) lactone 
 is converted into the [0) modification by com- 
 bining it with HCl and distilling the product. 
 Both lactones combine with bromine, and both 
 are changed to iS-aeetyl-propionic aoid by boiling 
 with water or by treatment with cold aqueous 
 baryta. This reaction is easily explained, for 
 the oxy-acids CH3.C(0H):CH.CHj.C0jH and 
 CH;:C(OH).CH2.CH2.C02H into which the lac- 
 tones should be converted, would both change (by 
 Erlenmeyer's rule) into CH3.CO.CHj.CH2.CO2H. 
 
 (a).AngeUco-lactone CH3.C:CH.CH2.C0.0 
 
 [18°]. (168°). V.D. 3-6. S. 5 at 15°. Is also formed 
 by the action of water on the bromide of 
 /3-bromo-j3-acetyl-propionic acid. Colourless 
 neutral liquid, gradually turns yellow. It has a 
 pleasant odour and bitter taste. At 0° it solidi- 
 fies to white needles which are not hygroscopic 
 and are volatile. The lactone dissolves in most 
 solvents. It is separated by KjuO^ from its 
 aqueous solution. If left a few hours with cold 
 water the liquid becomes acid. 
 
 Beactions. — 1. NH3 converts it into j3-acetyl- 
 propion-amide. — 2. Combines with bromine in 
 CS2 forming the lactone of di-bromo-oxy-valerio 
 acid {q. v.). — 3. Combines with HCl forming the 
 lactone of chloro-oxy-valerio aoid (j. v.). 
 
 {P)-Angelico-lactom CHjiC.CHj.CHj.CO.O. 
 
 (209°) at 750 mm. (84°) at 25 mm. S.G. 2 1-1084. 
 Colourless neutral liquid. It does not solidify at 
 — 15°. It is partly converted into its (o) isomer- 
 
 ide every time it is distiUed under atmospheric 
 pressure. Misoible with water, has a pleasant 
 odour. May be left for 4 hours with cold water 
 without production of an aoid. 
 
 Beactions. — 1. Boiled with water it is very 
 slowly converted into levulic acid. — 2. Combines 
 with bromine in CSj. — 3. Does not combine with 
 HCl. 
 
 ANGELYI. The radicle OjHjO. Also ap- 
 plied by Hofmann to monovalent Pentenyi 
 (2- «•)• 
 
 ANGUSTUEA Oil CijHj^O. (266°). S.G. 
 •93. Obtained by distilling true Angustura 
 bark (Cuspariafebrifuga) with steam (Herzog, /. 
 1858, 444). The bark contains also ousparine 
 and gasipeine {q. v.), . 
 
 ANHYDEIDES — Oxides which react with 
 water to form acids {q. v.), or are obtained from 
 acids by withdrawing water, or wMch react 
 with basic oxides to produce salts : e.g. 
 
 S03 + H,0 = H2SOi; 2HNO3 - HjO = N2O5 ; 
 
 S03 + BaO = BaSO,; CrOa + BaO = BaCrO^. 
 Solutions of anhydrides in ether or other liquid 
 quite free from water do not exhibit an acid 
 reaction towards litmus. The greater number 
 of the oxides of non-metals are anhydrides ; the 
 metallic oxides which belong to this class are 
 usually those containing the greatest quantity 
 of oxygen relatively to the metal. The more 
 negative the character of an element the more 
 do the lower oxides of that element exhibit the 
 properties of anhydrides ; the most positive 
 elements do not form anhydrides. Metallic 
 anhydrides do not, as a rule, produce acids by 
 reacting with water, but most of them may be 
 obtained from the corresponding hydrated oxides, 
 having feebly-marked acid characters, by the 
 action of heat; e.g. Nb^O^, PtO, PtOj, TiOj, 
 SnOj, &o. The formation of salts from these 
 anhydrides is usually accomplished by fusing 
 them with more basic oxides or hydrates; e.g. 
 TajOj + K3O (fused) = K2Ta205 ; in some cases the 
 metallic anhydride dissolves in strong aqueous 
 potash or soda to form a salt ; e.g. 
 Au203 + 2KOHAq = K2Au20<Aq + H20. A defi- 
 nite connexion can be traced between the posi- 
 tion of an element in the olassifioatory scheme 
 founded on the periodic law and the existence 
 or non-existence of anhydrides containing that 
 element {v. Oxides; also Olassieication ; and 
 Pebiodio Law). 
 
 As a broad rule the anhydrides of the poly- 
 basic acids may be obtained from these acids by 
 the action of heat (the anhydrides are usually 
 the final products, before they are reached new 
 acids are produced), but this rule has excep- 
 tions ; e.g., P2O5 cannot be obtained by heating 
 H3PO4. The anhydrides of monobasic acids are 
 usually obtained indirectly, often by the action 
 of an acid chloride on a salt, e.g. ClCl -1- HgClO = 
 HgCl + CI2O (this method is largely used in pre- 
 paring organic anhydrides, v. next article) ; these 
 anhydrides are sometimes obtained from their 
 acids by withdrawing water by the action of 
 dehydrating agents; e.g. 2HNOs + P205 = 
 N2O5 + PjOjHjO. A few anhydrides are produced! 
 by heating salts of the corresponding acids ; e.g. 
 FeSOi when heated in air forms Fe2S20„ and 
 this on further heating gives Fa^j and 2SO3. 
 
 Besides their characteristic reactions with 
 water and basic oxides, many anhydrides combina 
 
ANHYDRIDES. 
 
 with normal salts to produce 'acid' salts 
 <c. Saixs); e.g. KjOrO^ + CrO, = KjCr^O,. 
 ^iVfOt + VfO, = K^Wfi,. Many of the non- 
 tnetallio anhydrides combine with their own or 
 other acids to form new acids ; e.g. the follow- 
 ing compounds are thus produced, (HN0s)2N205, 
 H^SO^SOs, HCISO3, HSO2NO3, &c. A few an- 
 hydrides react with basic oxides to form salts not 
 ■of their own but of other acids ; e.g., NjO reacts 
 ^thNa^OjAq to produce NaNOjAq (not NaNO) ; 
 such anhydrides seem to be obtainable, indirectly, 
 ■from more than one acid, thus N^O is got by 
 heating HNOAq or by heating sohd NH^NOs. 
 
 Most anhydrides may be regarded as con- 
 stituted of two or more acid radicles united by 
 oxygen atoms ; on this view such formulse as 
 these would be applicable i—NOj.O.OjN; Cl.O.Cl, 
 &o. The mutual relations between acids and 
 ■anhydrides are repeated to a great extent in the 
 relations of basic hydrates, or hydroxides, to 
 their oxides ; e.g. Pe^OjHj when heated yields 
 .3H2O and Fe^Oj; CaO when added to H^O 
 produces CaO^Hj, &o. 
 
 At one time the name anhydride included 
 both base-producing and acid-producing oxides ; 
 then the former class was distinguished as 
 basic-anhydrides ; but now the name is almost 
 universally employed with the meanings given 
 to it in this article. The following are the best 
 marked anhydrides containing metals : — SbjOj, 
 8h,0,; AbA.As.A; (?BiA); CrO,; (?DiA); 
 AuA; IrA; PbO^; MnO^-, M0O3; NbA; 
 OsO^; PtO, PtOj-, TaA; SnO, SnO^; TiO^; 
 WOj ; UOs ; V^O,, Yfi^ ; ZrOj. The sulphides, 
 ■or hydrosulphides, of certain elements react with 
 the anhydrides of thio-aoids ; e.g. ASjSj dissolves 
 in KHSAq to form KAsSjAq, but the acid corre- 
 sponding to this thio-arsenite is unknown ; again, 
 WS3 dissolves in KHSAq to form K^WS^Aq, 
 which reacts as the potassium salt of thio- 
 tungstic acid (HjWSJ, which acid has not itself 
 been prepared. The thio-acid corresponding to 
 .the thio-anhydride SnS^, viz. H2SnS3, has been 
 prepared ; CS2 again is the thio-anhydride of 
 thio-carbonie acid H2CS3. It is not, however, 
 customary to apply the term anhydride to any 
 sulphides even when an acid, or a series of 
 salts, can be obtained from them. M. M. P. M. 
 
 ANHYDRIDES, OEGANIC.-The anhydride 
 ■of au organic substance is a body derived from 
 it by elimination of water. The water may be 
 derived from one molecule, or several molecules 
 may become united in the process ; in the latter 
 ■case 'condensation' is said to take place— a 
 •term which is also used when closed chains are 
 ■produced. A molecule of water may be derived : 
 
 A. From two carboxyls. 
 
 B. From one carboxyl and one hydroxyl. 
 
 C. From two hydroxyls. 
 
 D. From one hydrogen and one hydroxyl. 
 
 E. From carboxyl and amidogen. 
 
 F. From carbonyl and amidogen. 
 
 G. From hydroxyl and amidogen. 
 
 A. Feom two Cakboxyls. 
 Acid Anhydrides. 
 FormaHon. — 1. On application of heat most 
 smonooarboxylio acids distil undeoomposed, while 
 di-carboxylio acids in which the carboxyls are 
 attached to adjacent atoms of carbon give 
 anhydrides, e.g. 
 
 carboxyls are attached to the same atom of 
 carbon, COj is split off : 
 
 CHs.CH(C02H)2 = OH3.OH2.CO2H H- COj. 
 
 2. Anhydrides of monobasic acids are got 
 by the action of acid chlorides on alkaline salts 
 (Gerhardt, A. Ch. [3] 37, 285). Mixed anhy- 
 drides of monobasic acids may be got in the 
 same way. Instead of the alkaline salt the free 
 acid may be used (Linnemann, A. 161, 169). 
 An acid heated with its chloride gives its anhy- 
 dride in the following cases amongst others: 
 acetic, trichloro-aoetic, butyric, benzoic, and suo- 
 cinic acids. Acetyl chloride heated with dibasic 
 acids gives anhydrides of the dibasic acid in the 
 following cases amongst others (a mixed anhy- 
 dride is perhaps first formed) : succinic, chloro- 
 succinic, bromo-suooinic, maleio, acetyl-maUc, 
 diaoetyl tartaric, diacetyl raoemic, citraconic, ita- 
 oonic, camphoric, phthalio and diphenic acids. 
 These anhydrides of dibasic acids readily absorb 
 water from the air forming the corresponding 
 hydrates, from which, however, they may be 
 separated by chloroform which dissolves the an- 
 hydrides only. Benzoyl chloride acts like acetyl 
 chloride. In neither case are mixed anhydrides 
 formed. 
 
 Acetic anhydride at 120°-150° also converts 
 dibasic acids into their anhydrides, e.g. : 
 succinic, camphoric, phthalic, and diphenic acids 
 (Anschiitz, A. 226, 12). 
 
 3. Anhydrides are also formed by the action 
 of lead nitrate on acid chlorides {Lachowioz, B. 
 17, 1281), e.g. : 
 
 2AcCl -I- Pb(N03)2 = AC2O + PbClj + N2O5. 
 
 4. By passing phosgene over heated salts 
 (Hentschel, B. 17, 1285) : 
 
 2NaOAc +00012= AcjO + 2Na01 -I- CO,,. 
 
 5. By warming the chlorides of the acids 
 with dry oxalic acid, e.g. 2Ph.C001 + H2C204= 
 (Ph.00)20 + 2H01 + CO2 + CO (Anschutz, A. 226, 
 14). 
 
 BeactUms. — 1. Simple anhydrides may 
 usually be distilled or sublimed, but mixed 
 anhydrides such as BzOAo are split up by heat 
 into two simple ones : 2BzOAc = BZjO -I- AC2O. — 
 
 2. They are insoluble in water, but slowly con- 
 verted by it into the corresponding acid ; a con- 
 version that is more rapidly effected by alkaUs. — 
 
 3. 4fco/ioZ forms ethyl ethers of the corresponding 
 acids. — 4. Ammonia forms an amide and an am- 
 monium salt: Ao20-h2NH3 = AcNH2 + AoONH„ 
 or, in the case of anhydrides of dicarboxyho acids, 
 an amicacid. — 5. Sodmrn-amaZsram reduces them 
 to aldehydes and alcohols (Linnemann, A. 148, 
 249).— 6. PCI5 forms POClj and acid chlorides.— 
 7. Heated with NaOAo in sealed tubes at 200° 
 some anhydrides yield ketones (Perkin, 0. J, 
 49, 325) : 
 
 CH3.C02Na + (0H3C0)20 = 
 CHjlCO.CHj H- OO2 -I- CH3.C02Na. 
 
 CH3.C02Na + (03H,C0)20 = 
 CjH^.CO.CHj + OOj-i- 03H,.C02Na. 
 Intermediate addition-produsts, such as 
 CH3.C(0.C0.CsH,)j.ONa, are perhaps the cause 
 of this reaction. 
 
 B. Fbom Hidboxyl amb Cabboxyl. 
 This is the ordinary process of etherifioation ; 
 BtOH -I- CHj-OOsH = H2O -h CH3.CO.OBt. 
 
ANHYDKO-NAPHTHOL SULPHONIC ACID. 
 
 269' 
 
 When hydroxy] and oarboxyl are both present 
 in the same molecule, spontaneous etherifica- 
 tion may take place, the reaction taking place 
 between two molecules, as in the formation of 
 
 laotide, 0<:^qq ^gj^g^O, from lactic acid 
 
 HO.CHMe.CO2H, or by splitting off water from 
 one molecule, e.g. 
 
 GH3.CH(0H).CHs.CHj.C0,H = 
 CHs.CH.CHj.CH2.C0.0. 
 
 I I 
 
 In the latter case the aloohoUc part of the mole- 
 cule etherifies the acid part, and the product is 
 called a lactone (v. Lactones). Hydroxyl in the 
 y and 8 positions gives rise to lactones. 
 
 C. Fbom two Htdeoxyls. 
 
 The elimination of water between two 
 hydroxyls in different molecules produces an 
 oxide or simple ether. The result is brought 
 about by first forming an intermediate com- 
 pound, e.g. : 
 
 EtOH + HjSO, = EtO.SOjH + H^O 
 EtO.S03H-i-EtOH = EtOEt-hH2SO, (v. Ether). 
 When two hydroxyls are attached to one atom 
 of carbon they usually split off water spon- 
 taneously, producing carbonyl. 
 
 Two hydroxyls attached to contiguous atoms 
 of carbon may give rise to an oxide or internal 
 ether, an intermediate body being first prepared, 
 
 HO.CHj.CH,OH + HCl = Cl.CH^.CH^OH + H,0 
 C1.0Hj.CHjOH-t- KHO = CH,.CH, + KCl + H,0. 
 
 V 
 
 
 D. Feom one Htdboobn and one HynEoxTii. 
 
 Water can be eliminated by the union of 
 hydroxyl with hydrogen when they are attached 
 to adjacent atoms of carbon. This readily 
 occurs with P-oxy acids, e.g. : 
 
 CHj(0H).CH2.C02H = H,0 -^ CH,:CH.C02H. 
 OeH5.CH(OH).CH,.C02H = 
 HjO + C8H5.CH:CH.CO.,H. 
 
 B. From Cabboxtii and Amidoqen. 
 
 Water can be formed either from the hy- 
 droxyl and hydrogen, e.g. 
 
 C,H,<«^^CO-OH = H,0 + C,H<SOs,CO 
 or from the oxygen of the carbonyl and hydrogen: 
 ^•=f<NHf °'°^ = H,0 + O.H^'^jO^C.OH. 
 Compounds resulting from the first mode of 
 dehydration are called lactams, those resulting 
 from the second mode of dehydration being 
 termed lactims. 
 
 It is very diificult to say which formula best 
 represents a given compound ; Baeyer considers 
 that the arrangement represented by the lactim 
 is the more stable, but that before undergoing 
 chemical reactions it usually changes to the 
 transition or labile condition represented by the 
 lactam. The pre&xpseudo is frequently applied 
 to distinguish a lactam from a lactim. In the 
 aromatic series the elimination of water takes 
 place spontaneously when the two side-ohaina 
 are in the ortho position, and when the condensa- 
 tion can produce a, ring, containing 5 or 6 atoms. 
 
 Thus C„H,<^^='^^-^°^S 
 
 condenses to C„H,<^ ^' ^^ ^C.QH while 
 
 p XT /CH2.CH2.CH2.COJH ^ „„ , , 
 '^o-tli'xjjjj ' * does not produce aa 
 
 anhydride. 
 
 F. From Carbonyl and Amidogen. 
 
 The case in which carbonyl forms part of 
 carboxyl has already been mentioned. 
 
 Mono-alkoyl-o-diamines and o-amido-alkoyl- 
 phenols exhibit a tendency to split off water and 
 form Anhydro compounds, e.g. 
 
 CA<^H.C0.CH3^H^0.C.H,<NH^C.CH. 
 
 ^«^<NHf ■^'^' = H^0 + C,H,<O^C.C.H, 
 (Hubner, A. 208, 278 ; 209, 339 ; 210, 328). Th& 
 first class of compounds may be viewed as 
 amidines. These anhydro-compounds are formed: 
 (1) From aromatic alkoylamides or alkyl phenols 
 by nitration and reduction with tin and glacial 
 acetic acid. (2) From [1:2] amido- (or oxy) 
 nitro-compounds by heating with acid chlorides 
 or anhydrides, and reducing the product. (3) 
 From o-diamines or o-amido-phenols by heating 
 with acid chlorides or anhydrides. 
 
 Gr. From Hydroxyl and Amidogen. 
 
 Alkyls can be introduced into amidogen by 
 heating an amine with an alcohol or phenol, 
 especially in presence of dehydrating agents: 
 thus aniUne boiled with (/3)-naphthol gives 
 phenyl- ( j3) -naphthylamine. 
 
 ANHYDEO-ACET-DI-AMIDO-BENZENE t>. 
 Ethenyl-phenyibne-diamine. 
 
 ANHTDEO - ACET - DI -AMIDO -BENZOIC 
 ACID V. Ethenyl-di-amido-benzoio acid. 
 
 ANHTDEO-ACETYL- v, Ethenyl-. 
 
 ANHYDRO-DI-ACETYl-ACETAMIDIL v. 
 Aoetamidinb. 
 
 ANHYDEO-DI-AGETYI-ACETAMIDINE v. 
 
 ACETAMLDINE. 
 
 ANHYDEO - - AMIDO - PHENOI - ACETO - 
 ACETIC EIHEE v. Pkopenyl-o-amido-phenol a. 
 
 OABBOXYLIO ETHER. 
 
 ANHYDEO - AMIDO - PHENOXY - ACETIC 
 ACID V. Glycollio acid. 
 
 ANHYDEO-AMIDO-TOLYI-OXAMIC ACID 
 
 V. Dl-OXY-METHYLQUINOXALINE. 
 
 ANHYDEO-ATEOPINE v. Atropyl-tropein. 
 
 ANHYDEO-BENZ- v. Benzenyl-, 
 
 ANHYDEO-BENZ-DIAMIDO-BENZENE v. 
 Benzenyl-phenylene-diamine. 
 
 ANHYDEO-BENZ -DIAMIDO- TOLUENE v. 
 Benzenyl-tolylene-diamine. 
 
 ANHYDEO-BENZ-DI-AMIDO-TOLUIC ACID 
 V. Benzenyl-phenylene-diamine oaeboxylio aoid, 
 
 ANHYDEO-BENZOYI- v. Benzenyl-; or 
 named as derivatives of benzamidine. 
 
 ANHYDEO - BENZOYL - AMIDO-DI - TOLYL- 
 AMINE V. Benzenyl-tolyl-tolylene-diaminb. 
 
 ANHYDEO - CHIOEO - FOEMYL - AMIDO - 
 PHENYL MERCAPTAN v. Chloro-methenyl- 
 
 AMIDO-PHENYL MERCAPTAN. 
 
 ANHYDEO-CINNAMOYL- v. Cinnambnyl-. 
 
 ANHYDEO-TEI-ETHYL-STJLPHAMIC ACID 
 1). SVi-Ethyl-amine. 
 
 ANHYDEO-FOEMYL- v. Methbnyl- or 
 named as derivatives of formamidine, 
 
 ANHYDRO-GLYCOLYL- v. Oxy-bthenti.-. 
 
 ANHYDEO-LUPININE «. Lupinine. 
 
 ANHYDEO-NAPHTHOL SULPHONIC ACID 
 V. Naphtbol-bulphonio acid. 
 
270 
 
 ANHYDKO-OXALYL-AMIDO-PHENYL MEROAPTAN. 
 
 ANHJDSO - OXALYL - AMIDO - PHENYL 
 MEECAPTAN 0„H,N,S, i.e. 
 
 OA^^^O— C<^|>C,H,. [about 300°]. 
 
 Formation. — 1. By heating amido-phenyl 
 mercaptan with oxalic acid and PCI3.— 2. By the 
 action of the chloro-methenyl-amido-phenyl 
 mercaptan on methenyl-amido-phenyl mer- 
 captan. — 3. By heating chloro - methenyl- 
 amido-phenyl mercaptan with zinc. — 4. By the 
 action of acetyl chloride or benzoyl chloride at 
 150° on methenyl-amido-phenyl mercaptan. 
 
 Preparation.— 1. By heating acetanilide (5 
 pts.) with sulphur (3 pts.) to boiling for 30 
 hours ; yield 25 to 30 p.c— 2. By leading (CN)^ 
 gas into an alcoholic solution of amido-phenyl 
 mercaptan. 
 
 Properties. — Sublimable. Colourless glisten- 
 ing plates. Nearly insoluble in aU solvents ; 
 dissolves best in toluene. Bitter taste. 
 
 Reactions. — ^By fusing with EOH at 200° it 
 is readily split up into amido-phenyl mercaptan 
 and oxalic acid. On reduction with HI and P at 
 150° it gives aniline and ethenyl-amido-phenyl 
 mercaptan (Hofmann, B. 13, 1226). 
 
 ANHTDRO - OXALYl - DI - PHENTLENE - 
 TETKA-AMINE C„H,„N, i.e. 
 
 C,H,<^jj^C.C^^g^C5H^. [above 800°]. From 
 
 o-di-nitro-oxanilide, Sn, and glacial HOAc (Hub- 
 ner, A. 209, 370). Yellow needles ; insol. water, 
 CSj, and light petroleum, m. sol. glacial HOAc, 
 b1. sol. alcohol, ether and benzene. 
 
 Salt B.— B"2HC1 2aq.— B"H2S0, 2aq. 
 ANHYDEO-OXALYL-DI-TOLYLENE-TETEA. 
 AUINE 
 
 C„H3(CH3)<^2>C-C<NH>^«^3(^H^)- 
 [193° ?]. Formed by heating oxalyl-di-tolylene- 
 diamine to above 200° (Hinsberg, B. 15, 2691). 
 Or from di-nitro-di-tolyl-oxamide, Sn, and HCl 
 (Hiibner, A. 209, 373). 
 
 Salts.— B"H2Cl2.—B"(Ac0H)2 : gUstening 
 plates. — B"2H2S04 4aq : needles. 
 
 ANHYDEO-PHENYl-ACETYL- v. Phenyl- 
 
 ETHENYL-. 
 
 ANHYDEO - PHTHALYL - AMIDO-PHENYL 
 MEECAPTAK C^oH.jN^Sj i.e. 
 
 C A<^>C-0,H„- C<^>C.H,. [112°]. 
 
 Prisms or needles. Insol. water, sol. alcohol. 
 Weak base. Prepared by heating amido- 
 phenyl mercaptan hydrochloride with phthalyl 
 chloride. Salts. — B'HCl: decomposed by 
 water (B'HGljjPtCl^ : slender needles (Hof- 
 mann, B. 13, 1233). 
 
 ANHYDEO-PEOPIONYL- v. Pkopenyl-. 
 
 ANHYDEO-PYEOGALLO-KETONE v. Hexa- 
 
 OXY-BENZOPHENONE. 
 
 ANHYDEO-SALICYL- v. Oxy-benzenyl-. 
 ANHYDEO - STJCCINYL - AMIDO - PHENYL 
 MEEOAPTAN C.jHijNjS^ i.e. 
 
 C,H,<|>C.CH,.CH,.0<^>C„H,. [137°]. 
 
 Prepared by the action of succinamide on amido- 
 phenyl mercaptan. Colourless needles. Dis- 
 solves in acids forming unstable salts. Very 
 stable towards reducing agents. By fusing 
 ■with KOH amido-phenyl mercaptan is repro- 
 duced. Salts.— B'HCl: yellow needles, de- 
 tomposed by water.— (B'HC^jPtCli : sparingly 
 
 soluble spangles.— B'HClAuClj : yellow needles 
 (Hofmann, B. 18, 1231). 
 
 ANHYDRO-SULPHAMIDO- v. Sulpbo-. 
 
 ANHYDEO - TOLU YL - DI -AMIDO-BENZENE 
 
 v. ToLnBNYL-PHENTLENE-EIAMINE. 
 
 ANHYDEO-TOLUVL-DIAMIDO-TOLUENE v. 
 
 TOLUENYL-TOLYLENE-DIAMINE. 
 
 ANHYDEO-VALEEYL- v. Pentenyl-. 
 
 ANIL- V. Phenyl-imido-. 
 
 ANIL - ACEXOACETIC ACID v. p. 19, 
 
 BeacUon 18. 
 
 ANIL-BENZYL-MALONIC ETHER C^oa.NO, 
 i.e. CsH5.N:C(0„H5).CH(C0,Et)2. [75°]. Formed 
 by the action of «a;o-chloro-beuzylidene-aniline 
 CjHj.CChNPh upon sodio-malonic ether (Just, 
 B. 18,2624). Large crystals; v. sol. alcohol and 
 ether, insol. water. It contains a hydrogen atom 
 readily displaceable by sodium. Heated with 
 dilute HCl at 120° it is split up into acetophe- 
 none, aniline, ethyl chloride, and CO2. By heat- 
 ing alone to about 150° it eliminates alcohol and 
 is converted into (Py. l:3:2)-oxy-phenyl-quino- 
 line-carboxylic ether 
 
 „„/C(0H):C.C02Et. 
 
 ° '\N^=CPh. 
 
 Di-anil-benzyl-malonic ether CajHjjNjOj i.e. 
 (PhN:CPh)2C(C02Et),. Formed by the action of 
 exo-chloro-benzylidene-aniline upon the sodium 
 compound of mono-anil-benzyl-malonic ether (J.). 
 Plates. By heating with dilute HCl or H.^SOj at 
 120° it is split up into benzoic acid, aniline, 
 acetic acid, ethyl chloride, and CO^. 
 
 ANILIDES. — Substances derived from acids 
 by displacement of the hydroxyl by phenyl-ami- 
 dogen (NHPh). They are usually described 
 under the acids to which they belong. The term 
 anilide may also be applied more generally to 
 phenyl-amides and phenyl-imides. 
 
 Anilides of acids. 
 
 Formation. — 1. From aniline and acid chlor- 
 ides : C„H,C0C1 + NPhHj = HCl + CACO.NPhH. 
 2. By boiUng amides with the equivalent quantity 
 of aniline until no more NHj comes off, and 
 purifying by washing with ether (Kelbe, B. 16, 
 1199) . X.CO.NH2 -h NPhHj = X.C0.NPhH + NH,. 
 B. In some cases, e.g. formic and acetic acids, 
 anilides are formed by simply heating aniline 
 with the dry acid (cf. Tobias, B. 15, 2866).— 
 
 4. By action of aniline upon compound ethers. — 
 
 5. By the action of aniline on acid anhydrides. 
 
 Properties. — Solid crystalline substances, v. 
 b1. sol. water. 
 
 Reactions. — Split up into acid and aniline by 
 boiling aqueous or alcoholic EOH, by heating 
 with HCl in a sealed tube, or by heating with 
 cone. H^SO, at 100°. 
 
 Anilides of phosphorous acid. 
 
 Tri-anilide P(NHPh)3D. Aniline, r«aci. 29. 
 
 Di-anilide P(NHPh)2(0H). Prepared by 
 heating a mixture of auilme (3 pts.) and PCI3 
 (1 pt.), extracting with ether and ppg. with water 
 (Jackson a. Menke, Am. 6, 89). White 
 amorphous mass ; sol. alcohol and ether. 
 
 Anilides bf phosphoric acid. 
 
 Tri-anilide PO(NHPh),. [208'J. From 
 aniline and POClj (Schifl, 4. 101, 302; MiohaeUs 
 a. Soden, A. 229, 335). Thin needles or six-sided 
 trimetric plates (from alcohol). Insol. water, 
 aqueous acids, or alkalis. Forms a hexa-bromo 
 derivative, [253°]. 
 
ANILINE. 
 
 271 
 
 Dianilide P0(0H)(NHPh)2. [197°]. 
 Prom aniline (2 pts.) and POCI3 (1 pt.), the pro- 
 duct being treated with water (M. a. 8.). Insol. 
 water. Saponified by water or acids, not by 
 alkalis. 
 
 Anilide of thio-phosphoric acid PS(NHPh),. 
 [78°]. From PSCl, and aniline (Ohevrier, Z. 
 1868, 639). Insol. water. 
 
 Anilide of arsenic acid AsO(OH)2(NHPh). 
 Formed by heating aniline arsenate (B6ohamp, 
 C. B. 56, X172). 
 
 AnUide of boric acid Bj03NPhH2(?). From 
 ethyl borate and aniline. Decomposed by water 
 (Schiff, A. Suppl. 5, 209). 
 
 AKILISO- V. Phbnyl-amido-. 
 
 ANILINE OsHjN i.e. O^H^NH^. Phenyl- 
 amine. Mol. w. 93. [-8°] (Lucius, S. 5, 154). 
 (185° cor.). {Private communication from E. J. 
 FrisweU) ; (183-7°) (Thorpe, C. J. 87, 221). S.G. 
 % 1-0379 (T.). =j° 1-0216 (Briihl) ; {% 1-0242 
 (Friswell). C.E. (0°-10°) -000866; (0°-100°) 
 •000925 (T.). (14°-2o°) -000818 (P.). H.F.p. 
 -17450 (Thomsen); 2747 (Ramsay). H.F.v. 
 -19190 (Th.). 1^^ 1-6043 (B.). Roo 49-83 (B.). 
 S.V. 106-37 (T.) ; 106-08 (R. Schiff, B. 19, 566) ; 
 109-1 (Ramsay). Vapour pressure : Ramsay a. 
 Young (0. J. 47, 647, 655). S. 5 at about 15° ; 
 the S.G. of the saturated aqueous solution is 
 if 1-0023 ; |l 1-001. 100 pts. of a solution of 
 water in aniline at 8° contain 4-6 pts. water 
 (W. AlexejefE, B. 10, 709). Anihne saturated 
 with water has S.G. i| 1-025 (Priswell). 
 
 Formation. — 1. Discovered by Unverdorben 
 (P. 8, 397) among the products of distillation of 
 indigo, and called by him crystalline. — 2. Re- 
 discovered in coal tar byEunge (P. 31, 65, 513 ; 
 32, 831) and called by him cyanol. — 8. Obtained 
 by distilling indigo (from Indigofera ' Anil ') 
 with potash (Pritzsche, J. pr. 20, 453 ; 27, 153 ; 
 28, 202) and then first called aniliiie. — 4. Ob- 
 tained from nitro-benzene by reducing with 
 ammonium sulphide by Zinin (J. pr. 27, 149 ; 
 36, 98) and called by him bensidam. Also 
 obtained by reducing nitro-benzene with other 
 agents: e.g. Zn and HCl (Hofmann, A. 55, 
 200), ferrous acetate (Bfichamp, A. Ch. [3] 42, 
 186), aqueous As^Oj and NaOH (Wohler, A. 102, 
 127), zinc dust and water (Kramer, J. pr. 90, 
 255). — 5. In Dippel's animal oil (Anderson, A. 
 70, 32). — 6. By dry distillation of amido-benzoic 
 acids (Hofmann a. Muspratt, A. 53, 221).— 
 7. By distilling isatin with potash (Hofmann, 
 A. 53, 11). — 8. From di-phenyl-urea or di-phenyl- 
 thio-urea by action of PjO^, zinc chloride, 
 or HCl (Hofmann, Pr. 9, 274) : C0(NPhH)2 = 
 NPhHj + C0:NPh.— 9. Among products of dis- 
 tiUation of peat (Vohl, /. Ph. [8] 36, 319).— 
 
 10. By heating potassium benzene sulphonate 
 with sodamide (Jackson a. Wing, B. 19, 902). — 
 
 11. By the action of Br in alkaline solution upon 
 benzamide (Hofmann, B. 18, 2737).— 12. From 
 phenol, and NH,: — (a) Together with diphenyl- 
 amine by heating phenol with zinc-chloride- 
 ammonia, Zn(NH3)2Clj, at 300° to 350°. The 
 addition of NH^Cl diminishes the quantity of 
 diphenylamine and improves the yield of aniline. 
 The best yields (c. 55 p.c. aniline and 15 p.c. 
 diphenylamine) are obtained by heating 1 pt. of 
 phenol with 4 pts. Zn(NH3)2Gl2 and 4 pts. NH^Cl 
 under pressure at 330°-340° for 20 hours.— (6) 
 Together with diphenylamine by heating phenol 
 
 with a mixture of NH^Cl and ZnO ; also in this 
 case an excess of NH^Cl diminishes the quantity 
 of secondary amine formed. The best yields 
 (c. 55 p.c. aniline and 20 p.c. diphenylamine) 
 are obtained by heating 2 pts. phenol with 
 2 pts. ZnO and 3 pts. NHjCl at c. 330° for 
 20 hours under pressure.— (c) About the same 
 results are obtained by substituting Zn(NH3)2Brj 
 NHjBr for the chlorides in (a) and (6).— 
 (d) Together with diphenylamine by heating 
 phenol with NHjCl and MgO. A yield of 
 45 p.c. aniline and 20 p.c. diphenylamine was 
 obtained by heating 20 pts. phenol with 8-8 pts. 
 MgO and 24 pts. NH,C1 for 40 hrs. at 340^- 
 350°.— (e) Small quantities of aniline and diphe- 
 nylamine (0. 4 p.c. aniline and 15 p.c. diphenyl- 
 amine) are formed by heating phenol (1 pt.) with 
 NHjCl (2 pts.) alone, at 370°-400° (Merz a. 
 Miiller, B. 19, 2901).— 13. Diphenylamine heated 
 with cone. HCl at 320° yields small quantities of 
 aniline and phenol. 
 
 Preparation. — • By reducing nitro-benzene 
 with iron filings in presence of a small quantity 
 of hydrochloric or acetic acid : 
 
 4PhN0, + 4H,0 + 9Fe = 4PhNH, -1- 3Fe304. 
 Nitrobenzene (100 pts.), water (40 pts.), iron 
 borings (25 pts.), and HClAq (9 pts.) are mixed 
 in a cast iron vessel and the reaction started by 
 admission of steam ; more iron borings (90 pts.) 
 are then slowly added. When the reduction is 
 complete, Hme is added, and the aniline (67 pts.) 
 distilled over with steam. Pure aniline is best 
 prepared from pure benzene. Aniline may be 
 purified by conversion into its acetyl derivative, 
 recrystallising this from water, and saponifying 
 it with alkalis or acids. Aniline phosphate is 
 less readily soluble in water than o-toluidine 
 phosphate (Lewy, C. J. 46, 46). 
 
 Properties. — Colourless oil; si. sol. water, 
 misoible with most other menstrua. Turns red 
 in air. Soluble in aqueous solutions of aniline 
 hydrochloride. Its aqueous solution does not 
 change the colour of red litmus or yellow tur- 
 meric but it changes the violet colour of dahlia 
 to green. Congo red may also be used as an 
 indicator (Julius, 8. 0. 1. 9, 109). Aniline pps. 
 ferrous, ferric, aluminium, and zinc, hydrates 
 from their salts ; it forms double salts with 
 PtClj, AuClj, HgCl^, SbClj, and SnCl^. It gives a 
 brownish pp. with tannin. It coagulates al- 
 bumen. Potash, soda, and lime expel aniline 
 from its salts. NHj is expelled when aqueous 
 ammonium salts are boiled with aniline, but 
 aniline is liberated when NH3 is added to cold 
 aqueous solutions of its salts. 
 
 Detection. — 1. Very dilute aqueous solutions 
 give a violet colour with bleaching powder ; the 
 colour is destroyed by shaking with ether (Runge). 
 2. Extremely dilute aqueous solutions treated 
 successively with bleaching powder and a drop 
 of ammonium sulphide give a rose colour (Jao- 
 quemin, Bl. [2] 20, 68).— 3. A solution of aniline 
 in cone. HjSOj mixed with a little solid KjCrjO; 
 gives after some time a splendid blue colour; 
 the reaction is hastened by gently warming 
 (Beissenhirz, A. 87, 376).— 4. If a drop of 
 CuSOjAq is added to an aqueous solution of 
 aniline an apple-green crystalline pp. is formed 
 even if the solution is very dilute ; in extremely 
 dilute solutions a green coloration is produced 
 (Friswell). 
 
272 
 
 ANILINE. 
 
 Reactions. — 1. Aniline vapour passed through 
 a red-hot tube forms C, NH3, HON, benzene, 
 benzonitrile (Hofmann, Pr. 12, 383), oarbazol 
 (Graebe, A. 167, 125), iso-benzidine («. di-Ammo- 
 diphenyl), and quinoline (Bernthsen, B. 19, 420). 
 
 2. Electric sparks passed through liquid 
 aniline form carbon, and a gas containing 
 hydrogen (65 p.c), acetylene (21 p.c), prussic 
 acid (9 p.c), and nitrogen (5 p.c.) (Destrem, CM. 
 99,138). 
 
 3. Dilute HjSO^ and MnO^ form NHj 
 (Matthiessen, Pr. 9, 637), and a little quinone 
 (Hofmann, Pr. 13, 4). 
 
 4. Chromic acid, CrOj, sets fire to aniline. 
 
 5. Chromic acid mixture produces quinone. 
 
 6. Potassium chlorate and hydrochloric 
 acid give tetraohloroquinone (ohloranil) and 
 trichlorophenol (Hofmann, A. 47, 67 ; 53, 28). 
 
 7. Potassium permanganate gives some azo- 
 benzene (Glaser, A. 142, 364), NH,, and oxalic 
 acid (HoogewerfE a. Dorp, B. 10, 1936 ; 11, 1202). 
 
 8. Hydrogen peroxide also produces azo- 
 benzene (Leeds, B. 14, 1384) ; which is also 
 formed by passing aniline vapour over heated 
 PbO (Behr a. Dorp, B. 6, 755). 
 
 9. Potassimn permanganate in acid solution 
 forms aniline black. 
 
 10. Strong nitric acid violently attacks 
 aniline; picric acid is among the products. 
 Aniline nitrate dissolved in a large quantity of 
 HjSO, produces j»-nitro-aniline and a small 
 quantity of ^-nitro-aniline (Levinstein, B. 18, 
 Eef. 203). 
 
 11. A mixture of aniline, o-toluidini, and p- 
 toluidine, is converted by oxidising agents such 
 as nitric acid, mercuric chloride, lead nitrate, 
 silver nitrate, arserdc acid, and sta/nnic chloride 
 into aniline red (■;;. EosAurLiNK). 
 
 12. Nitrous acid converts cold aqueous salts 
 of aniline into salts of diazo-benzene (v. Di-Azo- 
 COMPOUNBS) ; on boiling the solution nitrogen is 
 evolved and phenol formed. Nitrous acid passed 
 into a cold alcoholic solution of aniline produces 
 fliazo-benzene aniUde. 
 
 13. When aniline is boiled with sulphur H^S 
 IB evolved and di-amido-di-phenyl sulphide (thio- 
 aniline) is formed together with other products 
 of substitution of hydrogen by sulphur (Merz a. 
 Weith, B. 3, 978). 
 
 14. Potassium produces NH3 and azobenzene 
 (Girard a. Caventou, Bl. [2] 28,580). 
 
 15. Chlorine acts upon dry aniline with great 
 violence, producing a black mass containing tri- 
 ohloro-aniline. 
 
 16. Bromine behaves like chlorine. Bromine- 
 water added to solutions of salts of aniline gives 
 a pp. of tri-bromo-aniHne CsH^BrsNHj [2:4:6:1]. 
 Bromine has no action on a solution of aniline 
 in cone. H^SO, (Morley, C. J. 61, 582). 
 
 17. Iodine dissolves in aniline forming 
 hydriodide of jp-iodo-anihne. 
 
 18. Hot cone, sulphuric acid forms jp-amido- 
 benzene sulphonio acid ; hot fuming H^SOj forms 
 amido-benzene disulphonio acid (Buckton a. 
 Hofmann, C. J. 9, 260). 
 
 19. Sulphide of carbon forms di-phenyl thio- 
 urea. 
 
 20. Sulphide of carbon and ammionia pro- 
 duce crystals of C,4H,8N,S3or(PhNH,.NH.CS)jS, 
 decomposed by boiling water into OSj, NH3, and 
 
 di-phenyl-thio-nrea (Hlasiwetz a. Kachler, A. 
 166, 142). 
 
 21. Carbon tetrabromide forms diphenyl-jB- 
 amido-benzamidine hydrobromide 
 PhNH.C(NPh).CsH4.NHjHBr (Bolas a. Groves, 
 A. 160, 174). CCl. acts similarly (Hofmann, Pr. 
 9, 284). 
 
 22. Cyanogen forms a ' cyan-aniline ' 
 (C3H3NHj)2C2Nj, [210°-220°] (Hofmann, A. 66, 
 129 ; 73, 180 ; B. 3, 763). Insol. water, si. soL 
 alcohol. Boiling acids decompose it into phenyl- 
 oxamide, di-phenyl-oxamide, oxamide, aniline, 
 and NH3. Nitrous acid produces a base 
 CnH.jNA (Seuf, J.pr. [2] 31, 543). Salts of 
 Cyananiline: B"2HC1. - B"H2PtCls. — 
 B"2HAuCl,.— B"2HBr.— B '2HNO3. 
 
 23. Chloride of sulphur diluted with CS,. 
 forms tri-phenyl-guanidine (di-phenyl thio. 
 urea being first formed, Glaus a. Erall, B. 3, 
 527 ; 4, 99). 
 
 24. Heated with persulphocyanic acid it 
 gives phenyl-thio-biuret. 
 
 25. Carbonylchloride,COCl2,giyB3 di-phenyl- 
 urea. 
 
 26. Gaseous cyanogen chloridetoTmsii--phenjU 
 guanidine (melanUine) ; in presence of water 
 phenyl-urea is formed (Hofmann, A. 70, 130). 
 CyCl passed into an ethereal solution forma, 
 phenyl cyanamide (cyananilide, Cahours a. 
 Cloez, C. B. 38, 354). Solid chloride of cyanogen 
 forms 'ohlorocyananilide ' CisHijClNj (Laurent, 
 A. 60, 273). 
 
 27. Cyanic acid forms phenyl-urea. 
 
 28. When treated in ethereal solution with 
 perchloromethylmercaptan CCI3.SCI it yields the 
 compound CCI3.S.NHC5H5. If the ethereal solu- 
 tion of the latter body is mixed with aleoholio 
 EOH or NHj it sphts off HCl and a crystalline' 
 compound separates which has the probable 
 constitution COI2.S.NC5H5, (Rathke, B. 19, 395). 
 
 29. Phosphorus trichloride acts vigorously, 
 producing ' phosphaniline hydrochloride ' 
 PCls3C3H,N (Tait, Z. [2] i., 649). It is perhaps 
 the anilide of phosphorous acid P(NPhH)33HCl. 
 PtCl2PCl3 forms (PhNH)3PPtCl2NHjPhH01 
 whence water produces (PhNH)3PPtCl(0H) 
 (Quesneville, Monit. scient. [3] 6, 659). 
 PCl32PtCl2, alcohol, and aniline produce 
 P(OEt)3PtClj(C„H,N)2 and Pj(0Et)3PtClj(C„H,N), 
 (Cochin, C. B. 86, 1402). 
 
 30. Phosphorus oxychloride produces very 
 unstable anilide of phosphoric acid, PO(NPhH), 
 (Schiff, A. 101, 302 ; Michaelis a. Soden, A. 229, 
 335). 
 
 31. Aniline, isohutyric acid, and ZnCl^ give 
 iso-butyrio anilide (Bardwell, Am. 7, 116). 
 
 32. Aniline-zinc-chloride and isoamyl alco- 
 hol give amido-phenyl-isopentane. 
 
 38. Chloroform at 190° forms di-phenyl- 
 formamidine, CH(NPh)(NPhH). 
 
 34. Chlorides, bromides, and iodides of alco- 
 holic or acid radicles act upon aniline as they 
 do upon other primary amines {v. Amines). 
 Alkyls may also be introduced by heating aniline 
 hydrochloride or, better, hydrobromide with alco- 
 hols (Staedel a. Eeinhardt, B. 16, 29). Methyl- 
 aniline hydrochloride is converted by heat 
 into toluidine hydrochloride (Hofmann, B. 5, 
 720) ; similarly aniline hydrochloride heated 
 with MeOH at 290° forms OjHjMeNMej, 
 
ANILINE. 
 
 273 
 
 0„H.Me,NMej, C^jMe,NMe„ CsHMe^NMe,, and 
 O.Mej (Hofmann a. Martins, B. 4, 742). 
 
 85. Aldehydes act upon aniline with elimina- 
 tion of water : e.g. 
 CH,.CHO + 2H,NPh = H,0 + CHa.OHfNHPh), 
 CH,.OHO + HjNPh =HjO + CHj.OHtNPh 
 (Sohifi, A. Suppl. 3, 344). The last formula 
 ought perhaps to be written (CH3.CH)2(NPh)2 
 
 (v. MbTHYLENE-ANILIKE ; ElHYLlDENE-ANItilNE ; 
 
 Chloro-ethylidene-aniIjINE, &0.). Aniline acts 
 Bimilarly upon glucose, levulose, and galactose, 
 forming C,H,(OH),(NPh) (Sohiff, A. 154, 30; 
 Sorokin, B. 19, 513). 
 
 36. Amline sulphite gives with an ethereal so- 
 lution of aldehyde prisms of PhNH^C^H^OSOj or 
 PhNH.SO2.CHMe.OH (SchifE, A. 140, 127; 210, 
 129). 
 
 37. Chloral and aqueous SO., produce un- 
 stable crystals of PhNH3SO'.CH(OH).CCl3 
 (SchifE, A. 210, 129). 
 
 38. Acetone and aqueous SO^ form an un- 
 stable compound, PhNHj CsHjO SO2 which is 
 perhaps Me„C(0H).S02.NHPh (S.). 
 
 39. Acetone (1 mol.) and P2O5 two days at 
 180° form Me,G:NPh, (200°-220°) (Engler a. 
 Heine, B. 6, 642 ; cf. Pauly, A. 187, 222). 
 
 40. Aniline hydrochloride heated with 
 acetone or mesityl oxide at 190° forms some 
 (Py. 1, 3)-di-methyl-quinoline (Engler a. Biehm, 
 B. 18, 2245, 3296). 
 
 41. A mixture of aldehyde and acetone at 
 100° give (Py. 1, 3)-di-methyl-quinoiine (Beyer, 
 J.pr. [2] 33,393). 
 
 42. Paraldehyde and oono. HCl at 100° form 
 (Fy. 3)-methyl-quinoIine (quinaldine, Doebner a. 
 von Miller, B. 16, 2464). 
 
 43. Aniline (1 pt.) distilled with glycerin 
 (1 pt.) and HjSO, (2 pts.) forms guinoline 
 (Konigs, B. 13, 911). Quinoline is also formed 
 by distilling aorolein-aniline, or by heating 
 aniline with glycerin, nitrobenzene, and H2SO4 
 (Skraup, M. 2, 141). Aniline-sinc-chloride heated 
 with glycerin forms skatole (Fischer a. German, 
 B. 16, 710). 
 
 44. Aceto-acetic ether at 120°-150° gives 
 aoeto-acetic anihde CH3.CO.CH2.CO.NPhH (cf. 
 AoETo-AOETio ACID, reaction 18), [85°]. SI. sol. 
 water and NHjAq, v. sol. NaOHAq and acids. 
 DistUled with aniline it gives s-di-phenyl urea. 
 Boiling potash produces aniline, acetone, and 
 acetic acid. I'ejClj colours its aqueous solution 
 violet. Br produces CHs.OO.CHBr.CONPhH, 
 [138°]. Cone. HjSO, forms (Py. 3, l)-oxy- 
 methyl - quinoline. Nitrous acid forms 
 CH3.C0.C(N0H).C0.NPhH, [100°] (Knorr, A. 
 236, 75). 
 
 45. Acetophenone cyanhydrin gives rise to 
 CjH5.CMe(NHPh)CN (Jaooby, B. 19, 1515). 
 
 46. An alcoholic solution of guinone pro- 
 duces CBH2(NHPh)202 and hydroquinone. The 
 former dissolves in cone. HjSO, forming a crim- 
 son solution. 
 
 47. Tetrachloro-guinone (chloranil) produces, 
 similarly, C8Cl2(NHPh)202 (Hofmann, Pr. 13, 4 ; 
 Hesse, A. 114, 292 ; Knapp a. Sohultz, A. 210, 
 164). 
 
 48. Aniline mixed with an aniUde and PClj 
 produces a phenyl-amidine : e.g. 
 
 3PhNH2 + 3CH3.CO.NHPh + 2PC1, = 
 3CH3.C(NPh).NHPh -I- PjO, -h 6HC1 (Hofmann, Z. 
 1866, 161). 
 Vol. I. 
 
 49. Aniline hydrochloride and acaionitriU at 
 170° produce phenyl-aoetamidine : 
 
 CH3ON + HjNPh = CH3C(NPh).NH2. 
 
 50. With benzo-trichloride, PhCCla (1 mol.), 
 aniline (2 mols.) on warming acts violently 
 forming the hydrochloride of di-phenyl-benz- 
 amidine, C„H5C(NPh)(NPhH)2HCl : aniline in 
 glacial acetic acid, ZnClj and PhOClj give, 
 chiefly, the same body. 
 
 51. But aniline hydrochloride (40 pts.), niiro- 
 benzene (45 pts.), benzo-trichloride (40 pts.), and 
 iron filings at 180° form the chloride of di- 
 amido-tri-phenyl-oarbinol (g. v.). 
 
 52. Aniline (2 mol.) boiled with chloro-acetic 
 acid (1 mol.) and water produces phenyl-amido- 
 acetic acid and phenyl-imido-di-acetio acid ;' the 
 aniline salt of the latter, PhN(CH2.C02NH,Ph)j, 
 crystallises in needles, [99°] (P. Meyer, B. 14, 
 1325). 
 
 53. An alcoholic solution of aniline, chloro- 
 acetic acid, and ammonium sulphocyanide at 
 100° deposits crystals of phenyl-thio-hydantoio 
 acidNH2.C(NPh).S.CH2:C02H, [148'-152°]. This 
 acid is decomposed by boiling with dilute (20 p. 0.) 
 HjSOi into phenyl-urea and thio-glycollio acid 
 (Jaeger, J. pr. [2] 16, 17 ; Claesson, B. 14, 732 ; 
 Liebermann, A. 207, 129). 
 
 54. Acetamidoxim hydrochloride is converted 
 by heating with aniline into acetanilidoxim, 
 CH3.C(N0H).NHPh, [121°] (Nordmann, B. 17, 
 2753). 
 
 55. .Z'mcei^ifieformszincanilide Zn(NHPli)2, 
 which is decomposed by water into Zn(0H)2 and 
 aniline (Erankland, Pr. 8, 504). 
 
 Salts. — (Beamer a. Clarke, Am. 1, 151 ; B. 
 12, 1066 ; Hjortdahl, Z. K. 6, 471). — B'HCl. 
 [192°] (Pinner, B. 14, 1083). Needles or plates, 
 V. sol. water and alcohol; may be sublimed. — 
 B'jHjPtClj : yellow needles. — B'jHjSnClj : 
 monoclinic. — B'^HjCuCl^. — B'HBr : trimetrio. 
 a:6:c = -723:1: -818. — B'HCdBrj: trimetric. — 
 B'HI.— B'HBil^ (Kraut, A. 210, 323).— B'HF ; 
 pearly scales, sol. water and boiling alcohol. — 
 B'HClOa : long white prisms, sol. alcohol and 
 ether, m. sol. water ; explodes at 75°. — B'HCIO^. 
 — B'HIO,. S.G.iai-48. Explodes at 125°- 130°. 
 — B'HCNHg(CN)2. [88°]. White needles or 
 tables (Claus a. Merck, B. 16, 2737). — 
 B'jHiFeCyj : small micaceous crystals, v. sol. 
 water, insol. alcohol and ether (Eisenberg, A. 
 205, 267). — WJi^EeCy^. — B'jHjCoCye. — 
 B'jHjPtCy,: triclinio (Bcholtz, M. 1, 904). — 
 B'jHjPO, : laminsB, v. sol. water, ether, and hot 
 alcohol (Nicholson, A. 59, 213 ; Lewy, B. 19, 
 1717). — B'jHsPO^. — B'HPO,. — B'^U.Pfi,. — 
 B'jHjSOj : m. sol. water, si. sol. alcohol, insol. 
 ether. Does not form an alum with aluminium, 
 sulphate (Wood, C.N. 38, 1).— B'H^SO, : large, 
 plates; converted by water into the neutral 
 sulphate (Wellington a. Tollens, B. 18, 3313). 
 — B'jHjSjOe (Malozewsky, J. B. 11, 364). — 
 B',(H,SOj)3Hl5 (Jorgensen, J.pr. [2] 14, 384).—. 
 B'HNOs. — Chloro-acetate. [88°]. — Di, 
 chloro-acetate. [122°]. — Tri-chloro- 
 acetate. IU5°].— Oxalate B'^fifl^: tri- 
 clinic columns, v. sol. water, si. sol. alcohol, 
 insol. ether. — Phenate, B'HOPh. [30°]. 
 (181°) (D.). (195°) (D. a. S.). Crystals resembUng 
 naphthalene (from alcohol or light petroleum) 
 (Dyson, C. J. 43, 466). Formed by boiling 
 equivalent quantities of phenol and aniline 
 
274 
 
 ANILINE. 
 
 together Dale a. Schorlemmer, C. J. 43, 186). 
 
 — Phthalate, [146°]: needles.— {$)-Naph- 
 tholate, [82-4°] ; oryatalliue powder (from light 
 petroleum) (Dyson, G. J. 43, 469). Other salts 
 of aniline are described under the Tarious acids. 
 
 Combinations.— {SahiS, C. B. 56, 268, 1095 ; 
 Vohl, Ar. Ph. [2] 148, 201 ; Leeds, J. 1882, 500). 
 — B'j/SiPJj : minute needles, insol. benzene or 
 petroleum-spirit; may be sublimed; converted 
 by water or alcohol into aniline silico- 
 fluoride (Jackson a. Comey, B. 18, 3195). — 
 B'^AgjSO, 2aq : hair -like crystals (Mixter, Am. 
 1, 239). — B'jZnSO,. — B'^ZnCl^. ~ B'^ZnBr^.— 
 B'jZnIj.— C,H5NH.HgCl : amorphous pp. got by 
 mixing hot alcoholic solutions of aniline and 
 HgClj (Forster, A. 175, 30).— B'^HgCl^: needles, 
 got by mixing cold ^coholio solutions of aniline 
 and HgClj.— B'jHgBr^ [112°) (Klein, B. 13, 835). 
 
 — B'^Hglj. [60°]. Decomposed by alcohol.— 
 B',Hg(N0s)2: pp., converted by hot water into 
 C,H5NH.HgN03 4aq and (PhN)2Hgs(NOs), 2aq. 
 — B'.CaClj.— B'jCdCl,.— B'^CdBr^.- B'jCdl,.— 
 B',Cd(N03),.-B'JiCl^.— B'jSnlj.— B'sSbClj.— 
 B'^UrO^Clj.- B'jMnClj.— B'.,MnBrj.— B'^Mnl,.— 
 B'2FeCl2.-B'jSnCl4.— B'sAsClj. [c.90°]. (c.208°). 
 
 — B'jSbCl,. [80°]. — B'sBiClj. — B'BiOCl.— 
 B'jCoOlj 2EtOH : red leaflets, prepared by adding 
 aniline (2 mols.) to an alcoholic solution of 
 CoClj (1 mol.) ; at 100° it becomes blue B'^CoCl^ 
 (Lippmann a. Vortmann, B. 12, 79). — 
 B'jNiCl^ 2EtOH : small green needles, similarly 
 prepared; at 100° it becomes yellowish green 
 B'jNiClj (L. a. V.).— B'^CuCl^ (Destrem, Bl. 30, 
 482).— B'^CuSOi.— B'jPtClj (Gordon, B. 3, 176 ; 
 Cochin, Bl. 31, 499). — B'PtOljC^H^HCl. — 
 B'PtClAH, (Griess a. Martius, A. 120, 326). 
 
 Acetyl derivative CsHgNO i.e. 
 0,H5NH.G2H30. AcetamUde. Mol. w. 135. 
 [114°]. (295°). S. -34 at 14° ; 6-59 at 102-5° 
 l^visveQ., prvoate com.). V.D. 4-8 (calo. 4-7). 
 
 Formation. — 1. From aniline and AcCl 
 (Gerhardt, A. 87, 164).— 2. By boiling aniline 
 with glacial acetic acid (GreviUe Williams, O. J. 
 17,106; u. also Chbmioaij Change). — 3. By heating 
 aniline with acetamide (Kelbe, B. 16, 1199). — 4. 
 From acetophenone-oxim and H^SO, at 100° 
 (Beckmann, B. 20, 1507). 
 
 Properties. — Laminae (from water) ; v. sol. 
 alcohol, ether, and benzene. A saturated 
 aqueous solution boils at 102-5° (Friswell). 
 
 Reactions. — 1. Passed through a red-hot 
 tube it forms di-phenyl-urea, aniline, benzene, 
 andCNH (Nietzkj, B. 10, 476).— 2. ZnCl^at 260° 
 gives flavanUine C,bH„N2. — 3. PCI5 forms 
 CHj-CCl^NHPh which readily splits up into HCl 
 and CHj.CChNPh. The latter is converted by 
 water into HCl and aoetanilide, and by aniline 
 into di-phenyl-acetamidiue, CHs.C(NHPh):NPh. 
 CHj.CCbNPh changes a little above its melt- 
 ing point [50°] into the hydrochloride of 
 CH3.C(NPh).CHj.CCl:NPh, [117°] which at 160° 
 changes to the hydrochloride of amorphous 
 C.sHnNj (WaUaoh, A. 184, 86 ; cf. Michael, J. pr. 
 [2] 35, 207).— 4. P2S5 forms thio-acetanilide (Hof- 
 mann a. Simpson, B. 11, 339 ; Jacobsen, B. 19, 
 1071; V. Thioaoetio acid). — 5. Heating with sul- 
 phur produces oxalyl-amido-phenyl mercaptan, 
 
 C,H^<;^^C.C<^>0^„ and some ethenyl- 
 
 amido - phenyl mercaptan (Hofmann, B. 13, 
 
 1226). — 6. Dry NaOEt at 170° gives ethyj. 
 aniline AoNHPh + NaOEt = EtNHPh + NaOAo. 
 7. Nitrous acid passed into a solution of aoet- 
 anilide in glacial HOAo forms an unstable 
 nitrosamine, PhNAc.NO, [41°] (0. Fischer, B. 
 9, 463). — 8. Nitric acid converts acetanilide 
 dissolved in 4 pts. of HjSO, chiefly into ^-nitro- 
 aeetanilide, some o- being formed. If the 
 acetanilide is dissolved in 20 pts. HjSO, a small 
 quantity of the m-oompound appears (Noltina a. 
 CoUin, B. 17, 261). 
 
 Sodium acetanilide OjHjNAcNa (Eunge, 
 E. [2] 6, 119). Formed by distilling off the 
 alcohol from an alcoholic solution of equivalent 
 quantities of acetanilide and sodium ethylate 
 (Seifert, B. 18, 1358). Crystalline powder. 
 Absorbs COj in the cold, becoming sodium 
 acetyl-phenyl-carbamate, CjHjNAc.COjNa. 
 
 Mercury acetanilide (C5H5NAc)2Hg. 
 [215°]. Formed by melting acetanilide with 
 HgO (Oppenheim a. Pfaff, B. 7, 624). 
 
 Hydrochloride (CbH5.NHAc)2HC1 crystal- 
 lises in needles, decomposed by water. By 
 heating for half-an-hour at 250° it splits off 
 acetic acid and yields the hydrochloride of di- 
 phenyl-acet-amidine CH3.C(NPh).NHPh. By 6 
 hours' heating at 280° it gives flavaniline. At 
 a still higher temperature quinoline bases are 
 formed in small quantity (Nolting a. Weingart- 
 ner, B. 18, 1340). 
 
 y-Chloro-aoetanilide C3H5.NCIA0. Ace- 
 tyl-phenyl-chloro-amide. [172°]. Prepared by 
 adding a cone, solution of bleaching powder to a 
 cone, aqueous solution of aoetanilide containing 
 excess of acetic acid, as long as a pp. is formed. 
 Colourless needles. Scarcely soluble in water. 
 Crystallises well from very_ dilute acetic acid. 
 Heated to 172° it suddenly changes, with explo- 
 sive violence, to the isomeric p-chloro-acetanilide. 
 This change is also produced by cold cone. HCl 
 with a violent reaction. It dissolves in warm 
 absolute alcohol at first unaltered, but after a 
 few moments a violent reaction sete in and the 
 above change takes place. Alkalis and amine 
 bases replace the CI by H. It converts aceto- 
 acetio ether into chloro-aoeto-acetic ether. Not 
 attacked by boiling water (Bender, B. 19, 2272). 
 
 Diacetyl derivative C,|,H„N02 i.e. 
 C5H5NA02. [111°]. Diacetanilide. From phenyl 
 thiooarbimide and HOAo at 140° (Hofmann, B. 
 3, 770) : PhNCS + 2H0Ac = PhNAc^ + CO^ + H^S. 
 Plates. On distillation it gives aoetaniUde (Gum- 
 pert, J". i)n [2] 32, 293). 
 
 Benzoyl derivative CjHjNHBz. [159°]. 
 
 Formation. — 1. From aniline and BzCI 
 (Gerhardt, A. Ch. [3] 37, 327).— 2. By the action 
 of phenyl oyanate upon benzene in presence of 
 AICI3 ; the reaction probably being : 
 (a) PhN:CO + HCl = PhNH.COCl. 
 (6) PhNH.COCl + C^Hj = PhNH.COCjHj + HCl 
 (Leuckart, B. 18, 873). 3. Prom benzophenone 
 oxim and H2SO4 at 100° (Beckmann, B. 20, 1507) 
 
 Properties. — Volatile plates ; insol. water. 
 
 Reactions.— 1. PCI5 forms PhNH.CCljPh 
 and then PhN:CClPh, [40°] (Wallach, A. 184, 
 79) . — 2. Boiling with sM^pterproduces benzenyl- 
 amido-phenyl mercaptan, 
 
 Oxim CisHijN^O i.e. C5Hj.C(N0H)NHC,H, 
 Beng-anilidoxim. [136°] Obtained by heating 
 
ANISOL-PHTHALIC ACID. 
 
 275 
 
 tniobenzanilicle with hydroxylamine hydro- 
 ohloride and Na^COj in alooholio solution lor 
 about an hour (MuUer, B. 19, 1669). Slender 
 needles. Sol. hot water, alcohol, ether, chloro- 
 form, and benzene, si. sol. ligrom. Dissolves 
 both in acids and alkalis. Salts. — B'HGl: 
 Bol. alcohol.— B'jHjCl^PtClj". Ethyl ether 
 CjH5.C(NHPh):N0Bt. [56°]; white pp. Ben- 
 toyl derwative C8H5.C(NHPh)NOBz. [116°]; 
 white glistening needles; sol. alcohol, ether, 
 nnd benzene, insol. water and ligrom. 
 
 Bi-henzoyl derivative NPhBzj. [136°]. 
 From benzanilide and BzCl (Gerhardt a. 
 Chiozza, C. B. 37, 90). 
 
 Preparation. — Benzanilide (18 g.) is heated 
 with BzCl (14 g.) for 3 hours. 
 
 Properties. — Needles (from alcohol). With 
 dilute HOI at 120° it gives aniline and benzoic 
 acid (Higgin, O. J. 41, 132). 
 
 Bi-henzoyl derivative CjHjNBzj. 
 [160°] (isomeric with preceding?). From ben- 
 zoic acid (13 g. and phenyl thiocarbimide (6 g.) 
 at 220° for 6 hours (Losanitoh, B. 6, 176; 
 Higgin, O. J. 41, 133): PhN:CS + 2H0Bz = 
 PhNBzj + CO^ + H^S. 
 
 Properties. — Plates (from alcohol). With 
 dilute HCl at 120° it gives aniline and benzoic 
 acid. 
 
 ANILINE BLACK CjoHaNj. Nigraniline. 
 Formed by mixing aniline, a chlorate (of K, Na, 
 or Ba) and a metallic salt (of Cu,Fe,V, Mn, or Ce) 
 (Lightfoot, G. N. 11, 65 ; Lauth, Bl. [2] 2, 416 ; 
 Higgin, Bl. [2] 7, 93 ; Guyard, Bl. [2] 25, 58 ; 
 Bosenstiehl, Bl. [2] 25, 356 ; 0. B. 81, 1257 ; 
 Kruis, D. P. J. 222, 347 ; Goppelsroder, O. B. 
 82, 331, 1392 ; CoquUlion, O.B. 81, 408; Glenk, 
 D. P. J. 248, 234). The quantity of metallic 
 salt may be small ; ammonium vanadate added 
 to a solution of aniline hydrochloride (6 pts.) and 
 NaClOa or KCIO3 (4 pts.) in water (100 pts.) con- 
 verts 100,000 times its weight of aniline into black. 
 An aniline black is formed at the positive pole 
 when a solution of an aniline salt is electrolysed. 
 Aniline black is purified by washing with water, 
 alcohol, ether, and benzene. It is the hydro- 
 chloride of a base, C3gH25N52HCl ; and can be 
 reduced by tin and HCl, or by HI and P, to 
 p-phenylene-diamine and p-diamido-diphenyl- 
 amine NH2.OBHj.NH.CsHj.NH2 (Nietzki, B. 
 11, 1093). Electrolytic anUine black appears to 
 be C24H2„N42HC1 (Goppelsroder). 
 
 ANILINE GARBOXYLIG ACID v. Fbenyl- 
 
 CABBAMIC ACID. 
 
 ANILINE STES v. Eosaotmne, Mauveine, 
 
 CHRTSAKlirNE &C. 
 
 ANILOTIC ACID is Nitro-saUoylio acid v. 
 
 NriBO-OXT-BENZOIO AOLD. 
 
 ANILOXALBENZAMIC ACID v. Fhentl- 
 
 OXAMIDO-BENZOIC ACID. 
 
 ANIL- PYRUVIC ACID CjH^NOj i.«. 
 CH3.0(NPh).0O2H. [122°]. Formed by the 
 action of aniline on pyruvic acid (Bottinger, B. 
 16,1924;^. 188, 336). Crystals, v. sol. water. In 
 contact with water it condenses to aniluvitonio 
 or {Py. 3, l)-methyl-quinoline carboxylic acid 
 {a. v.). On bromination it yields tribromanil- 
 mbromopyruvio acid. Salt.— BaA'^: v. e. sol. 
 
 ANIL-rVITONIC ACID v. (Fy. 3>Meihyl 
 QciNOLiKE {Py. l)-oarboxylio acid. 
 
 Amide of methyl-^-oxY- 
 
 ANISAMIDE. 
 
 BENZOIC AOID. 
 
 ANISANILIDE. Anilide of methyl-p-oxz- 
 
 BENZOIO AOID. 
 
 ANIS-BENZ-ANIS-HYDROXYLAMINE o. 
 
 Hydkoxtlamine. 
 
 ANIS - BENZ - HYDEOXAMIC ACID v. 
 Hydboxylamine. 
 
 DI - ANIS . BENZ - HYDROXYLAMINE v. 
 
 Hydroxylamine. 
 
 ANISE, OIL OF. The essential oil obtained 
 by distilling the seeds of Pimpinella anisum or 
 Illicium anisatum with water. It contains 
 anethol (q.v.). If the oil is heated with dilute 
 HNO3 (S.G. 1-2) and the resulting heavy oil 
 shaken with warm NaHS03Aq, so-called 
 anisoic or thiauisoio acid C|„HnS04 [below 
 100°] is formed (Limpricht a. Bitter, A. 97, 364; 
 Staedeler a. Wiichter, A. 116, 169). It is a very 
 soluble crystalline mass. NHjA'aq. — NaA'aq. — 
 MgA'2 5aq.— OaA'2 2aq.— BaA'2 3aq.— AgA'. 
 
 ANISE CAMPHOR. A name for anethol (ff.t;.). 
 
 ANISHYDRAMIDE C24H2,N203 i.e. 
 (MeO.OjH4.0H)3N2. Tri-methyl-iri-oxy-hydro- 
 benzamide. [c. 120°]. Formed by action of cone. 
 NHjAq upon jp-methoxy-benzoic (anisic) alde- 
 hyde. Prisms, insol. water, sol. boiling alcohol, 
 ether, or cone. HOlAq (Cahours, A. Ch. [3] 14, 
 487 ; Bertagnini, A. 88, 128). Changes at 170° 
 into An is in, a basic isomeride which forms 
 salts: B'HClaq.— B'jHjPtCls. 
 
 ANIS-HYDROXAMIC ACID v. Hydboxyl- 
 amine. 
 
 ANISIC ACID V. ^-Mei%Z-OxT-EENzoio aoid. 
 
 ANISIC ALDEHYDE v. p-Methyl-OKY-SEHzoio 
 
 ALDEHYDE. 
 
 ANISIC ALCOHOL v. ^-Jlfai%Z-OxY-BENZYii 
 
 ALCOHOL. 
 
 ANISIDINE V. Methyl derivative of Amido- 
 
 PHENOL. 
 
 ANXSIL CieHnO, i.e. 
 CsH,(OMe)— CO-CO-OBH,(OMe). [133°]. Pre- 
 pared by oxidation of anisoin with Fehling'a 
 solution (Bosler, B. 14, 327). Yellow needles. 
 Distils undecomposed. Sol. hot, si. sol. cold, 
 alcohol, insol. water. On boiling with alcoholic 
 KOH it gives anisilic acid. 
 
 ANISILIC ACID CibHijOj i.e. 
 (MeO.C3Hj2C(OH).C02H. [164°]. Prepared by 
 boiling anisil with aloohoKc KOH (Bosler, B. 14, 
 328). Slender white needles. Sol. alcohol, si. sol. 
 water. Dissolves in strong H2SO4 with a violet 
 colour. On oxidation with CrOj it gives di- 
 methoxy-benzophenone. 
 
 ANISINi7. Anishydkamide. 
 
 ANISOIN C.^HisO, i.e. 
 MeO.C5HjCH(OH).C0.05H4.0Me. Di-methyl-tri- 
 oxy-phenyl-benzyl-ketone. [113°]. Prepared by 
 boiling ^-methoxy-benzoic (anisic) aldehyde with 
 alcoholic KOH (yield 60p.o.; Bosler, B. 14, 326), 
 or KCy (Eossel, Z. [2] 5, 562). Needles ; v. si. 
 sol. water, si. sol. cold alcohol and ether. Strong 
 H2SO4 dissolves it with red colour, rapidly 
 changing to pale green, and on heating, to yellow 
 and then purple. See also Hydbo-anisoin, 
 
 ANISOlC ACID V. Anethol. 
 
 ANISOL V. Methyl-FsENor.. 
 
 ANISOL - ISATIN v. JDi-methyl-di-OxY-m- 
 phenyl-oxindole. 
 
 ANISOL-PHTHALIC ACID v. Methyl-Oxt^ 
 
 BENZOFHENONE CABBOXTLIO AOID. 
 
 18 
 
276 
 
 ANISCmiTEILE. 
 
 ANISONITEILK v. Nitrile of Methyl-p-OxY- 
 
 BENZOIO ACm. 
 
 ANISO-DIXTBEIDE v. Methyl-OxY-SE^z^T^-zii- 
 
 OI-CBEA. 
 
 ANISUBIC ACID C,„H„NO, i.e. 
 MeO.C„H^.CO.NH.CH2.COjH. Methyl-oxy-ben- 
 xoyl-glycocoU. — From silver amido-acetate and 
 methyl-^-oxy-benzoyl chloride. Also secreted 
 when methyl-p-oxy -benzoic (anisic) acid is taken 
 into the stomach. Laminae. Split up by acids 
 into glycocoU and anisic acid. 
 
 Salts: CaA'a 3aq.— AgA' (Cahours, A. 103, 
 90 ; 109, 32 ; Graebe a. Schultzen, A. 142, 348). 
 
 ANISYL. This name is usually given to 
 the radicle methyl-p-oxy-phenyl, CHjO.CjHj, 
 but sometimes also to methyl-jj-oxy-benzoyl, 
 CHsO.CuHj.CO, which could more appropriately 
 be called anisoyl. 
 
 ANISYL BEOMIDE v. ^-Bbomo-phbnoi., 
 Methyl-ether and Mei%Z-oxT-BENzoYL bbomide. 
 
 ANISYL CABBAMIDE v. Methyl-p-Ox^- 
 
 PHENYL-UBEA. 
 
 ANISYL CHLOBIDE v. jp-Chlobo-phenoi,, 
 
 Methyl-ether and Miji%Z-oxT-BENZoyi, chloelde. 
 
 ANISYL METHYL KETONE v. Methyl-OxY- 
 
 AOETOPHENONE. 
 
 ANISYL-THIO-TIREA v. Methyl-OxY-iu^^Yh- 
 
 IHIO-UEEA. 
 
 ANISYL-TIEEA v. Ifeifej/Z-OxT-PHENYL-TiEEA. 
 
 ANOL CsH,„0 i.e. H0.CbHj.CH:CH.CH3. 
 [92-5°]. (o. 250°). Formed by heating anethol 
 with KOH. Shining laminse (from alcohol, 
 ether, and chloroform) sol. KOHAq and reppd. 
 by acids (Ladenburg, B. 2, 871). 
 
 ANTHEMENE CisH,^. [64°]. (440°). 
 S.G. 15 -942. V.D. 127 (calc. 131). S. (alcohol) 
 •033 at 25°. Extracted from flowers of chamo- 
 mile (Anthemis nobilis) by light petroleum_(Nau- 
 din, Bl. [2] 41, 483). Minute needles, • insol. 
 water, sol. ether, petroleum, CSj, chloroform, and 
 hot alcohol. 
 
 ANTHEMOL C,„H,50. (214°). Occursinoilof 
 chamomile {Anthemis nobilis). Thick liquid with 
 camphor-like smell (Koebig, A. 195, 104). Boiling 
 dilute HNO3 produces terephthalio and ^-toluic 
 acids. Acetyl derivative C,|,H,50Ac. (235°). 
 
 ANTHOCYANIN. Blue colouring-matter of 
 flowers V. Pigments. 
 
 ANTHOXANTHIN. ' Yellow colouring matter 
 ol flowers, v. Pigments. 
 
 ANTHEACENE C„Hi„ i.e. 
 
 CH OH CH 
 
 CH CH CH 
 
 Mol. w. 178. [213°]. (c. 360°). H.P.p. - 115,000 
 (v. Eeohenberg). S.V. 195-8 (Eamsay). Alcoholic 
 solutions containing less than '03 p.o. exhibit 
 absorption bands in the ultra-violet part of the 
 spectrum (Hartley, C. J. 39, 162). S. (ether) 
 1-17 at 15°; S. (HOAc) -44 at 15°. S. (benzene) 
 1-7 at 15°. S. (alcohol) -08 at 16° ; (dilute alco- 
 . hoi, S.G. -84) -46 at 15° (Versmann, J. 1874, 
 423 ; Beochi, B. 12, 1978). 
 
 Occurrence. — In coal tar (Dumas a. Laurent, 
 A. Ch. [2] 60, 187). From crude anthracene 
 
 the following bodies may be extracted by acetic 
 ether: — (o) Soluble in cold alcohol : carbazol, 
 phenanthrene, fluorene, and a hydrocarbon 
 [130°]. Carbazol is insoluble in CSj, the others 
 dissolve, but can be separated by their picrates. 
 (b) Soluble in cold benzene : synanthrene and 
 two hydrocarbons [104°] and [97°].— (c) Soluble 
 in hot benzene : anthracene (insoluble in dilute 
 alcohol) and pseudophenanthrene (soluble in 
 dilute alcohol). — (d) Insoluble in benzene ; car- 
 bazol (Zeidler, A. 191, 302). 
 
 Formation. — 1. By passing through red-hot 
 tubes a mixture of ethylene with benzene, di- 
 phenyl, or chrysene ; or a mixture of benzene 
 and styrene (Berthelot, Bl. [2] 7, 223 ; 8, 231 ; 
 9, 295) or benzene and petroleum (Letny, B. 10, 
 412; 11, 1210), or benzene and oil of turpentine 
 (Schultz, B. 7, 113). — 2. By passing benzyl- 
 toluene, Ph.CH2.C5H1.CH3, through a red-hot 
 tube, or over heated litharge (Behr a. Dorp, B. 
 
 6, 754 ; A. 169, 216).— 3. By action of AICI3 on 
 a mixture of benzene and s-tetra-bromo-ethane 
 (Anschiitz a. Bltzbacher, B. 16, 623).— 4. By 
 action of sodium on o-bromo-benzyl bromide 
 (Jackson a. White, Am. 2, 392; B. 12, 1965).— 
 5. By heating benzyl ethyl oxide, PhOH2.0.Et, 
 with P2O5 (J. Schulze, J.pr. [2] 27, 518).— 6. By 
 action of CHClj or CHjClj on benzene in presence 
 of AICI3 (Friedel, Crafts, a. Vincent, Bl. [2] 40, 
 97; 41,325). — 7. By heating benzyl chloride with 
 water at 200° and distilling the product (Lim- 
 pricht, A. 139, 303 ; Zincke, JB. 7, 278).— 8. By 
 heating a mixture of alizarin with zinc dust at 
 low red heat (Graebe a. Liebermann, A. Suppl. 
 
 7, 297). — 9. By distilling o-tolyl phenyl ketone 
 with zinc dust (Behr a. Dorp, B. 7, 17).— 10. To- 
 gether with toluene by the action of AIOI3 on 
 benzyl chloride (Perkin a. Hodgkinson, 0. J. 37, 
 726).— 11. By distilling benzyl-phenol with P^Os 
 (Paterno a. Fileti, B. 6, 1202).— 12. By heating 
 o-benzoyl-benzoic acid with zinc dust (Gresly, 
 4.234,238). 
 
 Properties. — Four- or six-sided monoclinic 
 white tables with blue fluorescence. Insol. 
 water, si. sol. alcohol, ether, benzene, glacial 
 HOAc, chloroform, CSj, and light petroleum. 
 Changed in sunlight into para-anthracena 
 (paraphotene) [244°], which is insoluble in most 
 menstrua, but is reconverted into anthracene by 
 fusion. 
 
 Estimation. — Anthracene (1 g.) is dissolved 
 in boiling glacial HOAc (45 o.c), filtered if 
 necessary, and a solution of CrOj (10 g.) in 
 glacial HOAc (5 c.c.) diluted with water (5 o.c.) 
 is slowly added ; a slight excess of OrO, should 
 be left after long boiling. The liquid is diluted 
 with water (150 c.c.) andtheppd. anthraquinone 
 washed, dried at 100°, and weighed (Luck, B. 6, 
 1347 ; V. also Meister, Lucius, a. Briining, Fr. 
 16, 61 ; Paul a. Cownley, C. N. 28, 175 ; Lucas, 
 O. N. 30, 190 ; Nicol, G. J. 30, 553 ; J.T.Brown, 
 C. J. 31, 232; Versmann, O. /. 30, 347). 
 
 Reactions.— 1. Cono. HI at 280° forms an- 
 thracene hydrides, toluene, and various paraffins. 
 
 2. Chromic acid produces anthraquinone. — 
 
 3. Nitric acid also produces anthraquinone, 
 and not nitro-anthracene. — 4. Sulphuric acid 
 forms Bulphonates. — 5. COClj forms the chloride 
 of anthracene (4)-carboxylio acid. — 6. H^Oj pro- 
 duces anthraquinone (Leeds, B. 14, 1382). 
 
 CombinaUons. — With picric acid it forms 
 
ANTHRACENE OHLORIDB. 
 
 277 
 
 C„H„C.H,(N02),0H [188°] ; red needles.— With 
 dinitrothiophene: C„H,„0,Hj(N02)2S [162°] 
 (Bosenberg, B. 18, 1778).— With nitric acid: 
 0„H,„N03 [125°]. Formed bypassing nitrous 
 fumes into anthracene suspended in glacial 
 HOAo at 20°. White needles or prisms, sol. 
 alcohol or benzene, unstable when damp ; con- 
 rerted by alkalis into nitroso-anthrone OjjHgNOj, 
 [146°] and nitroso-hydroanthrone C„H„NOj 
 (Liebermann a. Lindermann, B. 13, 1535). — 
 With nitric peroxide: C^HioNjO, [194°]. 
 Formed by passing nitrous fumes into anthra- 
 cene dissolved in glacial acetic acid cooled below 
 15°. Needles or plates, si. sol. alcohol and 
 benzene ; unstable when damp ; converted by 
 alkalis into nitroso-anthrone. — Hydro -an- 
 thracene-nitrite, 05H,:C2H2(0N0)2:CsH4 (?) 
 [125°] is isomeric with the last body. It is 
 formed by the action of HKO3 on an acetic 
 acid solution of anthraoene-di-hydride. Small 
 crystals. Easily soluble in benzene. On boil- 
 ing with alkalis nitroso-oxanthranol dissolves 
 whilst nitronitrosoanthrone remains insoluble. 
 Oxidation with CrO, converts it into anthra- 
 quinone (Liebermann a. LandshoS, B. 14, 467). 
 
 Constitution. — The constitutional formula 
 given above is founded chiefly upon Formation 
 3, 4, and 2, and upon the formula assigned to 
 anthraquiuone (q. v.). Substitution in one of 
 the benzene nuclei may be indicated by B pre- 
 fixed to a number exactly as in the naphthalene- 
 derivatives ; substitution in the C^Hj group is 
 indicated by the prefix A. But in this dictionary 
 the notation employed for anthracene derivatives 
 is usually exactly the same . aa that used for 
 other benzene compounds («. Benzbitb). 
 
 Additional References. — Graebe a. Lieber- 
 mann, Z. [2] 4, 279, 503, 724 ; 5, 602 ; 6, 257 ; 
 Fritzsohe, N. Petersb. Acad. Bull. 9, 385 ; 13, 
 
 631. V. also METHYIi-ANIHRACENE, ElHYIi-AN- 
 THBACENE, BuTTL-ASTHBACENE, AlHTL-AiraHKACENE, 
 
 and their hydrides; also Chloko-, Bromo-, 
 
 N1TBO-, ANTHRACENE, AnIHBAMINE, AnTHROL, An- 
 
 THBANoii and Sulpho-anthbacbne oaeboxtlio 
 
 ACID. 
 
 Isoanthracene C„H,o. [134°]. Obtained by 
 passing di-benzyl-toluene, C2,H2„ (from toluene, 
 benzyl chloride, and zinc dust) through a red- 
 hot tube (Weber a. Zincke.B. 7, 1156). Laminse; 
 more soluble than anthracene. Converted by 
 CrOj into a quinone ChHjOj. 
 
 Fara-anthracene C^H,,,. [244°]. Deposited 
 when solutions of anthracene are exposed to 
 sunlight. V. si. sol. alcohol, ether, and benzene. 
 Changed into anthracene by fusion. Does not 
 combine with picric acid (Schmidt, /. pr. [2] 9, 
 248). 
 
 ANTHRACENE BKOMIDE CnH,„Br2. Crys- 
 tals formed by adding bromine to a solution of 
 anthracene in CSj at 0° (Perkin, C. N. 89, 
 145). Split up by heat into HBr and bromo- 
 snthracene. 
 
 ANTHEACENE CAEBOXYLIC ACID 
 C.sHjoOj i.e. 0„H,.C08H. [280° corr.]. Two 
 anthracene oarboxylio acids can be obtained by 
 distUling dry crude potassium anthracene sulpho- 
 nate with K^FeCy,, and saponifying the mixture 
 of nitriles that results (Liebermann, B. 8, 246 ; 
 13, 48). They may be separated by baryta- 
 water which forma a soluble salt with the (;8)- 
 
 acid, and an insoluble one' with the M-acid. 
 Nevertheless the two acids may be identical. 
 
 (/3) -Anthracene carboxylic acid. [c. 260°]. 
 Yellow needles (from alcohol). Insol. water, 
 si. sol. benzene and ether. Gives anthracene 
 when heated with soda-lime, and anthraquinone 
 carboxylic acid when oxidised by CrOj. Salts 
 with heavy metals are v. sol. water. The acid 
 and its salts show blue fluorescence. 
 
 (7) -Anthracene carboxylic acid. [c. 280°]. 
 Formed also by reducing anthraquinone car- 
 boxylic acid with zinc dust and ammonia (Born- 
 stein, B. 16, 2609). Small plates or needles. 
 May be sublimed. Sol. acetic acid and hot 
 alcohol, si. sol. cold alcohol and chloroform. 
 Its solutions have a blue fluorescence. CrO, 
 gives anthraquinone carboxylic acid [285°]. 
 
 Salts. — NaA' : small spangles, si. sol. water; 
 fluorescent. All the salts of the heavy metals 
 are tolerably insoluble. 
 
 Ethyl ether A'Et : [135°], white plates, 
 with blue fluorescence. 
 
 Chloride CnHj.OOCl: yellow crystals, 
 soluble in alcohol, ether, benzene, and CSj with 
 an intense green fluorescence. 
 
 Amide C„H9.C0NHj: [295°], slender yellow 
 needles or plates, si. sol. alcohol with a blue 
 fluorescence, insol. water, benzene, CS, and 
 chloroform. 
 
 Anthracene (^.)-carboxylic acid 
 C,H,:C2H(C02H):C,H4. [206°]. From anthra- 
 cene and COCI2 at 200°, and saponifying the 
 chloride by NajCOjAq (Graebe a. Liebermann, 
 B. 2, 678). Formed also by heating {A. 1)- 
 chloro-anthracene {A. 2)-carboxylic acid with 
 alcoholic potash (Behla, B. 20, 701). Silky 
 needles (from alcohol) ; decomposed by heat into 
 CO2 and anthracene. V. si. sol. water. CrO, 
 gives anthraquinone. CI or Br (1 mol.) gives 
 (A. l)-chloro- (or bromo-) anthracene (A. 2)- car- 
 boxylic acid. A larger quantity (2 mols.) of CI or 
 Br give {A.)- di-chloro- (or bromo-) anthracene. 
 Cone. H2S04 gives (B.)-sulpho-anthracene {A.)- 
 carboxylic acid. Salt. — AgA'. 
 
 Methyl ether MeA'. [111°]. Yellowish 
 prisms or tables. 
 
 Anthracene-di-m-carbozylio acid 
 (1) 
 -CHv (2:4) 
 
 0»H.< I >CjH,(C0jH)j. [above 830°]. Formed 
 \CH^ 
 
 (6) 
 
 by reduction of an ammoniacal solution of the 
 corresponding anthraquinone - m - di - carboxylic 
 acid with zinc - dust. Crystalline powder. 
 Scarcely sol. water, m. sol. other solvents (Elbs 
 a. Giinther, B. 20, 1365). 
 
 Anthracene-di-carboxylic acid 
 (1) 
 .CH. (3:4) 
 
 OsHZ I >C8H2(C0jH)j. [345°]. Formed by 
 
 (8) 
 
 reduction of an ammoniacal solution of anthra- 
 quinone-di-carboxylic acid [340°] with zinc-dust. 
 Yellow crystalline powder. Scarcely sol. water, 
 si. sol. other solvents (Bibs a. Eurioh, B. 20, 
 1363). 
 
 ANTHRACENE CHLORIDE 0„H,„Clj. From 
 anthracene dissolved in OS, at 0° by passing 
 in 01 (Perkin, 0. J. 31, 209). Needles (from 
 
278 
 
 ANTHRACENE CHLORIDE. 
 
 benzene). Splits up into HOI and chloranthra- 
 oene even in the cold. 
 
 ANTHKACENE HYDRIDES. 
 
 Anthracene di-hydride ChH,^. [108^. (313°). 
 Formed by heating anthracene at 160° with 
 HI and red P, or by treating a solution in 
 alcohol (95 p.c.) with sodium-amalgam. Pre- 
 pared by heating anthraquinone (30 pts.), HI 
 (140 pts. of S.G. 1-8), and red P (10 pts.) with 
 inverted condenser for one hour on a sand bath 
 (Liebermann, A. Swppl. 7, 265 ; 212, 5). Large 
 monoclinio plates (from alcohol) or needles (by 
 sublimation). Insol. water, v. sol. alcohol, ether, 
 and benzene. Volatile with steam. Its solu- 
 tions fluoresce blue. 
 
 Reactions. — 1. Warm cone. HjSOj forms 
 anthracene and SO2. — 2. Br added to its solu- 
 tion in CS2 forms di-bromo-anthracene.— 3. 
 Cone, nitric acid forms hydro-anthraoene-nitrite 
 {v. sup.) and dinitroanthrone. — 4. CrOj gives 
 anthraquinone. 
 
 Anthraeeneliexa-hydriaeC„H,e. [63°]. (290°). 
 From oxy-anthraquinone (or anthracene dihy- 
 dride), fuming HI and red P by boiling for 20 
 hours (Liebermann, A. 212, 25 ; Suppl. 7, 273). 
 Plates (from alcohol). Volatile with steam ; v. 
 sol. alcohol, ether, and benzene. At a red heat 
 it is split up into hydrogen and anthracene. 
 
 ANTHRACENE - HYDRIDE CARBOXYLIC 
 ACIDS. 
 
 Anthraoene-di-hydride carboxylio acid 
 C.^HiA i-e- C„H„(C02H). [203°]. Formed, 
 together with the following acid, by reduction 
 of anthraoene-carboxylio acid, [280° cor.], with 
 eodium-amalgam (Bornstein, B. 16, 2612). 
 Colourless plates. V. sol. ordinary solvents. 
 
 Anthracene-tetra-hydride carboxylic acid 
 C„H,3(C02H). [165°]. Colourless trimetric tables. 
 
 Anthracene-hexa-hydride carboxylic acid 
 C,jH,5(C02H). [232°]. Formed by reduction of 
 anthraoene-carboxylio acid by heating it with 
 HI (1-7) and P at 220° (B.). Slender needles. 
 
 ANTHRACENE-DI-HTfDRIDE STJLPHONIC 
 ACID C,iH„.HS03. Prepared by reduction of 
 sodium anthraquinone sulphonate with HI (S.G. 
 1-8) and red P (Liebermann, B. 12, 189, A. 212, 
 44). Decomposed by fusion with KOH with 
 formation of anthracene and anthracene hydride. 
 NaA' aq : long soluble needles. — BaA'2. — CaA'j. 
 
 ANTHRACENE STJLPHONIC ACID 
 ChHjSOsH. 
 
 Fm'mation. — From anthraquinone sulphonic 
 acid, HI (S.G. 1-7), and red P, by boiling for half 
 an hour (Liebermann, A. 212, 48). 
 
 Preparation. — From sodium anthraquinone 
 sulphonate (500 g.), zinc dust (750 g.) and 
 ammonia (3 litres of S.G. -88), at 100° 
 (A. 212, 57 ; B. 15, 852). On oxidation by 
 HNOs it gives anthraquinone sulphonic acid. 
 
 Salts — NaA'4aq, v. si. sol. water. — BaA'j. — 
 PbA'j 2aq. 
 
 The existence of (o)- and (;3) -anthracene sul- 
 phonic acids amongst the disulphonic acids 
 obtained by sulphonation of anthracene (Linke, 
 J.pr. [2] 11, 222) has been denied by Liebermann 
 (B. 12, 692). 
 
 (a)-Anthracene-disulpIionic acid 
 [l|] CA(SO.H):C^,:C,H.SO,H [^4]. 
 
 Preparation. — 1 pt. of anthracene is gently 
 heated on a water bath with 3 pte.of H^SO^ for 
 
 an hour. After dilution with water, the fllterei 
 solution is neutralised with PbCOj, and the lead 
 salts converted into the sodium salts. 
 
 Since the sodium salt of the (a) -acid is mneb 
 less soluble in water containing NajCO, than 
 the sodium salt of the (j3)-acid it can be readily 
 separated from the latter (which is formed 
 simultaneously) (Liebermann a. Boeok, B. 
 11, 1613 ; 12, 182, 1287). 
 
 Properties. — Minute needles. By fusion 
 with KOH it gives (o) - dioxyanthracene 
 (chrysazol), which is converted on oxidation into 
 chrysaziu v. Di-oxy-anthbaquinone. 
 
 S alt s.— Na^A" 4aq.-K2A" aq.— CaA" 5aq.— 
 BaA" 4aq. 
 
 (i3)-Aiithracene-disnlphonic acid 
 [l I] C,H3(S03H):0,H,:C„H3.S03H [| 1]. 
 
 Preparation. — 1 pt. of anthracene is heated 
 to 100°C. with 3 pts. of H^SO, till half has 
 dissolved. It is separated from the (a)-acid, 
 simultaneously formed, by conversion into the 
 sodium salt. By fusion with KOH it gives a 
 dioxyanthracene, which on oxidation is con- 
 verted into anthrarufin v. Di-oxy-ANTHEAQUiNONE. 
 
 Salts. — Na2A"3aq; white leaflets, easily 
 soluble with a blue fluorescence. — BaA" 4aq ; 
 white leaflets. — A"Pb : crystalline pp. — CaA" 3aq 
 (Liebermann a. Boeok, B. 11, 1613 ; 12, 182, 
 1287). 
 
 Anthracene - di - sulphonic acid (Flav-). 
 C„H„(S03H)2. Prepared by reduction of sodium 
 («) -anthraquinone di-sulphonate with zinc-dust 
 and NH3 (Schuler, B. 15, 1807). 
 
 Salts. — A"Na2: solublecrystals,its solutions 
 have a blue-violet fluorescence. — A"Ba: white 
 crystalline powder. 
 
 ANTHRACHRYSONE v. tetra-OxY-mTssK- 
 
 QUINONE. 
 
 ANTHRACYL-AHINE v. Antheamine. 
 ANTHRAFLAVIC ACIDtj. Di-oxy-antheaqtji. 
 
 HONE. 
 
 ANTHRAGALLOI v. (1, 2, 3)-iri-0xT-ANTHBA. 
 
 QUINONE. 
 
 ANTHRAHYDROQUINONE v. Oxantheanol. 
 
 ANTHRAMINE 0„H,iN i.e. 
 CjHj:(02H2):C3H3NH;. Anthracylamine. Amido- 
 anthracene. Anthrylamine. [237°]. 
 
 Formation. — 1. By heating amido-anthra- 
 quinone with HI and P. — 2. By heating anthrd 
 with acetamide at 280° and saponifying the 
 acetyl derivative so produced. — 3. By heating 
 anthrol vnth 10 p.c. aqueous NH, at 250° ; the 
 yield is nearly theoretical. — 4. By heating an- 
 throl with alcohol and ammonia at 170°. 
 
 Properties. — Yellow plates (from alcohol). 
 May be sublimed ; si. sol. alcohol, the solution 
 having a splendid green fluorescence. Is a weak 
 base, dissolving with difficulty in boiling Hd. 
 Forms a blue mass when fused with arsenia 
 acid. Is readily methylated. 
 
 Reactions. — 1. Does not give the carbamine 
 or mustard oil tests. — 2. Boiling HOAo gives 
 di-anthramiue. — 3. Chloroform and alcohoUo 
 potash give rise to di-anthryl-formamidine 
 CnHg.NH.CH:N.C„H3.— 4. Nitrom acid givea 
 CjsHjiNaO, [250°], a body which forms a red solu- 
 tion in CSj, and a blue solution in HjSO,. 
 
 Salts. — BUOl: white iridescent plates, sL 
 sol. water; formed by adding HCl to an alaobolis 
 
ANTHKAQUINONE. 
 
 279 
 
 solution of the base. Its solution does not 
 fluoresce.— B'jHjSO, : v. si. sol. water. 
 
 Acetyl derivative OnHjNHAo. [240°]. 
 Plates. Its alcoholic solution fluoresces blue. 
 CrOj gives aoetyl-amido-anthraquinone. 
 
 Formyl derivative OuHsNH.OHO. 
 [242°]. Small yellowish-green crystals, si. sol. 
 alcohol, with green fluorescence. 
 
 References.— Eoemer, B. 15, 223 ; Liebermann 
 a. BoUert, B. 15, 226, 852; 16, 1635; A. 212, 57. 
 
 Di-anthramine C^U^^ i.e. (C,^,)^^.. Di- 
 anthracylamine. Prepared by boiling anthra- 
 mine with acetic acid (Bollert, B. 16, 1636). 
 Does not melt at 320°. Small glistening plates. 
 Very sparingly soluble in all solvents. 
 
 ANTHRAMINE-DI-HYDBIDE C„H„.NHj. 
 Slender colourless needles. Very soluble in 
 alcohol. Formed by reduction of anthramine with 
 sodium-amalgam. — BTECl: sparingly soluble 
 white needles (Liebermann a. Bollert, B. 15, 853). 
 
 ANTHEANIL CjHsNO i.e. C,n,<:^^^ (?). 
 
 o-Ainido-benzoic lactam, (c. 213°). V.D. 
 4-14 (obs.). Formed by reduction of o-nitro- 
 benzaldehyde with tin and acetic acid (Fried- 
 lander a. Henriques, B. 15, 2105). Colourless oil ; 
 volatile with steam. Soluble in ordinary solvents, 
 but sparingly in water. Veryweakbasicproperties. 
 Beduces salts of gold and silver to the metal. 
 By alkalis it is converted into anthranilic acid 
 of which it is the anhydride. Double compound 
 CjH^NOHgCl^: [174°]; slender needles, sol. 
 alcohol and hot water, b1. sol. cold water. 
 
 .CO 
 
 Benzoyl derivative CjHi"^ | . [123=]. 
 \nBz 
 (above 360° with decomposition). Formed by 
 heating isatoic acid with BzCl (E. v. Meyer, J. 
 pr.-[2] 33, 19). Long white needles; readily 
 takes up HjO forming benzoyl-anthranilic acid 
 (Friedlander a. Wleugel, B. 16, 2229). 
 
 ANTHEANIL 1/-CABBOXYLIC ACID v. 
 
 ISATOIO ACID. 
 
 ANTHKANILIC ACID v. o-Amido-benzoic 
 
 ACID. 
 
 ANTHBANOL C„H„0 i.e. 
 
 ,C(OH) 
 ' / ■ 
 
 C,H,< 
 
 \, 
 
 CH 
 
 
 OjH^. (163°-170°). From an- 
 
 thraquinone ^30 g.), HI (140 g. of S.G. 1-75), 
 and red P (8 g.), by 15 minutes' digestion 
 (Liebermann, A. 212, 6). Needles (from benzene). 
 Its alcoholic solution shows blue fluorescence. 
 Decoinposed by heat, becoming greenish. Dis- 
 solves in aqueous KOH, forming a yellow liquid, 
 whence CO^ pps. the anthranol. The alkaline 
 solution is oxidised by air, some anthraquinone 
 being formed. CrOj in glacial HOAc completely 
 oxidises anthranol to anthraquinone. 
 
 Acetyl derivative. [126°-131°]. White 
 needles (from dilute alcohol). 
 
 ANTHBANOL DIHYSBISE 
 
 C»H<CH(OH)>CeH. [76°]. 
 Preparation. — 50 grms. of anthraquinone are 
 mixed with 100 grms. of zinc dust and heated 
 over a water-bath with 300 c.c. ammonia and 
 200 c.c. of water. The liquid turns at first blood- 
 red from oxanthranol, but after three hours this 
 is reduced, the liquid becoming yellow. The 
 liquid is filtered, the pp. dried at 15°, and 
 
 CjsH^A »•«• CH,/^C(OH)-C(OH)< 
 
 extracted with boiling benzoline (40°-60°), from 
 which the anthranol dihydride crvstallises on 
 cooling (H. E. v. Perger, J. pr. [2] 23, 139). 
 
 Properties. — Slender satiny needles, which dis- 
 solve in benzoUne, forming a solution with bluish 
 fluorescence. May be crystallised from boiling 
 water, but by long-continued boiling with water 
 or with alcohol it is converted into anthracene : 
 PIT ^OHv 
 
 °'=*<OH(OH)>0'H. = O.B.^^_)O.H.+H.O. 
 
 DIANTHBANYL 0,.H,, i.e. 
 C,H, CA 
 
 /\ /\ 
 
 HC — 0-0 — OH. [300°]. Yellowish plates, 
 
 \/ \/ 
 
 CsHj O5H4 
 Formed by heating anthrapinacone OjsH^jO, 
 with acetyl chloride (K. Schulze, B. 18, 3035). 
 
 ANIHBAPINACONE 
 
 OeS., C,H. 
 
 |/\0Hr 
 
 CjHj CgH, 
 
 [0. 182°]. Formed as a by-product of the re- 
 duction of anthraquinone to dihydroanthranol 
 by means of zinc-dust and NHj. Long slender 
 white needles. Sol. hot benzene, toluene, or 
 xylene, si. sol. alcohol, insol. petroleum-ether. 
 On heating with acetyl chloride, 2H20 is removed 
 giving dianthranyl C,jH,b (Schulze, B. 18, 3034). 
 ANTHRAPTJEPUBIN v. rri-OxY-ANiHBAQni- 
 
 NONE. 
 
 ANTHRAQUINOL v. Oxanthranol. 
 ANTHBAQUINOLINE C„H„N t.«. 
 H 
 
 /C-0^ ^CH 
 
 CsHK I II I [170O]. (446"^. 
 
 ^C-0 ^C-N=CH 
 
 ^ ^0 _ CH = bH 
 
 Formation. — 1. By heating alizarin-blue 
 with zinc-dust. — 2. By heating a mixture of 
 anthramine, nitrobenzene, glycerin, and HjSO, 
 (Graebe, B. 17,170; A. 201, 344). 
 
 Properties. — Tables, insol. water, sol. alcohol 
 and ether ; its solutions show intense blue fluo- 
 rescence. Its salts are yellow and possess in 
 solution an intense green fluorescence. B'HCl. — 
 B'^H^PtCls.- B'HL— B'H^SO^. 
 
 Combinations. — With picric acid it forms 
 C„H„N C„H2(N02)30H : slender yellow needles. 
 With ethyl iodide: B'Btl; golden needles, v. 
 sol. hot, si. sol. cold, water. 
 
 Quinone C„H„N02. [185°]. Formed from 
 the preceding by CrOj. Yellow prisms or needles, 
 insol. water, sol. in alcohol and ether. Salts . — 
 B'HCl : sulphur-yellow needles, si. sol. water, 
 but slowly decomposed by it.— B'jHjPtClj. Picric 
 acid compound B'CsHjNjO, : golden needles. 
 
 ANXHBAQTTINONE 
 
 C„Sfiii.e. C;E,<^^^yC,S^. Mol. w. 208. 
 
 [273°]. S. (alcohol) -05 at 18°; 2-25 at 78°. 
 V.D. 7-8a (calc. 7-20) (Graebe, B. 5, 15). 
 
 Formation. — 1. By oxidation of anthracene 
 (Laurent, A. Ch. [2] 60, 220 ; 72, 415 ; A. 34, 
 287 ; Anderson, C. J. 15, 44).— 2. From phthalyl 
 chloride by heating with benzene and zinc-dust 
 in sealed tubes at 220° (Piccard, B. 7, 1785) or 
 
2£0 
 
 ANTHKAQUINONE. 
 
 by treatment with AlCl, (Friedel a. Oralis, Bl. 
 [2] 29, 49).— 3. By dry distillation of calcium 
 phthalate (Panaotovits, B. 17, 312).— 4. To- 
 gether with benzophenone by distillation of 
 calcium benzoate (KekulS a. Franchimont, B. 
 5, 908). — 5. By heating o-(but not p-) benzoyl- 
 benzoic acid withPjO, at 200° and extracting 
 with benzene (yield 20 p.c. ; Behr a. Van Dorp, B. 
 7, 578). — 6. In small quantity, by distUling 
 benzoic acid with P2O5 (K. a. P.). — 7. From 
 phenyl o-tolyl ketone, MnOj, and H^SO^Aq (Behr 
 a. Dorp, B. 6, 753 ; 7, 16).— 8. By acting on 0- 
 bromo-benzyl bromide dissolved in ether with 
 Na and oxidising the product (anthracene) with 
 CrOj (Jackson a. White, Am. 2, 390).— 9. By 
 action of water on ' anthraquinone chloride ' 
 OuHbCIjO, obtained by passing chlorine into 
 phenyl o-tolyl ketone at 110° (Thorner a. Zincke, 
 B. 10, 1479). 
 
 Preparation. — ^Anthracene is dissolved in 
 glacial acetic acid; KjCr^O, or CrO, is added; 
 the liquid is then heated to 100°, the acetic 
 acid is distilled off and the anthraquinone ppd. 
 by water. Large quantities are prepared by 
 oxidising anthracene (100 kilos.) with K2Gr20, 
 (150 kilos.) sulphuric acid (200 kilos.) and water 
 (2,000 kilos.). 
 
 Properties. — Yellow needles (by sublimation). 
 Insol. water, t. b1. sol. alcohol, si. sol. benzene. 
 Not attacked by alcohoUo KOH at 200°; or by 
 cold Br. 
 
 Beactions. — 1. Bromine at 100° forms di- 
 bromo-anthraquinone (g. v.). — 2. HI and P form 
 anthranol and anthracene dihydride. — 3. Heated 
 with zinc dust to dull redness it is reduced to 
 anthracene. — 4. Zinc dust and aqueous NaOH 
 giveoxanthranol, Ca'H.M2^02):Gi^'Rt{q.v.): when 
 alkyl iodides are added alkyl oxanthranols are 
 got. When stronger soda is used and the 
 alkyl iodide is not added until the reduction is 
 complete, alkyl-hydro-anthranols {v. Htdbo- 
 anthbanoij) are got (Liebermann, A. 212, 100). — 
 5. Zinc dust and aqueous NH, give dihydro- 
 oxanthranol, CeH,:(C2H,O2):05H4.— 6. PCI5 di- 
 luted with PCI, at 200° forms chlorinated 
 anthraquinones (draebe a. Liebermann, A. 160, 
 121). — 7. Potash-fusion at 250° forms potassium 
 benzoate. 
 
 Constitution. — The formation of anthra- 
 quinone from phthalyl chloride (g. v.) and ben- 
 zene might be thought to indicate the formula 
 
 .COv 
 ObH.< >0 This formula is open to 
 
 \c/0.H,. 
 several objections : — (a) the group OjH,:0 is 
 unknown; (6) it represents a lactone which 
 should be converted by KOH into an oxy acid : 
 (c) anthraquinone reacts with hydroxylamine 
 while phthalide and its derivatives do not 
 (B. V. Meyer, J.pr. [2] 29, 139, 496 ; V. Meyer, 
 B. 17, 818). There remains the formula 
 
 CO 
 OjHj^PQ^OjH,, which agrees with that of 
 
 XHv 
 
 anthracene C.H,f I yOM, and must there- 
 
 \oh/ 
 
 fore be adopted. Bromo-phthalic acid, benzene, 
 and AIOI3 give bromo-benzoyl-benzoic acid, 
 CX);^.0jH3Br.C0.0<,H„ in which it is evident that 
 the carbonyls are to one another. Oonc. HjSO, 
 esndeaaes this acid to bromo-anthraquinoiM, 
 
 whence potash-fusion forms an oxy-anthraqni. 
 none from which phthalic (not oxy-phthalic) acid 
 can be obtained by nitric acid. Hence the two 
 carbonyls are to one another in both beneene 
 nuclei (Pechmann, B. 12, 2125). 
 
 Derivatives of anthraquinone are described as 
 
 CHJiOBO-ANTHBAQUraONE, BbOMO-ANTHBAQUINONB, 
 Oxy - ANIHBAQUINONE, OxY - METHYL - ANTHBAQUI- 
 NONE, METHTL-ANIHBAQtriNONE. 
 
 ANTHRAQUINONE CABBOXYLIC ACID 
 C„Kfi, i.e. CeH,:(0A):0.H3C0,H. [282°- 
 284°]. Obtained by boiling methyl-anthracene 
 (WeUer, B. 7,1186; 0. Eigoher, B. 7, 1196; 
 Liebermann, 4. 183, 166; J.ipp a. Sohultz, B, 
 10, 1051), methyl - anthraquinone (Hammer- 
 Bohlag, B. 11, 82), or anthracene oarboxylia 
 acid [280°] (Liebermann a. v. Eath, B. 8, 248), 
 with CrOs and HOAc, or the compound OigH^O 
 (obtained by action of cone. H^SO, on amyl- 
 oxanthranol) with CrO, and H^SO^ (Liebermann, 
 A. 212, 97). 
 
 Properties. — Compact yellow prisms (from 
 alcohol) ; yellow needles (by sublimation) ; v. 
 si. sol. HOAc, benzene, and alcohol, v. sol. 
 acetone. Decomposed by heat into CO^ and 
 anthraquinone. The sodium salt is insol. 
 NaOHAq. 
 
 Salts. — ^BaA'j(?Aq) needles, v. sol. hot 
 water.— CaA'2(?Aq). 
 
 The following derivatives are got from the 
 acid obtained by oxidising methyl-anthraquinone 
 (Liebermann a. Glock, B. 17, 888). 
 
 Ethyl ether ACBt: [147°], needles, easily 
 soluble in alcohol. 
 
 Chloride C„H,02.C0C1: [147°], needles, 
 very stable towards water. 
 
 Amide C.iHiOj.CO.NHj: [above 280°], 
 needles, very stable compound. 
 
 Anilide C.jHA-CO.NHPh: [260°], needles, 
 very sparingly soluble in most solvents. 
 
 (7) -Anthraquinone carboxylic acid. [285°]. 
 From the corresponding anthracene carboxylic 
 acid (Liebermann a. Bisohof, B. 13, 49). Yellow 
 needles (from glacial HOAc). Its alkaline solu- 
 tions do not fluoresce. Its barium salt is v. si. 
 sol. water. This acid may be identical with the 
 preceding. 
 
 Anthraqoiuone-di-m-carbozylic acid 
 (1) 
 
 CeH,<;^Q>OsHj(COjH)j. [above 830°]. Formed 
 
 (6) 
 by oxidation of the corresponding m-di-methyl- 
 anthracene. Yellow needles. Nearly insol. 
 water, si. sol. other solvents. Dissolves in 
 aqueous NH, with a red colour ; the NH^ salt 
 crystallises in easily soluble small red warts ; 
 its solution gives with AgNOj a reddish pp. of 
 A"Ag2. By zinc-dust and aqueous NH, the acid 
 is reduced to anthracene-m-di-carboxylio acid 
 (Elbs a. Giinther, B. 20, 1364). 
 
 Anthraquiuone-di-carboxylic acid 
 
 0,H,<;^0>C,H2(C0JH)j. [340°]. Formed by 
 
 (6) 
 
 oxidation of di-methyl-anthraquinone [183°] by 
 HNO3 (1-2) at 220°. Yellow needles. Scarcely 
 sol. water, si. sol. most other solvents. Dissolves 
 in aqueous NH, with a red colour. On heeting 
 it loeee 11,0, giving the anhydride. By sino- 
 
ANTHROL. 
 
 281 
 
 dust and aqueous HH, it is reduced to anthra- 
 sene-di-oarboxylio acid [345°]. The solution of 
 the NH, salt gives pps. with CaOlj, Pb{OAo)j, 
 and AgKOj. 
 
 Anhydride 0,H^.OA.OeHj<°°>0 : 
 
 [290°] ; sublimes in small yellow needles (Elba 
 a. Burioh, B. 20, 1362). 
 
 ANIHBAQUINONE-OXIU 
 
 C.H<gg^O^)>C,H, 
 
 Formed by heating anthraquinone with hydroxyl- 
 amine hydrochloride and alcohol at 180° (Gold- 
 Bchmidt, B. 16, 2179). Bed crystalline powder. 
 Sublimes without melting above 200°. Dissolves 
 in HjSO, with an intense yellow colour. 
 
 ANTHRAQUlNOIirE SXJLFHONIC ACID 
 OuHgSOs i.e. C5H,:(CO)2:0sH3.SO8H. Formed 
 together with the disulphonio acid by heating 
 anthraquinone (1 pt.) with H^SO, (2J pts.) at 
 260°. Also from diamido-anthraquinone sul- 
 phonio acid by diazo reaction; and from o- 
 benzoyl-benzoio acid and fuming H^SO^ (Lieber- 
 mann, A. 160, 131 ; Swppl. 7, 805 ; y. Perger, 
 J. pr. 12] 19, 218). 
 
 Properties. — Yellow scales, v. sol. water and 
 alcohol, v. si. sol. HjSO^ and ether. 
 
 Beactions. — 1. Fused with potash it forms 
 alizarin, oxy-anthraquinone, and benzoic, p- 
 oxy-benzoio and protocatechuio acids. — 2. HI 
 and F form anthracene sulphonio acid and its 
 dihydride. — 3. Anthracene sulphonio acid is also 
 produced by sodium-amalgam, and by zinc-dust 
 and ammonia. — 4. Ammonia at 190° forms 
 amido-anthraquinone. — 5. Distillation of the 
 sodium, salt produces, besides small quantities 
 of anthraquinone and ozyanthraquinone, chiefly 
 a compound C^sS-nOg which melts far above 
 300°. This compound forms minute reddish- 
 yellow needles (from glacial HOAc) , si. sol. HOAc, 
 toluene, phenol, and aniline, y. si. sol. alcohol. 
 At a high temperature it may be sublimed. It 
 is insol. alkalis, but forms a crimson solu- 
 tion in cone. H^SOj. Distilled with zinc dust 
 it yields anthracene. Fused with potash it 
 gives alizarin. Its constitution is perhaps 
 0,H^:(CO)j:CeH,O.C;H:30:(CO)2:C,Hj. Chromio 
 acid oxidises it to colourless CnHjOj, [296°], 
 possibly CgBt:{C0)2i0sB.j02. This forms trans- 
 parent plates, insol. aqueous alkalis, v. si. sol. 
 boiling benzene, si. sol. acetic acid, m. sol. 
 aniline. It may be sublimed. Alcoholic EOH 
 forms a violet solution decolorised by shaking 
 with air. Distillation with zinc dust produces 
 anthracene (A. G-. Perkin a. W. H. Per^n, jun., 
 B. 18, 1723 ; C. J. 47, 682). 
 
 Salts. — BaA'jaq; small leaflets, si. sol. 
 water. — CaA'j 2aq : si. sol. water. — NaA' aq : 
 white leaflets, si. sol. water. 
 
 Chloride CnHA-SO,Cl. [193°]. Light 
 yellow plates ; sol. benzene and acetic acid, v. 
 b1. sol. alcohol and ether. Converted by di- 
 methyl-aniline into the sulphone 
 C„H,0j.S02.0eH,NMe2. [171°]. 
 
 Amide C^HjOj.SOjNHj. [261°]. Long yellow 
 needles ; almost insoluble in alcohol, chloroform 
 and CSj. 
 
 Anilide C„H,Oj.SOjNHPh. [198°]. Long 
 prisms ; sol. alcohol and acetic acid. 
 
 Additiojial Beferences. — Liebermann, A. 212, 
 42; B. 12, 189, 1293, 1697; MoHoul, £. 13, 692. 
 
 (a)-Anthraqainons disulphonio acid 
 OnH502(S03H)jj. When anthraquinone (1 pt.) Is 
 heated with fuming H^SO, (2J pts.) at 170°, or 
 when dichloro-anthracene or di-bromo-anthra- 
 cene is similarly treated, a mixture of (a) and 
 (0) disulphonio acids is got. The salts of the (a) 
 acid are less soluble and less crystalline than 
 those of the {$) acid. The (a) acid is converted 
 by potash-fusion into anthraflavin (di-oxy-anth- 
 raquinoue), oxy-anthraquinone sulphonio acid, 
 and flavopurpurin (tri-oxy-anthraquinone). 
 
 Salt s.— Na^A" 7aq.— BaA" aq.— PbA" aq. 
 
 (3) -Anthraquinone di-sulphonic acid. Pre- 
 pared as above. Potash-fusion produces iso-anth- 
 raflavin (di-oxy-authraquinone) and iso-purpurin 
 (tri-oxy-anthraquinone). The sodium salt 
 heated with NHjAq at 180° produces 
 OuH5(OH)(NH2)(S03H) (Bourcart, Bl. [2] 33, 264). 
 
 S a 1 1 s.— NajA" 4aq.— BaA" 2aq.— PbA" aq. 
 
 X-Anthraquinone-disulphonic acid Ci^HgOgS, 
 i.e. OsH3(SOsH):(CO)2:C5H3.SOjH. Prepared by 
 oxidation of (3)-anthraoene-di-sulphonio acid. 
 On fusion with KOH it first gives ohrysazin (di- 
 oxy-anthraquinone) and then oxychrysazin (tri- 
 oxy-anthraquinone). 
 
 Salts. — NajA"4aq: yellow prisms. 
 
 (p) -Anthraquinone-disnlphonic acid 
 
 0,.HAS. i.e. [3 1] 0,H3(SO3H)(00)AH,SO,H 
 
 n el. Prepared by oxidation of (a)-anthra- 
 
 cene-disulphonic acid. On fusion with KOH 
 it first gives anthrarufin (di-oxy-anthraquinone) 
 and then oxy-chrysazin. Salts. — Na|5A"5aq: 
 yeUow leaflets, sol. water. 
 
 Beferences. — Graebe a. Liebermann, A. 160, 
 134 ; B. 3, 636 ; 7, 805 ; Liebermann a. Dehnst, 
 B. 12, 1288 ; Perkin, C. N. 22, 37 ; A. 158, 323 ; 
 Schuuok a. Boemer, B. 9, 379 ; 10, 1821. 
 
 ANTHBAQUINONE CHLORIDE v. Anthba- 
 QUINONE, Formation 9. 
 
 ANTHRARUFIN v. Di-OxT-ANTHEAQuiNONB. 
 
 ANTHROL a,.H,„0 i.e. CsH,(02HJG,H30H. 
 
 Formation. — 1. From oxy-anthraquinoue and 
 HI. — 2. By fusing anthracene sulphonio acid 
 with potash. 
 
 Preparation. — Crude sodium anthraquinone 
 sulphonate (1 pt.) is heated on a water bath for 
 a few hours with 1|^ pts. of zinc-dust and 7 pts. 
 of cone, ammonia ; the anthracene sulphonate 
 thus obtained is fused with NaOH. Leaflets or 
 needles (from dilute alcohol). Insol. water, v. sol. 
 alcohol, acetone, or ether. Decomposes at 200°. 
 Insol. in NHjAq, soluble in KOHAq or baryta- 
 water, forming a yellow solution with green fluo- 
 rescence. Its alcoholic solution shows a violet 
 fluorescence. Cone. HjSOi gives a yellow so- 
 lution, turned blue by heat. A drop of fuming 
 HNO3 added to its solution in glacial acetic acid 
 gives a transient green colour. Its alcoholic 
 solution reduces warm AgNOj. 
 
 Acetyl derivative [198°]. Microscopio 
 leaflets. Difficultly soluble in cold acetic acid, 
 easily in CjHj. CrOj in HOAc converts it into 
 the acetyl derivative of oxy-anthraquinone. 
 
 Ethyl derivative [146°]. Needles. 
 
 Methyl derivative [0. 178°]. 
 
 Beferences. — Liebermann a. Hormann, B. 13, 
 589 ; L. a. Hagen, B. 15, 1427 ; L. a. Bollert, B. 
 15, 226 ; L., A. 212, 26, 49. 
 
 Isomerides have been described by Linke, /. 
 pr. [2] 11, 2^7. 
 
282 
 
 ANTHROL-SULPHO^^[C ACID. 
 
 ANTHROL-STILPHONIC ACID 
 C„H8{OH)(S03H). Pormed by careful fusion of 
 ftnthracene-di-sulphonio acid witli KOH. 
 
 S alts. — A'Na : crystals si. sol. cold water. — 
 A'jBa : plates or needles (Sohuler, B. 15, 1808). 
 
 ANTHEOPIC ACID. Shown by Heintz (P. 
 84, 238 ; 87, 233) to be a mixture of palmitic 
 and stearic acids. 
 
 AKTHBOPOCHOLIC ACID C,sHj80< 2a(l. 
 [145^. [o]d 50°. The ohoHo acid of human 
 bile. The bile is extracted with alcohol ; evapo- 
 rated ; extracted with dry alcohol, and the pp. 
 (probably a mixture of sodium glyoo-, and tauro-, 
 anthropocholates) is decomposed by boiling with 
 barytft-water {Bayer, H. 3, 293). 
 
 Properties. — Groups oJE prisms, insol. water, 
 V. e. sol. alcohol, v. sol. ether, m. sol. chloroform. 
 Lsevorotatory. Fusion changes it into an amor- 
 phous dyslysin CiaH^sOa. 
 
 Salts.— KA.': V. e.sol. water.— BaA'j (? Aq): 
 silky plates, si. sol. water. 
 
 ANTHEOXANIC ACID 
 
 CANO,i.e.CeH,<;^|>0 (?) 
 
 [191°]. Obtained by oxidation of anthroxanic 
 aldehyde with dilute KMnO, (SohiUinger a. 
 Wleiigel, B. 16, 2224). White felted needles. 
 Sol. acetone and hot water, v. si. sol. cold water, 
 si. sol. alcohol, ether, and benzene. Strong acid. 
 On reduction with PeSOj and NHjit yields isatic 
 acid. 
 
 ANTHBOXANIC ALDEHYDE 
 
 ,C-CHO 
 C.H,NO, i.e. C,H / | >0 
 
 (?) 
 
 [73°]. Obtained by heating a solution of o-nitro- 
 (;8)-oxy-cinnamio acid in an equal weight of 
 acetic acid to 100° for a few hours, diluting the 
 product with water, neutralising with CaCOj, 
 distilling with steam, and extracting the distillate 
 with ether. Long yellowish needles. Sublimable. 
 Volatile with steam. Easily soluble in hot water 
 and in most other solvents except ligroine. 
 
 The addition of zinc-dust to the dilute 
 ammoniacal solution produces a reddish-violet 
 colouration. It combines with bisulphites and 
 reddens fuchsin-sulphurous acid. With aniline 
 it yields a crystalline anilide which melts at 
 about 40° (SohiUinger a. Wleugel, B. 16, 2222). 
 
 DI-ANTHBYL-FORMAMIDINE v. Anthra- 
 MiNE, reaction 3. 
 
 AirTIARINC„H2„05 2aq(?). [221°]. Poison- 
 ous substance in the milky juice of Antiaris toxi- 
 caria or Upas Antjar, used to poison arrows 
 (Mulder, A. 28, 304 ; Ludwig a. de Vry, Z. 1869, 
 351 ; Pelletier a. Caventou, A. Ch. 26, 57). 
 
 ANTIMONIDES. — Binary compounds, or 
 rather alloys, of Sb with more positive metals. 
 Most (J£ these bodies are of somewhat vague 
 compositions ; some occur as minerals (v. Anii- 
 MONY, Combinations, No. 10). 
 
 ANTIMONY. Sb. {Antimonium, or Stibium 
 tnetallicum; Begulus antimonU). At. w. 120. 
 Mol. w. probably 120, v. Biltz a. Meyer, B. 22, 
 725. [about 425°] (between 1090° and 1450") 
 (Carnelley a. Williams, C. J. 35, 566). S.G. 6-71 
 to 6-86; ^^, 6-697 (Schroder, J. 1859. 12) 
 S.G. (melted) 6-53 to 6-65 (Playfair a. Joule, C. 
 
 S. Mem. 8, 57). S.H. (0°-100°) -0495 (Bunsen 
 P. 141, 1); -0523 (Kopp, A. Suppl. 3, 66); 
 (0°-83°)-049; ( - 21° to 0°) -048 ; (-75° to -21°) 
 •047 (Pebal a. Jahn, W. 27, 584). C.E. (cub. 
 0°-100°) -003161 (Matthiessen, P. 130, 50); 
 Gin. 40°) -00001152 (Fizeau, C. B. 68, 1125). 
 T.C. (Ag = 100) 4-03 (Lorenz, W. 13,422). E.O. 
 (Hg at 0° = 1) 2-05 at 0°, 1-42 at 100° (Lorenz, 
 Z.c). Chief lines in spectrum, 6128-6, 6078, 
 6003-5 (Tha,Un,A. Ch. [4] 18, 243). CrystaUisea 
 in rhombohedra, approaching cubes (Marx, S, 
 59, 211) ; isomorphous with As, Bi, and Te. 
 
 Occurrence. — Native ; but chiefly as sulphide 
 SbjSj (Stibnite), and as double sulphide with 
 PbS, CuS, AgjS, NiS, &c.; as oxide in small quan- 
 tities ; in various iron ores ; in ferruginous 
 mineral waters ; in some gas coals ; in certain 
 river sands (CampbeU, P.M. [4] 20, 304 ; 21, 318). 
 
 Preparation. — The sulphide is fused, to sepa- 
 rate gangue, and roasted in air ; the oxide thus 
 produced is reduced by heating with charcoal or 
 coal. Or the sulphide is reduced by charcoal or 
 by iron. The crude metal (16 parts) is purified 
 by fusion with dry NajCOj (2 parts) and SbjS, 
 (1 part), for an hour in a Hessian crucible; the 
 regulus is separated and again fused for an hour 
 with 1| parts Na^COs, and this is repeated with 
 1 part Na^COj a second time (Bensoh, A. 5, 20). 
 Or the crude metal is fused with NaNOj and 
 NajCOs (details, v. Meyer, A. 66, 238). Pure Sb 
 is prepared by Dexter (/. pr. 18, 449) by fusing 
 dry HjSbO, with lampblack, and then with a 
 little SbjOj. Oapitaine (P. 100, 563) prepares 
 the pure metal by heating tartar-emetic in a 
 closed crucible. Bongartz (B. 16, 1942) digests 
 pure SbClj with (NHJ^SAq in Pt vessels, 
 electrolyses, fuses with pure Na^COj, treats with 
 dilute HClAq, cleans with sea sand, and dries. 
 Cooke (P. Am. A. [2] 5, 1) reduces NaSbO, by 
 KCN, and fuses the Sb under Sb^Oj for several 
 hours. Pure crystalline Sb may be obtained, 
 according to ¥ieiieT{A. 209, 161), by electrolysing 
 a solution of SbClj in HCIAq containing not 
 more than 7 p.c. SbClj. MetalUo antimony 
 seems to have been known since the end of tha 
 15th century. The sulphide was known to the 
 ancients as Stibium. 
 
 Properties. — Brittle, hard, silver-white, metal- 
 like ; easily crystallised, isomorphous with As 
 and Te, melts easily [425°] ; volatilises at bright 
 red heat in open vessel with simultaneous pro- 
 duction of SbjOj ; scarcely volatilises in absence 
 of air ; but slightly volatile in vacuo at 292° 
 (DemarQay, 0. B. 95, 183) -, may be distilled in 
 H at white heat. Unchanged in air at ordinary 
 temperatures ; melted on charcoal before blow- 
 pipe and then exposed to stream of air, pure Sb 
 burns easily to Sb^Oj ; if traces of lead or iron 
 are present a yellow or reddish sublimate is 
 produced on burning before blowpipe. By 
 electrolysis of SbClj in HCIAq, under special con- 
 ditions, a lustrous silver-like deposit is obtained 
 on the negative electrode ; this deposit when dry 
 explodes when rubbed with a hard substance, 
 or when heated to 200°, with formation of 
 clouds of SbClj ; a similar change occurs when 
 the deposit is heated under water to 75°, but at 
 ordinary temperatures it may be rubbed with a 
 hard body under water without change. This 
 so called explosive antimony contaias SbOl, 
 varying from 3 to 20 p.o. A similar ei- 
 
ANTIMONY. 
 
 28S 
 
 plosive aabsiance is obtained by electrolysing 
 SbBrs in HBrAq, or Sblj in HIAq ; the former 
 contains 18 to 20 p.o. SbBrj, it explodes at 
 160° ; the latter contains 22 p.o. HI and 
 also Sblj, it explodes at 160° (Gore, Pr. 9, 70 
 and 304; iUd. G. 3. [2] 1, 365; Bottger, J. pr. 
 73, 484 ; 107, 43). According to Bottger (C. G. 
 1875. 674) ea^loswe antimony also contains 
 occluded hydrogen. 
 
 The atomic weight of Sb has been deter- 
 mined (i.) by analysing and determining V.I), of 
 certain gaseous compounds, particularly SbClj 
 and Sb(CH3)3 ; (ii.) by measuring the S.H. of 
 Bb ; (iii.) by comparing isomorphous compounds 
 of Sb, As, and Bi ; (iv.) by analyses of SbjSj 
 (Schneider, P. 98, 293), SbClj (Weber, P. 98, 
 455 ; Dexter, P. 100, 563 ; Dumas, G. B. 46, 
 951; Kessler, P. 95, 204, 118, 134), SbBrj 
 and Sblj, and by synthesis of SbjS, (Cooke, 
 P. Am. A. [2] 5, 1 ; 7, 251 ; 9, 1 ; B. IB, 951) 
 (comp. also Kessler, B. 12, 1044; Schneider, 
 J. pr. [2] 22, 181 ; and Bongartz, B. 16, 1942). 
 Some of the earlier determinations gave the 
 number 122 ; but the researches of Cooke have 
 established the value 120. The atom of Sb is 
 trivalent in gaseous molecules, SbClj, Sb(CHs)3. 
 Antimony combines with oxygen and chlorine 
 with production of heat : [Sb2,0', 3^0] = 167,420, 
 [Sb^ OS SffO] = 228,780, [Sb, CP] = 91,390, 
 [Sb, Cl=] = 104,870 (Th. 2, 240). Antimony is 
 oxidised by strong HNO,, or by heating with 
 various metallic oxides, e.g. MnOz, PbO^; hot 
 cone. H2SO4 forms Sb^.SSOi ; Sb combines with 
 CI or Br with production of light. Pure Sb is 
 unacted on by HClAq out of contact with air ; 
 in presence of a little HNOjAq solution pro- 
 ceeds rapidly (Cooke, P. Am. A. [2] 5, 1). 
 Antimony forms three oxides Sb^Oj, Sb.,©,, and 
 SbjOj; various compounds corresponding to the 
 first and third are known. Antimony is more 
 metallic than arsenic, whether considered 
 physically or chemically. Hydrated antimo- 
 nious oxide, Sb205.3H20( = Sb(OH)3), is known, 
 and reacts as a feeble base ; if one-third part of 
 the H is replaced by K the remaining OH groups 
 may be replaced by the residue of tartaric acid, 
 with formation of Sb.OK.C^HjOg {v. Antimonious 
 OXIDE, Reactions, No. 4). Various compounds 
 of SbjOj with SO3 (v. Antimonious oxide, Be- 
 actions, No. 3), and at least one with N2O5 
 are known. A ifew unstable salts derived from 
 the hypothetical hydrate SbO.OH ( = Sb203-H20) 
 are known, so that SbjO, acts both towards 
 strong acids and strong alkalis as a feeble salt- 
 forming oxide : thus [2HClAq, 2Sb'0»Aq] = 4,720 ; 
 whereas [2HCUq, 2Na20Aq] = 25,500 {Th. 2, 
 241). The thio-antimonites are few in number and 
 their stability is decidedly less than that of the 
 thio-arsenites. The compounds of Sb which most 
 decidedly exhibit negative or acidic functions are 
 Sb^OsandSbjSs; the same holds good for As. The 
 haloid compounds of Sb form many weU-marked 
 double salts. Many oxyhaloid compounds are 
 also known. SbH, does not combine with 
 acids, but compounds of the type SbE^X where 
 B = 0„H2„+„ and X is a halogen or even OH, 
 have been prepared {v. Antimont, Compounds 
 with oeoanio eadicles). For further disous- 
 Bion of the chemical relations of Sb, v. Bismuth, 
 
 CHESIICAI. BELATIONS Of j and NlTBOGBN OBOCF OF 
 ELEMKNTS. 
 
 BeacHons. — 1. Water is not decomposed at 
 ordinary temperatures by Sb ; but at a red heat 
 it reacts with steam to produce oxide of Sb and 
 H. — 2. Dilute rdtric acid digested with finely 
 powdered Sb forms a compound of SbjO, with 
 N2O5; stronger acid forms chiefly Sb^Oj-KHjO 
 and SbjO^— 3. Sulpkuricacid reacts with Sbonly 
 when eonc. and hot ; SOj is evolved, and a com- 
 pound, or compounds, of Sb203 with SO3 pro- 
 duced. — 4. By the action of aqueous sulphurous- 
 acid at 200° in a closed tube Sb^Sj is produced. 
 5. Hydrochloric acid forms SbCl3 when heated 
 with powdered Sb ; in absence of air no action 
 occurs (Cooke, P. Am. A. [2] 5, 1).— 6. Aqua 
 regia dissolves Sb forming SbClj.— 7. Solid 
 phospJwric acid and carbon heated with Sb form 
 phosphide of Sb. — 8. Alkali nitrates and chlo- 
 rates heated with Sb form alkali antimonates 
 and generally also SbjOj.— 9. Alkali sulphates 
 form Sb2S3, alkali sulphide, alkali antimonate, 
 and SbjOj. 
 
 Combinations. — 1. With nascent hydrogen 
 SbHj is formed (g. v.). — 2. With chlorine^ 
 bromine, or iodine, the compounds SbClj and 
 SbClj, SbBrj, and Sbl^ are produced {q. v.). — 
 8. With fluorine (action of HPAq on Sb^Oj. 
 and Sb^Os.BH^O) SbPs and SbFj are formed 
 (q. v.). — 4. Sb combines with oxygen to form 
 SbjOe and Sb^Oj (q. v.) ; Sb^Oj (q. v.) is pro- 
 duced by the action of cone. HNO3. — 5. The 
 sulphide Sb^Sj (g. u.) may be obtained by heat- 
 ing Sb with sulphur ; the pentasulphide Sb^Sj 
 (q. V.) is best produced by decomposing NajSbS^ 
 by an acid. — 6. Heated with selen/ion Sb^Se, 
 is formed as a greyish metal-Hke solid (Berze- 
 lius ; also Hofacker, A. 107, 6 ; v. also Uelsmann, 
 A. 116, 124). Sb2Se3 fused with Se and an alkali 
 forms alkali seleno-antimonate {e.g. NajSbSeJ ; 
 this compound is decomposed by acids, in 
 absence of air, with ppn. of brown Sb^Sej. 
 (Hofacker, I.e.). — 7. With tellurium (Oppen- 
 heim, J. pr. 71, 277) Sb forms either iron-grey 
 SbTe, or tin-white Sb^Te, (S.G. of latter 
 >E = 6-47-6-51 ; Bodeker a. Giesecke). — 
 
 8. Phosphorus is said to combine with Sb to 
 form a tin-white brittle phosphide containing 
 15-5 p.c. P (Landgrebe, S. 53, 469). By the 
 action of P (in CS^) on SbBr3 (in CSj) a red 
 powder, PSb, is obtained (Macivor, B. 6, 1362). — 
 
 9. Sb combines with arsenic, by fusion under- 
 boric acid, to form crystalline SbjAs (Descampes, 
 C. B. 86, 1065). The compound Sb2As3 occurs 
 native as allamontite. — 10. Antimony forms- 
 alloys with many metals ; they are usually pro- 
 duced by melting together Sb and the specified 
 metal. The alloys with E and Na are produced by 
 fusing Sb with K2CO3 (or NazCOj) and C, or by 
 reducing Sb40j with KH.C4H4OS at high tem- 
 peratures ; they decompose water with evolution 
 of H and separation of Sb ; if containing much 
 K or Na they take fire in the air. The alloys 
 of Sb are usually lustrous, hard, and brittle. 
 The alloys with Cu and Sn wiU be described, 
 under those metals. An alloy of iron is formed' 
 when Sb2S3 is reduced with excess of Pe ; a mix- 
 tare of 7 parts Sb and 3 parts Fe heated to white- 
 ness in a charcoal-lined crucible produces a very 
 hard white alloy. Gold loses its malleability 
 by the presence of about jroi; °^ ^^- Leai 
 alloys with Sb in all proportions; the lead is 
 hardened ; type metal is an alloy of about 
 
1'84 
 
 ANTIMONY. 
 
 17-20 parts Bb with lead and sometimes Bi or 
 8n (v. Lead, alloys or). With nickel two alloys 
 are known ; NiSb sublimes in prisms ; Ni^Sb 
 occurs as breithauptite containing a little Fe 
 and PbS. Two alloys with silver, Ag^Sb and 
 AgjSb, occur native as antimonial silver. With 
 einc at least two crystalline alloys of definite 
 composition are known, SbZuj and SbZn^ (Cooke, 
 Am. S. [2] 18, 229 ; 20, 222). 
 
 Many of these alloys are used in manufac- 
 tures. Antimony compounds are also used in 
 medicine. 
 
 Detection. — Most Sb compounds are insoluble 
 in water and in excess of cone. HNOjAq, but 
 many dissolve in HClAq, especially if tartaric 
 acid is added ; insoluble compounds may be 
 dissolved by fusion with KNO, and KjCOa and 
 treatment with HClAq; when Sb compounds 
 are fused with NaNOj and NajCOj, NaSbOj, in- 
 soluble in water, is formed. 
 
 Indryway. Heated on charcoal with NauCOj 
 and KCN, all Sb compounds yield a brittle lustrous 
 metaUic bead. In the upper reduction-flame of 
 the Bunsen lamp, Sb compounds give a green 
 colour to the flame; in the oxidation-flame, a 
 white oxide film is obtained (on porcelain) which, 
 moistened with neutral AgNOjAq and then blown 
 «n with ammoniacal air, gives a black spot 
 <Ag.O). 
 
 In wet way. I. Antimonious com- 
 pounds, (i.) Sulphwrettedhydrogen^^s.or&nge- 
 red Sb^S, from acidulated solutions, soluble in 
 KOHAq or NaOHAq, less soluble in NHjAq, 
 insoluble in KH^HCOjAq, soluble in K^SAq and 
 (NHJjSAq, insoluble in dilute acids, but dis- 
 solved by boiling with cone. HClAq. Dilute tartar 
 emetic solution is not ppd. by H^S, the liquid turns 
 red ; cone, solutions are completely ppd. (Schulze, 
 J. pr. [2] 27, 320). (ii.) Heated with gold chloride 
 solution in presence of HClAq, Au is ppd. along 
 with SbjOj. (iii.) Caustic and carbonated alkalis 
 pp. white SbjOj soluble in KOHAq and 
 NaOHAq ; the ppn. is slow and incomplete in 
 presence of tartaric acid, (iv.) Zinc pps. Sb as 
 a black powder ; in presence of acids and Pt 
 the Sb is deposited on the Pt, and a little SbHj 
 is also formed ; the deposited Sb is insoluble in 
 cold HClAq, but easily dissolves in HNOjAq. 
 (v.) Zinc and iron powder, added to a solution of 
 an antimonious compound in cone. NH4ClAq con- 
 taining NHjAq, ppt. Sb on the Zn without pro- 
 duction of any SbHj ; under similar conditions 
 arsenious compounds yield AsHj. (vi.) Zinc and 
 dilute JS^SOfAq, in absence of HNOjAq, evolve 
 H, mixed with SbH^, which may be burnt in air 
 with production of Sb^Oj, or decomposed by heat 
 into Sb and H, or led into AgNOjAq whereby 
 silver antimonide is ppd. mixed with Ag, or 
 passed over S in sunshine whereby orange Sb^Sj 
 is formed (v. Jones, C. J. [2] 14, 649 ; this is a 
 very delicate test ; v. Marsh's test for arsenic, 
 under Aksenio, Detection op), (vii.) Dissolvedin 
 KOHAq, and treated with silver nitrate, a brown 
 black pp. is obtained, from which NHjAq re- 
 moves AgjO, leaving black AgjO. 
 
 11. Antimonic compounds. — (i.) Sul- 
 phuretted hydrogen pps. orange-red SbjSj from 
 acidulated solutions, soluble in KOHAq, in 
 KjCOjAq, in (NHJjSAq, and more slowly in 
 NHjAq. (ii.) Heated with hydrochloric acid 
 and potasman iodide, Sbl, and I are formed 
 
 (Sb A + lOKIAq = 2SbI,Aq + 5K,0Aq -f- 41). Aa 
 antimony trioxide has no action on KI, this re- 
 action may be used to detect Sb^Oj in SbiO,. 
 (iii.) Gold salts, chromates, and perma/nganates, 
 are not reduced by antimonic compounds ; nor 
 is AgNOjAq acted on (compare tests (ii.) and (vii.) 
 for antimonious compounds), (iv.) Towards 
 zinc, or iron, and acids, antimonic compounds 
 behave similarly to antimonious («. Antimonoso- 
 ANTiMONio oxide). Antimony tetroxide SbjOi 
 gives the reactions both of SbjO, and Sb^Oj ; an 
 alkaUne solution reduces AgNOjAq and A.uCl,Aq 
 slowly. 
 
 (For details of procedure in cases of suspected 
 poisoning by Sb compounds a manual of toxi- 
 cology must be consulted, e.g. Taylor On Poisons, 
 or Taylor's Medical Jurisprudence.) 
 
 Antimony may be separated (qualitatively) 
 from tin and arsenic by treating the sulphides 
 with cone. (NH^)HCOaAq, which dissolves only 
 ASjSj, then dissolving the SnS (or SnSj) and 
 SbjSj in cone. HClAq, boiling off HjS, ppg. Sb in 
 one portion by Zn, reducing SnCl^ to SnCL, in 
 another portion by boiling with Cu turnings, and 
 ppg. by HgCljAq; or the solution containing 
 SbCl, and SnClj may be diluted and boiled with 
 a slight excess of iron wire whereby Sb is ppd. 
 and SnCl, is reduced to SnClj (Classen, J. pr. 93, 
 477). SbjSj is completely converted into SbCl, 
 by dry HCl at ordinary temperatures, whereas 
 SnS is unacted on (Tookey, /. pr. 88, 485). A 
 little As in Sb compounds may be detected by 
 fusing with 2 pts. NajCOj and 4 pts. NaNOj, and 
 dissolving in water, NajAsO, goes into solution 
 and NaSbOj remains. 
 
 Estimation. — I. Gravimetric methods. 
 Antimonious compounds are ppd. by H2S in 
 presence of HClAq and tartaric acid, excess of 
 HjS is removed by COj, the pp. of SbjSj is col- 
 lected (after boihng for 15-20 mins. ; Sharpies, 
 Fr. 10, 343), on a weighed filter, dried at 100° 
 and weighed ; a portion is then dried by heating 
 in a stream of dry COj and again weighed ; if a 
 portion of the pp. dried at 100° yields S on 
 treatment with hot cone. HClAq, the pp. con- 
 tains SbjSs or free S ; in this ease the other por- 
 tion must be heated in dry COj until S is no 
 longer volatilised ; the residue is now pure Sb2Sj 
 {v. also Cooke, P. Am. A. 13, 1 ; 17, 13). Or the 
 pp. of SbjSj (perhaps mixed with SbjSj and S) 
 may be converted into Shfi, by treatment with 
 cone. HNOjAq (for details v. Bunsen, A. 106, 3). 
 Schneider (P. 110, 634) decomposes the Sb^Sj by 
 HClAq, leads the H^S into an alkaline solution 
 and determines it by volumetric methods (iodine 
 method, or ppn. by excess of titrated As^OjAq 
 and determination of excess of AsjO, by iodine). 
 
 II. Volumetric methods, (i.) Antimo- 
 nious compounds are oxidised to antimonic by 
 iodine in alkaline solutions (SbjOj + 41 + 2H2O = 
 Sb205 + 4HI). NaHCOjAq is the best alkaline 
 solution ; titrated I solution is run in until a 
 blue colour is produced Vfith starch, (ii.) Anti- 
 monious compounds are oxidised to antimonic 
 in presence of tartaric acid, by KjMn^Oa solution 
 (attention must be paid to details, v. Guyard, Bl. 
 6, 89). For other methods of estimating Sb, 
 especially in presence of As, or of As and Sn v. 
 Bunsen, A. 106, 3j 192, 317; Clarke, Am. S. [2] 
 49, 48. 
 
 Eeferencei.—ln addition to those in the text, 
 
ANTIMONY. 
 
 ;!85. 
 
 Che following older memoirs are important: — 
 Bergmann, Opusc. 3, 164 ; Thtoard, A. Oh. 32, 
 257; Proust, G. A. 25, 186; Berzeliua, S. 6, 
 144 ; 22, 69 ; 34, 58 ; P. 20, 365 ; 87, 163 ; Ber- 
 thier, A. Ch. [2] 22, 239 ; 25, 379 ; H. Eose, P. 
 S, 441; 42, 532; 24, 165 ; Vauquelin, S. 21, 219. 
 
 Antimony, acids of, and their salts (compare 
 arts. Acids; Aoids, basicity of; Hydroxides). 
 The oxides SbjO, and SbjOj are scarcely soluble in 
 water, but each reddens moist blue litmus paper; 
 the oxide Sh fi^ is slightly soluble in water, but 
 is without action on litmus. A few feebly marked 
 salts are known which may be regarded as de- 
 rived from the hypothetical hydrate . Sb^Oj.H^O 
 ( = SbO.OH) ; two sodium salts, so-called anti- 
 monites, are obtained according to Terrell {A. Oh. 
 [4] 7, 380) by dissolving SbjO^ in boiling NaOHAq 
 and allowing to cool {v. infra). Two hydrates 
 of SbA, viz. Sb.Oe-^H^O and Sb.O^.eH^O have 
 been obtained (v. Antimonious oxide) ; but 
 neither seems to possess acidic properties. The 
 oxide SbjOj reacts with NajCOj when the two 
 are fused together, but on adding water Shflg 
 is ppd. and NaOH remains in solution. The 
 acid-forming character of Shfle is therefore ex- 
 tremely feeble {v. further Antimonious oxide). 
 
 No hydrate of Sb^O, is known; but by 
 fusing this oxide with KOH or KjCOj, a com- 
 pound, SbjO^.KjO, insoluble in cold water, is 
 produced; by dissolving this in hot water and 
 adding various metallic compounds, several 
 compounds of SbjO^ with metallic oxides, e.g. 
 Sb204.CaO and SbjO^.CuO (which both occur 
 native as rome'ite and ammioUte respectively 
 [? merely mixtures]) are obtained. A solution 
 of Sb204 in KOHAq (obtained by fusion) is 
 easily decomposed : e.g'. on boiling and then 
 diluting, SbjOj is ppd. and SbjOs.ajH^O is then 
 thrown down on addition of acids ; on standing 
 in air, without boiling, KSbOj is produced. The 
 oxide SbjOj cannot therefore be regarded as a 
 definite anhydride, nor can any acid, or well- 
 marked series of salts, be said to exist corre- 
 sponding with this oxide (v. Antimony, oxides 
 of). 
 
 Three hydrates of antimonic oxide are known 
 (v. infra): SbA-HjO ( = HSb03), SbA-aH^O 
 ( = H^SbjO,) , and Sba05.3a,0 ( = HjSbO,) . The 
 first and third may be obtained from 
 H4Sb20,.2H20 which is a product of the action 
 of water on SbClj ; dried over H^SO,, HjSbO, is 
 obtained, and at higher temperatures HSbO, is 
 produced {v. Antimonates). Several fairly 
 marked salts are known, antimonates, derived 
 from HSbO,; two series of metanUmonates 
 (M4Sb20. and M^B^Wofi,) exist (v. infra) ; no 
 salts of the hydrate SbA-SHjO ( = HaSbO j have 
 been obtained, Antimonates are usually obtained 
 by fusion ; aqueous alkalis dissolve the hydrate 
 SbjOyHjO without change; some metantimonates 
 are produced from the hydrate SbA-^HjO by 
 the action of alkalis in the wet way. Antimonic 
 oxide is evidently a feebly marked acid-forming 
 oxide. The only definite compounds of Sb 
 hitherto obtained which exhibit acidic characters 
 are then HSbO, and H^SbjO,. 
 
 The following thermal data are given by 
 Thomsen [Sb^ 0', 3ffO] = 167,420; 
 [Sb,O^H,H^O] = 117,890; [Sb^ 0«, 3ffO] = 
 228,780; [Sb, O', H, ffO] = 145,570 ; 
 [SbO'H',0] = 30,680. 
 
 I. Aniimonitbs.— Two sodium salts are 
 described by Terrell (A. Ch. [4] 7, 880) r 
 NaSb02.3H20, lustrous octahedral crystals, 
 obtained by dissolving SbA in boiling NaOHAq 
 and allowing to cool; NaSbOj.Sb.^Oj.H^O. 
 large crystals, insoluble in water, obtained froms 
 very concentrated alkaline solutions. 
 
 II. Antimonoso-antimonates. — Thisnamehas 
 been given to the compounds of SbaO^ with- 
 metaUic oxides ; it implies that these bodies are 
 compounds of antimonites with antimonates ; 
 very little, however, is known of their properties. 
 Two potassium salts KjO.SbjO^ (?KSb03.KSb02V 
 and K20.2Sb20, are said to be produced, the 
 former by fusing SbjO^ with KOH or K.COj and 
 washing with cold water, the latter by the action 
 of a Uttle HClAq on the former. An aqueous- 
 solution (the salt dissolves in hot water) of 
 KjO.SbjOj is said to give pps. with various 
 metallic salts. These salts might perhaps be 
 regarded as derivatives of the hypothetical 
 hydrates Sb^O^.H^O ( = H2Sbj05) and 2Sb204.HjO 
 ( = H2Sb,0g) ; but our knowledge of them is 
 almost nil. 
 
 III. Antimonates, and Antimonic acids. — 
 Three hydrates of SbjOs are known. By ppg. 
 ESbOjAq by HNOjAq, washing the pp. and 
 leaving it for a whole summer, Geuther obtained 
 the hydrate Sbj05.3H20 ( = H3SbOJ (/.^Jr. [2] 
 4, 438) : at 175° this hydrate gives HSbO, 
 ( = Sb205.HjO). The hydrate Sb205.2H20- 
 ( = HjSbjO,) is obtained by adding hot water to 
 SbClj, and drying the pp. of HjSb20,.2H20 at 
 100° ; it is also produced by decomposing the 
 salts M^Sb^O, by aoids : this hydrate is easily 
 decomposed to HSbOj, even by standing in- 
 contact with water (Dubrawa, A. 186, 110 ; 
 Conrad, O. N. 40, 197). HSb03 may also ba 
 obtained by decomposing MSbOj by acids, or by 
 oxidising Sb by HNO3. The hydrate HSbOj is 
 slightly soluble in water, insoluble in NHjAq, 
 and easily soluble in KOHAq ; HjSb^O, is more 
 soluble in water, and dissolves in both NHjAq 
 and KOHAq: little is known of the hydrate 
 Sb205.8H20. The antimonates belong to the 
 two types MSbOj, and M^Sb^O,; the former are 
 usually called antimonates, the latter metanti- 
 monates. 
 
 Antimonates: investigated by Berzelius,, 
 then by Fremy (A. Oh. [3] 12, 499 ; 22, 404), 
 and by Heffter (P. 86, 418 ; 98, 293). These 
 salts are obtained by fusing Sb or Sb^Oj with 
 nitrates, or HSbOa with carbonates, or by double 
 decomposition from the K salts ; aqueous alkalis 
 dissolve HSbOj without change. Some of the 
 K and NH, salts are soluble in water, the others 
 are slightly soluble or insoluble. The normal 
 antimonates are converted into acid salts by the 
 action of weak acids (e.g. CO^Aq), they are 
 decomposed by stronger aoids with separation of 
 HSbOj; the antimonates are decomposed by 
 fusion with NH^Cl, the whole of the Sb being 
 volatilised as SbCl, ; those which are soluble in 
 water or acids are decomposed by (NHj)jSAq, 
 with production of thio-antimonates. 
 
 Ammonium antimonate NH4SbOa.2H20 ; 
 white crystalline powder, insoluble in water, 
 easily decomposed with loss of NH,: obtained 
 by dissolving HSbOj in warm NHjAq. 
 
 Barium antimonate Ba(SbOa)2 ; obtained by 
 adding BaCl^Aq to KSbOjAq; pp. at first 'vs 
 
286 
 
 ANTIMONY. 
 
 flooculent but becomes crystalline. By adding 
 BaOljAq to boiling NaSbOjAq a flocculent pp. 
 of Ba{Sb03)2.5H20 (air-dried) is obtained. 
 
 Potassium antimonates. — The normal salt 
 KSbOj is obtained by fusing 1 part Sb with 4 
 parts KNOj, and washing with hot water ; it 
 dissolves after long boiling with water, and is 
 obtained as a mass of white crystals when the 
 fiolutiou is evaporated until a crust forms. 
 Another form of this salt is described by Fremy 
 as a gummy mass, obtained by evaporating the 
 foregoing solution nearly to dryness, or more 
 easily by long-continued fusion, either alone or 
 with KOH or K^COj, of the product obtained by 
 melting together 1 part Sb and 4 parts ENO,. 
 The gum-like salt dried in vacuo is i'KSbO^.SB.fi, 
 it is easily soluble in hot water ; dried at 160° it 
 leaves 2KSb03.3H20 which is changed to the 
 gum-like salt by boiling with water ; at a red 
 heat all the water is removed, and the product is 
 gradually changed to the gum-like salt by contact 
 with hot water. When the normal salt is boiled 
 with water, a residue of 2KSbOs.Sb2O5.10H2O is 
 obtained ; and a similar salt with 6H2O is pro- 
 duced bj the action of COj on the normal salt 
 (Heftter, P. 86, 418; v. also v. Knorre a. 
 Olschewsky, B. 18, 2353). 
 
 Sodium antimonates. — The salt 
 aNaSbOj.THjO is obtained similarly to the 
 normal KSbOj ; also in octahedra by the action 
 of NaOH.Vq on Sb^Ss- NaSb03.3HjO is said to 
 be formed by the action of NaOHAq on Sb2S5, 
 filtration, and addition of more NaOHAq (v. also 
 V. Knorre a. Olschewsky, B. 18, 2853). 
 
 Many other antimonates are described by 
 Fremy and Heffter ; the chief are the salts 
 Ca(Sb03) J, Co(Sb03)2, Cu(Sb03)2.5H30, Pb(Sb03)2, 
 LiSbOs, Mg.2Sb03.12H20, Hg(Sb03)2, 
 Sr(Sb03)2.6H20, Sn(SbO,)2.2H20 (v. also Schiff, 
 A. 120, 47 ; Unger, Ar. Ph. [2] 147, 193). 
 
 Metantimonates. These salts fall into two 
 classes — normal salts M^SbjO,, and acid salts 
 MjH^SbjOj; they are formed from the antimo- 
 nates by addition of metallic oxide or water 
 (2MSbOs + Mfi = MjSbjO, ; and 2MSb03 + H^O = 
 MjHjSbjO,) ; conversely the metantimonates lose 
 MjO (or H2O) and form MSb03. The metanti- 
 monates as a class are insoluble in water, the 
 alkali salts are crystalline ; they are decomposed 
 by acids ; they have been chiefly investigated by 
 Fremy {A. Ch. [3] 12, 499). 
 
 Ammonium metantimonates. — H^SbjO, dis- 
 solves slowly in cold NHjAq ; a cone, solution 
 on addition of alcohol gives the acid salt 
 (NHj2H2Sb20,.5H20 ; this salt is easily decom- 
 posed by heating, either in presence or absence 
 of water, into (NH^)Sb03. ^he normal salt has 
 not yet been isolated. 
 
 Potassium metantimonates. — By fusing KSb03 
 (best the gum-like salt) With about 3 parts KOH, 
 dissolving in water, and crystallising, the salt 
 KjSbjO, is obtained as deliquescent, easily solu- 
 ble, crystals. The acid salt KjHjSbjOi.eHjO is 
 produced by decomposing the normal salt by a 
 little water (KOHAq is also produced), or by 
 dissolving SbCl3 in excess of KOHAq, oxidising 
 by K^MujOjAq, and crystallising (Eeynoso, A. 
 Ch. [3] 23, 325) ; at 200° the dehydrated salt 
 IC.H^SbjO, is obtained, and at 300° KSbOs is 
 formed. The acid salt is slightly soluble in 
 cold water, more easily in water at40°-50°, with 
 
 gradual production of the gum-like KSbO,; an 
 aqueous solution of this salt precipitates sodium 
 salts. Other metantimonates are described by 
 Fremy (i.e.). 
 
 Seleno-antimonates. — A few salts are 
 known, derived from the hypothetical seleno- 
 antimonic acid HjSbSej. Na3SbSej.9H20 forma 
 orange-red tetrahedral crystals, and is obtained 
 by fusing Na^COs, SbgSej, Be, and ; the salt 
 Na3SbSsSe.9H20 is obtained as yellow tetrahe- 
 dral crystals by boiling NasSbS^Aq with Sa 
 (Hofacker, A. 107, 6). 
 
 Antimony, alloys of, v. Antimony, Combina- 
 tions, No. 10. 
 
 Antimony, arsenide of, v. Antimony, Combi- 
 nations, No. 9. 
 
 Antimony, bromide of. SbBrj. No other 
 bromide is known. Mol. w. 359-28 ; [90°-94°] 
 (Serullas, P. 14, 112). (275°-280°) (Kopp, A. 
 94,257; Codke, P. Am. A. [2] 5,72). V.D. 180 
 (Worcester, P. Am. A. [2] 10, 61). S.G. 3^' 
 4-148 (Cooke, I.e.) ; fused 20° 3-641 (Kopp, l.c.). 
 If the vol. of fused SbBr3 = l for d° = 0°, then 
 the vol. at «° = 1 -1- -000576d -^ •000001B465(Z^ 
 where d = t°-90° (Kopp, Z.c). H.F. solid Sb, 
 gaseous Br,[Sb,Br»] = 76,900 (Guntz, O. B. 101, 
 161). 
 
 Formation. — 1. By shaking powdered Sb 
 into a retort containing Br and connected with 
 a condenser. — 2. By distilling a mixture of Sb 
 sulphate and KBr (Macivor, C. N. 29, 179). 
 
 Preparation. — 1. By adding powdered Sb to 
 a solution of Br in dry CSj at 0°, distilling oft 
 CS2, adding powdered Sb, distilling off the SbBr, 
 and recrystallising it from CS, (Cooke, P. Am. A. 
 [2] 5, 72 ; Nickl^s, C. B. 48, 837). 
 
 Properties and Beactions. — Deliquescent tri- 
 metric crystals; o:6:c = 1-224:1:1-064 (Cooke, 
 l.c.) ; sublimes when heated. Decomposed by 
 water ; cold water produces Sbj05Br2, hot water 
 10SbABr2.SbBr3 (Macivor, 0. N. 29, 179). The 
 compound Sb^OsBr^ is also produced by heating 
 SbBr3 with alcohol to 160° (Macivor, Z.c). The 
 action of air and sunlight on SbBr, in CSj pro- 
 duces an oxybromide, probably SbOBr (Cooke, P. 
 Am. A. [2] 5, 72). Combines with KCl to form 
 SbBr3.3KCl, which aocordingtoAtkinsonis identi- 
 cal with SbCl3.3KBr obtained by action of SbCl, 
 on KBr in presence of a little water (C J. 43, 290). 
 
 Antimony, chlorides of. Sb and CI combine 
 directly to form two compounds SbCl, and 
 SbClj ; the former may be gasified, the latter ia 
 decomposed by heat at ordinary pressures into 
 SbCl3-i-Cl3 («.m/ra). 
 
 I. Antimonious chlobidb. SbClj. Mol. w. 
 226-11. [73°-2] (Thorpe, 0.^.37,387). (223-5°) 
 (216°, Cooke, P. Am. A. [2] 5, 72). S.G. ''f 
 2-6753 (Thorpe, l.c.). S.G. 3-064 (Cooke, P, 
 Am. A. [2] 5, 72). V.D. 115-6. V = 
 l + -0008054£e + -00001032(J^ where a!= degrees 
 above M.P. (73-2°) (Thorpe, Z.c.). [Sb,01»]- 
 91,390 (Thomson). 
 
 Formation. — 1. By dissolving Sb.SbjOj, or 
 Sb2S3, in HClAq with a little HNOaAq, evapo- 
 rating, and then distilling. — 2. By the action of 
 CI on SbjSa.— 3. By distilling together 1 part 
 powdered Sb with 2 parts HgOlj ; or 3 parts 
 SbjSs with 7 parts HgCl^ ; or 1 part Sb2(S0j), 
 with 2 parts dry NaCl. — 4. By distilling 2 parts 
 SbjOj (impure), with 6 parts dry NaCl, 4 parts 
 HjSOj, and 2 parts H^O and changing tha 
 
ANTIMONY. 
 
 287 
 
 reoBJvfir as soon as the distillate begins to solidify 
 on cooling. 
 
 Preparation. — 1. By passing dry CI into a 
 retort containing powdered Sb, until most of 
 the Sb IB transformed into SbCls ; a little more 
 Sb is then added, the stream of 01 is stopped, 
 and the SbClj is distilled off into a dry receiver. 
 Cooke (P. Am. A. [2] 5, 72) saturates warm CSj 
 ■with SbCls and cools by freezing mixture. A 
 solution of SbClj in cone. HClAq (generally pre- 
 pared by the action of the acid on SbuSj) is used 
 in pharmacy. 
 
 Properties. — A colourless, translucent, crys- 
 talline, mass. Melted and allowed partially to 
 solidify, or dissolved in hot CSj and cooled, 
 trimetric crystals are obtained, a:b:c = 
 l-263:l:l-09 (Cooke, P. Am. A. [2] 5, 72). Very 
 caustic. Soluble in alcohol without change; 
 on heating this solution oxychlorides of Sb 
 (2.«.), HCl, and CjHsGl, are formed. It absorbs 
 moisture from the air and forms a clear liquid, 
 from which crystals of SbClj are obtained by 
 standing over HjSO,. 
 
 Beactions. — 1. With water various oxychlo- 
 rides are produced (SbClj dissolves unchanged 
 in a very little water at ordinary temperatures) ; 
 if a little cold water is added (about 2 parts to 
 1 part SbClj), and the pp. is washed with ether, 
 SbOCl (2. V.) is obtained (PeUgot, A. 64, 280 ; 
 Sabanajew, Bl. [2] 16, 79). When from 5 to 50 
 parts H2O are added to 1 part SbClj, the com- 
 pound SbjOsOL; (g. V.) is obtained (Sabanajew, 
 I.e.). Other observations point to a varying 
 composition for the product of the mutual action 
 of SbCl, and HjO ; by continued washing the 
 whole of the CI may be removed {v. Duflos, S. 
 67, 268 ; Johnston, J. pr. 6, 55 ; Malaguti, /. pr. 
 6, 253 ; Peligot, A. 64, 280 ; Schneider, P. 108, 
 407; Sehafier, A. 152,314). Thomsen {Th. 2, 
 240) gives these data: [SbCP,Aq] = 8,910 
 when Sb^OsCl^ is formed, and = 7,730 when 
 SbjOjAq and HClAq are formed. According to 
 WiUiams (C. N. 24, 225) boiling water produces 
 lOSbjCljOs.SbClj. Formation of oxychlorides is 
 prevented by tartaric acid. — 2. AnUmonious 
 oxide dissolves in boiling SbClj to form oxychlo- 
 rides; SbOC1.7SbCl3 is described by Schneider 
 (P. 108, 407).— 8. Alcohol heated with SbClj in 
 proportion C2H50:SbCl3 in a closed tube to 160° 
 forms SbOCl ; heated to 140° in the proportion 
 30jH,0:SbCls, Sb^O^CL, is formed (Schaffer, A. 
 152, 314). — 4. Aqueous solution of sodium thio- 
 sulphate reacts on solution of SbClj to form a 
 double compound of Sb^Oa and ■ SbjSj, probably 
 Sb203.Sb2S3 (v. ANimoNT, oxysulphides of). — 5. 
 Boiling Sb0l3 dissolves powdered antimony tri- 
 Bulphide, on cooling a crystalline mass of sulpho- 
 ohloride, SbSC1.7SbCl3, is obtained ; on washing 
 with alcohol 2SbSC1.3Sb2S3 remains (Schneider, 
 P. 108, 407). 
 
 Combiiiations. — 1. With chlorine, SbClj is 
 formed. — 2. Ammonia forms SbOl3.NH3 which 
 on warming gives ofi aU its NH,. — 3. By 
 mixing cone, solutions of SbClj and alkaline 
 chlorides and evaporating, double salts are 
 formed, e.jr. 2NH,Cl.SbCl5; 2(BaCl2.SbCl3).3H20; 
 BKCLSbCl, ; BNaCLSbCl,. With KBr the salt 
 SbCl3.3KBr is formed identical with SbBra.SKCl 
 obtained by the action of KGlAq on SbBr, (Atkin- 
 son, C. J. 43, 290). 
 
 II. AmciMONio CHLOBiDE SbOIj. Mol. w. un- 
 
 known ; vapour obtained by heating consists of 
 SbCl, + Clj. [-6°] (Kammerer, B. 8, 507). S.G. 
 fg° 2-346 (Haagen, P. 131, 117). (79° at 22 mm.; 
 68° at 14 mm.) (Anschiitz a. Evans, G. J. 49, 
 708). 
 
 Preparation. — Powdered Sb is heated in a 
 retort in a rapid stream of dry CI ; SbCl, 
 (and CI) distils over, and SbCla remains. Or 
 melted SbClj is saturated with CI, and distilled 
 in a stream of CI (or under greatly diminished 
 pressure, Anschiitz a. Evans, O. J. 49, 708). 
 
 Properties. — Colourless, or slightly yeUow, 
 liquid, with an offensive smell, fuming in moist 
 air ; solidifies at a low temperature ( < — 6°) ; 
 absorbs moisture from air and changes to a 
 crystalline mass. According to Anschiitz a. 
 Evans (C. J. 49, 708) SbCl^ may be distilled un- 
 changed at low pressures. 
 
 Beactions. — 1. Dissolves in a very little 
 water ; solution over H^SO, deposits crystals of 
 SbCl5.4H20. Kept cold by ice, and water added 
 drop by drop in proportion SbClsiHjO, SbOOl, 
 (g.u.) is formed (Dubrawa, A. 184, 118). Addition 
 of more water produces SbOjCl, which is de- 
 composed by hot water, giving H4Sb20j.2H20, 
 soluble in HClAq. Decomposition by H^O hin- 
 dered by tartaric acid. Thomsen {Th. 2, 242) gives 
 the number [SbCP, Aq] = 35,200, when SbjOjAq 
 and HClAq are formed. — 2. Dry sulphuretted hy- 
 drogen produces white crystals of SbSClj, which 
 are decomposed by heat into SbClj and SjCl, 
 (Cloez, J. pr. 51, 459). — 3. Heated in closed 
 tube to 140° with antimonic oxide, in proportion 
 3SbCl5:Sb205, SbjOCl,, and Sb304Cl, (j. v.) are 
 produced (WiUiams, G. J. [2] 10, 122).— 4. With 
 phosphorus trichloride (in CHCI3) reacts to form 
 PCls.SbCls, and SbClj (v.Gombinaticms).—S. Chlo- 
 rinates many carbon compounds, e.g. CHCI3 to 
 OCl4,C2H4to GJB.fil,, &o. (v. Chloro-oompounds). 
 6. With nitrogen ietroxide forms SbClj-NOCl 
 (Weber, P. 123, 347). 
 
 Combinations. — 1. With ammonia forms 
 brown SbCl5.6NH3 which may be sublimed un- 
 changed. — 2. With hydrocyanic acid forms white 
 crystals of SbClj.SHCN, which volatilise with 
 partial decomposition under 100°, and are de- 
 composed by HjO (Klein, A. 74, 85).— 3. With 
 gaseous cyanogen chloride forms SbClj-CNCl 
 (Klein, l.c.). — 4. Combines with some non-metallic 
 chlorides to form double compounds which 
 usually deliquesce in air and are decomposed by 
 heat ; the more important are SbClj-PClj (Weber, 
 P. 125, 78; Kohler, B. 13, 875); SbClj-POCls, 
 SbCl^.SeCl, and SbClj-SCl^ (Weber, I.C.); and 
 SbCls.SeOClj (Weber, P. 125, 325).— 5. Also 
 combines with C^HsPClj to form SbClj.CjHsPCl, 
 (Kohler, B. 13, 1626). — 6. Combines with various 
 alcohols, and with ether (Williams, C. J. [2] 
 15, 463). 
 
 Antimony, fluorides of. Sb203 dissolves in 
 HFAq to form SbF,; Sb205.a!H20 dissolves in 
 HPAq to form SbFj. Neither has been gasified, 
 so that mol. ws. are unknown. 
 
 I. Anhmonious pluobidb SbPj [abt. 292°] 
 (CarneUey, C. J. 33, 275). 
 
 Preparation. — (BerzeUus, P. 1, 84; Dumas, 
 A. Ch. [2] 31, 435 ; Eliickiger, A. 84, 248).— 
 1. By dissolving Sb^Oj in HEAq, evaporating at 
 70°-90° and crystallising.— 2. By distilling Sb 
 with HgPj. 
 
 Properties. — White, trimetric, octahedral 
 
288 
 
 ANTIMONY. 
 
 deliquesoent, soluble in a,0 without decompo- 
 sition. 
 
 Beactions. — 1. Solution in water on evapo- 
 ration yields an oxyfluoride (composition un- 
 known). — 2. Deliquesced SbFj pressed between 
 paper gives 2SbPs.Sb20s ( = SSbOF.SbFa), which 
 is decomposed by heating into SbF, and Sb203. 
 
 Combinations. — With alkali fluorides to 
 lorm double compounds, SbFj combining with 
 MF, 2MF, or 3MF, where M = K, Na, &o. These 
 compounds are best obtained by dissolving SbjOj 
 and MjCOj in the proper proportions in HFAq, 
 and evaporating. The principal compounds are 
 SbFa.2NH4F; SbF3.2KF, SbFs.EF; SbF3.2LiF; 
 and SbF3.2NaF {v. Fluckiger, A. 84, 248). 
 
 II. Ajitimonic rLUOBiDE, SbFj. Obtained by 
 Berzelius, investigated more fully by Mariguac 
 (4.145,239). 
 
 Preparation. — ^By dissolving hydrated SbjOj 
 in HFAq, and evaporating. 
 
 Properties. — A gum-like amorphous mass, 
 decomposed by heat; very slowly decomposed, in 
 solution, by HjS. 
 
 Combinations With the alkali fluorides, to 
 
 form double compounds, which are easily solu- 
 ble in water, crystallise badly, and yield oxy- 
 fluorides when evaporated in aqueous solutions, 
 e.g. SbOFs-NaF from SbP5.2NaF (Marignac, A. 
 145, 239). These solutions are very slowly de- 
 composed by HjS, KOHAq, and KjCOjAq. The 
 more important compounds are SbFj.NHjF, 
 2(SbF5.2NHjF).HjO; SbF^.KF, SbF5.2KF.2H,0 ; 
 SbFj-NaF. 
 
 Antimony, haloid compounds of. SbFj, SbFj; 
 SbCl^SbCls; SbBr,; Sbl,, (?Sbl5). Only SbCl, 
 has been gasified and V.I). determined; SbOlj 
 is decomposed by heat. The formulae of the 
 trihaloid salts are probably molecular, v. Anti- 
 mony, ELUOBIDES OP, OHLOBIDES OF, BROMIDES OP, 
 
 IODIDES OP ; V. also art. Haloid compounds. 
 
 Antimony, hydride of {v. also art. Hydbides). 
 SbH3. (Antimoniuretted hydrogen ; Stibine). 
 Only one hydride of Sb, SbH3, is certainly known ; 
 and this has not been obtained except mixed with 
 much H. Marchaud (J. pr. 84, 381) described a 
 black powder obtained by electrolysing cone. 
 KHjClAq with a rod of Sb as neg. and a thick 
 Pt wire as pos. electrode. When a powerful 
 battery was used, gas came oft which burnt in 
 the air ; the powder was supposed to be a solid 
 hydride of Sb, and the gas a spontaneously in- 
 flaromable hydride {v. also Euhland, S. 15, 418). 
 But Marchaud's results were not confirmed by 
 Bottger (/. pr. 68, 372), who obtained only the 
 ordinary products of the electrolysis of NHjClAq, 
 viz. H, NHs, and N chloride. Wiederhold (0. C. 
 1864. 995) described a graphite-hke powder ob- 
 tained by the action of dilute HClAq on an alloy 
 of 1 part Sb with 5 parts Zu ; after drying at 100° 
 this powder gave off -001 p.o. H at 200° (SbjH re- 
 quires -004). The gaseous hydride is almost cer- 
 tainly SbHj (v. especially Jones, C. J. [2] 14, 647), 
 but it has not yet been obtained free from H. 
 
 Preparation. — By treating an alloy of 2 parts 
 Zn and 1 part Sb (Capitaine, B. J. 20, 89), or 3 Zn 
 and 2 Sb (Lassaigne, B. J. 22, 104), with dilute 
 HjSO^Aq. Schiel (A. 104, 223) decomposes an 
 alloy of Sb with K with dilute HClAq. Hum- 
 pert (C. C. 1865. 863) treats cono. SbCljAq with 
 Na amalgam. Jones obtained a gas containing 
 about 4 p.o. SbH, by dropping cono. solution 
 
 of SbOlj in cone. HClAq on to granulated Zn ; 
 the gas was partially decomposed as it was 
 formed (0. J. [?] 14, 641). 
 
 Properties. — A colourless gas, with nauseating 
 smell and intensely disagreeable taste, slightly 
 soluble in H^O but decomposed by long contact 
 into Sb and H ; easily decomposed by heat ; 
 burns in air to Sb^O^ and H^O, or in limited 
 supply of air to Sb, Sb40j, and HjO; de- 
 composed by electric sparks into Sb and H. 
 The gas obtained by reacting on an alloy ol 
 2 parts Sb with 3 parts Zn with dilute H^SOjAq, 
 and collecting the first portions only, solidified 
 at — 91'5°, and decomposed, with separation of 
 Sb, between -65° and -56° (Olszewski, M. 7, 
 371). 
 
 Beactions. — 1. With oxygen and heat, explo- 
 sion occurs and formation of SbjO^ and H2O; 
 the same products are obtained by burning in 
 air. — 2. Decomposed by chlorine, bromine, or 
 iodine, with formation of SbClj, SbBrj, or 
 Sblj; passed through a hot tube containing a 
 little I, an orange-yeUow or brown ring of Sbl, 
 is formed (Husson, J. pr. 106, 314). — 3. Passed 
 over sulphur in sunshine, or at temperatures 
 over 100°, orange-coloured SbjSj is formed ; very 
 minute quantities of the gas may be thus de- 
 tected (2SbH3 + 6S = SbjS3 + 3H2S) (Jones, C.J. 
 [3] 14, 649). — 4. Deoormposea sulphuretted hydro- 
 grere in sunshine forming Sb^Sj (2SbH3 + 3H2S = 
 SbjSj + GHj) (Jones, I.e.). — 5. With antimonious 
 chloride, Sb and HCl are formed. — 6. Easily oxi- 
 dised by nitric acid. — 7. Decomposed by aqueous 
 potash or soda with separation of a black powder 
 (? SbOHj or ? SbjO, v. Jones, l.c. ; also Dragen- 
 dorfE, Fr. 5, 200) which is at once dissolved on 
 shaking in air. — 8. With aqueous silver nitrate 
 the whole of the Sb is ppd. (as AgjSb mixed with 
 Ag, Lassaigne, B. J. 22, 104 ; v. also Jones, I.e.). 
 
 References. — Thompson, B. J. 18, 135 ; 
 Pfafi, P. 40, 339 ; Simon, P. 42, 369 ; Vogel, 
 J. pr. 13, 57 ; Meissner a. Hankel, J. pr. 25, 243. 
 
 Antimony, hydroxides of. Several compounds 
 of Sb, H, and are known ; some of them are 
 probably best regarded as hydrated oxides ; 
 others react as acids, especially HSbO, and 
 HjSbjO,; V. Aniimony, Acids op (v. also arts. 
 AoEDS and Hydroxides). 
 
 Antimony, iodide of. Sbl,. Only one iodide 
 of Sb is known with certainty; van der Espt 
 {Ar. Ph. [2] 117, 115) asserts that Sbl^ is pro- 
 duced by heating 1 part Sb with 5 parts I, or 
 by leading SbH, into I in alcohol; but as Sbl, 
 is known to be produced by such processes the 
 existence of the pentiodide is extremely doubtful 
 (comp. Pendleton, 0. N. 48, 97). Mol. w. 499'62. 
 [167°] (Cooke, P. Am. A. [2] 5, 72). (401° at 
 760 mm.) (Cooke, P. Am. A. [2] 7, 251). V.D. 
 252 (Worcester, P. Am. A. [2] 10, 61). S.G. 
 hexagonal M° 4-848, monoclinio 2i° 4-768 (Cooke, 
 I.C.). H.F. solid Sb, gaseous I, [Sb, IT = 45,400 
 (Guntz, C. B. 101, 161). 
 
 Formation. — 1. By the action of powdered Sb 
 on I in CS2. — 2. By the action of SbH, on I. — 
 3. By subliming together SbjS, with 31 in a 
 globe (Schneider, P. 109, 609). 
 
 Preparation. — Powdered Sb is added little 
 by little to I, with gentle heating, until no further 
 action occurs; the Sbl, is then separated by 
 sublimation in H or CO,. 
 
 Properties. — Bed crystals, which melt on 
 
ANTIMONY. 
 
 i.'80 
 
 beating and volatilise in red vapourg ; soluble in 
 boiling C9j, and boiling benzene, but separates 
 out on cooling ; almost insoluble in CHClj ; 
 soluble in HIAq. Exists in three forms : 
 (a) hexagonal ruby-red crystals, by crystallisation 
 {rom CS^, M.P. = 167°, a:o = 1:1-37 ; (6) trimetrio 
 greenish-yellow crystals, by subliming the hexa- 
 gonal form at temperatures not above 114° ; at 114° 
 the change is sudden, the' external form of the 
 hexagonal crystals is preserved but each crystal 
 is found to consist of a mass of trimetric crystals ; 
 heated above 114° the hexagonal form is re- 
 produced ; (c) mouoolinic crystals {a:J):c = 
 1-6408:1: -6682) obtained by exposing a solution 
 of Sblj in CSj to direct sunlight ; at 125° they 
 are changed into the hexagonal form (Cooke, 
 P. Am. A. [2] 5, 72). 
 
 Reactions. — 1. Water decomposes Sblj with 
 production of HIAq, which dissolves part of the 
 Sbl„ and oxyiodide of Sb (g. v.). — 2. Aqtieous 
 alkalis atid alkali carbonates produce SbjOs and 
 alkali iodide (SeruUas, J. Ph. 14, 19).— 3. Cone. 
 sulphuric acid or nitric acid separates I. — 
 4. Alcohol or ether partly dissolves Sbl, and 
 partly changes it to yellow oxyiodide (Maoivor, 
 C. J. [2] 14, 328).- 5. Chlorine forms SbCla and 
 ICl (Macivor, l.c.). — 6. AnUmony trisulphide 
 reacts with molten Sblj to form SbSI ; this 
 Bulphoiodide is obtained as a lustrous brown-red 
 powder by treating the fused mass with dilute 
 HClAq ; it is decomposed by HjO and KOHAq ; 
 boiled with H^O and ZnO the oxysulphide 
 SbjOS; is formed (Schneider, P. 110, 147). 
 
 Combinations. — Dissolves in aqueous solu- 
 tions of the iodides of the alkali metals, on 
 evaporation double compounds are obtained. 
 These compounds are soluble in HClAq, 
 H.C^HjO^Aq, and H^.C^H^OsAq ; they are de- 
 composed by H^O, yielding Sb oxyiodide; CS.^ dis- 
 solves out Sblj. The following salts are described 
 by Schaeffer {P. 109, 611) : aSblj.SKI.BH^O ; 
 
 2Sbl3.3NaI.12H.,0 ; 4Sbl3.3NH,I.9H20 ; 
 SbI,.BaL,.9H,0. Niokl^s (O. R. 51, 1097) de- 
 scribes two series of compounds MI.SbI3.2H2O, 
 and MI.Sbl3.H,0 where M = K, Na, or NH„ 
 obtained usually by the action of I on Sb in 
 presence of saturated MIAq ; these salts are 
 isomorphous with corresponding double salts 
 ofBi. 
 
 Antimony, livers of. This name is applied 
 to the impure double sulphides obtained by 
 heating Sb^S, with various metallic sulphides, 
 more especially with the alkali and alkaline 
 earth sulphides. These bodies are obtained 
 either by fusing SbjSj with K^S, &o., with 
 K,S02 <feo. and C, or by dissolving SbjSs in 
 K^SAq, &c. The behaviour of aqueous solutions 
 varies according to the relative quantities of 
 SbjSs and alkali sulphide employed ; it not more 
 than 2 parts Sb^Sj are used to 1 part alkali 
 sulphide, the product is whoUy soluble in water; 
 if more SbjS, is used the product is partly, or 
 wholly, insoluble (because of production of anti- 
 raonate and SbjO^ v. Antimonious sulphide. 
 Reactions, No. 15). Solutions of these bodies 
 dissolve SKS3 on boiling ; the SbjSj pps. again 
 on cooling;' they readily absorb from the 
 air, forming antimonate and thioantimonate 
 (v. AirriMONious sulphide. Reactions, No. 15). 
 Addition of alkali bicarbonates pps. thio- 
 antimonite. 
 
 Vol. I. 
 
 Antimony, oxides of. Three oxides are known: 
 SbjOo, SbjOj, and SbjO,; only the first of these 
 has been gasified ; the molecular weights of the 
 others are not known. The pentoxide acts as 
 an anhydride; the two others are feebly salt- 
 forming whether they react with strong acids or 
 strong alkalis {v. Amiimont, acids of). Marchand 
 (/. pr. 34, 381) described an oxide, SbjOj, said 
 to be obtained by the electrolysis of a solution 
 of cream of tartar ; but Bottger (J. pr. 68, 372) 
 failed to obtain anything except antimonio acid 
 by repeating the experiments. 
 
 I. Antimonious oxide Sb^O, (Antimomons 
 acid). Mol. w. 575-76. S.G. trimetrio 5-5 to 5-6, 
 regular octahedra 5-1 to 5-2 (Terrell, C. R. 58, 
 1209). V.D. 286-5 (at abt. 1550° ; Meyer, B. 12, 
 1284). S.H. -0927 (18° to 100°; Neumann, P. 
 126, 123). C.B. (40° cub., Senarmo7itite) 
 •00005889 (Fizeau, A. Ch. [4] 8, 335). 
 
 Occurrence.— 'Sa.tive ; as Antimony bloom in 
 trimetric prisms, as Seruzrmontite in octahedra. 
 
 Formation.— 1. By heating Sb in a loosely 
 covered crucible, and then raising the tempera- 
 ture, when SbjOg mixed with a little Sb^Oj sub- 
 limes on to the crucible cover. — 2. By treating 
 Sb with dilute HNOjAq and washing thoroughly 
 with water and then with very dilute NaaCOjAq 
 (Rose, P. 53, 161).— 3. By fusing Sb with KNO, 
 and KHSO4 and boiling fused mass in water 
 (Preuss, A. 31, 197).— 4. By washing the white 
 pp. obtained by adding H^O to SbClj with dilute 
 KOHAq and then with H^O. — 5. By adding 
 excess of NHjAq to hot KSb.CjHjO^q, heating 
 pp. for a short time in contact with the liquid, 
 collecting, and washing. 
 
 Preparation. — 1. 8 parts finely powdered St> 
 are heated with 7 parts cone. H^SOj ; the crude' 
 Sb sulphate is treated repeatedly with hot water, 
 and then with very dilute Na^COjAq, and thfr 
 oxide is collected and dried.— 2. 1 part powdered 
 Sb is heated, so long as an action occurs, with 
 4 parts HNOjAq, S.G. 1-2, and 8 parts H.p ; the 
 nitrate of Sb is treated as the sulphate in 1. 
 
 Properties. — A white, more or less crystalline,, 
 powder (regular octahedra) ; very slightly soluble' 
 in water, fairly soluble in glycerine (Kohler,. 
 D. P. J. 258, 520) ; becomes yellow when heated,, 
 but white again on cooling; melts at a dark, 
 red heat, and crystallises on cooling. Volatilisesi 
 rapidly about 1550° (Meyer, B. 12, 1284). In- 
 soluble in HNOjAq and H^SOjAq ; dissolves 
 easily in HClAq and Hj.GjHjOjAq ; also in 
 KOHAq and NaOHAq, from these solutions Sb^O, 
 is ppd. on cooling (Mitscherlich, A. Oh. [2] 33, 
 394), but according to Terrell the pp. is an 
 antimonite (A. Ch. [4] 7, 380). Sb.O,, is formed 
 in trimetrio prisms {a:b:c = -394:1:1-414) by burn- 
 ing Sb or SbjSj in air, by heating oxyohloridu 
 (obtained by adding HjO to SbCl,) with H3O to 
 150° (Debray, 0. R. 68, 1209), or by rapidly 'sub- 
 liming the octahedral crystals (Terrell, O. R. 62, 
 302) ; SbjOg is formed in regular octahedra by 
 subliming at a dark red heat. Both forms are 
 obtained by saturating hot Na^COsAq with Sb.,03 
 or SbCl, and allowing to cool (Mitscherlich, 
 P. 15, 453) ; or by passing a slow stream of dry 
 air through a porcelain tube containing Sb, the 
 tube being heated at first only where the Sb 
 is, but after a few hours also at the point whera 
 the prisms might condense, after about 12 hours 
 prismatic crystals are found near the Sb, prisms 
 
 V 
 
390 
 
 ANTIMONY. 
 
 mixed with ootahedra further on, and ootahedra 
 onlynear the end of the tube (Terreil, i.e.). Shfi^ 
 IB isodimorphoua with As fig (g^. v.). According 
 to Guntz (C. B. 98, 303) the change of prismatic 
 BbjO, to octahedral is attended with production 
 of 1200 gram units of heat per 576 grms. Sbfis 
 changed. 
 
 Beactions. — 1. Heated in air or oxygen, Sb^O, 
 is formed.— 2. Cone, hot wiiric acid oxidises to 
 Bbfit and SbjOj ; it dissolves in cold fuming HNO, 
 and forms Sb^O^.NA (Peligot, C. B. 23, 709).— 
 3. Treated with fuming sulphuric acid, small 
 lustrous crystals are obtained, which, after dry- 
 ing for six months in contact with burnt clay 
 have the composition SbjOj.2SOs'; by treating 
 these crystals with H^O the salt SbjO^.SOa is 
 obtained (Peligot, Z.c). Schultz-Sellac (B. 4, 
 13) describes the salt Sb,.3S0, ( = SbA-6S03) as 
 long lustrous needles obtained by evaporating 
 solutions of Sb^Oj in fairly cone. H2S04Aq ; this 
 salt is unchanged in dry air, but gives off SOj on 
 heating, and is decomposed by water. Sb2(SOj3 
 is also formed by dissolving Sb^Sj in hot cone. 
 H^SOjAq (Hensgen, B. T. C. i, 401) {v. Shl- 
 PHATEs). — 4. SbjO„ dissolves in solution of 
 potassium-hydrogen tartrate, forming the salt 
 CjH^KSbO,, which is probably the K salt of the 
 acid Sb.C4H4Oe.OH (v. Clarke and Stallo, B. 13, 
 1787). — 5. Sb^Oj acts as a reducing agent towards 
 salts of silver, gold, &o. {v. Antimony, detec- 
 xiotioF,Antimonious compounds). — 6. Sb^Oj 
 does not directly combine with water, but two 
 hydrates have been prepared : — (a) Sb203.2H20, 
 by adding CuS04Aq to Sb^Sj dissolved in KOHAq 
 until the filtered liquid gives a white pp. 
 (SbjOj.SHjO) on addition of an acid (Fresenius ; 
 V. also Schaffner, A. 61, 182) ; (6) Sb,03.3H.,0, a 
 white powder which begins to lose water above 
 150°, obtained by the spontaneous decomposition 
 of an aqueous solution of the acid H.C4H4SbO, 
 obtained by decomposing (C4H4SbO,)2Ba by the 
 proper quantity of H^SOjAq (Clarke a. Stallo, 
 JB. 13, 1793). — 7. Dissolves in boiling antimonious 
 chloride to form oxychlorides ; SbOCl.7SbCl3 is 
 described by Schneider (P. 108, 407). 
 
 II. Antimonio oxide SbjOr, (Antimonic acid). 
 Mol. w. unknown. S.G. 3"78 (Playfair a. Joule, 
 C. 8. Mem. 3, 83). 
 
 Preparation. — By dissolving powdered Sb 
 in aqua regia, or cone. HNOjAq, evaporating 
 to dryness, andheating [not above 275°] (Geuther, 
 J.pr. [2] 4, 438; Dubrawa, A. 186, 110). 
 
 Properties. — Citron-yellow powder ; insoluble 
 in water, but reddens moist blue litmus paper ; 
 loses at 300° (Geuther, I.e.) giving SbjOj ; 
 soluble in cone. HClAq, slightly soluble in cone. 
 KOHAq. 
 
 Beactions. — 1. Heated with antimony or 
 antimony sulphide, Sb^Oj is formed. — 2. Heated 
 in chlorine, SbCl3 and Sbj^Oj are produced. — 3. 
 Heated with ammonium chloride, is completely 
 volatilised.— 4. Reacts with alkaline carbonates 
 on fusion, with evolution of CO2 (v. further 
 AuTiMONT, DETECTION OT, Antimonic com- 
 j)0unds).^5. Hydrates are not produced by the 
 direct action of water, but indirectly the three 
 compounds, Sbi,Os.3H30, SbA-2HjO, and 
 Sb^Oj.HjO, have been obtained (u. Antimont, 
 ACIDS OF, Antimonates). Forms many com- 
 pounds with WO3 and MoO, {v. Gibb», O. N. 48, 
 106 ; Am. 7, 209 and 313). 
 
 III. ASTIMONOSO-ANTIMONIO OXIDE Sb^O, 
 
 {Antimony tetroxide). Mol. w. unknown. S.G. 
 4-074 (Playfair a. Joule, G. 8. Mem. 3, 83) ; 6'5 
 (Boullay, A. Ch. [2] 43, 266). S.H. (23°-99°) 
 •09535 (Eegnault, A. Ch. [3] 1, 129). 
 
 Occurrence. — Native, as AnUmony-ochre. 
 
 Preparation. — 1. By heating Sb,Oj in air.— 
 2. By oxidising Sb, Shfi^, or SbjSs, by cone. 
 HNOjAq, evaporating to dryness, and strongly 
 heating. 
 
 Properties. — White powder, becoming yellow 
 on heating ; has not been melted or volatilised ; 
 insoluble in water, but reddens moist blue litmus 
 paper ; very slightly acted on by acids. 
 
 Reactions.— 1. Heated with solution of cream 
 of tartar,Bh20^xliifi remains and solution contains 
 CjHjKSbO,.- 2. Solution in HClAq dropped into 
 water, is decomposed into SbjOj and Sb.^O,. — 3. 
 Heated with antimony SbjO, is formed. — 4. 
 With molten potash forms K20.Sb204 {v. 
 Antimont, aoids of ; Antimonoso-antimonates) ; 
 solution of this in water slowly reduces AgNOjAq 
 and AuCljAq. Sb204 reacts as a compound of 
 Sb.^03 and Sb.^Oj ( = SbjOg) ; it is sometimes re- 
 garded as antimony! antimonate (Sb0)Sb03, 
 derived from HSbOj. 
 
 Antimony, oxybromides of. Two oxybromidea 
 are obtained by the action of Sfi on SbBrj, viz. 
 SbjOjiBrj and lOSbjOsBr^.SbBrj ; SbOBr is pro- 
 bably formed by the action of sunlight on SbBr, 
 in CS2 {v. Antimony, bkomide of). 
 
 Antimony, oxychlorides of. At least six 
 compounds are known; SbOCl, SbOC1.7SbCl3, 
 SbjOjClj, and 10Sb4O3Cl2.SbCl3, obtained from 
 SbCl, ; SbO^Cl, and SbOClj, from SbClj. 
 
 When SbOla is added to a little water, SbOCl 
 is obtained (sometimes mixed with SbCl3). This 
 oxychloride seems to exist either as a white 
 amorphous powder, or as nionoelinio crystals 
 isomorphous with SbOI (Cooke, P. Am. A. [2] 5, 
 72) ; the crystals are best obtained by using 10 
 pts. SbClj and 17 pts. H2O, allowing to stand 
 for a day or two, pressing, and washing with 
 ether (Sabanajew, Bl. [2] 16, 79) ; the amorphous 
 powder is best prepared by adding 3 pts. H^O to 
 1 pt. SbCl3, filtering at onoe, drying over H^SOj, 
 and washing with ether. Crystalline SbOCl ia 
 also obtained by heating SbClj with C^HjO (in 
 ratio SbCl3:C2HjO) in a closed tube to 160° 
 (Sohaffer, A. 152, 314). By the action of much 
 water on SbCl, (5 to 50 parts to 1 part SbCl, 
 according to Sabanajew, I.e.) the oxychloride 
 SbjOsClj is obtained as an amorphous powder, 
 which becomes crystalline on standing. To pre- 
 pare the crystalline forms it is best to use 30 
 parts of cold water, or 8 parts of water at 60° 
 to 70° (in the latter case allowing the pp. to 
 remain a few hours before collecting) ; there are 
 some differences in the forms of the two sets of 
 crystals (Sabanajew, I.e.). Crystals (trimetric 
 Sohaffer, A. 152, 314 ; monoclinic, Cooke, P. Am 
 A. [2] 5, 72) of SbjOjClj are also obtained by 
 heating SbCl3 with C^HjO (in ratio SbCljiSOjHaO) 
 to 140°-150° (Schaffer, I.e.). The compound 
 SbjOjClj is also produced by the action of alcohol 
 on SbOCl (Schneider, P. 108, 407) ; and also by 
 heating dry SbOCl (5SbOCl = Sb403Cli, +SbCl3; 
 Sabanajew, l.c.). 
 
 The product of the action of much H^O on 
 SbCl3 is known as powder of Algaroth ; the com- 
 position varies according to temperature, quan- 
 
ANTIMONY. 
 
 S91 
 
 tity of water, and quantity of HCl in the solution 
 of SbCl, used (oomp. Duflos, S. 67, 268; John- 
 ston, J. pr. 6, 55 ; Malaguti, J.pr.6, 253 ; Peligot, 
 A. 64, 280). 
 
 According to Williams (C N. 24, 224) the 
 action of hot water on SbCl, produces 
 lOSbjCl^Os-ShOlj ; Williams also describes two 
 oxychlorides obtained by heating Sb^Oj with 
 SbClaiSbjOsiSSbCl,) to 140° in a closed tube; 
 Sb30Cl,3M.P. = 85°, and SbjOjCl, M.P. = 97-5°. 
 
 Cooke (P. Am. A. [2] 5, 72) describes another 
 oxyohloride SbgOuClj; and Schneider (P. 108, 
 407) two others, SbOC1.7SbCl, and 2SbOCl.Sb20s. 
 
 According to Thomsen {Th. 2, 240) the heat 
 of formation of Sb^OsClj from SbClj and Aq is 
 8910 gram-units (v. also Guntz, O. B. 98, 512). 
 By dropping the calculated quantity of very cold 
 water on to SbClj, Dubrawa (A. 184, 118) ob- 
 tained SbOClj _(SbCl5 + H,0 = SbOCl3 + 2HCl); 
 this oxychloride is a yellowish, somewhat crys- 
 talline, mass, soluble in alcohol ; it deliquesces to 
 a yellow liquid, from which needle-shaped crystals 
 separate in dry air. When heated it melts and 
 decomposes (probably to SbOCl-^Cl2). It is de- 
 composed by NaaCOjAq (2SbO0l3 + SNajCOjAq = 
 
 BNaCLAq -H 20 + 3C0., + Sb-A)- 
 
 Antimony, oxyfluoride of. SSbOF.SbPj ob- 
 tained by deliquescence of SbF, (v. Antimony, 
 
 FLUORIDES of). 
 
 Antimony, oxyiodides of.' Sb^OsIj and SbOI. 
 SbjOjIj is obtained as light yellow crystals by 
 evaporating a solution of SbClj in KIAq, adding 
 HjO and evaporating again. The composition 
 of the oxyiodide obtained by the action of H.^O 
 on Sblj varies according to the conditions of its 
 preparation ; by pouring Sbl3 in HIAq into hot 
 HjO, Sb^OjIj is obtained (v. Maoivor, O. J. [2] 
 14, 328). By the action of air and sunlight on 
 Sblj in CS.2 both oxyiodides are formed, produc- 
 tion of SbOI proceeding rapidly (Cooke, P. Am. 
 A. [2] 5, 72). When SbOI is heated in a current 
 of an inert gas to 150°, Sbl, begins to sublime, 
 and at 200° is given off rapidly ; no further 
 change occurs till 350° is reached, when Sbl, 
 again sublimes and crystals of SbjOj remain 
 (Cooke, P. Am. A. [2] 5, 72). By the action of 
 HCLAq, HN03Aq, or H^SO^Aq, on SbOI, I is 
 separated. 
 
 Antimony, oxysulpMdes of. Various oxy- 
 Bulphides of Sb, or more probably mixtures 
 of Sb2S3 and SbjOj, were formerly used in phar- 
 macy. The compound Sb203.2Sb2S3 occurs 
 native as antimony blende (v. H. Eose, P. 3, 452). 
 The oxysulphide SbjOS^ is obtained as a red- 
 brown powder by boiliiig SbSI {v. Antimony, 
 loxiDE of) with ZnO and HjO (Schneider, P. 
 110, 147) ; also by the action of NajSAM o° 
 SbCl3 in HCLAq (Bottger, C. C. 1857. 333). A 
 compound of SbjSs and Sb203 is much used as 
 a brilliant crimson-red pigment; it is probably 
 SbA-2Sb2S3(=3Sb20S3), {v. Bottger, l.c.; 
 Wagner, J. 1858. 235 ; Kopp, 0. C. 1859. 945). 
 
 Antimony, phosphides of, v. Antimony, Com- 
 binations, No. 8. 
 
 Antimony, selenides of, v. Antimony, Cmn- 
 binations, No. 6. 
 
 Antimony, seleno-acid of, v. Sei>eno-anti- 
 MONATES, p. 286. 
 
 Antimony, sulphides of. Two sulphides are 
 known, Sb2S3 and Sb^Sj; neither has been 
 gasified, and therefore mol. w. of neither is 
 
 known. Unger {Ar. Ph. [2] 147, 193) supposed 
 he had obtained a disulphide, Sb.^Sj, by the 
 action of NaOHAq on Sb^Sj; but the existence 
 of this SbjSj is very doubtful. SbjSj is a feebly 
 marked salt Jorming sulphide, e.g. it dissolves in 
 NaOHAq to form Na^SbaS^ {v. Antimony, thio- 
 AoiDS of). SbjSj is a distinctly salt-forming 
 sulphide ; the thio-antimonates (q. v.) are well- 
 marked salts. The trisulphide, SbjSj, occurs 
 native ; the pentasulphide does not. 
 
 I. Antimonious sulphide (Antimony trisul- 
 phide, Mineral Kermes,&a.) Sb^Sj [low red heat]. 
 S.G. (stibnite) 4'51-4-75 ; (amorphous) 4-15 ; 
 (fused, by direct union of Sb and S) 4-892 (Ditto, 
 O.iJ. 102, 212). S.H. (23°-99°) -08433 (Eegnault, 
 A. Ch. [3] 1, 129 ; v. also Neumann, P. 23, 1). 
 Two forms are known ; crystallised (trimetrio ; 
 a:6:c = -985:1:1-0117) and amorphous. 
 
 Occurrence. — Native as Stibnite or Antimony 
 glance, crystallised in trimetrio prisms, usually 
 containing P, As, Fe, and Cu. 
 
 Preparation. — [a) Crystallised: by gradu- 
 ally heating to redness, in a covered crucible, a 
 mixture of 13 parts of finely powdered Sb well 
 mixed with 5 parts pure S ; then fusing for some 
 time under a layer of NaCl ; cooling, powdering, 
 mixing with a little S, and again fusing under 
 NaCl. (6) Amorphous: by boiling 4 parts 
 KOHAq, S.G. 1-25, and 12 parts H^O, with one 
 part crude Sb^Sj, out of contact with air f oi some 
 time, adding 50 parts boiling H^O, filtering 
 quickly, and decomposing the solution by dilute 
 H^SOjAq; the pp. is collected, boiled with very 
 dilute HjSOjAq, washedwith cold water, digested 
 with aqueous tartaric acid (to remove any Sb^O,), 
 again washed with cold water, pressed, and 
 dried at a low temperature. Cooke (P. Am,. A. 
 [2] 5, 1) dissolves Sb in large excess of HNOjAq 
 (S.G. 1-35), keeping the temperature as low as 
 possible, neutralises with NaOHAq, dissolves in 
 large excess of Hj.OjHjOjAq, pps. by H^S in an 
 atmosphere of COj, collects and washes pp. and 
 dries below 210°. The amorphous sulphide is 
 also produced by melting crystalline Sb S3 in a 
 glass tube, and after a time throwing it into a 
 large quantity of cold water (Fuchs, P. 31, 578). 
 An impure SbjSj, containing Sb203, known as 
 Kermes, is prepared for commercial purposes by 
 heating crude antimony sulphide with aqueous 
 alkalis or alkaline carbonates. 
 
 Properties. — (as) Crystalline: grey-black 
 trimetrio prisms ; melts easily. (6) Amorphous: 
 prepared by ppn., is a reddish-brown, loose, 
 powder which marks paper with a brownish 
 streak ; prepared bymeltingandsuddenly cooling 
 the crystalline Sb^S,, it is a hard greyish mass ; 
 melted and cooled slowly it yields the crystalline 
 form ; heated to 210°-220° it becomes grey 
 (Cooke, P. Am. A. [2] 5, 1). Both forms of 
 SbjSj are insoluble in water, and in NH,Aq, 
 dissolve in KOHAq, in HClAq, and very slowly 
 in tartaric acid. They may be distilled un- 
 changed in a stream of N. 
 
 Reactions. — The products of the reactions of 
 crystalline and amorphous Sb^Sj are, in almost 
 every case, the same; the actions usually proceed 
 more rapidlywith the amorphous than with the 
 crystalline form. 1. Boiled with water, is par- 
 tially decomposed to Sb^Oj and HjS (De Cler- 
 mont a. Frommel, C. R. 87, 330 ; Lang, B. IH, 
 2714).— 2. Heateiin hydrogen, Sb is formod.— 
 
 u2 
 
292 
 
 ANTIMONY. 
 
 8. Calcined in air, Sb,Oj, or Sb^O^, and SOj are 
 produced.— 4. Heated in chlorine, SbCl, and 
 SjClj result. — 5. Aqueous hydrochloric acid 
 forms SbCl, and HjS ; after a time the action 
 stops, but if the H^S is removed the whole of 
 the Sb^Sa is decomposed («, Lang, B. 18, 2714; 
 also Berthelot, C. B. 102, 22).— 6. Cone, nitric 
 acid oxidises to nitrate and sulphate of Sb mixed 
 with S. — 7. Aqiia regia forms SbClj, H^SO,, and 
 S. — 8. Dilute solutions of sulphuric acid have no 
 action on crystalline SbjSa, but slowly evolve B.^S 
 from amorphous Sb^S, ; cone. H^SO^Aq evolves 
 SOj, separates S, and forms Sb2(SO,)3 (Hensgen, 
 B. T. G. i, 401).— 9. Fused with at least 17 parts 
 nitre, KSbOj is formed, with Sb sulphate ; with 
 less than 17 parts nitre, Sb.^Oj is sometimes 
 formed in addition to the other products, or a 
 part of the SbjSj remains unoxidised and com- 
 bines with KjS formed to produce a thio- salt. — 
 10. Melted vdth excess of lead oxide, Sb^Oj, SOj, 
 (andPb), areformed. — 11. Melted with^oiossmm 
 cyanide, Sb is produced, along with KCNS and 
 a compound of SbjSj and K^S. — 12. Iron, zinc, 
 and many other metals reduce Sb^Sj, when 
 heated with it, forming Sb and a metallic sul- 
 phide ; metals whose sulphides are basic {e.g. K) 
 generally combine with part of the Sb^Sj to form 
 thio- salts. — 13. Many easily reduced metallic 
 oxides when heated with Sb^Sj form SbjOj and 
 SOj. — 14. M.a,nj metallic sulphides combinewheu 
 heated with Sb2S3 with production of double 
 compounds ; several of these double compounds 
 occur native, e.g. Sb^Sj.PbS ; Sb2S3.Cu2S ; 
 SbjSj.SAgjS; &c. — 15. Alkali sulphides corahine 
 with Sb.^Ss either when heated in the solid state 
 or in solution; the compounds produced are 
 generally known as livers of antimony, q. v. 
 {v. also next reaction) ; aqueous solutions of 
 these compounds absorb forming Sb^Og, anti- 
 monates, and thio-antimonates. — 16. Caustic 
 alkalis react with Sb2S3, when fused together, or 
 when in aqueous solutions, toproduce antimonite 
 and thio-antimonite : thus, 4Sb2S3 + 4K,,0 = 
 GKSbS^ -I- 2KSb02 ; or 4Sb2S3 + SKOHAq = 
 3(Sb.,S3.K2SAq) [ = 6KSbS2Aq] + Sb^Oj.K.OAq 
 [ = 2KSb02Aq]+4H20. Addition of HClAq to 
 this solution pps. Sb^S,; 
 (GKSbS^Aq + 2KSbOjAq + 8HClAq = 
 4Sb.,S3 + 8KClAq + 4H20). If, however, much 
 Sb2S3, relatively to the amount of KOH, is used, 
 formation of KSbS^Aq proceeds, but the ESbOj 
 being much less soluble pps. along with some 
 oxysulphide and Shfi^ which has not combined 
 with KOH [crocus of antimony). The solution 
 of KSbSj is acted on by air, giving finally an- 
 timonate and thio-antimonate (eKSbSzAq +G0 = 
 4KSbS3Aq-H2KSb03Aq).— 17. Solutions of car- 
 bonated alkalis, K2C03 and Na^COsAq, dissolve 
 SbjS, only on heating ; the solutions behave 
 similarly to those obtained by KOHAq and 
 NaOHAq ; on boiling in air a pp. of KSbOj 
 (SbjOj.KjO) combined with Sb2S3 is obtained 
 (Kermes) , and KSbSj remains in solution. When 
 1 pt. SbjSj is fused at a strongred heat with 3 pts. 
 NajCOj, and H^O is added, a solution contain- 
 ing antimonate and thio-antimonate is obtained, 
 and Sb is ppd. (probably, lONaSbO^Aq + 2H2O 
 = 6NaSbOsAq + 4NaOHAq + 4Sb). The action 
 of alkalis on Sb^S, has been chiefly investigated 
 by Liebig {A . 7, 1). 
 
 Cwnbinations. — With metallic sulphides to 
 
 form thio-antimonites {v.tupra), q.v. under Akti- 
 
 MONT, THIO-AOIDS OF. 
 
 Antimonious sulphide ; hydrated. 
 The orange-red pp. obtained by passing HjS 
 into a solution of SbClj or CiH^ESbO, containing 
 little acid is amorphous hydrated Sb^Sj, which 
 is fully dehydrated only at 200° (Fresenius ; ac- 
 cording to Wittstein the pp. contains no chemi- 
 cally combined H^O, Fr. 1870. 262). It behaves 
 towards acids, alkalis, &o. in the same way aa 
 amorphous Sb.^S3. When this pp. is treated with 
 peroxide of hydrogen, in presence of NHjAq, a 
 portion of it is oxidised to antimonio acid, some 
 of which separates out and some remains in 
 solution as NHj.SbOa (Easchig, B. 18, 2743). 
 
 II. Antimonio sulphide SbjSj {Antimony 
 pentasulphide or persulphide, Oolden sulphuret 
 of antimony, &o.). Mol. w. unknown. Not 
 found native. Sb2S3 does not directly combine 
 with S ; but by heating SbjS,, S, and Na.^COj 
 together, Na3SbS4 is formed, from which Sb^Sj is 
 obtained by the action of acids. 
 
 Formation.— 1. By the action of H^S on 
 SbCls in H2.CjHjO„Aq, or on Sb.^05.a;H20 sus- 
 pended in water.— 2. By decomposing solutions 
 of thio-antimonates by dilute acid. 
 
 Preparation. — 10 parts crystallised 
 Na3SbS4.9H20 (g. v. under Antimony, thio-acids 
 or) are dissolved in 60 parts H^O ; the solution 
 is poured (with constant stirring) into a cold 
 solution of 3'3 parts pure HjSO, in 100 parts 
 H2O ; the pp. is washed by decantation, then on 
 a filter, with cold water, as quickly as possible ; 
 to remove all traces of acid, the pp. is now di- 
 gested with a cold solution of 1 part NaHCOj in 
 20 parts H-fi for a few days; it is again washed 
 then pressed, and dried in a dark place at a low 
 temperature. 
 
 Properties. — A dark-orange powder; insoluble 
 in water ; completely soluble in aqueous alkalis ; 
 in absence of air, soluble in NH3Aq, and in 
 aqueous alkali sulphides ; soluble in Na.^C03 or 
 K2C03Aq, not in (NHJ^COsAq. 
 
 BeacUons. — 1. Heated out of contact with 
 air, Sb^Sj and S are formed. — 2. Decomposed 
 by boiling with hydrochloric acid, giving SbClj 
 and HjS. — 3. Caustic alkalis dissolve SbjSj, form- 
 ing antimonate and thio-antimonate. — 4. Car- 
 bon disulphide dissolves out a little S (about 5 
 P.O., Eammelsberg, P. 52, 193). That this is due 
 to a decomposition of SbjSj, and not to the 
 action of CS^ on admixed S (it has been supposed 
 that the action of CSj proves the non-existence 
 of SbjSj), is shown by the fact that much lesa 
 than Sj is withdrawn from each SbjSj by CSj, 
 and also by the reactions of the SbjSj, especially 
 the solubility in NH3Aq in which Sb^S, is in- 
 soluble, and the insolubility in (NHJ^COjAq 
 which dissolves Sb2S3. 
 
 Combinations. — With alkali sulphides to form 
 thio-antimonates, q.v. under Antimony, thio- 
 acids or. 
 
 Antimony, sulpho-acids of, v. Antimony, ibio- 
 ACiDS or. 
 
 Antimony, snlpho- (or thio)- chlorides of. 
 SbSC1.7SbCl3, and 2SbSCl.Sb,S3, obtained by 
 action of SbjS, on SbCl,; and SbSCl, obtained by 
 the action of H^S on SlbCl^ (v. Antiuont, celo- 
 
 BID£S OP). 
 
ANTIMONY. 
 
 893 
 
 Antimony, snlplio- (or thlo)- iodides of. 
 SbSI ; by action of Sb^S, on Sblj, or of I on 
 SbjSs {v. Antimony, lonroE of). 
 
 Antimony, tellurides of, v. Antimokt, Com- 
 binations, No. 7. 
 
 Antimony, thio-acids ef. No thio-acids of Sb 
 are known, but a few thio-antimonites, MSbSj 
 and one M^SbSs, and a considerable number of 
 well-marked thio-antimonates, MjSbS,, have been 
 prepared. The thio-antimonites may be regarded 
 as derived from the hypothetical acid HSbS^ 
 ( = SbS.SH) ; they correspond in composition with 
 the antimonites MSbOj and with the meta-thio- 
 arsenites MAsSj. The thio-antimonates may be 
 regarded as derived from the hypothetical acid 
 HjSbSj ( = SbS(SH)3) ; no corresponding anti- 
 monates are known (MSbOj and M^SbjO; repre- 
 sent the antimonates) ; the thio-arsenites are re- 
 presented by three series, one of which (the ortho- 
 series) corresponds with the thio-antimonates. 
 
 Thio-antimonites. A very few of these salts 
 have been prepared. Addition of absolute 
 alcohol to a solution of Sb^Sj in NaOHAq pps. 
 amorphous NaSbSj, soluble in water. By heat- 
 ing to 30° equivalents of Sb^S, and NaOH 
 (in cone, solution) copper-coloured 2NaSbS2.H20 
 is formed (Unger, /. 1871. 325). The silver 
 salt AgjSbSs is said to be obtained as a grey 
 mass, reddish when powdered, by heating 
 AgaSbSj out of contact with air (Eammels- 
 berg, P. 52, 193). Several minerals may be 
 regarded as thio-antimonites, e.g. PbS.SbjSj ; 
 Ag2S.Sb,S3 ; Cu,S.Sb2S3 ; FeS.Sb^Sj &c. 
 
 Thio-antimonates MjSbSj. Investigated 
 chiefly by Eammelsberg (P. 52, 193). Some of 
 these salts are obtained by the action of alkali 
 sulphides on Sb^Sj ; but they are better obtained 
 by acting on Sb.^S3 with aqueous solutions of 
 alkali sulphides in presence of sulphur, or with 
 aqueous solutions of alkali polysulphides. They 
 are also obtained by fusing Sb^Sj with alkali 
 sulphides (or with sulphates and earbon) and 
 sulphur. The decomposition, in air, of alkaline 
 livers of antimony also often yields thio-antimo- 
 nates {v. Antimonious sulphide. Reactions, No. 
 15 and 16). The thio-antimonates of the alkali 
 metals are soluble in water, many of the others are 
 insoluble and are obtained from the alkali salts 
 by ordinary double decompositions, the metallic 
 salt solution being added in quantity less than 
 sufficient to decompose the whole of the alkali 
 thio-antimonate. Solutions of thio-antimonates 
 are easily decomposed by acids, even by the 
 COj of the air, with ppn. of SbjSs, and, when 
 exposed to air, of alkali thio-sulphate. The 
 alkali thio-antimonates are not decomposed by 
 heating out of contact with air ; the salts of the 
 heavy metals lose S, and give thio-antimonites. 
 The more important thio-antimonates are those 
 of potassium and sodium. 
 
 Potassium thio-antimonate. 2K3SbSj.9H20 ; 
 slightly yellow deliquescent crystals ; prepared 
 by boiling, for several hours, 1 part S, 6 parts 
 KjCOs, 3 parts CaO, and 20 parts H^O, with 11 parts 
 SbjSj, filtering, and cooling out of contact with 
 air. A salt K3SbSj.KSbO3.5H2O is obtained, in 
 long white needles, by adding cold cone. KOHAq 
 to SbjS,, filtering from 2KH(Sb03)2.5H,p which 
 separates out, and evaporating {v. Schiff, A. 
 114, 302). 
 
 Sodium thio • antimonate NaaSbSi.OHjO 
 
 (known as Schlippe's salt). Prepared by fusing 
 together 16 parts dry Na^SO^, IB parts Sb^S,, 
 and 4-5 parts wood charcoal, dissolving in 
 water, boiling with 2^ parts sulphur, filtei- 
 ing and evaporating; the crystals are washed 
 with very dilute NaOHAq and then with water, 
 and dried quickly at a low temperature. The 
 salt may also be prepared by boiling Na^COjAq 
 with CaO, SKSj, and S. Sodium thioantimonate 
 forms large yellowish monometric tetrahedra ; 
 it dissolves in 2-9 parts HjO at 15°, the solution 
 has an alkaline reaction. The crystals are best 
 kept in contact with their mother liquor to 
 which a little NaOHAq is added ; they decom- 
 pose in air, giving Sb2S3, SbjSa, Na^S, Naj,CO„ 
 and NajSjOj. When the mother liquor from 
 Schlippe's salt is evaporated, crystals of a double 
 salt Na3SbS.,.Na2S2O3.20H2O are obtained. Solu- 
 tion of tartar emetic is decomposed by Na3SbS4Aq 
 thus ; 6CjH,KSbO,Aq + 2Na3SbSjAq = 
 
 6CjHjKNaOj -1- Sb A + SbA -H Sb^Ss. 
 Theotherthio-antimonates are generally obtained 
 from the sodium salt : the best-marked are 
 Ba3(SbS4)j.6H,0 ; Cu3(SbSj2; Pb3(SbSj2; 
 Hg3(SbS4)2 ; AgjSbSj ; a few others are known 
 (e.g. of Cd, Co, Mn, Ni, V, Zn) but they are very 
 easily decomposed, and not many have been 
 obtained in definite forms. M. M. P. M. 
 
 ANTIMONY, Compounds with organic 
 radicles. 
 
 Meferences. — Lowig a. Schweizer, .4. 75, 815; 
 Landolt, J. pr. 52, 385; 57, 134; 84, 330; 
 A. 78, 91; 84, 44; Buckton, C..J. 13, 115; 
 16,17; Lowig, ^.88, 323; 97,322; C.J. 8, 261; 
 BerU, /. pr. 65, 385 ; Scheibler, J. pr. 64, 505 ; 
 Friedlander, J. pr. 70, 449 ; Cramer, Pharm. 
 Cerei. 1855, 465; Hofmann, .4. 103,357; Strecker, 
 A. 105, 306; v. Bath, P. 110, 115; Jorgessen, 
 J. pr. [2] 3, 342 ; Le Bel, Bl. [2] 27, 444 ; 
 MichaeHs a. Eeese, A. 233, 42. 
 
 Tri-methyl-stibine SbMej. Mol. w. 107. 
 (81°). S.G. 15 : 1-523. 
 
 Preparation. — An alloy of antimony (4 pts.) 
 and sodium (1 pt.) is mixed with sand and Mel 
 and distilled. Mel and SbMe, pass over but 
 unite in the receiver to form SbMe,I, which when 
 distilled with an alloy of antimony and potas- 
 sium in a current of COj gives SbMe, (Landolt). 
 
 Properties. — Liquid, smelling of onions, 3I. 
 sol. water ; may take fire in air. Takes fire in 
 chlorine. Reduces salts of silver and mercury. 
 
 Salts.— Unites directly with non-metals. — 
 SbMcjClj: hexagonal crystals, si. soluble in 
 water. Formed also from SbClj and HgMe,. — 
 SbMe3Cl2SbMe30 : octahedra, sol. water. — 
 SbMesBrj. — SbMe3Br2,SbMe30 : octahedra, sol. 
 water. — SbMe3l2 : formed by heating Sb with 
 Mel at 140°.— SbMe3l„SbMe30 : octahedra.— 
 SbMe3S : scales.— SbMe"3(N03)2.—SbMe3S04. 
 
 Tetra-methyl-stibonium salts. SbMeJ. S. 80 
 at 23°. From SbMe, and Mel : six-sided plates. 
 When distilled the vapour (SbMe3 + Mel) takes 
 fire in air. — SbMe^.OH : from moist AgjO and the 
 above. Deliquescent alkaline crystals : absorbs 
 CO2 from air, and expels NH3 from its salts. Pps. 
 baryta from Bal^, also the hydrates of Pb, Oa, 
 Cu, Hg, Ag, and Zn ; only the last pp. is soluble 
 in excess. — SbMCjCl: very soluble hexagonal 
 plates; v. si. sol. ether.- (SbMOjCljaPtCl^: 
 difficultly soluble orange powder ; si. sol. water, 
 insol. alcohol and ether. — SbMCjBr. — fSbMeJ ,S : 
 
294 
 
 ANTIMONY. 
 
 Boluble green powder; oxidises rapidly, — 
 SbMe^NOj [150°] : crystals, t. sol. water, not 
 deoomposed by boiling concentrated H^SO,.— 
 SbMe^SO^H: soluble plates.— (SbMeJ^SO^ 5aq. 
 
 Di-methyl-stlbiue sulphides (SbMe2)2S3 
 [c. iqo°] and (SbMeJjS are formed by passing 
 HjS into an ethereal solution of SbMea that has 
 been oxidised by exposure to air. 
 
 Antimony penta-methide SbMoj. (o. 98°). 
 Formed together with antimony tetra-methide, 
 jSbMeJj (o. 90°), by distilling trimethyl stibine 
 iodide with ZnMe^. Both are oils which do not 
 fame in air. 
 
 Methyl-tri-ethyl-stibonium salts SbMeEtjI. 
 S. 50 at 20°. From SbEtj and Mel. Glassy 
 prisms, sol. alcohol, insol. ether ; the solutions 
 are Isevorotatory. HgCl^ gives a precipitate of 
 SbEtaMelliHglj.— SbMeEt-OH ; from moist 
 AgjO and the iodide, or from the sulphate and 
 baryta. Pps. metallic salts, the hydrates of 
 zinc and aluminium dissolving in excess. — 
 SbMeEtsCl: small needles. — SbMeEt^IHglj. — 
 (SbMeEt3)2C03 : amorphous. — (SbMeEt3).,S04 : 
 [100°], deliquescent, shining, bitter crystals. — 
 (SbMeEt3)2C204: glassy needles, m. sol. water. — 
 SbMeEtaCjOjH : needles, v. sol. water.— The 
 acetate, formate, and hutyrate are crystalline. 
 
 Tri-ethyl-stibine SbEtj. Mol. w. 209. (159°). 
 e.G. IS: 1-324. V.D. 7-44 (calc. 7-18). 
 
 Formation. — 1. From SbCl, and ZnEtj. — 
 2. From EtI and a mixture of sand with an 
 alloy of Sb and potassium. — 3. From SbClj and 
 HgEtj.— 4. By distilling SbEtjI^ with Zu. 
 
 Properties. — Oil, smelling of garlic, v. sol. 
 alcohol and ether. Takes fire in air ; hence it 
 should be kept under water. Decomposes fuming 
 hydrochloric acid with evolution of hydrogen : 
 SbEtj + 2HC1 = SbEtjClj + H.,. When slowly 
 oxidised it forms SbEtaO and SbEt3(SbOJj. 
 Combines directly with S, Se, I, Br, and CI. 
 Dilute HNO3 dissolves it, giving off NO and 
 forming SbEt3(N03)2. In all these reactions 
 tri-ethyl-stibine behaves like a metal. An 
 alcoholic solution of SbEtj shaken with HgO 
 liberates Hg while SbEtjO remains in the 
 solution. 
 
 Tri-ethyl-stibine-oxide SbEt30. 
 
 Formation. — 1. From SbEtjI^ and AgjO. — 
 2. From SbEtjSOj and baryta. — 3. By slow 
 oxidation of an alcoholic or ethereal solution of 
 SbEt3 ; SbEt3(Sb02).^ is formed at the same time, 
 but this differs from SbEt^O in being insol. 
 ether. — 4. By shaking alcoholic SbEtj with HgO. 
 
 Properties. — A syrup, v. sol. water and 
 alcohol, m. sol. ether ; combines with acids and 
 precipitates metals as hydrates from solutions 
 of their salts. If its aqueous solution is free 
 from SbEt3(Sb02)2, no pp. is produced by HjS ; 
 otherwise a pp. of SbEt3(SbSJj is formed. 
 Potassium converts it into SbEtj. 
 
 Tri-ethyl-stibine salts. 
 
 Chloride.— ShEtfil^. S.G.i^: 1-540. Oil, 
 soluble in alcohol. Ppd. by adding HGl to 
 an aqueous solution of the iodide or sulphate. 
 Cono. HjSOj decomposes it, giving off HCl. 
 
 Oa;j/-c;jZoriie.— SbEt3Cl2,SbEt30. From 
 the oxy-iodide and HgCl2. Deliquescent solid. 
 
 Bromide. — SbEtjBrj. S.G. ^i 1-953. 
 Bolidifies at —10°. Insol. water, soL alcohol 
 and ether. Behaves like a metallic bromide. 
 
 Iodide .—SbEtjIj. [71°]. Formed by heating 
 
 Sb with EtI at 140° ; or by adding iodine to an 
 alcoholic solution of SbEt, at —15°. Needles 
 (from ether). Unlike the chloride, it is soluble 
 in water. Potassium removes the iodine thus : 
 SbEt3l2 -f Kj = 2KI -H SbBt3. 
 
 Oxy-iodide. — SbEt3l2,SbEt30. Formed by 
 treating the iodide with NH3 ; or by mixing the 
 iodide with the oxide SbEt30. 
 
 Sulphide. — SbEt3S. From the oxide and 
 HjS or from SbEt3 and S. Soluble in water and 
 alcohol. Its aqueous solutions pp. metals as 
 sulphides from their salts. 
 
 Nitrate.— ShM,(NOs)i. [63°]. Formed by 
 dissolving SbEt3, or its oxide, in dilute HNO3. 
 Ehombohedra, soluble in water. 
 
 Oa!^-wiira<e.— SbEt30,HN03. From the 
 oxy-iodide and AgN03. 
 
 Sulphate.— ShEt^BOt [100°]. From the 
 sulphide and CuSO^. Small prisms, sol. water 
 and alcohol. 
 
 Oxy-sulp hate.—{8l)^%0)2'S.SOi. From 
 the oxy-iodide and AgjSOj. Gummy mass. 
 Tetra-ethyl-stibonium salts. 
 Iodide.— BhEi J., l|aq (and faq). S. (anhy- 
 drous) : 19 at 20°. From SbEtj, water, and EtI 
 at 100°. Hexagonal prisms, sol. alcohol and 
 ether.— SbEt J fHglj.- SbBt^I fHglj. 
 
 Hydrate.— SbM fiU. From moist AgjO 
 and the above. Alkaline syrup. Pps. metallic 
 hydrates from salts : stannic oxide and alumina 
 dissolve in excess. Expels NH3 from its salts. 
 
 Chloride. — SbEt^Cl. Hygroscopic needles. 
 Forms compounds with HgGl2 and with PtCl,. 
 Bromide. — SbEt^BrAq: needles. 
 Periodide. — SbEt4l3. 
 Nitrate. — SbEtjN03: deliquescent needles. 
 Sulphate. — (SbEtJjSOj : deliquescent mass. 
 Oxalate.- (SbEtJjO^O,. 
 Antimony-penta-ethide SbEtj (?). (0. 165°). 
 From SbEtjIj and ZnEt,. 
 
 Tri-isoamyl-stibine S'b(05H|,)s. From an alloy 
 of Sb with K by CsH„I. Fuming liquid, does not 
 take fire in air. 
 
 Oxide.— Sh{C^'H.j,)fi: insoluble resin, solu- 
 ble in alcohol. 
 
 Salts. — Sb(C5H,,)3Clj: oil, heavier than 
 water, soluble in alcohol, ppd. by water. — 
 Sb(G,H„)3Br2 : oil. — Sb(C5H„)3l2 : oil. — 
 Sb(C5H„)3(N03)2: [20°] slender crystals, insoluble 
 in water, soluble in alcohol. — Sb(C5H„)3S04 : oil. 
 Antimony di-isoamyl Sb2(03H„)4 (?). Formed 
 by distilling Sb(C3H„)3. A heavy oil, soluble in 
 alcohol. Does not fume in air, but explodes in 
 oxygen. Its salts are amorphous. 
 
 Tri-phenyl-stibine SbPh3. [48°] (above 
 360°). S.G. 12 1-500. From SbCl, (1 pt.), 
 chloro-benzene (1 pt.) and Na; benzene being 
 used as diluent. Small quantities of SbPhjClj 
 and SbPhjClj are also formed. The benzene 
 deposits crystalline SbPh3 ; this is warmed with 
 alcohol containing HCl, which dissolves SbPh-jClj, 
 and the residual SljPhj is converted into 
 SbPhjClj by chlorine. The latter is reduced by 
 alcoholic ammonia and hydrogen sulphide: 
 SbPhjClj + H3S = SbPh, + 2HC1 + S. 
 Properties. — Colourless triclinio tables a:b:c 
 = -697 : 1 : -889. a = 100° 38'. = 103° 37'. 
 7 = 75° 25' ; si. sol. alcohol, v. b. sol. ether, ben- 
 zene, glacial HOAc, CSo, chloroform, and petro- 
 leum ; insol. water and aqueous HCl. It does not 
 decompose HCl; but it combines directly with 
 
ARABIC ACID. 
 
 395 
 
 halogens ; it reduces ouprio, to cuprous, chloride. 
 With mercuric chloride it reacts as follows : 
 
 SbPh, + SHgClj = SbCl, + 3HgPhCl. 
 Fuming HNO3 forms SbPhjINOs)^. 
 
 Salts.— SbPhjClj [143°] : long thin needles; 
 not affected by water ; insol. light petroleum, 
 b1. sol. ether and alcohol, v. sol. benzene and OS,. 
 — SbPhjErj. [216°1. — SbPh,!,. [153°] ; white 
 tables. — SbPh3(0H)2. [212°]. From the bro- 
 mide and alcoholic KOH. Amorphous powder, 
 sol. glacial HOAc and reppd. unaltered by water. 
 Insol. ether, v. e. sol. alcohol. Converted byHCl, 
 HBr, or HI into haloid salt.— SbPh3(N03)2. 
 [156°]. Insol. water, sol. alcohol. 
 
 Antimony di-phenyl chloride SbPh^Cljaq. 
 [180°]. Obtained as a by - product in pre- 
 paring SbPh3. Needles, insol. water, sol. hot 
 dilute HCl, v. e. sol. alcohol. Alcoholic NHj 
 converts it into Ph2SbO(OH), a white powder, 
 insol. water, ammonia, alcohol, ether, or 
 Na^COjAq, but sol. NaOHAq and glacial 
 HOAo. 
 
 ANTIFYSINE v. Oa;i/-(ii-METHYL-QniNiziNE. 
 
 APHROD.ffi;SCIN. A substance contained 
 in the cotyledons of the horse-chestnut (v. 
 ^soiNio acid). 
 
 APIIIJ'. When common parsley (Apium 
 petroselinum) is extracted with boiling water 
 the filtrate gelatinises on cooling. The jelly is 
 dried at 100° and extracted with alcohol, and 
 the alcohol poured into water. The operation 
 of dissolving in alcohol and ppg. with water is 
 repeated several times, and the apiin finally 
 crystallised from alcohol, with stirring. Apiin 
 also occurs in parsley seed ; if this is boiled with 
 water, apiol distils over, while apiin separates out 
 from the residue. 
 
 Properties. — Needles ; si. sol. cold water, v. 
 sol. hot water, separating again as a jelly ; v. 
 Bol. alcohol ; insol. ether. Its solution in boil- 
 ing water gives a blood-red colour with FeSO,. 
 Gives picric acid with HNO3 ; and phloroglucin 
 by potash fusion. 
 
 Apigenin CisHioOj. Boiling dilute H^SOj 
 splits up apiin into apigenin and glucose : 
 C„H3,0,5 + H,0 = C„H,„05 -H 2C,H„0,. 
 Crystallises in plates (from alcohol). It sublimes 
 near 294°. SI. sol. hot water, v. sol. alcohol, 
 insol. ether. Potash fusion gives phloroglucin, 
 protocatechuio acid, ^-oxybenzoio acid, and 
 oxalic acid. 
 
 References. — Bump, Buchner's Bepert. f. 
 Pharm. 6, 6 ; Braconnot, A. Ch. [3] 9, 250 ; v. 
 Planta a. Wallace, A. 74, 262 ; Lindenborn, B. 
 9, 1123 ; V. Geriohten, B. 9, 1121 ; Whitney, Ph. 
 [3] 10, 585. 
 
 APIOL CijH^O^. [30°]. (0. 300°). Extracted 
 by alcohol from parsley seeds (v. Geriohten, B. 
 9, 1477). Needles ; insol. water. Alcoholic 
 KOH converts it into two crystalline bodies. 
 [54°] and [114°]. The essential oil obtained by 
 distilling parsley seeds with water contains apiol 
 but consists chiefly of a terpene, (160°-164°), 
 S.G. ia -865, [a] -30-8°. It has a strong smell 
 of parsley. A small quantity of a hydrochloride, 
 [116°], can be got from it. 
 
 References. — Lowig a. Weidmann, P. 46, 53 ; 
 V. Gerichten, B. 9, 258, 1121, 1477 ; Pabitzky, 
 Braunschw. Ameiger, A.D. 1754 ; Blanchet a. 
 Sell ; A. 6, 301 ; Martins, A. 4, 267 j HomoUe a. 
 
 Joret, J. Ph. [3] 28, 212; and the referencea 
 under Apiin. 
 
 APO-. Compounds beginning with this prefix 
 are described under the wordd to which it ia 
 prefixed. 
 
 APOCYNIN. The root of Apocynum Oanna- 
 6mm contains amorphous resinous apocynin, 
 sol. alcohol and ether, v. si. sol. water, and a 
 glucoside, apocynein (Schmiedeberg, Ph. [3] 
 13,942). 
 
 APOPHYLENIC ACID. The methylo- 
 hydroxide of cinchomeronio acid ; v. Pyeidinb 
 
 »I-0AEEOXYLIO ACID. 
 
 APPLES. The artificial essence of apples 
 contains iso-amyl iso-valerate dissolved in 
 rectified spirit (Hofmann, A. 81, 87). 
 
 APRICOTS. The artificial essence of apricots 
 contains isoamyl butyrate and isoamyl alcohol. 
 
 AQUA BEGIA v. Chlorhydkio acid. 
 
 AQUA VIT.ffi. Alcohol. 
 
 ARABIC ACID (Arabin) C,.,H,,0„ ; nC^H.^O^ 
 (Neubauer, J. pr. 62, 193; 71, 255) ; CisH^Ai 
 (Scheibler, B. 6, 612); Oa,H,„0,j (O'Sullivan, 
 C. J. 45, 41). 
 
 Occurrence. — It is a constituent of probably 
 all Isevorotatory gums, and has been isolated 
 from Levantine, Senari, Bast Indian, Senegal, 
 and Turkey, gum ; these gums contain also, as 
 a rule, other acids different from, but closely 
 allied to arable acid (O'Sullivan). It exists in 
 sugar-beet (Scheibler), and in the extract of yeast 
 obtained by boiling water (Schiitzenberger, BL 
 [2] 21, 204 ; C. R. 78, 493). The beet gum is 
 probably related to arable acid, but there is no 
 evidence that the yeast-extract body belongs to 
 the arabin group. Many gum-like constituents 
 of seeds and roots are referred to as gums, but 
 the great bulk of them obviously hold no relation 
 to arable aeid. It is found in certain animals 
 (Stadeler, A. Ph. Ill, 26). 
 
 Formation.— It is a product of the action ol 
 sulphuric acid on algsB-muoilage (Brown, Ed. 
 Ph. I. 26,409); on quince, linseed, and flea-wort 
 mucilages, cellulose being at the same time pro-, 
 duced (Kirchner a. ToUens, A. 115, 205); and 
 on metagummic acid (Fr^my, C. R. 50, 12.3). 
 Cellulose is transformed into gum in planls 
 (Mercadante, G. 5, 408). In none of these cases 
 have we any information as to the character of 
 the gum produced. 
 
 Preparation. — The Isevorotatory gums are 
 principally potassium, magnesium, and calcium 
 salts of arable or allied acids ; they contain 
 from 12 to 18 p.c. water, and yield 27 to 30 p.c. 
 ash consisting almost wholly of carbonates of 
 these metals. Any one of these gums is dis- 
 solved in the least possible quantity of water, 
 the solution is allowed to stand, and, when 
 clear, decanted from any insoluble matter. To 
 the clear liquid twice or thrice as much HCl 
 as is sufficient to convert the bases into chlorides 
 is added, and the gum-acid or acids are precipi- 
 tated by a moderate excess of alcohol. It the gum 
 contains only arable acid, the whole pp. can be 
 purified as is described below when dealing with 
 one of the fractions ; but if, as is very frequently 
 the case, other allied-acids are also present, it ia 
 necessary to have recourse to fractional pre- 
 cipitation to isolate the arable acid. It ia 
 found in the fractions least soluble in dilut'O 
 alcohol, and may be obtained as follows ; — The 
 
29G 
 
 ARABIC ACID 
 
 curdy pp., produced by excess ot alcohol in 
 presence of HCl, is well washed with spirit, and 
 then pressed as free from it as possible. It is re- 
 dissolved in warm water, care being taken to avoid 
 heating for any length of time, because even 
 the small quantity of HCl retained by the pp. has 
 a tendency on heating even for a short time to 
 decompose the arabic acid, as will be described 
 below. The solution is cooled, and alcohol 
 gradually added with continual stirring. In 
 this way, the liquid can be made milky without 
 the formation of a pp. ; from this ' milk ' the 
 acid or acids can be precipitated in successive 
 fractions by the addition of HOI in carefully 
 graduated quantities. If 4 or 5 fractions are 
 obtained, one or more of them is arable acid. 
 Each fraction is freed from ash by repeated 
 precipitation from aqueous solution with alcohol 
 in the least possible excess in presence of HCl, 
 and from HCl by repeated preoipitAtion from 
 concentrated solution by the rapid addition of 
 strong alcohol, whereby the production of a 
 ' milk ' is obviated. The fractions thus purified 
 are treated with alcohol (S.G. -81) to render 
 them friable, rubbed down to a powder, filtered 
 out, pressed, and dried over sulphuric acid. 
 Thus prepared they are white, friable bodies, 
 easily soluble in water. If in this state they 
 are exposed for any length of time to a tem- 
 perature ot 100°, they are converted into the 
 meta modifications (meta acids) which are in- 
 soluble in water and only swell up to jelly-like 
 masses when treated with it. If, however, they 
 are previously dried i;i a vacuum over sulphuric 
 acid until the weight becomes constant, they can 
 then be dried at 100° without becoming insoluble. 
 The fraction or fractions which are found to 
 have an optical activity, [o]j = —26° to —23°, 
 and which, when again divided, yield fractions 
 each of which has the same activity, consist of 
 arabic acid. 
 
 Properties. — Arabic acid, when slowly dried 
 out of syrupy solutions, on glass plates, is a 
 brittle, transparent, colourless, glassy body, solu- 
 ble in water. During the drying process, espe- 
 cially if a little mineral acid is present, the 
 acid is frequently converted into the meta modi- 
 fication. Solutions of the body are strongly 
 acid to litmus paper, and have a sharp acid 
 taste; they completely neutralise solutions of 
 the alkalis and alkaline earths, and decompose 
 carbonates. The salts of the alkaline earths 
 are precipitated out of solution by alcohol ; those 
 of the alkalis are not precipitated under the 
 same conditions, but yield peculiar milky or 
 opalescent solutions from which arabic acid, 
 with some of the alkaline salt, is precipitated on 
 the addition of stronger acids. BaSOj, PbS, and 
 other sulphides, and some hydrates precipitated 
 ill solutions of arabic acid, cannot be filtered out, 
 but pass, in greater part, through the filter. 
 Fine animal charcoal is carried through in the 
 same way (C.O'S.). Gum arable prevents the pre- 
 cipitation of the alkaloids by phosphomolybdic 
 acid, potassium-mercury iodide, and tannin 
 (Lefort a. Thibault, J. Ph. [5] 6, 169). These 
 are properties common to all the gum acids. 
 The defining characters of arabic acid are its 
 optical activity, viz. [o]j = —26° to —28°, for 
 solations containing 5 to 6 grams dry substance 
 in 100 CO., and the composition of its neutral 
 
 barium and calcium salts ; in the dry stale, the 
 former contains 6'0 p.c. BaO and the latter 
 2-28 p.c. of CaO (O'S.). Solid gum roasted with 
 oxalic acid yields metagummic acid (Fr6my),thi3 
 is dissolved by solutions of the alkalis and alka- 
 line earths with the reproduction of arabic acid 
 (v. Bhem. D. P. J. 216, 539). Gum arable and 
 tragacanth are rendered insoluble by potassium 
 bichromate and light (Bder. J. pr. 19, 299). 
 Gum, even in small quantities, injected into 
 the blood diminishes the elimination of urine, 
 large doses completely stop the secretion, with 
 a marked increase of blood pressure (Bichet a. 
 Montard-Martin, O. B. 90, 88). 
 
 Reactions. — 1. Heated withmoderately strong 
 nitric acid, arabic acid yields muoic (v. Kiliani, 
 B. 15, 34), saccharic, oxalic, and tartaric (Liebig) 
 acids ; with fuming nitric acid it yields substitu- 
 tion products. — 2. Gum heated in sealed tubes 
 with bromine yields a colourless or yellowish 
 liquid, probably C,2H2„0,„Brj, which, when treated 
 with silver oxide, load oxide, or caustic soda, 
 is converted into isodiglycolethylenio acid, 
 C|2Hj„0,2 (Barth a. Hlasiwetz, A. Ch. Pharm. 
 122, 96). It is possible some of the decomposi- 
 tion products of arabic acid would yield the 
 same results. -3. Gum arabic or arabin when 
 heated to 150° with 2 parts acetic anhydride 
 yields tetraoetyl-diarabin (?) C,2H„(C2H30)iO,|,; 
 and, when heated to 180' with 6 to 8 parts of 
 the anhydride, a body having the composition 
 C,2H,5(G2H30)50,|i; these acetyl derivatives are 
 white amorphous powders (Sohiitzenberger a. 
 Naudin, A. Ch. [4] 21, 235). These bodies are 
 certainly not derived from arabic acid as a 
 whole, but from some one of its decomposition 
 products (C. O'S.). — 4. Pepsin, in dilute HCl solu- 
 tion, acts on dextrorotatory gum acid, arabiuose 
 being amongst the products ; pancreatin has no 
 action (Pudakowski, B. 11, 1072).— 5. (a) Gum 
 arabic left for some time in contact with 
 sulphuric acid is converted into dextrin (I) and, 
 on boiling, yields a sugar probably identical with 
 galactose (Berthelot, C. 0. 21, 219). (6) Strong 
 sulphuric acid converts a strong solution of 
 gum in a few hours into metagummic acid ; but 
 gum arabic freed from lime by oxalic acid is not 
 transformed in the same way (Pr6my). (c) Pul- 
 verised gum arabic, triturated with strong sul- 
 phuric acid, yields sulphogummic acid and a 
 peculiar gum resembling that produced from 
 linen by the action of sulphuric acid (Braconnot) 
 and not capable of fermenting with yeast (Gu^rin- 
 Varry). (d) Arabic acid, digested with dilute 
 sulphuric acid, yields a crystallisable sugar, a 
 non-crystallisable one, and an acid the barium 
 salt of which is insoluble in alcohol: gums from 
 different sources yield these bodies in various 
 proportions, some varieties yielding scarcely 
 any of the crystallisable sugar (Scheibler, B. 
 6, 612). (e) A solution containing 30 grams 
 arabic acid (pure), 100 c.o. water, and 2 grams 
 sulphuric acid, yields, on digestion at 100° for 
 15 minutes, at least two sugars and a new acid 
 the Ba salt of which is insoluble in alcohol : the 
 following equations represent the change : — 
 I. Cg8H„jO,4 -^ HjO = CmHisjOj, +GJi,fii 
 arable acid a-arabinosic acid a-arabinoae 
 
 n. G,,n,,,Oe,+T^O= C„H,„C„ -t-C^H.^O. 
 
 jS-arabiuosio acid o- or ^-arabinose 
 
 III. C„H|320tJ4 + H30= CjjH^gOsp +CaHi20j 
 
 T'-arabinosio ooid ^-«mblno3e. 
 
ARALEIN. 
 
 397 
 
 Ooutinued digestion produces changes that 
 may be represented as follows:— 
 III. IV. V. VI. VII. and VIII. 
 C„H,,,0„4 + 9H,0 = C«H, A, + 60,H„0, 
 
 6-arabinosio acid, jS-y-^-arabiuose. 
 On further digestion we get : 
 
 IX. C^,Hs,03,+ H,,0 = C35H^O,2 + C,H,A 
 
 i-arabinosic acid 5-arabinose (?) 
 
 X. Cj^H^aOj, + H^O = G,,B.,fi„ + CeH,,0„ 
 
 jc-arabinosic acid, 6-arablnose (?) 
 
 XI. O^sH^sOj, + H,0 = G.Ji,fl^^ + C,H„0„ 
 
 A-arabiao3lo acid S-arabinose (?) 
 
 This last acid is very stable, resisting the 
 Botion of a boiling 3 to 4 p.e. solution of sul- 
 phuric acid for a considerable time (O'Sullivan, 
 C. J. 45, 41). a-arabinose is not yet fully de- 
 seribed ; j8-arabinose ' is Soheibler's arabinose, 
 7-arabinose is probably identical with galactose, 
 and the remaining sugar or sugars are imper- 
 fectly described. These reactions convey some 
 idea of the constitution of the gums of the 
 arabin group, i.e. of those which are salts of a 
 gum-acid with alkaline or alkaline-earthy bases, 
 and enable us to understand some of the differ- 
 ences observed in their properties. Those 
 bodies vary considerably in optical activity ; this 
 is due (a) to the varying proportions of different 
 closely related acids they contain. O'Sullivan 
 found the acid of some samples of gum arable 
 to consist almost wholly of arable acid, whilst 
 others contained also a-arabinosio acid, [o]j = 
 -36°, and an acid (CssHisjOjj), [a]j = -23°, with 
 a CjHijOs group more than arable acid, (b) To 
 the character and position of the CbHijOj group 
 in the acid from the C.^jHigO^j body upwards. 
 Iviliani {I.e.) shows that different varieties of 
 gum yield, when oxidised with HNO,, proportions 
 of mucic acid varying between 14-3 and 38'B 
 p.c, thus indicating a difference in the number 
 of galactose (7-arabinose) -yielding groups they 
 contain (see also Scheibler). And (c) possibly to 
 the structure of the C^-JH^fi^ group itself. The 
 gums, too, vary much in the character of the 
 solutions they yield (Gm. 15, 194) ; some give a 
 thin syrupy solution, others a thick and jelly- 
 like one ; this is due to the varying proportion 
 of the acid naturally converted into the meta 
 modification — the gums which yield the thinnest 
 solutions are those which contain the greatest 
 amount of ash. Gums from the same source 
 have not always the same optical activity ; 
 Pcheibler found the beet gum of one season -I- , 
 and of another — ; Kiliani states that East Indian 
 gum, and gum arable elect, are + , the samples 
 of these gums examined by O'Sullivan were — ; 
 the sample of Australian gum examined by the 
 former was + , that by the latter, inactive. From 
 this it would appear that the same plant does 
 not produce the same gum in every season, but, 
 on the whole, it is fairly certain that the acids 
 of all the gums ave constituted in the same way 
 as arabic acid described above. 
 
 Combinations. — The arabic salts of the alka- 
 line earths are prepared by exactly neutralising 
 moderately strong solutions of the pure acid 
 with clear solutions of the earth the salt of 
 which is required, precipitating with alcohol, 
 
 ' According to Kiliani (S. 20, 339a, 1233) the formula 
 of arabinose is 0,H„0, ; ehould this prove to be so, the 
 formula of arabic acid and of the arabinosic acids mnBt be 
 diminiahed by a CH.O gronp for eTery moleoale of 
 aratrinose-yielding group they oontahi. 
 
 treating the pp. with strong alcohol until it 
 admits of being powdered, collecting the powder 
 on a filter, pressing, and drying over sulphuric 
 acid. The Ba salt contains C8„Hn„0„BaO (6-0 
 p.c. BaO) and the CaO salt, Cg|,H„26„CaO (2-28 
 p.c. CaO). When the syrupy solutions of these 
 salts are allowed to dry spontaneously they 
 yield glassy, transparent masses, like natural 
 gums : the salts of the arabinosic acids yield 
 similar bodies. C. O'S. 
 
 ABABITE CsHjoOs which is probably 
 CH,(OH).CH(OH).0H(0H).CH(0H).CH2(0H). 
 Penta-oxy-n-pentane. [102°]. Obtained by 
 reduction of arabinose with sodium-amalgam, 
 keeping the solution carefully neutralised. 
 Small prisms or needles. V. sol. water and hot 
 90 p.e. alcohol, v. si. sol. cold alcohol. Sweet taste. 
 Does not reduce Fehling's solution. Does not 
 lose water at 100° (diff. from sorbite) (Kiliani, 
 B. 20, 1283). 
 
 ABABONTO ACID v. Tetba-oxy-valeeio Aoro. 
 
 ABACHIC ACID C^B.^„0^. Mol. w. 312. [75-5°]. 
 AracMdic acid. 
 
 Occurrence. — 1. In the oil from the ground 
 nut Arachis hypogaa, from which it is obtained 
 after saponification (Gossmann, A. 89, 1). — 2. In 
 butter (Heintz, P. 90, 146).— 3. As glyceryl 
 ether in the fruit of Nephelium lappaceum (Oude- 
 mans, J. pr. 99, 407). 
 
 Formation. — 1. By potash-fusion from bras- 
 sidic acid (Goldschmiedt, J. 1877, 728).— 2. From 
 stearic acid by converting it into the correspond- 
 ing alcohol, O^HssCHjOH, and iodide CnHjsCHjI. 
 The latter gives octadecyl aceto-acetio ether 
 when treated with sodio-aceto-acetio ether, and 
 alcoholic KOH thence produces arachic acid 
 (Schweizer, Ar. Ph. [3] 22, 753). 
 
 Properties. — Small shining plates ; v. sol. 
 boiling alcohol, and ether ; insol. water. Gives 
 a nitro-, [70°], and an amido- [59°], arachic acid. 
 
 Salts. — (Scheven a. Gossmann, A. 97, 257). 
 AgA' : prisms (from alcohol) — CuA'^ : needles 
 (from alcohol) — BaA'^ : hardly soluble in alcohol. 
 — SrA'2 — MgA'2 : crystalline powder (from alco- 
 hol).— KA': usually gelatinous. 
 
 Methyl ether. [55°]. Scales (Caldwell, 
 A. 101, 97) ; [53°] (Schweizer). 
 
 Ethyl ether. [49-5°]. (296°) at 100 mm. 
 
 Iso-amyl ether. [45°]. Scales. 
 
 Arachins. Prepared artificially by heating 
 arachic acid with glycerin (Berthelot, A. Ch. [3] 
 47, 35S) ; they are insol. ether. Di-arachin 
 C3H5(OH)(OC2„H3,0)2 melts at [75°]. 
 
 Arachyl chloride CjoHsjO.Cl. [67°]. 
 Unstable (Tassinari, B. 11, 2031). 
 
 Arachamide CjjHjjO.NH^. [99°]. Prisms 
 grouped in stars ; insol. water, sol. hot alcohol 
 (Gossmann a. Scheven, A. 97,, 262). 
 
 Acetio-arachic anhydride 
 Cj„H350.0.Ac. [60°]. From AcCl and potassium 
 arachate. Scales (from ether) (T.). 
 
 Valeric-arachic anhydride 
 0,.H33O.0.C,H3O [68°] (T.). 
 
 ABALEIN. The bark of Aralia spinosa con- 
 tains a tannin which gives a green colour with 
 Fe^Cla, and a gluooside called aralein. The latter 
 is a neutral, light-yellow substance, sol. water 
 and alcohol, insol. ether, benzene, and CHOI,. 
 Gives no pp. with lead acetate, HgCl^, or PtCl,. 
 Boiling dilute HOI converts it into white arali- 
 retin, insol. water (Holden, Ph. [3] II, 210). 
 
208 
 
 ARBOL-A-BREA RESIN. 
 
 AEBOL-A-BHEA EESIN. The prodnot of a 
 tree (Ganarium albwn) growing inthePhilippine 
 Islands (Maujean, /. Ph. 9, 45 ; Bonastre, J. Ph. 
 10, 199). Baup (/.^. 55, 83) finds four crystal- 
 line substances in it : A m y r i n [174°] ; B r e i d i n, 
 S. -39 3120°; Brein [187°]; and Bryoidin 
 [135°]. 
 
 ARBUTIN C.jH.jO, iaq. [166°]. 
 
 Occurrence. — Together with methyl-arbutin 
 in the leaves of the red bearberry, Arctosta- 
 phylos Uva Ursi (Kawalier, 4. 82, 241; 84, 356), 
 and in the leaves of a species of winter-green, 
 Pyrola umbellata (Zwenger a. Himmelmann, 
 A. 129, 203). 
 
 Preparation. — The aqueous infusion of the 
 leaves is ppd. by lead acetate, excess of lead re- 
 moved by HjS, the filtrate evaporated and the 
 arbutin extracted and crystallised by a mixture 
 of ether (8 pts.) and alcohol (1 pt.). The pro- 
 duct is a mixture of arbutin and methyl- 
 arbutin, which can be separated by crystallisa- 
 tion from water (H. Schiff, G. 11, 99; 13, 538; 
 A. 221, 365 ; cf. Habermann, M. 4, 753). 
 
 Properties.— "Long glistening needles which 
 melt at 165°, but, on second fusion, at 187° (H. 
 Schiff, B. 14, 304 ; A. 206, 159). V. sol. alco- 
 hol and boiling water, v. si. sol. ether. Its 
 aqueous solution gives no pp. with lead acetate 
 or subacetate. Does not reduce alkahne cupric 
 solution. Dilute Fe^Cl, gives a blue colour. 
 
 Reactions. — 1. Split up by emulsin or by boil- 
 ing dilute H2SO4 into hydroquinone and glucose 
 (Streoker, A. 107, 229).— 2. H^SO, and MnO^ 
 form quinone. — 3. Converted by Ag20 into water 
 and di-arbutin, an extremely soluble syrup, 
 whence arbutin can be recovered by reduction 
 with Zn and H^SOj (Schiff, A. 154, 244).— 4. 
 Chlorine passed into an aqueous solution forms 
 di-, and tri-chloro-quinones (Strecker, A. 118, 
 295). 
 
 Acetyl derivative C,2H,,AojO,. Plates 
 or needles (from alcohol), insol. water. 
 
 Benzoyl derivative OiaH^Bz^O,. Crystal- 
 line powder, si. sol. alcohol. 
 
 Di-nitro-arbutin C^^^^I^Sii0^fi,. Golden 
 needles (from water) ; insol. ether (Hlasiwetz, 
 a. Habermann, A. 177, 343). Gives an orange 
 pp. with lead subacetate. Boiling dilute H2SO4 
 gives di-nitro-hydroquinone. Converted by AcjO 
 into C,fi^ka^(^0.,)fi,. 
 
 Methyl-arbutin C,^,fi, i.e. 
 C„H,0(OH)j.O.C,H,.OMe.[169°] (Michael); [175°] 
 (Schiff). Occurs in nature associated with 
 arbutin. Formed synthetically by the action of 
 acetochlorhydrose upon potassium hydroquinone 
 methyl ether, KO.Gja.,.OMe (Michael, Am. 5, 
 178; B. 14, 2097). Also from crude arbutin by 
 converting the free arbutin into methyl-arbutin 
 (by Mel and KOH) or into benzyl-arbutin (H. 
 Schiff, G. 12, 464 ; A. 221, 366). 
 
 Properties. — Colourless silky needles, with 
 bitter taste. Contain aq and melt at 169° 
 (Michael); contain faq and melt at 175° (Schiff). 
 Sol. water and alcohol, v. si. sol. ether. Gives 
 no blue colour with FejClj. 
 
 Benzyl-arbutin C^^fi, i.e. 
 PhCH,0.C„H,0.C,H„05 aq. [161°]. S. -19 at 23°. 
 From PhCHjiSr, commercial arbutin (containing 
 methyl-arbutin), and KOH in boiling alcohol. 
 Excess of KOH is removed by COj, and after 
 evaporating and adding water, benzyl-arbutin 
 
 is ppd. while methyl-arbutin remains in solution. 
 Arborescent needles. Soluble in boiling water, 
 very soluble in alcohol. Does not reduce 
 Pehling's solution, except after short boiling 
 with HjSOj which splits it up into glucose and 
 benzyl-hydroquinone. Gives on nitration yellow 
 needles which are benzyl-nitro-arbutin, 
 C,sH2,(N02)0„ [143°], split up by dilute H^SO, 
 into glucose and benzyl-nitro-hydroquinone 
 (Schiff a. Pellizzari, A. 221, 365). 
 
 Isoamyl-arbutin. From the mixture of arbu- 
 tin and methyl-arbutin by amyl bromide and 
 NaOH (S. a. P.). Needles. On decomposition 
 gives iso-amyl-hydroquinone and glucose. 
 
 ABCHIL or Orseille is a purple dye obtained 
 from various lichens (Boccella, Lecanora, and 
 Variolaria) containing acids {erythric, lecanoi'ic, 
 &o.), which on decomposition yield orcin (g. v.) 
 which is converted by air and ammonia into red 
 orcein. When K2CO3 orNajCOj as well as am- 
 monia is added to the lichens litmus is produced. 
 
 ABGININE OsHuN^Oi,. Easily soluble in 
 water; reacts alkaline. Occurs to the extent 
 of about 3-4 p.c. in the young shoots of the 
 lupine (J,v/pinus luteus). The shoots are ex- 
 tracted with water ; tannin and lead acetate are 
 added to the extract ; the filtrate is acidified with 
 HjSOj, again filtered, and ppd. with phospho- 
 molybdic acid; the pp. is washed and treated 
 with cold milk of lime, and the solution of the 
 base finally neutralised with HNO3 and evapo- 
 rated to crystallisation. 
 
 Salts. — B'HNOsiaq: slender white soluble 
 needles ; with phospliomolybdic acid it gives a 
 white pp. soluble in hot water ; with picric acid 
 a yellow crystalline pp. is formed on standing. 
 — B'HCl : large crystals. — B'jCu(N03)2 3aq : 
 formed by heating a solution of the nitrate with 
 cuprio hydrate ; dark-blue prisms, si. sol. cold 
 water (Sohulze a. Steiger, B. 19, 1177). 
 
 ABGOL, Crude acid potassium tartrate de- 
 posited from wine. 
 
 ARGYE^SCIN C^jH^Oij. A glucoside in 
 the cotyledons of the horse-chestnut. Minute 
 tables (from dilute alcohol). Split up by dilute 
 HCl into argyrsBscetin C^^'B-^fi^ and glucose. 
 Potash produces propionic acid and sescinic acid 
 (g. V.) (Eochleder, J.pr. 87, 1 ; 101, 415). 
 
 AEIBINE C^aHjjN,. S. 12-9 at 23°. A base 
 extracted by dilute H^SOi from the bark of 
 Arariba rubra, the solution being treated with 
 lead acetate and the base dissolved in ether, from 
 which it separates as anhydrous pyramids or 
 (with 8 aq) as four-sided prisms. V. sol. water 
 and alcohol, m. sol. ether (Eieth a. Wohler, A. 
 120, 247). Salts.— B"2HCl.—B"H,PtCl,.— 
 B"H2S0^.— B" 2H2SO,. 
 
 AEICINE CjsHjjNjO,. [188°]. S. (ether) 
 5 at 18°. ' Cusconine,' Ginchovatime. Yellow 
 Cusco bark contains -24 p.c. aricine and '37 p.c. 
 cusconine. Occurs also in bark of cinchona 
 cuprsea (Hesse, Ph. [3] 12, 517). Prisms (from 
 dilute alcohol) ; insol. water, v. e. sol. chloro- 
 form, m. sol. ether, v. si. sol. alcohol. Solutiona 
 are not fluorescent. LsBvorotatory in alcoholio 
 or ethereal solutions ; its solution in dilute 
 HCl is inactive. In a 1 p.c. ethereal solution 
 [a]D=_94-8°; in a 1 p.c. alcoholic (97 p.c.) 
 solution [o]d = — 54°. Aricine is turned dark 
 green by cono. HNO3. Bleaching-powder and 
 NH3 only give a yellowish colour. 
 
AROMATIC SERIES. 
 
 3i^ 
 
 Salts. — B'HCiaaq. — B'^nCl^5a.q. — 
 BHL — B'HNOa. — B'jH^SO^: slender needles, 
 m. sol. cold water. — B'H^SO, : small prisms, v. 
 b1. sol. cold water. — B'HOAc 3aq : grains, v. si. 
 sol. cold water.— B'HjCaO, 2aq : white prisms, 
 quickly changing to rhombohedra, S. •049, si. 
 Bol. hot alcohol. — B'HSCy. — Salicylate 
 B'0,H„03 2aq. 
 
 iJe/crewces.— Pelletier, A. Ch. [2] 42, 330; 
 51, 185 ; Pelletier a. Corriol, J. Ph. [2] 15, 575 ; 
 Leverkohn, Bepert. f. Pharm. 33, 357 ; Manzini, 
 J. Ph. [3] 2, 95 ; Howard, Ph. [3] 5, 908 ; Hesse, 
 A. 166, 259 ; 181, 58 ; 185, 321 ; 200, 303. 
 
 ARNICIN CjoHjjO, {?). An amorphous sub- 
 stance present in the root, leaves, and blossoms 
 of Arnica montana (Walz, N. Jahrb. Pharm. 
 13, 175 ; 14, 79 ; 15, 329). 
 
 AROMATIC SERIES. Substances whose mole- 
 cules contain a benzene nucleus are said to 
 belong to the aromatic series. 
 
 Elements attached to a carbon atom belong- 
 ing to the benzene nucleus are more firmly 
 fixed than when attached to a carbon atom not 
 in that nucleus : in the former case the deriva- 
 tive (called an eso derivative) has the character 
 of a derivative of benzene, in the latter case the 
 derivative (called an exo derivative) behaves like 
 a fatty compound. Thus ea;o-chloro- toluene 
 (benzyl chloride) CsHjCH^Cl behaves like ethyl 
 chloride, being readily converted into an alcohol, 
 amine, or cyanide, by treatment with KOH, NHj, 
 or KCN, respectively; while eso-chloro-toluene, 
 CjHjCl.CHj, is not affected by these reagents. 
 
 It must, however, be added that the ease with 
 which a given atom or radicle in the molecule 
 of an aromatic compound may be displaced 
 depends not only upon its position in relation to 
 the carbon atoms but also upon the existence 
 and position of other elements or radicles in the 
 molecule. Thus o- and p-, but not m-, chloro- 
 nitro-benzene are converted by hot aqueous 
 potash into nitro-phenols, and by NH, into 
 nitro-anUines ; while chloro-phenols and chloro- 
 benzene sulphonic acids are converted into di- 
 oxy -benzenes by potash-fusion. 
 
 Halogens acting upon cold hydrocarbons in 
 the presence of carriers (such as I) enter the 
 benzene nucleus, but when acting alone upon 
 hydrocarbons at 100° or upwards they enter a 
 side chain (exo position). Direct sunlight has 
 the same effect as elevation of temperature, but 
 its effect is entirely counteracted by the presence 
 of iodine (Schramm, B. 18, 606). Halogens 
 attack a benzene nucleus that already contains 
 hydroxyl, amidogen, or SOjH, with much greater 
 vigour than when its carbon atoms are united 
 only to hydrogen and carbon. 
 
 Cone. HNOj and cone. HjSO, attack aromatic 
 compounds, NO^ and SOgH displacing H in the 
 nucleus ; they do not act upon fatty compounds 
 in this way. 
 
 The constitution of the molecule of benzene, 
 and the methods by which the relative position 
 of elements or radicles in the molecules of its 
 derivatives have been determined will be dis- 
 cussed in another article, v. Benzeke. 
 
 Laws of Substitution. — I. When one of the 
 following radicles has displaced one of the atoms 
 of hydrogen in the benzene molecule, forming 
 the compound CbHjA, any new group on enter- 
 
 ing will take up a position meta to A. Here A 
 may be CO^H, SO3H, or NO2, and probably also 
 CN, CHO, SOjPh, and CO.OH3 (Hubner, B. 8, 
 873 ; Nolting, B. 9, 1797 ; cf. Armstrong, C. J. 
 51, 259 ; Morley, O. J. 51, 579). 
 
 II. If in a substituted benzene, CeH^B, the 
 substituting element or radicle be not one of the 
 preceding, then any new group on entering will 
 take up an ortho or a ;para position: usually 
 chiefly p with a little o. Examples of B are 
 NHj, NHAc, OH, CI, Br, I, CH, and all chains 
 of carbon atoms except such as begin with CO. 
 
 These laws tell the chief product of the 
 substitution; small quantities of isomerides at 
 variance with these laws may also be formed. 
 
 The radicles that induce meta substitution 
 are all composed of an element (N, C, or S) 
 united to a chlorous group ; CCI3 is also a radicle 
 of this kind, and it gives a m-nitro-derivative, 
 but it also gives a ^-chloro-derivative. 
 
 The radicles that induce ^ or substitu- 
 tion are either single elements, or elements 
 united to basylous elements or groups. The 
 radicles CHjCl and CHCl^ are intermediate in 
 character ; the latter appearing to resemble 
 CCI3, the former resembling CH3. Armstrong 
 points out that the radicles producing m deriva- 
 tives are unsaturated, and might form additive 
 compounds before substitution takes place. 
 
 Amido compounds in presence of excess of 
 H2SO4 (20 pts.) when treated with the calculated 
 quantity of HNO3 dissolved in H^SO^, added at 
 0°, give chiefly meta-nitro derivatives, some of 
 the jp-nitro derivative being also formed. Ex- 
 amples: aniline, acetanilide,toluidine, xylidine, 
 ^-bromo-aniline (Nolting a. Collin, B. 17, 261), 
 di-methyl-aniline, di-ethyl-aniline (Groll, B. 19, 
 198), ethyl-aniline (Nolting a. Strecker, B. 19, 
 546). The amount of meta-nitro derivative 
 formed is increased by increasing the quantity 
 of sulphuric acid present. In all these cases 
 nitrogen ia attached to a chlorous radicle, aniline 
 sulphate being CuH5N(O.S03H)H3, and might 
 therefore be expected to produce a meta deri- 
 vative. It is, however, curious that a solution of 
 aniline sulphate in a small quantity of sulphuric 
 acid gives very little m-nitraniline on nitration. 
 
 When a new element or radicle enters a 
 benzene nucleus in which more than one H is 
 already displaced if it can satisfy the require- 
 ments of each of the substituents already present 
 it will do so ; if not it obeys the most powerful 
 substituent present. The following appears to 
 be the order of priority, beginning with the 
 strongest : 
 
 HO; NH^; halogens; CHj; other alkyls; NO^;. 
 CO2H and SO3H. The conversion of ji-nitro- 
 phenol into CsH3(0H)Br(N0.,) [1:2:4], and that of 
 o-nitro-phenol into C3H3(OH)Br(N02) [1:5:2], by 
 the action of Br are instances where both NOj 
 and OH are obeyed ; but in the action of Br upon, 
 p-bromo-phenol and of HNO3 upon C5H3(OH)Clj 
 [1:2:4] the new substituent obeys the stronger 
 radicle, producing CjH2(OH)Br3 [1:2:4:6] and 
 C3H2(OH)Cl2(N02) [1:2:4:6] respectively. 
 
 When a hydrocarbon radicle is introduced 
 by the agency of AICI3 it does not always follow 
 the foregoing rule; thus m-xylene is the chief 
 product of the action of MeCl upon benzene ira 
 presence of AICI3. 
 
800 
 
 AROMATIC SERIES. 
 
 Differences between o, m, and p compounds. 
 Ortho, meta, and para compounds usually boil 
 at about the same temperature, but the para 
 ■compounds have the highest melting-points. 
 The ortho compounds are usually the most, and 
 the para compounds the least, volatile with 
 steam. In the oxidation of ortho compounds 
 the benzene ring is liable to be broken up, v?hile 
 in the meta and para compounds this is not the 
 case (v. Htdkocabbons). Ortho compounds 
 readily give rise to products of condensation in 
 which the side chains may be supposed to be 
 joined in the form of a ring ; this tendency is 
 •observed to some extent in the para series but 
 not at all in the meta series. Thus by loss of 
 HjO o-amido-phenyl-glyoxylic acid gives isatin ; 
 •o-amido-oiunamio acid gives carbostyril, o-oxy- 
 cinnamic acid gives coumarin; phthaUc acid 
 ^ives phthalio anhydride. 
 
 o-nitraniline hydrochloride is readily decom- 
 posed by water, jp-nitraniliue hydrochloride less 
 so, and TO-nitraniline hydrochloride is hardly 
 ■decomposed by water (LeUmann, B. 17, 2719). 
 In general, the introduction of a radicle into the 
 jre-position produces less change in the pro- 
 perties of a compound than the introduction of 
 the same radicle into the o and p position, and 
 of the resulting derivatives the meta are the 
 most stable. Thus m-xylene is oxidised with 
 difficulty, while dilute HNOj readily converts o-, 
 ■and p; xylene into toluio acids. Ortho-, and 
 para-, oxybenzoic acids are converted into phenol 
 by heating with aqueous HCl in sealed tubes, 
 while Mi-oxybenzoio acid, like benzoic acid itself, 
 is unaffected. Ammonia converts o- and p- nitro- 
 ■anisols into nitranilines, but does not affect m- 
 nitro-anisol or anisol itself ; similarly ammonia 
 converts o-, and p-, bromo-nitro-benzenes into 
 nitranilines, but does not affect jra-bromo-nitro- 
 ■benzene or bromo-benzene itself. Boiling alkalis 
 convert o-, and p-, nitraniline into nitrophenols, 
 but do not affect m-nitraniline or anUine. Aniline 
 and ;?i-nitraniline resemble one another in 
 readily uniting with phenyl thio-carbimide (form- 
 ing diphenyl-thio-urea and nitro-di-phenyl-thio- 
 urea respectively), while p-, and o-, nitraniline 
 require to be heated for some time with phenyl 
 ihio-carbimide before they will combine. Ben- 
 zoic acid and m-oxy-benzoic acid are readily 
 reduced by sodium-amalgam to benzyl alcohol 
 and m-oxy-benzyl alcohol respectively, while o-, 
 ■and 23-, oxybenzoic acids are not attacked. Ortho- 
 and para-nitro-acetanilide dissolve in cone, 
 potash ; the former is readily saponified by the 
 potash, giving potassium acetate and o-nitro- 
 aniline ; a similar decomposition occurs with the 
 latter, but with greater difficulty. Meta-nitro- 
 .acetanilide is insoluble in cone, potash, and is 
 scarcely affected by it (Kleemann, B. 19, 336). 
 The substitution of an atom of hydrogen in the 
 nucleus by an atom of bromine is accompanied 
 ly absorption of heat ; in an actual experiment 
 this is not observed, being more than counter- 
 balanced by the heat developed in the simul- 
 taneous formation of HBr (Werner, Bl. 46, 
 282). 
 
 Occasional reactions. 
 
 1. Acetyl bromide not only displaces H by Ao 
 ^ut sometimes even turns out an alkyl ; thus it 
 «onverts di-methyl-anUine and di-ethyl-aniline 
 
 into methyl aoetanilide, and ethyl-aoetanilide 
 respectively (Staedel, B. 19, 1947).— 2. Benzoyl 
 chloride sometimes behaves in the same way, 
 converting di-methyl-aniline and di-ethyl-ani- 
 line into methyl-benzanilide and ethyl-benzani- 
 Ude respectively. —3. Nitric acid in nitration 
 sometimes turns out acetyl, converting ethyl 
 acetanilide into C5H3(N02)2NEtH [1:3:4], a,nd 
 behaving similarly towards methyl aoetanilide 
 (Norton, B. 18, 1997). Nitric acid sometimes 
 turns out bromine ; thus it converts ^-bromo- 
 aniline into tri-nitro-aniliue (picramide) (Hager, 
 B. 18, 2578). — 4. Potash converts di-nitro-di- 
 methyl-aniline, 08H3(N02)2NMe2 [4:2:1] into di- 
 nitro-phenol, di-methyl-amine being given oft. 
 
 Molecular changes. 
 
 At high temperatures o-oompounds may 
 change to p-, and both o- and p- to m-. At 100° 
 o-phenol-sulphonio acid changes to ^-phenol- 
 sulphonio acid. At 220° potassium salicylate 
 changes to p-oxybenzoate, while sodium sali- 
 cylate is not affected at that temperature. Eesor- 
 oin is obtained by potash-fusion from benzene 
 p-disulphonio acid, ^-chloro-benzene sulphonic 
 acid, and o- and ^-bromo-phenol. 
 
 Methyl can pass from combination with 
 nitrogen into the nucleus ; thus dimethylaniline 
 methylo-iodide at 220° gives o- and p- dimethyl 
 toluidine, methyl-xylidine, and di-methyl-xyli- 
 dine ; while at 336° it gives ili-cumidine, 
 CsH^MejNHj (Hofmann, Pr. 21, 47). 
 
 Ethyl aniline hydrochloride at 320° changes 
 similarly to ethyl-phenyl-amine, CjH^EtNHj, 
 while isoamyl-aniline hydrochloride becomes 
 isoamyl-phenyl-amine, CjHj(G5H„)NHj, (Hof- 
 mann, B. 7, 526). In these cases it may be 
 supposed that Mel, MeCI, EtCl, and CsHnCl re- 
 spectively are split off and then attack the nu- 
 cleus ; this action of MeOl is seen in the conver- 
 sion of xylidinehydroohlorideintoif'-oumidineby 
 heating with methyl alcohol at 280° (Hofmann, 
 B. 13, 1730). 
 
 Conversion of fatty compounds into aromatie. 
 1. By passing acetylene (q. v.) through a red 
 hot tube. — 2. By heating acetone or allylene 
 with sulphuric acid mesitylene is formed.— 3. 
 Uvitic acid, OsBJUeiCO^B.)^ [1:3:5] is formed by 
 boiling pyruvic acid with baryta. — 4. Oxy-uvitio 
 ether is formed by the action of chloroform on 
 sodium aoeto-acetic ether. — 5. Sucoinylo-sucoinic 
 ether from suocinyl chloride, sodium, and 
 succinic ether is di-oxy-di-hydro-terephthalio 
 ether ; when heated with KOH it gives hydro- 
 quinone. Hydroquinone is also formed when 
 succinates are subjected to dry distillation. — 6. 
 Phloroglucin tri-carboxylic ether is formed by 
 the action of sodium or of ZnEtj on malonic 
 ether (Baeyer, B. 18, 3457 ; Lang, B. 19, 2937). 
 7. Tri-mesio ether is formed by the action 
 of sodium on a mixture of formic and aoetio 
 ether (Piutti, B. 20, 537).- 8. Hexyl iodide and 
 bromine at 200° gives hexa-bromo-benzene 
 (Krafft, B. 9, 1085; 10, 801).— 9. K and CO 
 combine, forming Cg(OK)g (Nietzki a. Benckiser, 
 B. 18, 1833). 
 
 Conversion of aromatie compounds into fatty. 
 
 1. Carbonic, oxaUo, and formic acids are pro- 
 ducts of oxidation of aromatic compounds, — 
 
ARSENIC. 
 
 301 
 
 3. Benzene is converted by KOlO, and HCl into 
 C5H3CI3O3, which is converted by baryta into 
 lumario acid. — 3. Nitrous acid converts pyrooa- 
 teohiu in ethereal solution into dioxytartaric 
 Boid. — 4. HCl and KCIO3 convert gallic acid into 
 tri-ohloro-glyoerio acid. — 5. Chlorine passed into 
 a cold aqueous solution of phloroglucin gives 
 dichloro-aoetic acid (Hlasiwetz a. Habermann, 
 A. 155, 132). 
 
 Aromatic acids. The principal aromatic acids 
 are those containing SO3H and those containing 
 COjH. The former will be discussed as Sdl- 
 PHONic ACIDS, the latter will be briefly character- 
 ised here (v. also Acms, iMEDO-, bbomo-, CHLoito-, 
 10DO-, and NiTKO-acids). 
 
 Formation. — I. By oxidation of homologues 
 of benzene or derivatives of such homologues. 
 KjCrjO, (2 pts.), Hj,SO, (3 pts.), and water (3 to 
 5 pts.), is a convenient mixture for the purpose ; 
 but it converts all side chains into carboxyls, 
 thus TO- and 'p- xylene become iso-, and tere-, 
 phthalic acids, while mesitylene becomes trime- 
 sic acid. Dilute HNO3 (S.G. 1-2) and aqueous 
 KMnOj oxidise more gradually, attacking one 
 side chain at a time, thus converting 0- and ^- 
 xylene into 0- and p- toluic acid and mesitylene 
 into mesitylenio acid. — 2. By passing CO^ over 
 a mixture of a bromo-derivative and sodium : 
 CsHjBr + COj + Na2= CsHjCO^Na + NaBr(Kekul6, 
 A. 137, 178). — 3. By heating a bromo-deriva- 
 tive with ohloroformic ether and sodium, thus : 
 C ABr + ClCOjEt + Nai, = CsH^CO^Et -t- NaCl + 
 NaBr (Wurtz, A. Suppl. 7, 125).— 4. By the 
 action of COCl^ or COj on aromatic hydrocarbons 
 in presence of AlCl, (Friedel a. Crafts, v. Anj- 
 MiNinii OHLOEiDB, p. 147) the product being 
 treated with water. The amides may be pro- 
 duced in a similar way by using Cl.OO.NHj 
 instead of COClj (Gattermann a. Schmidt, B. 20, 
 858). — 5.By heating sulphonates with sodium for- 
 mate : PhSOaK + HCOjNa = Ph.CO^Na + HSO3K 
 (V. Meyer, A. 156, 273). — 6. By saponification of 
 nitriles. The nitriles may be obtained either by 
 heating sulphonates or exo-chloro derivatives 
 with potassium cyanide or by heating thio-car- 
 bimides with copper (Weith, B. 6, 212). Nitriles 
 may also be obtained by distilling the formyl 
 derivatives of amines with zinc-dust, e.g. : 
 PhNH.0HO = H2O + PhCN.— 7. By oxidation of 
 alcohols or aldehydes. — 8. Aromatic acids con- 
 taining carboxyl in the side chain can be pre- 
 pared by synthesis with aid of aceto-acetic ether 
 (2. V.) or of malonic ether {q. v.). — 9. Oxy-aoids 
 are formed by boiling diazo-aoids with water, or 
 by potash-fusion from chloro-, bromo-, iodo-, or 
 Bulpho-, acids. — 10. By passing CO^ into sodium 
 phenols at 180° or potassium phenol; in the 
 former case CO^H takes up a position ortho to 
 the hydroxyl. Potassium phenol at 140° gives 
 saHcylio acid, but at 170°-200° it gives jp-oxy-ben- 
 zoio acid. The reaction takes place in two stages: 
 
 C,H..O.Na + C02= C^Hs.O.COjNa; 
 C,H,.0.C02Na = C,H,(0H).C02Na 
 
 {v. OxY-BENZOic Acros).— 11. By heating phenols 
 with dilute alcoholic solution of CCl, and 
 NaOH at 100°: CsH^OH h- CCl^ h- 6NaOH = 
 CeH4(ONa)C02Na + 4NaCl + 4HjO (Tiemann a. 
 Eeimer, B. 9, 1285). The carboxyl takes up 
 positions para and ortho to the hydroxyl. — 
 
 12. Perkin's synthesis of oinnamio acid and its 
 homologues is described and discussed in the 
 article on Aldehydes. —13. Eesorcin and ita 
 homologues are converted into {1, 3, 4) and 
 1, 3, 2) di-oxy-benzoic acids and their homo- 
 logues by heating with ammonium carbonate 
 and water ; while hydroquinone and its homo- 
 logues heated with potassium bicarbonate, water, 
 and a Utile K2SO3 give (1, 4, 2) di-oxy-benzoio 
 acid and its homologues (Senhofer, Sitz. B. 80, 
 504; 81, 430, 1044; M. 2, 448). 
 
 Beactions. — 1. The aromatic acids are sub- 
 ject to the general laws governing substitution 
 in the benzene nucleus. — 2. They are usually 
 si. sol. water but v. sol. alcohol and ether. The 
 homologues of benzoic, and of salicylic, acid 
 are volatile with steam, to-, and p-, oxy-benzoic 
 acids are not volatile with steam. Sahcylic acid 
 and its homologues are soluble in chloroform, 
 p-oxy-beuzoio acid and its homologues are not. 
 Ortho-oxy-acids are also characterised by giving 
 a violet colouration with FCaClj. — 3. Ortho-oxy- 
 acids of the form CsH,(0H).CH2.C0jH or 
 0„H,(OH).CHj.CH2.C02H have a tendency to 
 produce anhydrides or lactones ; ortho-amido 
 acids of the form C8H<(NH2).CH2.C0jH or 
 C8Hj(NH2).CH2.CH2.COjH readily form anhy- 
 
 drides, similarly called lactams : CjHj^jttj^^CO, 
 
 or lactuns : CeH^<^*^^'=^C.OH.— 4. Benzene is 
 
 produced by fusion with NaOH from benzoic acid 
 (75 p.c), trimellitic acid, hydrocinnamic acid, and 
 cinnamio acid (50 p.c.) ; a little diphenyl is also 
 formed. Fusion with NaOH converts 0-, and p-, 
 oxy-benzoic acids into phenol (50 to 60 p.c.) ; 
 protoeatechuic acid into resorcin (50 to 60 p.c.) ; 
 (1,3, 5) -di-oxy-benzoio acid into resorcin (60 p.c), 
 phloretic acid and ^-coumaric acid into ^-oxy- 
 benzoic acid and finally into phenol ; oxy-tere- 
 phthalic acid into salicylic and ^-oxy-benzoic 
 acids, and finally into phenol (Barth a. Schreder, 
 B. 12, 1255). 
 
 Aromatic bases. The preparation and pro- 
 perties of the aromatic bases have been dis- 
 cussed in the article on Amines. They may be 
 divided into two classes according as the 
 nitrogen is attached to carbon in a benzene 
 nucleus or in a side chain ; bases of the latter 
 form resemble fatty amines. Amines containing 
 amidogen attached to the benzene nucleus are 
 weakened in basic power by introduction of 
 nitroxyl or halogens into the nucleus, more 
 especially if these radicles do not occupy a 
 position meta to the amidogen. Triohloraniline, 
 dinitraniline, and trinitraniline do not combine 
 with acids ; the latter is even saponified by 
 potash with formation of trinitrophenol. 
 
 ARSENATES. Salts of arsenio acid, v. 
 Abbenic, Acids of, p. 305. 
 
 ARSENIC. As (Arsenicum, Regulus arsenici, 
 hpaeviKdv. By the term (Tavtapiicri Aristotle seems 
 to mean a compound of arsenio and sulphur, 
 called afi^eviK6v by Theophrastus). At. w. 74'9. 
 Mol. w. 299-6 ; 149-8 at c. 1700° (Biltz a. Meyer, 
 jB. 22, 725). Melts only under great pressure 
 (Landolt; also MaUet, C. N. 26, 97). S.G. 
 5-23 to 5-76: pure, crystalline J-f 5-726-5-728; 
 grey, pearly crystals ^ ill (Bettendorff, A. 
 
302 
 
 ARSENIC. 
 
 144. 110); amorphous 'jf 4-710-4-716 (ibid. 
 l.c.) ; fused If 5-709 (Mallet, O. N. 26, 97). 
 V.D. 147-2 at 860° (Deville a. Troost, G. B. 
 66, 871) ; 153-7 at 640-670° (Mitsoherlich, A. 
 12, 159). S.H. crystallised, -083; black, 
 amorphous, -0758 (Bettendorff a. Wiillner, P. 
 133, 293). C.E. (linear at 40°) -00000559 
 (Fizeaux, C. B. 68,1125). B.C. (HgatO° = l) 
 2-679 at 0°, 1-873 at 100° (Matthiessen a. Bose, 
 T. 152, 1). S.V.S. cryst. 13-1 ; amorph. 15-9. 
 
 ^^-^xat. wt. 15-4 (Gladstone, Pr. 18, 49). 
 
 Chief lines in emission spectrum, v. Huntington, 
 P. Am. A. [2] 9, 34; Hartley a. Adeney, T 
 1884. 124. 
 
 Occurrence. — Found native, but more fre- 
 quently associated with other metals and 
 ■sulphur, in widely distributed ores. Obtained 
 as a principal product chiefly tvomnative arsenic, 
 ■arsenical iron FeAs.. and Fe^ASj, and arsenical 
 pyrites FeAsFeSj ; obtained as a secondary 
 product from snialtine, cobalt glance, arsenical 
 cobalt, rdckel glance, i!aa,nyfahl-ores,&c. Occurs 
 also in ferruginous deposits of certain mineral 
 waters (Will, A. 61, 192) ; in nearly all iron ores 
 (Walohner, A. 61, 205) ; in soils, from the 
 weathering of iron pyrites (Sonnenschein, 
 Ar. Ph. [2] 143, 245) ; in the residue obtained 
 by evaporating sea water (Daubrfie, Ann. M. [4] 
 19, 669) ; frequently found in metallic bismuth 
 (Schneider, /. pr. [2] 20, 418) ; in various kinds 
 of pyrites, and hence in most samples of com- 
 mercial sulphuric acid, and in many substances 
 in the manufacture of which this acid is used 
 (v. H. A. Smith, P. M. [4] 44, 370). 
 
 Preparation. — On the large scale by heating 
 to redness, out of contact with air, arsenical 
 iron or arsenical pyrites ; arsenic sublimes ; iron, 
 or ferrous sulphide, remains. Prepared in small 
 quantities at a time by heating As^Oj with pow- 
 dered charcoal, or with ' black flux,' in crucibles 
 covered with conical iron caps. Also by heating 
 ASjSj with charcoal, an alkaline carbonate, 
 and KCN. Purified by resublimation after 
 mixing with powdered charcoal ; or by heating 
 with a Httle I (Ludwig, Ar. Ph. [2] 97, 23) ; or 
 by boiling with moderately cone. K^CrOi Aq 
 acidified with H^SO^ (Bottger, J. pr. [2] 2, 134). 
 Arsenic was first prepared from arsenious acid 
 in 1694 by Schroder; its chemical nature was 
 further investigated by Brand (1733), Macquer 
 (1746), Mamet (1773), and others. Soheele dis- 
 covered arsenic acid and arsenuretted hydrogen 
 in 1775. 
 
 Properties. — Very brittle, steel grey, lustrous ; 
 crystallises by sublimation in hexagonal rhom- 
 bohedra isomorphous with Sb and Te ; 
 ^:c = l:l-4025.H = 3-5. When As is sublimed 
 in a rapid H stream in a glass tube the sublimate 
 nearest the heated part of the tube consists 
 chiefly of rhombohedra, that farther from the 
 hottest part but still on a warm portion of the 
 tube (210°-220°) of black amorphous As, while 
 the coolest part of the tube is filled with yellow 
 fumes which condense to grey crystals 
 (Bettendorff, A. 144, 110). Black amorphous As 
 is also obtamed by condensing As vapour at a 
 ■fairly higli temperature ; by decomposing As 
 diompounds by heating in glass tubes to 
 
 moderately high temperatures {e.g. AsHj), or by 
 heating with reducing agents {e.g. AsjOj ■with C) ; 
 or by reduction of As compounds in the wet 
 way (Engel, O. B. 96, 497). As can be obtained 
 in regular octahedra by heating a mixture of 
 much H -with a little ABH3 (Cooke, Am. S. [2] 
 31, 91). Amorphous As is changed to crystal- 
 line by heating for some time at 310° (Engel, 
 C.B. 96, 1314); by heating to 358°-360'' 
 (Bettendorff, A. 144, 110). Amorphous As when 
 subjected to a pressure of 6500 atmospheres 
 acquires metallic lustre and its S.G. increases 
 (Spring, B. 16, 326). The vapour of As is citron- 
 yeUow (Le Boux, C. B. 51, 171). The spectrum 
 of As shows lines in the orange (6169-5), yeUow, 
 and green (5331) (Thalen, A. Ch. [4] 18, 244) ; 
 also many more refrangible lines (1). Hartley, T. 
 1884. 124). As combines with CI and with 
 production of heat; [As, 01^ = 71,390; 
 [As^ 0^ = 154,670; [As^ O', Aq] = 147,120 ; 
 [As2, 0^ = 219,380; [As^, 0=, Aq] = 225,380 
 (Thomsen). As volatilises at a dark red heat 
 without previous fusion at ordinary pressures. 
 The molecule of As is tetratomic (AsJ ; the atom 
 is trivalent in gaseous molecules (AsHj, AsClj, 
 &c.). The atomic weight has been determined 
 (1) by analysing, and determining V.D. of, 
 various gaseous compounds, ASH3, AsClj, ASI3, 
 ASjOj, &c. ; (2) by determining S.H. of As ; 
 (3) by comparing isomorphous compounds of 
 As, Sb, and Bi, arsenates with phosphates and 
 vanadates, &c. (Wallace, P. M. [4] 18, 279 ; 
 Dumas, A. Ch. [3] 55, 174; Kessler, P. 95, 
 204). 
 
 As is insoluble in alcohol and ether, but is 
 said to be dissolved by certain oils. It oxidises 
 fairly rapidly in air at ordinary temperatures ; 
 heated in air, it burns to As fig with a bluish . 
 flame ; is oxidised by nitric and sulphuric acids, '' 
 and by fusion with alkalis. As forms twoMfies 
 of compounds, of which As^O^ and .^Bvare 
 representatives. ^^■ 
 
 In many of its physical • properties" As 
 is metallic, but in its chemical relations it is 
 decidedly non-metallic or negative. Exhibits 
 allotropy ; oxide.s are acid-forming (1;. Absenio, 
 OXIDES OF ; also Aesehio, acids or) ; at the same 
 time ASjOj appears to react ■w'ith SO3 to form a 
 salt, and with KH.CjH^O, to form a compound 
 analogous with tartar emetic, and with cone. 
 HClAq to form AsClj (v. Aesenious oxide, under 
 Aksenic, oxides of). Arsenious acid is unknown, 
 and an aqueous solution of the oxide behaves 
 towards alkalis as a very feeble salt-forming 
 compound ; but arsenic acid is as strong an acid 
 as phosphoric, their relative affinities are nearly 
 equal (v. Affinity, p. 67). The haloid compounds 
 of As do not show any marked tendencies to form 
 double salts. The hydride AsH, does not com- 
 bine ■with acids, as NH, and PH3 do ; but at the 
 same time compounds belonging to the form 
 AsEjX, where E is an alcoholic radicle C„H2„+„ 
 and X is a halogen or even OH, are known 
 (v. Aesenio compounds, oeganio). For a fuller 
 discussion of the chemical relations of arsenic 
 V. arts. Bismuth, chemical relations of ; and 
 
 NiTEOGEN GEOUP OF ELEMENTS. 
 
 Beactions. — 1. Hydrochloric acid, no action 
 in absence of air ; in presence of air a little AsClj 
 is formed. — 2. Nitric acid and ax[ua regia react 
 with production of much heat; oxides of N, 
 
ARSENIC. 
 
 303 
 
 A84O,, &nd HjAsO,, are formed.— 3. Hot. cono. 
 tulphuric add evolves SO2 and forms As^O^. — 
 i. Molten potash or soda produces an arsenite and 
 H. — 5. Molten nitre or potassium chlorate pro- 
 duces potassium arsenate ; the action is more or 
 less explosive. — 6. Solution of sulphur dioxide 
 reacts, when heated with As in a closed tube to 
 200°, to produce As^O^, S, and H.SO^Aq, but no 
 sulphide of As (Geittuer, /. 1864." 143).— 7. Am- 
 monia solution is without action on As. 
 
 Combinations. — 1. With nascent hydrogen 
 AsHj and AsH are formed (g. ■!;.). — 2. With 
 chlorine, bromine, or iodine, AsClj, AsBrj, or 
 ASI3 (j. V.) is produced. — 3. With fluorine (action 
 of HF on ksfie) AsFj is formed (g.t).).- 4. With 
 oxygen As combines to form As^O^ (g. v.) ; As^Oj 
 (g.v.)is produced by heating one of its hy- 
 drates. — 5. The sulphides AsjSj and As^Sj and 
 AS2S5 (g. V.) are produced by heating together 
 arsenic and sulphur ; the sulphide AS2S5 is, how- 
 ever, best obtained by decomposing solutions of 
 alkaUne sulpharsenates by acid. — 6. Tellurium 
 combines with arsenic to form AsjTej and As^Te,, 
 ■when the two elements are melted together in 
 the required proportions (Oppenheim, J. pr. 71, 
 266). — 7. When arsenic is melted with sulphur 
 and selenion in the proportions represented by 
 the formulsB As^SeSj and As2SSe2, two bodies 
 having the compositions indicated are obtained. 
 The first is a lustrous red semi-transparent 
 mass from which the whole of the Se separates 
 out after some days. This body is easily soluble 
 (when powdered) iuNH^HSAq. The bodyAs^SSe^ 
 is a crystalline opaque solid which may be dis- 
 tilled unchanged ; it is less easily soluble in 
 NnjHSAqthanAs2SeS2(v.Gerichten,B. 7, 29).— 
 
 8. Arsenic appears to be incapable of combining 
 with phosphorus directly [older experiments by 
 
 (fendgrebe {S. 60, 184) probably yielded only a 
 mi^ire of P and As] ; but if AsHj is led into 
 PG^fcW'Hs into AsClj, a red-brown solid is ob- 
 tainlHBEter drying it appears as a darker powder 
 withM^ lu st aa,), which is insoluble in alcohol, 
 ether, and flmjlj, but fairly soluble in CSj. This 
 solid is PAs ; it is changed by water into PjASjOj 
 with which chlorine reacts to produce AsClj and 
 POCI3. The compound PAs is rapidly oxidised 
 by concentrated HNO3, less rapidly by dilute 
 HNO3, giving H3ASO4 and H3PO4 ; solutions of 
 KOH, NH4OH, or Ba(0H)2, easily decompose PAs 
 (rapidly when warm) producing PHj, ASH3, 
 H3PO2, H3ASO3, and As. Heated in air PAs burns 
 to ASjOa and P2O3 ; heated in absence of air, or 
 in CO2, phosphorus sublimes and then arsenic. 
 The reactions of P2AS3O2 are very similar to 
 those of PAs {v. Janowsky, B. 6, 216 ; 8, 1636).— 
 
 9. Arsenic forms aZZo?/s with many wieteZs. Some 
 of these are produced by very strongly compress- 
 ing the constituents (Spring, B. 16, 324). These 
 alloys are generally brittle, they are only par- 
 tially, in many cases not at all, separated into 
 their constituents by the action of heat out of 
 contact with air; they are generally oxidised to 
 arsenates, and oxides of the metals, by fusion 
 with nitre ; fused with alkaline carbonates and 
 sulphur, thio-arseniteorthio-arsenate of the alkali 
 metal is generally produced, and the metals for- 
 merly alloyed with the arsenic are completely 
 separated as sulphides. Arsenides of heavy 
 metals are scarcely if at all attacked by nitric 
 acid or aqua regia. Many alloys of arsenic are 
 
 definite compounds; several of them occur 
 native as minerals (u. Winkler, J.pr. 91, 193; 
 S6uarmont, A. Gh. 80, 221 ; Bammelsberg, P. 
 128, 441). The alloys with cobalt, which are 
 brittle and iron-grey in colour, are formed, with 
 production of heat, by melting the elements 
 together. CoAs occurs native as Smaltvne ; it 
 always contains more or less iron and nickel re- 
 placing part of the arsenic. OojAs^, generally 
 containing more or less iron, also occurs native 
 as Skutterudite, or Modumite. Arsenic alloys 
 with copper to form white solids which tarnish 
 in the air. According to Lippert (J. pr. 81, 168) 
 the grey deposit obtained by heating copper in 
 an HCl solution of arsenious oxide is CU5AS2 ; 
 when this body is heated in hydrogen Cu^As re- 
 mains. The compounds CU3AS, CUjAs, and 
 Cu^s, occur native as Domeykite, Algodonite, 
 and Darwinite, respectively. The alloys of 
 arsenic and iron are brittle solids formed by 
 melting the elements together ; FeASj and Fe^Asa 
 occur native as Arsenical iron, sometimes con- 
 taining Ag, Au, and Cu. Arsenic alloys with 
 lead to form brittle solids. With nickel, arsenic 
 alloys easily ; Ni2As is obtained by melting the 
 elements together. The minerals Copper-nickel 
 NiAs, and Cloanthite NiAs2, occur native ; they 
 contain varying quantities of Sb, Fe, Pb, Co, and 
 Cu. A lustrous crystalline alloy Ni3As2 is ob- 
 tained by reducing arsenate of nickel by char- 
 coal at a high temperature ; Ni3As is said to be 
 formed when KCN, As, and NiO are fused toge- 
 ther (Desoamps, C. B. 86, 1065). Arsenic also 
 alloys, with production of much heat, with 
 potassium and sodium ; the products are de- 
 composed by water with formation of KOH (or 
 NaOH)Aq, AsHj, and As. An alloy of 15 parts 
 tin and 1 part arsenic forms large leaf-like 
 crystals. Arsenic is not much used in technical 
 chemistry ; the alloy with lead is employed in 
 making shot. Arsenic appears to form alloys 
 with several other metals, especially Hg (?) Pd 
 and Pt. By strongly compressing (6500 atmos.) 
 As with various metals. Spring (B. 16, 326) ob- 
 tained several well-defined alloys, e.g. ZnjASj, 
 CujAs,, &c. &c. 
 
 Detection. — In rtry way. Arsenic heated 
 with slight access of air volatilises with a garlic - 
 like odour (probably due to a little As.,0„) and 
 condenses on cooling as a lustrous black deposit, 
 which is easily converted into a white crystalline 
 sublimate (ASjOs) by heating in presence of 
 plenty of air. Sulphides or oxides of arsenic, 
 and the salts of arsenious and arsenic acid, yield 
 sublimates of black amorphous arsenic when 
 heated with an alkaline carbonate alone or 
 mixed with charsoal or KCN (v. Fresenius, A. 49, 
 301 ; Bose, P. 90, 193). Oxide of arsenic heated 
 with much NaC2H302 in a tube closed at one end 
 yields cacodyl oxide, recognised by its foul smell. 
 In wet way. I. Arsenious compounds. 
 (i.) Sulphuretted hydrogen 'ps.sseSiVa.io a solution 
 of ASjOj, or an arsenite, acidified with HCl, 
 forms a bright yellow pp. of AS2S3, soluble in 
 NHjOH, NHjSH, and (NHJ2CO3, solutions, and 
 reprecipitated by HGl. AS2S3 is said to be 
 soluble in a considerable quantity of boiling 
 water and in boiling dilute HOI (Odling, Quy's 
 Eosp. Bep. [3] 1, 239). (ii.) Neutral solution 
 of silver nitrate produces a canary-yellow pp. of 
 Ag3As03 easily soluble in most acids and in 
 
804 
 
 AKSENIO. 
 
 ammoma. (iil.) Neui/ral solution of copper sul- 
 phate precipitates green CuHAsO., (Soheele's 
 green) easily soluble in aoids and in ammonia. 
 (iY.) heinsch's test (J. pr. 24, 244). A warm so- 
 lution of an arseuious oompouud acidified with 
 HOI deposits a film of arsenic on a piece of 
 bright copper kept in contact with it for some 
 time ; this deposit may be oxidised to As^Oj by 
 heating in air (v. supra). The deposit consists 
 of. AsjCuj according to Lippert (J. pr. 81, 168). 
 Arsenic oompoundsmay be detected byEeinsoh's 
 test, if present inconsiderable quantity (Werther, 
 J. pr. 82, 286), even in small quantity if heated 
 for some time with HCl (Eeinsch, N. J. P. 16, 
 135) ; the HCl used must not be weaker than 
 S.G. 1-1 (Bettendorft, Z. [2] 5, 492). According 
 to J. M. Soberer {Fr. 3, 200) the deUeacies of the 
 wet tests are as follows ; AgNO, detects _J 
 
 part of As, CuSO. detects .J_ part, H-S 
 
 ' 13,600 '^ ' ^ 
 
 detects — !_ part, and Beinsch's test detects 
 
 640,000 -^ 
 
 ' part, or after boiling for J hour . — !_ 
 
 130,000 -^ ' o t 250,000 
 
 part of As. (v.) Marsh's test. When hydrogen 
 is evolved in contact with an acidified solution 
 of an arsenious compound, whether by the 
 action of zinc (Marsh, B. J. 17, 191 ; 20, 190 ; 
 22, 175), magnesium (Eoussin, J. 1866. 801), or 
 the electric current (Bloxam, 0. J. 13, 14), 
 arsenic trihydride is evolved ; arsenic may be 
 separated by passing the gas through a glass 
 tube heated at one part, or by burning the gas 
 in a limited supply of air and presenting a cold 
 surface of porcelain, or thick platinum (Davy, J. 
 1858. 609), on which the arsenic condenses. 
 The deposit of arsenic is easily soluble in 
 HNOs, S.G. 1'2 to 1-3; the solution contains 
 arsenious acid (which on boiling for some time 
 is changed to arsenic acid), it gives the cha- 
 racteristic yellow pp. of AgjAsOj (v. supra) ; the 
 deposit of arsenic is also easily soluble in 
 aqueous NaClO free from CI; if the deposit is 
 warmed in dry H^S yellow As^Sj is produced 
 which is not changed when warmed in a 
 current of dry HCl gas. Arsenious hydride 
 passed into aqueous AgNOj precipitates Ag, but 
 the whole of the As remains in solution along 
 with HNO3 formed in the reaction, and may be 
 detected by filtering and carefully neutralising 
 the filtrate with dilute ammonia, when yellow 
 AgjAsOg is produced. [SbHs precipitates Ag from 
 AgNOa but the whole of the Sb is at the same 
 time thrown down ; the deposit of Sb obtained 
 by heating, or burning, SbHj is insoluble in 
 NaClO solution free from CI, and is much less 
 soluble than As in HNOaAq of S.G. 1-2 to 1-3 ; 
 moreover, the solution in HNOjAq gives no 
 reaction with AgNOjAq and ammonia. The 
 reactions of the two gases towards AgNOj solution 
 affords a means for separating them (Husson, 
 C. JR. 83, 199).] The electrolytic method of 
 preparing AsHj has the advantages (a) of 
 avoiding the use of zinc which generally contains 
 arsenic ; (6) of not interfering with the sub- 
 sequent testing for other metals ; (c) of allowing 
 the separation of antimony if present — this is 
 done by adding a little HjS to the liquid, whereby 
 ASjSj and SbjSa are formed ; the former is easily, 
 the latter not at all, decomposed by the current 
 (Bloxam, 0. J. 13, 14, 338). The presence of 
 HNO, prevents the formation of AsH, (Blondlot, 
 
 /. 1863. 681). (vi.) Bettendorfs test (Z. J2J 
 5, 492). Stannous chloride in furm/ng HCl, added 
 to a solution of As40a or ASjOj in the same acid, 
 precipitates metallic As mixed with a little SnO^. 
 This test is said to be extremely delicate ; it 
 may be used to detect As in presence of Sb, also 
 to remove As from HClAq (v. also Hager, /. 1870. 
 966). II. Arsenic compounds, (i.) Neutral 
 silver nitrate precipitates red-brown AgjAsOj 
 soluble in NHjOHAq and in HNOjAq, but less 
 soluble in HNOjAq than AgjAsO.,, so that if 
 AgNOj is mixed with a solution of an arsenite 
 and an arsenate in HNOjAq, and NH^OHAq ia 
 then added drop by drop, AgjAsOj is precipitated 
 before AgjAsOa ; a solution of arsenic acid in 
 nitric acid is precipitated by AgNOj if a few 
 drops of a concentrated solution of an alkaline 
 acetate are added (Avery, Am. 8. [2] 47, 25). 
 (ii.) Neutral copper sulphate precipitates bluish 
 green CuHAsOj soluble in HNOjAq and in 
 NHjOHAq. (iii.) An alkaline solution of mag- 
 nesium sulphate, containing enough NH^Cl to 
 prevent precipitation of magnesia, precipitates 
 white Mg(NH,)As04 ; delicacy 1 part of As in 
 56,000 (Levol, B. J. 28, 130) {cf. Estimation of 
 Arsenic), (iv.) Ammonium molybdate in excess 
 precipitates bright yellow arseno-molybdate of 
 ammonium from warm (not cold) solutions of 
 arsenates containing HNOj. (v.) Sulphuretted 
 hydrogen slowlyreduces arsenic to arsenious acid 
 and then (in presence of HCl) precipitates yellow 
 AS2S3 mixed with S. (vi) Marsh's test. Arsenic 
 compounds in solution are reduced to AsH^ by 
 hydrogen evolved in contact with the solution i 
 the reduction takes place under the same con- 
 ditions as, but more slowly than, the reduction 
 of arsenious compounds {v. supra). 
 
 Arsenic may be reduced to arsenious com- 
 pounds by such deoxidising agents as sulphurous 
 or phosphorous acid ; the reverse change may be 
 accomplished by heating with HNOjAqj-HClAq 
 and KCIO3, &o. ^"^ 
 
 Detection in cases of poisoning, — Arsenious 
 oxide or white arsenic is the usual form in 
 which the poison is administered. Because of 
 the insolubility of this compound, small solid 
 particles of it may sometimes be picked out of 
 the food or contents of the intestine ; these 
 should be tested by reduction to metallic arsenic, 
 &c., in the dry way. The poison is, however, 
 usually mixed with large quantities of organic 
 matter which must be removed or destroyed, 
 after which the arsenic may be ppd. as ASjSj 
 by long-continued passage of H^S, the pp. may 
 then be dissolved in warm HClAq with a crys- 
 tal of KCIO3, free chlorine removed by warming, 
 or the pp. may be dissolved in warm H^SOjAq, 
 and Eeinsch's, or better Marsh's, test used for de- 
 tecting the arsenic in solution. The organic 
 matter may be removed by diffusion (Graham) ; 
 or it may be destroyed by (a) treatment with warm 
 concentrated HjSO^Aq, (6) warming with HClAq 
 and crystals of KCIO, added from time to time, 
 (0) warming with HClAq and a little HNOjAq, 
 {d) passing CI into the liquid instead of adding 
 KClOs, (e) heating with HNOjAq till the residue 
 is semi-pasty and yellow, adding NaOHAq till 
 the acid is neutralised, mixing with powdered 
 NajCOj and a little NaNOs, drying in a crucible 
 and gradually heating until the mass fuses 
 (Wohler ; v. also Meyer, A. 66, 237). All re- 
 
AKSENIO. 
 
 805 
 
 agents used must be carefully treed from arsenic ; 
 a blank experiment should be conducted with the 
 reagents alone. ' (Buiz a. Schulz find that cer- 
 tain parts of the animal organism reduce AsjOj 
 and also oxidise As^Ou; they think that the 
 poisonous effects of AS4O5 are due to rapid de- 
 oxidation and reoxidatiou, v. B. 12, 2199 ; 14, 
 2400 ; 15, 1388.) 
 
 Estimation.-— I. Qravimetrio methods. 
 (i.) As magnesium-ammonium arsenate. 
 Solution of MgSO, is mixed with excess of 
 NHjOHAq and allowed to stand for 12 hours ; 
 this liquid is added to the solution containing 
 arsenic acid to which an excess of NH^OHAq 
 has previously been added. After some time 
 the pp. is collected on a weighed filter, washed 
 with ammonia-water, and either (a) dried in 
 vacuo over H^SO,, when it has the composition 
 Mg.NH4.AsO4.6H2O, or (6) dried at 100° to 110° 
 whereby 2(Mg.NH,.As04)H20 is produced, or (c) 
 strongly heated over a Bunsen lamp (tempera- 
 ture being gradually raised) whereby Mg2As20, 
 is formed. Method c is recommended by PuUer 
 {Fr. 10, 41), who states that the best means of 
 converting As^Sj into arsenic acid is treatment 
 with red fuming HNO, {v. also Eammels- 
 berg, B. 7, 544; Wood, Am. S. [3] 6, 368; 
 Macivor, O.N. 82, 283). — (ii.) As arsenious 
 sulphide. Arsenates are reduced to arsenites 
 by SO2 solution ; the arsenious solution is acidi- 
 fied with HClAq, and As^Sj is ppd. by long-con- 
 tinued passage of H^S ; the pp. is washed with 
 CS2 to remove any S which it may contain, 
 eoUeoted on a weighed filter, and dried at 
 100°-110° (Puller, Fr. 10, 41). — (iii.) As 
 uranyl pyroarseuate. Urauio acetate in 
 presence of ammonium salts pps. ammonium- 
 uranyl arsenate NH^.UOj.AsOj -h Aq, insoluble 
 in water and acetic acid, but soluble in mineral 
 acids. When this pp. is washed, dried, and 
 gradually heated to bright redness, the pyro- 
 arsenate (UOJjAs^O, is obtained. This method 
 is recommended by Puller {I.e.) ; ASjSj may 
 be dissolved in HClAq + KCIO3, and the As ppd. 
 after adding NH^.O^HjOj and H.CjHjO^ aq. 
 
 II. Volumetric methods. — (i.) By 
 iodine. Arsenious, is converted into arsenic, 
 acid, by Iodine in presence of alkali ; a solution 
 of NaHCOj saturated in the cold and used in 
 excess is the best alkali (Waitz, Fr. 10, 158). — 
 (ii.) By potassium dichromate. Arsenites 
 are converted into arsenates by the action of 
 KjCrjOjAq in acid solutions ; the residual 
 KjCr^O, is determined by a solution of FeSO^ ; 
 excess of HCl should be avoided (Kessler, Fr. 
 10, 205). — (iii.) By potassium permanga- 
 nate. Arsenites are oxidised to arsenates by 
 KjMn^OgAq in solutions containing H^SOj ; an 
 excess of K2Mn20j is added, and the residual 
 K,Mn20j is determined by FeSO^ solution 
 (Waitz, I.C.). 
 
 ^ Minute attention to detailed precautions must be ob- 
 served in testing for arsenic in poisoning cases. These 
 detfiils will be found in the following memoirs and 
 treatises;— Marsh, B. J. 17, 191; 20, 190; 22, 176; Eeg- 
 nault, A. Ch. [3] 2, 159; Fresenius a. v. Babo, .4.49, 287; 
 Wdhler, A. 69, 364 ; Schneider, P. 85, 433 ; Fyfe, P. M. 
 2, 487 ; Zenger, Fr. 1, 394 ; Wbhier, a. v. Siebold, Diu 
 forens-gericht. VetfahrenbeieinerArsenik-Vergiftitng(_l8i7) ; 
 Otto, Attsmillelung der Oifte [English ed. On Poisons] ; 
 Dragendorff, Die gerichtlich-chemiselie Ermittelv.ng der Qifle 
 (1868); Duflos, Pi-ufung chem. Oifte (1867); Taylor's 
 Uedical Jmisprudence ; Taylor On Poisons. 
 Vol. I. 
 
 References. — ^Besides the papers referred to 
 in the article, the following older memoirs on 
 arsenic and its compounds may be consulted:^ 
 Scheele, Opus. 2, 28 ; Bergmaim, Opus. 2, 272 ; 
 Buohholz, S. 15, 537 ; Laugier, A. Oh. 85, 26 ; 
 Fischer, S. 6, 236; 12, 155 ; 39, 364 ; Thomson, 
 S. 17, 422 ; 29, 430 ; BerzeUus, A- Oh. [2] 5, 
 179 ; 11, 225 ; 8. 84, 46 ; P. 7, 1, 187 ; Gehlen, 
 8. 15, 501 ; Gay Lussao, A. Oh. [2] 3, 136 ; 
 Pfaff, 8. 45, 95 ; Buchner, S. 45, 419 ; Soubeiran, 
 P. 19, 991 ; Mitscherlich, A. Oh. [2] 19. 
 
 Arsenic acid and Arsenates v. Absenic, 
 
 ACIDS OF. 
 
 Arsenic, acids of. — (In connection with these 
 compounds v. arts. Acids ; Aoids, Basicity oe ; 
 Hydkoxides.) Arsenious oxide, ASjOg, dissolves 
 in alkalis, forming salts from which other arse- 
 nites may be obtained ; no hydrate of ASjOj is, 
 however, known. The heat of solution of the 
 oxide is negative; [As W, Aq] =— 15,100. Ar- 
 senic oxide, AS2O5, dissolves in water with for- 
 mation of the hydrate H3ASO4, which crystal- 
 lises from concentrated solutions as 2H3ASO4.H2O ; 
 these crystals heated to 100° lose water, and 
 arsenic acid, HjAsO,, remains. By the action 
 of heat on this acid, two other acids are pro- 
 duced, viz. at 140°-180' pyroarsenic acid 
 H4AS2O,, and at 200° metarsenic acid HAsOj ; 
 these acids dissolve in water with reproduction 
 of H3ASO4. Each arsenic acid yields a series of 
 salts; Xhe arsenates (or ortho-arsenates), divisible 
 into three classes of the forms MHjA.s04, M2H.4ls0 „ 
 and M3ASO4 ; the pyroarsenates M4AS2O, ; and 
 the metarsenates MAsOj. The pyro- and met- 
 arsenates have not been much investigated, 
 they appear to exist only as solids and to yield 
 arsenates when brought into contact with water^ 
 Thomsen's thermal examination of the behaviour- 
 of aqueous solutions of the two oxides of arsenic- 
 towards soda shows that these solutions differ- 
 much as regards reactions and hence also as. 
 regards composition. In each case the thermal 
 behaviour of the oxide of arsenic is compared 
 with that of the corresponding oxide of phos- 
 phorus (the formula AS2O3 is used as being: 
 directly comparable with P2O3). 
 X [As^O'Aq, xNaOHAq] Difl. [P^O'Aq, aiNaOHAq]., 
 1 7,300 . < , 14,800 
 
 3 
 
 13,800 
 15,000 
 
 6,500 13,700 
 
 1,200 
 600 
 
 400 
 
 28,500 
 28,900 
 
 6 15,600 
 
 X [As-0=Aq, a;NaOHAq] DifE. [P=0'Aq,a;NaOHAqJ. 
 
 1 14,800 , 1 15,000 
 
 12,300 12,600 
 
 2 27,100 27,600 
 
 6,900 8,400 
 a 34,000 36,000 
 
 1,300 1,400 
 6 35,300 37,400 
 
 The mean thermal value of the reaction which 
 occurs when one formula-weight of soda is 
 added to an acid is 13,500; this value is 
 reached when 2NaOHAq is added to As203Aq, 
 but a little more heat is produced when a third 
 formula-weight of soda is added. The values 
 when baryta solution is used are [As-O'Aq, 
 BaOAq] = 14,000 ; [As^^O^Aq, 2Ba0Aq] = 15,600. 
 It seems probable that the soda reacts with 
 
806 
 
 ARSENIC. 
 
 water and arsenious oxide, not with arsenious 
 acid, to produce an arsenite NaAsOjHAsOj, 
 analogous to potassium arsenite, and that 
 addition of more soda changes this either into 
 the normal, or some other, arsenite. 
 
 I. Arsenious aoid and Arsenites (Pasteur, 
 A. 68, 308; Filhol, A. 68, 308 ; Kiihn, Ar. Ph. 
 [?T 69, 267 ; Streng, A. 129, 238 ; Stein, A. 74, 
 218 ; Eeynoso, 0. B. 31, 68 ; Girard, 0. B. 34, 
 918; 36, 973; Bloxam, 0. J. 13, 281). No 
 arsenious acid has been obtained in separate 
 form; but an aqueous solution of the oxide 
 AS4OS reacts with bases to form unstable salts 
 the compositions of which may be well repre- 
 sented by regarding them as derived from one 
 or other of the three hypothetical arsenious 
 acids, H3As03( = As(OH)3), HAs02( = AsO.OH), 
 H,As20,( — ASaO(OH),). The arsenites as a class 
 are very easily decomposed ; the ammonium 
 salt gives off ammonia at ordinary temperatures 
 and pressures, its aqueous solution yields pure 
 ASjOj on evaporation ; the potassium and sodium 
 salts are decomposed in solution by carbon 
 dioxide with separation of ASjO^. CaO, BaO, and 
 SrO, dissolve when boiled with water and ASjOj, 
 addition of lime- baryta- or strontia-water pre- 
 cipitates arsenites insoluble in water, but solu- 
 ble in acids and in ammonia. Solutions of 
 arsenites of metals which form sulphides soluble 
 in water are decomposed by Hj,S with precipita- 
 tion of AS2S3 ; if the metal of the arsenite forms a 
 sulphide insoluble in water then H^S precipitates 
 this sulphide along with As^S,,. Many arsenites 
 are not, however, decomposed by metals even 
 when the oxide of the metal of the arsenite is 
 insoluble in potash. Insoluble arsenites are 
 obtained by adding a soluble salt of the metal 
 to a solution of K or Na arsenite. All arsenites, 
 with the exception of those of the alkali metals, 
 are partially or wholly insoluble in water ; when 
 formed they usually retain some arsenious oxide, 
 so that it is difficult, and sometimes impossible, 
 to obtain definite compounds of fixed composi- 
 tion. Most arsenites are decomposed by heat 
 with formation of an arsenate and arsenic ; 
 heated with carbon, or with carbon and borax, 
 the whole of the arsenic is usually separated in 
 the metallic state. Heated with ammonium 
 chloride, most arsenites yield AsCl, and chloride 
 of the metal of the arsenite. Solutions of the 
 alkaline arsenites exposed to the air absorb 
 oxygen and produce arsenates (Fresenius, J. 
 1855. 382). 
 
 Arsenites. Ammcyiw/wm arsenites NH,.AsO|, 
 (Pasteur, Bloxam); (NHJ^As^Oj (Stein). By dis- 
 solving ASjOj in cone, aqueous NH3; white 
 lustrous prisms, very soluble in water. 
 
 Barium arseraiics Ba{As02)j; white gelatinous 
 pp. by adding BaCljAq to KAsOjAq (PUhol). 
 BaH4(As03)2 ; by mixing BaCl^Aq with As^OjAq 
 and NH|^q (Bloxam). Ba2As205.4H20 ; by dis- 
 solving As^Oj in BaOAq (Stein). 
 
 Calcium arsenites. Solutions of the various 
 potassium arsenites mixed with CaOl^Aq yield 
 pps. of varying composition (FiUiol, Stein). A 
 foiling solution of As^Oj added to CaOAq pre- 
 cipitates Ca3(As03)2 (Kilhn). CaCljAq mixed with 
 AsjOsAq and NHjAq precipitates Ca(As02)2 
 (Simon,P.40,417). ASjOsAqwithexoessof CaOAq 
 precipitates OajASjOj (Stein). 
 
 Cobalt arsenite. CojH|i(As03)4.H20 ; rose-red 
 
 pp. produced by reaction of KAsOaAq with 
 CoOljAq in presence of NHiClAq. 
 
 Copper arsenites. OuSO^Aq + KAs02Aq, or 
 ammoniacal CuS04Aq + AS405Aq, yields a light 
 green pp. (Scheele's green) of OuHAsOj ; soluble 
 in NHjAq with formation of HjAsOj and CujO ; 
 soluble in KOHAq with formation of K3ASO4, 
 and CU2O, which precipitates; when heated, 
 CuHAsOa evolves As and H2O, and a mixture of 
 CuO and copper arsenide remains. By digesting 
 CUCO3 with H2O and AS4O5 and evaporating the 
 solution, a yeUow-green salt, probably Cu(As02)2. 
 is produced. 
 
 Iron arsenites. Ferrous arsenite Fe2As205 
 is a greenish-white pp., soluble in NH3Aq, ob- 
 tained by mixing FeSOjAq with As40BAq and a 
 little NHjAq. Various ferric arsenites appear 
 to exist. Freshly precipitated Fe2(OH)8 digested 
 with cone. As40jAq containing not more than 
 i as much ASjO^ as there is Fe2(0H)s, completely 
 converts all the AS4O5 into an insoluble salt 
 (Bunsen) ; with less Fe2(0H)„ the whole of the 
 As40e is not removed from solution, a basic salt, 
 FeAsOa.FcjOa, is produced from which water 
 removes some AS4OS. A basic salt (rusty-red, 
 hard, soluble in NaOHAq), 2FeAsOs.Fe2O3.7H2O, 
 is produced (a) by adding Fe23S04Aq or FeaCl^Aq 
 to KAsOjAq, (6) by oxidising FeSOjAq by aqtia 
 regia, neutralising by NHjAq, adding a satu- 
 rated solution of Asfls in NaOHAq, and allow- 
 ing to stand for twelve hours. Another salt, 
 2FeAsO3.Fe2O3.5H2O, is obtained, as an ochre- 
 yellow pp. drying to a brown mass, on mixing 
 ASjOiiAq or KAs02Aq with Fe2(C2H302)iiAq ; water 
 withdraws part of the aoid from this salt ; it is 
 decomposed by heat, losing all its arsenious 
 aoid (Simon) ; only a part of its acid (Bunsen ; v. 
 also Grimaux, Bl. [2] 42, 211). 
 
 Lead arsenites. Pb(As02)2 is a white pp. 
 (Filhol), melting to a yellow glass (BerzeUus), 
 obtained by adding KAs02Aq to Pb(C2Hj02)2Aq. 
 Other salts are known : Pb2As.20(?) by precipita- 
 ting Pb(02H302)2Aq by As405Aq and NHjAq 
 (Filhol, Bloxam) ; Pb3(As03)2, by precipitating 
 Pb(C2Hs0.2)2Aq by (a) boiling ASjO^Aq (Kvihn, 
 Bloxam), or (6) Asfig in NaOHAq (Streng, A. 
 129, 238). 
 
 Magnesium arsenites. A solution of AS4O, in 
 excess of NHsAq mixed with MgSOjAq with 
 NH4ClAq gives a pp. whiohis Mg3(As03)2 (Stein), 
 MgHAsOs-HjO (Bloxam) ; heated to above 250° 
 Mg2As20s remains. Other salts appear to exist, 
 but their composition is vague and uncertain 
 {v. Filhol, I.C.). 
 
 Manganese arsenite. Mn3H5(AsOs)4.2H20 is 
 a light rose-red pp. obtained by adding 
 NH4As02Aq to MnS04Aq. 
 
 Mercury arsenites. Composition undecided. 
 Hg2N0jAq mixed with ASjO^Aq gives a white 
 pp. soluble in KAs02Aq ; if excess of KOH is 
 present Hg is precipitated. An arsenite of mer- 
 cury seems to be formed by mixing HgNOjAq 
 with KAsOjAq, or by digesting As^OjAq 
 with Hg. 
 
 Nickel arsenite. Ni3H3(As03)4H20 is ob- 
 tained as a greenish -white pp. on adding KAsOjAq 
 to NiCl2Aq containing much NH4CI ; heated in 
 air, this salt loses H2O, then ASjO,,, and yellow 
 infusible Ni3(AB04), remains. 
 
 Potassium arsenites. The aoid salt 
 KAsO2.HAsOj.H2O is produced by adding alcohol 
 
ARSENIC. 
 
 307 
 
 to a solution of muoh As^Oj inKOHAq (Pasteur, 
 Bloxam). By digesting this salt with KjCOjAq 
 tlie neutral salt KAsO^ is produced (Pasteur, 
 Filhol) ; by treating this with KOHAq and pre- 
 cipitating by alcohol the salt KjAsjOj is formed 
 (Bloxam). Two double salts, KAsOa-HAsO^-AsOI 
 and K2Bi2-3As205.2KI are described by Emmet 
 (Am. S. [2] 18, 583), and Harms (A. 91, 371), 
 obtained by adding KIAq to As^OjAq, or KIAq 
 to KAsOjAq containing so much HOjHjOa that 
 no brown colour is produced with turmeric 
 paper. 
 
 Silver arsenites. AgjAsOj, a yellow pp. ob- 
 tained by adding ASjO^Aq neutralised by NHjAq 
 to AgNOsAq (Eiihu, Filhol, Bloxam) ; soluble in 
 HNOj, H.C2H3O2, NHjAq, and solutions of ammo- 
 nium salts, also in KOHAq; solutions are not 
 precipitated by KClAq, but dissolve freshly pre- 
 pared AgCl. Heated alone or with alkalis it 
 is decomposed ; 
 
 4Ag3As03 = AgjO + 2Ag + 2Ag3As04 + As^Os 
 (Wohler, A. 101, 863). Other silver arsenites 
 are described by Harms (l.c.). 
 
 Sodium arsenites. None obtained pure ; 
 seem to be all very soluble in water (Pasteur, 
 Filhol, Bloxam). 
 
 Strontium arsenite. Sr(As02)2.4H20. By 
 mixing SrClzAq with KAsOjAq and allowing to 
 deposit crystals slowly (Stein). 
 
 Tin arsenites. Scarcely known ; both stan- 
 nous and stannic arsenites seem to exist. 
 
 II. Aesenioacid and Arsenates.— (Setterberg, 
 B. J. 26, 206 ; Baumann, Ar. Ph. 36, 36 ; Kod 
 Echonbey, /. pr. 49, 182 ; Field, C. /. 11, 6 
 Uelsmann, Zeits. f. d. ges. Naturwiss. 23, 347 
 Schiff, A. 112, 88 ; Maumenfi, 0. B. 58, 250 
 Debray, A. Ch. [3] 61, 419, also G. B. 59, 40 
 Lechartier, O. B. 65, 172; Salltowski, J.pr. 104, 
 129). The conditions of formation of the three 
 arsenic acids, H3AsO„ HAsOj, and H^As^O, have 
 been already described (p. 305). The following 
 thermal data are given by Thomsen (Th. 2, 236) 
 [As, OS H'] = 215,630; [As,OS H»,Aq] = 215,230; 
 [As'O', 3H20] = 6,800; [AsO<H», Aq] = 
 - 400; [As', 0', HT = 360,830 ; [As'O', Aq] = 6,000 ; 
 [AsW, 0^ = 64,710; [As=0»Aq, 0^ = 78,260. 
 The following heats of neutralisation are also 
 given by Thomsen {Th. 1, 196) : 
 
 n [NaOHAq, jiH'AsO^Aq] ; 
 i 6,233 
 
 11,972 
 13,790 
 i 14,994 
 
 2 14,724 
 
 n [wNaOHAq, HsAsO^Aq]. 
 i 7,862 
 
 1 14,994 Diff. 
 
 12,586 
 
 5 27,580 
 
 7,836 
 8 35,916 
 
 1,484 
 
 6 37,400 
 
 The acid HjAsOf is therefore tribasic ; but as 
 the reaction of the third formula-weight of soda 
 is accompanied by the production of not much 
 snore than half the quantity of heat which 
 accompanies the reaction of the first or second 
 formula-weight, it is probable that this acid 
 belongs to the same class of tribasic acids as 
 
 phosphoric acid, which class is represented by 
 Thomsen by the typical formula HE(0H)2H 
 {v. AoiDS, BASICITY ov). The relative affinity of 
 arsenic acid (v. A?finitt) is 21 (that of HNO3 = 
 100) which is a little less than the value for 
 phosphoric acid. 
 
 The acid H3ASO4 forms translucent crystals ; 
 the acid HjAsjO, clear lustrous crystals ; and 
 the meta-aoid HAsOj a white somewhat irides- 
 cent solid ; the ortho-acid dissolves in water with 
 disappearance of heat (v. supra), the other acids 
 dissolve with production of heat and formation 
 of the ortho-acid ; [H'AsW, Aq] = 1,800 (Thom- 
 sen, B. 7, 1003). 
 
 The following facts refer to the ortho-acid 
 H3ASO4. 
 
 Formation.— By action of HNOjAq on As or 
 As,0,. 
 
 Preparation. — Arsenious oxide is suspended in 
 water and chlorine is passed in; the solution is eva- 
 porated to dryness in a platinum dish, the tempe- 
 rature not being allowed to rise muoh above 100° ; 
 the residue is dissolved in water and evaporated 
 slowly at 100° ; after a time small needle-shaped 
 crystals of H3ASO4 separate out (E. Kopp, J.pr. 
 69, 270). 
 
 Properties. — Action of heat already described 
 [v. p. 805). Aqueous solution tastes sour and 
 metallic ; it burns the skin. The most concen- 
 trated solution has S.G. 2-5 ; the following table 
 gives some data regarding S.G-. of aqueous 
 solutions (Schifif, A. 118, 183). 
 S.G. at 15° 1-7346 Potge. of H3ASO4 67-4 
 „ 1-3973 „ 45-0 
 
 „ 1-2350 „ 800 
 
 1-1606 „ 22-5 
 
 „ 1-1052 „ 15-0 
 
 1-0495 „ 7-5 
 
 Beactions. — 1. Heated with carhon, many 
 metals, or potassium cyanide, it yields arsenic. — 
 2. Heated with cone, hydrochloric acid AsCl, 
 and 01 are produced ; if the S.G. of the aqueous 
 HOI used is less than 1-04 no ASCI3 is produced 
 (Presenius and Souchay, Fr. 1, 448) ; with acid 
 of S.G. 1-1 traces of AsCij are formed (Mayrhofer, 
 A. 158,826). — 3. Sulphwrous acid produces arse- 
 nious oxide and sulphuric acid (Wohler, A. 30, 
 224). — 4. Zinc and iron dissolve in aqueous 
 H3ASO4 with evolution of H and AsH, and pro- 
 duction of gelatinous solids (? arsenates of Zn or 
 Fe) ; in presence of HjSOj, these metals pre- 
 cipitate As, and evolve H and AsH,, — 5. Sul- 
 phydric acid (HjS) reduces HjAsO, in solution 
 to AS2O3, with precipitation of S, and then 
 throws down As^Sg; this reaction takes place 
 slowly at 10°-15°, but more rapidly at 60°-70°. 
 6. Sodium thiosulphate solution, in presence of 
 HOI, produces a pp. of AsjSj (j. «.).— -7. Tung- 
 states of potassium, ammomvim, and silver when 
 evaporated with KHjAsO, solution yield complex 
 compounds, viz., 6WOa.AS2O5.3K2O.3H2O ; 
 6W03.AS205.4(NHJ20.5H20; and 
 16WOs.As203.6Ag20.11H20 (Gibbs, P. Am. A. 
 15, 1 ; 16, 109 ; v. also Debray, C. B. 78, 1408 j 
 and Seyberth, B. 7; also Sonnensohein, J.pr. 
 53, 339, 891). Perivatives of arsenic acid in 
 which OH is replaced by 01, or Br, or I, are 
 not known. 
 
 Arsenates. Arsenates are isomorphous with 
 corresponding phosphates. The arsenates of the 
 alkali metals, and the acid arsenates of the 
 
 x2 
 
808 
 
 ARSENIC. 
 
 ftlkaline earth metals, are soluble in water ; they 
 lose all their arsenic as chloride by strongly 
 heating -with sal-ammoniac (Rose, P. 116, 453). 
 The neutral and basic arsenates are easily solu- 
 ble in mineral acids, including arsenic acid. 
 Debray {I.e.) describes a series of amorphous 
 arsenates, MHjAsOj.HjO, obtained by precipi- 
 tating alkaline arsenates by salts of the metals 
 M ; these arsenates become crystalline, accord- 
 ing to Debray, by long-continued digestion with 
 the liquids in which they are produced. By 
 fusing chlorides and fluorides with arsenates, 
 Lechartier {I.e.) obtained a serieB of crystalline 
 salts analogous in composition to Wagnerite and 
 Apatite ; thus : 
 
 Corresponding to Wagnerite [(PO,.F.Mgj)]. 
 AsO4.Cl.Ca2 
 As04.Cl(F).Mg, 
 AsO,.Cl.Mg2 
 AsO4.Cl.Mn2 
 Corresponding to AjgaUte [(POJa.C^Fj.CaJ. 
 (As04)3.Cl.Ca5 (AsOJs.Cl.Sr5 
 
 (AsOJ,.Cl(F).Ca5 (AsOJ3.Cl.Ba5. 
 
 (AsOJ3.Cl.Pb5 
 Debray also obtained the following crystallised 
 insoluble arsenates by digesting arsenic acid 
 solution with carbonates of the various metals : 
 2AsO.CaH.Hi,0 ; AsOiCuH; 2AsOjCuH.3H20 ; 
 (ASOJ2CU3.4H2O ; and As04Cu.(CuOH). Arse- 
 nates are usually prepared by adding 
 Na2HAs04Aq to solutions of salts of the various 
 metals, using the calculated masses of the re- 
 acting bodies. 
 
 Alumimum arsenate. White pp. by adding 
 a soluble arsenate to a solution of an Al salt. 
 
 AmmorUum arsenates. (NH4)2.H2As04 ; by 
 adding NHjAqto cono. HjAsO, until the pp. which 
 forms is dissolved (Salkowski). (NHiJjAsOj.SHjO; 
 by adding considerable excess of NHjAq to 
 HjAsO^Aq. NHjHjAsOj ; by adding one for- 
 mula-weight H3ASO4 to one formula-weight 
 (NHJ2HASO4. 
 
 Barium arsenates. BaHAsOj ; crystalline, 
 obtained by adding NajHAsOjAq to BaCljAq. 
 Ba,2As04; crystalline, obtained by adding 
 ^a^AsOjAq to BaCl2Aq; acted on by water 
 it forms the salt BaHAsO, (Field). The salt 
 BaHj(As04)2 is obtained by dissolving BaHAsO, 
 in warm HjAsOjAq and allowing to crystallise 
 (Setterberg). Two barium-ammonium arsenates 
 2Ba.NH4.AsO,.H20, and BaH2(NH4)2(As04)2 are 
 described (Baumann, Mitscherlich). 
 
 Bismuth arsenate. 2BiAs04.H20 ; yellow- 
 ish white pp. insoluble in water and HNOjAq, 
 soluble in HClAq ; insoluble in a cone, solution of 
 Bi3N0., containing a little free acid (Schneider, 
 J.pr. [2] 20,418). 
 
 Cadmium arsenates. White crystalline pps. 
 obtained by precipitating solution of Cd salts by 
 Na^HAsOjAq ; two are known, Cdj(AB04)2.3Hj0 
 and Cd5H2(As04)4.4H20 (Salkowski). 
 
 Caleium arsenates. Ca.H.As04 ; prepared like 
 BaHAs04; occurs native as FharmaeoUt-e. By 
 treatment with NHjAq this salt yields Ca3(AsO)4 
 (Kotschonbey). Two calcium-ammonium ar- 
 senates are described, CaH2(NH4)2(AB04)2 and 
 CaNH4.As04.6 or TB.fi (Baumann, Kotschonbey; 
 also Bloxam, O. N. 54, 163). The salt Ca2As20, 
 is obtained fcystrongly heatingCa.NH4.AsO4.7H2O 
 (Bloxam). 
 
 Ceriwm arsenate. Ce.H.As04; insoluble in 
 water, soluble in excess of H3A304Aq. 
 
 Cobalt arsenates. C0HASO4 is unknown ; 
 CoH4(As04)2 obtained by evaporating m vacua 
 solution of CoO.HjO in exoessof HjAsOjAq. Cobal- 
 tic arsenate, C032ASO48H2O (Karsten, P. 60, 266) 
 is areddish powder obtained byprecipitating the 
 solution of a Co salt by NajAsOjAq; occurs 
 native as Cobalt-bloom. An impure basic arsen- 
 ate of cobalt is known in commerce as Chaux 
 mitalligue. 
 
 Copper arsenates. Cu5H2(As04)4.2H20 ; ob- 
 tained as a blue pp. by adding (NHj2HAs04Aq 
 to CuS04Aq and drying at 130° (Salkowski). 
 Cu3(As04)2 is a green powder obtained by pre- 
 cipitating CuS04Aq with NajHAsOjAq ; this 
 salt dissolves in NHjAq, and on long 
 standing, clear blue crystals having the 
 composition [(NH3)2Cu]3(As04)2 separate out 
 (Damour, B. J. 26, 247 ; and 27, 181). Various 
 basic arsenates of copper occur native as 
 minerals {v. Coloriano, Bl. [2] 45, 707). 
 
 Ghromiwm arsenates. Chromic arsenate is 
 a green pp. obtained by mixing solutions of a 
 chromic salt and K3ASO4 ; composition uncertain. 
 By mixing solutions of K2Cr04 and HjAsO, 
 Schweizer {J.pr. 39, 267) obtained a gelatinous 
 pp. having the composition (dried at 100°) 
 (CrO)3As04.K2H(As04)2.4H20. 
 
 Didymi/um arsenate. 
 Dis(As04)a.DiH(As04)2.H20; by boiling H3As04Aq 
 with DijOs (Marignac, A. Ch. 88, 185). 
 Iridium arsenate is a brown pp. 
 Iron arsenates. The ferrous salt is obtained 
 by double decomposition; it oxidises easily; 
 after drying, its composition is E'e20As04.55H20 
 (Wittsteiu, Viertel-jahrsschr. pr. Pharm. 15, 
 185). The ferric salt (?FeH3(As04)2) is obtained 
 by mixing Fe2Cl|,Aq with Na2HAs04Aq ; it is a 
 white powder which loses water on heating and 
 becomes reddish, soluble in H3As04Aq, but this 
 solution soon decomposes, unless very con- 
 centrated, depositingPe2(OH)u (Lunge, Fr. 6, 185). 
 Various other ferric arsenates of uncertain com- 
 position have been described by Berzelius {v. also 
 Grimaux, Bl. [2] 42, 211). 
 
 Lead arsenates. The salt PbHAsO, is ob- 
 tained by double decomposition (Salkowski); 
 when treated with NHjAq it yields Pb3(As04)2. 
 
 Lithium arsenates. 2Li3As04.H20 is a 
 white powdery pp. obtained by dissolving 
 Li2C03 in HjAsOjAq and adding NHjAq ; when 
 this salt is dissolved in HjAsOjAq, trimetrio 
 prisms of 2LiH2As04.8H20 crystallise out (Eam- 
 melsberg, P. 128, 311). 
 
 Magnesium arsenates. 2MgHAs04.13H20 ; 
 white pp. by mixing 5 parts NajHAsO, in solution 
 with a dilute solution of 3 parts MgSO, (Graham, 
 A. 29, 24). Mg3(As04)2 is obtained byboiUngthe 
 preceding salt for some time with cone. 
 Na2HAB04Aq. A magnesium-ammonium ar- 
 senate MgNH4AB04.6H20 is obtained by adding 
 HjAsOjAq with excess of NHjAq to MgS04Aq 
 containing NH4CI ; it is slightly soluble in 
 NHjCLAq, strongly heated it loses NH3 and 
 Mg2As20, remains [H. Eose ; Field ; Wittstein ; 
 Puller ; Fresenius {Fr. 3, 206) ; Levol {A. Ch. 
 [S] 17, 50)]. A magnesium-potassium arsenate 
 MgKAsO,, and a corresponding sodium salt, are 
 obtained by fusing MgHAs04 with KjCO, and 
 EOH (or Na^CO, and NaOH). 
 
ARSENIC. 
 
 300 
 
 Manganese arsenates. MnHAsO^ is pro- 
 duced by saturating HjAsOjAq with MnCOa ; 
 nsing excess of HjAsO^Aq the salt MnH^ (AsOJj 
 is formed (Sohiefer). The manganese-ammonium 
 salt MnNHjAsOi-GHjO is obtained like the 
 corresponding Mg salt as a gummy pp. which 
 becomes crystalline. Some basic Mn arsenates 
 are described by Coloriano (Bl. [2] 43, 709). 
 
 Mercury arsenates. The mercurous salt 
 HgjHAsO, is a yellowish white pp., which be- 
 comes orange red, produced by adding HjAsO^Aq 
 to HgNOaAq; it is insoluble in water and 
 H.02Hs02Aq, soluble in HNOjAq. When heated, 
 this salt loses TLfl and Hg, and a mercuric 
 salt (probably Hg^As^O,) remains. By adding an 
 excess of HjAsOjAq to the mercurous salt, and 
 evaporating, the meta-salt Hg2(AsOs)2 is obtained 
 as a white powder, somewhat soluble in 
 HNOjAq, decomposed by HClAq with formation 
 of HgCl, decomposed by KOHAq with withdrawal 
 of half its arsenic as HjAsO, (Simon, P. 41, 424). 
 
 Molybdenum arsenate is a grey pp. (for com- 
 binations of AsjOs with M0O3 and KjO v. 
 Aesenio Acid, Reactions, No. 7). 
 
 Nickel arsenates. Analogous to cobalt 
 arsenates (3. v.). The salt Ni3(As04)2.8H20 
 occurs native as Nickel-bloom. 
 
 Palladi^tm arsenate is a clear yellow 
 pp. obtained by heating NajHAsO^Aq with 
 Pd.2N03Aq. 
 
 Platinum arsenate is a light-brown pp. 
 obtained like the Fd salt. 
 
 Potassium arsenates. The salts E3ASO4 and 
 KjHAsOj are obtained by adding KjCOj or KOH 
 to HjAsOjAq ; the former crystaUises from very 
 cone, solutions (Graham, P. 32, 47). By heat- 
 ing together equal parts of KNO3 and ASjO^, 
 dissolving in water and evaporating, or by 
 adding KOHAq to HsAsO^Aq until neutral to 
 litmus and crystallising, the salt EHjAsO, is 
 obtained. The crystals of this salt are fairly 
 soluble in water (S. 6° = 19), insoluble in alcohol. 
 Heated above 288° the salt melts to a glassy 
 mass. 
 
 Silver arsenates. AgjAsO^ is a dark red- 
 brown pp. produced by mixing HjAsO^Aq, or 
 solution of an alkaline arsenate, with AgNOjAq ; 
 it melts to a brownish-red glass, it is decom- 
 posed by HClAq to AgCl and HjAsO^Aq, it is 
 soluble in HCJEaOjAq, NHjAq, and solutions of 
 many NH^ salts. By digesting this salt for some 
 time at a gentle heat with HjAsO^Aq a white 
 salt, 2AgAsOs.As205, is obtained. 
 
 Sodium arsenates. Na2HAs04.12H20, S.Q-. 
 1-67 (Sohiff), is obtained in large crystals, 
 isomorphous with common sodium phosphate, 
 by adding a slight excess of NajCOjAq to 
 HjAsOjAq, and evaporating at a temperature 
 not higher than 18° (Fresenius, J. pr. 56, 30). 
 The crystals which form at 20' and upwards 
 contain 7H2O, S.G. 1-87 (Schiff) ; the crystals 
 with I2H2O effloresce quickly, those with 7H2O 
 do not. The salt melts when heated forming 
 a clear transparent liquid. At 0° a salt 
 crystallises with IS^HjO (Setterberg). The 
 salt NaHjAsOi.HjO is formed in large crystals 
 by adding NajCOaAq to HjAsOjAq until the 
 solution is no longer ppd. by BaCl^Aq; iso- 
 morphous with the corresponding phosphate; 
 S.G. 2-635 (Schiff). A solution of S.G. about 
 1-7 gives crystals of NaHjis04.2H20 (Joly a. 
 
 Dufet, C. B. 102, 1391). A oono. solution of 
 HjAsO, decomposes NaOlAq and NaNOj on heat- 
 ing. Two double salts, viz. NaKHAs04.7H20 
 (Schiff), or 9H2O (Kotschonbey), and 
 NaNH4HAsO,,.4H20, are described (Uelsmann). 
 The former is obtained by neutralising 
 NaH2As04Aq by KjCOaAq, the latter by mixing 
 solutions of Na2HAs04 and (NH4)2HAsOj. The 
 compound Na3As04.NaP.12H.;0 crystallises in 
 monometric octahedra ; it resembles common 
 alum in appearance ; S.G. 2-849 ; S. (25°) = 10-5 ; 
 S. (75°) = 50. This salt is obtained by fusing 
 together, with special precautions, 1 part ASjOj, 
 4 parts Na^OOa, 3 parts NaNOj, and I part 
 0aF2 (Briegleb, A. 97, 95). Two compounds 
 of sodium arsenates with sulphates seem to 
 exist NajAs„0,g.2Na2S04 (Mitscherlich), and 
 NajASjOi.NajSOj (Setterberg). 
 
 Strontiu/m arsenates. By nfldingNft^ TTA gn^Aq 
 to SrCl2Aq a pp. of SrNaAs04.H20 is obtained ; 
 the filtrate from this when evaporated gives a 
 white pp. of SrHAsOj (Salkowski). 
 
 Tin arsenates. 2SnHAs04.H20; a white pp. 
 produced by adding excess of K^HAsOiAq to 
 SnCljAq ; by the reverse process the salt 
 Sn(Sn01)As04.H20 is said to be formed (Lenn- 
 sen, A. 114, 113). 
 
 Zinc arsenate Zn3(As04)2.3H20 is a gela- 
 tinous substance (Eottig, J.pr. 48, 182 and 
 256); the salts ZnHAsOi, ZnH4{AB04)2, and 
 Zn3(As04)2.NHj, are also known {v. also Friedel, 
 Bl. [2] 5, 433). 
 
 The compositions of the remaining arsenates, 
 which have been very slightly investigated, are 
 expressed by the following formulse : — 
 
 Thallium, Tl.AsO4.2H2O. Thorium, 
 Th.HAs04. Uranium, (UO)2HAs04.4H20 ; 
 the salts (UO)2NaAs04 and (UO)4Cu(As04)28H20 
 are also known (Werther, A. 68, 312). Vana- 
 dium, VH2(As04)2. Yttrium, YHASO4. Arsen- 
 ates of titanium and zirconium are said to 
 have been obtained. 
 
 Arsenic, alloys of, v. Arsenic, Combinations 
 of. No. 9. 
 
 Arsenic, ammonio-chloride of, v. Absenio 
 OHiiORiDE, Combinations of. No. 2. 
 
 Arsenic, bromide of. AsBr, {Arsenioua 
 bromide, Tribromide of arsenic). Mol. w. 
 314-25. [20°-25°]. (220°). S.G. 3-66 (Boedeker, 
 /. 1860.17). V.D. 157-5. H.P. 59,100 soUd As, 
 gaseous Br (Guntz, 0. B. 101, 161). S.V.S.85-8. 
 
 Preparation. — 1. Powdered arsenic is shaken 
 into a retort filled with Br vapour, and the 
 bromide is distilled from the excess of As. — 
 2. Powdered arsenic is added to a mixture of 
 1 part Br with 2 parts OS™ until the liquid ia 
 colourless ; more Br is then added, followed by 
 more As, until the colour ia no longer removed 
 on the addition of As ; the liquid is then filtered 
 and evaporated ; on standing, the bromide ia 
 deposited in crystals (Nicklte, 0. B. 68, 837 ; 
 /. Ph. [3] 41, 142). 
 
 Properties. — Colourless deliquescent prisma 
 with strong arsenical odour, melting to a pale 
 yellow liquid which fumes but slightly in the 
 air. Volatilises unchanged and yields a crystal- 
 line sublimate. 
 
 Beactions. — 1. Water, added in small quan- 
 tity, produces AsOBr and HBr (?with a little 
 arsenious oxide) (SeruUas, S. S5, 345) ; added in 
 large quantity, decomposes it into HBr and 
 
SIO 
 
 AESENIO. 
 
 AS4O, (Serullas, l.c.). An aqneouB solution 
 containing HBr deposits the oxy - salts 
 2AsOBr.3As20a-12H20 and 2AB0Br.3H20 
 (Wallaoe, P. M. [4] 17, 261). — 2. Ammmmm 
 bromide added to a cold concentrated aqueous 
 solution pps. six-sided tables consisting chiefly 
 of AsBrj (WaUaoe, P. M. [4] 17, 261). — 
 
 3. Sodium thiosulphate at first produces AsOBr, 
 and then AsjSj (NicklSs, J. Ph. [3] 41, 142).— 
 
 4. ArsenioiLS oxide dissolves in molten AsBrj ; 
 on cooling to 150° the liquid separates into two 
 layers, tha upper of which is AsOBr, and the 
 lower probably 3AsOBr.ASjOa (WaUaoe, P. M. 
 [4] 17, 261). 
 
 Combinations. — With the alkaline bromides 
 to form rather unstable jorystalUsable com- 
 pounds (NickUs, I.e.). 
 
 Arsenic, chloride of. AsClj (Arsenious 
 chloride. Trichloride of arsenic, Butter of 
 arsenic, Caustic oil of arsenic). Mol. w. ISl-ll. 
 [below 29°]. (130°-2) (Thorpe, 0. /. 37, 352). 
 S.G. ^ 2-205 (Thorpe, i.e.). V.D. 9075. 
 Volume at i° = vol. atO° 
 
 + -000991338* + •000000849t' + -0000000027551*3 
 (Thorpe, Z.C.). S.H.p. -1122 ; S.H.v. -7034 ; 
 H.V. 69-74 (Eegnault, J. 1863. 77). H.P. 
 71,460 [solid As and gaseous CI] {Th. 2, 326). 
 Ea 49-59 (Haagen, P. 131, 122). S.V. 94-37 
 (Thorpe, I.e.). 
 
 Formation. — 1. By distilling As^Oj with cone. 
 HjSOj and NaCl (Glauber in 1648 ; Dumas, P. 
 9, 308). — 2. By distilling AS4O5 with cono. HCl. 
 3. By leading dry HCl gas over powdered 
 ASjOg.— 4. By passing dry HCl gas over gently 
 heated powdered ASjOj : Asfi^ + lOHCl = 
 2ASCI3+ 2Cl2-t-6H.O(Mayrhofer, A. 158, 326).— 
 
 5. By adding HjSO, to a solution of As^Oj in 
 cone. HCl.— 6. By heating As^Sa with SHgClj in 
 a, retort (Ludwig, Ar. Ph. 97, 23).— 7. By the 
 action of S^Clj on As (Wohler, A. 73, 374).— 
 8. By the action of PClj on ASjO^ or on AS2O5 
 (POCls, and in the case of AsjOj free CI, is also 
 formed) (Hintzig and Geuther, A. Ill, 171). 
 
 Preparation. — Coarsely powdered arsenic is 
 heated in a retort, dry chlorine is then led in, 
 and the contents of the retort are heated ; the 
 distillate is collected in a dry receiver, and freed 
 from excess of chlorine by redistillation from 
 arsenic, or by shaking with mercury, pouring 
 off from the black solid which is formed, and 
 redistilling. Or the product may be distilled 
 upwards for some time in a current of dt-y CO^ 
 (Thorpe, i.e.). 
 
 ProperUes. — A colourless, oily, fuming, very 
 poisonous, liquid; mixes with alcohol, ether, and 
 liquid oils ; it is decomposed by water {v.infra). 
 Distilled with aqueous HCl, AsClj is partly vola- 
 tilised ; HCl prepared from arsenic containing 
 HjSO., always therefore contains AsClj ; arsenious 
 chloride when hot dissolves phosphorus and 
 sulphur, but they crystallise out again on cool- 
 ing. 
 
 Reactions. — 1. With a little water the solid 
 oxychlorideAsOCl.H20( = A3(OH)2Cl)isproduced 
 (Wallace, P. M. [4] 16, 358). With more water, 
 especially if hot, AsClj is decomposed into HCl 
 and ASjOj, a great portion of the latter separating 
 in the solid form. — 2. With arsenic hydride 
 it reacts to form HCl and As. — 3. By the action 
 of NOj it is converted into ASjO^, NOCl being 
 
 simultaneously produced (Geuther, J. pr. [2] 8, 
 854). 
 
 Combinations. — 1. Arsenious oxide dissolves 
 in boiling AsClj, and on distillation the oxy- 
 chloride AsOCl {q. v.) is obtained (Wallace, P. M. 
 [4] 16, 358). — 2. Ammonia gas is absorbed by 
 AsClj with production of a white solid, 
 2ASCI3.7NH3 according to H. Eose (P. 52, 62), 
 2AsClNH.4NH4Cl.NH3 according to Pasteur 
 {A. Ch. 68, 307), Miohaelis suggests the for- 
 mula 2As(NH3Cl)3.NHa (Lehrbuch der anorg. 
 Chem. ii. 459, [1881]) ; this compound is de- 
 composed by heat, giving, off NH3 and then a 
 white sublimate containing NH^Cl ; it is soluble 
 in alcohol, but is decomposed by cold water with 
 production of heat and ammonia, from the solu- 
 tion six-sided plates crystallise out, having the 
 composition A34Cl2N2H,„05,these are decomposed 
 by cono. ammonia with production of (NH4)As02 
 which soon decomposes (Pasteur, I.e.). — 3. Sul- 
 phur dichloride, SCl^, is said to form a com- 
 pound 2ASCI3.3SCI2, but according to NUson, the 
 product of the action is merely a mixture (/. pr. 
 [2] 12, 295).— 4. With alcohol forms easily de- 
 composed crystals of AsClj.CjHjO (De Luynes, 
 C. B. 50, 831). 
 
 Arsenic, fluoride of. AsFa {Arsenious fluoride). 
 Mol. w. 131-9. (60°-4) (Thorpe, C. J. 37, 352). 
 S.G. f ; 2-666 (Thorpe, I.e.). V.D. 66-1. 
 S.V.S. 49-5. 
 
 Formation. — By heating sodium or ammo- 
 nium fluoride with arsenious bromide or chloride 
 (Macivor, C. N. 30, 169). 
 
 Preparation. — Equal parts of dry powdered 
 fluorspar and arsenious oxide are heated in a 
 leaden vessel with 5 parts cono. H2SO4 ; the dis- 
 tillate is collected in a dry glass receiver. 
 
 Properties. — A transparent, very volatile, 
 fuming, liquid ; it acts slowly on glass in a 
 closed vessel, but exposed to the air it absorbs 
 moisture with production of AsjO,,, and HP 
 which acts on the glass. Dropped on the skin 
 it evaporates at once but leaves a painful wound 
 (Dumas, A. Ch. [2] 31, 434). It absorbs dry NH, 
 in large quantities ; miscible with alcohol and 
 ether (Macivor, I.e.). 
 
 Reaction. — With water it forms a clear 
 liquid (heat is produced) which soon decomposes 
 to AS403 and HP. 
 
 Arsenic, haloid compounds of. AsF, ' AsCl, ; 
 AsBr3 ; Aslj and Aslj, (? Aslj). All gasified, 
 except the di- and pent- iodide, and molecular 
 weights known ; v. the arts. Aksenic, tluokide 
 
 or, OHLOEIDE of, BROMIDE OF, IODIDES OF, V. alSO 
 
 art. Haloid compounds. 
 
 Arsenic, hydrides of. (In connection with 
 these compounds v. art. Htdkides.) Two 
 hydrides are known ; gaseous AsHg, and solid 
 tcAsH. 
 
 I. AiiSENio lEiHYDBiDE. ABH3 {Arsenurettcd 
 hydrogen, Arsine).Uo\.w.^^■9.[-llS°■5'].( - 54°-8) 
 (Olszewski, Sits. W. 5, 127) (about -40°). V.D. 
 39-1 (Dumas, ^. Cfe. 33, 355). H.P.- 361,700 
 (solid As) (Ogier, A. Ch. [5] 20, 5). Discovered 
 by Scheele in 1775. 
 
 Formation. — 1. By dissolving zinc or iron 
 in dilute HClA.q or H^SOjAq containing ASjO, 
 or AS.2O5. — 2. By electrolysis of solution of 
 AsjOjAq or ASjOjAq. — 3. By the action of organic 
 matter on many arsenic compounds -, e.g. the 
 action of paper on Scheele's green (the air o( 
 
ARSENIC. 
 
 311 
 
 rooms the papei ou the walls o{ which is 
 coloured with Scheele's green usually contains a 
 little AsH^). 
 
 Preparation. — 1. By the action of water, or 
 better very dilute HCl or H^SOj, ou the solid 
 alloy of As and Na which is obtained by heating 
 Na in AsH, obtained by the action of acids on 
 Zn containing As (Janowsky, B. 6, 216). — 2. By 
 the action of H2SO4 diluted with 3 times its 
 weight of water on the alloy of As and Zn ob- 
 tained by heating equal parts of finely granu- 
 lated Zn and powdered As in a covered crucible 
 (Soubeiran, A. Ch. [2] 23, 307 ; 43, 207). The 
 gas is coUeoted over boiled water. 
 
 Properties. — A colourless gas with repulsive 
 odour; excessively poisonous (in working with 
 this gas it is impossible to be too careful ; more 
 than one chemist has been killed by it, e.g. 
 Gehlen in 1815). Easily decomposed by heat 
 into its elements even when mixed with much 
 hydrogen. By the action of the silent electric 
 discharge it yields solid As hydride (Ogier, A. 
 Ch. [5] 20, 5). Slightly soluble in water. Dry 
 oxygen has no action at ordinary temperatures. 
 
 Beactions. — 1. Heated in a/i/r it burns to 
 As fig and H^O ; in a limited supply of air, to As 
 and BUO. — 2. Mixed with oxygen and subjected 
 to electric discharge, complete decomposition to 
 ASjOj and Kfi occurs explosively. — 3. Concen- 
 trated acids decompose it into its elements; 
 cone. H.jSO.,Aq forms also AS2S3 (Humpert, /. 
 pr. 94, 392) ; cone. HClAq acting for some 
 time forms also AsCl, (Napoli, J. pr. 64, 93). — 
 4. Decomposed by chlorine, bromine, or iodine, 
 with production of much heat and formation of 
 haloid compounds of As. — 5. Sulphuretted 
 hydrogen at about 300° forms As^Sa and H. — 
 6r The haloid acids HCl, HBr, HI, are without 
 action on AsHj at ordinary temperatures. — 
 
 7. Heated with sulphur, ASjSj and H^S are pro- 
 duced (Jones, C. J. [2] 14, 648).— 8. Eeaots 
 with PCI3 to produce AsP and HCl (v. Aksenio, 
 Combinations of. No. 8). — 9. Many metals, e.g. 
 K, Na, Sn, heated in AsHj form alloys with As 
 and set free H. — 10. Many metallic oxides, e.g. 
 CuO, decompose AsHj when heated with it, 
 forming arsenides and water (the quantity of 
 AsH, in a gaseous mixture may be thus de- 
 termined). — 11. Absorbed and slowly decomposed 
 by alkalis, and by water containing oxygen or 
 air. — 12. Many metallic salts in aqueous solu- 
 tions absorb and decompose AsHj ; salts of 
 metals whose oxides are easily deoxidised 
 produce water and arsenious oxide ; salts of 
 metals whose oxides are not so easily deoxidised 
 produce water and arsenic which is precipitated 
 with the metal. Thus with (1) AgNO,, and (2) 
 CuSOj, solution, the reactions are 
 
 (1) 24AgNOsAq + 4AsH3 + 6H20 = 
 
 As fiM + 24HNOsAq -t- 24Ag ; 
 (2) 2ASH3 -I- 3CuS0^Aq = ASjCu^ + SH^SO.Aq. 
 Gold chloride in solution is reduced to gold, 
 while As,0|i remains in solution. 
 
 Beferences. — (Besides those in the text) Marsh, 
 B. J. 17, 191; 20, 190; 22, 175; Stromeyer, 
 Comment. 80c. Oott. 16, 141 ; Proust, Scher. J. 
 
 8, 285 ; Fischer, P. 9, 261 ; Myers, A. 159, 127 ; 
 Parsons, C. N. 35, 235. 
 
 II. SOMI) ABSENIO HTDKLDB, JlAsH. Mol. W. 
 
 unknown. Janowsky (B. 6, 220) states that 
 when potassium or sodium arsenide is decom- 
 
 posed by water, a solid, brown, velvet-like, com- 
 pound of As and H, in the ratio As:H, separates 
 out. When dilute acids are used in place of water, 
 AsHj is evolved and As deposited. According 
 to Ogier (A. Ch. [5] 20, 5), solid mAsH is pro- 
 duced by the action of the silent discharge on 
 AsHj. Older observations recorded the produc- 
 tion of a solid compound of As and H by the 
 action of dilute acids on arsenide of zinc 
 {v. especially Wiederhold, P. 118, 615), but these 
 are contradicted by Janowsky (l.c.). According 
 to Bloudlot (A. Ch. [3] 68, 186), a solid hydride 
 of arsenic is produced (1) in a Marsh's apparatus 
 when a little HNO3 is present, and (2) when 
 AsHj is passed into aqueous AgNOj, excess of 
 Ag is remoyed by adding NaCl, a drop of HNOjAq 
 is added, and a piece of Zn is placed in the 
 liquid. 
 
 Arsenic, hydroxides of. The compounds of 
 As, 0, and H, are acids ; v. Arsenio, aolds of 
 (v. also arts. Acids, and Hydkoxidbs). 
 
 Arsenic, iodides of. 
 
 I. Arsenious iodide, AbI, (Triiodide of ar- 
 senic). Mol. w. 454-59. (394° to 414°) (Carnelley 
 a. Williams, 0. /. 33, 283). S.G. 4-39. V.D. 
 227-3. S. 30-12 at 100°. H.P. solid As, gaseous 
 I [As, P] = 28,800 (Guntz, O. iJ. 101, 161). S.V.y. 
 103-6. 
 
 Formation. — 1. By subliming together 1 part 
 As and 3 parts I in a retort arranged so that the 
 sublimate condenses in the neck ; the sublimate 
 is treated with hot alcohol from which the Aslj 
 crystallises on cooling (Bette,.;!. 33, 349). — 2. By 
 boiling 3 parts powdered As and 10 parts I wi lb. 
 water, filtering, and evaporating (Plisson, S. 55, 
 335). — 3. By acting on AsClj with cone. HI 
 solution [HCl is evolved] (Hautefeuille, Bl. [2] 
 7, 198).— 4. By adding a concentrated solution 
 of KI to a hot solution of AsjO^ in HClAq (Bam- 
 berger a. Philipp, B. 14, 2643). 
 
 Preparation. — A saturated solution of iodine 
 in ether is heated to boiling with excess of 
 powdered As in a flask with an upright con- 
 denser ; the liquid is filtered while hot : on 
 cooling, well-formed crystals of Asia are obtained 
 (Wiggers, Michaelis's Leh/rbuch der anorgan. 
 Chem. [1881] 2, 462). 
 
 Properties and Beactions. — Lustrous, red, 
 hexagonal, tables, a:c = 1:2-998 (details of cryst. 
 form, V. Friedliinder, Z. K. 3, 214). Soluble in 
 alcohol, ether, benzene, &o. ; soluble in much 
 water; soluble without change in alcohol; de- 
 composed by a little water with formation of 
 4AsOI.3ASj05.24H20 ; action of boiling H^O pro- 
 duces AsOI.ASjOj which deposits on cooling 
 (Wallace, P. M. [4] 17, 122). 
 
 Combitiations. — 1. With iodides of the alkali 
 metals to form very unstable compounds (Nickl^s, 
 G. B. 48, 237). — 2. When ammonia is passed 
 into a solution of ASI3 in benzene, a bulky white 
 pp. of 2ASI3.9NH3 is produced (Bamberger a. 
 Philipp, B. 14, 2643). 
 
 Beactions. — 1. Heated with oxygen, iodine is 
 evolved and As^O^ is produced. — 2. Heated with 
 alcohol, ethylic iodide is formed (Bamberger a. 
 Philipp, B. 14, 2643). 
 
 II. Arsenic dhodidb. AsIj (Bamberger a. 
 Philipp, B. 14, 2643). Mol. w. unknown. 
 
 Preparation. — One part As is heated with 2 
 parts I to 230° in a sealed tube, the product is 
 
S12 
 
 ARSENIC. 
 
 dissolved in CSj in an atmosphere of CO2, and 
 the liquid is allowed to deposit crystals. 
 
 Properties. — Thin prisms of a dark oherry- 
 red colour. 
 
 Beactions. — Very easily oxidised. Decom- 
 posed by water to Aal, and As; (3As 1^ = 
 2ASI3 + AS). 
 
 III. Aksenio pentiodide. According to Sloan 
 (O. N. 46, X94) a brown crystalline solid, con- 
 taining As and I in the ratio As:5I, is obtained 
 by heating As with a slight excess of I to 100° 
 for some time in an atmosphere of' COj. The 
 body is easily decomposed to Asl, and I, by heat 
 or by solution in ether or CSj. 
 
 Arsenic, oxides of. (In connection with 
 these compounds, v. art. Oxides.) Arsenic forms 
 two well-defined oxides, arsenious oxide ASjOj, 
 which has been gasified; and arsenic oxide, As^O^, 
 which has not been gasified : both act as anhy- 
 drides ; the acid corresponding to the former is 
 not known, but many arsenites, MsAs03, have been 
 prepared. Three arsenic acids are known corre- 
 sponding in composition to the three phosphoric 
 acids, two of these exist only as solids, they all 
 readily lose water yielding the anhydride ASjOj. 
 The greyish film which forms on the surface of 
 arsenic exposed to the air has been regarded as 
 a suboxide, but no definite proof of the existence 
 of an oxide with less than As^O, has been 
 given. 
 
 I. Aksenious Oxide. As^O^. Mol. w. 395'36. 
 (Arsenic trioxide. White arsenic, Arsenious an- 
 hydride, Arsenious acid.) Vitreous As^Oj melts 
 under pressure, crystalline vaporises without 
 melting (Wohler, Om. i, 255). S.G-. vitreous 
 3-698 to 3-788 ; oryst. 3-85 to 4-15 (v. Claudet, 
 C. J. [2] 6,179,andGroth,P.137,426). V.D. 198 
 (at white heat, V. Meyer,B.12, 1117). O.E. (cubic 
 at 40°) -00012378 (Fizeau, C. B. 62, 1138). S. 
 (13°) vitreous, 4 ; cryst. 1-2 to 1-3. S. (100°) 11 
 (Bussy, A. 64, 286). S. (15° standing for some 
 days) cryst. -28 ; vitreous -92, S. (saturated at 
 100° and then cooled to 15-') cryst. 218; 
 vitreous, 3-33 (Buohner, J. Ph. [3] 1, 421). 
 S. (alcohol, 15°) cryst. -25; vitreous, 1-06 
 (Girardin, J. Ph. [3] 46, 269). S. (ether) 0. 
 H.F. 309,340; H.F. in aqueous solution, 
 294,240 ; [As'0»,Aq] = -15,100 [Th. 2, 236). S.H. 
 cryst. -1279. S.V.S. vitreous, 106-3, cryst. 98-9. 
 
 Occurrence. — Native, as the mineral Arsenite 
 (or ArsenoKte) ; whenever arsenic volatilises in 
 contact with air, or arsenic-containing minerals 
 are heated in air. 
 
 Preparation. — Obtained as a principal pro- 
 duct in the roasting of arsenical pyrites, and as 
 a secondary product in the roasting of arsenical 
 ores of Sn, Co, Ni, or Ag. The oxide is condensed 
 in chambers, and purified by resublimation. 
 Extremely poisonous ; doses of 0-6 gram are 
 usually fatal (but v. Boscoe ' On the alleged 
 Practice of Arsenic-eating in Styria,' Mem. of 
 Lit. and Phil. Soc. of Manchester, 1860). 
 
 Properties. — Exists in three forms, amor- 
 phous, regular octahedra, and trimetric prisms 
 {a:b:c: - -3758:1: -35) ; the first passes slowly into 
 the second form on keeping ; the third is ob- 
 tained under special conditions {v. infra). The 
 change from amorphous to octahedral arsenious 
 oxide is attended with production of 5,300 gram- 
 units of heat, and that from amorphous to pris- 
 matic with 24,950 units per As^O,, grams (Favre ; 
 
 Troost and Hautefeuille, O. B. 69, 48). Amor, 
 phous arsenious oxide is produced by con- 
 densing the vapour on a surface slightly cooler 
 than the temperature of volatilisation of the oxide; 
 it is a transparent glass-like solid which gradu- 
 ally becomes opaque because of formation of 
 octahedral crystals. The octahedral oxide is 
 produced by cooling the vapour quickly; by 
 crystallising either of the other forms from 
 water; by treating the amorphous iorm with 
 ammonia solution and washing with water. 
 This form is obtained pure by fusing commercial 
 arsenious oxide with carbonate of sodium and 
 nitre, dissolving the arsenate of sodium so formed 
 in water, filtering from sodium antimonate which 
 remains, and reducing with SO^ solution. Ac- 
 cording to H. Rose (P. 35, 481) a solution of 
 2-3 parts amorphous As^O, in 1-2 parts boiling 
 cone. HClAq deposits crystals of the octahedral 
 oxide when very slowly cooled, the formation 
 of each crystal being accompanied by a flash of 
 light ; a similar solution of the crystalline 
 oxide does not behave in this way. The tri- 
 metricprismatic variety of ASjOj is obtained 
 by saturating with A.s fi,, and then allowing to 
 cool, a boiling solution of potash (Pasteur, O. B. 
 24, 474) ; Wohler found this oxide in an oven in 
 which arsenical ores had been roasted (P. 26, 
 177) ; Claudet found it native at San Domingos, 
 in Portugal (0. J. [2] 6, 179) ; Kiihn obtained it 
 from a solution of AgjAsOj in HNO3 (J. 1852. 
 378 ; V. also Uhrich, /. 1858. 173) ; Scheurer- 
 Kestner found it in pipes leading from the 
 pyrites burners to the chambers of a sulphuric 
 acid works [Bl. [2] 10, 444). The three forms 
 of ASjO^ may be obtained, according to Debray 
 (0. B. 58, 1209), by heating the oxide in a closed 
 glass tube half immersed in sand, in an upright 
 position, the lower part being at about 400° ; on 
 cooling, the lowest part of the tube contains 
 amorphous, the middle part trimetric crystals, 
 and the uppermost part octahedral crystals, 
 of AsjOj. Arsenious oxide is iso-dimorphous 
 with antimonious oxide. The vitreous (amor- 
 phous) variety may be fused before volatilising ; 
 the crystalline sublimes without melting, even 
 under pressure (Wohler, Om. 4, 255). The 
 vapour is colourless and inodorous. The solu- 
 bilities in water of the three forms are diiierent 
 {v. supra); long-continued contact with hot water 
 decreases the solubility of the vitreous form 
 inasmuch as it is thus changed to the octahedral 
 form. Many acids dissolve As^Oj, the vitreous 
 more rapidly than the crystalline varieties 
 (Bacaloglo, /. pr. 83, 111) ; from these solutions 
 the oxide crystallises on cooling ; in the case of 
 HClAq some AsCl, remains in solution, tartaric 
 acid is, however, said to form a salt analogous to 
 tartar emetic. An aqueous solution of ABft, 
 slightly reddens litmus, but no acid has been 
 obtained in definite form. The oxide must be 
 regardedasafeeblyaoid-forming oxide possessing 
 at the same time salt-forming tendencies (v. 
 Absenious acid and Aesenites ; and also, infra, 
 Beactions, especially Nos. 2, 10, and 11; and 
 Combinations, No. 2). 
 
 Beactions. — Arsenious oxide acts both as a 
 reducing and an oxidising agent ; it deoxidises 
 nitric, manganic, chromic, hypochlorous, acids, 
 &a., with formation of arsenic acid ; it oxidises 
 carbon, sulphur, phosphorus, hydrogen, sodium, 
 
ARSENIC. 
 
 Sli! 
 
 potaBsium, carbon monoxide, potassium cyanide 
 &o. , when heated with these bodies. The oxide in 
 solution is oxidised to arsenic oxide by chlorine, 
 bromine, or iodine, in presence of alkaline bicar- 
 bonates ; on this fact is based the use of ASjO^Aq 
 in volumetric analysis. 1. Chlorine passed over 
 the dry oxide at a moderate temperature forms 
 AsCla (Weber, P. 112, 619) ; in solution chlorine 
 produces arsenic acid and HOlAq ; iodine and 
 bromine act similarly in presence of alkaline 
 bicarbonates. — 2. Hydrochloric acid forms some 
 AsClj, but in presence of HNO3 or KCIO3 only 
 ASjOs is produced. — 3. Free oxygen does not 
 oxidise As^Oj at ordinary temperatures, but if a 
 plate of Pt is partly immersed in solution of 
 ASjOj in HClAq the oxygen coming off from the 
 Pt produces As.Oj (Berthelot, C. B. 84, 1408).— 
 4. An aqueous solution of As^Oj heated to 200° 
 with phosphorus yields phosphide of arsenic 
 (Oppenheim, Bl. [2] 1, 163). — 5. Na amalgam 
 appears to reduce AsjO^Aq with production of a 
 solution which acts as an energetic reducer 
 (Fremy, O.B. 70,61). — 6. Phosphorus trichloride 
 reacts at 110°-130° according to the equation 
 SAs^O^Aq + I2PCI3 = 2As, + 6Ffl^kq + 12As01sAq 
 (Michaelis, J. Z. 6, 239). — 7. Phosphorus penta- 
 chloride produces AsClj and POCI3 (Hurtzig 
 a. Geuther, A. Ill, 159).— 8. When As^OjAq 
 is shaken with ammonia solution, an unstable 
 compound is formed (De Luynes, C. B. 44, 
 1353). — 9. Phosphorous and hypophosphorous 
 acids precipitate arsenic and produce phosphoric 
 acid. — 10. Sulphydric acid (H^S) passed into an 
 aqueous solution of As^Oj forms AS2S3 which is 
 ppd. on addition of an acid {v. Arsenious sul- 
 phide). — 11. Ammonium hydrogen tartrate solu- 
 tion is said to dissolve &.sfie ". on cooling, crystals 
 of a double salt isomorphous with tartar emetic 
 separate out (Marignac, Ann. M. [5] 15, 288). 
 Pelouze (A. Ch. [3] 6, 63) describes a somewhat 
 similar salt containing K in place of NHj. 
 Neither tartrate has, however, been satis- 
 factorily examined. — 12. Heated in a tube with 
 a dry acetate, cacodyl oxide, As2(CH3)jO, is pro- 
 duced. — 13. Heated with dry alkaline earth 
 oxides or with dry carbonates of the fixed alkalis, 
 an arsenate of the metal is produced along with 
 arsenic which sublimes. — 14. Theoxide dissolves 
 in hot solutions of the alkalis but most of it 
 pps. again on cooling in the air {v. Akseniotjs 
 ACID AND ABSENiTEs). — 15. The higher oxidised 
 compounds of many metals are reduced by 
 ASjO^; thus CuO is reduced to CUjO, in presence 
 of alkali. — 16. Many metals, e.g. zinc, reduce acid 
 solutions of Ksfl, with ppn. of As and formation 
 of AsH,.— 17. ASjOjAq is reduced by a Ou-Zn 
 couple with formation of ASH3 (Gladstone a. 
 Tribe, C. J. 33, 306).— 18. Palladium or pla- 
 tinum charged with hydrogen separates As from 
 As fis Aq without formation of AsHj (Gladstone, 
 7_£..). — 19. Some metallic salts which act as 
 reducing agents convert the oxide into arsenic ; 
 e.g. SnClj Aq produces SnOl^, As, and AsH, 
 (Kessler, /. 1861, 265).— 20. Freshly ppd. ferric 
 hydrate reacts with AsjOjAq or with alkaline 
 arsenites to form an insoluble compound, pro- 
 bably arsenite of iron ; on this fact is based the 
 use of ferric hydrate as an antidote in cases of 
 arsenic poisoning (v. Bunsen and Berthold, 
 Das Eisenoxydhydrat, ein Qegengift der a/rseni- 
 yen Saure, Gottingen, 1834). 
 
 Combinations. — 1. Fused with arsenic oxidte 
 the body ASjO^-AsnOj is probably produced 
 (Bloxam, 0. /. 18, 62). Other compounds oi 
 ASjOj and As^Oj are obtained by oxidising As^O, 
 by warm HNOjAq {v. Joly, C. E. 100, 1221)— 
 2. Dissolves in fuming sulphuric acid; on evapo- 
 ration yields needle-shaped crystals of AS4O5.4SO, 
 which are decomposed by water (Sohultz-Shellac, 
 B. 4, 109, gives the formula As2(SOJ,.S03). A 
 compound of AsjOj and SO3 was obtained by 
 Schafhautl {B. J. 22, 118), in the fumes from 
 copper-smelting works in Wales ; and by Eeieh 
 in a canal which carried off the sulphurous acid 
 from a pyrites work near Freiberg {J. pr. 90, 
 176). — 3. By cooling mixed hot aqueous solu- 
 tions of KI, KBr, or KOI, and KASO2, the com- 
 pounds ASjOj.KI, ASjOj.KBr, and AsjO^.KOl, 
 are obtained (RildorS, B. 18, 1441 ; v. also 
 Sohife a. Sestini, A. 228, 72). Eudorff {B. 19, 
 2678) also describes NH^LASiO,, NH^Br.ASjOj, 
 and 2NH4C1.AS405. Forms a complex series of 
 compounds with MoO, and WO, and various 
 bases (v. Gibbs, Am. 7, 209 a. 313 ; O. N. 48, 
 155). 
 
 II. Arsbnio OXIDE. ASjOj. Mol.w. unknown; 
 not less than that represented by formula. {Arse- 
 nic pentoxide. Arsenic anhydride.) S.G. 3-734 
 (fused oxide). S.V.S. 61-6. H.F. 219,400 ; H.F. 
 in aqueous solution, 225,400. [As20Aq,0^] 
 = 78,350(2';i. 2, 236). 
 
 Preparation. — Not produced by heating 
 arsenic in air or oxygen. If arsenic or arsenious 
 oxide is digested with HNOjAq, or with a mixture 
 of 1 part HClAq and 12 parts HNOjAq in a 
 retort, or if chlorine is led into a warm solution 
 of ASjOj, arsenic acid, H3ASO4, is produced and 
 may be obtained as crystals by cooling a con- 
 centrated solution. When this acid is heated to 
 low redness the anhydride ASjOj is produced. 
 
 Properties. — ^A white solid which slowly 
 absorbs moisture from the air with formation of 
 H3As04Aq. Slowly but completely dissolves in 
 water forming HjAsOjAq. Heated above low 
 redness it yields As^Oj and 0. 
 
 Beactions. — 1. Heated with cha/rcoal, many 
 metals, or potassium cyanide, it yields As.— 
 
 2. Heated with cone, hydrochloric acid it yields 
 ASOI3 ; with HCl gas even in the cold the same 
 product is obtained (Souchay, Fr. 1, 189 ; 
 Mayrhofer, A. 158, 326).— 3. Eeacts with 
 phosphorus pentachloride thus : ASjOs + 5POI5 = 
 5POCl3-h2Cl, + 2AsOl3 (Hurtzig a. Geuther, A. 
 
 3, 159). — i. According to Michaelis (/. Z. 6, 
 239), the oxide is not acted on by POCl, even 
 at 200°. — 5. Eeduced in aqueous solution by 
 nascent hydrogen with formation of ASH3 ; but 
 if chlorides are present only a trace of AsHj is 
 produced according to Bloxam (C.J. 15, 56). — 6. 
 Stannous chloride, in the cold,produces stannous 
 pyroarsenate and arsenite, in warm solutions 
 produces arsenic and AsH, (Schiff , J. 1861. 278 ; 
 Kessler, ibid. 265). — 7. With water it reacts 
 to produce arsenic acid, HjAsOjAq. Joly (C. B. 
 106, 1262) describes a hydrate AS2O5.4HJO. 
 Arsenic oxide reacts as a strongly acid-forming 
 oxide and exhibits no tendency to form 
 corresponding salts by reactions with acids 
 (v. e.g. reaction with HOlAq). — 8. Forms a 
 large series of compounds with MoOj or WO, 
 and bases {v. GibbB, Am. 7, 209 a. 313 ; O. JV. 
 48, 155). 
 
314 
 
 ARSENIC. 
 
 Arsenic, ozybromides of. AsOBr {Bromar- 
 semousacid); and ?As40jBrs. Mol. w. unknown, 
 not less than represented by above formulse. 
 
 Formation. — AsOBr is produced by the action 
 of HjO in limited quantity on AsBrj. 
 
 Preparaiion. — Arsenious oxide is dissolved 
 in molten AsBr, ; the dark viscid liquid which 
 results is distilled till it becomes rather thick, 
 and is then cooled to 150° whereat it separates 
 into two layers, the upper of which contains the 
 oxybromide AsOBr, and the lower probably con- 
 tains the other oxybromide A.OijBra {WaUaoe, 
 P. M. [4] 17, 261). 
 
 Properties. — Brown, waxy, solid. Decom- 
 posed by heat to AsBr, and ASjOj. 
 
 Combinations. — With water ; a hydrate of 
 arsenic oxybromide, 2AsOBr.3H20 is obtained 
 as thin white pearly crystals by placing a cold 
 concentrated aqueous solution of AsBrj, con- 
 taining BLBr, over sulphuric acid (Wallace, I.e.). 
 If the solution of AsBr, in HBr is boiled, another 
 compound, said to have the composition 
 4AsBr3.11As40j.24H20, separates out (Wallace, 
 
 I.C.). 
 
 Arsenic, oxychlorides of. AsOCl {Ohlorar- 
 serdous acid) ; and ASjOjCl. Mol. ws. unknown, 
 not less than represented by above formulse. 
 
 Formation. — When AsCla is mixed with less 
 than suiScient water to completely decompose it, 
 AsOCl is formed. 
 
 Preparation of AsOCl. — By distilling until 
 frothing begins the liquid obtained (a) by dis- 
 solving ASjOj in boiling AsClj in the proportion 
 AS4O5 : 2AsClj, or (6) by leading dry HCl gas 
 over dry warm ksfi^ until almost the whole of 
 the latter has been changed to AsClj, and allow- 
 ing to cool. 
 
 Properties of AsOCl. — Obtained as above, it 
 is a hard, translucent, slightly-fuming solid 
 which slowly absorbs oxygen from the air 
 (Wallace, P. M. [4] 16, 358 ; Hurtzig a. Geuther, 
 A. Ill, 172). 
 
 Combinations. — 1. A solution of AsClj in 
 cono. HClAq mixed with solid ammonium 
 chloride, and allowed to stand, deposits crystals 
 of AsOCl.HjO, but after some days white fibrous 
 needles are formed, which, when dried over 
 U.,SO„ have the composition AsOC1.2NHjCl.— 2. 
 with water; a hydrate of AsOCl, having the 
 composition AsOCl.HjO ( = As(0H)2Cl) is obtained 
 by adding water to AsGl, in about the propor- 
 tion SHjOiAsClj and allowing to stand for some 
 days. The hydrate forms small star-like crystals 
 (Wallace, Uc.J. 
 
 AS3O4CI IS said to be obtained, as a hard, 
 glass-like solid, when AsOCl is heated until 
 AsjOj begins to sublime from it (about 218°) 
 (Wallace, I.e.). 
 
 Arsenic, oxyiodide of. AsOI.ASjOj. Mol. w. 
 unknown. Produced in thin pearly laminse, 
 according to Wallace (P. M. [4] 17, 122) by 
 slowly cooling a hot cone, solution of Aslj in 
 H.^0, drying between filter paper, and then over 
 H,SO,. 
 
 Arsenic, pentaflnoride of ; double compounds 
 containing. No gaseous compound of arsenic 
 of the type ASX5, where X is a monovalent atom 
 or atomic group, has yet been obtained. Solid 
 compounds are, however, known, one of the 
 constituents of which seems to be the group 
 AsFj. The following are described by Marignao 
 
 (A. 145, 237) : — 1. Potassic-arsemic fluoride, 
 2(KF.AsF5).H20 ; formed in weU-developed 
 rhombic prisms by dissolving potassium arse- 
 nate in much hydrofluoric acid. — 2. Potassic- 
 arsemic oxyfluoride, KP.AsOF3.H2O ; formed ia 
 acute rhombic plates by repeated evaporation 
 of the solution from which compound No. 1 
 is obtained, or by dissolving potassium arsenate 
 in a small quantity of HFAq.— 3. Dipotassic- 
 arsenic fluoride, 2EF.AsF5.H2O; large, lustrous, 
 rhombic prisms, obtained by adding KFAq to 
 a solution in HFAq of either of the preceding 
 salts, and evaporating. — 4. The double salt 
 4KF.AsF5.AsOF3.3H2O is said to be produced 
 when a solution in HFAq of salt No. 3 is 
 repeatedly evaporated. 
 
 Arsenic, phosphide of, v. Absenio, Combina- 
 tions, No. 8. 
 
 Arsenic, selenides of, and Seleno-snlphides 
 of, V. Aksenio, Combinations, No. 7. 
 
 Arsenic, sulphides of. (In connection with 
 these compounds v. art. Sulphides.) Three 
 salphideg of arsenic are known ; AS2S2, AS2S3, 
 and ASjSj. None of these has been gasified, 
 hence the formulcs do not necessarily represent 
 molecules of the compounds. ASjSj and 
 ASjSj occur native as Realgar and Orpiment 
 respectively. The two sulphides AS2S3 and 
 ASjSs are salt-forming ; they dissolve in alkali 
 sulphides with production of thio-arsenites 
 M3ASS3 &o., or thio-arsenates M3ASS4 &e. {v. 
 irifra). The disulphide, AS2S2, is not salt-forming ; 
 Berzelius's statement that it combines with 
 various metallic sulphides has been shown to ba 
 erroneous (Nilson, B. 4, 989). 
 
 I. Aksenio disulphide. AS2S2 {Realgar, 
 Bed orpiment, Ruby sulphur). S.G. 3'4-3'6. 
 H. 1-5-2. Mol. w. unknown. S.V.S. 61-1. ^ 
 
 Occu/rrence. — Native, as Realgar, accompany- 
 ing ores of silver and lead, &c. 
 
 Preparation. — 1. By heating together As and 
 S, or ASjSa with As, in the proper proportions. — 
 
 2. By heating As^O, with S, in the proportion 
 AS405:7S, repeatedly subliming the mass from 
 end to end of a glass tube in a stream of CO^ 
 (Nilson, J. pr. [2] 8, 89).— 3. By heating AsjSs 
 with NaHCOjAq in a closed tube to 150° ; 
 crystals are thus obtained ^ mm. long (S6nar- 
 mont, A. Ch. [8] 82, 129).— 4. On the large scale, 
 impure, containing AS4O, (Hausmann, A. 74, 
 196), by subhming a mixture of arsenical pyrites 
 and iron pyrites. 
 
 Properties. — Occurs native in monoclinio 
 prisms, a:b:c = l-82:l:-4866 ; = 85°16' ; orange- 
 red, more or less translucent, resinous lustre, con- 
 ohoidal fracture. Pure AS2S2 is transparent, ruby 
 colour, easily fusible, and crystalline after fusion ; 
 it burns in the air with a blue flame forming SO^ 
 and ASjOj. It is used as a pigment, also in pyro- 
 techny. 
 
 Reactions. — 1. Nitric acid oxidises AsjSjt* 
 H3ASO4, H2S03Aq, H2S04Aq, and S.— 2. Heated 
 in a current of chlorine, SjClj and AsClj are pro- 
 duced (Nilson, /. pr. [2] 12, 295; 13, 1).— 
 
 3. Heated in hydrogen. As and HjS are formed 
 (N.). — 4. Solution of potash partially dissolves 
 AS2S2, with formation of AsjS, which then 
 forms KAsSjAq, and production of As (N.). — 
 5. It is slightly soluble in solutions of the 
 alkali-metal sulphides. — 6. It is electrolysed 
 to As and S by a powerful battery (Lapschiu- 
 
ARSENIC. 
 
 315 
 
 Tiohanowitsch, C. G. [2] 6, 613).— 7. Heated 
 with iodine, the compound As2S3.AsI,( = AsSI) is 
 produced (Schneider, J. pr. [2] 23, 486). 
 
 II. Aksekio tkisulphide. AsjSg (Arsenious sul- 
 phide, Sulpharsemicms anhydride, Orpiment, 
 Yellow sulphide of arsenic). Mol. w. unknown. 
 S.G. 8-46-3-48. S.V.S. 70-9. 
 
 Occurrence. — Native as Orpiment. 
 
 Formation. — 1. By heating to 70°-80° a so- 
 lution of NajCOj saturated with ASjSj (Nilson, 
 J.pr. [2] 12, 295; 13, 1).— 2. Impure, commer- 
 cial, by subliming together 7 parts powdered 
 ASjOs with 1 part S. 
 
 Preparation. — 1. By subliming together As 
 and S in the proper proportions. — 2. By satu- 
 rating ASjOjAq with H2S a little HClAq being 
 added. li no mineral acid is added the As^S, 
 produced remains in solution in a colloidal form 
 (Schneider, J.pr. [2] 25, 431). 
 
 Properties.— Occurs native in trimetric prisms 
 {a:b:c = ■603:1: '674) translucent,lemon-or slightly 
 orange-yeUow. Prepared in the wet way it 
 forms a lemon-yellow powder which becomes 
 darker when heated. Melts easily and volati- 
 lises at a higher temperature. When H^S is 
 passed into As^OgAq, As^Sj is formed but remains 
 in solution in colloidal form; a saturated so- 
 lution contains 34-46 p.c. AsjSj; it is slowly 
 decomposed on standing, but may be boiled 
 without precipitation of AS2S3; bone char re- 
 moves all the ASuSj from solution ; most acids 
 and many salts precipitate ASjSj (Schneider, 
 J.pr. [2] 25, 431). Used as a pigment, also as 
 a reducing agent in dyeing, also as a depi- 
 latory. 
 
 Reactions. — 1. Long-continued action of hot 
 water produces HjS and As^OjAq according to 
 Field (C. N. 8, 114).— 2. Dilute acids do not act 
 on AS2S3 ; cone. HClAq produces AsClj ; cone. 
 HNOjAq produces H^SOjAq, S, and HjAsOiAq. 
 8. Fused with potassium-hydrogen sulphate, 
 SOj is evolved, and KHAsOj and K2SO4 remain. 
 4. Chlorine acts readily, a brown liquid is 
 formed said to be a chlorosulphideof As (H.Bose) ; 
 heated with chlorine, ASCI3 is produced (Ludwig, 
 Ar. Ph. 97, 23). — 5. Passed over hot irmi, silver, 
 &o., sulphide of the metal is formed, and arsenic 
 which partially alloys with the metal.— 6. Passed 
 over red-hot lime, sulphide and arsenate of 
 calcium, and arsenic are produced. — 7. Heated 
 with sodium or potassium carbonate, a mirror of 
 As is obtained, along with arsenate and thio- 
 arsenate of the alkali metal ; if the mixture is 
 heated in hydrogen the arsenate is reduced 
 (Bose, P. 90, 565). — 8. Heated with an alkaline 
 carbonate and charcoal or potassium cyanide, a 
 mirror of As is obtained; according to Fresenius 
 (A. 49, 287), the whole of the As in the AsjSj is 
 thus obtained ; according to Bose (Ph. C. 1853. 
 594), some of the As forms thio-arsenate (KCNS 
 being also produced) which is not reduced. No 
 mirror of As is obtained (Bose) if ASjSj is mixed 
 with excess of S and heated with ECN; the 
 presence of an easily reduced metal is also said 
 to prevent the formation of As, because the As 
 alloys with the metal. If the mixture of As^Sj 
 with NajCOa (or K2CO3) and KCN is heated in 
 hydrogen, the whole of the arsenic is obtained as 
 metal (comp. Bose, P. 90, 565, with Nilson, A. 
 49, 287). — 9. ASjSj readily dissolves in cold 
 
 aqueous potash, soda, or ammonia, forming aa 
 arsenite and a thio-arsenite ; thus : 
 2As2SsH-4EOHAq = 
 KAsOjAq + 3KAsS2Aq + 2H2O ; 
 on adding an acid to the solution the whole of 
 the As is precipitated as AsjSj ; thus : 
 
 KAsOjAq + SKAsSjAq + 4HClAq = 
 4K01Aq + 2AS2S3 + 2H2O. 
 
 If oxide of Ag or Pb is added to a solution 
 of AS2SS in NHjAq and the solution is boiled, 
 the whole of the S is precipitated as AgjS or 
 PbS, and Ag or Pb arsenite remains in solution. 
 10. When ASjSj is boiled with a solution of 
 sodium or potassium carbonate, ASjSj is precipi- 
 tated, CO2 and HjS are evolved, and the solution 
 contains the following salts, NajS.SASjSj; 
 Na20.2As2S302; Na3AsS4; NajHAsO,; NaHCOa; 
 (Nilson, J. i)r. [2] 14, 1, 145).— 11. ASjSj is 
 easily soluble in a hot solution of potassium- 
 hydrogen sulphite; thus, 2As2S3 + 16KHS03Aq = 
 4KAs02Aq + 6K2S203Aq + 7S02Aq + 3S + SH^O. 
 
 Combinations. — ASjSj acts as a salt-forming 
 sulphide, or anhydride of a thio-acid ; it com- 
 bines with the sulphides of the alkali and 
 alkaline earth metals, and with some metallic 
 hydrosulphides, to form thio-arsenites (q.v. under 
 Aksenic, thio-acids op). The following are the 
 typical reactions : 
 
 1. As2S3-HK2SAq = 2(AsS.SKAq). 
 
 2. AS2S3 -I- 6NH,HSAq = 2(As.(SNH,)3Aq) + SH^a 
 
 3. AS2S3 -I- 2(NH,)2SAq = As2S(SNHJ,Aq. 
 
 III. — Aesenio pentasulphide. AS2S5 (Per- 
 sulphide of Arsenic). Mol. w. unknown. 
 
 Preparation. — 1. By melting As with con- 
 siderable excess of S, a thin, transparent, liquid 
 is obtained which solidifies to an elastic mass, 
 and after some time becomes hard ; if this hard 
 solid is powdered and treated with NHjAq a 
 solution of AsjSj is obtained from which the 
 sulphide is thrown down on addition of HCliii 
 (G61is, A. Ch. [4] 30, 114).— 2. A solution c,f 
 NajS is digested with AS2S3 and enough S to 
 form AS2S5, on evaporating and cooling large 
 crystals of 2Na3AsS4.15H20 are obtained 
 (Rammelsberg, P. 52, 249 ; 90, 40) ; whenHClAq 
 is added to a solution of this salt, ASjSj is pre- 
 cipitated and H^S is evolved (Puohs, Fr. 1, 189 ; 
 Fliiokiger, Vierteljahrsschr. pr. Pharm. 12, 330 ; 
 Eokert, ibid. 13, 357). The product of the 
 action of H2S on HjAsO^Aq is not AsjSj, as was 
 once supposed, but is a mixture of AS2S3 and 8 
 
 (2H3As04Aq + 2B.^S = As.OsAq -h SHjO + S2 ; 
 ASiOjAq + 3H2S = AS2S3 + 3H2O) {v. Ludwig, 
 Ar. Ph. [2] 97, 32 ; also H. Bose, P. 107, 186). 
 
 Properties. — A yellow powder, easily fusible;, 
 may be sublimed in a stream of a gas which 
 does not act on it. 
 
 Beactions. — 1. Heated in a stream of 
 hydrogen, it is reduced to metallic As, and H.S. 
 2. Dissolves easily in aminonia, potash, and 
 soda solutions, with production of thio-arsenate,. , 
 and arsenate, of the alkali metal. — 8. Dissolves 
 easily in solutions of alkali sulphides, forming 
 thio-arsenates. The sulphide AS2S5 behaves as 
 a salt-forming compound, or as the anhydride 
 of thio-arsenio acid ; the salts which are generally 
 formed directly from it are pyro-thio-arsenates 
 MjASjS, ; these yield two other series of salts, 
 viz. ortho-thio-arsenates M,As5l4, and meta-thio^ 
 arsenates MAsS, [v. AnsEric, thio-aoibs oj). 
 
316 
 
 ARSENIC. 
 
 Arsenic, sulpho-acids of, v. Absenio thio- 
 
 AOIDS OF. 
 
 Arsenic, sulpho- (or thio.) bromide of. 
 AsS2Brs( = AsSBr.SBr2). Mol. w. unknown, 
 £ — 17°]. Dark red crystals deposited at -18° 
 on addition of a small quantity of powdered 
 As to a solution of S in Br in ratio S:Brj; 
 decomposed by water into As^OjAq, HBrAq, and 
 S (Hannay, C. J. 33, 291). 
 
 Arsenic, sulpho- (or thio-) iodide of. AsSI. 
 Said to be formed by the mutual action of ASjSj 
 and I (Schneider, J.pr. [2] 23, 486). 
 
 Arsenic, Bulphydrates (or hydrosulphides) of. 
 Only one compound As, S, and H is definitely 
 known, AsS(SH)3; v. Thioarsenicacids under 
 Arsenic, thio-acids of {v. also the art. Htdko- 
 
 fiULPHIDEs). 
 
 Arsenic, tellurides of, v. Arsenic, Combina- 
 tions, No. 6. 
 
 Arsenic, thio-acids of. (In connection with 
 these compounds v. the art. HYDKOsniiPHiDES.) 
 Arsenious sulphide, ASjSj, dissolves in alkalis or 
 alkali sulphides to form salts, and from these 
 •other salts are obtained by double decomposition. 
 'The sulphide As^Sj may be regarded as the anhy- 
 dride of three thio-aoids AsS.SH, As(SH)3, and 
 As2S(SH)4, corresponding to the three hypothe- 
 tical oxy-acids (v. Akseniods acid) ; none of these 
 acids is known, all attempts to prepare them 
 having resulted only in the production of AS2S3 
 and H2S, but thio- or sulph- arsenltes are known 
 belonging to the three types, MAsSj, M3ASS3, 
 and M4AS2S5. The more important of these salts 
 are described below. Arsenic pentasulphide, 
 AS2S5, dissolves in alkalis and alkali sulphides 
 to form salts from which other salts are obr 
 tained (v. infra). According to Nilson {J.pr.[2] 
 14, 1, 145) the pp. obtained by adding dilute 
 HClAq to a solution of NajAsSj {v. Arsenic 
 PENTASULPHIDE, Preparation of) has the compo- 
 sition of ortho-thio-arsenic acid HjAsSj [ = 
 AsS(SH)3; no other thio-arsenio acid is known, 
 but the salts may be divided into three classes, 
 ■analogous to the arsenates, viz. : pyro-thio- 
 arsenates MjASjS, (hypothetical acid = H,As2Sj), 
 meta-thio-arsenates MASS3 (hypothetical acid = 
 TIASS3), and ortho-thio-a/rsenates MjAsS. (acid 
 (?) H,AsS,). 
 
 I. Thio-aesenites. As already stated, no 
 thio-arsenious acid is known. The salts which 
 have been examined belong for the most part to 
 the type M^As^Sj ; they are produced either by 
 the direct union of ASjS, with metallic hydro- 
 fiulphides, e.g. Ba^ASjSj, or by ordinary double de- 
 composition of (NHJjAsjSjAq by solutions of 
 metallic salts, e.g. Pb^As^Ss. A few salts belong- 
 ing to the forms MAsS^ and M3ASS3, are also 
 Icnown, e.g. KAsS^ and KsAsS3 ; they are formed 
 by the action of alkali sulphides on As^Sj 
 ■(comp. reactions given for Arsenic trisulphide, 
 p. 315). The thio-arsenites of the alkali and 
 alkaline earth metals and of magnesium are 
 soluble in water, but the solutions are decom- 
 posed on boiling, the others are insoluble in 
 water. Most of these salts give off all their sul- 
 phur when strongly heated out of contact with 
 air. These salts have been chiefly investigated 
 by Berzelius (v. Gm. 4, 275). 
 
 Only those salts which have been fairly 
 satisfactorily examined are mentioned in the 
 following brief account : — 
 
 Ammonium thdo-arsenites. (NHJ^As^Sj is 
 obtained by dissolving AS2S3 in (NH4)2SAq and 
 adding alcohol ; if NH,HSAq is added before 
 precipitating by alcohol the salt obtained has the 
 composition (NHJ3ASS3. 
 
 Bariu/m tMo-arsenites. BajAsjSs is obtained 
 as a pasty brownish-red very soluble mass by 
 digesting As^Ss with BaS^HjAq; from the solu- 
 tion alcohol throws down Ba3(AsS3)2. 
 
 Calcium thio-arsenites. The salt Ca3(AsS3), 
 is obtained as crystals by digesting AS2S3 with 
 milk of lime and allowing the solution to evapo- 
 rate ; from the brownish mother-liquor alcohol 
 precipitates white Ca3(AsS3)2.15H20. 
 
 Lithium thio-arsenites. Closely resemble 
 the potassium salts (q.ii.). 
 
 Potassium thio-arsenites. The salt KAsSj 
 may be obtained in solution by dissolving AS2S3 
 in KjSAq, but this solution decomposes on 
 evaporation ; in the solid form by heating KAsSj 
 or by fusing AS2S3 with K2CO3. By adding alco- 
 hol to a solution of AS2S3 in KjSAq, a white pp, 
 of K3ASS3 is obtained. AU these salts readily 
 undergo change in aqueous solutions. Berzelius 
 describes several other more or less indefinite 
 bodies as potassium thio-arsenites. 
 
 Sodium thio-arsenites. Closely analogous 
 to the potassium salts. 
 
 The following thio-arsenites seem also to 
 exist; they are generally obtained from 
 (NHj4As2S5Aq by double decomposition: — 
 (BiS)jAs2S5| Ce2As2S5; Cd2As2S5; CO2AS2S5; 
 CU2AS2S5; FejAsjSs; Au4(As2S5)3; Mg2As2S5; 
 Mn2As2S3; HgjAsjSj ; Hg(AsS2)2; Ni2As2S3; 
 SnjASjSs, SnASjSs ; PtjASzSj ; AgjASjSs ; 
 (US)iAs2S5; Zn2As2S5. Thio-arsenites of chro- 
 mium, molybdemim, and zirconium, seem also 
 to exist. 
 
 II. Thio-aesenaies. As already stated, it is 
 probable that ortho-thio-arsenio acid H3AsSj 
 has been prepared. The thio-arsenates may be 
 divided into three classes, of which the three 
 potassium salts are representatives : K^As^S,, 
 KjAsSj, and KAsS,. The thio - arsenates are 
 obtained : 1. By digesting ASjSj with solutions 
 of the alkali sulphides, on cooling some ASjSj is 
 precipitated. — 2. By dissolving AS2S3 in solutions 
 of alkaU-polysulphides. — 3. By precipitating 
 solutions of arsenates by HjS, or by (NH4)2SAq ; 
 in the latter case the liquids must be boiled to 
 remove NH3. — 4. By fusing ASjSj with alkali 
 carbonates. — 5. By dissolving ASjSj in KOHAq 
 or NaOH aq ; arsenate is formed as well as thio ■ 
 arsenate. The thio-arsenates of the alkali metals 
 are yellow or red, very soluble in water, crystal- 
 lisable, fairly stable, compounds ; their aqueous 
 solutions are slowly decomposed by exposure to 
 air. The other thio-arsenates are more easily 
 decomposed ; those of the heavy metals are in- 
 soluble in water ; they are best prepared by de- 
 composing the solution of an alkali thio-arsenate 
 by a solution of a salt of the metal. Soluble 
 thio-arsenates are decomposed by HClAq with 
 precipitation of AsjSj. The salts obtained by 
 the methods enumerated are usually ^yro-thio- 
 arsenates M^AsjS, ; the meto- and oriho- salts 
 are produced from these, very frequently by the 
 action of alcohol on their solutions ; alcohol 
 usually precipitates an ortho- salt and leaves 
 a wteia- salt in solution. The ortho- salts are fre- 
 quently crystalline ; most of the others are 
 
ARSENIC COMPOUNDS, ORGANIC. 
 
 317 
 
 Biuorphous. Heated in absence o£ air, most 
 thio-arsenates yield thio-arsenites, and then 
 AS2S3 which sublimes, and a metallic sulphide 
 which remains ; some, however, are unchanged 
 by heat alone, e.g. MjAsS, where M = Li, K, Na. 
 Heated in air, the thio-arsenates, as a class, give 
 off AsjSa and As^Oj, and leave a sulphate in the 
 cases of alkaline salts, or an oxide in the cases 
 of salts of heavy metals. The thio-arsenates 
 have been chiefly investigated by Berzelius (v. 
 Gm. i, 275) ; also by Nilson IJ.pr. [2] 12, 295 ; 
 13,1). 
 
 The following are the thio-arsenates which 
 have been fairly well investigated : — 
 
 Aminonium thio-arsenates. The pyro- salt 
 (NHj),As2Sj has not been obtained as a solid : a 
 solution of AsjSj in (NHJjSAq probably contains 
 this salt, it is decomposed on evaporation ; 
 alcohol precipitates the ortho- salt {NH4)3AsS4 
 in white prismatic crystals, while the meta- salt 
 NH4ASS3 remains in solution. 
 
 Barium thio-arsenates. A solution of 
 BaHAsO, is decomposed by H^S, but the pure 
 p2/ro-thio-arsenate, Ba^As^S,, has not been ob- 
 tained ; this solution is decomposed by alcohol 
 into Ba3(AsS J2 which precipitates, and Ba(AsS3)j 
 which remains in solution. 
 
 Magnesium thio-arsenates. The pyro- salt 
 MgjASjS, is a yellow solid, very soluble in water ; 
 by adding Mg(SH)2Aq to this solution until HjS 
 ceases to come off, and evaporating in vacuo, 
 crystals of Mg3(AsS4)2 are obtained ; alcohol 
 decomposes this salt, dissolving out MgjAs^S,. 
 
 Potassium thio-arsenates. The pyro- salt, 
 KjASjS,, is best obtained by treating KjHAsOjAq 
 with HjS and evaporating m vactio ; it forms a 
 yellow viscid mass which liquefies on exposure 
 to the air and then crystallises in rhombic 
 plates. By adding alcohol to a cone, solution of 
 this salt an oily liquid is obtained which 
 crystallises when warmed giving K3ASS4, and 
 KASS3 remains in solution. A salt containing 
 both sulphur and oxygen, AsSO.OK.HjO is 
 described by Bouquet and Cloez {A. Ch. [3] 13, 
 44), produced by the action of H2S on cold 
 saturated KjHAsOjAq; it may perhaps be re- 
 garded as a double compound of the hypothetical 
 oxysulphide ASjSjO, with KjO, but the data are 
 very meagre. 
 
 SodiMm thio-arsenates. The ortlio- salt 
 2NasAsS4.15H20 is obtained in large white, or 
 yellowish, monoolinic prisms, by digesting 
 Na2SAq with ASjSs, or with AS2S3 and suiEeient 
 S to form AS2S5, and allowing to crystallise (Prese- 
 nias, Fr. 1, 192). The same salt is also obtained 
 by decomposing Na2HAs04Aq by HjS, and adding 
 alcohol to the solution; according to the con- 
 ditions under which this liquid is allowed to 
 crystallise, crystals of varying form and some- 
 what varying appearance are obtained (Berze- 
 lius). The crystals are not dehydrated in dry 
 air, but when slowly heated the salt may be 
 obtained without water of crystallisation. It is 
 doubtful whether the meta- and ^yro-thio- 
 arsenates have been obtained; the solution 
 from which the orth/j- salt is thrown down by 
 alcohol probably contains NaAsSs, and the solu- 
 tion before alcohol is added probably con- 
 tains Na^ASjS,. The double thio-arsenate 
 NasCNHJajAsSJj is also described by Berzelius 
 (l.c.)- 
 
 Besides the above salts, the following thio- 
 arsenates seem to have been obtained in fairly 
 definite forms : Oa2As2S„ Ca3(AsS.,)2 ; Ce2As2S„ 
 Ce3(AsS4)2, Ce4(As2S,)3 ; CojAsaS, ; Au4(As2S,)3 ; 
 Fe4(As2Sja, PcjAsjS,; PbjAsjS,, Pb3(AsS4)2; 
 Mn2As2S,; HgjAsjS,, Hg4As2S,; Ag^AsaS, ; 
 (US)4As2S,. Thio-arsenates of Sb, Be, Bi, Cd, 
 Or, Li, Ni, Pt, Sr, T, Zn, and Zr, probably exist. 
 
 Arsenic acid and Arsenates v. Absenio, i.oii>3 
 
 07. 
 
 Arsenides. Binary compounds of arsenic 
 with more positive elements, v. Aesenio, Com- 
 binations, No. 9. 
 
 Arsenious acids and Arsenites, v. Absenio, 
 Aoms or. M. M. P. M. 
 
 ARSENIC COMPOUNDS, OBGANIC. . This 
 article is devoted to compounds in whose mole- 
 cules arsenic is supposed to be directly united 
 to carbon. They are produced by distilling 
 alkyl iodides with an alloy of arsenic with 
 potassium or sodium (thus Mel gives As2Me4, 
 AsMe3, and AsMCiI — Cahours a. Eiohe, O. JR. 
 39, 541), or by heating AsClj with compounds 
 of mercury with alkyls or aromatic radicles or 
 by the action of sodium on a mixture of AsClj 
 and a haloid derivative. The methyl derivatives 
 will be described first, followed by the methyl- 
 ethyl, ethyl, phenyl, and finally by the benzyl, 
 derivatives. The nomenclature employed is 
 somewhat different from that used for derivatives 
 of nitrogen. Thus the radicles AsMe, AsMej, 
 AsMBj, and AsMe4 are called methyl-arsine, di- 
 methyl-arsine, tri-methyl-arsine, and tetra- 
 methyl arsonium respectively. 
 
 Methyl-arsine dichloride AsMeCl2. (133°). 
 At 40°-50'' di-methyl arsine trichloride pro- 
 duces AsMeCIj thus : AsMejClj = MeCl + AsMeClj. 
 Liquid which does not fume. M. sol. water but 
 not decomposed by it. It violently attacks the 
 mucous membrane. At —10° absorbs CI2 form- 
 ing AsMeCl4 which at 0° splits up into MeCl 
 and ASCI3 (Baeyer, A. 107, 257). 
 
 Methyl-arsine di-iodide AsMelj. [c. 25°]. 
 Prom the oxide, AsMeO, and HI. From caoodyl 
 and iodine (Cahours, 0. B. 50, 1022). Yellow 
 needles (from alcohol). Converted by H2S into 
 AsMeS, and by HCl into AsMeClj. 
 
 Methyl-arsine sulphide AsMeS. [110°]. 
 From H2S and AsMeCl2. Plates (from alcohol). 
 Insol. water. Pps. Ag, Cu, and Pb, as sulphides 
 from their salts. 
 
 Methyl-arsine disulphide AsMeSj. Formed 
 by passing H2S into an acidified solution of 
 methan«-arsonio acid (G. Meyer, B. 16, 1440). 
 
 Methyl-arsine oxide AsMeO. [95°]. Formed 
 by action of K2CO3 on the chloride AsMeClj. 
 Crystallises from CS2 in irregular cubes, smells 
 like Asa foetida. M. sol. cold, v. sol. hot, water j 
 slightly volatile in vapour of water and alcohol ; 
 V. sol. aqueous acids forming neutral solutions. 
 
 Methane arsonio acid MeAsO(OH)2. From 
 AsMeClj and excess of moist AgjO. From 
 AsMeO in aqueous solution by action of HgO. 
 From aqueous sodium arsenite and Mel (M.). 
 Large spear-shaped laminaj composed of small 
 needles (from alcohol). 
 
 Salts. — BaA'',5H20: ppd. as anhydrous 
 rhombic crystals, by adding alcohol to aqueous 
 solution ; the crystals soon change to hydrated 
 needles.— AgjA" ; nacreous crystals which ex- 
 plode above 100°— CaA" aq. 
 
318 
 
 ARSENIC COMPOUNDS, ORGANIC. 
 
 Tetra-methyl di-arsenide As.Me,. Cacodyl. 
 Alkarsin. Mol. w. 210. [e. -6°]. (o. 170°). 
 V.D.7-l{air = l). 
 
 Preparation. — ^By heating di-methyl-arsine 
 chloride (oaeodyl chloride) with zinc at 100° in 
 bulbs filled with CO^ (Bunsen, P. 40, 219 ; 42, 
 145; A37, 1; 42,14; 46,1). 
 
 Properties. — Stinking oil ; heavier than 
 water. Takes fire in air or in chlorine. Reduces 
 HgCl2 to mercurous chloride. 
 
 Reaction. — As2Me4 + 2MeI = AsMe J + AsMsjI 
 <Cahours, A. 122, 209). 
 
 Combinations. — When gradually mixed with 
 air, chlorine, or bromine, it forms derivatives 
 of cacodyl, behaving like a molecule of such 
 a metal as potassium : (AsMe2)2 + Clj = 
 2(AsMe2)Cl ; and {AsMej)^ + = (AsMej)^^ 
 
 Tetra - methyl - di - arsine oxide (AsMe2)20. 
 Cacodyl oxide. Mol. w. 226. [0.-25°]. (120°). 
 S.G. i£ 1-462. V.D. 7-55 (oalc. 7-83). 
 
 Formation. — Cadet's fluid (Grell. N. Chem. 
 Arch. 1, 212), obtained by distilling KOAo with 
 an equal weight of As^Oj, is cacodyl oxide mixed 
 with some cacodyl. HgO converts both into 
 cacodylic acid, whence a mixture of HgCl^ and 
 fuming HCl forms cacodyl chloride. The latter 
 is converted into cacodyl oxide by distilling 
 with aqueous potash in a current of COj 
 (Baeyer, A. 107, 282) : 2AsMe2Cl + 2KH0 = 
 H20 + 2KCl+(AsMe2)20. 
 
 Properties. — Pungent, stinking oil. Slowly 
 oxidises in air forming cacodylic acid. Acids 
 convert it into salts of cacodyl. 
 
 Compounds. — Forms with HgClj a com- 
 pound (AsMe2)202HgCl2, crystallising in tri- 
 metrio plates. S. 3-47 at 100°. Distilled with 
 fuming HCl this forms cacodyl chloride. — • 
 (AsMej)20 2HgBr„.— (AsMe2)oO f AgNOj : explodes 
 at 100°. — (AsMe2)20PtCl2aq : red-brown pp. 
 converted by KBr into (AsMe2)20PtBr2aq, and 
 by KI into (AsMe2)20Ptl2. 
 
 Dl-methyl-arsine chloride AsMe2Cl. (o. 100°). 
 V.D. 4-56 (calo. 4'85). Obtained from cacodylic 
 acid as above ; or by action of chlorine-water 
 on cacodyl. — Heavy oil ; attacks the mucous 
 membrane ; combines with Clj forming AsMe^Clj. 
 Zn, Sn, and Fe liberate AsjMej. 
 
 Compounds. — AsMcjOl CuCl (Bunsen). — 
 (AsMe2Cl)2PtCl4. 
 
 Di-methyl-arsine bromide AsMejBr : yellow oil. 
 
 Di-methyl-arsine iodide AsMejI (160°): oil 
 (Cahours a. Riche, A. 92, 864). 
 
 Di-methyl-arsine cyanide AsMojCy. [33°]. 
 (140°). V.D.4'63. Prisms. Excessively poisonous. 
 
 Di-methyl-arsine sulphide (AsMe2)2 S. Com- 
 bines with S to form (AsMe2)2S2 [50°]. 
 
 Di-methyl-arsine fluoride AsMejF. Liquid. 
 
 Di-methyl-arsine trichloride AsMe2Cl3. 
 Cacodyl trichloride. From PCI3 and cacodylic 
 acid ; or from cacodyl chloride and CI2. 
 
 Reactions. — 1. At 60° it splits up as follows : 
 AsMe2Cl3 = MeCl + AsMeCl2.— 2. With water it 
 forms cacodylic acid. 
 
 Di-methyl-arsinic acid AsMe20(0H). Caco- 
 dylic acid. Mol. w. 138. [200°]. 
 
 Formation. — From cacodyl and HgO in 
 presence of water. 
 
 Properties.— Large prisms (from alcohol), 
 without odour, but poisonous. V. sol. water, 
 m. sol. alcohol, insol. ether. Not acted on by 
 HNO„ HCl, aqua regia, KMnOj or CrOj. 
 
 Reactions.— 1. H3PO3 reduces it to cacodyl 
 oxide. — 2. Aqueous HjS forms cacodyl sul- 
 phide. — 3. An alcoholic solution gives with 
 alcoholic HgCl^ a pp. of (AsMe2)203Hg20l2. — 
 4. Caoodylates are converted by dry HjS into 
 thio-caoodylates ; e.g. (AsMe2S2)2Pb. — AsMe2S2Cu. 
 — (AsMe2S2)sSb.— (AsMe2S2)3Bi.— AsMe2S2Au. 
 
 Salts. — Soluble in water, but amorphous. 
 AgA': needles.— AgH2A'3 : needles. — AgA'AgNO,. 
 
 Compounds. — HCl forms a crystalline com- 
 pound (AsMejOjH HCl) decomposed by water. 
 This compound distUled in a current of HOI 
 splits up thus: AsMeaOiH HCl + 2HC1 = 
 AsMeOl2 + MeCl-H2H20.— HA'HP : prisms. 
 
 Tri-methyl arsine AsMCj. Mol. w. 120. 
 (0. 100°). Formation.—!. 2AsCla-l-3ZnMe2= 
 3ZnCl2 -F 2AsMe3 (Hofmann).— 2. FromAsMeJ 
 and solid potash (Cahours, O. R. 49, 87). 
 
 Properties. — 1. Combines directly with 
 CI2, Br2, I2, S, and 0. 
 
 Iodide AsMcal,. Splits up on distillation 
 into Mel and AsMOjI, cacodyl iodide. — Oxide. 
 AsMOsO: deliquescent crystals. — Sulphide 
 AsMe3S : prisms (from alcohol). — Bromide 
 AsMcjErj. 
 
 Tetra-methyl-arsoninm iodide AsMe^I. 
 
 Formation. — 1. From sodium arsenide and 
 Mel at 180°, and treating the product (AsMe JAsIj) 
 with KOH (Cahours, C. R. 36, 1001 ; 4. 122, 192). 
 
 Properties. — Plates (from alcohol mixed with 
 Mel). 
 
 Combinations. — AsMe4ll2. — (AsMe^^jZnlj. 
 — (AsMe4l)2Cdl2.— AsMeJAsI,. 
 
 Reactions. — 1. With ZnMe, gives AsMe5(?) 
 (Cahours). — 2. KOH no action. — 3. Moist AgjO 
 gives AsMe^OH, deliquescent alkaline crystals. — 
 4. AgaSO, gives crystalline (AsMeJ^SO^. — 
 6. AgNOj forms crystalline AsMe^NOj. 
 
 Penta-methyl-arsenide AsMe,. Prom AsMe,I 
 and ZnMOj. With iodine forms Mel and AsMe^I ; 
 with HCl forms CHj and AsMe^Cl (Cahours). 
 
 Di-methyl-ethyl-arsine. -^ AsMcjBt. From 
 AsMbjI and ZnEtj. Liquid (Cahours). 
 
 Methyl-di-ethyl-arsine AsMeEtj. From 
 AsMelj and ZnEtj (Cahours). 
 
 Di-methyl-di-ethyl arsonium salts. 
 
 Iodide. — AsMejEtjI. Fromcacodyl andEtl, 
 thus: As2Me4-f2EtI = AsMe2EtJ + AsMe2Cl (Ca- 
 hours a. Riche, C. R. 39, 544). ' 
 
 Hydroxide: very deliquescent. 
 
 Chloride AsMe2Et2Cl : deliquescent needles. 
 
 Platino-chloride (AsMe2Et2Cl)2PtOl4. 
 
 Bromide AsMCjEtjBr: deliquescent. 
 
 Iodide AsMcjEtjI: prisms. 
 
 Periodide ksM.e.^'EtJ.,: lustrous prisma. 
 
 Nitrate AsMe2Et2N03 : deliquescent grains. 
 
 Sulphate (AsMe2Et2)2SOj : ootahedra. 
 
 Ethyl-arsine iodide AsEtlj. From AsEt^I 
 and I2 (Cahours, C. R. 50, 1022 ; A. 116, 367). 
 With moist Ag^O it forms the acid AsBtO(OH)2. 
 
 Ethyl-arsine chloride AsEtCl^. (156°). From 
 HgEtj and ASCI3 (La Coste, A. 208, 33). Liquid, 
 m. sol. water. 
 
 Ethane arsonic acid EtA50(0H)2. From the 
 preceding by the action of diluted HNO,. Small 
 crystals (from alcohol). — AgjA": pearly scales. 
 
 Tetra-ethyl-di-arseuide ASjEt,. Mol. w. 266. 
 (185°-190°). From an alloy of arsenic and sodium 
 on EtI (Landolt, A. 89, 319). Heavy stinking 
 oil, takes fire in air. Reduces salts of silver and 
 mercury. Unites directly with sulphur and 
 
ARSENIC COMPOUNDS, ORGANIC. 
 
 319 
 
 halogens. Alcoholic HgClj gives a crystalline 
 precipitate AsEt,Cl32Hg20(?). 
 
 Iodide AsEtjI. (c. 230°). Oil. 
 
 Di-ethyl-arsinic acid AsEt20(0H). [190°]. 
 From AsEtj and HgO under water (Landolt, A. 
 92, 365). Large plates, soluble in water. Not 
 Attacked by HNO, or aqua regia. 
 
 Salts.— BaA'2HA'2aq. Very sol. in water, 
 difficultly sol. in alcohol. 
 
 Xri-ethyl-arsine AsEtj. Mol. w. 162. 
 <140°-170°). S.G. il 1-151. V.D. 5-28 (oalo. 
 5-62). 
 
 Formation. — 1. From AsClj and ZnEta 
 (Hofmaim a. Cahours, G. B. 41, 831).— 2. To- 
 gether with AsjEtj by the action of EtI on an 
 alloy of arsenic and sodium. — 3. By distilling 
 AsEtjI with solid potash (Landolt, A. 89, 322). 
 
 Properties. — OHof disagreeable odour. Fumes 
 strongly in air. Combines directly with non- 
 metals. Does not reduce ammoniacal silver 
 nitrate (difference from AsjEtJ. 
 
 GcrmMimtions. — ^AsEtjBrj : deliquescent. — 
 AsEtjIj,. [160°], (190°). (Cahours a. Eiche, 
 A. 92, 365).— AsEtsS. [c. 100°]. Prisms (from 
 ether) ; pps. sulphides from solutions of metallic 
 salts. — (AsEtJ^PtCl.,. — (AsEt3),PtClj. — 
 (AsEt3)2PdCl2 (Cahours a. Gal, 0. B. 71, 208).— 
 (AsEt30AsEt3Cl2HgjCl2(?). — AsEtjAuOl. — 
 AsEt3PBt3(C2HjBr)Br. 
 
 Tri-ethyl-arsine oxide AsEt30. Formed by 
 exposure of an ethereal solution of AsEt3 to the 
 air. An oil, insoluble in acids, except HNO3. 
 
 Tetra-ethyl-arsonium iodide AsEt^I. 
 
 Formation. — 1. From AsEt3 and EtI 
 (Landolt, A. 89, 331).— 2. Arsenic with EtI at 
 180° gives red needles of AsEt^I Asl,, which is 
 then boiled with potash (Cahours a. Eiche, G.B. 
 39, 546). — 8. An alloy of arsenic with Zn or 
 Cd heated with EtI gives (AsEt^Ij^Znlj or 
 (AsEtj^jCdlj ; these are boiled with potash 
 (Cahours, A. 122, 200). 
 
 Properties. — Needles, v. sol. water and 
 alcohol, insol. ether. 
 
 Beactions. — 1. With moist AgjO, gives an 
 alkaline hydrate. — 2. Combines with l^ forming 
 brown needles of AsEtjIj. 
 
 letra-ethyl arsaniam salts (Landolt, A. 
 92, 371). 
 
 Ghloride AsEtjCHaq: deliquescent crys- 
 tals, insol. ether. — (AsEt,Cl)4(BiCl3)2 (Jorgensen, 
 J. pr. 12] 3, 3i6). 
 
 Platino -chloride (AsEt4Cl)2PtClj : si. sol. 
 cold water. 
 
 Bromide AsEt^Br: deHquescent mass. — 
 (AsEt4Br)3(BiCl3),. 
 
 Sulphate AsEtjSOjH : grains, v. sol. water 
 and alcohol, si. sol. ether. 
 
 Eromo - tetra - ethyl - arsonium bromide 
 {CH2Br.CH.2)AsEt3Br. From ethylene bromide 
 and AsEtj at 50° (Hofmann, Pr. 11, 62). 
 Ehombic dodecahedra (from alcohol). V. sol. 
 water, al. sol. alcohol. Aqueous AgNOj pps. 
 half its bromine as AgBr. 
 
 Beactions. — 1. With moist Ag20 it gives vinyl 
 triethyl arsonium hydroxide, CjH3AsEt3(0H). — 
 2. With AsEt3itgivesAS2(C2Hj)Et8Br2.— 3. With 
 ammonia at 100° it gives a compound 
 NAs(C2H4)Et3HsBrj. This compound and the 
 preceding are converted by Ag^O into oxides 
 and thence into platinochlorides (e.g. 
 NAs(C„H4)Et3H3Cl2PtCl4) and other salts 
 
 4. AuCla gives crystals of AsEtjAuCl.- 5. PtCl, 
 gives crystals of AsjEt^Pt (Hofmann, A. 
 103, 357). 
 
 Di-methyl-di-isoamyl-arsoninm iodide 
 AsMe2(C5H„)jI. From cacodyl and iso-amyl 
 iodide at 180°, as follows: As2Me4-(-2C5H„I = 
 AsMe2(05Hii)jI-HAsMe2l (Cahours a. Eiche). 
 
 Tri-propyl-arsine AsPr,. At 180°, arsenio 
 combines with PrI forming AsPrjIAsI,. Dis- 
 tilled with solid potash, this gives AsPrj (Ca- 
 hours, 0. B. 76, 1383). Arsenic acta similarly 
 on isobutyl iodide at 180° (Cahours, C. R. 77, 
 1406). Calcium butyrate distilled with As^O, 
 gives a distillate resembling Cadet's liquid, pro- 
 bably containing the propyl homologues of caco- 
 dyl compounds (Wohler, A. 68, 127). Potassium 
 valerate distilled with AS2O3 appears similarly 
 to give ' butyl-cacodyl ' derivatives (Gibbs, Am. 
 
 5. [2] 15, 118). 
 
 AEOMATIC DEEIVATIVES. 
 
 Literature. — Michaelis, A. 201, 184; 207, 
 195 ; 208, 1 ; 233, 60 ; B. 8, 1316 ; 9, 1566 ; 10, 
 622; 11, 1883; 13, 2176; 14, 912; 15, 1952, 
 2876 ; 18, 42; La Coste, A. 184, 1; 208, 1. 
 
 Di - phenyl - di - arsenide CjHjAsiAs.CsHj. 
 Arseno-benzene. [196°]. Prepared by reduction 
 (best with phosphorous acid) of an alcoholic 
 solution of phenyl-arsine oxide (Michaelis a. 
 Schulte, B. 14, 912; 16, 1952). YeUowish 
 needles. Sol. benzene, chloroform, and CSj ; si. 
 sol. alcohol, insol. water and ether. On heat- 
 ing it gives triphenyl-arsine and arsenic. 
 
 Beactions. — 1. Heated with 1 mol. of sulphur 
 phenyl-arsine sulphide is formed, with more sul- 
 phur, phenyl sulphide and As^Sj. — 2. Alcoholic 
 NHjHS reduces it on heating to benzene, AS2S3, 
 and As ; HI acts in a similar manner. — 3. On 
 oxidation it gives benzene-arsonic acid. — 4. Com- 
 bines directly with halogens. 
 
 Di-iodide. — Ph.AsI.AsI.Ph. Yellow needles. 
 Very unstable. Prepared by reduction of phenyl- 
 arsine iodide (which is formed by dissolving 
 phenyl-arsine oxide in HI). 
 
 Phenyl-arsine chloride PhAsCl2 (c. 253°). 
 Obtained in theoretical quantity by heating AsOlj 
 (800g.) withHgPhj (70 g.). Colourless liquid with 
 unpleasant odour ; insol. water, sol. KOHAq. 
 
 Phenyl-arsine tetra-ohloride PhAsClj. [45°]. 
 Formed by passing CI into the preceding at 0°. 
 Yellow needles, fuming in moist air ; readily 
 decomposed into CI2 and PhAsClj ; when heated 
 at 150° it gives C.HjCl and ASCI3. 
 
 Phenyl-arsine bromide PhAsBr2. (285°). 
 S.G. 1- 2-10. Colourless liquid formed by the 
 action of cone. HBr upon PhAsO. Gives with 
 bromine ABBr3 and PhBr. 
 
 Phenyl-arsine iodide PhAsIj. Oil. 
 
 Phenyl-arsine oxide PhAsO. [120°]. Formed 
 by treating PhAsCl2 with Na2C03. Crystals (from 
 alcohol) ; smells Uke anise ; insol. water ; si. sol. 
 cold, m. sol. hot, alcohol ; slightly volatile with 
 steam. Heated with HCl it forms PhAsClj. 
 Above its melting-point it decomposes thus : 
 3PhAsO = AsPhj -1- AsjOj. 
 
 Phenyl-arsine oxy-chloride PhAsOClj. [100°], 
 Formed by decomposing the tetrachloride with 
 the theoretical quantity of water ; or by the union 
 of chlorine with the oxide. Crystalline ; dis- 
 solved by water, being converted into benzens 
 arsonic acid. At 120° it splits up thus : . 
 PhAsOCU = PhCl + AsOCl. 
 
320 
 
 AESENIO COMPOUNDS, OKGANIO. 
 
 Beuzene-arsonic acid 0„H5AsO(OH)-!. 
 Formed by dissolving PhAsClj or PhAsOClj in 
 water. Long columns ; begins to soften at 138°, 
 changing to an amorphous anhydride, which 
 is re-converted by water into the acid. M. sol. 
 odd, V. sol. hot, water. 
 
 ileactions. — 1. Not afiected by reducing or 
 oxidising agents. — 2. Potash fusion produces 
 phenol. 
 
 Salts.— NHjHA": needles.— KHA": amor- 
 phous. — BaHjA''^: needles, v. sol. water. — . 
 CaH2A"j: needles.— CaA"2aq.—CuA": v. si. sol. 
 water.— PbA" : insol. water. 
 
 Xetra-phenyl-di-arsenlde As2(C8H5)4. Phenyl- 
 caeodyl. [135°]. Formed by reduction of tetra- 
 phenyl-di-arsine oxide with phosphorous 
 acid. White crystals. SI. sol. alcohol and 
 ether. It quickly oxidises in the air, forming 
 di-phenyl-arsinic anhydride (Ph^As20s). 
 
 Di-phenyl-arsine chloride PhjAsCl. Phenyl- 
 cacodyl chloride. (333°). S.G. is 1-42. Pre- 
 pared by heating HgPh^ with a large excess of 
 PhAsClj at 320°. The product is then fraction- 
 ally distiUed. Yellow oil, insol. water, sol. alco- 
 hol, ether, and benzene, si. sol. aqueous alkalis. 
 Not affected by heating with NajCO,. Combines 
 with bromine and chlorine. Cone. HNOj slowly 
 converts it into di-phenyl-arsinic acid. 
 
 Di-phenyl-arsine trichloride Ph^AsClj. 
 [174°]. From the preceding and chlorine. Colour- 
 less tables (from benzene). At 200° it decomposes 
 thus : PhjAsCls = PhAsCLj + PhCl. 
 
 Di-phenyl-arsine ohloro-bromide PhjAsClBr^. 
 Formed by passing dry bromine-vapour into 
 PhjAsCl. Excess of Br produces di-bromo- 
 benzene. 
 
 Tetra-phenyl-di-arsine oxide (PhjAs).^. [92°]. 
 Formed by heating PhjAsCl with alcoholic KOH. 
 
 Di-phenyl-arsine bromide Ph^AsBr. (356°). 
 From the oxide and HBr. 
 
 Di-phenyl-arsine oxy-chloride (PhjAsOyjO. 
 [117°]. From the oxide and chlorine. 
 
 Di-phenyl-arsinic acid PhjAsO.OH. [174°]. 
 S.G. 1'55. From the oxy-chloride or the tri- 
 chloride by the action of water. White needles ; 
 sol. water and alcohol, si. sol. benzene and ether. 
 Not attacked by CrOj or boiling cono. HNO,. 
 
 Salts. — ^NaA'. — NHjA': unstable feathery 
 crystals.— BaA'2.—CuA'2.— HO.CuA'.—AgA'.— 
 PbA'j. 
 
 Tri-phenyl-arsine AsPh,. [59°]. (above 360°). 
 S.G. 1-306. Prepared by heating phenyl-arsine 
 oxide at 200°, thus: SPhAsO^AsPhsH-AsA- 
 More readily by the action of sodium (50 g.) on 
 AsClj (54 g.) and ohloro-benzene (101 g.), diluted 
 with 4 vols, dry ether. Is also a by-product in 
 preparing Ph^AsClf rom PhAsClj and HgPh2. Tri- 
 clinic crystals isomorphous with SbPhj (Philips, 
 B. 19, 1031). Insol. water and dUute acids, 
 V. sol. hot alcohol, benzene, and ether. With 
 HgClz it forms leaflets of AsPh3HgCl2, whence 
 aqueous KOH forms AsPhs(0H)2, [108°], thus : 
 AsPhsHgCl^ + 2E0H = AsPh3(0H)2 + 2KCU Hg. 
 
 Tri-phenyl-arsine chloride PhsAsCLj. [171°]. 
 From AsPhj and chlorine. Tables; decomposed 
 at 280° into Ph^AsCl and PhCl. 
 
 Tri-phenyl-arsine sulphide PhgAsS. [162°]. 
 Prepared by digesting PhjAs with S dissolved in 
 CS^; or by action of ammonium sulphide on 
 PhaAsClj. Silky needles, insol. water and ether. 
 
 Tri-phenyl-arsine ozy-nltrate 
 (C„H5)3As(OH)N03. [84°]. Formed by adding 
 HNOj to an aqueous solution of the hydroxide 
 (C5H5)3As(OH)2 (Philips, B. 19, 1033). Long 
 gUstening needles. Y. sol. alcohol, si. sol. water. 
 
 Tri.nitro-tri-phenyl-arsine oxide 
 {C8H,.N02)3AsO. [254°]. Formed by nitration 
 oftri-phenyl-arsine-hydrate,(C5H5)3As(OH)2,with 
 HNOj and H2SO4. Nearly colourless large crystals. 
 V. sol. acetic acid, insol. alcohol and ether. 
 
 Tri-amido-tri-phenyl-arsine (CbH4.NH2)3As. 
 [0. 176°]. Formed by reduction of tri-nitro-tri- 
 phenyl-arsine oxide (C5H5.N02)3AsO with tin and 
 HCl in acetic acid solution (P.). Colourless 
 crystalline solid. V. sol. alcohol and dilute 
 acids, insol. water. 
 
 Salts. — B"'H3Cl3: crystalline solid, easily 
 soluble in water and alcohol.— (B"'H3Cl3)2(PtClj)3: 
 yellow pp., insol. cold water. 
 
 Tri-acety I -derivative (CjH4.NHAc)3Ag. 
 [0. 230°]. Very sparingly soluble in alcohol^ 
 more easily in acetic acid. 
 
 Tri-^-ethoxy-trl-phenyl-arsiue 
 (EtO.CjHJjAs. Tri-phenetyl-arsine. [89°]. 
 Formed by the action of sodium upon a mixture 
 of ^-bromo-phenetol and AsClj (Michaelis a. 
 Weitz, B. 20, 52). 
 
 tri-^-methoxy-tri-phenyl arsine 
 (MeO.OjHJjAs. Tri - anisyl - arsine. [156°]. 
 Obtained by the action of sodium upon a mix- 
 ture of ^-bromo-anisol and AsClj containing 
 some acetic ether. Transparent colourless 
 crystals. V. sol. benzene, si. sol. alcohol and 
 ether. HI splits it up into di-anisyl-arsine 
 iodide (CjH,.0Me)2AsI and anisol; by longer 
 and higher heating anisol and Asl, are formed. 
 By heating with an excess of AsCl, it 
 yields anisyl-arsine chloride CjH4(0Me).AsClj 
 (Michaelis a. Weitz, B. 20, 48). 
 
 Di-p-methoxy- di - phenyl - arsine chloride 
 (0sHj.0Me)2AsCl [1:4]. Di-anisyl-arsine chloride. 
 [80°]. Formed by dissolving the oxide in HCL 
 Long thin needles. V. sol. ether, less in alcohol. 
 
 Di-methoxy-di-phenyl-arsine oxide 
 {(C5Hj.OMe)2As|jO [1:4]. Di-anisyl-arsine 
 oxide. Tetra- anisyl -di- arsine oxide. [130°]. 
 Crystalline. Formed by the action of alkalis on 
 the iodide which is obtained by heating tri- 
 anisyl-arsine with HI. 
 
 ^-IVCethoxy-benzene-arsine chloride 
 C5H4(OMe).AsCl2 [1:4]. p-Anisyl-arsine chloride, 
 (230° at 117 mm.). Colourless liquid. Formed 
 by heating tri-anisyl-arsine (0jH4.OMe)3As with 
 an excess of AsClj at 200°. Alkalis yield the 
 oxide C5H4(OMe).AsO, a colourless crystal- 
 line solid. It combines with Clj to form 
 CjHj(0Me).AsCl4 which is a thick yellow liquid 
 decomposed by water giving anisyl-arsinio acid 
 C8H4(OMe).AsO(OH)2. 
 
 p-Methoxy-benzene-arsonlc acid 
 (C|,H4.0Me).AsO(OJI)2. Anisyl - arsirdo acid. 
 [160°]. Formed by the action of water upon 
 the chloride CeH4(OMe).AsOl4. Colourless crys- 
 talline solid. Sol. hot, si. sol. cold, water ; v. 
 sol. alcohol. On heating it gives the anhydride 
 C5H4(OMe).As02.— AgjA" : white pp. 
 
 Phenyl-di-methyl-arsine PhAsMcj. (200°). 
 From ZnMe, and PhAsCl^. Mobile liquid, soL 
 alcohol and benzene, insol. water. 
 
 Fhenyl-tri-methyl-areoninm iodide 
 PhAsMejI. [244°]. From the preceding and 
 
AESENIO COMPOUNDS, ORGANIC. 
 
 321 
 
 Mel. White needles ; sol. water and alcohol, 
 insol. ether.— (PhAsMejC^jPtCl, [219°] ; v. sol. 
 hot water. 
 
 Di-phenyl-methyl-arsiae Ph^AsMe. (306°). 
 From PhjAsOl and ZnMe^ in benzene (Miohaelis 
 a. Link, A. 207, 199). Insol. water. 
 
 Si-phenyl-di-methyl-arsonium iodide 
 PhjAsMe^I. [190°]. From the preceding and 
 Mel. Needles ; si. sol. cold, v. sol. hot, water. 
 Decomposed by heat into Mel and Ph^AsMe. — 
 (Ph2AsMe,Cl)jPtCl< [219°]. 
 
 Phenyl-di-ethyl arsine PhAsEt^. (240°). 
 From PhAsClj and ZnEtj. Colourless liquid. 
 Combines with CI, forming PhAsEt^Clj. 
 
 Phenyl-tri-ethyl-arsonium iodide PhAsEtjI. 
 [113°]. From the preceding and EtI at 100°. 
 Prisms, turned yellow by sunhght; sol. water 
 and alcohol, insol. ether. Decomposed when 
 heated in an indifferent gas into EtI and 
 PhAsEtj. Gives with AgCl the chloride 
 PhAsEtaCl; whence (PhAsEtjC^^PtClj. Gives 
 with AgjO the hydroxide PhAsEtjOH, an 
 alkaline syrup, absorbing COj from the air. 
 
 Di-phenyl-ethyl arsine Ph^AsEt. (320°). 
 From PhjAsCl and ZnEt^. Colourless liquid. 
 
 Di-phenyl-ethyl-arsine chloride Ph^AsEtClj. 
 [137°]. From the preceding and CI. Needles 
 (from benzene) ; fumes in the air ; decomposed 
 by water. 
 
 Si - phenyl - di - ethyl - arsonium iodide 
 PhjAsEtjI. [184°]. From Ph^AsEt and EtI. 
 Flat white needles. 
 
 Di - phenyl -methyl - ethyl - arsonium iodide 
 Ph^AsMeEtl. [170°]. S. 1-1 at 15°; 84-4 at 
 100°. From Ph^AsMe and EtI or from PhjAsEt 
 and Mel. Trimetrio prisms; insol. ether. 
 Split up by heat into EtI and PhjAsMe. 
 
 DerwalMies.—{VhjLsM.eEii)^iC\s. [214°]. 
 
 Picrate Ph2AsMeEt.O.C,iH2(NOj)3. [9S°]. 
 SI. sol. cold water. 
 
 Tolyl-arsine chloride CjHjAsClj. 
 
 Ortho (265°). Para [31°]. (267°). 
 
 From AsClj and mercuric di-tolyl (o- or p-). 
 Bromine converts them into di-bromo-toluenes. 
 
 Tolyl-arsine tetrachloride 0,H,AsCl4. 
 
 Tolyl-arsine oxide CjH,AsO. 
 
 Ortho [145°]. Para [156°]. 
 
 From OjHjAsClj and aqueous NajCOj. Com- 
 bine with Clj, forming oxy-chlorides. 
 
 Toluene arsenic acid CH3.CsH4.AsO(OH)2. 
 Ortho [160°]. The para compound decomposes 
 above 300° without previous fusion. 
 
 From the tetrachloride or the oxychloride, 
 OjHjAsGClj, by treatment with water. The" 
 ortho acid forms a crystalline anhydride 
 CjHjAsO^.— AgjA".— BaA".— CaA" (La Coste a. 
 Michaelis, A. 201, 255). 
 
 Di-p-tolyl-arsine chloride (CjHJjAsCl. 
 (c. 343°). From C^HjAsCl^ and Hg(C,H,)2. 
 Liquid ; not affected by aqueous NajCOj. 
 Chlorine gives (CjHJjAsClj. 
 
 Tetra-^-tolyl-di-arsine oxide ( (C,H,)2As)20. 
 [98°]. Silky needles (from ether). Obtained 
 by boiUng the preceding with alcoholic KOH. 
 
 Di-jj-tolyl-arsinic acid (C,H,)2AsO.OH. 
 [167°]. Formed by boiling (CjE^jjAsCla with 
 water. Oxidised to ' dibenzarsinic ' acid. 
 
 Tri-p-tolyl-arsine (C,H,)aAs. [145°]. Obtained 
 by heating 0,H,AsO. 
 
 Tri-^-tolyl-arsine dichloride (C,H,)3As01j. 
 [214°]. Not attacked by water. 
 
 Vol.. I. 
 
 p-Carhoxy-phenyl-arsine chloride 
 CO2H.C5HJASCI2. [158°]. From the correspond- 
 ing iodide and AgCl ; or from the produci 
 (COCI.C5HJ.ASCIJ (?) of the action of PCI3 upon 
 C02H.C|iH,.AsO(OH)j by treating with water. 
 Needles (from benzene) ; decomposed by water. 
 
 p-Carboxy-phenyl-arsine iodide 
 C02H.C,H,Asl2. [153°]. 
 From C02H.C„H,.As0(0H), by HI and P. 
 Yellow needles (from chloroform). 
 
 j3-Carboxy-phenyl-arsine hydroxide 
 C02H.CbH4As(OH)2. Benzarsenious acid. From 
 the preceding by heating with aqueous NajCOj. 
 Colourless needles (from water). At 145°-160° 
 it gives off HjO leaving the oxide 
 C02H.CsH4AsO. — Ca(C,H„AsOj).Aq : plates ;. 
 changing at 200° into Ca(C,HjAs03)2.— 
 AgC,H,As03. 
 
 ^-Carboxy-benzene arsenic acid 
 C02H.CjHjAsO(OH)2. Bensarsinic acid. Formed 
 by oxidising toluene arsonio acid with alkaline 
 KMnO.|. Transparent interlaced needles ; m. 
 sol. water, v. si. sol. alcohol. At 190° it becomes 
 COiH-OoHjAsOj; at 230° it gives off benzoic 
 acid. — AgjA'"- — CaHA"' aq. — KHjA'",. — 
 MeH2A"'. 
 
 ^-Di-oarboxy-di-phenyl-arsine iodide 
 (COjH.CjHJjAsI. [above 280°]. From 
 
 (C02H.C,HJ2AsO.OH, cone. HI, and P. Con- 
 verted by aqueous NajCOj into the hydroxide 
 (COjH.CjHJjAsOH. {Dibenzarsenious acid). — 
 CaA" 2aq. 
 
 ^-Di-carboxy-di-phenyl-arsinio acid 
 (CO2H.C5HJ2AsO.OH. Dibenzarsinic acid. 
 ]?ormed from (C,H,)2AsO.OH and alkaline 
 EMnO, at 60°. Leaflets, insol. water, si. sol. 
 alcohol.— MejHA'" [above 280°]. 
 
 j)-Tri-oarboxy-tri-phenyl-arsine 
 (C02H.C5H4)3As. Tribenzarsenious acid. From 
 the following acid and HI. Small colourless 
 needles.— NajA"' 2aq.— AgjA"'. 
 
 _p-Tri-carboxy-tri-phenyl-ar8ine hydroxide 
 (C02H.CsH4)3As(OH)2. Tribenzarsinic acid. 
 
 From tri-tolyl-arsine and alkaline KMnO, ^ 
 
 (CO2K.CSHJ3ASO. 
 
 Benzyl-arsine chloride PhCH2ABCl2. (175°) 
 at 50mm. Formed by heating tri-benzyl-arsine 
 with excess of AsCl,. Easily oxidised by air : 
 PhCHjAsClj + = PhOH2Cl -h AsOCl. 
 
 Di-benzyl-arsinic acid (Ph.CH2)2AsO.OH 
 [210°]. 
 
 Preparation. — Sodium [50 g.) acting upon a 
 solution of benzyl chloride (100 g.) and AsClj 
 (72 g.) in dry ether (500 g.) containing acetic ether 
 (5g.) forms (PhCHajjAs, (PhCH2)2AsCl3, and' 
 (PhCH2)3AsCl2. Alcohol extracts the first, and 
 converts the two latter into (PhCH2)2AsCl(0H)j 
 and (PhCH2)3AsCl(OH) respectively, and they 
 are then converted by aqueous NaOH into 
 (PhCH2)2AsO.ONa and (PhCH2)3AsO (Michaelia 
 a. Paetoff, A. 238, 60). 
 
 Properties. — Pearly white plates (from aU 
 cohol) ; attacks the mucous membrane ; v. sol, 
 hot alcohol, m. sol. hot water, si. sol. ether. 
 When strongly heated it gives benzoic aldehyde 
 and dibenzyl. 
 
 Salt s.— BaA'2 8aq.— CaA'2 6aq.— AgA'. 
 
 Beactions. — 1. Cone. HCl forms AsClj tolu- 
 ene, and benzyl chloride. — 2. Boiling dilute 
 HNO3 has no effect ; HNO3 of S.G. 1-8 forms a 
 compound (PhCHJjAs(OH)2N03 [129°] ; cone 
 
 y 
 
822 
 
 AKSENIC COMPOUNDS. ORaANIU. 
 
 HNO3 forms benzoic and arsenic acids. — 3. Com- 
 bines with HCl forming (PbCH,)jAsCl(0H)2 
 which crystallises from aqueous HOI in needles 
 [128°]; this is decomposed by more water, 
 giving (PhCHjjjAsO.OH again.— 4. HBr forms 
 (I'hCH2)2As0(0H)HBr. 
 
 Si-beuzyl-thio-arsinic acid (PhCH^jjAsO.SH. 
 [199°]. From di-benzyl-arsinic acid and H^S in 
 alkaline solution. 
 
 Tri-benzyl-arsine (PhCH2)3As. [104°]. The 
 preparation is described under di-benzyl-arsinio 
 acid {v. sup.). Monoclinic needles (from alcohol). 
 Insol. water ; v. sol. ether, benzene, and glacial 
 acetic acid ; si. sol. cold alcohol. Like AsMej, 
 but unlike AsPh,, it combines with alkyl iodides. 
 It is not affected by boiMng cone. HCl. It com- 
 bines with S and halogens. Boiling dilute' HNO3 
 forms benzoic and arsenic acids. An ethereal 
 solution gives with an ethereal solution of 
 HgClj a pp. of (PhCH2)3AsHgCl2 [159°]. 
 
 Tri-benzyl-arsine oxide (PhCH^jsAsO. [220°]. 
 From tri-benzyl-arsine chloride or oxychloride 
 by treatment with alkalis ; or together with di- 
 benzyl-arsinic acid by the action of wet ether 
 upon the product of the action of sodium upon 
 benzyl chloride and AsClj. Prisms (from dilute 
 alcohol) ; v. e. sol. alcohol, si. sol. water and 
 ether. 
 
 Tri-benzyl-arsine ozy-chloride 
 (PhCHJaAsC^OH). [163°]. Formed by union 
 of HCl with the preceding. V. e. sol. alcohol ; 
 insol. dilute HCl. 
 
 Tri-benzyl-arsine ozy-bromide 
 (PhCH2)3AsBr(OH). [129°]. Tables (from alcohol). 
 
 Tri-benzyl-arsine iodide (PhCHJjAsI^. 
 [c. 95°]. Formed in impure condition by action of 
 aqueous HI on the oxide. Converted by alcohol 
 into the oxy-iodide, (PhCHj)3AsI(0H) aq [78°]. 
 
 Tri-benzyl-arsine-oxy-nitrate 
 (PhCH2)3As(N03)(OH). [170°]. Slender needles 
 (from alcohol). 
 
 Tri-benzyl-arsine sulphide (PhCH2)3AsS. 
 [214°]. Prisms (from glacial HOAc). insol. 
 alcohol and ether. 
 
 Tri-benzyl-methyl-arsouium iodide 
 (PhGHi,)3AsMeI. [143°]. From (PhCH2)3As and 
 Mel at 100°. Slender needles (from water). 
 Gives with moist Ag^O the alkaline hydroxide, 
 (PhCHJaAsMe(OH). 
 
 Tri-beuzyl-methyl-arsonium chloride 
 (PhCH2)3AsMeCl.[201°]. — Platino chloride 
 (fPhOH2)3AsMe)2PtCl,. [173°]. 
 
 Tri-benzyl-ethyl-arsonium iodide 
 (PhCH2)3AsEtI. [148°]. White plates (from water). 
 
 Tri-benzyl-propyl-arsonium iodide 
 (PhCH2)3AsPrI. [146°]. The isomeride, 
 (PhCHJjAsPrl melts at [148°]. 
 
 Tri-beuzyl-isoamyl-arsoulum iodide 
 (PhCH,)3As(C,H„)I. [146°]. 
 
 Tetra-benzyl-arsonium chloride 
 (PhCH3),ABCl. [160°]. From (PhCH,)3A3 and 
 PhCHjCl at 170°. Triclinio crystals containing 
 aq (from water) ; insol. dilute HOI. Con- 
 verted by aqueous KBr into the bromide 
 (PhOH2)4AsBr, [173°], and by aqueous EI into 
 the iodide, (PhOHj^AsI, [168°], which forms 
 a periodide, (PhCHJ^AsIs, [150°]. Moist Ag^O 
 forms an alkaline hydroxide, split up by heat 
 thus : (PhOH^) ,AsOH = PhOH, -1- (PhCHj)5AsO. 
 
 Platinochloride ((PhCHj)4As)jPtOl8. 
 
 Di-naphthyl di-arsenide C,gH,.As:As.C,gH,, 
 Arseno-naphthalene. [221°]. Prepared by heat- 
 ing an alcoholic solution of naphthyl-arsine 
 oxide vdth phosphorous acid (Michaelis a. 
 Schulte, B. 15, 1954). Slender yellow needles ; 
 si. sol. alcohol, benzene, CSj B,nA. chloroform ; 
 insol. water and ether. Converted by 01 into 
 C,„H,AsOl2. With sulphur it gives C,„H,AsS. It is 
 oxidised by HNO3 to naphthalene arsonio acid. 
 
 Naphthyl-arsine chloride OuHjAsClj. [63°]. 
 From mercury di-naphthyl and AsCl,. OrystaUino 
 powder ; insol. water, v. sol. alcohol. 
 
 Naphthyl-arsine oxide 0,„H,AsO. [245°], 
 From the preceding by treatment with aqueous 
 Na^COj. Powder; si. sol. alcohol, ether, and 
 water. On dry distUlation it gives 0, As, and 
 naphthalene. 
 
 Naphthalene arsenic acid C,„H,AsO(OH)2. 
 [197°]. Needles. Formed by action of water 
 on C,„H,AsClj, which is obtained by treating 
 Ci„H,As0l2 with chlorine (W. Kelbe, B. 11, 1503). 
 
 ASAFCETIDA. A gum-resin obtained by drying 
 the juice contained in the root of Ferula asafcetida, 
 a Persian plant. Potash fusion gives resoroiu 
 and protocatechuic acid. Asafcetida contains 
 ferulic acid (g. v.), but its odour is due to 3 p.o. 
 of an essential oil (135°-140°) which appears to 
 be a mixture of OiaH^^S and G^^^Bp Its alco- 
 holic solution is ppd. by HgCl^ (PeUetier, Bull. 
 Pharm. 3, 556; Johnston, P. M. Dec. 1838; 
 Hlasiwetz, A. 71, 23). 
 
 ASARITE. — Impure asarone. 
 
 ASAEONE C,jHis03. [59°]. (296°). S.G. « 
 1'165. Contained in the root of Asarwm euro- 
 pcBum. Needles or plates ; v. sol. alcohol, ether, 
 and glacial HOAc, si. sol. hot water (Blanchet a. 
 Sell, A. 6, 296; 0. Schmidt, A. 53, 156 ; Butle- 
 row a. Eizza, B. 17, 1159 ; Bl. [2] 43, 114 ; Po- 
 leck,B. 17, 1415). 
 
 ASCLEPIONE CjoHj.Oa. [104°]. Extracted 
 by ether from the coagulum got by heating the 
 milky juice of Asclepias syriaca. Badiating 
 crystals ; insol. water and alcohol. Not attacked 
 by boiling KOHAq (List, A. 69, 125 ; Gram, C. C. 
 1886, 735). 
 
 ASEBOTOXIN. C. 60-5 p.c. ; H. 74 p.c; 
 0. 32-1 p.c. [120°]. A glucoside extracted by 
 water from the leaves of Andronneda japonica. 
 Brittle mass. The addition of cone. HCl to its 
 alcoholic solution gives a blue colour (Eijkman, 
 B. 1, 224 ; Ph. [3] 13, 365). It is accompanied 
 by a glucoside, asebotin CjjHzjOjj, crystallising 
 in yellow needles [147'5°J and also by asebo- 
 quercetin CjjHuO,, and asebofusein C,bH„0, 
 (Eijkman, /. 1888, 1410; R. 2, 99, 200). 
 
 ASH OF ORGANIC BODIES. 
 
 The inorganic constituents contained in 
 vegetable and animal products are usually 
 determined by incineration of the substance, 
 and determination of the weight and composition 
 of the ash. The first question to be considered 
 is —Does this ash accurately represent the inor- 
 ganic constituents of the substance ? 
 
 The sulphuric acid originally present is un- 
 doubtedly but imperfectly represented. The 
 tendency to the reduction of sulphates to 
 sulphides during ignition with - carbonaceous, 
 and especially with nitrogenous, matter, is 
 generally overborne by the oxidation of the 
 sulphur contained in the albuminoids. The 
 sulphuric acid found in the ash is thus greater 
 
ASH OF ORGANIC BODIES. 
 
 323 
 
 ttan that originally present ; it entirely fails, 
 however, to represent the sulphur present in the 
 original substance; this must be determined by a 
 special experiment. 
 
 The carbonic acid originally present in the 
 substance is generally quite undisooverable by 
 an analysis of the ash. Carbonic acid may be 
 lost by the decomposition of calcium and 
 magnesium carbonates during ignition; or by 
 the decomposition of carbonates by the action of 
 sUioa, or of phosphates containing less than 
 three equivalents of base. On the other hand 
 carbonates are produced when tribasic alkali 
 phosphates are ignited with carbon ; they are 
 also formed in large quantity during the incinera- 
 tion of organic substances containing nitrates, 
 or salts of organic acids. Treatment of an ash 
 
 Phosphoric acid may be lost if acid phos- 
 phates are heated to a high temperature with car- 
 bonaceous matter. The alkali metals are also 
 liable under some circumstances to suffer loss 
 by volatilisation. 
 
 The ash constituents are obtained with the 
 smallest loss when the ignition is conducted at 
 a low temperature, preferably in a muffle. In 
 some oases an excess of lime or baryta must be 
 added to prevent losses of phosphoric acid and 
 chlorine ; this treatment also prevents the fusion 
 of the ash (Strecker, A. 73, 366). 
 
 1. Ash op Animals. — The proportion of ash 
 in some of the principal parts and products of 
 the animal body, and its percentage composi- 
 tion, are shown in the following table. The 
 figures are taken from WoKE's Aschen Analysen 
 
 ASH OF ANIMAL PAETS AND PEODUCTS 
 
 
 
 
 
 
 
 Pure 
 
 100 parts of pure 
 
 ash contain 
 
 
 
 
 "MnmliPT 
 
 asli in 
 
 
 
 
 
 
 
 
 J-l UJJ.LMW.L 
 
 Ot 
 
 100 dry 
 
 
 
 
 
 
 
 
 
 
 
 Analyses 
 
 sub- 
 stance 
 
 K,0 
 
 Na,0 
 
 CaO 
 
 MgO 
 
 Pe,0, 
 
 P.O. 
 
 SO. 
 7-1 
 
 SiO. 
 
 CI 
 
 Blood, human . 
 
 4 
 
 _ 
 
 26'6 
 
 24-1 
 
 0-9 
 
 0-5 
 
 8-2 
 
 8-8 
 
 
 
 30-7 
 
 „ ox ... 
 
 7 
 
 3-77 
 
 7-6 
 
 45-0 
 
 11 
 
 0-6 
 
 9-4 
 
 5-3 
 
 31 
 
 0-8 
 
 34-4 
 
 „ calf . . . 
 
 2 
 
 
 
 11-2 
 
 41-0 
 
 1-8 
 
 1-2 
 
 8-3 
 
 7-8 
 
 1-3 
 
 — 
 
 34-7 
 
 „ sheep . 
 
 2 
 
 — 
 
 7-1 
 
 45-0 
 
 1-1 
 
 0-6 
 
 9-6 
 
 5-5 
 
 1-9 
 
 — 
 
 35-8 
 
 1) pig • • • 
 
 3 
 
 4-29 
 
 23-3 
 
 29-4 
 
 1-3 
 
 1-4 
 
 8-9 
 
 12-2 
 
 1-0 
 
 — 
 
 28-0 
 
 „ horse . 
 
 1 
 
 — 
 
 29-5 
 
 21-2 
 
 1-1 
 
 0-6 
 
 9-5 
 
 8-4 
 
 6-3 
 
 — 
 
 28-6 
 
 „ dog 
 
 8 
 
 
 
 37-1 
 
 39-9 
 
 1-0 
 
 1-1 
 
 90 
 
 12-6 
 
 3-3 
 
 — 
 
 320 
 
 Flesh of mammalia 
 
 8 
 
 4-32 
 
 7-0 
 
 10-1 
 
 2-4 
 
 3-2 
 
 0-4 
 
 41-2 
 
 10 
 
 0-7 
 
 4-7 
 
 „ fowls. 
 
 2 
 
 — 
 
 30-9 
 
 18-7 
 
 3-3 
 
 4-2 
 
 — 
 
 36-4 
 
 — 
 
 — 
 
 8-1 
 
 „ marine fish 
 
 1 
 
 — 
 
 21-8 
 
 14-9 
 
 15-2 
 
 3-9 
 
 — 
 
 34-5 
 
 — 
 
 — 
 
 11-4 
 
 Meat extract . 
 
 H 
 
 20-89 
 
 43-9 
 
 12-8 
 
 0-7 
 
 3-1 
 
 0-4 
 
 29-8 
 
 2-2 
 
 09 
 
 10-0 
 
 Meat flour 
 
 2 
 
 1-80 
 
 5-4 
 
 3-0 
 
 22-4 
 
 3-5 
 
 13-3 
 
 43-5 
 
 1-2 
 
 0-9 
 
 1-8 
 
 Bone of ox carcase . 
 
 1 
 
 — 
 
 — 
 
 — 
 
 53-5 
 
 1-0 
 
 0-2 
 
 40-3 
 
 — 
 
 0-5 
 
 — 
 
 Wool, unwashed . . 
 
 3 
 
 8-33 
 
 79-4 
 
 4'3 
 
 2-4 
 
 0-6 
 
 0-7 
 
 1-0 
 
 4-7 
 
 2-9 
 
 4-5 
 
 „ washed. . 
 
 1 
 
 1-11 
 
 19-1 
 
 2-7 
 
 24-7 
 
 6-0 
 
 18-2 
 
 3-2 
 
 — 
 
 25-3 
 
 0-8 
 
 Colostrum, cow . 
 
 1 
 
 1-18* 
 
 7-2 
 
 5-7 
 
 34-9 
 
 2-1 
 
 0-5 
 
 41-4 
 
 0-2 
 
 
 
 11-3 
 
 Milk, human . . . 
 
 4 
 
 0-49* 
 
 33-8 
 
 91 
 
 16-7 
 
 2-2 
 
 0-2 
 
 22-7 
 
 1-0 
 
 — 
 
 18-4 
 
 „ cow 
 
 9 
 
 0-72* 
 
 24-1 
 
 6-1 
 
 23-2 
 
 2-6 
 
 0-4 
 
 28-0 
 
 1-3 
 
 — 
 
 13-5 
 
 „ ewe • . . 
 
 2 
 
 0-73* 
 
 21-3 
 
 3-8 
 
 29-3 
 
 0-1 
 
 1-0 
 
 35-8 
 
 1-6 
 
 20 
 
 7-5 
 
 „ mare • • . 
 
 1 
 
 0-37* 
 
 25-1 
 
 3-4 
 
 30-1 
 
 30 
 
 0-4- 
 
 31-9 
 
 — 
 
 — 
 
 7-5 
 
 „ sow . 
 
 1 
 
 1-05* 
 
 6-2 
 
 6-7 
 
 39-2 
 
 1-8 
 
 0-9 
 
 37-2 
 
 1-3 
 
 — 
 
 9-3 
 
 „ bitch 
 
 2 
 
 0-73* 
 
 11-9 
 
 5-8 
 
 33-7 
 
 1-6 
 
 01 
 
 37-2 
 
 — 
 
 — 
 
 131 
 
 Whey, cow 
 
 3 
 
 0-54* 
 
 30-8 
 
 18-8 
 
 19-3 
 
 0-4 
 
 0-6 
 
 17-1 
 
 2-7 
 
 — 
 
 15-8 
 
 Hen's egg, without shell. 
 
 3 
 
 3-48 
 
 17-4 
 
 22-9 
 
 10-9 
 
 1-1 
 
 0-4 
 
 37-6 
 
 0-3 
 
 0-3 
 
 9-0 
 
 „ white 
 
 3 
 
 4-61 
 
 31-4 
 
 31-6 
 
 2-8 
 
 2-8 
 
 0-6 
 
 4-4 
 
 2-1 
 
 1-1 
 
 28-8 
 
 „ yolk 
 
 3 
 
 2-91 
 
 9-3 
 
 5-9 
 
 13-0 
 
 2-1 
 
 1-7 
 
 65-5 
 
 — 
 
 0-9 
 
 1-9 
 
 * Tliese numbers represent per cent, of pure asb in fresb substance. 
 
 with ammonium carbonate, and re-ignition, is 
 sometimes employed with the view of converting 
 caustic lime and magnesia into carbonates. Such 
 treatment converts sulphides and cyanides into 
 carbonates ; sulphate of calcium is also partially 
 converted into carbonate if only a small propor- 
 tion of alkali carbonate is present. Treatment 
 with carbonic acid water is more free from objec- 
 tion, but its action is slow. 
 
 The chlorides found in an ash may be below 
 the truth from volatilisation of alkali chlorides, 
 if too high a temperature has been employed ; or 
 from loss of hydrochloric acid due to the action 
 ot organic acids produced during the charring 
 of the organic matter ; or from a similar action 
 of sUica, or dibasic phosphates, at a high tem- 
 perature. 
 
 (1880), with the exception of the analysis oi 
 bone ash, which is quoted from C. J. 24, 80. 
 The bone-ash represents the mean composi- 
 tion of aU the carcase bones of the 'fat ox' 
 analysed at Eothamsted. In this analysis, 
 alkalis, and sulphuric and carbonic acids, were 
 not determined ; the whole amount of these con- 
 stituents was, however, but 4'5 p.c. The ' pure 
 ash' in Wolfi's Tables is exclusive of sand, 
 charcoal, and carbonic acid. 
 
 The amount of ash yielded by the entire 
 bodies of the principal animals reared on the 
 farm, and its composition, have been determined 
 by Lawes and Gilbert (T. 1883. 865) ; they also 
 separately analysed the ash of the carcase and 
 ofial parts. The percentage composition of the 
 ash of the entire bodies of calf, ox. Iamb, sheep, 
 
 y2 
 
824 
 
 ASH OF ORGANIC BODIES. 
 
 *nd pig will be found below. The composi- 
 tion in 1,000 parts of the fasted live weight 
 of the animal body is also given. The latter 
 will afford data for calculating the loss which 
 a farm suSers by sale of stock. The fasted live- 
 weight is inclusive of contents of stomach and 
 intestines, but the constituents of these con- 
 tents are not reckoned among the animal con- 
 etituents. The ' pure ash ' is inclusive of 
 carbonic acid. 
 
 2. Ash or Plants. The composition of the 
 ash of plants of agricultural importance will be 
 given under the headings of the different crops, 
 some general considerations will, however, be 
 best made in the present place. 
 
 podiacetB, and of silica by the EquisetJ,cecB and 
 Orammacece. 
 
 The ash constituents which enter the circula- 
 tion of the plant are (1) partly employed in the 
 formation of new tissue ; (2) partly deposited as 
 inornsting matter on the older tissues ; while (3) 
 soluble salts that are of no advantage to - the 
 plant first accumulate in the sap, and then are 
 gradually removed from the plant by the action 
 of rain, and possibly by difiusion into the soil 
 through the roots. The ash constituents most 
 largely consumed in the formation of tissue are 
 potash and phosphoric acid ; in all the actively 
 growing parts of a plant potash and phosphoric 
 acid greatly preponderate. Magnesia, lime, 
 
 Percentage Composition of Ash from 
 
 entire Bodies 
 
 of Animals. 
 
 
 
 
 K.O 
 
 Na.O 
 
 OaO 
 
 MgO 
 
 Fe,0, 
 
 P.O. 
 
 SO. 
 
 SiO, 
 
 01 
 
 CO, 
 
 Fat calf . 
 
 5-4 
 
 3-8 
 
 44-0 
 
 2-2 
 
 0-5 
 
 40-4 
 
 1-1 
 
 0-1 
 
 1-6 
 
 1-3 
 
 Half -fat ox . 
 
 4-4 
 
 3-1 
 
 45-3 
 
 2-0 
 
 1-0 
 
 40-2 
 
 0-9 
 
 0-2 
 
 1-2 
 
 20 
 
 Fat ox . . , 
 
 4-5 
 
 3-0 
 
 46-6 
 
 1-5 
 
 0-4 
 
 39-8 
 
 0-8 
 
 01 
 
 1-5 
 
 2-1 
 
 Fat lamb . 
 
 5-7 
 
 3-6 
 
 44-6 
 
 1-8 
 
 0-8 
 
 390 
 
 1-2 
 
 0-3 
 
 1-9 
 
 1-6 
 
 Store sheep . 
 
 5-6 
 
 3-9 
 
 431 
 
 1-8 
 
 1-2 
 
 39'0 
 
 I'S 
 
 0-7 
 
 2-3 
 
 l-l 
 
 Half-fat old sheep 
 
 5-3 
 
 3-4 
 
 44-4 
 
 1-7 
 
 1-4 
 
 39-2 
 
 1-1 
 
 0-6 
 
 1-6 
 
 1-8 
 
 Fat sheep . 
 
 5-5 
 
 3-6 
 
 44-6 
 
 1-8 
 
 1-0 
 
 38-7 
 
 1-0 
 
 0-9 
 
 1-6 
 
 1-7 
 
 Very fat sheep . 
 
 5-5 
 
 4-5 
 
 48-3 
 
 1-9 
 
 1-0 
 
 38-7 
 
 1-0 
 
 0-6 
 
 2-3 
 
 1-7 
 
 Store pig . 
 
 7-4 
 
 4-2 
 
 40-6 
 
 2-0 
 
 0-9 
 
 40-1 
 
 2-3 
 
 0-2 
 
 2-2 
 
 0-6 
 
 Fat pig 
 
 8-6 
 
 4-4 
 
 38-5 
 
 2-0 
 
 0-8 
 
 40-1 
 
 2-2 
 
 0-1 
 
 2-8 
 
 1-2 
 
 Composition of Animal Bodies, 
 
 per 1,000 parts fasted 
 
 live weight. 
 
 
 
 
 rat 
 
 Calf. 
 
 Hall-fat 
 Ox. 
 
 Fat Ox. 
 
 Fat 
 Lamb. 
 
 Store 
 Sheep. 
 
 Half-fat 
 
 old 
 Sheep. 
 
 Fat 
 Sheep. 
 
 Very fat 
 Sheep. 
 
 store 
 Kg. 
 
 Fat Pig, 
 
 Contents of stomach 
 
 
 
 
 
 
 
 
 
 
 
 and intestines, moist 
 
 32-0 
 
 82-0 
 
 60-0 
 
 85-0 
 
 60-0 
 
 91-0 
 
 60-0 
 
 52-0 
 
 52-0 
 
 40-0 
 
 Water. 
 
 630-0 
 
 515-0 
 
 455-0 
 
 478-0 
 
 573-0 
 
 502-0 
 
 434-0 
 
 352-0 
 
 551-0 
 
 413-0 
 
 Fat ... . 
 
 148-0 
 
 191-0 
 
 301-0 
 
 285-0 
 
 187-0 
 
 236-0 
 
 356-0 
 
 458-0 
 
 233-0 
 
 422-0 
 
 Nitrogenous substance 
 
 152-0 
 
 166-0 
 
 145-0 
 
 123-0 
 
 148-0 
 
 140-0 
 
 122-0 
 
 109-0 
 
 137-0 
 
 109-0 
 
 Crude ash . 
 
 38-0 
 
 46-6 
 
 39-2 
 
 29-4 
 
 31-6 
 
 31-7 
 
 28-1 
 
 29-0 
 
 26-7 
 
 16-5 
 
 Pure ash . 
 
 37-8 
 
 46-1 
 
 38-8 
 
 28-9 
 
 30-6 
 
 30-6 
 
 26-8 
 
 28-6 
 
 26-5 
 
 16-3 
 
 KjO . 
 
 2-06 
 
 2-05 
 
 1-76 
 
 1-66 
 
 1-74 
 
 1-68 
 
 1-48 
 
 1-58 
 
 1-96 
 
 1-38 
 
 Na,0 .... 
 
 1-48 
 
 1-46 
 
 1-26 
 
 1-03 
 
 1-20 
 
 1-04 
 
 0-97 
 
 1-29 
 
 1-10 
 
 0-73 
 
 CaO .... 
 
 16-46 
 
 21-11 
 
 17-92 
 
 12-81 
 
 13-21 
 
 13-50 
 
 11-84 
 
 12-40 
 
 10-79 
 
 6-36 
 
 MgO .... 
 
 0-79 
 
 0-85 
 
 0-61 
 
 0-52 
 
 0-56 
 
 0-52 
 
 0-48 
 
 0-55 
 
 0-53 
 
 0-32 
 
 Fe^Oj .... 
 
 0-21 
 
 0-41 
 
 0-24 
 
 0-26 
 
 0-37 
 
 0-42 
 
 0-34 
 
 0-30 
 
 0-22 
 
 013 
 
 PA .... 
 
 15-35 
 
 18-39 
 
 15-51 
 
 11-26 
 
 11-88 
 
 11-99 
 
 10-40 
 
 11-08 
 
 10-66 
 
 6-54 
 
 SO3 . 
 
 0-41 
 
 0-38 
 
 0-33 
 
 0-39 
 
 0-52 
 
 0-35 
 
 0-31 
 
 0-29 
 
 53 
 
 0-29 
 
 SiOj .... 
 
 0-05 
 
 0-13 
 
 0-06 
 
 0-12 
 
 0-21 
 
 0-20 
 
 0-26 
 
 0-16 
 
 0-05 
 
 0-03 
 
 CI ... . 
 
 0-63 
 
 0-59 
 
 0-55 
 
 0-53 
 
 0-72 
 
 0-51 
 
 0-44 
 
 0-66 
 
 0-57 
 
 0-43 
 
 COj, . 
 
 0-47 
 
 0-87 
 
 0-71 
 
 0-43 
 
 0-37 
 
 0-53 
 
 0-41 
 
 0-49 
 
 0-21 
 
 021 
 
 The ash constituents of a plant are obtained 
 from the soil by the roots. All matters in the 
 soil which are soluble and diffusible will enter 
 the plant by the root, the abundant evaporation 
 of water from the surface of a growing plant 
 maintaining a rise of liquid in the capillary 
 vessels. The substances entering the plant are 
 not, however, limited to those existing in solu- 
 tion in the soil, as the roots of plants exercise a 
 solvent or digestive action on constituents of the 
 soil not otherwise soluble in water. The wide 
 differences in the assimilating powers of the 
 roots of different plants are well illustrated by 
 the special assimilation of alumina by the Lyco- 
 
 oxide of iron, and sulphuric acid, must also be 
 reckoned as essential for plant growth. The 
 inorusting ash constituents are calcium salts and 
 silica ; these are chiefly precipitated in the 
 leaves, where evaporation is most active. The 
 soluble salts remaining unused in the sap 
 generally contain a large proportion of chlorides, 
 and of sodium salts. 
 
 A vigorous plant will take from a rich soil a 
 much larger quantity of ash constituents, es- 
 pecially of alkali salts, than is necessary for its 
 growth. For the same reason a plant growing 
 on different boUs may yield a very different ash. 
 Thus a clover or bean plant will be rich in 
 
ASPARTIO ACID. 
 
 325 
 
 potash or lime according as one or the other 
 preponderates in the soil. On the other hand 
 plants clearly exercise a selective power, potash 
 being stored up in large quantity, though soda 
 rather than potash may be abundant in the 
 soil. This selective power is apparently not 
 a property of the roots, but simply results from 
 the fact that potash is removed from the sap to 
 form tissue, while soda is not ; potash salts can 
 thus continue to enter the roots by diffusion or 
 otherwise, while sodium salts having accumulated 
 in the sap the tendency of diffusion is now for 
 them to pass through the roots into the moist 
 soil (see Deh6raiu, Cours de Chimie agricole 
 [1873] 77). The Eothamsted experiments show 
 that potash greatly preponderates in hay, and in 
 barley straw, when the soil supplies n, sufficient 
 quantity ; but when potash fails, soda is retained 
 by the plant to a considerable extent. 
 
 The variations in the composition of the ash 
 of any plant do not extend to the seed ; the ash 
 of this is of very definite composition whatever 
 the nature of the soil. The ash of a seed con- 
 sists chiefly of potassium phosphate; soda is 
 practically absent. 
 
 While the seed is forming, a migration of 
 phosphoric acid and potash, and of nitrogenous 
 matter and carbohydrates, sets in from all parts 
 of the plant, the roots included ; a great part 
 of these important constituents is finally 
 stored in the seed. The extent to which the 
 exhaustion of the plant, and the enrichment of 
 the seed, proceeds, depends on the climate during 
 the ripening period. E. W. 
 
 ASFARAGINE 
 C^HgNaO, i.e. C02H.CH2.CH(NH2).CO.NHi, or 
 CONH2.CH2CH(NH2).C02H. Amido-succinamio 
 acid. M. w. 150 (containing aq) S.G. i* 1-52. S. 
 0. 1-8 at 10-5°; 53 at 100°. Occurs in juice of 
 most plants, especially in growing buds and 
 germinating seeds (e.g. asparagus, marsh-mallow, 
 comfrey, potatoes, deadly nightshade, chestnuts, 
 liquorice root, lettuce, convolvulus root, dahlia 
 tubers, young shoots of vetch, peas, beans, and 
 other leguminous plants). Lupine seeds that 
 have not begun to grow contain no asparagiue ; 
 after 15 days' germination more than 20 p.o. of 
 asparagine may be extracted by water (Schulze 
 a. Barbieri, J. pr. [2] 27, 339). When twigs full 
 of young leaf-buds of the plane, birch, or horse- 
 chestnut are cut off and allowed to open by 
 placing the cut end in water, the leaves are 
 found to contain asparagine (S. a. B., J.pr. 133, 
 145). Asparagine may be formed by adding 
 cone, ammonia to mono-ethyl aspartate (Schaal, 
 A 157, 24). 
 
 Properties. — Trimetrio prisms (containing aq) 
 exhibiting left-handed hemihedry. Sol. water, 
 acids, and alkalis ; iusol. alcohol and ether. Its 
 solution in water or alkalis is Isvorotatory, in 
 acids it is dextrorotatory. In HCl solution 
 [o]d = about + 36° ; in aqueous solution about 
 — 6° ; in ammoniacal solution about — 11°. 
 
 Beactions. — 1. Boiling with lime, or baryta- 
 water, or with dilute H^SO, rapidly converts it 
 into aspartic acid. — 2. Nitrous acid forms malic 
 acid. — 3. Impure asparagine is liable to undergo 
 fermentation, changing to ammonio succinate. 
 4. Mel and KOH produce an amide of fumario 
 acid, CO,H.CH:CH.GONH., (Michael a. Wing, 
 Am. 6, 419 ; Griess, B. 12, 2117> 
 
 Salts. — HA'HCl. — (HA%H01. — CuA'^.— 
 CaA'j. — ZnA'j. -- HA'HgCl^. — AgA'. — 
 HA'(AgN03)2. — HA'C,H,(N0j30H: yeUow 
 prisms (Smolka, M. 6, 915). 
 
 Estimation. — Heat the extract containing it 
 with dilute HCl for some hours and determine 
 the amount of NH^Cl formed. This corresponds 
 to half the nitrogen in asparagine (Sachsse, 
 J. pr. [2] 6, 118). Glutamine also splits o3 
 half its amidogen as ammonia when treated 
 with HCl. Or the extract may be treated with 
 bromine and NaOH (measuring evolved Nj) both 
 before and after heating with HCl (Sachsse). 
 But asparagine gives off too much Nj when so 
 treated (Morgen, Fr. 20, 37). It even gives off a 
 little Njwheu treated with NaBrO before heating 
 with HCl. These two errors nearly balance 
 one another (E. Schulze, /. pr. [2] 31, 235). 
 Solutions of sodic aspartate give oS no Nj with 
 NaBrO, but if NH3 be present more Njis evolved 
 than corresponds to the NH3. The increase 
 may be 6 p.o. Leucine behaves in the same way 
 as asparagiue, but tyrosine behaves in exactly 
 the opposite manner. Urea has the same in- 
 fluence as NHj. It is therefore better to de- 
 termine the free NH3 by distilling with MgO, CaO 
 or even NaOH (comp. Berthelot a. Andrfi, 
 0. B. 103, 1051). The presence of peptones 
 wiU, of course, invalidate the determination, 
 these are often absent from vegetable solutions j 
 if present they must be removed : albuminoids 
 may be ppd. by lead salts, peptones by tannin or 
 phosphotungstic acid (E. Schultze, l.c.), 
 
 Seztro-asparagine 
 CjH3(NH2)(C02H).CO.NHj. Dextro-hemihedral 
 crystals. Dextrorotatory [a]i, = -i- 5°41'. Very sweet 
 taste (ordinary asparagine is tasteless). Bather 
 more soluble in water than ordinary asparagine. 
 Occurs in the mother-liquors obtained in re- 
 crystaUising the crude asparagine prepared 
 from the shoots of the vetch ; 20 kilos of crude 
 asparagine, obtained from 6500 kilos, of vetch 
 gave 100 grms. of the pure dextro-asparagiue. 
 
 The compounds prepared from dextro- 
 asparagine exhibit the same properties as those 
 prepared from the Isevo-asparagine except that 
 their rotatory power is reversed. By heating 
 with 2 mols. of aqueous HCl at 170°-180° both 
 asparagines give the same inactive aspartio 
 acid (Piutti, C. B. 103, 134 ; B. 19, 1691). 
 
 Additional Beferences. — Vauquehn a. Eobi- 
 quet, A. Ch. 57, 88 ; Dessaignes, A. 82, 237 ; 
 Piria, A. Ch. [3] 22, 160 ; Pasteur, A. Ch. [3] 
 31, 70 ; Mercadante, G. 5, 187 ; Portes, B. 9, 1934 ; 
 Dubrunfaut, J. pr. 53, 508 ; Gorup-Besanez, A. 
 125, 291 ; Champion a. Pellet, B. 9, 724 ; Becker, 
 B. 14, 1031 ; De Luca a.Ubaldini, C.B. 59, 527 ; 
 Buchner, Z. 1862, 117 ; Campani, Z. [2] 6, 87 ; 
 E. Schulze, B. 15, 2855 ; J. pr. [2] 20, 397 ; 27, 
 339. 
 
 ASPARTIC ACID C^H^NO^ i.e. 
 C02H.CH2.CH(NH2).C02H. Amido-succinic acid. 
 Mol. w. 133. S.G. m 1-66. S. -45 at 20° ; 5-4 
 100°. 
 
 Formation. — 1. By boiling asparagine with 
 lime, baryta, PbO, KOH, or HCl dissolved in 
 water. — 2. By boiling albumen or casein with 
 dilute H2SO4 (Kreussler, /. pr. 107, 239 ; Eitt- 
 hausen, J. pr. 107, 218). — 3. By treating pro- 
 teids with bromine (Hlasiwetz a. Habermann, 
 A. 159, 325). — 4. From casein by treatment 
 
32C 
 
 ASPARTIC ACIT). 
 
 with SnCL, and HCl (H. a. H., A. 169, 162).— 5. 
 From diazo-sueoinic ether by reduction with 
 zinc dust and acetic acid (Curtius a. Koch, B. 
 19, 2460). 
 
 Pre^gwration: 100 grms. of asparagine are 
 boiled for 2 or 3 hours with an inverted con- 
 denser with 408 0.0. of pure aqueous hydrio 
 chloride (containing -11925 g. HCl per c.c). To the 
 cooled solution is then added 204 c.c. of aqueous 
 NH3(correspondingtothe aoidvolumefor volume). 
 On standing for several hours the aspartio 
 Boid separates in colourless crystals. The yield 
 is 90 p.c. of the theoretical (Sohiff, B. 17, 2929). 
 
 Properties. — Small trimetric rectangular 
 plates. SI. sol. water, insol. alcohol. Its solu- 
 tions in alkalis are Isevorotatory ; its solution 
 in HClAq is dextrorotatory, [a]i,= -1-28°. The 
 rotation is affected by the nature of the solution 
 (Beelser, B. 14, 1035). Aspartic acid (1 mol.) 
 prevents the ppn. of Cu{0H)2 (1 mol.) by KOH. 
 
 Reactions. — 1. Nitrous acid converts it into 
 pialic acid. — 2. Mel and KOH form fumario 
 acid (Eorner a. Menozzi, B. Istit. Lombard. 13, 
 352). — 3. Not affected by boiling water or by 
 magnesia. — 4. Heating in a current of HCl at 
 130°-200° produces two anhydrides: (a) 
 insoluble in water (CajHjjNsOi,), (6) slightly 
 soluble in water (CisHuNjOj). Both are con- 
 verted by boiling baryta into aspartio acid ; but 
 when the former is heated for 2 hours at 125° 
 with half its weight of urea it produces a gummy 
 mass, soluble in water forming a solution that 
 has all the characters of a proteid. It is ppd. 
 by acids, by NaCl, MgSO^, tannin, and HgClj 
 forming gelatinous pps. CuSOj and KOH give 
 a violet solution (Grimaux, C. B. 93, 771). 
 
 Salts.— HjA' HCl: deliquescent crystals. — 
 E2A"H2S04. — NaHA" aq : trimetric prisms ; S. 
 89 at 12°.— BaH2A"2 4aq.— BaA"3aq.— CaA"4aq 
 — HgA". — PbHjA'V — PbA". — AgHA". — 
 AgjA".- CuA" 4iaq. S. -035 at 15° ; -43 at 100° ; 
 V. sol. dilute HOAo. The insolubility of this salt 
 may be used to detect and to isolate aspartic 
 acid (Hoffmeister, Sits. B. 75, 469).— CuA"3aq 
 (Curtius a. Koch, B. 19, 2460). 
 
 Mono-ethyl ether A"BtH. Its hydro- 
 chloride (A"HEt)2HCl forms large colourless 
 needles, [199°]. 
 
 Di- ethyl ether A"Et„. Its hydrochloride 
 A"Etj,HCl forms excessively hygroscopic con- 
 centric needles. 
 
 Di-methyl ether ^''tie^. Its hydro- 
 chloride A"Me2,HCl forms very hygroscopic 
 glistening prisms (Curtius a. Koch, B. 18, 1293). 
 
 Amide v. Aspabagine. 
 
 Di-phenyl - amide 
 C02H.02H3NHj.C0NPhj. [230°]. Formed, toge- 
 ther with phtlialimide, by the action of NHj on 
 the diphenylamide of phthalyl-amido-suocinic 
 acid C02H.C2H3N(C202C,H,).CONPh2 (Piutti, O. 
 16, 14). 
 
 Inactive aspartio acid CjHjNOj. S. '42 at 7°. 
 
 Formation. — 1. By the action of boiling HCl 
 on the product obtained by heating the acid 
 ammonium salts of malic, maleio or fumaric 
 acid. — 2. By heating an aqueous solution of the 
 hydrochloride of active aspartio acid for several 
 hours at 170° (Michael a. Wing, B. 17, 2984 ; 
 Am. 7, 278). 
 
 Prqpcriics.— Monooliuio needles. Converted 
 by nitrous acid into inactive malic acid. 
 
 Sa Us.— PbA".— AgjA".— HjA"HCl. 
 
 Lsevo-aspartic acid CjHjNO,. Obtained from 
 dextro-asparagine by treatment with HCl 
 (Piutti, B. 19, 1693). Lsevorotatory. Its proper- 
 ties are the same as those of the dextrorotatory 
 acid. Combines with dextro-acid to form an 
 inactive modification. 
 
 Additional Beferences. — Plisson, A. Ch. 40, 
 303; 45, 315; Boutron-Chautard a. Pelouze, 
 A. Ch. 52, 90 ; Liebig, P. 31, 232 ; A. 26, 125, 
 161 ; Wolff,^.75, 293; Piria, A. Ch. [3] 22, 160; 
 Dessaignes, 0. B. 30, 324 ; 31, 432 ; A. 83, 83 ; 
 J. Ph. [3] 32, 49 ; Pasteur, A. Ch. [3] 34, 30 ; 
 
 A. 82, 324 ; Pott, /. pr. [2] 6, 91 ; Eadziszewski 
 a. Salkowski, B. 7, 1050 ; Bitthausen a. Kreussler, 
 J.pr. [2] 3, 314; Scheibler, J. Ph. [4] 4, 152 : 
 
 B. 2, 296 ; Kreussler, Z. [2] 6, 93. 
 ASPHALT. A natural product of the de- 
 composition of vegetable substances. It is found 
 on the shores of the Dead Sea, also in a molten 
 state in Trinidad, and as a mineral deposit at 
 Seyssel. It frequently impregnates other rocks. 
 When distilled with water, petrolene CjoHjj 
 (280°), S.G. SI -89, V.D. 9-5, passes over (Bous- 
 singault, A. Ch. [2] 64, 141 ; Voelokel, A. 87, 139). 
 
 ASPIDOSAMINE C^^H^sNA- [o- 100°]. In 
 quebracho bark (Hesse, A. 211, 263). Turns 
 yellow in air. V. e. sol. ether, chloroform, 
 benzene or alcohol, v. si. sol. light petroleum, 
 insol. water. Its alcoholic solution turns 
 litmus blue, neutralises HCl and tastes bitter. 
 
 Reactions. — 1. Solution of hydrochloride gives 
 with Fe^Clg a brownish-red colour. — 2. Cone. 
 HjSOj gives a bluish solution. — 3. Cone. H^SO, 
 and MoOj gives a blue liquid. — 4. Cone. H^SO, 
 and Kfiifi, gives a dark blue colour. — 5. Boihng 
 aqueous IICIO, gives a magenta colour. 
 
 P latinoohloride. — B'jHjPtCl,, 3aq. 
 
 ASPIDOSPERMATINE G^U^^fi^. [162°]. 
 In quebracho bark (Hesse, A. 211, 259). Crystal- 
 line. V. sol. chloroform, alcohol, or ether. In 
 alcohol (97 p.c.) it turns litmus blue, has a 
 bitter taste, and is lasvorotatory [a]], = — 72-3° at 
 15° in a 2 p.c. solution. 
 
 Beactions. — 1. HCIO, gives a magenta colour. 
 
 2. Cone. HjSO., and K^CrjO, give no colour. — 
 
 3. FejClj gives no colour. 
 
 Salts. — Dilute HCl is neutralised by aspido- 
 spermatine. NaOH or NHj give in the solution 
 a flocculent pp. (m. sol. pure water) which soon 
 becomes crystalline. Salts are amorphous. — 
 (B'HCl)2PtCl,4aq. 
 
 ASPIDOSPEKMINE C^jHajNA- [206°] 
 [o]d (alcohol) - 100-2° ; (chloroform) -83-6°; 
 (dilute HCl) — 62° (in all cases 2 p.c. solution at 
 15°). S. (alcohol) 2 at 14° ; (ether) -74 at 14° 
 (Wulfsberg, Ph. [3] 11, 269). An alkaloid 
 present (with others) in bark called in the 
 Argentine Republic quebracho bianco or 
 quebracho Colorado (Fraude, B. 11, 2189 ; 
 Hesse, A. 211, 251; Arata, 0. /. 40, 622). 
 Needles or pointed prisms (from alcohol or light 
 petroleum). M. sol. alcohol, si. sol. ether or 
 light petroleum, v. sol. benzene or chloroform. 
 Lsevorotatory. 
 
 Reactions. — 1. HCl and PtCl, give a blue 
 pp. — 2. HCIOj gives a magenta colour. — 3. Cono. 
 HjSOj no colour. — 4. Cone. H^SOj and MoO, no 
 colour. — 5. Cone. H^SO, and KjCrjO,, a brownish- 
 red turning dark green. — 6. Salts give with 
 
ATMOSrHi;RE. 
 
 327 
 
 NHj, NaOH, Na^CO,, or NaHCOj, a white 
 flooculent pp. becoming crystalline. 
 
 Salts. — Very unstable; even ether or CHCI3 
 can partly decompose them. — B'^H^PtClj 4aq. 
 
 ASSAMAB. A name given by Beiohenbaoh 
 (A. 49, 3) to a bitter, deliquescent, transparent 
 yellow solid which may be extracted by alcohol 
 from toasted bread. It is insol. ether. The 
 same name was given by Tolckel {A. 85, 74) to 
 a thick yellow neutral syrup obtained from the 
 aqueous portion of the product of the distilla- 
 tion of cane-sugar. It is sol. ether. Both sub- 
 stances reduce aqueous AgNOj. 
 
 ASYMMETRIC CARBON. A name applied 
 to an atom of carbon that is united to four 
 different atoms or radicles. All compounds that 
 in the liquid state or in solution rotate light 
 contain asymmetric carbon (Van 't Hoff, La 
 chimie dans I'espace ; Le Bel, Bl. [2] 22, 337). 
 
 ATHAMANTA, OIL OF. C.jH,^. (163°). 
 S.G. -84. An essential oil obtained from the 
 leaves of Atkamanta oreoselinum. It forms a 
 liquid compound with HCl (190°) (Schneder- 
 mann a. Winckler, A. 51, 336). 
 
 ATHAMANTIN CjjHs.O,. [79°]. In the 
 root and seeds of Athamanta oreoselinum. 
 Fibrous, silky crystals, or sometimes rectangular 
 prisms ; insol. water, v. sol. alcohol and ether. 
 It gives valeric acid on dry distillation. Aqueous 
 acids and alkalis split it up into valeric acid and 
 oreoselone CuHijOj. Chloro-, and tri-uitro-, 
 athamantin are amorphous (Schnedermann, A. 
 51, 315 ; Geyger, A. 110, 359). 
 
 ATHEROSPERMINE [128°]. An alkaloid 
 in the bark of Atherosperma moschatum. A 
 greyish-white powder with bitter taste. V. si. 
 sol. water, m. sol. alcohol, si. sol. ether. The 
 solution of its hydrochloride gives pps. with 
 phosphomolybdic acid, picric acid, tannin, and 
 PtCl,. It liberates iodine from iodic acid (Zeyer, 
 J. 1861, 769). 
 
 ATMOSPHERE. The word Atmosphere 
 (ciTfids, vapour ; iTipaipa, a globe) in its most ex- 
 tended sense signifies the gaseous envelope which 
 surrounds any liquid or solid body: more com- 
 monly, however, it is taken to mean the invisible 
 elastic fluid which surrounds the earth. A variety 
 of phenomena, e.g. solar and terrestrial radiation, 
 animal and vegetable life, weather, the dis- 
 integration of rocks and the formation of 
 soils, the propagation of sound, (fee, are de- 
 pendent on the existence of a terrestrial atmo- 
 sphere. The earth is not the only planetary 
 body which possesses an atmosphere. The Sun, 
 Jupiter, Mars, Saturn, have doubtless very 
 dense atmospheres, but as yet we have no 
 exact knowledge of their physical and chemical 
 natures. 
 
 The phenomena of solar eclipses, and the 
 facts that a single star seems to disappear 
 instantly when it is occulted opposite the smooth 
 part of the moon's limb, and that there is no 
 change of colour or other effect such as a re- 
 fractive atmosphere would occasion, make it 
 certain that the moon's atmosphere, if it exists 
 at all, must be of extreme tenuity. This con- 
 clusion is strengthened by evidence afforded by 
 the spectroscope. It has been observed that 
 the spectrum of the moon's light is identical 
 ■with the solar spectrum and there is no trace of 
 any absorptive action ; moreover, it is lound that 
 
 the spectrum of a star during its oceultatioa 
 disappears as suddenly as the star itself. 
 
 WoUaston's arguments as to the finite ex- 
 tent of the terrestrial atmosphere were deemed 
 inconclusive even by his contemporaries. There 
 is indeed direct evidence for the belief that air 
 is present in a state of sensible density at much 
 greater heights than 40 or 45 miles which was 
 the limit WoUaston assigned. Liais, from ob- 
 servations on the phenomena of sunlight at Eio 
 Janeiro, arrived at a superior limit of 200 miles ; 
 and Secchi, from observations on luminous 
 meteors, calculated that air exists of appreciable 
 density even at a height of 200 kilometres above 
 the earth's surface. It is in fact probable that 
 no actual limit exists. Up to the present it has 
 been impossible to arrive at direct results other- 
 wise than by astronomical observations, as the 
 law of the diminution of temperature which in 
 great measure governs the extent of the repul- 
 sion among gaseous particles is unknown for 
 the upper strata of the atmosphere. No argu- 
 ments can be based on the finite expansibility 
 of gases. Faraday's experiments on the limits 
 of vaporisation of mercury have been contro- 
 verted by Merget. It is obvious that the relative 
 distribution of the mass of the air wiU be 
 modified by the increase of attraction at the 
 poles as compared with that at the equator ; by 
 the increase of temperature as we approach the 
 torrid zone ; and by the earth's motion. 
 
 The ponderability of air although suspected 
 before the time of Aristotle was first conclusively 
 demonstrated by Galileo, who found that a 
 copper ball containing condensed air weighed 
 more than when filled with air of ordinary 
 tension. The weight of 1 litre of air, freed from 
 aqueous vapour, carbonic acid, and ammonia, at 
 0°C., and under a pressure of 0'76 m. of mercury, 
 at Paris (lat. 48° 50'), and at a height of 60 m, 
 above the sea level, was found by Eegnault to 
 be 1'293187 grams. According to Eegnault 
 1 litre of oxygen at the normal temperature and 
 pressure weighs 1'429802 grams ; 1 litre of nitro- 
 gen under the same conditions weighs 1-256167 
 grams. If x be the volume of oxygen contained 
 in 1 litre of air, and 1-x that of the nitrogen, 
 then l'429802a! + {1-x) 1-256167 = 1-293187, 
 whence a; = 0-2132 or in per cents. 21-32, which 
 is considerably higher than that found by eudio- 
 metric analysis. According to Magnus 1 litre 
 of pure air at 0° and -76 m. weighs at Berlin 
 (lat. 52° 36') 1-29306 grams. Ph. v. Jolly found 
 that at Munich (lat. 48° 8', 515 m. above the 
 sea's level) 1 litre of oxygen at 0° and -76 m. 
 weighed 1-429094 grams ; and 1 litre of nitrogen 
 under the same conditions weighed 1-257614 
 grams. Eeducing these numbers to the lat. of 
 Paris and to a height of 60 m. above the sea's 
 level, they become : 
 
 Jolly Regnault 
 
 Oxygen . 1-429388 1-429802 
 Nitrogen . 1-257873 1-256167 
 
 The Bureau Intemat. des Foids et Mesures 
 adopts for the weight of 1 litre of dry air under 
 a normal barometric height of 1 mm. and at tho 
 normal temperature t 
 
 p ._ 1-298052 i_ 
 " IH- 0-00367 ■•■ 760 
 on the assumption that the air contains -QOOl 
 
328 
 
 ATMOSPHERE. 
 
 parts o£ carbonic acid, and that '00367 is the 
 coefBcient of expansion ol air at constant pres- 
 sure for a normal degree. 
 
 This expression is obviously only true for a 
 particular ratio of oxygen and nitrogen. The 
 composition of the air varies sufficiently to 
 affect its value at different times (Ph. v. Jolly, 
 W. 6, 520). 
 
 The pressure exerted by the atmosphere upon 
 the earth's surface, at the sea's level or upon 
 any substance at that, level, may be expressed 
 by saying that it is equivalent to a barometric 
 column about 76 centimetres (29'92 inches) 
 high. Now at ordinary temperatures 1 c.c. of 
 mercury weighs 13-58 grams. If we suppose 
 that the base of the mercurial column is 
 1 sq. centimetre it follows that the weight 
 of the counterbalancing atmospheric column is 
 76 X 13'58 = 1032 grams. This is equivalent to 
 14-73 lbs. upon a sq. inch. It can be readily 
 calculated that the total weight of the atmo- 
 sphere of this average pressure is about llf 
 trillions of pounds, or S^ trillion kilos. Allow- 
 ing for the space occupied by the land above 
 the sea's level, the mass of the atmosphere may 
 
 be taken as 
 
 part of that of the earth 
 
 (Herschel), 
 
 The heights of the counterbalancing columns 
 of air and mercury wiU of course be in the 
 same ratio as the weights of equal volumes 
 if it be assumed that the air is of uniform 
 tension throughout. The height of this homo- 
 geneous atmosphere is between five and six 
 miles : it was first calculated by Eobert Boyle 
 to disprove the conjectures of Kepler and 
 others that the air could not extend beyond a 
 couple of miles or so from the earth's surface. 
 
 As the air is an elastic fluid it follows from 
 Boyle's law that its pressure must diminish as 
 we ascend ; hence the mercurial column stands 
 lower on a mountain top than in the vaUey 
 below. The fact that the barometric column is 
 less on the top of an elevation than at the 
 bottom was first noticed in 1643 by Claudio 
 Bereguardi from observations on the tower of 
 Pisa — that is, five years before Perrier made 
 his famous experiments on the Puy-de-Dflme. 
 The relation between the pressure and density 
 of the air at different altitudes may be seen 
 from the following table : — 
 
 Metres above 
 aea level 
 
 Bulk ol air 
 
 Density 
 
 Barometer 
 mm. 
 
 
 
 1 cub. metre 
 
 1- 
 
 760 
 
 5,520 
 
 2 
 
 0-5 
 
 380 
 
 11,040 
 
 4 „ 
 
 0-25 
 
 190 
 
 16,560 
 
 8 „ 
 
 0-125 
 
 95 
 
 22,080 
 
 16 „ 
 
 0-062S 
 
 47-5 
 
 27,600 
 
 32 „ 
 
 0-0312 
 
 23-8 
 
 A pressure equivalent to the average pres- 
 sure of the atmosphere at the level of the sea 
 is frequently adopted by engineers and others 
 as a unit of pressure and is styled an, atmo- 
 sphere. In this country an atmosphere is the 
 pressure equal to 29-905 inches of mercury at 
 32° F. at London, and is about 14-73 lbs. on the 
 sq. inch. In the metric system it is the pres- 
 sure of 700 mm. (29-922 inches) of mercury at 
 0°C at Paris, and is equal to 1-033 kilos on a 
 
 sq. centimetre. Hence the English ' atmo- 
 sphere' is 0-99968 that of the metric system. 
 
 That the mercury in the Torricellian tube, or 
 barometer as it was termed by Boyle, is constantly 
 varying in height even at the same place, and 
 that these variations are due to the fluctuating 
 pressure of the atmosphere, appears to have 
 been first clearly recognised by Descartes and 
 by Boyle in 1658. It is, however, only within 
 the last few years that we have acquired any 
 very definite information respecting the dis- 
 tribution of the mass of the atmosphere over the 
 earth. The pressure of the air at any given 
 spot depends upon its relative position on the 
 earth's surface : at this spot it varies also with 
 the season of the year and the hour of the day. 
 According to Buchan, whose isobario charts are 
 really the foundation of our exact knowledge of 
 the subject, there are two broad belts of high 
 pressure passing completely round the globe, 
 one to the north and the other to the south of 
 the equator. The southern belt of high pres- 
 sure is nearly parallel to the equator ; but 
 the northern belt is more irregular in outline in 
 consequence of the unequal distribution of land 
 and water in the northern hemisphere. Between 
 them is the low pressure of the tropical regions, 
 through the centre of which is a narrow belt of 
 still lower pressure towards which the north 
 and south trades blow. A region of low pressure 
 exists also round each pole ; that round the north 
 pole having two distinct centres, one in the north 
 Atlantic, the other in the Pacific : at each of 
 these the diminution of pressure is much below 
 the average of the north polar depression. As 
 regards the seasons, it is found that in January 
 the highest pressures are over the continents of 
 the northern hemisphere, and the lowest pres- 
 sures are over the northern portions of the 
 Atlantic and Pacific, S. America and S. Africa, 
 and the Antarctic Ocean. The maximum mean 
 pressure at this time is found in Central Asia 
 where it is 30-4 inches, the minimum is in the 
 K. Atlantic and round Iceland, where it is only 
 29-34 inches. The area of high pressure passes 
 westwards through central and southern Europe, 
 over the N. Atlantic between the parallels of 
 5° and 45°, across N. America (except to the 
 North and North West), and over some portion 
 of the Pacific. In July the mean pressure of 
 Central Asia is only 29-468 inches — or one inch 
 less than in January. The lowest pressures of 
 the western hemisphere are now to be found 
 over the continents, whilst the highest are over 
 the ocean between 50° N. lat. and 50° S. lat. 
 Pressures are also higher at this time over 
 S. Africa and Australia. 
 
 Speaking generally, atmospheric pressure is 
 more regular throughout the year over the 
 ocean than over the land. To the westward of 
 each continent there is at all seasons an area of 
 higher pressure over the ocean than over the 
 land, in amount varying from 0-1 to 0-3 inch. 
 These regions of high pressure extend over 
 about 30° of longitude and attain their maxima 
 during winter. The prevailing winds and the 
 general circulation of the atmosphere are in- 
 timately associated with these areas of high and 
 low pressure. Winds, in fact, are caused by thi3 
 flowing away of air from regions of high 
 pressure to those of low pressure, in accordance 
 
ATMOSPHERE. 
 
 329 
 
 with Buys-Ballot's law, which has been thus 
 expressed by Buohan. ' The wind neither blows 
 round the space of lowest pressure in circles 
 returning on themselves, nor does it blow di- 
 rectly towards that space, but it takes a direc- 
 tion intermediate, approaching, however, more 
 nearly to the direction and course of circular 
 curves than of radii to a centre. More exactly 
 ihe angle ia not a right angle, but from 45° 
 to 80°.' 
 
 The most important of the influences affect- 
 ing atmospheric pressure during the months are 
 temperature, and, as a secondary effect of tem- 
 perature, humidity. By comparing the average 
 pressure during the two months which exhibit 
 the greatest divergence of temperature, viz. 
 January and July, Buchan finds the following 
 general result : — The January pressure exceeds 
 that in July over the whole of Asia except in the 
 north east, the highest pressures being near the 
 middle of the continent; over Europe to the 
 south and east of a line drawn from the north 
 of Eussia to the south of Norway, thence to the 
 north coast of Germany, across France to Bor- 
 deaux, along the north of Spain, and pass- 
 ing out into the Atlantic at Corunna ; over 
 N. America except in the N. East and N. West. 
 The July pressure exceeds that in January over 
 the whole of the southern hemisphere, over the 
 northern portion of the N. Atlantic, and over the 
 northern part of the Pacific. The pressure which 
 is thus removed from Asia, Europe, and America 
 in the northern hemisphere in July is trans- 
 ferred partly to the southern hemisphere, and 
 partly to the more northerly portions of the 
 Atlantic and Pacific Oceans.' 
 
 At all places on the earth's Surface where 
 the alternation of day and night exists, the pres- 
 sure of the atmosphere exhibits a remarkable 
 diurnal variation. Generally speaking, the pres- 
 sure is highest at about 9 a.m. and 9 p.m., and 
 lowest at about 3 a.m. and 3 p.m., but the exact 
 times vary somewhat with the locality and with 
 the season of the year. The regularity of this 
 variation within the tropics is so great that, as 
 Humboldt remarked, the hour of the day may 
 be approximately ascertained from the height of 
 the mercurial column. This oscillation in atmo- 
 spheric pressure is not confined to the sea's 
 level: it takes place with equal regularity at 
 heights of 13,000 feet. Within the tropics the 
 oscillation amounts to about 2-2 mm., but as we 
 approach the poles it decreases, until at 70° N. 
 lat. it is only 0-3 mm. In our latitudes these 
 horary variations are much less strongly marked 
 than in the tropics, and are usually masked by 
 climatic disturbances; but by comparing the 
 results of a large number of observations, the 
 fluctuation, which in these islands amounts to 
 about 0'5 mm. on the mean of the year, can be 
 clearly made out. In Paris eleven years' obser- 
 Tation shows that the mean barometric oscilla- 
 tion amounts from 9 a.m. to 3 p.m. to 0'756 mm., 
 and from 3 p.m. to 9 p.m. to 0-373 mm. The 
 amount of the diurnal variation differs during 
 the seasons of the year, being greater in summer 
 
 * For further details Bee Buchan, ' The mean pressure 
 oi the Atmosphere and the proTailing Winds oyer the 
 Globe for the Months of the Tear' (,T.E. 25) ; also Julius 
 Hann's Erdkunie; and B, H. Scott's Elementary Me- 
 Xeoi'ology. 
 
 than in winter. This peculiar phenomenon has 
 given rise to much discussion, but as yet the 
 cause cannot be said to be satisfactorily deter- 
 mined. Unlike the oceanic tide, it cannot be 
 ascribed to the influence of the moon, since 
 Bouvard has shown that the portion of the 
 horary oscillation of the pressure of the atmo- 
 sphere which depends on the attraction of the 
 moon cannot raise the mercury in the barometer 
 at Paris more than 0-018 mm., whilst the total 
 variation deduced from the 11 years' observation 
 amounts to 1-129 mm. The fact that the two 
 maxima of pressure occur when the temperature 
 is about equal to the daily mean, and the two 
 minima when the temperature is at its highest 
 and lowest, has led to the supposition that the 
 fluctuations in pressure are connected with the 
 daily march of temperature, and also with the 
 humidity of the air. Dove, Sabine, and Hopkins 
 have offered explanations based on such con- 
 nections, but they are insuflioient to account for 
 the facts. Lament and Brown have sought to 
 refer the phenomenon to the magneto-electrio 
 influence of the sun, or in other words to connect 
 it with the cause of the diurnal changes in ter- 
 restrial magnetism. There is every reason for 
 supposing that the cause of the diurnal variation 
 in atmospheric pressure is in some way depen- 
 dent on, or originates with, the sun, but that its 
 effects are greatly modified by a variety of local 
 or accidental circumstances, as for example the 
 prevailing winds, the amount of moisture in the 
 air, and the relative distribution of land and 
 water. 
 
 The atmosphere appears to receive its heat 
 (1) from the direct rays of the sun, (2) by the 
 reverberation of those rays from the surface of 
 the earth, (3) by contact with the ground, 
 and (4) through the influence of aqueous 
 vapour. 
 
 Although the air is not absolutely diather- 
 manous, the heat received by the air from the 
 direct rays of the sun is the least important of 
 the sources enumerated. We know very little 
 at present as to whether the diathermancy of 
 air varies with its density: that is, we have 
 little evidence to determine whether the absorp- 
 tion of the sun's rays increases as they pass 
 further into an atmosphere compressed by its 
 own weight. 
 
 The greater portion of the heat which finds 
 its way into the atmosphere is due to radiation 
 from the earth's surface and to the air being in 
 contact with the ground. The amount of heat 
 thus sent into the air depends to a great extent 
 on the nature of the soil which receives the 
 solar radiations and on its capacity for retaining 
 heat. Hence places in the same latitudes and 
 not very far distant from each other, and in the 
 same condition as regards protection, may have 
 very different mean temperatures on account of 
 the different capacities of various soils for ab- 
 sorbing and retaining heat. 
 
 Aqueous vapour is one of the most important 
 agents in modifying the temperature of the 
 atmosphere. A relatively large amoimt of heat 
 is rendered latent in the process of evaporation 
 from the surface of the earth, and becomes sen- 
 sible on the condensation of the vapour in the 
 upper regions of the air. Aqueous vapour also 
 acts even when in the condition of a perfect gas 
 
830 
 
 ATMOSPHERE. 
 
 by retarding the transmiseion of the sun's rays 
 through the air. As the quantity of aqueous 
 vapour decreases as we ascend through the 
 atmosphere, it follows that the amount of this 
 absorption increases as the sun's rays penetrate 
 further into the atmosphere. 
 
 The temperature of the atmosphere varies 
 with a multitude of causes, such as the latitude, 
 the season of the year, the hour of the day, the 
 degree of humidity, &c. Among the causes 
 which tend to raise the temperature of the air 
 may be enumerated : the proximity of a western 
 coast in the temperate zone ; the divided con- 
 figuration of a continent into peninsulas with 
 deeply indented bays and inland seas ; the aspect 
 or position of a portion of the land with reference 
 either to a sea of ice spreading far into the polar 
 circle, or to a mass of continental land of con- 
 siderable extent lying in the same meridian, 
 either under the equator or at least within a 
 portion of the tropical zone ; the prevalence of 
 southerly or westerly winds on the western shore 
 of a continent in the temperate northern zone ; 
 chains of mountains acting as protecting walls 
 against winds coming from colder regions ; the 
 infrequency of swamps which in the spring and 
 beginning of summer long remain covered with 
 ice ; and the absence of woods in a dry sandy 
 soil ; finally the constant serenity of the sky in 
 the summer months ; and the vicinity of an 
 oceanic current bringing water which is of a 
 higher temperature than that of the surrounding 
 sea. 
 
 On the other hand, the following causes lower 
 the temperature of the air of a place : elevation 
 above the level of the sea, when not forming 
 part of an extended plain; the vicinity of an 
 eastern coast in high and middle latitudes ; the 
 compact configuration of a continent having no 
 littoral curvatures or bays ; the extension of 
 land towards the poles into the regions of per- 
 petual ice without the intervention of a sea 
 remaining open in the winter; a geographical 
 position in which the equatorial and tropical 
 regions are occupied by the sea, and conse- 
 quently the absence under the same meridian of 
 a continental tropical land having a strong 
 capacity for the absorption and radiation of 
 heat; mountain chains whose form and direc- 
 tion impede the access of warm winds ; the 
 vicinity of isolated peaks occasioning the de- 
 scent of cold currents of air down their declivi- 
 ties ; extensive woods which hinder the insolation 
 of the soil by the vital activity of their foliage, 
 which produces great evaporation owing to the 
 large surface it exposes, and increase the sur- 
 face that is cooled by radiation, acting conse- 
 quently in a three-fold manner — by shade, 
 evaporation, and radiation; the frequency of 
 swamps or marshes which in the north form a 
 kind of subterranean glacier in the plains lasting 
 till the middle of summer; a cloudy summer 
 sky which weakens the action of the solar rays ; 
 and finally a very clear winter sky favouring 
 the radiation of heat (Humboldt : Becherches 
 sur Us Causes des Inflexions des Lignes Iso- 
 thermes. See also Mohn's QrundzUge der 
 Meteorologie). 
 
 The temperature of the air varies in different 
 strata of the mass, decreasing generally after a 
 certain elevation in proportion as the distance 
 
 from the earth's surface increases, but it is not 
 possible to connect the diminution in tempera- 
 ture with the elevation in accordance with any 
 definite law. It is usually assumed that the 
 temperature falls about 1°0. for every 300 feet 
 of perfectly dry air. As, however, the air in- 
 variably contains moisture, which is condensed 
 by cooling and so produces heat, the decrement 
 may be taken practically at about 1°C. for every 
 500 feet. This estimate can only be taken as an 
 extremely rough approximation, for it is obvious 
 that the rate of cooling must be affected by a 
 great variety of causes. Indeed the extensive 
 series of aeronautical observations made at the 
 instance of the British Association showed 
 such great irregularities in the rate of diminu- 
 tion that Mr. Glaisher concluded that no law 
 exists. 
 
 The atmosphere always contains free electri- 
 city, which is generally positive, that is, of an 
 opposite kind to that of the earth. Atmospheric 
 electricity increases rapidly after sunrise, and 
 reaches its first maximum for the day at about 
 8 A.M. In general the variation in potential fol- 
 lows the diurnal range of atmospheric pressure. 
 In summer the hours of maxima appear to be 
 8 A.M. and 10 f.m. and the minima i a.m. and 
 4 P.M. In winter the hours of maximum intensity 
 are 9 a.m. and 10 p.m. and the minima 4 a.m. and 
 4 P.M. This diurnal variation seems to depend 
 mainly on the degree of humidity of the air, the 
 humid months manifesting the greatest potential. 
 The potential seems to increase from July to 
 January, and then to decrease. According to 
 Everett, the maxima occur in February and 
 October, and the minima in June and November. 
 
 In clear weather the air is usually positively 
 electrified ; it is only during rain, or more 
 properly speaking when rain begins, that the 
 electricity is negative. On the approach of a 
 storm, the air is almost invariably negatively 
 electrified, even when the storm-clouds are at 
 a considerable distance from the place of obser- 
 vation. When rain begins, the drops show nega- 
 tive electricity like the air. In hght rain the 
 potential is moderate, but heavy rain is almost 
 invariably accompanied by a high potential. 
 Dellmann's observations have shown, however, 
 that the air may have a very high potential, 
 extending over many days, without any other 
 evidences of an approaching storm. 
 
 The sources from which the electricity of the 
 atmosphere is derived are not clearly recognised. 
 De la Eive attributed it mainly to chemical 
 action at work on the earth; Pouillet to the 
 evaporation of water ; Volta and Saussure to 
 the inequalities of atmospheric temperature. 
 In all probability atmospheric electricity is not 
 wholly due to any one of these causes : they 
 may all be regarded as contributing to the 
 amount. 
 
 The sun's light in its passage to the earth is 
 partially absorbed and refiected by the atmo- 
 sphere. Clausius has calculated that of the 
 direct sunhght entering the atmosphere on a 
 clear day 6'4 p.o. is absorbed, 18-6 is reflected 
 and diffused, leaving therefore 75 p.c. to reach 
 the earth. This light is, of course, refracted 
 in its. passage in amount depending upon the 
 density of the air. Each ray entering the at- 
 mosphere otherwise than perpendicularly may be 
 
ATMOSPHERE. 
 
 331 
 
 supposed to describe a curre in coming to the 
 earth, and as objects are seen in the tangent of 
 the curve on entering the eye, all celestial bodies 
 not in the zenith appear further removed from 
 the horizon than they actually are. 
 
 The refractive power of dry air free from 
 carbonic acid is the mean of the refractive powers 
 of the oxygen and nitrogen under the pressure 
 which each gas exerts in the mixture. This 
 fact furnishes a proof of the physical nature of 
 the atmosphere ; since, as Dulong has shown, the 
 refractive power of a compound gas is not equal 
 to the refractive powers of its components, but is 
 sometimes greater and sometimes less. Moist 
 air is rather less refractive than dry air : precipi- 
 tated vapour, as mist or fog, slightly increases 
 the refractive power. 
 
 Although many of the more striking physical 
 properties of the air were recognised even in the 
 earliest ages, it is only within comparatively re- 
 cent time that anything very definite has been 
 known concerning its chemical nature. 
 
 It had long been observed that many metals 
 on exposure to fire lost their peculiar lustre, 
 and it was also known that by the prolonged 
 action of heat they were ultimately converted 
 into calces or earthy powders often possessing 
 characteristic colours. The fact that the calx 
 weighs more than the metal from which it was 
 derived was known to Geber, and was well under- 
 stood by the alchemists of the 16th century. 
 Cardan (1506-1576) in noticing the increase of 
 weight which accompanies the calcination of 
 lead, says that it is due to a gas (flatiis) which 
 feeds flame and rekindles a body presenting 
 an ignited point; and Cesalpinus in the De 
 Metallicis (published at Nuremberg in 1602) 
 also states that the ' orasse ' which forms on 
 the surface of lead exposed to heated air con- 
 tains an aerial substance which increases the 
 weight of the metal. Eey of Perigord seems to 
 have first clearly recognised that the augmenta- 
 tion in weight was due to the action of the air. 
 'Je responds et soutiens glorieusement que ce 
 surorolt de poids vient de I'air qui dans le vase 
 a 6t6 fipaissi.' Hooke in 1665 asserted that air 
 contains a principle analogous to if not identical 
 with that contained in nitre, and he seems to 
 have believed that a certain portion only of the 
 air is required to support combustion and re- 
 spiration. The conception of the complex nature 
 of the air was greatly strengthened by the obser- 
 vations of Mayow on respiration : his experi- 
 ments are so precise and his facts so incontest- 
 able that, to quote Chevreul, one is surprised 
 that the truth was not fuUy recognised until a 
 century after his researches. Boyle also con- 
 siderably extended our knowledge of the physical 
 and chemical constitution of the air in the 
 various treatises which he published between 
 1672 and 1692. 
 
 Two years after the sagacity of Eutherford 
 had demonstrated the existence of nitrogen, 
 Priestley obtained oxygen gas by heating the 
 calx of mercury or red precipitate. The signifi- 
 cance of this discovery in its relation to the 
 constitution of the air and true nature of calci- 
 nation was first clearly and irrefragably demon- 
 strated by Lavoisier. By heating mercury in 
 eon tact with a measured volume of air, he 
 showed that about one-fifth of the volume of 
 
 the air is absotbed by the metal with the forma- 
 tion of ' red precipitate,' from which the gasi 
 can be recovered by heating to a still higher 
 temperature, and that the remaining four-fifths- 
 had all the properties of the ' mephitic air,' or 
 nitrogen, of Eutherford. This experiment not 
 only demonstrated the compound nature of the- 
 air and the character of its constituents, but it 
 also showed approximately the relative quanti- 
 ties in which these constituents were present.. 
 It was of course quickly recognised that the 
 active properties of air depended upon oxygen,, 
 and it was reasonable to assume that the rela- 
 tive amount of this gas determined the quality 
 of air ; hence arose the art of eudiometry.. 
 Priestley, who discovered nitric oxide in 1772, 
 had observed that this gas became red in con- 
 tact with the air and that the ruddy gas, unlike 
 nitric oxide, was readily soluble in water. When 
 it was subsequently ascertained that the forma- 
 tion of the soluble red gas was due to the action 
 of oxygen on the nitric oxide, the idea of basing 
 a eudiometric method upon this reaction was- 
 suggested by Priestley. Careful experimenters 
 were, however, unable to distinguish air which 
 was reputed to be unhealthy from that which 
 experience had proved to be beneficial and 
 salubrious. Thus, in Priestley's hands, air- 
 from the country seemed no better than that 
 obtained from the worst-ventilated workshops 
 of Birmingham. Cavendish, after a critical 
 examination of the method, made numerous 
 analyses of air. 'During the last half of the 
 year 1781,' he says, 'I tried the air of near 
 sixty different days in order to find whether it 
 was sensibly more phlogisticated at one time- 
 than another, but found no difference that I 
 could be sure of, though the wind and weather 
 on these days were very various, some of them 
 being very fine and clear, others very wet, and 
 others very foggy ... On the whole, there is 
 great reason to think that the air was in reality 
 not sensibly more dephlogistioated on any one 
 of the sixty days on which I tried it than the- 
 rest.' Cavendish devised a scale of graduation 
 applicable to all nitric oxide eudiometers, by 
 means of which the late Dr. Wilson calculated 
 that the mean of his results furnished the 
 following numbers, expressing the centesimal 
 composition of the air by volume : 
 
 Oxygen . . , 20-833 
 
 Nitrogen . . 79-167 
 
 100-000 
 
 Cavendish concludes his account of these 
 observations by pointing out the character of 
 the information furnished by the eudiometer. 
 Etymologically the name was without signifi- 
 cance. 'In so far as the instrument takes- 
 cognisance of the impurity of the atmosphere,, 
 it betrays no difference between one specimen 
 of air and another ; so that, apparently, there- 
 are no degrees of goodness to be measured .... 
 Thus it may be inferred that our sense of" 
 smelling can, in many cases, perceive infinitely 
 smaller alterations in the p.urity of the air 
 than can be perceived by the nitrons test ' 
 (Cavendish, 'Account of a New Eudiometer,' 
 T. 1783). 
 
 These conclusions were confirmed by Hum- 
 boldt and Gay-Lussac in their oelebratedJ 
 
332 
 
 ATMOSPHERE. 
 
 memoir on the composition ol the air, published 
 in 1804. They employed the eudiometrio method 
 of Volta, i.e. explosion with hydrogen, and from 
 an extensive series of analyses made on air 
 collected in the most variable weather they 
 concluded that 100 vols, of air contained 21 of 
 oxygen and 79 of nitrogen. 
 
 The constant proportion of the two principal 
 constituents of the atmosphere appeared now 
 to be so well established that many chemists, 
 after the recognition of the atomic theory, were 
 inclined to think that air was a definite com- 
 pound of oxygen and nitrogen. The two main 
 constituents of the air are, however, not present 
 in the simple ratio demanded by the law of 
 Gay-Lussac. There is no evidence of chemical 
 combination on mixing oxygen and nitrogen in 
 the proportion in which these gases are present 
 in air : the properties of the mixture are identi- 
 cal with those of air and are such as might be 
 predicated to result from such a mixture. 
 Moreover, oxygen and nitrogen can be isolated 
 from air by mechanical means, or by taking 
 advantage of the different intestinal movements 
 of the gases. Graham separated the gases by 
 atmolysis, and Bunsen demonstrated that the 
 two gases were absorbed by solvents on which 
 they exerted no chemical action in exact accord- 
 ance with the law of partial pressures. Lastly 
 the more accurate eudiometric processes of the 
 last forty years have shown that the proportion 
 of oxygen to nitrogen even in so-called normal 
 air is not absolutely constant. This fact was 
 first clearly demonstrated by Bunsen: in a 
 series of analyses made duflng January and 
 February 1846, he found that the percentage 
 amount of oxygen varied from 20-97 to 20-84 
 by volume, i.e. a difference of 0-13 p.c, whereas 
 the error of experiment never exceeded -03 p.c. 
 iEven wider variations were found by Eegnault 
 in the course of a long series of analyses made 
 on air collected in different parts of the world. 
 In more than 100 analyses of air taken at 
 various times of the year in and about Paris the 
 lowest quantity of oxygen found was 20-913 and 
 the highest 20-999 ; an extreme difference of 
 0-086 ; the experimental error being 002 p.c. 
 Air collected from different parts of Europe, 
 from valleys and from the tops of mountains 
 and during different seasons of the year, showed 
 variations in the amount of oxygen from 20-903 
 to 21-0 p.c. 
 
 Angus Smith found similar differences in 
 London air in the course of numerous analyses 
 made during 1869 ; the percentage amount of 
 oxygen varied between 20-857 and 20-95. That 
 these variations are due to local or accidental 
 causes in the case of a town is established by 
 the circumstance that the air in the streets is 
 almost invariably poorer in oxygen than the 
 air of the parks and open spaces. As types of 
 normal air, Angus Smith found the following 
 means of numerous analyses of ait in Scotland 
 (1863-6): 
 
 Oxygen 
 Seashore and the heath 20-999 
 Tops of hills 20-98 
 
 Kot mountainous 20-978 
 
 Forests 20-97 
 
 In marshy places the oxygen sank as low as 
 
 20-922. 
 
 In Glasgow, in a series of 30 analyses tlia 
 oxygen varied from 20-889 in the closer parts 
 to 20-929 in the more open places. A. B. Leeds 
 found that the air of New York showed varia- 
 tions from 20-821 to 21-029 p.c; and lastly 
 Jolly found that air in Munich freed from car- 
 bonic acid and aqueous vapour varied in weight 
 as much as 9 mgm. per litre, this variation 
 depending upon the direction of the wind. By 
 eudiometric measurement he obtained variations 
 from 20-53 to 21-01 p.c. Southerly winds as a 
 rule showed arelatively low percentage of oxygen. 
 According to E. W. Morley these deficiencies in 
 the relative amount of oxygen are to be attributed 
 to the down-rush of air poorer in oxygen from 
 the higher regions of the atmosphere. It was 
 conjectured by Dalton and Babinet that air in 
 the upper strata of the atmosphere contained 
 relatively less oxygen than that immediately 
 above the earth. 
 
 From Begnault's observations it would seem 
 that sea-air contains slightly less oxygen than 
 laud air. The mean of 17 samples collected in 
 the Arctic seas was 20-91, the extremes being 
 20-94 and 20-85. The mean of all the samples 
 collected at sea was 20-84 ; in a series of twenty 
 only five showed amounts of 20-96 and upwards. 
 On the other hand, the observations of Lewy indi- 
 cate that sea-air differs but little in composition 
 from land-air, but that in the tropics it expe- 
 riences close to the sea a diurnal variation in 
 the amount of oxygen and carbonic acid, due 
 to the action of the sun's heat in disengaging 
 these gases from the water. Subsequent ex- 
 periments on the composition of air over the 
 sea have not confirmed these observations so 
 far as the carbonic acid is concerned (vide 
 infra). 
 
 We have comparatively little information in 
 regard to the relative quantities of the consti- 
 tuents of the air at great heights. Such 
 experimental evidence as exists seems to indi- 
 cate that air contains relatively less oxygen 
 in the higher strata than near the surface of the 
 earth. 
 
 Very little is known respecting the proportion 
 of ozone in the atmosphere, or of the circum- 
 stances which influence its production. The 
 ozonometric methods hitherto devised are in- 
 capable of affording accurate quantitative esti- 
 mations. Air over marshes or in places infested 
 by malaria contains little or no ozone. No 
 ozone can be detected in towns or in inhabited 
 houses. 
 
 Houzeau (A. Oh. [4] 27, 5) determines the 
 relative amount of ozone in the air by exposing 
 strips of red-litmus paper dipped to half their 
 length in a 1 p.c. solution of potassium iodide. 
 The paper in contact with ozone acquires a 
 blue colour from the action of the liberated 
 potash upon the red litmus. The iodised litmus 
 paper is preferable to iodised starch paper 
 (Schonbein's test-paper) which exhibits a blue 
 coloration with any reagent which liberates 
 iodine, e.g. nitrous acid, chlorine, &o. From ob- 
 servations made with iodised litmus paper 
 Houzeau concludes that ozone exists in the air 
 normally, but the intensity with which it acts at 
 any given point of the atmosphere is very vari- 
 able. Country air contains at most jj^^ios °' 
 its weight or ^555 of its volume ol ozone. 
 
ATMOSPHERE. 
 
 anit 
 
 Xbe frequency of the ozone manifestations 
 varies with the seasons, being greatest in spring, 
 strong in summer, weaker in autumn, and 
 weakest in winter. The maximum of ozone is 
 found in May and June, and the minimum in 
 December and January. In general ozone is 
 more frequently observed on rainy days than in 
 fine weather. Strong atmospheric disturbances, 
 as thunder storms, gales, and hurricanes, are 
 frequently accompanied by great manifestations 
 of ozone. According to Houzeau atmospheric 
 electricity appears to be the most active cause 
 of the formation of atmospheric ozone. 
 
 The existence of hydrogenperoxide in air was 
 first established by Meissner in 1863, but we 
 have no knowledge of the proportion in which it 
 is present. All information as to its relative 
 distribution is obtained from determinations of its 
 amount in rain water and snow. The proportion 
 seems to vary, like that of ozone, with the seasons 
 of the year and with the temperature of the air. 
 It is not improbable that the amount of hydro- 
 gen peroxide in air is greater than that of ozone, 
 and it is possible that many so-called ozone 
 manifestations are in reality due to peroxide of 
 hydrogen {v. Houzeau, O. iJ. 76, 491 ; Schon- 
 bein, J.pr. 106, 270 ; Meissner, J. 68, 181 ; Schone, 
 B. 12, 346 ; 18, 1503). 
 
 The amount of aqueous vapour in the air is 
 subject to great variations. It depends princi- 
 pally upon the temperature, on the distance 
 from the equator, and on the level of the sea ; on 
 the form in which the aqueous vapour is pre- 
 cipitated ; on the connexion between such pre- 
 cipitations and the change of temperature ; and 
 on the direction and succession of winds. The 
 air is rarely saturated with aqueous vapour. In 
 our moist climate saturation is sometimes very 
 nearly attained, but in some parts of Central 
 Asia, Eussia, and Africa, extraordinary degrees 
 of dryness have been noticed. In these islands 
 the most humid month is January, and the dries 
 is May. 
 
 The existence of carbonic acid in the atmo- 
 sphere was first inferred by Dr. Macbride of 
 Dublin, in 1764, from the observation that 
 quicklime after exposure to the air effervesced 
 on treatment with an acid. From the ease with 
 which determinations of its amount may be 
 effected our knowledge of the distribution of 
 atmospheric carbonic acid and of the causes 
 which affect its proportion is probably more 
 precise than in the case of any other consti- 
 tuent of the air. In fresh country air the 
 amount is remarkably constant, and may be 
 stated as about -034 p.o. In large towns and 
 cities it is usually greater ; thus Angus Smith, 
 from numerous analyses made in London during 
 November 1869, found as a mean -044 p.c. : in 
 upwards of 70 analyses the proportion fell below 
 •04 p.c. on only 5 occasions. In Glasgow, Smith 
 found on an average -05 p.c. The amount wUl 
 of course be affected by any circumstances 
 which interfere with the rapid diffusion of the 
 carbonic acid produced by respiration and the 
 combustion of fuel : hence during fogs the pro- 
 portion is very greatly increased, an amount 
 as high as 0-1 p.c. having been occasionally 
 noticed. Smith gives the following summary 
 of results obtained in Manchester {Air and 
 Bain, p. 52). 
 
 Per cent. 
 In Manchester streets in usual weather -0408 
 
 During fogs -0679 
 
 Where the fields begin .... -OSBg 
 In country air the amount of carbonic acid is 
 invariably greater at night than during the day. 
 This remarkable diurnal variation was first 
 pointed out by Saussure (P. 19, 391), and has 
 been fuUy confirmed by subsequent observers. 
 Thus, as the mean of numerous analyses made 
 at Clermont-Ferrand, Truchot (C. B. 77, 675) 
 obtained during the day '0358, and during the 
 night -0403 (v. also G. F. Armstrong, Pr. 1880. 
 343; and Muntz a. Aubin, C. B. 92, 1299). 
 These differences are mainly due to the exha- 
 lation of carbonic acid from plants at night. 
 In the air of towns, and in the absence of 
 vegetation, no such diurnal variations can bo 
 detected. 
 
 The amount of carbonic acid in the air is 
 not sensibly altered by rain : this indeed would 
 follow from the law of partial pressure. Over 
 the sea the amount of carbonic acid is about 
 •08 p.c, and, contrary to the statement of Lewy, 
 no diurnal variation in the amount can be 
 perceived (Thorpe, C. J. [2] 5, 189). Schulze 
 \Landw. Versuchs.-St. 14, 866) obtained 
 similar results with sea air at Bostock : the 
 mean of a large number of observations made 
 from 1868 to 1871 was -0292 p.c. No definite 
 change in the amount was observed at different 
 seasons of the year or at different times of the 
 day. Fog and also a fall of snow were often 
 associated with an increase of carbon dioxide 
 {v. also Fittbogen a. Hasselbarth, C. C. 1874. 
 694). 
 
 Very little is known concerning the distribu- 
 tion of carbonic acid in the higher strata of 
 the atmosphere. According to Saussure and 
 Schlagentweit the amount of carbonic acid on 
 the mountains is greater than on the plains : 
 Truchot, however, found only -0203 on the top 
 of the Puy-de-D6me (1446 m.), and -0172 on the 
 Peak of Sancy (1884 m.), as against •0318 at 
 Clermont-Ferrand. Additional observations are 
 required. 
 
 The existence of nitric acid in the air was- 
 first inferred by Priestley. The amount, how- 
 ever is so small that it can only be detected 
 in rain - water. Nitroxygcn compounds are 
 occasionally produced during thunder-storms, 
 and it is said that the rain collected during' 
 a storm often contains notable quantities of 
 nitrous and nitric acids. Boussingault found 
 that a million parts of rain water contained 0-83 
 parts of nitric acid. Eeichardt found in hail- 
 stones collected during a thunderstorm 0'526 
 parts per million. 
 
 According to Barral each hectare at Paris 
 receives annually from the rain about 63'6 kilos 
 of combined nitric acid. Bineau found that 
 1 litre of rain-water at Lyons contained in 
 winter 08 mgm. nitric acid ; in spring 1-0 ; in 
 summer 2-0 mgm.; and in autumn 1^0 mgm. 
 Bobierre found that a cubic metre of rain-water 
 collected at Nantes in 1863 contained on an 
 average 7'36 grams in the upper part, and 
 5'682 grams in the lower part, of the town (C.B. 
 1864, 755). Angus Smith (Air and Bain, p. 287;^' 
 obtained the following results from a large num< 
 ber of observations on rain-water. 
 
334 
 
 ATMOSPHEEE. 
 
 NitJic acid 
 (pt3. per million) 
 
 Scotland: inland country places" . . 0'305 
 
 Ireland— Valentia 0-370 
 
 England — sea coast country places . . 0'371 
 
 Scotland „ country places, west . 0'372 
 
 „ „ „ east . 0'476 
 
 .. n II average 0-424 
 
 Liverpool 0-582 
 
 England : inland country places . . 0-749 
 
 London : 1869 0-840 
 
 England : towns 0-863 
 
 Manchester : mean of 1869 and 1870 . 1-032 
 Scotland: towns (Glasgow excluded) . 1-164 
 Glasgow 2-436 
 
 The amount of nitric acid in the rain-water 
 of towns is uniformly greater than in rain- 
 water collected in the country, from which we 
 infer that much of the nitric acid in the air is 
 due to the oxidation of ammonia derived from 
 the decomposition of nitrogenous organic matter. 
 
 The ammonia in the air exists partly as 
 carbonate, partly as nitrate and nitrite ; ammo- 
 nia itself being converted into nitrous and nitric 
 acids and water by ozone. Scheele observed that 
 a bottle containing hydrochloric acid became 
 coated near the stopper with a film of sal ammo- 
 niac on exposure to the air. A piece of pipe- 
 clay heated to redness and exposed to the air 
 for a few days yields a perceptible amount of 
 ammonia when reheated : this is not the case if 
 the clay is kept in a stoppered bottle. 
 
 The quantity of ammonia contained in the 
 air is extremely variable : the results on record 
 differ from 135 to 0*1 of ammonia (calculated 
 as carbonate) in 1,000,000 parts of air. Fresenius 
 found that a million parts by weight of air con- 
 tained during the day 0-098 parts of ammonia, 
 and during the night 0169 parts. According to 
 H. T. Brown the amount ordinarily present is 
 much larger than this : a million parts of country 
 air at a height of 2 metres from the ground 
 contained from 5-1 to 6-08 parts ; the same 
 amount of town air contained from 4-06 to 8-73 
 parts of ammonium carbonate {Pr. 18, 286). 
 Direction of wind appears to have no influence 
 on the amount. The quantity decreases after 
 heavy rain but is restored to the normal amount 
 (about 6 pts. in 1,000,000) in a few hours. 
 Truchot (C. B. 77, 1159) found from 0-93 to 
 2-79 mgm. per cubic metre in the air of Auvergne, 
 the highest results being obtained on misty days 
 and the lowest on clear days. From observa- 
 tions made on the Puy-de-Dome, Truchot con- 
 cludes that the quantity increases with the 
 elevation and is greater in cloudy than in clear 
 air. On the other hand, Muntz and Aubin 
 (C. B. 95, 788), from observations made on rain- 
 water, find that the upper strata of the air 
 contain much less ammonia than air near the 
 surface of the earth. Nitric acid also was 
 entirely absent from rain water collected at an 
 elevation of 2877 m. Lewy (O. B. 91, 94) finds 
 that the air in summer contains invariably larger 
 quantities of ammonia (2-3 mgm. NH, in 1000 
 cm.) than in winter (1-7 mgm. in 1000 cm.). 
 
 The proportion of ammonia contained in 
 rain water is as might be expected subject to 
 equally wide variations. Lawes and Gilbert 
 found that 1,000,000 pts. of rain-water collected 
 
 in the country contained from 0-927 to 1'143 
 pts. of ammonia. Water collected in towns 
 always contains much larger amounts than that 
 collected in the country. Barral found that 
 1,000,000 parts of Paris rain-water contained 
 3-49 pts. of ammonia. Angus Smith obtained 
 1'07 pts. of ammonia in the rain-water of inland 
 country places in England, whereas the water 
 collected in the inland country places and mora 
 sparsely populated districts of Scotland con- 
 tained only 0-53 pts. of ammonia per million. 
 The rain water of London contained 3-45 ; that 
 of Liverpool 5-38 ; that of Manchester 6-47; and 
 that of Glasgow 9-10 parts per million. Thelarger 
 proportion in the cities is due to the influence 
 of animal life and to the constant presence of 
 azotised organic matter in the air of thickly 
 populated districts. Dews and fogs and snow 
 always contain larger quantities of ammonia 
 than rain-water. (For references, see Angus 
 Smith, Air and Bain.) 
 
 In addition to these substances- oxygen, 
 nitrogen, carbon dioxide, ozone, water-vapour, 
 ammonia, and nitrous and nitric acids — which 
 are the essential and necessary constituents of 
 atmospheric air, it frequently contains a variety 
 of accidental substances such as common salt, 
 alkaline sulphates, and organic matter dead and 
 living, derived from the proximity of the sea 
 and of marshy districts, or to the influences of 
 towns. Mosoati nearly 80 years ago observed that 
 the dew condensed on bottles filled with ice and 
 suspended over the rice-fields of Tuscany, when 
 coUeoted quickly became putrescent and de- 
 posited flakes of a body containing nitrogen; 
 and similar appearances were noticed byEigaud 
 de Lisle in 1812 in the dew collected in the 
 marshes of Languedoc. The water deposited 
 flakes of nitrogenised organic matter and gave with 
 silver nitrate a precipitate which became imme- 
 diately purple. (Compare A. H.Smee,Pr. 20, 442.) 
 Vogel also observed that the moisture condensed 
 on cold surfaces in inhabited rooms quickly 
 became putrid owing to the presence of organic 
 matter resembling albumin. Angus Smith found 
 that the moisture condensed from breath after 
 standing for some time formed a thick glutinous 
 mass, which was seen under the microscope to 
 be a closely-matted confervoid growth. Between 
 the stalks of the confervse a number of greenish 
 globules were to be seen in a state of constant 
 movement ; also various species of volvox accom- 
 panied by monads many times smaller. As far 
 back as 1722, Loewenhoeck (Opera omnia, vol. 
 i. 1722) showed that rain-water, even when 
 recently coUeoted, contained infusoria derived 
 apparently from the air. Similar observations 
 were made by Ehrenberg and Gaultier de Claubry 
 (0. B. 41, 645). The first attempt to throw 
 light upon the question of the relative distribu- 
 tion of the organisms present in air was made by 
 Pasteur, by subjecting certain putrescible solu- 
 tions to the action of the air obtained from 
 various localities. 
 
 Tyndall {Les Microbes, Paris, 1882) has 
 shown that the micro-organisms contained in 
 air are rapidly deposited in the absence of any 
 strong aerial currents. Upon this fact Hessa 
 {Mittheilungen atis dem Jcaiserlichen Oesund- 
 heitsamte: Berlin, 1884) has based a method 
 .for quantitatively estimating the relative pro- 
 
ATMaSPHERB. 
 
 83a 
 
 portion of micro-organisms in air. The method 
 consists in aspirating air through wide-mouthed 
 glass tubes, coated internally with gelatine- 
 peptone, prepared according to Koch's method, 
 which is afterwards kept at a temperature of 
 20°-26° for a few days, when the organisms 
 which have been arrested — consisting of the 
 various monads, bacilli, and micrococci, capable 
 of development and growth in the nutrient 
 gelatine — are recognised by the colonies to 
 which they give rise. By means of this method 
 Dr. Percy F. Frankland has made a number of 
 estimations of the micro-organisms contained 
 in the air of towns, and in the country, and in 
 inhabited buildings. By simultaneously ex- 
 posing small circular glass dishes partially 
 filled with the nutrient gelatine to the action 
 of the air, a rough estimate was obtained not 
 only of the number of micro-organisms in a 
 given volume of the air, but also of the number 
 which fell during a given time on a definite 
 horizontal area. As the mean of a series of 
 observations made on the roof of the South Ken- 
 sington Museum between Jan. and June 1886, 
 it was found that there were 35 organisms in 
 10 litres of air, whilst 279 was the average 
 number which fell in 1 sq. ft. in 1 minute. 
 Similar experiments made near Eeigate and in 
 the vicinity of Norwich showed an average of 
 14 organisms in 10 litres of air, whilst 79 fell 
 per sq. ft. per minute. Experiments made in 
 Kensington Gardens, Hyde Park, and on Primrose 
 Hill, gave an average of 24 organisms in 10 
 litres, and a deposition of 85 per sq. ft. per 
 minute. At St. Paul's Cathedral, 56 organisms 
 were found at the base, 29 in the Stone Gallery, 
 and 11 in the Golden Gallery, in 10 litres of air. 
 At Norwich Cathedral 18 at the base, 9 at a 
 height of 180 ft., and 7 at 300 ft. In inhabited 
 buildings great variations were observed ; as a 
 rule the number of micro-organisms was less 
 than that found in the open air when the air of 
 the room was undisturbed, but rose rapidly when 
 the air was set in motion by draughts or by the 
 presence of many people (P. F. Frankland, Pr. 
 40, 609). 
 
 Angus Smith has sought to base a system of 
 chemical climatology on the examination of rain- 
 water collected under different conditions and at 
 various places. Eain falling through the air 
 over the sea always contains common salt and 
 sulphates, the latter in larger proportion to the 
 chlorides than is found in sea-water. The sul- 
 phates increase inland : they seem to be a 
 measure of the products of decomposition, the 
 sulphuretted hydrogen which is evolved in the 
 putrefaction of certain organic compounds being 
 oxidised in the atmosphere. In large towns, the 
 amount of the sulphates is greatly increased 
 owing to the combustion of coal containing iron- 
 pyrites. Indeed the rain water of large towns is 
 frequently acid from the presence of free sul- 
 phuric acid. Wien rain contains 40 parts per 
 million of free acid, vegetation is rapidly affected. 
 The following analyses by Angus Smith will 
 serve to show the general character of the rain- 
 water (and therefore of the impurity of the 
 atmosphere) in various parts of Great Britain. 
 The results, which are the mean of many ex- 
 periments, are expressed in parts per million of 
 rain-water. 
 
 
 I. 
 
 II. 
 
 III. 
 
 IT. V. 
 
 VI. 
 
 VII. 
 
 Sea Air: 
 
 
 
 
 1 
 
 
 Scotland 
 
 12-28 
 
 3-ei 
 
 
 
 0-74 0-105 
 
 •424 
 
 •013 
 
 England 
 Inland' 
 entry, air : 
 
 not dot. 
 
 5-88 
 
 
 
 1-90 notdet. 
 
 •371 
 
 notdet. 
 
 
 
 
 1 
 
 
 
 Scotland 
 
 3-37 
 
 2-06 
 
 
 
 0-53 -04 
 
 •305 
 
 •264 
 
 England 
 
 3-99 
 
 6-22 
 
 
 
 1-07 -109 
 
 •749 
 
 ■466 
 
 Towns: 
 
 
 
 
 
 1 
 
 
 
 Loudon 
 
 1-25 
 
 20-49 
 
 3-87 
 
 3-46' -205 
 
 •840 
 
 notdet. 
 
 LiverpL 
 
 10-16 
 
 39-69 
 
 11-66 
 
 6-38 -169 
 
 •682 
 
 3-896 
 
 Mnolistr. 
 
 5-83 
 
 44-82 
 
 10-17 
 
 6-47 -261 1-032 
 
 -4401 
 
 Glasgow 
 
 8-97 
 
 70-19 
 
 16-13 
 
 9-10 -300 2-436 
 
 10^040 
 
 II. 
 
 III. 
 
 IV. 
 V. 
 
 VI. 
 
 vn. 
 
 I. Amount of hydrochloric acid (chlorides). 
 
 sulphuric acid (sulphates). 
 
 apidity (free sulphuric acid). 
 
 ammonia. 
 
 albuminoid ammonia; decomposition 
 
 of organic matter, 
 nitric acid, 
 weight of oxygen required to oxidise 
 
 organic matter (measure of organic 
 
 matter and nitrites). 
 
 Although the atmosphere is subject to con- 
 tinual change from a multitude of causes, such 
 as the respiration of animals and plants, the 
 combustion of organic matter, various processes 
 in the arts &o., stiU from its immense mass and 
 uninterrupted motion such changes have only 
 the very slightest effect on its composition. Let 
 us very briefly consider the chief circumstances 
 which tend to influence the proportion of its 
 components. 
 
 Nitrogen is undoubtedly a primitive sub- 
 stance: no other body occurs in such large 
 quantities as an element. This gas is probably 
 the source of all nitrogenous bodies, in the for- 
 mation of which it is continually abstracted from 
 the air. A portion only of the nitrogen so 
 abstracted finds its way back to the air as such : 
 the most considerable compensating influence 
 known to us is the nitrogen evolved by volcanoes. 
 
 By the respiration of animals and the oxi- 
 dation of the spent portions of their tissue, by 
 the respiration of plants at night-time, and by 
 the combustion of fuel, large quantities of car- 
 bonic acid are being continually added to the 
 atmosphere. Enormous quantities also are 
 evolved from volcanoes and other subterranean 
 sources. Poggendorff has indeed calculated that 
 the amount so added is at least ten times as 
 much as is derived from all other sources put 
 together. Taking the weight of carbonic acid 
 in the air as -06 per cent., it can be calculated 
 from the area of the terrestrial oblate spheroid 
 that the weight of the carbonic acid in the 
 atmosphere is about 3,223,000 x 10 kilos (Le 
 Conte, P.M. [5] 15, 46; v. also B. H. Cook, 
 P. M. [5] 14, 387). At least 50,000 million 
 kilos of carbonic acid are daily added to the 
 air. The main compensating influence is of 
 course the action of growing plants in sunshine ; 
 carbon dioxide is also removed directly and 
 indirectly by zoophytes and by certain chemical 
 actions such as the conversion of felspar into 
 kaolin, &a. Sterry Hunt (' Chemical and Geo- 
 logical Belations of the Atmosphere,' Am. S. 
 1880) has calculated that a weight of carbonic 
 acid equal to more than twenty-one times that 
 of our present atmosphere- would be absorbed in 
 the production from orthoclase of a layer of 
 kaolin extending over the earth's surface with a 
 thickness of 500 metres, an amount representing 
 
836 
 
 ATMOSPHERE. 
 
 but a_ small proportion of the results of fel- 
 Bpathio decay in the sedimentary strata of the 
 globe. 
 
 Dumas and Boussingault, in their ■well-known 
 memoir on the Composition of the Air (A. Oh. 
 [3] 3) made some interesting calculations on 
 the duration of the supply of atmospheric oxy- 
 gen. They found that, taking all the known 
 sources of diminution, and assuming that the 
 oxygen disengaged by plants compensates only 
 for the causes of diminution at present unknown, 
 then even in this exaggerated case three times 
 the amount of oxygen thus abstracted would 
 only amount in 100 years to about j^ of the 
 total quantity, an amount barely appreciable by 
 our most exact eudiometrie methods. — T. E. T. 
 
 ATOMIC AND MOLECULAR WEIGHTS.— 
 Two theories regarding the ultimate constitution 
 of matter have opposed each other from the 
 beginnings of philosophy; one asserts that any 
 mass of apparently homogeneous matter is 
 really homogeneous ; the other affirms that 
 every portion of matter of sensible size is built 
 up of a vast number of small particles which are 
 not themselves capable of further sub-division. 
 The earliest exponent of the second theory of 
 whom we possess any definite record was the Greek 
 philosopher Democritus, who flourishedabout450 
 B.C. The doctrines of Democritus were developed 
 by Epicurus, and the teachings of the Epicurean 
 philosophy are preserved in the Latin poem of 
 Lucretius (b.c. 99-55). These early atomists 
 tried to assign to the atoms, of which they said 
 matter is composed, only such properties as 
 should suffice for their presentation in time and 
 space. They taught that nothing exists save 
 atoms and empty space ; that the atoms or ' first- 
 beginnings,' are of many different forms, and 
 different weights, and the number of atoms of 
 each form is infinite ; that all change is only 
 combination or separation of atoms ; and that 
 Ihe atoms are in constant motion. To meet 
 the objection that if a mass of matter is at rest 
 the parts of it cannot be in motion, Lucretius 
 uses the illustration of a flock of grazing sheep 
 with skipping lambs ; to one looking from a 
 distance the flock appears as a white motionless 
 patch on the green hillside, but a closer view 
 shows that the parts of the flock are continually 
 changing their positions. Every atom, Lucre- 
 tius asserts, is indestructible, and its motion is 
 indestructible likewise ; if this were not so how 
 could we account for the preservation of fixed 
 types in nature ? Eoses always bear roses, and 
 each animal reproduces its like, because the 'first 
 beginnings ' (or atoms) of which each is composed 
 are the same and are never destroyed or worn 
 out. ' First-beginnings are of solid singleness, and 
 in no other way can they have been preserved 
 through ages during infinite time past in order 
 to reproduce things.' ' Here we see how clearly 
 the early atomists recognised that every event in 
 nature occurs in accordance with strict laws. 
 Nothing happens by chance, was a fundamental 
 doctrine of these philosophers. ' I . . . teach 
 ... by what law all things are made, what 
 necessity there is then for them to continue in 
 that law, and how impotent they are to annul 
 
 ■ Lucretius, De Rerum Natwra, I. 548-«50 (Munro's 
 translation). 
 
 the binding statutes of time.' ' The way to 
 gain a knowledge of the laws of nature, Lucretius 
 teaches, is to examine natural events. (See for 
 instance the analysis of the efieots of the 
 thunderbolt in Book vi. 323-398.) The differences 
 between a hard body such as iron, and a soft 
 body such as air, depend, according to Lucretius, 
 on the motions of the atoms of the two bodies ; 
 in the hard body the atoms move to and fro 
 within very small distances, in the soft body 
 they move freely and rebound from each other 
 only at comparatively long intervals. ' Bodies 
 are partly first-beginnings of things, partly 
 those which are formed by a union of first 
 beginnings.' ^ The latter are produced by the 
 atoms grouping themselves in concilia ; this term 
 seems to mean something very like our expres- 
 sion in combination. The properties of the body 
 formed by the grouping together of atoms need 
 not resemble the properties of the atoms them- 
 selves (see, for instance. Book I. 915-920). Not 
 only must the atoms enter into concilium, with 
 each other in order that any kind of matter may 
 be produced, but the properties of the matter 
 thus formed depend on the mutual relations of 
 the atoms ; ' it matters much with what others 
 and in what positions the same first-beginnings 
 of things are held in union, and what motions 
 they do mutually impart and receive.' ' 
 
 Although this theory was so nearly complete, 
 yet, as taught by Lucretius, it had few of what we 
 now regard as the essential features of a good 
 scientific theory; it was not stated in terms 
 which permitted of numerical applications to 
 actual phenomena. Few or no exact applica- 
 tions of the theory could be made to natural 
 phenomena. It was scarcely able to predict 
 events in nature except in a wide and loose way. 
 It savoured too much of a dogma. It was rather 
 a speculation as to what might be the cause of 
 natural occurrences, than an attempt to deter- 
 mine what these causes really were. 
 
 The teachings of the Epicurean philosophers 
 were opposed by those of the school of Aristotle. 
 The Aristotelians magnified the names of things 
 and made them as real or even more real than 
 the things themselves ; they identified ' modes 
 of predication with modes of existence ' (Lange). 
 Matter occupied a foremost position in the 
 Epicurean scheme of the universe, but by the 
 followers of Aristotle it was regarded only as the 
 ' potentiality of becoming anything or everything.' 
 Aristotelianism prevailed in the middle ages and 
 atomism fell more and more into disrepute. 
 
 But in 1592, Gassendi, Canon and Provost at 
 Digne in Provence, revived the atomic theory of 
 the Greek philosophers, and attempted to found 
 on it an interpretation of natural events. The 
 influence of Gassendi was continued through 
 Newton and Boyle ; the former of whom, as we 
 know, demonstrated that not only do masses of 
 matter attract each other, but that every par- 
 ticle of each mass attracts every particle of the 
 other mass with a force varying directly as the 
 masses of the particles and inversely as the 
 square of the distance between the particles. As 
 Newton accepted the atomic conception of the 
 structure of matter, his demonstration of the 
 action of the force of gravitation gave a new 
 
 ' Id. T. 65-51 
 
 ' Id. I. 483-4. • Id. II. 1007-9. 
 
ATOMIC AND MOLECULAR WEIGHTS. 
 
 337 
 
 point of departure for the theory of atoms. From 
 this time a science of atomic physics became 
 possible. But the difficulty was, and still is, to 
 form a clear mental picture of the mechanism 
 of the action of the force of gravitation in terms 
 of the atomic conception of matter. Newton 
 gave the mathematical construction, and clearly 
 separated this from the physical explanation 
 which belonged to the region of conjecture. 
 
 Not much was done, after Newton, to advance 
 the appHoation of the atomic theory until the 
 early years of the present century, when Dalton 
 made a serious attempt to determine the condi- 
 tions under which the atoms of elementary bodies 
 unite to form the atoms of compound bodies. 
 
 The great advance made by Dalton consisted 
 in his asserting the possibility of finding the rela- 
 tive weights of the atoms of all kinds of matter, 
 and in his demonstration of the method whereby 
 these relative weights could be determined. 
 
 Many analyses of chemical compounds had 
 been made before the time of Dalton; the 
 results were usually stated in percentages, and 
 they seemed to have but few mutual relations. 
 Bichter (1791-1802) had shown that a definite 
 mass of each acid combines with a specified 
 mass of a given base ; he had arranged several 
 aoids and bases in order of neutralisation. 
 Fischer, in 1803, published a table of chemical 
 equivalents which expressed the quantities of 
 bases which were of equal value as regarded 
 power of neutralising a constant quantity of a, 
 specified acid. Lavoisier, Cavendish, and others, 
 had to some extent grasped the conception of 
 the elements combining in definite proportions. 
 They had never doubted that every chemical 
 substance was of definite composition, and that 
 it would be possible by careful analyses of many 
 compounds to find the laws of elementary oombi^ 
 nations. Proust had analysed several pairs of 
 oxides of the same metal; from some of his 
 numbers the law of combining weights might 
 have been deduced, had he stated his results so 
 as to show the quantities of oxygen in combina- 
 tion with a fixed quantity of metal. 
 
 Dalton analysed two compounds of carbon and 
 hydrogen, and found that in one there was twice 
 as much hydrogen as in the other, combined with 
 the same quantity of carbon. He found similar 
 regularities in the quantities of oxygen which 
 combined with a specified quantity of carbon, in 
 the quantities of oxygen which combined with 
 a specified quantity of nitrogen, &c. Meanwhile 
 he had been thinking much regarding the 
 ultimate particles of bodies ; he had pictured to 
 himself a quantity of gaseous matter as re- 
 sembling a heap of small shot, as built up of little 
 definite parts or atoms. He saw how the facts 
 of chemical combination he had been studying 
 would help him to find the relative weights of 
 these small particles. Dalton's genius recog- 
 nised the unity which bound together so many 
 diverse physical and chemical facts. He at once 
 stated clearly the quantitative laws of chemical 
 combination and referred these laws to one un- 
 derlying conception, the conception namely of 
 the atom. 'In all chemical investigations it 
 has justly been considered an important object 
 to ascertain the relative weights of the simples 
 which constitute a compound. But unfortu- 
 natelv the inquiry has terminated here ; whereas 
 
 from the relative weights in the mass, the relative 
 weights of the ultimate particles or atoms of the 
 bodies might have been inferred, from which 
 their number and weights in various other com- 
 pounds would appear, in order to assist and 
 to guide future investigation, and to correct 
 their results. Now it is one great object of this 
 work to show the importance and advantage of 
 ascertaining the relative weights of the ultimate 
 particles both of simple and compound bodies, 
 the number of simple elementary particles which 
 constitute one compound particle, and the num- 
 ber of less compound particles which enter into 
 the formation of one more compound particle.' ' 
 ' That he might determine the relative weight 
 of the ' ultimate particle ' of an element it was 
 necessary for Dalton to have some means of 
 fixing the number of particles of that element in 
 one ' ultimate particle ' of several of its com- 
 pounds. Thus, masses of hydrogen and oxygen 
 combine in the ratio of 1 to 8 ; now, if we assume 
 that the ultimate particle, or atom, of water is 
 9 times heavier than the atom of hydrogen, the 
 most probable conclusion is that one atom of 
 water is formed by the union of one atom of 
 hydrogen, the mass of which is taken as unity, 
 with one atom of oxygen, the mass of which is 
 8 times that of the hydrogen atom; but if we 
 choose to assume that the atom of water is 16 
 times heavier than that of hydrogen, then the 
 experimental results — 1 of hydrogen combines 
 with 8 of oxygen, by weight— are most readily 
 interpreted by saying that one atom of water is 
 formed by the union of 2 atoms of hydrogen, 
 weighing 2, with one atom of oxygen, weighing 
 16, We cannot then determine howmany times 
 the atom of oxygen is heavier than that of hy- 
 drogen unless we have previously determined 
 how many times the atom of the compound 
 formed by the union of hydrogen and oxygen, 
 that is the atom of water, is heavier than the 
 atom of hydrogen. 
 
 Dalton framed certain empirical rules re- 
 garding the composition of the atoms of com- 
 pounds formed by the union of two elements. 
 His principal rules were these: 'If there are two 
 bodies, A and B, which are disposed to combine, 
 the following is the order in which combination 
 may take place, begiiming with the most simple, 
 namely: 
 
 latom ofA+latom of B=l atom of 0, binary; 
 latom of A+2atoms of B=l „ D, ternary; 
 
 2 atoms of A+1 atom of B=l „ E, ternary; 
 latom of A+3 atoms of B=l „ !P, quaternary; 
 
 3 atomffof A-f-1 atom of B=l „ G, quateruary.* 
 
 &c. &c. 
 
 '1st. When only one combination of two 
 bodies [elements] can be obtained, it must be 
 presumed to be a binary one, unless some cause 
 appears to the contrary. 
 
 ' 2nd. When two combinations are observed 
 they must be presumed to be a binary and a 
 ternary. 
 
 ' 3rd. When three combinations are obtained, 
 we may expect one to be a binary, and the other 
 two ternary. 
 
 ' 4th. When four combinations are observed, 
 we should expect one binary, two ternary, and 
 one quaternary, &c. &o.' 
 
 ' From the application of these rules to the 
 
 ■ Dalton, A Sew Sytem of Chemicdl PMUmphy (1808). 
 
 z 
 
838 
 
 ATOMIC AND MOT.EOULAR WEIGHTS. 
 
 chemical facts already well ascertained, we 
 deduce^ the following conclusions : 1st. That 
 water is a, binary compound of hydrogen and 
 oxygen, and the relative weights of the two ele- 
 mentary atoms are as 1:7 nearly [more correctly 
 1:8]. 2nd. That ammonia is a binary com- 
 pound of hydrogen and azote, and that the 
 relative weights of the two atoms are as 1:5 
 nearly [more correctly 1:4-66]. ... In all 
 these cases the weights are expressed in atoms of 
 hydrogen, each of which is denoted by unity." 
 But even if these rules were admitted, it was not 
 always possible to fix the relative weight of an 
 elementary atom ; thus, two compounds of carbon 
 and oxygen were known to Dalton, containing, 
 according to his analyses, 2-7 parts by weight of 
 carbon combined with (i) 7 and (ii) 3-5 parts by 
 weight of oxygen ; hence, by rule 2, the first of 
 these is a compound of one atom carbon with 
 one atom oxygen, and hence the atomic weight 
 of carbon is 27, and the second is a compound 
 of 2 atoms carbon ( = 5'4) with 1 atom oxygen 
 { = 3'5x2). But the results of analyses might 
 also be stated thus : (i) 5'4 carbon + 14 oxygen, 
 (ii) 5'4 carbon -f 7 oxygen; and the conclusion 
 might be drawn that the first is a compound of 
 1 atom carbon (5-4) with 2 atoms oxygen (7 x 2), 
 and the second is a compound of 1 atom carbon 
 (5-4) with one atom oxygen (7). Both ways of 
 stating the results of experiments would be in 
 keeping with Dalton's rules, but the first would 
 lead to the number 2'7, and the second to the 
 number 54, as representing the relative weight 
 of the atom of carbon. Another objection to the 
 Daltonian rules of atomic syntheses was that, 
 although to-day we may know of but one com- 
 pound of two specified elements, to-morrow we 
 may know of several compounds of these elements. 
 
 Berzelius continued the work which Dalton 
 had begun ; his aim was to discover the laws of 
 atomic combinations. Why does a specified 
 element by combining with oxygen produce only 
 two or perhaps three different oxides ? Why do 
 not the elementary atoms combine in a great 
 many different ratios ? What are the limiting 
 forms of the compound atoms produced by the 
 union of any specified elementary atoms? 
 Berzelius busied himself with such questions 
 as these. And that he might find some solu- 
 tions to such questions, Berzelius was obliged 
 to frame empirical rules, as Dalton had done 
 before him. 
 
 The following may be taken as an example 
 of the Berzelian rules. If an element forms 
 two oxides with twice as much oxygen by 
 weight in one as in the other, relatively to a 
 iixed mass of the element, the atom of that 
 compound which contains the smaller mass of 
 oxygen is to be regarded as composed of one 
 atom of oxygen and one atom of the specified 
 element, and the atom of the other compound 
 is to be regarded as composed of two atoms of 
 oxygen and one atom of the specified element ; 
 but if the masses of oxygen in the two oxides 
 are in the ratio 2:3 relatively to a specified 
 mass of the other element, then the atom of 
 the compound with less oxygen is to be regarded, 
 as before, as composed of one atom of oxygen 
 and one atom of the specified element, but the 
 
 ■ Dalton, Ij!. 
 
 atom of the compound with more oxygen is to 
 be regarded as composed of three atoms of 
 oxygen and two atoms of the other element. 
 
 Bat such rules were only empirical, and, 
 however satisfactory might be the particular 
 results obtained by their application, it was 
 impossible to rest contented until some general 
 principle had been attained which should admit 
 of universal application. In the course of his 
 inquiries regarding the syntheses of atoms, 
 Berzelius performed a vast number of very 
 careful analyses, the results of which firmly 
 established the quantitative laws of chemical 
 combination. These laws (v. Combination, 
 Chemical, Laws of) assert : — (1) that the masses 
 of the constituents of every homogeneous kind 
 of matter stand in an unalterable proportion to 
 one another, and also to the mass of the com- 
 pound they produce — the mass of the compound 
 being always equal to the sum of the masses of 
 the constituents ; (2) that when two elements 
 combine to form more than one compound, the 
 masses of one of the elements which combine 
 with a constant mass of the other element bear 
 a simple relation to each other; and (3) that 
 the masses of different elements which combine 
 with one and the same mass of another element 
 are also the masses of these different elements 
 which combine with each other, or they stand 
 in a simple relation to those masses. These 
 laws may all be expressed in the statement that 
 the elements combine only in the ratios of their 
 combining weights, or, in simple multiples of 
 these ratios. By the combining weight of an 
 element is here meant the smallest mass of that 
 element which is found to combine with one 
 part by weight of hydrogen or with 8 parts by 
 weight of oxygen. 
 
 As Berzelius was pursuing his investigations 
 into the gravimetric composition of compounds, 
 Gay-Lussao was making experiments on the volu- 
 metric composition of gaseous compounds. In 
 1809 this naturalist was able to prove (1) that 
 the volumes of the gaseous elements which com- 
 bine to form a gaseous compound stand in an 
 unalterable proportion to each other ; (2) that 
 when two gaseous elements combine to form 
 more than one gaseous compound, the volumes 
 of one of the elements which combine with a 
 constant volume of the other element bear a 
 simple relation to each other ; and (8) that the 
 volumes of different gaseous elements which 
 combine with one and the same volume of 
 another gaseous element are also the volumes 
 of these different elements which combine with 
 each other, or they stand in a simple relation to 
 those volumes. These laws may all be expressed 
 by saying that the gaseous elements combine 
 only in the ratios of their combining volumes, 
 or in simple multiples of these ratios. By the 
 combining volume of a gaseous element is here 
 meant the smallest volume of that element 
 which is found to combine with one unit volume 
 of hydrogen, and a unit volume of hydrogen is 
 defined to be the volume, at normal tempera- 
 ture and pressure, occupied by one unit mass of 
 this element. 
 
 Gay-Lussac argued that the ratios of the 
 masses of the combining volumes of gaseous 
 elements are also the ratios of the masses of the 
 atoms of these elements ; and the conclusion 
 
ATOMIC AND MOLECULAR WEIGHTS. 
 
 33B 
 
 \VM drawn that equal Tolumes of gaseous bodies, 
 measured at the same temperature and pressure, 
 contain equal numbers of atoms. This con- 
 clusion, if admitted, seems to put into our hands 
 a means for finding the relative masses of the 
 atoms of many compounds and hence of many 
 elements. But the application leads to unlooked- 
 for results. Consider the case of hydrogen and 
 oxygen : experiment shows that two volumes of 
 hydrogen— weighing two— combine with one 
 volume of oxygen— weighing 16 — and pro- 
 duce two volumes of water-gas— weighing 18 ; 
 hence, if equal volumes of gases contain equal 
 numbers of atoms, two atoms of hydrogen^ 
 weighing two— combine with one atom of 
 oxygen — weighing 16— and the product is two 
 atoms of water-gas — each weighing 9. But 
 each of these atoms of water-gas contains atoms 
 of hydrogen and oxygen ; now, the atom of 
 oxygen has been shown to weigh 16 times 
 as much as the atom of hydrogen ; hence the 
 atom of water-gas contains half an atom of 
 oxygen. Again, consider the case of hydrogen 
 and chlorine : experiment shows that one volume 
 of hydrogen — weighing one— combines with one 
 volume of chlorine — weighing 35-5 — and that 
 the product is two volumes of hydrochloric acid 
 weighing 36-5 ; hence, if equal volumes of gases 
 contain equal numbers of atoms, one atom of 
 hydrogen has combined with one atom of 
 chlorine to produce two atoms of hydrochloric 
 acid. But as each atom of hydrochloric acid 
 is composed of both hydrogen and chlorine, it 
 follows that each atom of hydrochloric acid is 
 formed by the union of half an atom of 
 hydrogen and half an atom of chlorine. But 
 these conclusions are at variance with the funda- 
 mental definition of the atom, which states 
 that the atom is the smallest mass of a body 
 that can exhibit the properties of that body. 
 
 The discovery that gaseous elements com- 
 bine in fixed quantities by volume had done 
 something to advance the study of atomic 
 synthesis, but it had not removed the funda- 
 mental difficulty, the difficulty, namely, of find- 
 ing some generally applicable principle by means 
 of which the relative weights of the ultimate 
 particles, or atoms, of compounds might be 
 determined. This difficulty was overcome by 
 Avogadro. In 1811 this Italian naturalist intro- 
 duced into chemistry the conception of two 
 orders of small particles — the molecule, and 
 the atom. The molecule of an element or a 
 compound, said Avogadro, is the smallest mass 
 of it which exhibits the properties of that ele- 
 ment or compound ; the molecule of an element 
 or a compound is formed by the union of smaller 
 particles of matter which we shall call atoms; 
 in the case of the molecule of an element the 
 atoms are all of one kind, in the case of the 
 molecule of a compound the atoms are of two, 
 or more than two, different kinds. As the 
 properties of the molecule of a compound are 
 very different from the properties of the atoms 
 which compose it, so it is probable that the 
 properties of the molecule of an element are 
 different from the properties of the atoms by 
 the union of which the molecule is produced. 
 A chemical action between two gases was con- 
 ceived by Avogadro as being separable, in 
 thought if not in actuality, into two stages ; in 
 
 the first stage the molecules of the reacting 
 gases are shattered, and in the second stage the 
 parts of these molecules, that is the atoms, are 
 rearranged to form the molecules of the new 
 bodies. 
 
 Avogadro modified the generalisation made 
 by Gay-Lussac, and re-stated itthasi—'Eqtial 
 volumes of gases, temperature and pressure being 
 the same, contain equal numbers of molecules.' 
 The reactions between hydrogen and oxygen, 
 and hydrogen and chlorine, which could not be 
 explained by the generalisation of Gay-Lussac, 
 are perfectly consistent with the generalisation 
 of Avogadro. Two volumes of hydrogen com- 
 bine with one volume of oxygen, and the pro- 
 duct is two volumes of water-gas; that is, in 
 terms of Avogadro's statement, 2p molecules of 
 hydrogen, each composed of x atoms, combine 
 with p molecules of oxygen, each composed of 
 x' atoms (x may or may not equal x'), and the 
 product is 2p molecules of water-gas. One 
 volume of hydrogen combines with one volume 
 of chlorine to form two volumes of hydrochlorio 
 acid ; that is, in terms of Avogadro's statement, 
 p molecules of hydrogen, containing x atoms, 
 combine with p molecules of chlorine, contain- 
 ing x' atoms (x may or may not equal x'), to 
 form ip molecules of hydrochloric acid. 
 
 Not only are these, and other, reactions, be- 
 tween gases explicable in terms of the generali- 
 sation of the Italian naturalist, but this state- 
 ment gives us a means of determining the rela- 
 tive masses of the molecules of all gaseous 
 bodies, and also of determining the minimum 
 number of atoms in each of these molecules. 
 That is to say, the generalisation of Avogadro 
 gives us what we could not obtain from the 
 rules of Dalton or Berzelius, or from the generali- 
 sation of Gay-Lussac. For it is evident that, if 
 the number of molecules in equal volumes of 
 two gases is the si;me, the masses of the two 
 kinds of molecules must be in the same ratio as 
 the densities of the two gases ; and hence, if 
 the density of one of the gases be taken as unity, 
 the density of the other, in terms of this one, 
 expresses the relative mass of a molecule of 
 this other gas. Let the two gases be hydrogen 
 and oxygen; experiment shows that a given 
 volume of oxygen is sixteen times heavier than 
 the same volume of hydrogen ; hence, if equal 
 volumes contain equal numbers of molecules, a 
 molecule of oxygen is sixteen times heavier than 
 a molecule of hydrogen. Let us call the mass 
 of a molecule of hydrogen one, then, in order to 
 find how many times greater than the mass of 
 this molecule is the mass of the molecule of any 
 gas, we have only to determine the density of 
 the specified gas in terms of hydrogen as unity ; 
 the number expressing the density of the gas 
 expresses also the relative mass of the molecule 
 of the gas. But, further, the generalisation ol 
 Avogadro puts into our hands a means whereby 
 the minimum number of atoms in a gaseous 
 molecule may be determined, and hence a means 
 whereby the maximum relative values to be 
 assigned to the masses of atoms may be deter- 
 mined. Consider the mutual action of hydrogen 
 and chlorine, hydrogen and bromine, nitrogen 
 and hydrogen, and oxygen and hydrogen. 
 Having regard only to the volumes of the re> 
 acting gaseous elements and the volumes of the 
 
 22 
 
340 
 
 ATOMIC AND MOLECULAR WEIGHTS. 
 
 gaseous compounds produced, the aotionsin ques- 
 tion may be stated thus : — 
 
 (i.) One volume of hydrogen combines with 
 one volume of chlorine to produce two volumes 
 of hydrochloric acid ; (ii.) One volume of hydro- 
 gen combines with one volume of bromine-gas 
 to produce two volumes of hydrobromic acid; 
 (iii.) one volume of nitrogen combines with three 
 volumes of hydrogen to produce two volumes of 
 ammonia ; (iv.) one volume of oxygen combines 
 with two volumes of hydrogen to produce two 
 volumes of water-gas. 
 
 Now, as equal volumes contain equal num- 
 bers of molecules, these statements may be put 
 as follows : — 
 
 (i.) p molecules of hydrogen combine with 
 p molecules of chlorine, and the product is 2p 
 molecules of hydrochloric acid ; (ii.) ^i molecules 
 of hydrogen combine withp molecules of bromine 
 gas, and the product is 2p molecules of hydro- 
 bromic acid ; (iii.) p molecules of nitrogen com- 
 bine with 3p molecules of hydrogen, and the 
 product is 2p molecules of ammonia ; (iv.) 
 p molecules of oxygen combine with 2p molecules 
 of hydrogen, and the product is 2p molecules of 
 water-gas. 
 
 Therefore in (i.) one molecule of hydrogen 
 has produced, by union with chlorine, two mole- 
 cules of hydrochloric acid, both of which are 
 composed of hydrogen and chlorine ; in (ii.) one 
 molecule of hydrogen has produced, by union 
 with bromine, two molecules of hydrobromic 
 acid, both of which are composed of hydrogen 
 and bromine ; in (iii.) one molecule of nitrogen 
 lias produced, by union with hydrogen, two 
 molecules of ammonia, both of which are com- 
 posed of nitrogen and hydrogen ; and in (iv.) 
 one molecule of oxygen has produced, by union 
 with hydrogen, two molecules of water-gas, both 
 of which are composed of oxygen and hydrogen. 
 In other words, in reactions (i.) and (ii.) every 
 molecule of hydrogen has separated into at least 
 two parts ; in reaction (iii.) every molecule of 
 •nitrogen has separated into at least two parts ; 
 and in reaction (iv.) every molecule of oxygen 
 has separated into at least two parts. 
 
 These parts of molecules are called atoms. 
 
 If we assume the truth of Avogadro's 
 generalisation, then the foregoing reactions are 
 most simply interpreted by saying that the mole- 
 cules of hydrogen, nitrogen, and oxygen, are 
 each built up or composed of two atoms. As 
 hydrogen is the standard element to which the 
 atomic and molecular weights of aU other bodies 
 are referred, we say that the atomic weight of 
 \hijdrogen is one, and, because of such reactions 
 •as those just stated, that the molecular weight of 
 'hydrogen is two. But if the molecular weight 
 of hydrogen is two, the molecular weight of 
 oxygen must be 32, the molecular weight of nitro- 
 gen must be 28, the molecular weight of hydro- 
 chloric acid must be 36"5, the molecular weight 
 of hydrobromic acid must be 81, the molecular 
 weight of ammonia must be 34, and the mole- 
 cular weight of water-gas must be 18 ; because 
 oxygen is 16 times heavier than an equal volume 
 -pf hydrogen, nitrogen is 14 times, hydrochloric 
 acid is 18'25 times, hydrobromic acid is 40'5 
 times, ammonia is 17 times, and water-gas is 9 
 times, heavier-thau an equal volume of hydrogen. 
 
 By such reactions and such modes of reascm- 
 
 ing as these, we arrive at the following practical 
 definition of the molecular weight of a gaseous 
 element or compound: — The molecular weight 
 of a gaseous element or comjpound is a wimiber 
 which expresses how many times greater than 
 two unit masses of hydrogen is the mass of the 
 specified element or compound which occupies 
 (vmder the same conditions of temperature and 
 pressure) the same volume as is occupied by these 
 two unit masses of hydrogen. 
 
 Determinations of the sp. gravs. of gases are 
 subject to several sources of error. But the 
 values to be assigned to the combining weights 
 of the elements, that is, the masses of the ele- 
 ments which combine with one part by weight of 
 hydrogen or 8 parts by weight of oxygen, can be 
 determined with great accuracy. Now, it is 
 evident that the molecular weight of an element 
 must be equal to the combining weight of this 
 element or to a simple multiple of this number, 
 and that the molecular weight of a compound 
 must be equal to the sum, or to a multiple of the 
 sum, of the combining weights of its constituent 
 elements ; hence the data which are required 
 for an accurate determination of the molecular 
 weight of an element are (i.) an exact determina- 
 tion of the combining weight of the element, 
 and (ii.) a measurement of the relative density 
 of the element in the state of gas; similarly 
 the data which are required for an accurate 
 determination of the molecular weight of a com- 
 pound are (i.) exact determinations of the 
 combining weights of the constituent elements, 
 and (ii.) a measurement of the relative density 
 of the compound in the state of gas. Thus, 
 35'37 parts by weight of chlorine combine with 
 1 part by weight of hydrogen, therefore the 
 molecular weight of chlorine is «B5'37; but a 
 given volume of chlorine is 35-5 times heavier 
 than an equal volume of hydrogen, therefore 
 the molecular weight of chlorine is approxi- 
 mately 35-5x2 = 71; now, 2 x 35-37 = 70-74 ; 
 hence the molecular weight of gaseous chlorine 
 is 70-74. Again, phosphorus hydride is com- 
 posed of masses of phosphorus and hydrogen 
 united in the ratio 10-32 to 1, therefore the 
 molecular weight of this compound is nll-32 ; 
 but this compound in the state of gas is 17 times 
 heavier than hydrogen, therefore its molecular 
 weight is approximately equal to 17 x 2 = 34 ; 
 now, 3x11-32 = 33-96; hence the molecular 
 weight of gaseous phosphorus hydride is 33-96. 
 
 Having thus arrived,bythehelpof Avogadro's 
 generalisation, at a definition of molecular 
 weight, and having determined that the mole- 
 cules of hydrogen, nitrogen, and oxygen, and of 
 some other elements, are very probably composed 
 each of two parts or atoms, we proceed to find 
 an exact meaning for the term atom. If the 
 atom is assumed to be the ultimate portion of 
 any homogeneous kind of matter of which 
 cognisance is to be taken in chemistry, then it 
 is evident that a molecule of a compound gas, 
 formed by the union of (say) three elements, 
 A, B, and C, must be formed by the union of at 
 least one atom of the element A, one atom of 
 the element B, and one atom of the element 0. 
 In general terms, no molecule of a compound 
 gas can be formed by the combination of less 
 than a single atom of each of the elements by 
 the union of which the compound in question ig 
 
ATOMIC AND MOLECULAR WEIGHTS. 
 
 341 
 
 produoad. This is eqaivalent to saying, the 
 atom of an element is the smallest mass ol that 
 element which combines with other atoms to 
 produce a molecule. 
 
 We cannot as yet determine the absolute 
 mass of the atom of any element, but we have 
 agreed to call the mass of an atom of hydrogen 
 unity, and to represent the masses of the atoms 
 of other elements in terms of the atom of 
 hydrogen; hence we arrive at the practical 
 definition of the maximum atomic weight of an 
 element as follows : — 
 
 The maximum atomic weight of an eletnent 
 is a number which expresses how many times 
 greater is the smallest mass of that element which 
 combines with other elements to form a compound 
 gaseous molecule, than the smallest mass of 
 hydrogen which combines with other elements to 
 
 14'435 times heavier than the same volume of 
 hydrogen at the same temperature and pressure ; 
 therefore the relative density of any gas referred 
 to air as unity multiplied by 14-435 x 2 ( = 28-87) 
 gives the relative deusity of that gas referred to 
 hydrogen as twice unity, that is, gives 
 (approximately) the molecular weight of the 
 gas. Let it now be required to determine the 
 atomic weight of oxygen; the definition, of 
 atomic weight teUs that the molecular weights 
 of several gaseous compounds containing oxygen 
 must be determined, that these compounds must 
 be analysed and the results in each case stated 
 in parts by weight of each element per molecule 
 of the compound, and that the smallest mass of 
 oxygen thus found in any molecule is to be taken 
 as the atomic weight of oxygen. Here are some 
 of the data which have been thus accumulated; — 
 
 Data for determining the atomic weight of Oxygen, 
 
 Gaseous compound 
 
 Sp. Gr.air=l 
 
 Sp.Gr.x 28-87; i.e. 
 
 approximate 
 molecular weight 
 
 Molecular 
 weight 
 
 Analysis, stated ia parts by wt. 
 per molecule 
 
 Carbon dioxide . 
 Sulphur dioxide . 
 Sulphur trioxide . 
 
 1-53 
 2-25 
 2-9 
 
 44-2 
 64-9 
 83-7 
 
 43-89 
 63-90 
 79-86 
 
 31-92 oxygen +11-97 carbon 
 31-92 „ + 31-98 sulphur 
 47-88 „ +31-98 „ . 
 
 froduce a compound gaseous molecule, such 
 smallest mass of hydrogen being taken as unity. 
 The term, and the conception underlying the 
 term, molecule, are applied to compounds and 
 elements alike; the term, and the conception 
 
 Were these the only known gaseous compounds 
 containing oxygen we should conclude that the 
 atomic weight of oxygen is 31-92, that of 
 hydrogen being unity. But the following numbers 
 show that this conclusion is incorrect : — 
 
 
 Data for determining the atomic weight of Oxygen. 
 
 Gaseous compound 
 
 Sp. Gr.air=l 
 
 Sp.Gr.x 28-87; i.e. 
 
 approximate 
 molecular weight 
 
 Molecular 
 weight 
 
 Analysis, stated in parts by wt. 
 per molecule 
 
 Carbon monoxide 
 Water . 
 Nitric oxide . 
 
 •97 
 
 ■63 
 
 1-04 
 
 27-97 
 
 18-2 
 
 30-0 
 
 28-93 
 17-96 
 29-97 
 
 15-96 oxygen + 11-97 carbon 
 15-96 „ +2 hydrogen 
 15-96 „ + 14-01 nitrogen 
 
 underlying the term, atom, are applied in 
 strictness to elements only. 
 
 The foregoing definitions of atomic weight 
 and molecuhir weight are practical, because 
 they indicate the nature of the data which must 
 be obtained before the atomic or molecular 
 weight of a gaseous body can be found. Suppose 
 it is required to find the molecular weight of 
 oxygen ; the mass of this element which com- 
 bines with unit mass of hydrogen must be 
 accurately measured; and the relative density 
 of oxygen gas must be determined, the standard 
 of reference being hydrogen taken as twice 
 unity. Now, the relative densities of gases are 
 determined by experiments in terms of air 
 taken as unity; but a specified volume of air is 
 
 These numbers show that at least three 
 compounds exist the gaseous molecule of each 
 of which contains 15'96 parts by weight of 
 oxygen ; hence, as no molecule is known con- 
 taining less than this mass of oxygen, 15-96 is 
 taken as the atomic weight of oxygen. Before, 
 then, the atomic weight of an element can be 
 determined with a fair degree of probability a 
 number of gaseous compounds of the element 
 must be analysed ; if only a few gaseous com- 
 pounds of a specified element are known it is 
 probable that the value deduced, from analyses of 
 these compounds, for the atomic weight of the 
 element, is too large ; it certainly cannot be too 
 small. Thus, let us consider the data for finding 
 the atomic weight of aluminium: — 
 
 
 Data for determining the atomic weight of Aluminium. 
 
 Gaseous compound 
 
 Sp. Gr. air=l 
 
 Sp.Gr.x 28-87; i.e. 
 
 approximate 
 molecular weight 
 
 Molecular 
 weight 
 
 Analysis, stated in parts by -nt, 
 per molecule 
 
 Aluminium chloride 
 „ bromide 
 „ iodide 
 
 9-35 
 18-6 
 270 
 
 270-0 
 537-5 
 180-0 
 
 266-26 
 532-54 
 813-22 
 
 54-04 aluminium + 212-22 chlorine 
 54-04 „ +478-5 bromine 
 54-04 „ + 759-18 iodine 
 
34S 
 
 ATOMIC AND MOLECULAR WEIGHTS. 
 
 Specific Beats of the Solid Elements." 
 
 Element 
 
 Spec, 
 beat 
 
 Temp. 
 
 Atomic 
 weight 
 
 Sp.ht. 
 xat.-wt. 
 
 Ob- 
 server 
 
 Element 
 
 Spec, 
 heat 
 
 Temp. 
 
 Atomic 
 weight 
 
 Sp. ht. 
 X at. wt. 
 
 Ob- 
 server 
 
 Lithium 
 
 •941 
 
 
 701 
 
 6-6 
 
 Bg. 
 
 Selenion 
 
 1 
 
 
 
 
 • Beryllium 
 
 ■6S 
 
 450° to 600° 
 
 9-1 
 
 6-6 
 
 hS. 
 
 cryttalHne 
 
 •084:' 
 
 78-8 
 
 6-7 
 
 B.W. 
 
 "Boron 
 
 ?-6 
 
 about 1000° 
 
 10-9 
 
 6-6 
 
 Wb. 
 
 Bromine 
 
 1 
 
 
 
 
 ' Carbon 
 
 •463 
 
 980° 
 
 11-97 
 
 6-6 
 
 Wb. 
 
 mm 
 
 •0843 -78° to -20° 
 
 79-75 
 
 67 
 
 Rg. 
 
 Sodium 
 
 ■293 
 
 -34° to-f 7° 
 
 23 
 
 6-7 
 
 Rg. 
 
 "* Zirconium 
 
 ■0666 
 
 90^0 
 
 60 
 
 M.D. 
 
 Ibgnesium 
 
 •246 
 
 
 24 
 
 6-9 
 
 Kp. 
 
 " Molybde- 
 
 
 
 
 
 
 11 
 
 •28 
 
 
 
 6^0 
 
 Kg. 
 
 num 
 
 •0722 
 
 
 96-8 
 
 6-9 
 
 Rg. 
 
 Aluminium 
 
 •202 
 
 
 27-02 
 
 6-6 
 
 Kp. 
 
 Rhodium 
 
 ■058 
 
 
 104 
 
 6-0 
 
 Rg. 
 
 „ 
 
 ■214 
 
 
 
 6-8 
 
 Rk. 
 
 Ruthenium 
 
 •0811 
 
 
 104^6 
 
 6-4 
 
 Bn. 
 
 .. . »» 
 
 •226 
 
 
 
 6-1 
 
 Mt. 
 
 Palladium 
 
 ■0593 
 
 
 106-2 
 
 6-3 
 
 Rg. 
 
 'iiUicoa 
 
 •203 
 
 232° 
 
 28 
 
 6-7 
 
 Wb. 
 
 Silver 
 
 ■066 
 
 
 107-66 
 
 80 
 
 Kp. 
 
 FhOBpho- 
 
 
 
 
 
 
 
 ■0659 
 
 
 it 
 
 8-0 
 
 Bn. 
 
 nacryit. 
 
 •174 
 
 -78° to +10° 
 
 3096 
 
 6-4 
 
 B?. 
 
 11 
 
 ■057 
 
 
 
 6-1 
 
 Rg. 
 
 » » 
 
 •189 
 
 
 ,^ 
 
 6-9 
 
 Bg. 
 
 Cadmium 
 
 •0642 
 
 
 112 
 
 80 
 
 Kp. 
 
 n M 
 
 •202 
 
 
 
 6-2 
 
 Kp. 
 
 
 ■0548 
 
 
 ,j 
 
 6-1 
 
 Bu. 
 
 rei 
 
 •170 
 
 
 
 6-3 
 
 
 
 ■0667 
 
 
 ,j 
 
 6-3 
 
 Eg. 
 
 Sulphur 
 
 •188 
 
 
 31-98 
 
 6-0 
 
 DJ. 
 
 Indium 
 
 ■057 
 
 
 llS-4 
 
 6-6 
 
 Bn. 
 
 „ ThtmAic 
 
 •163 
 
 
 
 6^2 
 
 Kp. 
 
 Tin 
 
 ■0548 
 
 
 117*8 
 
 6-6 
 
 Kp. 
 
 »> »» 
 
 •171 
 
 
 
 6-6 
 
 bS. 
 
 11 
 
 ■0659 
 
 
 It 
 
 8-6 
 
 Bn. 
 
 f» 11 
 
 ■178 
 
 
 ,^ 
 
 5-7 
 
 Eg. 
 
 
 •0582 
 
 
 )) 
 
 8-6 
 
 Rg. 
 
 ■ Potassium 
 
 •166 
 
 -78° to +10° 
 
 39-04 
 
 8-6 
 
 Rg. 
 
 jj 
 
 •0514 
 
 
 
 8-0 
 
 D.P. 
 
 Calcium 
 
 ■170 
 
 
 39-9 
 
 6-8 
 
 Bn. 
 
 Antimony 
 
 •0523 
 
 
 iso'-o 
 
 6-2 
 
 Kp. 
 
 Titanium 
 
 ■148S 
 
 0° to S03° 
 
 48 
 
 7-1 
 
 N.P. 
 
 jj 
 
 ■0495 
 
 
 ^J 
 
 6-9 
 
 Bn. 
 
 • Chromium 
 
 ■10 
 
 
 62-4 
 
 6-2 
 
 Kp. 
 
 
 ■0508 
 
 
 ^J 
 
 8-0 
 
 Rg. 
 
 ^ Manganese 
 
 •122 
 
 
 69 
 
 6-7 
 
 Rg. 
 
 11 
 
 ■0507 
 
 
 J, 
 
 6-0 
 
 D.P. 
 
 Iron 
 
 ■112 
 
 
 65-9 
 
 6-3 
 
 Kp. 
 
 Tellurium 
 
 ■0475 
 
 
 129 
 
 6-94 
 
 Kp. 
 
 11 
 
 ■114 
 
 
 11 
 
 6-4 
 
 Rg. 
 
 ^^ 
 
 ■0474 
 
 
 ,, 
 
 6-94 
 
 Rg. 
 
 11 
 
 ■110 
 
 
 
 6-1 
 
 d:p. 
 
 Iodine 
 
 ■0541 
 
 
 126^63 
 
 6-8 
 
 Eg. 
 
 Nickel 
 
 •108 
 
 
 68-6 
 
 6-3 
 
 Rg. 
 
 Lantha- 
 
 
 
 
 
 
 Cobalt 
 
 •107 
 
 
 69 
 
 6-3 
 
 Eg. 
 
 num 
 
 ■0449 
 
 
 138-5 
 
 8-2 
 
 Hd. 
 
 Copper 
 
 •093 
 
 
 63-4 
 
 6-0 
 
 Kp. 
 
 Cerium 
 
 ■0448 
 
 
 141 
 
 6-3 
 
 Hd. 
 
 11 
 
 •09S 
 
 
 
 61 
 
 Bg. 
 
 Didymium 
 
 •0458 
 
 
 144 
 
 6-6 
 
 Hd. 
 
 _. 11 
 
 •095 
 
 
 „ 
 
 6^1 
 
 d'p. 
 
 Tungsten 
 
 ■0334 
 
 
 183-6 
 
 6-0 
 
 Rg. 
 
 Zlno 
 
 ■0932 
 
 
 64-9 
 
 6-1 
 
 Kp. 
 
 Osmium 
 
 ■0311 
 
 
 193 
 
 6-0 
 
 Eg. 
 
 M 
 
 ■0936 
 
 
 „ 
 
 6-1 
 
 Bn. 
 
 Iridium 
 
 ■0328 
 
 
 194 
 
 6-2 
 
 Eg. 
 
 11 
 
 ■0966 
 
 
 11 
 
 8-2 
 
 Rg. 
 
 Platinum 
 
 ■0325 
 
 
 195 
 
 6-4 
 
 Kp. 
 
 11 
 
 ■093 
 
 
 
 6-0 
 
 d:p. 
 
 ,j 
 
 ■0324 
 
 
 „ 
 
 6-3 
 
 Eg. 
 
 • Gallium 
 
 ■079 
 
 12° to 23° 
 
 69 
 
 6-4 
 
 Bt. 
 
 
 ■0314 
 
 
 ^, 
 
 6-3 
 
 D.P. 
 
 Germanium 
 
 ■077 
 
 0° to 200° 
 
 72-3 
 
 6^84 
 
 N.P. 
 
 " Gold 
 
 ■0324 
 
 197 
 
 6-4 
 
 Rg. 
 
 Arsenic 
 
 
 
 
 
 
 '■ Mercury 
 
 1 
 
 
 
 
 canorphom 
 
 ■0761 
 ■083+ 
 
 
 74-9 
 
 y7 
 
 B.W. 
 
 ioHd 
 
 ■0319 -78° to -40° 
 
 199-8 
 
 6-4 
 
 Eg. 
 
 
 
 „ 
 
 6'2 
 
 B.W. 
 
 '« Thallium 
 
 ■0335 
 
 203-6 
 
 6-8 
 
 Ri. 
 
 11 
 
 ■0814 
 
 
 74-9 
 
 8-1 
 
 Eg. 
 
 Lead 
 
 ■0307, 
 
 206-4 
 
 6-3 
 
 Rg. 
 
 11 
 
 ■0822 
 
 
 n 
 
 8-2 
 
 n: 
 
 
 ■0315 
 
 ,^ 
 
 6-5 
 
 Kp. 
 
 * Selenion 
 
 
 
 
 
 
 ,, 
 
 ■0314 
 
 „ 
 
 6-6 
 
 Rg. 
 
 amarphoxu 
 
 ■0746 
 
 -27° to +8° 
 
 78-8 
 
 6-9 
 
 Rg. 
 
 Bismuth 
 
 ■0305 
 
 208 
 
 6-5 
 
 Kp. 
 
 trytlalltne 
 
 ■0746 
 
 -18° to +7° 
 
 If 
 
 6-9 
 
 Rg. 
 
 „ 
 
 ■0308 
 
 „ 
 
 6-3 
 
 Rg. 
 
 11 
 
 •0762 
 
 
 
 6-0 
 
 Ri. 
 
 Thorium 
 
 •0276! 
 
 S32-4 
 
 6-4 
 
 Nn. 
 
 » 
 
 •0861 
 
 
 11 
 
 6-8 
 
 N. 
 
 Uranium 
 
 •028 1 
 
 240 
 
 6-6 
 
 Zn. 
 
 * When no temp, is given the determinations were made somewhere between 0° and 100°, the numbers in 
 these cases may be regarded as approximately representing the mean specific heats for the temperature-interval 
 400-60°. 
 
 * The nnmber for beryllium is that calculated by Humpidge from a series of determinations, at temperatures 
 varying from 100° to 460°, made with a specimen of beryllium containing 99-2 per cent, of the metal. See further. 
 p. 343. 
 
 ■ • * Spec, heats of boron, carbon, and silicon are discussed on p. 343-4. 
 
 * The higher temperature (+10°) is not given in Begnault's paper, but judging from the context it appears to bg 
 approximately correct. 
 
 * This number for chromium Is probably too low ; see Kopp, A. Suppl. 3, 77 (note). 
 
 * The specimen of manganese employed contained a little silicon. 
 
 * Spec, heat of molten gallium between 109° and 119°= -0802 (Berthelot; Bl. [2] 31, 229). 
 
 * Spec, heat of amorphous selenion determined at high temperatures is abnormal, because of the large quantity of 
 heat absorbed before fusion. 
 
 " Spec, heat of zirconium calculated by Mixter and Dana from determinations made with a sample containing 
 known quantities of aluminium. 
 
 " Tha specimen of molybdenum employed contained carbon. 
 
 " Spec, heat of gold ia nearly constant from 0° to 600° : at 900° Sp. ht.= -0346, and at 1000°=-0352 (Vlolle, C. R. 
 at, 702). 
 
 " Spec, heat of liquid mercury at 55°=0-033 (Eegnault). 
 
 ^* The specimen of thallium employed contained a little oxide. 
 
 The numbers marked with % are probably too large. See Weber's papers referred to below. 
 
 The names of the various observers are abbreviated In the table: — 
 
 Rg. stands for Rsokault.— His papers on spec, heat are to be found in 
 
 Kp. „ Kopp 
 
 N. , Neduanm , 
 
 Bn. „ BUKSSN , 
 
 Wb. „ Webeb , 
 
 D.P, „ Dni.o!«a AND Petit , 
 
 Bt. „ ButrESLOT „ 
 
 Hd. , Hn.i.EBnAKD , 
 
 B. W. „ BETTENDOn» AKD WOlXNEB „ 
 
 M.D. „ MlXTEB AND DAHA k 
 
 Nn. „ Noses „ 
 
 N.P. „ NiLSOK AHD PbTTBBSBON „ 
 
 Ht. , Mallet , 
 
 Zn. , ZiHHBBHAinr , 
 
 He. „ HmipiDaE , 
 
 . Ch. [2] 73, 6 ; [3] 1, 128 ; 9, 332 ;26, 261 ; 
 38, 129 ; 46, 257 ; 63, 5 ; 67, 427. 
 A. 126, 362 ; and do. Suppl. 3, 1 and 289, 
 P. 126, 123. 
 P. 141, 1. 
 
 P. 164, 367 (translation in P. M. [4] 49, 
 A. Ch. 10, 396. iUl and 276), 
 
 C. R. 86, 786. 
 
 P. 163, 71 (translation in P. M. [6] 8, 109), 
 P. 133, 293. 
 
 A. 169. 388. 
 
 B. 15, 2619. 
 Z. P. C. 1, 27. 
 
 C. N. 46, 17g. 
 B. 16, 849. 
 Pr. it, 1. 
 
ATOMIC AND MOLECULAE WEIGHTS. 
 
 848 
 
 As no other gaseous oompouuds of aluminium, 
 except these three, have been prepared in a 
 state of purity and analysed, we conclude that 
 the atomic weight of this metal is not greater 
 than 54-04 ; but as only three gaseous compounds 
 of aluminium are known, it is not unlikely that 
 the true value to be assigned to the atomic weight 
 
 of this element is ^ or *^ or ^, &o. The 
 greater the number of compounds of a given 
 element which have been gasified and analysed, 
 the greater is the probability that the value 
 thence obtained for the atomic weight of the 
 element represents the true value of this con- 
 stant. 
 
 Avogadro's generalisation — equal volumes of 
 gases contain equal number of molecules — places 
 in the hands of chemists an instrument whereby 
 they may determine the relative weights of the 
 molecules of all gaseous or gasifiable compounds 
 and elements, and the maximum values to be 
 assigned to the atomic weights of all elements 
 which form gaseous or gasifiable compounds. 
 But at present the densities of only 14 ele- 
 ments have been determined in the gaseous 
 state, and gaseous compounds of only 42 different 
 elements have been prepared and analysed. 
 Hence the application of the method introduced 
 by Avogadro is limited. There are two other 
 methods of general applicability for determining 
 the values to be assigned to the atomic weights 
 of elements ; let us consider these methods briefly. 
 In 1819 a paper was published by two French 
 naturalists, Dulong and Petit, on the specific 
 heats of 13 soHd elements, viz., copper, gold, 
 iron, lead, nickel, platinum, sulphur, tin, zinc, 
 bismuth, cobalt, silver, and tellurium (A. Ch, 
 10, 395). 
 
 The products obtained by multiplying the 
 generally accepted atomic weights of the nine 
 elements from copper to zinc in this list by the 
 specific heats of these elements, and sub-multiples 
 of the generally accepted atomic weights of the 
 remaining four elements by the specific heats of 
 these elements, had all nearly the same value. 
 Generalising from these results, Dulong and 
 Petit concluded that ' the atoms of all the sim- 
 ple bodies have exactly the same capacity for 
 heat.' This generalisation has, on the whole, 
 been borne out by subsequent research. 
 
 The table on p. 342 contains most of the 
 well-established data regarding the specific heats 
 of solid elements in so far as direct determina- 
 tions are concerned. 
 
 The values to be assigned to the specific 
 heats of beryUium, boron, carbon, and silicon, 
 have been the subject of many experiments and 
 of much discussion. Nilson and Pettersson 
 {B. 13, 1451 ; V. also C. N. 42, 297) made a 
 series of determinations with a specimen of 
 metaUio beryllium containing about 5 per. cent, 
 of beryllium and iron oxides. The following 
 were the most important results : — 
 Specific Heat of Beryllmm (Nilson & Pettersson). 
 temp, interval Spec. ht. Spec. lit. x 9-1 Spec. ht. x 13-66 
 0°- 46 -3973 3-6 5-4 
 
 -DOO -4246 3-86 5-8 
 
 -214 '475 4-26 6-4 
 
 -300 -5055 4-6 6-9 
 
 Nilson and Pettersson concluded from these 
 nnmbers that the atomic weight of beryllium is 
 
 13-65 ; but L. Meyer (B. 13, 1780) showed that 
 the true values for the spec, heat of this metal 
 at various temperatures, as calculated from the 
 data summarised in the preceding table, are as 
 follows : — 
 
 Specific Seat of Beryllium (Meyer). 
 
 Increase in ««».*■., q« u* ., 
 Temp. SpecM. spec. ht. ^P^.™-'* ^^sl^j 
 
 20-2° -3973 3-62 5-43 
 
 •00101 
 73-2 -4481 4-08 6-12 
 
 •00085 
 157 -5193 4-73 7-10 
 
 •00063 
 256-8 -5819 5^29 8-94 
 
 These numbers show that the specific heat 
 of beryllium increases as temperature increases, 
 but that the rate of this increase is considerably 
 less for the interval 157° to 256° than for that 
 of 20° to 157°. Humpidge (Pr. 39, 1), working 
 with a specimen of berylUum prepared ■mih 
 great care and containing 99-2 per cent, of the 
 metal and '7 per cent, of beryllium oxide, 
 obtained the following results : — 
 
 Specific Heat of Beryllivm (Humpidge). 
 Temp. Spec, heat Spec. ht. x 9-1 
 
 100° -4702 4-28 
 
 200 -5420 4-93 
 
 400 -6172 5-61 
 
 500 -6206 5^65 
 
 The value approximates to a constant 
 between 450° and 500°. There can now be 
 little doubt that the specific heat of beryllium 
 is considerably larger at high than at low 
 temperatures, that this value is nearly constant 
 at about 500° and upwards, and that at these 
 temperatures beryllium is not an exception 
 to the law of Dulong and Petit. (For more 
 details 1). Bebvllium.) 
 
 Very varying values had been obtained for 
 the specific heats of the three elements, boron, 
 carbon, and sUicon, before the researches of 
 Weber. The following table summarises the 
 chief results: — 
 
 Specific Heats of Boron, Carbon, and Silicon 
 (Weber's numbers not included). 
 
 (Temp, about SS'-SS") 
 Spec. heat. Sp. ht. x at. wt. Observer. Date, 
 
 BOKOU 
 
 amorphoia -254 2-8 Kp. 1864 
 
 eryatallvne -230 28 do. do. 
 
 -262 2-8 M.D. 1873 
 
 „ -257 2-8 Eg. 1869 
 
 graphitic -235 2-6 do. do. 
 Oabbon 
 
 diamond -143 1-7 B. W. 1868 
 
 „ -147 1-8 Eg. 1841 
 
 „ -366 Temp. 20<'-1000° 4-4 Dewar 
 
 graphile -174 2-1 Kp. 1864 
 
 -188 2-3 B. W. 1868 
 
 „ -198 2-4 Eg. 1866 
 
 gat-mrhon -165 2-0 Kp. 1864 
 
 „ -186 2-2 B. W. 1868 
 
 „ -197 2-4 Eg. 1841 
 
 „ -32 Temp. XC-IOOO" 38 Dewar 
 
 SlUCON 
 
 fused -138 3-9 Kp. 1864 
 
 „ -166 4-6 Eg. 1861 
 
 erytlalline -UB 4-6 Kp. 1864 
 
 „ -171 4-8 M.D. 1873 
 
 „ -173 4-8 Eg. 1861 
 
 Weber, about 1872, made a careful series of 
 determinations of the specific heats of these 
 three elements (P. M. [4] 49, 161 and 276) ; his 
 
344 
 
 ATOMIC AND MOLECULAR WEIGHTS. 
 
 more important results are presented in the 
 following table ;— 
 
 Specific Heats of Boron, Carbon, and Silicon 
 (Weber). 
 
 
 Temp. Spec. heat. 
 
 Sp.M. X 
 at. wt. 
 
 Boron crystalline^ 
 
 -40° 
 
 •1915 
 
 211 
 
 » » 
 
 + 77° 
 
 ■2737 
 
 301 
 
 II » 
 
 177° 
 
 •3378 
 
 372 
 
 i> >i 
 
 233° 
 
 •3663 
 
 4-03 
 
 Cabbon diamond 
 
 -50° 
 
 •0635 
 
 0-76 
 
 11 I) 
 
 + 10° 
 
 •1128 
 
 1^35 
 
 >■ H 
 
 85° 
 
 •1765 
 
 2^12 
 
 II II 
 
 250° 
 
 •3026 
 
 3^63 
 
 II II 
 
 606° 
 
 •4408 
 
 5-29 
 
 If II 
 
 985° 
 
 •4589 
 
 5^51 
 
 „ graphite 
 
 -50° 
 
 •1188 
 
 1^37 
 
 If If 
 
 + 10° 
 
 •1604 
 
 1^93 
 
 II 11 
 
 61° 
 
 ■1990 
 
 •2-39 
 
 II II 
 
 201° 
 
 •2966 
 
 3-56 
 
 II II 
 
 250° 
 
 •325 
 
 3-88 
 
 »• II 
 
 641° 
 
 •4454 
 
 5-35 
 
 11 11 
 
 978° 
 
 •467 
 
 6^50 
 
 Porous wood carbon 
 
 0°-23° 
 
 •1653 
 
 1-95 
 
 U 11 
 
 0°-99° 
 
 •1935 
 
 2-07 
 
 11 11 
 
 0°-223° 
 
 •2385 
 
 2-84 
 
 BiuooN crystallised 
 
 -40° 
 
 •136 
 
 3-81 
 
 11 If 
 
 + 57° 
 
 •1833 
 
 5^13 
 
 11 II 
 
 128° 
 
 •196 
 
 5^50 
 
 ti 11 
 
 184° 
 
 •2011 
 
 0-6S 
 
 II II 
 
 232° 
 
 •2029 
 
 5-68 
 
 These numbers show that the specific heats 
 of boron, carbon, and silicon increase as tempe- 
 rature increases, but that, in each case, the 
 value of this increase for a given temperature- 
 interval is considerably less at high than at low 
 temperatures. The observed variation in the 
 rate of increase of the specific heat of crys- 
 tallised boron' is nearly identical with the 
 observed variation in the rate of increase 
 of the specific heat of crystallised carbon 
 for equal intervals of temperature up to 
 230-250° ; if it is assumed that this identity 
 remains at higher temperatures, then the specific 
 heat of crystallised boron' may be calculated, 
 from the observations made with crystallised 
 carbon, at temperatures up to about 1000°. The 
 value thus calculated for the specific heat of 
 boron at 1000° is ^50. The specific heat of 
 crystalline silicon attains an almost constant 
 value at about 230°. (For more details v. Bokon, 
 Cabbon, Silicon.) 
 
 Looking at the determinations of the specific 
 beats of solid elements as a whole, it appears 
 clear that the specific heat of any element varies 
 with the temperature, and that the relation 
 between the variation of specific heat and that 
 of temperature differs for each element; and, 
 moreover, that the value of the specific heat of 
 an element depends to some extent on the 
 physical condition of the element. But there 
 seems certainly to be an interval of tempera- 
 ture for which the specific heat of an element 
 attains a constant, or nearly constant, value; 
 this temperature-interval varies for each element, 
 especially for the non-metallic elements with 
 small atomic weights ; for many elements it 
 may be approximately taken as 0° to 100°(C.). 
 
 ' There is, however, oonsidernble doubt whether the 
 material used by Weber was pure boron. 
 
 For this interval of temperature only can any 
 element be said to obey the law of Dnlong and 
 Petit. 
 
 This law may now be stated in a practical 
 form thus : — The atomic heat, i.e. the product of 
 specific heat, at the temperature-intervalfor which 
 sp. ht. is nearly constant, into atomic weight, of 
 all solid elements is nearly a constant, the mean 
 value of which is 6-4. If this is granted it 
 follows that the atomic weight of any solid 
 element is approximately equal to the quotient 
 
 = : provided that the specific heat of 
 
 spec, heat 
 
 the element has been determined for a consider- 
 able range of temperature, and, if the specific 
 heat has been found to vary considerably with 
 variations of temperature, that the determina- 
 tions have been continued until a constant, or a 
 nearly constant, value has been obtained. 
 
 Attem{>ts have been made to determine the 
 specific heats of several elements by an indirect 
 method. The method is based on the generalisa- 
 
 A 
 tion, — ^= a constant (about 6^4); where A = the 
 
 n 
 formula-weight of a solid compound, = the 
 specific heat of the compound, and n= the 
 number of elementary atoms in the formula of 
 the compound. This generalisation has been 
 stated in various forms ; the earliest appears to 
 be that given by P. Neumann, in 1831: 'The 
 amounts of chemically similar compounds ex- 
 pressed by their formulae possess equal specific 
 heats ' (P. 23, 1). The statement is some- 
 times put thus : ' the molecular heat of a solid 
 compound is equal to the sum of the atomic 
 heats of its constituent elements; ' by ' molecular 
 heat ' is here meant the product of the specific 
 heat of the compound into the mass expressed 
 
 A C 
 by its formula. The form given above, — ^ = a 
 
 n 
 constant, is the outcome of investigations made 
 principally by Gamier (O. B. 35, 278; 37, 130), 
 and Caunizzaro {Bl. 1863. 171). 
 
 As an example of the appUcation of this 
 generalisation, to find a value for the specifio 
 heat of an element in the solid form, let us take 
 Kopp's calculation of the specifio heat of solid 
 chlorine {J.. Suppl. 3, 321). The data are these : — 
 molecular heats (as defined) of metaUic haloid 
 salts: RCl = 12-8, BBr = lB-9, EI = 13^4; B,Gl^ = 
 18'5, EI2 = 19^4. In each case E represents one 
 atom of a metal the atomic heat of which is 6'4. 
 The atomic heat of solid bromine = atomic heat 
 of solid iodine = 6'6 (approximately). Now, as 
 the metallic chlorides, bromides, and iodides, 
 examined are chemically similar, and as the 
 ' molecular heats ' of the similar salts are nearly 
 the same, Kopp has concluded that the atomic 
 heat of soUd chlorine is approximately equal to 
 6'4. This conclusion is in keeping with the 
 observed values; thus: ECl (12-8)-E(6-4) = 
 
 6^4; ECl2(18^5)-E(6^4) = 12^1, and l|i= 6-05. 
 
 Further data are presented by the following 
 ' molecular heats ' : EC103 = 24-8, KAs03 = 25^3. 
 The argument here is, that as these values are 
 nearly the same, and as the difference in com- 
 position between the two compounds is represented 
 by the exchange of CI for As, it follows that the 
 atomic heat of solid chlorine is approximately 
 
ATOMIC AND MOLECULAR WEIGHTS. 
 
 346 
 
 equal to that of arsenic ; but the atomic heat of 
 arsenic, as determined by direct experiment, is 
 6'1, hence the atomic heat of solid chlorine is 
 approximately equal to 6'1. 
 
 This indirect method often leads, as might 
 be expected, to several values for the specific (or 
 atomic) heat of an element. Thus, from determina- 
 tions of the ' molecular heats ' of various oxides 
 and other salts containing metals the atomic heat 
 of each of which has been directly determined to 
 be approximately 6*4, the following values for 
 the atomic heat of solid oxygen are arrived at : 
 From KO 4-6 
 
 „ RO^ 3-7 
 
 „ E,0, 4-8 
 
 „ KAsOj 4-2 
 
 , , KCIO4 3-5 (assuming at. ht. of CI = 6) 
 
 „ KMnO, 3-8 
 The mean of these values is 4"1. 
 
 The indirect method of finding the atomic 
 heat of an element is undoubtedly useful, but 
 no great stress can be laid on conclusions ar- 
 rived at by this method only. It is certain that an 
 erroneous conclusion regarding the value of the 
 atomic weight of an element may be deduced 
 from measurement of the specific heats of solid 
 compounds of that element. For example, 
 Bonath determined the specific heat of uranoso- 
 uranic oxide to be -0798 (JB. 12, 742) ; assuming 
 the specific heat of solid oxygen to be 0'25 
 
 (4*X\ 
 = — J, the specific heat of uranium was calcu- 
 lated to be -0497 ; now -0497 x 120 = 5-96, there- 
 fore, as analyses of compounds had proved that 
 the atomic weight of uranium is to120, it was 
 ■joucluded by Donath that the atomic weight of 
 uranium is 120. But pure metallic uranium 
 was prepared shortly afterwards, and the specific 
 heat of this metal was directly determined to be 
 •028; now •028x120 = 3-3, but -028x240 = 6-6; 
 hence the atomic weight of uranium is much 
 more probably 240 than 120. The larger value 
 (240) has been confirmed by the preparation 
 and analyses of two gaseous compounds of 
 uranium {v. regarding this subject, Kopp, B. 
 19, 813). 
 
 The following statements fairly summarise 
 the results of the determinations of the atomic 
 heats of the elements : 
 
 I. Solid elements, 45 in tvumber, the sjaecific 
 heats of which have been directly determined, 
 and the atomic heats of which are all approxi- 
 mately equal to 6-4 : Li, Na, Mg, Al, P, S, K, 
 Ca, Ti, Mn, Fe, Co, Ni, Cu, Zn, As, Se, Br, Zr, 
 Mo, Eu, Eh, Pd, Ag, Cd, In, Sn, Sb, Te, I, La, Ce, 
 Di, W, Os, Ir, Pt, Au, Hg, Tl, Pb, Bi, Th, U. . . (Cr). 
 
 II. SoUd elements, 6 in number, the specific 
 heats of which have been directly determined, and 
 vary considerably with temperature, and the atomic 
 heats of which appea/r to be approximately equal 
 to 5-5: Ga (? inaccurately determined). Be, B, 
 C, Si, Ge. 
 
 III. SoUd elements, S in number, the specific 
 heats of which have been indirectly determined 
 and the atomic heats of which are probably 
 approximately equal to 6^4 : V, Eb, Sr, Cs, Ba. 
 
 IT. Gaseous elements ; specific heats in solid 
 form very doubtful, and apparently variable ; 
 H, (F), N, 0, CI. 
 
 It has been already shown that the applica- 
 
 tion of Avogadro's law enables a maximum 
 value to be found for the atomic weight of any 
 element which forms one or more compounds 
 gasifiable without decomposition. The maxi- 
 mum value thus found for the atomic weight 
 of aluminium was 54-04 ; but as this value was 
 based on analyses of only three gaseous com- 
 pounds, it was asserted that the true value was pos- 
 sibly one-half or one-third, &c. of this number. 
 Now, the specific heat of aluminium has been de- 
 termined to be -22 ; hence, assuming the law 
 of Dulong and Petit, the atomic weight of 
 aluminium must be approximately equal to 30 
 
 (30 X -22 = 6-6); therefore the value ^°-^ = 27-01 
 
 is assigned to the atomic weight of this metal. 
 The maximum values assigned to the atomic 
 weights of iron (111-8), copper (126-8), and 
 gallium (138), by the application of Avogadro's 
 law have, in each case, been halved when 
 determinations have been made of the specific 
 heats of these metals. 
 
 Various observations on the connexions 
 between the chemical composition and the 
 crystalline form of solid compounds had been 
 made previous to the year 1819, in which year 
 the ' law of isomorphism ' was propounded by 
 E. Mitscherlich ; this law was subsequently 
 modified and extended, and in 1821 Mitscherlich 
 stated it as follows : ' Equal numbers of atoms 
 similarly combined exhibit the same crystalline 
 form ; identity of crystalline form is indepen- 
 dent of the chemical nature of the atoms, and 
 is conditioned only by the number and con- 
 figuration of the atoms.' Further research has 
 shown that Mitscherlich's statement was too 
 absolute. On the one. hand, many solid com- 
 pounds are known, the atomic compositions of 
 which are very similar, and which, nevertheless, 
 crystallise not only in different forms, but in 
 different systems, thus : 
 
 PbCrOi is monoclinic, but PbMoO, is quadratic ; 
 AgCl and AgBr are regular, but Agl is hexagonal ; 
 KNO3 is rhombic, but CsNOa and EbNOj are 
 hexagonal. 
 
 On the other hand, many solid compounds 
 crystallise in identical or very similar forms, 
 and nevertheless exhibit unlike atomic compo- 
 sitions ; thus the crystalline form of the following 
 salts is the same : K2TiFsH20, CuTiFs4H20, 
 K^NbOF^H^O, CuNbOF,4H20, K^WO^F^H^O, 
 CUWO2F44H2O. Many ammonium salts crys- 
 tallise in the same forms as the corresponding 
 salts of potassium, but the number of atoms in 
 one formula-weight of these salts is different. 
 It is indeed somewhat difficult to give an exact 
 meaning to the expression 'isomorphous crys- 
 tals ; ' by this phrase some naturalists mean 
 crystals any one of which is capable of growing 
 in unmodified form when immersed in a solution 
 of any other (Kopp, B. 12, 900 et seq.) ; others 
 include crystals belonging to the same system 
 but exhibiting very small differences in the 
 measurements of their angles, e.g. the rhombo- 
 hedral carbonates of magnesium, calcium, iron, 
 zinc, and manganese ; others even include 
 crystals which very closely resemble each other 
 but yet belong to different systems. The fact 
 that the same compound may crystallise in two, 
 or even three, distinct forms, further compli- 
 cates the connexion between isomorphism and 
 
346 
 
 ATOMIC AND MOLECULAR WEIGHTS. 
 
 chemical composition; thug, araenioua oxide, 
 A.S4O5, and antimonious oxide, SbjOe, both crys- 
 tallise in regular ootahedra and also in rhombic 
 forms; titanium dioxide, TiOj, crystallises in 
 two forms belonging to the quadratic system, 
 but exhibiting very different relations of crys- 
 talline axes, and also in a third form, viz* 
 rhombic prisms. 
 
 The constituents of isomorphous compounds 
 are sometimes themselves isomorphous ; e.g. the 
 double compounds SAgjS.Sb^Sa and SAgjS.ASjSa 
 crystallise in identical forms, and the sulphides 
 SbjSs and AsjSs also orystaUise in identical 
 forms. On the other hand, the constituents of 
 isomorphous compounds are sometimes not 
 isomorphous ; e.g. the sulphates of magnesium, 
 nickel, and zinc, crystallise in rhombic forms, 
 but the oxides of magnesium and nickel crystallise 
 in regular, and oxide of zinc, in hexagonal, 
 forms. Isomorphism is sometimes not shown 
 in comparatively simple analogous compounds of 
 two elements, while the more complicated ana- 
 logous compounds of the same elements crys- 
 tallise in identical or very similar forms; e.g. 
 many of the simpler compounds of cadmium are 
 not isomorphous with the analogous compounds 
 of the magnesian metals (Mg, Ca, Mn, Fe, Go, 
 Ni, Zn, Cu), but the comparatively complex 
 salts of cadmium, such as CdSO4.KjSO4.6H2O, 
 are usually isomorphous with the analogous 
 salts of the metals named. Hence it is neces- 
 sary to distinguish strict isomorphism as applied 
 to bodies which exhibit the same or nearly the 
 same crystalline form, from the isomorphism of 
 bodies which, although themselves crystallising 
 in different forms, nevertheless combine with 
 one and the same third body to produce com- 
 pounds into which they enter as corresponding 
 elements or groups, and which crystallise in the 
 same forms {v. Kopp, Lehrbuch der Physikal. 
 Chemie, 2, 141). The crystalline forms of 
 several elements have been determined, but the 
 statement that such or such elements form an iso- 
 morphous group usually means only that ana- 
 logous compounds of these elements are for the 
 most part isomorphous {v. Isomorphism). 
 
 Notwithstanding the many qualifying clauses 
 with which any general statement of the con- 
 nexion between crystalline form and chemical 
 composition must, at present, be guarded, it has 
 frequently been found possible to use the 
 knowledge we have of the connexion in question 
 as a guide in researches concerning the atomic 
 weights of elements. In these cases it is assumed 
 that, as a general rule, those masses of two 
 bodies which can mutually replace each other 
 in compounds without change of the crystalline 
 form of the compounds, or in other words those 
 masses which are crystallographically equivalent, 
 have similar atomic compositions. By compounds 
 of similar atomic composition is here meant 
 compounds which are very analogous in their 
 chemical relations, and the formulsB of which 
 contain equal numbers of atoms, or groups of 
 atoms which react through series of changes as 
 if each were a single atom. 
 
 Now, if the atomic weight of a specified 
 element is known, and if experiment shows 
 that the mass of this element expressed by its 
 atomic- weight is crystallographically equivalent 
 to X unit masses of another element, it follows 
 
 that the value of x is very probably the value 
 of the atomic weight of the second element. 
 Thus, the facts that gallium sulphate formed 
 a double compound with ammonium sulphate, 
 and that this double sulphate was isomorphoua 
 with the alums, indicated that the double sul- 
 phate in question was a true alum ; hence the 
 general formula which expresses the composi- 
 tion of alums expresses the composition of the 
 double sulphate of gallium and ammonium. The 
 formula in question is X23S04.M2S04.24:H20, 
 where M = an alkali metal or thallium ; but in 
 common alum X^ = Alj = 2x27-02 parts by weight 
 of aluminium; and in gallium alum Xj was 
 experimentally determined to be 138 parts by 
 weight of gallium. Hence, as two atoms of 
 aluminium were replaced by 138 unit masses of 
 gallium without change of crystalline form, and 
 as the aluminium and gallium compounds were 
 very similar in their chemical relations, the 
 conclusion was drawn that 138 represents the 
 relative weight of two atoms of gallium ; there- 
 fore the value i|fi = 69 was deduced for the 
 atomic weight of gallium. This number was 
 afterwards confirmed by analyses of gaseous 
 gallium chloride, and by determinations of the 
 specific heat of the metal. It was at one time 
 supposed by H. Eose (P. 108, 273) that a 
 metal existed closely allied to, but not the same 
 as, niobium ; but Marignac {A. Oh. 60, 257) found 
 that compounds obtained from this hypothetical 
 metal were isomorphous with the corresponding 
 compounds of tin and titanium, and that the 
 groiips of atoms SnF and TiF could be replaced 
 by an atom of Eose's ' hyponiobium ' without 
 change of crystalline form. Hence Marignac 
 suggested that ' hyponiobium ' was a compound ; 
 and, because of various reactions, that it was 
 a compound of niobium and oxygen in the pro- 
 portion expressed by the formula NbO, where Nb 
 has the value 9i. If this were admitted it 
 followed that the groups NbO, SnP, and TiP, 
 were crystallographically equivalent in various 
 compounds; but if so, it also followed, from 
 analyses of the various compounds, that one 
 atom of tin ( = 117'8 parts by weight), and one 
 atom of titanium ( = 48 parts by weight), were 
 replaced by 94 parts by weight of niobium in 
 isomorphous compounds; therefore the atomic 
 weight of niobium was 94. This value was con- 
 firmed by determinations of the relative densities, 
 and by analyses, of the gaseous chloride and 
 oxychloride of niobium. In this case the com- 
 parison of the crystalline forms of compounds 
 led at once to a determination of the atomic 
 weight of an element, to a proof of the non- 
 existence of a hypothetical metal, and to the 
 recognition that a body supposed to bean element 
 was really a compound. An analogous case is 
 furnished by Eoscoe's researches on vanadium ; 
 in this case also the study of isomorphism led to 
 the correct determination of the atomic weight 
 of vanadium, and to the discovery that the body 
 supposed to be vanadium was in reality a 
 compound of this metal with oxygen {T. 1868. 
 1 et sell-). 
 
 No practical definition of the atomic weight 
 of an element can be given in terms of the data 
 of isomorphism. The foregoing examples serve 
 to show how these data are applied to supple- 
 ment those gained by the analyses of gaseous 
 
ATOMIC AND MOLECULAR WEIGHTS. 
 
 347 
 
 oompounds, and by determinations of the specific 
 beats, of the elements. 
 
 If the atomic weight of calcium is known, 
 ihen the isomorphism of the carbonates of Mg, 
 Sr, Ba, Pb, Mn, Zn, and Fe, with the carbonate 
 of calcium, helps to fix values for the atomic 
 weights of these 7 elements ; the isomorphism 
 of the sulphates of Co, Ni, and Cu, with sul- 
 phate of iron gives data from which values may 
 be deduced for the atomic weights of Co, Ni, and 
 Cu ; values are found for the atomic weights of 
 Tl and Hg from considering oompounds of these 
 elements isomorphous with corresponding oom- 
 pounds of Pb ; similarly, Zn and Cd — Fe, Al, and 
 Cr — form many isomorphous oompounds; many 
 manganates are isormorphous with selenates 
 and ohromates, some chromates are isomorphous 
 with molybdates and tungstates, permanganates 
 are frequently isomorphous with perohlorates 
 and periodates, hence values are found for the 
 atomic weights of Se, Cr, 01, and I, and also for 
 Mo, and W ; from copper we pass to silver 
 through the isomorphism of CujS and Ag^S ; 
 silver leads on to sodium and the alkali metals 
 on the one hand and to gold on the other hand ; 
 the compounds ES2 and BAS2 are isomorphous, 
 hence conclusions can be drawn regarding the 
 atomic weight of As, and from this the passage 
 is easy to conclusions regarding the atomic 
 weights of P, V, Sb, and Bi ; iron is connected 
 with Ti, and this with Si, Zr, Sn, and Th ; lastly, 
 given the atomic weight of Pt, Ir, Pd, Bo, Eu, 
 or Os, values can be assigned to the other metals 
 of this group from a study of the composition 
 of isomorphous compounds of these metals. 
 Thus it is seen how helpful is the study of iso- 
 morphism in determining the atomic weights of 
 the elements. 
 
 These then are the three generally applica- 
 ble methods whereby values may be found for 
 the atomic weights of the elements : the method 
 founded on the law of Avogadro; the method 
 based on the study of the specific heats of sohd 
 elements ; and the method which considers the 
 relations between the chemical composition and 
 the crystalline form of similar compounds. 
 The first of these methods can be applied to 
 determine the atomic and molecular weights of 
 elements and the molecular weights of com- 
 pounds, but the application is restricted to 
 bodies which are gasifiable without decomposi- 
 tion ; the second and third methods can be 
 applied, strictly speaking, only to find values 
 for the atomic weights of solid elements or of 
 elements which form solid compounds. 
 
 All the methods are essentially physical ; they 
 are based on physical conceptions, and they are to 
 a great extent developed by physical reasoning. 
 
 The conception of the molecule of a gaseous 
 element or compound which is implied in the 
 statement, ' equal volumes of gases contain equal 
 numbers of molecules,' is wholly physical. The 
 image of the molecule which this statement calls 
 up in the mind is that of a small definite por- 
 tion of matter ' which moves about as a whole 
 BO that its parts, if it has any, do not part 
 company during the motion of agitation of the 
 gas ' (Clerk Maxwell). It is when this con- 
 ception is applied to chemical changes that we 
 are forced to admit that in many of these 
 changes the parts of molecules do part company; 
 
 thus we are led to the chemical conception of 
 the atom, as a portion of matter smaller than 
 the molecule, and either itself without parts, or 
 else composed of parts which, so far as we 
 know at present, do not part company during 
 any of the changes which the atom undergoes. 
 Then we proceed to study the properties of 
 these atoms; and among these properties we 
 seem to find two of great importance ; the pro- 
 perty namely which is expressed in the state- 
 ment that the atoms of all solid elements, at 
 certain temperatures, have equal capacities for 
 heat ; and the property which may be expressed 
 in the statement that identity of crystalline 
 form among compounds is usually accompanied 
 by equality in the number of atoms of which the 
 chemically reacting masses of these compounds 
 are composed. 
 
 But here we ask : are the molecules of iso- 
 morphous compounds built up of equal numbers 
 of atoms? Can the physical conception of 
 molecule, which has been gained by the study 
 of gaseous phenomena, be applied to solid com- 
 pounds ? And the answer at present is : it is 
 those smaU masses of isomorphous oompounds 
 which take part in chemical reactions, which as 
 a rule, are composed of equal numbers of atoms. 
 The physical definition of molecule cannot, in 
 the present state of knowledge, be safely applied 
 to solid and liquid bodies. Thus we seem to 
 arrive at two conceptions, and two definitions, 
 of the molecule. On the one side we have the 
 physical conception, as that of a small mass of 
 a gaseous element or compound which moves 
 about as a whole, and the parts of which do not 
 part company during the motion of agitation of 
 the gas ; and on the other side we have the 
 chemical conception, as that of the smallest mass 
 of an element or compound which takes part in 
 a chemical change, and which exhibits the pro- 
 perties of the specified element or compound. 
 
 The first of these definitions holds good 
 whether the small particles of a, gas are them- 
 selves composed of smaller particles, or are 
 chemically indivisible. The volume occupied by 
 a number of gaseous molecules is independent 
 of the numbers of atoms which by their union 
 form these molecules : in one case a gaseous 
 molecule may consist of a single atom (Hg and 
 Cd), in another case a gaseous molecule may bo 
 formed by the union of 2 atoms (HCl), 3 atoms 
 (H2O), 9 atoms (CjH^O), 11 atoms (OjHsOj), or 
 a much larger number of atoms ; but in every 
 case, equal volumes of the gases contain equal 
 numbers of molecules. But we know of no 
 single property of liquid and solid compounds 
 which is similarly independent of the number 
 of atoms forming the atomic complex or react- 
 ing chemical unit of the compound. 
 
 Let us consider the conception of the chemi- 
 cally reacting unit or collocation of atoms a 
 little more closely. We have already seen that 
 the application of the empirical laws of chemical 
 combination could not lead to final determina- 
 tions of the atomic weights of elements, because 
 these laws could not enable chemists to deter- 
 mine which of several values should be given to 
 the smallest mass of a compound capable of ex- 
 hibiting the properties of that compound. The 
 value 8, 16, 24, &c. would be assigned to the 
 atomic weight of oxygen, according as the 
 
S48 
 
 ATOMIC AND MOLECULAR WEIGHTS. 
 
 'atom' of water— that is, in Daltonian language, 
 the smallest mass of water which exhibits the 
 properties whereby water is distinguished from 
 all other kinds of matter — was assumed to be 
 9, 18, 27, &c. times heavier than the atom of 
 hydrogen. But a study of the properties of 
 water leads to the conclusion that the ' atom ' of 
 water very probably contains two atoms of hy- 
 drogen and one of oxygen, and that the atomic 
 weight of oxygen is therefore more probably re- 
 presented by the number 16 than by the number 
 8. Thus, if 9 grams of water react with 
 chlorine or bromine in sunlight 8 grams of 
 oxygen are evolved, and 36'5 grams of a com- 
 pound of hydrogen with chlorine, or 81 grams of 
 a compound of hydrogen with bromine, are pro- 
 duced; in the former case, the 36-5 grams of the 
 chlorine compound are proved by analysis to be 
 composed of 35-5 grams of chlorine and 1 gram 
 of hydrogen ; in the latter case, the 81 grams of 
 the bromine compound are proved to be com- 
 posed of 80 grams of bromine and 1 gram of 
 hydrogen ; in both cases the whole of the oxygen 
 of the 9 grams of water is removed from com- 
 bination with the hydrogen and makes its ap- 
 pearance as free oxygen. Again, if 9 grams of 
 water are acted on by potassium, -5 grams of 
 hydrogen are evolved, and 28 grams of a com- 
 pound of potassium, hydrogen, and oxygen, con- 
 taining 8 grams of oxygen — i.e. all the oxygen 
 originally combined with hydrogen in the 9 
 grams of water — are at the same time produced ; 
 if these 28 grams of the new compound are dried, 
 fused, and, while molten, are acted on by potas- 
 sium, -5 grams of hydrogen are evolved, and 47 
 grams of a new compound of potassium and oxy- 
 gen are produced, which 47 grams contain the 
 whole of the oxygen {i.e. 8 grams) originally 
 combined with hydrogen in the 9 grams of 
 water. These experiments prove that the hydro- 
 gen in a specified mass of water can be removed 
 from that mass of water in two equal portions, 
 but, so far as these experiments go, that the 
 oxygen in the same mass of water is either not 
 removed at aU, or is wholly removed, from com- 
 bination with hydrogen. Hence the conclusion 
 is drawn that the smallest reacting mass of 
 water contains one chemically indivisible mass 
 of oxygen, but two chemically indivisible masses 
 of hydrogen. But masses of hydrogen and oxy- 
 gen are combined in water in the ratio 1:8; 
 hence, if the smallest reacting mass of water is 
 composed of 2 smallest parts, i.e. atoms of hydro- 
 gen, and one smallest part, i.e. atom, of oxygen, 
 it follows that the atomic weight of oxygen is at 
 least 16, that of hydrogen being unity, and that 
 the relative mass of the smallest reacting portion, 
 that is the reacting weight, of water is repre- 
 sented by the number 18, not by the number 9. 
 What value is to be assigned to the reacting 
 weight of marsh gas? Masses of carbon and 
 hydrogen combine to form marsh gas in the 
 ratio 3:1 ; hence the value we are seeking can- 
 not be less, but may be greater, than 4. If 4 
 grams of marsh gas are acted on by chlorine, a 
 series of 4 compounds is produced ; the first of 
 these compounds contains chlorine and hydrogen 
 combined with carbon, the masses of carbon and 
 hydrogen being in the ratio 3: -75 ; the second 
 and third contain the same three elements, in 
 the second the carbon and hydrogen are in the 
 
 ratio 3: -6, and in the third in the ratio 3: -23 ; 
 the fourth is a compound of the whole of ths 
 carbon originally combined vrith hydrogen in 
 the 4 grams of marsh gas with chlorine, and con- 
 tains no hydrogen. If now 4 grams of marsh 
 gas are burnt in a plentiful supply of oxygen 
 11 grams of carbon dioxide are produced, or if 
 the same mass of marsh gas is burnt in a limited 
 supply of oxygen 7 grams of carbon monoxide 
 are produced ; in each case the oxide of carbon 
 formed contains the whole of the carbon origi- 
 nally combined vrith hydrogen in the 4 grams of 
 marsh gas used. No compound has yet been 
 obtained from 4 grams of marsh gas containing 
 a smaller mass of carbon than was originally 
 present in the marsh gas, i.e. containing less 
 than 3 grams of carbon. The conclusion drawn 
 from these experiments is that the smallest mass 
 of marsh gas which can take part in chemical 
 changes is itself most probably composed of at 
 least 4 atoms of hydrogen combined with at 
 least one atom of carbon ; but if this is granted 
 it follows that an atom of carbon is 12 times 
 heavier than an atom of hydrogen, and that the 
 reacting weight of marsh gas is represented by 
 a number certainly not smaller than 16. 
 
 We have thus determined, on chemical 
 grounds and by chemical reasoning, the follow- 
 ing values for the atomic weights of two ele- 
 ments : (H = l) = 12, = 16. Now let us 
 consider a compound of these elements. The 
 simplest formula that can be given to acetic acid 
 consistently with the values H = l, C = 12, 
 = 16, is CH2O. If this acid is neutralised by 
 soda, and the sodium salt so formed is analysed, 
 this salt is found to be composed of the same 
 masses of carbon and oxygen, combined with f 
 the mass of hydrogen, which were present in 
 the mass of acid used ; hence the smallest re- 
 acting mass of acetic acid must contain at least 
 4 atoms of hydrogen. But if this is granted 
 it follows, from the fact that the elements are 
 combined in the ratio C:2H:0, that this smallest 
 reacting mass must also contain at least 2 atoms 
 of carbon and 2 atoms of oxygen, and that the 
 formula expressing the composition of the re- 
 acting weight of the acid in question must be 
 written C2H4O2. Further evidence in support 
 of this conclusion is afforded by the preparation 
 of thio-acetic acid, which is composed of carbon, 
 hydrogen, oxygen, and sulphur, the carbon and 
 hydrogen being present in the same ratio as in 
 acetic acid, but the oxygen being present in the 
 ratio of 16 to 4 hydrogen (i.e. 0:4H), and the 
 sulphur in the ratio 32 to 4 hydrogen. Now the 
 atomic weight of sulphur is almost certainly 32 ; 
 hence the simplest formula which expresses the 
 composition of the reacting weight of thio- 
 acetic acid is CjHjOS. In this case, 5 of the 
 oxygen of the reacting weight of acetic acid is 
 replaced by sulphur without any further change 
 in the composition of the acid ; hence, there must 
 be at least 2 atoms of oxygen in the reacting 
 weight in question, because atoms are (by defi- 
 nition) chemically indivisible. 
 
 This is an example of the general proposition 
 
 that when - of a constituent element of the 
 n 
 
 reacting weight of a given compound can be re- 
 placed by another element without any othet 
 
ATOMIC AND MOLECULAR WEIGHTS. 
 
 340 
 
 thange in the oompositiou of the original sub- 
 stance, it follows that the reacting weight in 
 question must contain at least n atoms of the 
 element which has been removed; and that if 
 the atomic weight of the replacing element is 
 known, it is easy to calculate, from the com- 
 position of the original substance, the masses of 
 the other constituents which must be present 
 united with the n atoms of the specified element, 
 and hence to assign a minimum value to the 
 reacting weight of the original substance. 
 
 When a formula has been assigned to a 
 compound by such chemical methods as those 
 now sketched, it is frequently possible to argue 
 from this to the formulae of similar compounds. 
 Thus, the properties and the methods of forma- 
 tion of sulphide of hydrogen show that this com- 
 pound is similar to oxide of hydrogen (water) ; 
 but if the reacting weight of water is repre- 
 sented by the formula H^O, that of sulphuretted 
 hydrogen is probably represented by the formula 
 HjS; again, the marked analogies between the 
 sulphide, selenide, and teUuride, of hydrogen 
 suggest that these compounds have similar 
 compositions ; but if the first named is H2S, the 
 others are probably HjSe, and H^Te, respec- 
 tively. If these formulae are admitted, values 
 are at once found for the atomic weights of the 
 three elements, sulphur, selenion, and tellurium. 
 Again, the metal magnesium reacts with water 
 in the ratio of 24 parts by weight of the metal 
 to 18 parts by weight of water, the products of 
 this action being, (1) an oxide of magnesium 
 containing 16 parts by weight of oxygen united 
 with 24 parts by weight of magnesium, and (2) 
 two parts by weight of hydrogen ; hence, as 
 the reacting weight of water is represented by 
 the formula H^O, that of magnesium oxide is 
 probably represented by the formula MgO, where 
 Mg = 24 parts by weight of magnesium ; and hence 
 the atomic weight of magnesium is probably 24. 
 
 The chemical methods for determining the 
 atomic weights of elements then lead to a defi- 
 nition of atomic weight which may be stated 
 thus : the atomic weight of an element is a 
 number which tells how many times greater is 
 the smallest mass of that element found in the 
 chemically reacting weight of any of its com- 
 pounds than the smallest mass of hydrogen 
 found in the chemically reacting weight of any 
 compound of hydrogen, such smallest mass of 
 hydrogen being taken as unity. The diflaculty 
 in applying this definition lies in the vagueness 
 of the expression ' the chemically reacting weight 
 of a compound.' This expression cannot be de- 
 fined ; the illustrations already given indicate 
 the interpretation usually put upon it, and also 
 the methods whereby approximately accurate 
 values are obtained for it in special oases. 
 
 The physical conception of molecule is clear, 
 and admits of being put into words which have 
 a definite quantitative meaning; this conception 
 leads to that of the atom, the definition of 
 which may also be put into a quantitative form. 
 But the definition of the molecule is strictly 
 applicable only to gases ; hence arises the need 
 of a subsidiary definition. We conceive chemical 
 changes occurring among liquid and solid bodies 
 as occurring among the smallest particles of 
 these bodies which are capable of existing as 
 wholes and of exhibiting the properties of the 
 
 bodies in question. These smallest particles wu 
 may call the chemically reacting units, or the 
 reacting weights, of the bodies ; they are gene- 
 rally called molecules ; but if we use this term 
 we must not forget that it is employed in a 
 somewhat vague manner, and without the strict 
 quantitative signification which is attached to it 
 when we speak of the molecule of a gas. 
 
 It seems probable that the mass of the 
 chemically reacting unit of a compound varies, 
 within certain not very wide limits, in different 
 reactions. This mass must of course always be ex- 
 pressed by a whole multiple of a certain number ; 
 but it is probable that the value of the multiple 
 varies. Thus many of the reactions of potassium 
 permanganate can be simply expressed by 
 assigning to the reacting weight of this salt the 
 formula EMnO,; but other reactions indicate 
 that this formula should be doubled and written 
 KjMnjOg. Again, periodic acid generally reacts 
 as if the smallest particle which exhibits the 
 chemical properties of this acid had the mass 
 228, and were composed of hydrogen, iodine, 
 and oxygen, combined as shown in the formula 
 HsIOs; but some of the reactions of periodic 
 acid are more simply explained by doubling the 
 formula, and writing it 'R^J.-fi^p Indeed, even 
 in the case of gaseous elements and compounds, 
 we have sometimes direct evidence to show that 
 the molecular weight of the gas varies with 
 variations of temperature. Consider, for in- 
 stance, the following data : — 
 
 Spec. geav. of Iodine gas {Air = l), 
 
 Pressure 
 
 760 mm. 
 
 )» 
 
 »» 
 
 76 mm. 
 
 
 Temperature 
 
 448° 
 
 855 
 
 7 ri275 
 
 S { 1470 
 
 1 Ll250 
 
 
 Sp.gr. 
 8-74 
 8-07 
 5'82 
 5-06 
 4-72 
 
 Spec. geav. 
 
 OF SUIPHUR GAS 
 
 (A 
 
 ir = l). 
 
 Pressure 
 760 mm. 
 
 »» 
 
 (cf. 
 
 Temperature 
 520° 
 660 
 860 
 
 SULPHUE, vol. iv.] 
 
 
 Sp. gr. 
 6-62 
 2-93 
 2-23 
 
 Spec. geav. of Acetic acid gas 
 
 (A 
 
 r = l). 
 
 Pressure 
 760 mm. 
 
 
 Temperature 
 124° 
 
 
 Sp. gr. 
 3-20 
 
 130 3-11 
 
 „ 160 2-48 
 
 „ 230 209 
 
 „ 280 208 
 
 338 2-08 
 
 Spec. geav. op Niieogen teikoxide gas (Air = 1). 
 
 Pressure Temperature Sp. gr. 
 
 125 mm. -6° 3-01 
 
 138 „ H-1 2-84 
 
 760 „ 70 1-93 
 
 „ „ 135 1-60 
 
 „ .. 183 1-57 
 
 The density of iodine gas would be 8-77 if 
 the composition of the molecule were repre- 
 sented by I2, and 4-38 if the composition of the 
 molecule were represented by I: the numbers 
 given point to the existence of molecules 
 having the composition Ij at comparatively low 
 
850 
 
 ATOMIC AND MOLECULAR WEIGHTS. 
 
 fcemperaturea, and having the composition I at 
 high temperatures when the gas is under a 
 small pressure. The numbers given for sulphur 
 gas suggest the existence of molecules So at tem- 
 peratures from b.p. to c. 650°, and of molecules 
 Sj from c. 650° to o. 1000° ; but more recent re- 
 sults throw considerable doubt on the accuracy 
 of this conclusion (c/. Sulphub, vol. iv.) In 
 the case of acetic acid gas, experiments indicate 
 the existence of two different molecules ; the 
 data point to the existence of the molecules 
 OjHjOj (calculated sp. gr. = 2-08, air = l) at 
 about 230° and upwards, but to the existence of 
 heavier molecules, CsHbOj (calculated sp. gr. = 
 3-12, air = 1), at about 120°-130°. Lastly, the 
 existence of the molecules N2O4 (calculated 
 sp. gr. = 3'18) in gaseous nitrogen tetroxide at 
 low temperatures and pressures, and of the 
 molecules NOj (calculated sp. gr. = l-59) at 
 higher temperatures, is indicated by the numbers 
 which represent the observed relative densities 
 of this gas. The sp. gravs. of some gases slowly 
 decrease as temperature rises until a value is 
 attained which remains constant throughout a 
 considerable interval, e.g. iodine, acetic acid, 
 nitrogen tetroxide, gases ; in other cases the sp. 
 gr. remains nearly constant throughout a con- 
 siderable range of temperature, and then rapidly 
 decreases until another constant value is reached, 
 which again remains constant for a considerable 
 temperature-interval, e.g. sulphur gas {0. Dis- 
 BOCIATION, also Allotbopy, and Isomeeism). But 
 in both classes of gases the data point to the 
 existence, at different temperatures, of more or 
 less stable molecules, the mass of the heavier 
 of which is a whole multiple of that of the 
 lighter. 
 
 The practical conclusions to be drawn from 
 these facts are, that before the molecular weight 
 of u gas can be regarded as satisfactorily deter- 
 mined, observations of the sp. gr. of that gas must 
 be made throughout a considerable range of 
 temperature ; and that the number which 
 represents the sp. gr. in question for such a 
 range of temperature is to be taken as the basis 
 for calculating the molecular weight of the gas, 
 or it may be in some cases the numbers which 
 represent the sp. gravs., each for a considerable 
 temperature-interval, are to be used for finding 
 the different molecular weights of the gas. 
 
 If then the mass of the molecule of a gas 
 may have a different value, and therefore the 
 molecule be composed of a different number of 
 atoms, at a high than at a low temperature — 
 and so far as data goes it seems that the mass 
 of the molecule, if variable, is greater at tempe- 
 ratures near the condensation point than at 
 temperatures far removed from this point — it is 
 at least very probable that, if we carry over the 
 conception of the molecule from gases to liquids 
 and solids, we must be prepared to regard the 
 mass of the molecule of a liquid or solid com- 
 pound as considerably greater than that of the 
 molecule of the same compound in the gaseous 
 state. But, in practice, when we speak of the 
 molecular weight of a liquid or solid compound 
 we use the term molecular weight with a mean- 
 ing different from that which we assign to it 
 when we speak of the molecular weight of a gas. 
 In the latter case the term signifies a small 
 mass of matter, itself built up of smaller parts, 
 
 which collides with other similar small masses, 
 rebounds, vibrates, but yet remains intact, 
 when a number of these small parts of matter 
 are heated ; in the former case the term sum- 
 marises a number of chemical data in a con- 
 venient form, and asserts that the number of 
 atoms which are so associated as to act in 
 many changes as a chemical whole, is not less 
 than a certain specified number. 
 
 The chemical formulae of solid and liquid 
 bodies do not then stand on the same footing 
 as the formulae of gases (v. Fobmul2b). But the 
 question arises : are these collocations of atoms 
 which we have called reacting chemical units 
 also the reacting physical units of this or that 
 compound? Are the physical constants of com- 
 pounds conditioned by the masses of these re- 
 acting units? If these questions are answered in 
 the affirmative, it is possible that measurements 
 of some physical constant for a series of chemi- 
 cally similar compounds might enable just con- 
 clusions to be drawn regarding the relative masses 
 of the reacting units of- these compounds. Many 
 measurements of this kind have been made ; 
 but no wide generalisation has yet been found 
 which enables us to determine the relative 
 masses of the reacting units of solid and liquid 
 compounds from a knowledge of the physical 
 constants of these compounds. All the general- 
 isations which have been, or which at present 
 can be, ventured upon, are for the most part 
 empirical : the theory of the grained structure 
 of matter has been developed, so far as it has 
 been developed, only for gases ; as regards gases, 
 conclusions can be drawn from the fundamental 
 principles of the theory, and these conclusions 
 can be tested by experiment ; but as regards 
 liquids and solids, no such general conclusions 
 can be drawn, and the theory can be used as a 
 guide in experimental research only in a wide 
 and general manner. What is wanted now is 
 therefore not only further experimental deter- 
 minations of the physical constants of series of 
 chemically similar compounds, but a great 
 development of the general theory of the struc- 
 ture of matter, especially in the direction of 
 applying this theory to liquid and solid bodies 
 
 (■y. MOLEOULAB THEOBIES, alsO PhYSIOAIi METHODS). 
 
 The great difficulty lies in the fact that most 
 of the physical constants of liquid and solid 
 compounds appear to be conditioned both by 
 the nature and number, on the one hand, and 
 by the modes of combination, on the other 
 hand, of the atoms which form the atomic 
 complexes we have called reacting chemical 
 units. But the kinetic theory of gases has been 
 chiefly developed from the study of properties 
 which are independent of the nature and num- 
 ber, and are conditioned only by the states of 
 union, of the parts of molecules. 
 
 But although we must for a time be content 
 with the conception of the chemically reacting 
 unit of a liquid or solid compound, and although 
 we may at times wistfully contrast this with 
 the clear physical conception of the molecule of 
 a gas, yet there is one well-established chemical 
 generalisation by the application of which values 
 may be obtained for the atomic weights of many 
 elements. This generalisation may be stated 
 thus : — The properties of the elements vary 
 periodically with variations in the atomic 
 
ATOMIC AND MOLECULAR WEIGHTS. 
 
 351 
 
 of the elements ; or thus : — If the 
 elements are arranged in order of increasing 
 atomic weights, the properties of the elements 
 vwryfrom element to element, but return more 
 or less nearly to the same values at certain 
 fixed points in the series. Let the elements be 
 arranged in the order of their atomio weights, 
 from hydrogen to uranium ; let them be divided, 
 broadly, into series of sevens; let the second 
 series be placed under the first, the third under 
 the second, and so on ; then the elements con- 
 tained in any one vertical column are called a 
 group, and those in any one horizontal column 
 are called a series. In this arrangement hydro- 
 gen is placed in a series by itself, and under it, 
 that is in the same group, is placed the element 
 (lithium) which comes next after hydrogen in 
 order of increasing atomic weight ; certain gaps 
 are also supposed to occur in the list of elements, 
 so that an element which immediately succeeds 
 another in order of increasing atomic weights is 
 sometimes placed, not in the group immediately 
 succeeding, but in the group next but one or next 
 buttwo (fee. after, that which contains the element 
 with the smaller atomio weight. Thus uranium 
 (240) comes after thorium (232) in order of atomio 
 weights ; thorium is placed in group IV. ; but 
 uranium is placed in group VI. Certain elements 
 are also placed in an eighth group by themselves ; 
 and the last member of each series in this group 
 is repeated as the first member of the next 
 series in group I. 
 
 The following table shows the arrangement 
 of the elements in accordance with the periodic 
 law. The formula at the head of each group 
 represents the composition, either of the highest, 
 or of the most characteristic, oxide of the ele- 
 ments belonging to that group ; in each case 
 the formula gives the number of atoms of oxygen 
 referred to two atoms of the element. 
 
 parts, and to examine the nature of the con- 
 nexion between the atomio weights, and such 
 measureable properties, of the elements, as 
 atomic volume 
 
 ( i.e. the quotient 
 
 atomic weight 
 
 S.G. of solid element/ 
 
 position in electrical series, fusibility, composi- 
 tion of oxides, chlorides, &o., wave lengths of 
 characteristic lines in the spectra, heats of com- 
 bustion or of combination with chlorine, &o. 
 &o. The expression ' properties of the elements ' 
 is also to be taken as including the properties of 
 the compounds of the elements ; so that the 
 periodic law asserts that e.g. the melting-points 
 of similar compounds (say of chlorides) vary 
 periodically with variations in the atomio 
 weights of the elements. 
 
 The periodic law will be discussed in detail 
 in the article with that heading; meanwhile 
 sufiice it to say that the law rests on a firm 
 basis of well-established facts of diverse kinds. 
 We shall here make use of this law to establish 
 values for the atomic weights of one or two 
 typical elements. 
 
 At the time of the publication of Mendeldeff's 
 first memoir on the periodic law no elements 
 were known which could be placed in group III. 
 series 4 and 5. Calcium (40) and titanium (48) 
 were known; zinc (65) and arsenic (75) were 
 known : calcium and zinc evidently belong to 
 the group which comprises magnesium, stron- 
 tium, cadmium, and barium ; titanium must be 
 placed in the same group as carbon, silicon, and 
 tin ; and arsenic could not be separated from 
 phosphorus, vanadium, and antimony. Hence 
 two gaps occurred in group III. (series 4 and 5), 
 and one in group IV. (series 5). From consider- 
 ing the difference between the values of the 
 atomio weights of consecutive elements, (1) in 
 
 
 GEOUPS. 
 
 1 
 
 I. 
 
 II. 
 
 III. 
 
 lY. 
 
 V. 
 
 VI. 
 
 VII. 
 
 vin. 
 
 
 E.0 
 
 E,0, 
 
 EA 
 
 EA 
 
 EA 
 
 EA 
 
 E.0, 
 
 [EAl 
 
 1 
 
 2 
 
 H=l 
 
 Li=7 
 
 Be=B 
 
 B=ll 
 
 0=12 
 
 N=14 
 
 "3=16 
 
 F=19 
 
 
 3 
 
 4 
 
 Na=23 
 E=39 
 
 M:g=24 
 Ca=40 
 
 Al=27 
 So=44 
 
 Si =28 
 Ti=48 
 
 P=31 
 T=51 
 
 S=32 
 Cr=52 
 
 01 = 35-5 
 Ma=66 
 
 fFe=56 Ki=68-6 
 1 Oo=69 Ca=63 
 
 5 
 6 
 
 (Oa=63) 
 Bb=85 
 
 Zn=65 
 Sr=87 
 
 Ga=69 
 T=89 
 
 Ge=72 
 Zr=90 
 
 As=75 
 Nb=94 
 
 Se=79 
 Mo = 06 
 
 Br=80 
 (? 100) 
 
 fEIi=104 Eu=104-6 
 tPd=106 Ag=108 
 
 7 
 8 
 
 '^ET^tU 
 
 Od=112 
 Ba=137 
 
 In=114 
 La=139 
 
 Sn = 118 
 Oe=140 
 
 Sb = 120 
 Pi =144 
 
 Te=125 
 ? 149 
 
 1 = 127 
 ?150 
 
 ? 152— 166 4EIemeut8? 
 
 9 
 
 10 
 
 
 
 
 
 El-=166 
 Ta=182 
 
 ? 167 
 W=I8i 
 
 ? 169 
 7 190 
 
 
 ? 4 BU 
 ?170 
 
 .ments 166 to 162 ? 
 
 ? 172 Tb=173 
 
 ? 178 
 
 (Os=191 Ir=102-5 
 tPt=194 Aa=137 
 
 11 
 
 (Au = 197) 
 
 Hg=200 1 Tl=204 
 
 Pb=207 
 Th=232 
 
 Bi=208 
 ?237 
 
 
 
 
 ? 2 Elements 
 17=240 
 
 212 to 220 ? 
 ? 245 
 
 
 12 
 
 ? 3 Elements 220 to 230 ? 
 
 
 In order to establish the existence of a 
 periodic connexion between the atomic weights 
 and the properties of the elements, it is neces- 
 sary to break up the phenomena connoted by 
 the phrase ' properties of the elements ' into 
 
 the same series — the average value of this dif- 
 ference is about 2 in series 3, 4, and 5 — and (2) 
 in the same group— the average value of this 
 difference for the first, second, and third mem- 
 bers of groups I., II., and III., and for the first 
 
352 
 
 ATOMIC AND MOLECULAR WEIGHTS. 
 
 and second members of groups IV., V., VI., and 
 VII., is about 15, and for the succeeding members 
 of these groups it is about 23— MendelSeff 
 assigned the value 44 as approximately that of 
 the atomic weight of the unknown element in 
 series 4 of group III., and the value 69 as 
 approximately that of the atomic weight of the 
 unknown element in series 5 of the same group. 
 Mendel^efE also predicted many of the properties 
 of these two unknown elements from considering 
 the positions they occupied in the ' periodic ' 
 arrangement of the elements. Thus, the rela- 
 tions of the unknown element with atomic weight 
 44 to aluminium should be similar to those 
 between (1) calcium and magnesium, (2) tita- 
 nium and silicon, (3) vanadium and phosphorus, 
 (4) chromium and sulphur ; again the relations 
 between (1) beryllium and calcium, (2) carbon 
 and titanium, (3) nitrogen and vanadium, (4) oxy 
 gen and chromium, (5) fluorine and mangan* •,,' 
 ought to be similar to the relations between boron 
 and the unknown element. As regards the pro- 
 perties of the second unknown element with 
 atomic weight 69, it was known that (1) zinc is 
 more like magnesium than it is like calcium, (2) 
 arsenic more resembles phosphorus than it does 
 vanadium, (3) selenion shows closer analogies 
 with sulphur than with chromium, and (4) bro- 
 mine and chlorine are more like each other than 
 either is like manganese ; hence, it was argued, 
 the unknown element (69) will resemble alumi- 
 nium more closely than it resembles the other 
 unknown element (44), and more closely than 
 the second unknown element itself resembles 
 aluminium. The relationships indicated were 
 of course studied in detail by Mendel^eff. Thus, 
 take the pairs of consecutive elements in series 
 3 and 4 ; the resemblance between any of these 
 pairs (Na,K; Mg, Ca ; Si, Ti ; P, V; S, Cr; 
 CI, Mn) is less marked in the higher than in 
 the lower groups. Or, take the two elements in 
 each group belonging respectively to series 3 and 
 5 ; the resemblance between any of these pairs 
 (Na, Cu ; Mg, Zn ; . . .P, As ; S, Se ; CI, Br) 
 is more marked in the higher than in the lower 
 groups. 
 
 The relationships examined by Mende- 
 16efE were those between atomic weights, fusi- 
 bilities, atomic volumes, composition of oxides 
 chlorides and other compounds, acid or basic 
 character of oxides, power of forming double 
 salts and composition of these salts if formed, 
 &o. &o. As a result of his study of these 
 relationships, MendelSeft tabulated many pro- 
 perties of the two unknown elements. Since 
 the memoir of the Eussian naturalist was 
 published, several new elements have been dis- 
 covered ; some of the properties of two of these 
 elements will now be compared with the pro- 
 perties which MendeUef asserted ought to 
 characterise the elements belonging respectively 
 to series 4 and 5 of group III. 
 
 Mendeleiff's Eka-aluminium (III.-5). 
 
 Atomic weight about 69. 
 
 Eeadily obtained by reduction. 
 
 Melting-point low. Sp. gr. = 5'9. 
 
 Not acted on by air. 
 
 V^ill decompose water at a red heat. 
 
 Slowly attacked by acids or alkalis. 
 
 Will form a potassium alum more soluble. 
 
 but less easily orystallisable, than the corre- 
 sponding aluminium salt. 
 
 Oxide = El A- Chloride = EljOI,. 
 
 OalUum. 
 
 Atomic weight = 69. 
 
 Eeadily obtained by electrolysing alkaline 
 solutions. 
 
 M.P. = 30-15°. Sp. gr. = 5-93. 
 
 Non-volatile, and but superficially oxidised 
 in air at bright red heat. 
 
 Decomposes water at high temperatures. 
 Soluble in hot hydrochloric acid, scarcely 
 attacked by cold nitric acid ; soluble in caustio 
 potash. 
 
 Forms a well-defined alum. 
 
 Chloride = Qa-fil^. Oxide = Gufl,. 
 
 Mendelieff's Eka-boron (III.-4). 
 
 Atomic weight about 44. 
 
 Oxide EbjOj soluble in acids ; sp. gr. about 
 3'5 ; analogous to but more basic than AljO, ; 
 less basic than MgO ; insoluble in alkalis. 
 
 Salts of Eb colourless, and will yield gela- 
 tinous precipitates with KOH, KjCOj, Na^HPO,, 
 &o. 
 
 Sulphate, Ebj.SSO,,, will form a double salt 
 with K2S04, probably not isomorphous with the 
 alums. 
 
 Chloride EbCl, or Eb^Cl^, sp. gr. about 2, less 
 volatile than AljClj. 
 
 Scandium. 
 
 Atomic weight = 44. 
 
 Oxide S02O3 ; sp. gr. = 3-8 ; soluble in strong 
 acids ; analogous with but more decidedly basic 
 than AI2O3 ; insoluble in alkalis. 
 
 Solutions of So salts colourless and yield 
 gelatinous precipitates with KOH, K^CO,, and 
 NajHPO,. 
 
 Sulphate, SCj.3S0j, forms a double salt, not 
 an alum, Sc^SSOj-SK^SO,. 
 
 Gallium and scandium are, therefore, the ele- 
 ments which Mendel^eff named eka-aluminium 
 and eka-boron, and many properties of which 
 were accurately and in detail tabulated by him, 
 while the elements were yet unknown. 
 
 Much discussion has of late been carried on, 
 and a great deal of experimental work has been 
 done, regarding the value to be given to the 
 atomic weight of beryllium. Chemists are agreed 
 that the value in question is either (in round 
 numbers) 9 or 9 x l| = 13"5 ; if the former value 
 is adopted, beryllium must be placed in group II. 
 series 2 ; if the latter value is preferred, the metal 
 must find a place between carbon and nitrogen. 
 If the former value is adopted, the formula of 
 beryllium oxide becomes BeO ; if the latter 
 value is preferred, the formula of this oxide must 
 be written BCjOj. The periodic law is a guide in 
 the solution of this problem. Briefly, the law 
 directs us to study the properties of the element 
 itself and the composition and properties of its 
 compounds ; to compare these with those of 
 elements which must come in the same group 
 and the same series as beryllium ; to compare 
 the relations between beryllium and these other 
 elements with the relations which have been 
 established between elements occurring in posi- 
 tions similar to that occupied by beryllium and 
 the other elements in question; and to adopt 
 
ATOMIC AND MOLECULAR WEIGHTS. 
 
 353 
 
 that value for the atomic weight of beryllium 
 which best harmonises with the outcome of this 
 study. There can be no doubt that the value 
 which best harmonises with the results of this 
 Rtudy is 9 ; hence the atomic weight of beryllium 
 is almost certainly 9. This result is confirmed 
 by the application of the law of Dulong and 
 Petit, and also of the law of Avogadro ; for the 
 specific heat of beryllium at about 500° is 
 nearly constant and is approximately represented 
 by the number -62 (•62 x 9 = 5-6) , and the vapour- 
 densities of beryllium chloride and bromide show 
 that the formulae of these compounds, as gases, 
 are BeClj, and BeBr^, respectively (Be = 9). 
 
 The atomic weight of tellurium had for long 
 been supposed to be greater than that of iodine 
 (127) ; but if this were so tellurium must be placed 
 in group I. series 9 ; that is to say, in a group which 
 contains the alkali metals. This position cannot 
 be defended ; moreover, every chemist knows that 
 tellurium exhibits marked analogies to sulphur 
 and selenion. But if tellurium is to find a 
 place in group VI. the value to be given to its 
 atomic weight must be greater than 120 and 
 less than 127. In 1883 Brauner undertook an 
 experimental criticism of the methods whereby 
 the atomic weight of tellurium had beon de- 
 termined by different chemists. Brauner proved 
 that these methods almost necessarily gave too 
 large values ; he also made very careful deter- 
 minations of the atomic weight of the element by 
 two new methods, and obtained a series of 
 numbers varying from 124-94 to 125-4, with a 
 mean value of 125. The periodic law has, there- 
 fore, prevented chemists from finally adopting 
 an erroneous value for the atomic weight of 
 tellurium, notwithstanding the great weight of 
 authority which was in favour of regarding that 
 value as correct. 
 
 These examples will sufiBce to show how the 
 periodic law is used as a guide in determining 
 what multiple of the combining weight of an 
 element is to be adopted as the atomic weight of 
 that element. Incidentally, these examples 
 also impress ns with the extreme importance of 
 the constants which we call the atomic weights 
 of the elements. Given this constant for a new 
 element, and we may, to a considerable extent, 
 predict the properties of the element and its 
 compounds. The periodic law also enables 
 values to be given, if not to the molecular 
 weights, then certainly to the reacting weights 
 of compounds ; because the position of an ele- 
 ment in a group and series determines the 
 ^ formulae of the salts of that element, and, as we 
 assume the atomic weights of the other elements 
 in these salts to be known, therefore determines 
 the relative masses of the chemically reacting 
 units of these salts. There are at least one or 
 two elements in each group which form some 
 gasifiable compounds ; the molecular weights of 
 these compounds are therefore known; hence 
 conclusions may tentatively be drawn regarding 
 the molecular weights of similar compounds of 
 other elements in the same group. But no 
 great stress must be placed on such reasoning as 
 this. Aluminium and indium occur in group 
 III. (series 3 and 7), these metals exhibit fairly 
 marked analogies ; yet the molecular formula 
 of gaseous aluminium chloride is Al^Clg while 
 that of gaseous indium chloride is InCl, ; thallium 
 Voji. I. 
 
 belongs to the same group as aluminium and 
 indium (series 11), yet the formula of the only 
 chloride of thallium which is stable as a gas is 
 TlCl. 
 
 There is then at present one generally 
 applicable method for determining the molecular 
 weights of gaseous elements and compounds ; 
 this method springs out of the application of 
 the generalisation of Avogadro to chemical 
 changes occurring between gaseous elements. 
 The application of the generalisation in question 
 leads to practical definitions of the terms 
 molecular weight and atomic weight. In addition 
 to this method there are three others which 
 serve to determine, more or less accurately, the 
 values of the atomio'weights of the elements ; 
 and two of these are also employed to find the 
 relative masses of the small particles of solid 
 and liquid compounds which take part in 
 chemical changes. 
 
 The methods founded respectively on the laws 
 of Avogadro, Dulong and Petit, and Mitscher- 
 lich, are essentially physical methods ; they 
 are outcomes of the physical theory of the 
 grained structure of matter. The applications 
 of this theory to chemical phenomena which 
 have been considered in the present article have 
 been treated in a purely empirical manner. 
 But it is possible to deduce the law of Avogadro 
 from the first principles of the theory in question. 
 The theory assumes that the temperature of a 
 gas represents the mean kinetic energy of the 
 molecules of that gas ; hence, if M and M, 
 represent the masses, and V^ and V,^ the mean 
 squares of the velocities, of the molecules of 
 two gases at the same temperature, it follows, 
 from the laws of energy, that 
 
 MV'i = M,V,''. 
 But if the pressures of the two gases are equal, 
 then 
 
 MNV2 = M,N,V,''; 
 where N and N, represent the number of xaole- 
 cules in unit volume of the two gases ; because, 
 according to the theory, the pressure of a gaa 
 on the walls of the containing vessel is an effect 
 of the impacts of the molecules of the gas, and 
 this depends on the number and velocity per 
 unit of time of these molecules. Prom these 
 equations it follows that 
 
 N = N,; 
 that is, when two gases are at the same pressure 
 and temperature the number of molecules in 
 unit volume of either gas is the same. But this 
 is the law of Avogadro. 
 
 Neither the law of Dulong and Petit, nor 
 the law of isomorphism, can as yet be satis- 
 factorily deduced from the first principles of the 
 molecular theory. We know very little, if any- 
 thing, of the structure of gaseous molecules ; 
 and of the molecular phenomena of solids our 
 accurate knowledge may be said to be almost 
 nothing {v. AaoEEOATioN, States of, p. 87; 
 
 also MoiiEOOTAB STEUOIURE OF MATTEB, THEORIES 
 HEQAEDING ; alsO PhYSIOAIi METHODS APPLIED TO 
 CHEMIOAIi phenomena). 
 
 The atomic weights of all the known elements 
 have been more or less accurately determined ; 
 but only fourteen elements have been gasified, 
 and hence the molecular weights of only fourteen 
 elements have been determined. The molecules 
 of the greater number, but by no means of aU, 
 
 AA 
 
364 
 
 ATOMIC AND MOLECULAR WEIGHTS. 
 
 of these elements are most probably {v. remarks on 
 p. 340 regarding the molecules of hydrogen, <feo.) 
 composed of two atoms; they are diatomic. 
 The folio-wing table shows the classification of 
 
 the elementary molecules, so far as the availabls 
 data permit, in accordance with their atomicity, 
 that is, the number of atoms of which each 
 molecule is composed. 
 
 Atomicity op Elementaky Molbodles (the temperatures are approximate). 
 
 Monalomic 
 
 Biatomie 
 
 Triatomic 
 
 Tetratomic 
 
 Eexatomie 
 
 Sodium 
 
 Hydrogen 
 
 Oxygen as 
 
 Phosphorus 
 
 Sulphur at 450- 
 
 Potassium 
 
 Chlorine 
 
 ozone 
 
 Arsenic 
 
 550° 
 
 Zinc 
 
 Bromine 
 
 Selenion at 
 
 (both at temps. 
 
 (very doubtful) 
 
 Cadmium 
 
 Iodine at 200°-1000° 
 
 700°-800° 
 
 nearly up to 
 
 V. Biltz a. 
 
 Mercury 
 
 Oxygen 
 
 
 white heat) 
 
 Meyer, B. 21, 
 
 Iodine at o. 1500" 
 
 Sulphur at 800° and 
 
 
 
 2013) 
 
 (? Bromine ate. 1800°) 
 
 upwards 
 
 
 
 
 Antimony at o. 1700° 
 
 Selenion at 1200° and 
 
 upwards 
 Tellurium 
 Nitrogen 
 
 Phosphorus "1 at white 
 Arsenic J heat 
 
 
 
 
 
 
 
 
 The following table presents the data available for calculating the molecular weights of the 
 elementary gases : — 
 
 MoLEOniiAE Weights op Elementaky Gases. 
 
 I. 
 
 n. 
 
 III. 
 
 rv. 
 
 ^- 1 
 
 I. 
 
 II. 
 
 III. 
 
 IT. 
 
 y. 
 
 Name 
 
 Eelative 
 density 
 air=l 
 
 Temp, ot 
 
 Density 
 
 Molecular 
 
 Name 
 
 Eelative 
 density 
 air=l 
 
 Temp, of 
 
 Density 
 
 Molecular 
 
 of element 
 
 observation 
 
 X 28-87 
 
 weight 
 
 of element 
 
 observation 
 
 X 28-87 
 
 weight 
 
 ' Hydrogen 
 
 •06926 
 
 0° 
 
 2 
 
 2 
 
 " Bromine 
 
 6-64 
 
 100° 
 
 159-9 ) 
 165-3 / 
 
 169-6 
 
 '"Sodium 
 
 •87 
 
 1200°-1500'> 
 
 25-5 
 
 23 
 
 !• 
 
 6-38 
 
 100° 
 
 
 • Nitrogen 
 
 0-9713 
 
 0» 
 
 2804 
 
 28-02 
 
 !■ 
 
 4-43 
 
 abt. 1500° 
 
 117-9 
 
 ? 
 
 • Oxygen 
 
 1-106 
 
 abt. 1400° 
 
 31-94 ) 
 31-92) 
 
 31-92 
 
 " Selenion 
 
 5-68 
 
 abt. 1400° 
 
 161-1 
 
 157-6 
 
 « 
 
 1-10563 
 
 0° 
 
 31 
 
 6-37 
 
 abt. 1000° 
 
 183-9 
 
 ? 
 
 • „ (ozone) 
 
 1-658 
 
 — 
 
 47-86 
 
 47-88 
 
 3S 
 
 7-67 
 
 860° 
 
 221-4 
 
 236-4 
 
 • Sulphur 
 
 J-23 
 
 860° 
 
 64-4 \ 
 
 
 ^= Mercury 
 
 6-96 
 
 abt. 1000° 
 
 200-93 
 
 
 T 
 
 II 
 
 2-24 
 
 1040° 
 
 64-6 . 
 
 63-96 
 
 1) 
 
 6-98 
 
 446° 
 
 201-6 
 
 199-8 
 
 • 
 
 II 
 
 2-17 
 
 abt. 1400° 
 
 62-6 
 
 
 SB 
 
 II 
 
 703 
 
 424° 
 
 2030 
 
 
 • Zinc 
 
 2-38 
 
 abt. 1400° 
 
 68-7 
 
 64-9 
 
 as 
 
 6-7 
 
 882° 
 
 193-4 
 
 
 " Chlorin* 
 
 2-45 
 
 200° 
 
 70-73 
 
 
 " Iodine 
 
 8-8 
 
 250°-450° 
 
 264-0 ' 
 
 
 " II 
 
 2-61 
 
 abt. 1000° 
 
 76-35 ■ 
 
 70-74 
 
 28 
 
 II 
 
 8-72 
 
 185° 
 
 251-7 
 
 
 lU j^ 
 
 2-44 
 
 abt. 1200° 
 
 70-72, 
 
 
 II 
 
 8-70 
 
 447° 
 
 261-2 
 
 S63-01 
 
 " Cadmium 
 
 3-94 
 
 abt. 1000° 
 
 113-7 
 
 112-1 
 
 n 
 
 8-72 
 
 abt. 1000° 
 
 251-7 
 
 
 "•Antimony 
 
 9-78 
 
 1640° 
 
 136-1 
 
 120 
 
 " „ 
 
 8-84 
 
 250° 
 
 266-2 
 
 
 " Phosphorus 
 
 4-35 
 
 600° 
 
 125-6 , 
 129-9 1 
 
 123-84 
 
 ■■' 1, 
 
 8-55 
 
 666° 
 
 246-8 
 
 
 14 
 
 4-60 
 
 abt. 1000° 
 
 II 
 
 6-87 
 
 abt. 1100° 
 
 169-4 
 
 » 
 
 '• Arsenic 
 
 10-2 
 
 860° 
 
 294-6 1 
 307-4 1 
 
 299-6 
 
 as 
 
 4-76 
 
 abt. 1500° 
 
 137-4 
 
 [? 126-63] 
 
 II 
 
 10-66 
 
 644°-668° 
 
 " Tellurium 
 
 9-08 
 
 abt. 1400° 
 
 262-1 
 
 266 
 
 '•* „ 
 
 6-53 
 
 1430° 
 
 188-5 
 
 [?149-8] 
 
 
 
 
 
 
 ■ Regnault, C. B. 20, 976. "Scott, Pr. E. 14, 410. 
 
 • Begnault, I.e. ' V. Meyer, B. 12, 1426. 
 
 • Eegnault, l.e. ' Soret, C.R. 61, 941 ; 64, 904. 
 •' Deville a. Troost, C. iJ. 66, 891. 
 
 • V. Meyer, S. 12, 1112. 
 
 • Mensching a. Meyer, B. 19, 3296. 
 
 ■• Ludwig, B. 1, 232. " V. Meyer, B. 13, 400. 
 
 "•Id. B. 16, 2773 (mean of 6 experiments). 
 
 " Deville a. Troost, C. R. 49, 239. 
 
 "•Biltz a. Meyer, Z. P. C. 4, 249. 
 
 " •' D. a. T. C. R. 66, 891. " Id. I.e. 
 
 " Mitscherlich, A. 12, 159. 
 
 "•Biltz a. Meyer, Z. P. C. 4, 249. 
 
 " Mitscherlich, l.c. " V. Meyer, B. 13, 406. 
 
 " Crafts, C. B. 90, 183. " " " Deville a. Troost, l.e. 
 
 " T. Meyer, B. 13, 1107, 1110 (mean of 6 experiments). 
 
 " Dumas, A. Ch. [2] 33, 337. " Mitscherlich, l.e. 
 
 " Bineau, 0. B. 49, 799. 
 
 " V. Meyer ; a. Meier a. Crafts, B. 13, 868 (mean of 7 ex- 
 periments). 
 
 "• Dumas, l.e. " " Deville a. Troost, I.e. 
 
 " T. Meyer, B. 13, 396. "•Troost, C. B. 96, 30. 
 
 " T. Meyer, B. 13, 1116. " Id. 13, 1010. 
 
 " Deville a. Troost, I.e. 
 
 Biltz a. Meyer ^Z. P. C. 4, 249) have obtained values 
 which point to a mol. w. for phosphorus between P* and V„ 
 for bismuth between Bi, and Bi, and for thallium as Tl, ot 
 very high temperatures. 
 
 The following table presents a summary of the atomic weights of the elements and of the 
 evidence upon which each value is based ; — 
 
ATOMIC AND MOLEOULAR WEIGHTS. 
 
 86A 
 
 oa 
 
 P4 
 o 
 
 an 
 
 a 
 
 o 
 
 EH 
 •«1 
 
 
 •09^ 2 
 oj o<M eo 
 woo 
 
 d ad a , 
 
 l: * o 3 9 « 
 
 §!«"! 
 i-ai a 
 
 ^9 
 
 oJ?o 
 
 ' S s 
 
 ■3§ 
 o ^ 
 
 ."I 
 
 fg 
 || 
 
 «3 
 ■SI 
 
 ea-ga 
 
 !■ 
 
 ■0 ■- a 
 
 1-1 M i-« 
 
 5 ■§ 
 
 H 
 
 •§ 
 
 
 ■ss 
 
 0, 
 
 S'S 
 
 5 
 
 f 
 
 S! 
 
 
 ^^ 
 
 'S 
 
 ■s^ 
 
 g 
 
 SS'S^ 
 
 1. 
 
 . ^ 
 
 •0 
 
 II 
 
 "S 
 
 09 
 
 6^3 
 3 a 
 
 §1 
 
 
 
 
 
 i^ 
 
 r^ 
 
 1 
 
 Sodium 
 potass 
 oaloiui 
 
 Sodium 
 
 1^' 
 
 1^ 
 
 I I 
 
 iif.3 
 
 .4 eg e 3 
 .-»^ no 
 
 ■S'S^S 
 
 o aW s 
 
 o a q 
 1^ -«i 
 
 39 
 
 
 da 
 no 
 
 w'^ 
 
 bOM 
 
 3ra 
 
 
 si 
 ill 
 Si 
 
 o 5.2 o* 
 
 fl .- fl a K a 'rt 
 
 Q M O S^^ ^ 
 
 ili:i5| 
 
 ■S-S§5| 
 
 0} c9 o g O g 
 
 Ho 'Co HO 
 
 !a |l U 
 
 ^s ts «s 
 
 
 J* 
 
 
 1SSg§g|§£ 
 
 .. 2 ° 2 ° 
 
 •*£ n "ta to 
 S-O OSts 2 
 
 o^'C o ® E 
 SSggSg 
 .a o ►.a o ► 
 
 g O 
 
 && ^ 
 P d* O 
 
 •§■§■8 
 
 n 
 
 DM. 
 
 o 
 
 n 
 
 o 
 
 o 
 
 n 
 
 
 °- o-g°o -o- Jio: 
 
 W °W.E 
 
 Pi". 
 
 SRQ. 
 
 J'^ J^ Won ".JO g „-u -. 
 BO fe o 
 
 m 
 
 WqT 
 
 Or" 
 
 Ee4 
 
 to 
 o 
 
 -3 
 
 if 
 
 i3 n 
 
 d 
 o 
 
 s 
 
 m 
 
 o 
 
 a 
 
 o 
 
 M 
 
 O 
 
 
 o 
 
 & 
 
 O 
 
 d 
 
 8 
 
 I 
 Pi 
 
 I s 3 
 
 1 1 1 
 
 
 ■3 11 
 3.3 
 
 sa 
 
 - 5" • • a 
 
S66 
 
 ATOMIC AND MOLECULAR WEIGHTS. 
 
 
 ss 
 
 ■SlI'SS 
 
 ■* ® ►■a 
 
 •S P<cf> cB V 
 
 S 2.S 5 
 
 ^3*^ 
 
 .vs 
 
 P'2 
 
 a.gtt»3 
 
 Q 3 "S -S «« 
 ~J3 PIzi c, 
 
 «8„ CO 
 
 sal 
 
 'I? 
 
 
 «'a OS 
 
 _6 
 
 lis 
 
 W P 3 
 
 P4 
 
 03 
 
 
 ■a, 
 
 Z) O 
 
 § 111 
 
 3 5 9 9 
 
 II ill! 
 
 Oia Jfl O [>,(0 
 
 P< O m 
 
 M 
 
 ll 
 
 .S-2 S 
 ~ » o Sa 
 
 OS so.'B.. Sg'3 
 
 '^ '^^ 3 IT 
 
 : a 
 
 
 
 tj'oa 
 
 I I 
 
 ■S .15 
 .o"J:a 
 
 P4 
 
 go, 
 
 I'-'f 
 
 ia 
 u a 
 
 is 
 
 "I 
 
 ill 
 
 ST G3 O 
 
 ■■g.-rf 
 
 
 ^■ 
 
 pis II 
 
 a a el's S o 
 
 s t! a i ° s 
 
 II ^ 
 
 •naS-3 
 
 ,g Eei 
 
 "6g 
 
 o" > 
 •::°o . 
 
 a ® dQ 
 
 ■s-a 
 ll 
 
 Sk 
 
 
 ■Si 
 
 S°a 
 
 rt o 
 
 ..13 
 sail 
 
 11 
 
 a 
 
 .a 
 
 Q 
 
 ^.ac- 
 s§l 
 
 a « o 
 ~|£, 
 
 tn a ^ 
 
 " s-s 
 .aal 
 
 i 
 
 (HO . H F?tti R 
 
 .,™ 8 • - a o a^ 
 
 sS q! SB?"';? V 
 
 Sa KHfurfPHtUoa" 
 
 CO Ph 03 
 
 Ho3335g 
 
 6 
 
 D 
 O 
 
 5 
 
 
 i 
 
 o 
 
 09 
 O 
 
 El 
 
 n 
 
 i • § 
 
 g I g 
 s S f 
 
 Aon 
 
 a g 
 3 ^ 
 
 a 
 
 o • 
 
 I 
 
 13 
 
 d 
 
ATOMIC AND MOLECULAR WEIGHTa 
 
 357 
 
 3 
 
 aSo ■SS-Sao a— 
 
 S«B,§t§|? 8| 
 ..SB a"'s _*w 
 
 o °2 » A J, d 
 
 » do I I "2 
 
 ■s|„ta* «S 
 
 on «| g-a 
 m O 2 S aS o^ 
 
 : s s s 3 
 
 sa 
 
 
 D ffi -a Js ^ w 
 
 
 Sam 
 
 * 3 « 
 
 & PiO 
 
 -SB 
 
 
 ^a« 
 
 o o 
 OO.B 
 
 gpHg o 
 
 S . "^ 
 |Si'gS 
 
 a 8aS^ 
 a g i I a 
 
 I 
 
 i 
 
 in °S! a 
 « a a^ 
 
 Sa=^& „ 
 
 a H^ * „ o 
 o" ^g gS 
 
 ■s a-it a ? <j> 
 
 5^ 
 
 si 
 
 ^a 
 
 o h 
 
 5*3 
 
 a 
 
 
 3 O tn <S 
 
 ■=538 
 g.g.3 
 .. ag.'S 
 ►^ o a 
 
 s a « s'3 
 
 to •a oja a 
 a'-'"-'' a 
 
 o 
 
 
 s 
 
 o 
 
 OS 
 CD 
 
 5 
 a" 
 
 o 
 
 BO 
 J sg. 
 
 
 o 
 
 ''S3 
 5 
 
 o 
 
 C9 
 
 A 
 O 
 O 
 
 
 
 ap 
 
 
 woo 
 
 S'Sor .aow-J-sgi a 
 
 I— « i_j 1? 
 
 
 •2°* " I 
 = - .'^ ■§ 
 
 m S t- . a 
 
 M^r-,g^-05a 
 
 .a^s^N". 
 
 " ° a 
 
 .|i(o-«S OO 
 
 ill f- 
 
 9 1° ft '-' 
 
 H . O 
 
 cacQ ■<}< 
 
 
 i 
 
 Eh ^ " 
 
 ■^ ua 
 
 is 
 
 oa ■ 
 
 a ■§ 3 a"*^ - s 
 
 ■3.gl|a|g"33S 
 sSs 5- s ,§8 Is I 
 
 
 A* IS 00 
 
 n s 
 
 O03 f 
 
 of 
 
SfiS 
 
 ATOMIC AND MOLECULAB WEIQHTS. 
 
 as 
 
 Ml 
 
 s 
 
 SIIS 
 
 •sis g 
 
 £ V«4 CO 
 
 a « r «S 
 
 i-si i 
 
 o, 
 
 i I "ill 
 
 1 5 i S 
 
 ■a «> s»i ■-« 
 
 ^ •« I".?! 
 
 &0 O M^ 
 
 ga -as 
 
 ■s 
 
 B -a SB "as 
 
 _£»o Ro q H S 3 5 
 
 m OQ ^ 
 3 9 4 
 
 $•0 
 
 SssS 
 
 S I I 
 
 1* 
 1^ 
 
 $P4 
 
 
 8| 
 
 Xi^ 
 
 ..!? 
 
 ^s 
 
 §S 
 
 ^s 
 
 
 
 *)" 
 
 a a 
 
 
 
 II 
 
 ^S 
 
 SB 
 
 
 03 
 
 
 .a A A 
 
 •*a 43 -M 
 
 So . 
 
 M AM 
 1 S S*"* «" H" 
 
 i-o ^ M 43 M -^ 05 
 io^o'go'S 
 
 I 
 
 ci H " w S 
 
 S|gd'S8« 
 
 O 
 
 l3 
 
 
 gBH 
 
 QQ 
 
 CQ 
 
 "^1 
 
 o o s 
 m oD 
 
 03 
 
 a 
 
 IP'S 
 111 I 
 
 fSssJ 
 
 -is 
 
 
 o 
 
 i 
 
 I 
 
 s 
 I <^ 
 
 n 
 
 I 
 
 5 
 
 h 
 
 
 o 
 
 s 
 
 i 
 
 3 
 
 ^1 
 
 QQ 
 
 i 
 
 a 
 
 CQ 
 
 |^_^ 
 
 H' 
 
 R 
 
 BS"? 
 
 q 
 
 
 
 .QCQCa 
 
 M n h «a 
 
 o 
 
 -^ .1 M 
 
 U H El 
 
A.TOMI0 AND MOLECULAR WEIGHTS. 
 
 359 
 
 of" 
 CO oB 
 
 lis 
 
 a.s 
 ■a s* 
 
 ■SB'S 
 
 ■D ® ^ o o eft 
 
 fl-i3« 9«h5 «'*' 
 
 •s* BD^ N a v (O n 
 
 a: 
 
 ■ 1 '"O <» • 
 
 o^^ o " p. 
 
 o .. s M g 
 
 11= 
 
 IS. 
 
 ■a CO 
 
 ^ "G +3 00'-»3 
 
 
 CS o 
 SI 
 
 3 6 
 
 
 ISla g.o. 
 
 3 
 
 S 
 .§ 
 
 
 ■s2 
 
 bOM 
 
 =» a 
 
 ^ O 
 
 1^ 
 
 ^3 
 
 •g-3 
 
 -dm 
 
 O 4) 
 
 :§ 
 
 s 
 
 am 
 §■3 
 
 ■SI'S I 
 
 An o 
 
 •go a-g 
 oSm a 
 
 ga 
 
 O V 
 Oh 
 
 Hi 
 
 -!5 
 
 n 
 
 "3 Ho "3 i'a 
 S»jj3-s o.«m 
 
 ■°°-::a'°°a-£' 
 
 ..g5-2 BD-g 
 t^u ^a "'•■a °a 
 
 o P-'S tj o P.'O 
 u a d R oi If ii 
 
 a 
 «a 
 
 ^1 
 
 B 
 
 H 
 B 
 
 at 
 
 -^3 
 
 Km, 
 
 s: 
 
 3 CO 
 
 s 
 El 
 
 I 
 o 
 
 I 
 
 n 
 
 ^ 
 
 • 
 
 a 
 
 • 
 
 g 
 
 
 
 fi 
 
 
 H 
 
 * 
 
 g 
 
 t 
 
 s 
 
 1 
 
 l-l 
 
 'B 
 
 -d 
 
 ,a 
 
 49 
 
 
 
 ■H 
 
 
 
 hi 
 
 U 
 
 n 
 
 pq 
 
 N 
 
 Hi 11 
 
 ^ •a "g a 
 J. -a ° c 
 a 9 o s 
 
 s fl) " o .•.'3 
 
 |§.3-c«M§ 
 
 Ofl B o ij OrB 
 
 tea as 
 
 eg «s- 
 
 00 • B 
 
 oohj B 
 ^tH" is 
 
 gSsSs 
 s § § s i: 
 
 •a-g 2 -a a" 
 
 as a a 
 
 . ."^ .S 
 
 nhi„-o^ 
 
 " :^8 os= 
 
 0) 
 
 H 
 
 a = 
 
 O V 
 
 
 a 
 
 f 
 
 M 
 
 B 
 
 o 
 
 I 
 
 El 
 
 CO o 
 
 Is ^3 2k 
 
 SDR a B oT 
 .3 s : 3 1 3 
 
 is"' f '". 
 
 Is" i -I 
 
 ^- M 3a- 
 
 ■Si • s = 
 
 la s s^. 
 
 S ^ OS 
 
 Is '^ 
 
 •*• a -^ 5 
 
 "'<»; I 
 
 Sis . 
 
 . O us 
 
 .«)-^ao 
 
 
 . . -g lom 
 
 .SM 
 
 N3 SS 
 
 5' a; 
 
 
800 
 
 ATOMIC AND MOLECULAR WEIGHTS. 
 
 !3 a 
 
 1 M15B1-1 
 
 ■as-" g 
 ^ ,9 3 fl " 
 
 •S *H ■* « o 
 
 §■§» « 
 S fi 2 « 
 0'= 3 S 
 
 s.gs '-' 
 
 o 
 
 
 t-,a 
 
 pq 
 
 
 00 
 
 
 S8 
 93 
 
 ■0.0 
 
 H n - o -r o be-" _, 
 
 
 CQ Eh 
 
 9 s 
 
 
 "O m 
 i o 
 
 ••a 
 
 
 Jill 
 
 ft O 
 
 la S 
 
 5g : 
 
 
 9^ to 
 'SB'S 
 
 ■Sg§§ 
 
 u <q to 9 
 .03 M 
 
 p. <u 
 
 S-a 
 
 a t,^ 
 B-"„ 
 
 S.g2 
 
 S|S,i 
 
 Co «u 
 
 S.M -a 
 95 * 
 81 § 
 
 .sl I 
 
 -•° S." 
 sS'Jl.Sa'H 
 
 a bd o 2 
 
 GQ P 
 
 CO 
 
 a gm 5 
 
 £a 
 
 oja 
 
 
 
 11 a 
 
 Bttq 
 
 HO 
 
 W 
 
 ^ » 
 
 
 
 a" 
 
 
 
 ws 
 
 
 
 H 
 
 ft 
 
 .'§ 
 
 § 
 
 ^ 
 
 Th^ 
 
 3 
 
 .Q 
 
 MM 
 
 H 
 
 g 
 
 " H 
 
 ft 
 
 
 
 p 
 
 i 
 
 N' i 
 
 Om P4 
 
 
 >. a 
 
 .a 
 Eh 
 
 
 ss s 
 
 -3 a 
 
 B 
 
 <i 
 
 J3K1 gP a 
 
 H CQ 
 
 ■a !;« j^ 
 
 •S'>i'-rg^ 
 wllE^!^ 
 
 ^' 
 
 ««• 
 
 .a 
 
 ";s 
 
 H 
 
 S-'oo" 
 
 
 
 
 
 M 
 
 S5? 
 
 
 CO 
 
 Idsl 
 
 as 
 
 ■S-^KS 
 
 
 
 
 l| 
 
 
 
 
 nT" 
 
 uia.2ja 
 
 
 fe\ 
 
 8 ij:» 
 
 ^o a 
 
 ■^ 
 
 d.l 
 
 R 
 
 =5 
 
 0? 
 
 ^ 
 
 A 
 
 tj 
 
 !S 
 
 ;^ 
 
 tu 
 
 ^ 
 
 .Q 
 
 •■?, 
 
 "E 
 
 r^ 
 
 M 
 
 
 fl 
 
 M 
 
 
 
 o,!ip;'^.^ 
 
ATEONYLENE SULPHONIC ACID. 
 
 361 
 
 Notes to Table of Atomic Weights. 
 
 A. As the method based on isomorphism of 
 ooapounds is chiefly used as a means of verify- 
 ing values assigned to atomic weights by other 
 methods, no numbers are given in column IV., 
 but merely an indication of the various com- 
 pounds which have been compared crystallo- 
 graphically, and on which arguments for or 
 against a given value for the atomic weights in 
 column V. have been, or may be, baaed. 
 
 B. This column (VI.) is not to be regarded 
 as containing anything like a complete summary 
 of the processes employed for determining the 
 combining weights of the elements; only the 
 more important processes are indicated — 
 references are given to the original papers. 
 
 By combining weight is here meant the 
 smallest mass of the element which combines 
 with 8 parts by weight of oxygen, 1 part of 
 hydrogen, or 35'5 parts of chlorine. 
 
 A complete account of all researches on this 
 subject will be found in A Eecalculation of the 
 Atomic Weights, by F. W. Clarke [Part v. of the 
 Constants of Nature published by the Smith- 
 sonian Institution], and also in Die Atomgewichte 
 der Elemente, by L. Meyer and E. Seubert 
 [Leipzig, 1883]. 
 
 C. When the atomic weight given in column 
 V. section (2) is a multiple of the combining 
 weight in column VII., no number being given 
 in section (1) of column V., it is to be inferred 
 that, besides the argument drawn from the value 
 of the specific heat of the element in question, 
 there are other chemical reasons for adopting 
 the special multiple which appears in V. (2) ; 
 these reasons may be broadly described as based 
 on analogies between salts of the given element 
 and salts of other elements the atomic weights 
 of which have been established by the two 
 leading physical methods. M. M. P. M. 
 
 ATOMICITY. Term used to denote number 
 of atoms in any specified gaseous molecule, 
 usually in the molecule of an element. 
 
 ATOMIC VOLUMES v. Physical Methods; 
 
 Beet. VoLUMETEICAli. 
 
 ATRACTYLIC ACID C^oHs^S^Ois. Potassium 
 atractylate KjA'" occurs in the root of AtractyUs 
 gumrmfera, from which it may be extracted by 
 boiling 70 p.o. alcohol (Lefranc, Bl. [2] 11, 499 ; 
 J. Ph. [4] 9, 81; 10, 325; 17, 187,268; C. R. 
 67, 954 ; 76, 438). Boiling potash hydrolyses it, 
 forming valeric acid and so-called (j3)-atraetylic 
 acid, OajHjjSjOiB, which is further split up into 
 H2SO4, valeric acid and atractylin. 
 
 ATRACTYLIN CjoHsjOe. From ' (j8)-atractylic 
 acid' by boiling with aqueous EOH. White 
 gummy substance, with sweet taste, v. sol. 
 water and alcohol, insol. ether and aqueous 
 NaCl. Forms a violet-red solution in warm 
 H2SO4. Boiling EOH forms atractyligenin 
 and a saccharine substance. 
 
 ATRANORIC ACID C,JB.^fis. [190°-194°]. 
 Extracted by ether from certain lichens (ZJeca?iora 
 atra, Stereocauhnvesuvianitim, Cladoniarangi- 
 fonnis). Trimetric crystals ; a:6:c = l:-398: -306; 
 si. sol. alcohol, cold ether, and benzene; 
 m. Bol. hot benzene ; sol. alkalis forming 
 a yellow solution. Heated with water in a 
 sealed tube it splits up into atranorinic acid, 
 CjHijO,, and atraric acid, C,|,H,„05 (Paternd, 
 
 G. <i, 279; 10, 157; 12, 256; Coppola, 0. 
 12, 19). 
 
 ATRANORINIC ACID CgH,„0,. [101°]. 
 Formed by heating atranoric acid (j.d.) with 
 water. Needles, m. sol. water, sol. alcohol and 
 ether. Its alkaline solutions are yellow. Its 
 aqueous solutions give a green pp. with AgNOj, 
 a brownish-green colour with Fe^Cle, and a 
 blood-red colour with bleaohing-powder (Patern6, 
 G. 12, 256). 
 
 ATRARIC ACID C.jH.oOj. [141°]. Pro- 
 duced by heating atranoric acid with water 
 (Patern6, G. 12,257). Iridescent lamina, si. sol. 
 water, m. sol. alcohol and ether. Its alkaline solu- 
 tions are colourless. It gives a brownish pp. 
 with AgNOj and no colour with FejOl,,. 
 
 ATRIP a3£C acid CeHeO,2 6aq. [98° when 
 hydrated]. An acid obtained from the sugar 
 cane (Savary, O. C. 1884, 968). 
 
 Ethyl ether (184°-188°). 
 
 ATROGLYCERIC ACID G^^fit *•«■ 
 CH2(OH).CPh(OH).C02H. [146°]. afi-Di-oxy. 
 a-phenyl-propiomio acid. From oy3-di-bromo-a- 
 phenyl-propionic acid and excess of alkali (East, 
 
 A. 206, 30). Crystalline aggregates, sol. water 
 and ether. Salt s. — CaA'j. — BaA'^. 
 
 Nitrile CH20H.CPh(0H).CN. [57°]. From 
 benzoyl-carbiuol and HON (Plochl a. Blumlein, 
 
 B. 16, 1292). 
 
 ATROLACTIC ACID v. o-Oxy-o-phenvl-pbo. 
 
 PIONIO ACID. 
 
 ATEOLACTYI-TROPElNE OgHnNOCjHgOj. 
 Psevdo-atropine. [121°]. Crystalline solid. Very 
 similar in physiological action to atropine. 
 Formed by the action of dilute HCl on tropine 
 atrolactate. 
 
 Salts.— Mostly soluble. — B'HCIAuCla: spa- 
 ringly soluble tables. The pier ate also forms 
 sparingly soluble tables (Ladenburg a. Both, 
 B. 16, 1027 ; A. 217, 87). 
 
 .CHj— CH 
 
 ATRONENE 0,jH„ i.e. CeH, < || . 
 
 \CPhH.CH 
 
 Phenyl-naphthalene dihydride. (325° i.V.) 
 Formed, together with atronic acid, by the dry 
 distillation of (a)- or (|3)- iso-atropic acid (Fittig,.4. 
 206, 51). Liquid. Chronde acid oxidises it to 
 o-benzoyl-benzoio acid. 
 
 Atronene sulphonic acid CjgH^SOjH. [130°]. 
 Needles ; v. sol. water.— BaA'^. — CaA'j2aq. 
 
 ATRONIC ACID Ci,HnOj t.e. 
 
 CsH4<^^p^^^^^CH. (?) Phewyl-naphthalene 
 
 di-hydrideca/rboxylic acidly). [164°]. Formed, 
 together with atronene by the dry distillation 
 of (o)- or (i8)-iso-atropio acid (Fittig, A. 206, 
 46). Prisms ; insol. water, sol. alcohol and 
 glacial HOAc. Salts. — CaA'jeaq. — ^BaA'j4aq. 
 
 Iso-atronic acid C^HuO,. [157°]. Obtained 
 by heating (o)-, or (i3)-, iso-atropic acid with 
 cone. H2SO4 (Fittig, A. 206, 86). Leafiets, insol. 
 water, sol. alcohol, ether, and glacial HOAc. 
 
 Salt s.— CaA'2.— BaA'2 6aq. 
 
 ATRONYLENE SITLFHONIC ACID 
 O.sHii.SOaH. [c. 258°]. Formed by heating 
 (a)-, or (j3)-, iso-atropic acid or iso-atronio acid 
 with 9 pts. cone. H^SOi at 90° (Fittig, A. 206, 
 60). Prisms (from 50 p.o. acetic acid). Insol. 
 water, v. sol. alcohol. The aqueous solutions of 
 its salts when exposed to sunhght deposit small 
 
362 
 
 ATRONYLENE STJLPHONIC ACID. 
 
 needles of atronyl-sulphone C,„H,„S02. 
 [193°1. 
 
 ATROPIC ACID C,HaOj i.e. CH^tOPh.COjH. 
 o - Phenyl - acrylic acid. M. w. 148. [107°]. 
 (.203°) at 75 mm. S. -144 at 19°. 
 
 Formation. — l.Byboilingatropinewith baryta 
 (Eichter, J. pr. 11, 33 ; Kraut, A. 128, 282 ; Fittig 
 a. Wurster.l. 195,147). — 2. By heating atropine 
 with fuming HCl at 120° (Lessen, A. 138, 230). 
 
 3. By the action of HCl on ethyl-tropio aoid, 
 CH3.CPh(OEt).C02H, obtained from acetophen- 
 one chloride by alcoholic KCN and saponifica- 
 tion (Ladeuburg a. Eugheimer, B. 13, 2041). — 
 
 4. By action of boiling NaOH upon o-ohloro-j3- 
 phenyl-propionic acid which is formed by the 
 action of HCl upon acetophenone cyanhydrin or 
 by heating o-oxy-o-phenyl-propionio acid with 
 saturated HClAq at 130° (Spiegel, B. 14, 237 ; 
 1854). 
 
 Properties. — Needles (from water) or mono- 
 clinic prisms (from alcohol) ; v. sol. CSj. 
 
 Reactions. — 1. Chromic acid mixture forms 
 benzoic acid. — 2. Potash-fusion forms phenyl- 
 acetic acid. — 3. Sodium-amalgam reduces it to 
 a-phenyl-propionic acid. — 4. Fuming HCl forms 
 n-chloro-a-phenyl-propionic acid, which is con- 
 verted by aqueous Na^COj at 120° into tropic 
 acid, CH2(OH).CPhH.C02H.— 5. ClOH forms 
 chloro-tropio acid CH2(0H).CPhCl.C02H 
 (Ladenburg a. Eiigheimer, B. 13, 376).— 6. Cold 
 cone. HBrAq forms both o-, and j3-, bromo-a- 
 phenyl-propionio acid; at 100° it forms only 
 ;8-bromo-o-phenyl-propionio acid. — 7. Bromine 
 forms CH2Br.CPhBr.CO2H. 
 
 Salts. — Neutral atropates are not ppd. by 
 manganous salts (difference from cinnamates). — 
 CaA'jSaq (K.).— CaA'2 2aq (L.). 
 
 (a)-Iso-atropic acid C^gH^fi^ (?). [237°]. 
 
 Preparation. — (a)-, and (j3)-, isoatropic acids 
 are both formed when atropio acid is heated 
 alone or with water ; they may be separated by 
 crystallisation from 50 p.c. acetic acid. 
 
 Properties. — Crystalline aggregates, si. sol. 
 boiling water, sol. alcohol. Chromic acid gives 
 anthraquinone and o-benzoyl-benzoio acid. 
 V. also Atkonbne, Ateonic acid, and Atkontlene 
 
 SDLPHONIO ACID. 
 
 Salts .— CaA" 2aq.— BaA" 2iaq. 
 
 Ethyl ether 'Ei^" {180°). 
 
 (;3)-Iso-atropic acid CuHi^O,. [206°]. Eect- 
 angular tables (from water). More soluble in 
 water, alcohol, and HOAc than the (a) acid. 
 Gives the same reactions as the (a) acid. 
 
 S alts.— CaA" 3aq (Fittig, A. 206, 34 ; B. 12, 
 1739 ; compare E. Meyer, A. 219, 290). 
 
 ATROPINE C„H2,N0, i.e. 
 
 CHjOH.CPhH.CO.O.CH2.CH2.C5H,NMe. 
 Daturine. [114°]. S. -33. 
 
 Occurrence. — Together with hyoscyamine in 
 all parts of Atropa belladonna (Geiger a. Hesse, 
 A. 5, 43; 6, 44; Mein, A. 6, 67), and in the 
 seeds of Datu/ra stramonium (Geyger, A. 7, 272 ; 
 Planta, A. 74, 245). 
 
 formation. — Crystalline tropine tropate has 
 no action on the eyes, but when treated with 
 dehydrating agents, such as ZnClj, Ac^O, or 
 HCl, atropine is formed. It is best to evaporate 
 frequently with very dilute HCl at 100° 
 ILadenburg, A. 217, 78 ; B. 12, 942 ; 13, 104, 
 
 909 ; C. B. 90, 921). Tropine contains hydroxyl 
 which is etherified by tropic acid : 
 
 OH,(OH).OPhH.CO,H+HO.OHa.CHa.C.H,NMe= 
 CH»(OH).CPllH.CO.O.OH..CH..C.H,NMe+H 
 
 Preparation. — Dry belladonna leaves are di- 
 gested for three days with cold water, the extract 
 is evaporated, and after mixing with Na^CO, 
 the syrupy liquid is agitated with benzene. The 
 benzene solution is decanted ofl and shaken 
 with dilute sulphuric acid. The acid liquid ia 
 rendered alkahne with NajCOj and the solution 
 agitated with chloroform ; the extract is filtered 
 and, after addition of light petroleum, allowed to 
 evaporate spontaneously, when the atropine 
 separates out first, the mother liquors containing 
 another alkaloid (Pesoi, 0. 10, 426). 
 
 Properties. — ^Needles (from dilute alcohol). 
 SI. sol. water ; v. sol. alcohol, and chloroform, 
 m. sol. ether. The solutions are alkaline to 
 test-paper, and taste bitter. Its salts enlarge 
 the pupil of the eye. '05 to '2 g. is a fatal dose. 
 Three drops of a 1 p.c. solution of (artificial) 
 atropine enlarges the pupil to the maximum 
 extent. Atropine overcomes the stoppage of 
 the heart's action produced by muscarine. 
 
 Reactions. — 1. When evaporated to dryness 
 with fuming HNO, a residue is left which is 
 turned violet by alcoholic KOH. — 2. Chromic 
 acid mixture forms benzoic aoid. — 3. A solution 
 in HCl gives with gold chloride an oily pp. that 
 quickly changes to lustreless crystals which 
 melt under water or, when dry, at 136°. — 
 4. Tannin gives, in very dilute neutral solutions 
 a white pp., sol. HCl. — 5. Potassio-mercuric 
 iodide gives a white cheesy pp. — 6. I in KI 
 gives a brown oil which solidifies after some 
 time. — 7. Picric acid gives, in somewhat dilute 
 acid solutions, a crystalline pp.— 8. Cone. H^SO, 
 gives, on warming, a pleasant odour.— 9. Cya- 
 nogen gas passed into an alcoholic solution 
 gives, after some time, a red colour. — 10. Chlo- 
 ride of iodine forms a dark yellow pp., sol. on 
 warming, and separating out on cooling in 
 brown crystals (Dittmar, B. 18, 1612).— 11. De- 
 composed by hot baryta-water or cold cone. 
 HCl into tropic acid and tropine (Kraut, A. 
 128, 280 ; 133, 87 ; 148, 240 ; Lessen, A. 138, 
 230).— 12. Hot cone. HClAq at 120° gives 
 tropine, tropic acid, atropic acid, iso-atropic acids, 
 and (at 180°) tropidiue.— 13. With NaNOj, 
 HjSO,, and subsequently NaOH a violet colour 
 is developed. — 14. Glacial HOAc and H^SOj 
 produce on prolonged warming a greenish-yellow 
 fluorescence (Fliiokiger, Ph. [3] 16, 800).— 
 15. HoSOjand KCIO3 give a greenish-blue colour 
 (Vitali, Ph. [3] 12, 459). 
 
 Salt s.— B'HAuCl, [135°-137°].— B'^H^PtCl, 
 [208°].— B'HC12HgCL, (Gerrard, Fr. 24, 601). 
 B'HIIj : brown prisms (Jorgensen, Z. 5, 673). — 
 B'HII^.- B'jHjSO, : needles, got by adding an 
 ethereal solution to an alcoholic solution of 
 HjSO^ Valerate B'CsH.oOjiaq [42°] (GaU- 
 mann, J. pr. 76, 69). 
 
 Additional References. — Giinther, J. 1869, 
 781 ; Fr. 8, 476 ; Lefort, Ph. [3] 2, 1029 ; C. G. 
 1873, 797; Bruuner, B. 6, 96; Newark, C. C. 
 1872, 536 ; Gulielmo, Fr. 2, 404 ; Ludwig, Ar. 
 Ph. [2] 107, 129 ; Schmidt, A. 208, 196. 
 
 Ethyl-atropine C^HjjEtNO,. Formed by 
 action of AgjO on its hydriodide, B'HI, obtained 
 
AZAUROLIC ACIDS. 
 
 863 
 
 by heatiug atropine with EtI at 100° (Lossen, 
 A. 138, 239). A syrup, sol. water. 
 
 Apoatropine C„Hj,N02. [60°-62°]. Formed 
 by treating atropine with HKO, (Pesci, (?. 11, 
 538 ; 12, 60). Prisma ; si. sol. water, v. e. sol. 
 alcohol. Decomposed by baryta-water at 100° 
 into tropine and atropio acid. Does not enlarge 
 the pupil. Salts.— B'HAuCl, [180°] amor- 
 phous. — B'HjSO, 5aq. 
 
 Pseudo-atropine v. AmoLAOTTL-TKOPEiirai. 
 
 Hydro-apo-atroplne 
 CH3.CHPh.CO.O.CH2.0H2.05H,NMe. Prepared 
 by the action of nascent hydrogen on apo- 
 atropine (Pesci, Atta d. Acad, dei Limcei, 5, 829). 
 Oil. Decomposed by baryta-water at 100° into 
 o-phenyl-propionio acid and tropine. Forms 
 a crystalline compound with HgCl^. Neutral 
 KMnO, oxidises it to 'homo-apo-atropine ' 
 OisBLjjNOj, an alkaline oil which forms the 
 ■following salts: B'^COj, B'^H^PtCls, B'HAuCl^, 
 B'jHjSO, saq, B'^HaPdCl, ; its hydrochloride 
 gives white pps. with tannin, Mayer's reagent, 
 and HgCl,; and it gives a blood-red colour 
 with fuming HNO, ; heated with baryta-water it 
 gives a-phenyl-propionio acid and tropigeniue 
 (Pesci, a. 12, 285, 329 ; Merling, B. 15, 289). 
 
 Homo-atTopine v. PnEiiyLaiiycoLYL-iBOFEiNE. 
 
 Ueta-atropine v. Tbocine. 
 
 ATROPYL-TEOPElNE C^Hj.NOj. Anhydro- 
 Utropme. Obtained by heating tropine hydro- 
 chloride with atropio acid and HCl (Ladeuburg, 
 A. 217, 102; B. 13, 1085). Oil.— B'HAuCl, : 
 small needles. 
 
 ATBOXINDOLE v. o-AMiDO-a-PHENYL-PBOPi- 
 
 ONIO ACID, p. 179. 
 
 AUBANTIIN CjsHjsO.jiaq. [171°]. S. -33. 
 [o]]= — 64'57°. A glucoside in the flowers of 
 Citrus decumana (E. Hoffmann, B. 9, 691). 
 Yellow monoclinio prisms. Bitter taste. Gives 
 a brownish-red colour with FejClj. 
 
 AUBATES. Auric hydroxide AujO^Hj 
 (=Au203.H20) reacts with HNOjAq to form the 
 compound An(N0s)3.HN03.8H20 ; from this seve- 
 ral basic nitrates and one or two sulphates of gold 
 may be produced (Schottlander, A. 217, 312). 
 But AU2O3.H2O also dissolves in KOHAq, and on 
 evaporation at a gentle heat and finally m vactu), 
 crystals are obtained, which when dissolved in 
 water, recrystallised, drained, and dried in vacuo, 
 are said to have the composition AU2O3.K2O.3H2O 
 ( = Au204K2.3H20). Aurate of potassium is very 
 Bolnble in water, forming an alkaline liquid 
 which is easily decomposed by organic com- 
 pounds and by heat ; the solution gives pps. 
 with solutions of various metallic salts, e.g. CuClj; 
 these pps. are said to be aurates, but very little 
 is known about their composition. An aurate of 
 ammonium of indefinite composition, known as 
 fulminating gold, is formed by pptg. a solution 
 of a gold salt by excess of NHjAq, and boiling 
 in NHjAq ; or by digesting AajOaBfl in 
 (NH,)2S0iAq (Fremy, A. Oh. [3], 31, 480; 
 Figaier, id. [3] 11, 341). M. M. P. M. 
 
 ATTBIC ACID. The hydrated oxide of gold 
 AU2O3H2O is sometimes called auric acid because 
 of its salt-forming reactions with alkalis {v.supra). 
 This compound is best prepared by adding 
 NaOHAq to very dilute AuCljAq, in the ratio 
 ^NaOHrAuClj, (the AuCljAq should be prepared 
 in about the ratio AuClj-.SOOHjO) ; warming till 
 the liquid is dark brown; adding Na3S04Aq; 
 
 allowing pp. to settle; washing repeatedly by 
 deoantation, and then on a filter, until the 
 washings are free from H^SO^ and HCl ; boihng 
 pp. with cone. HNOjAq ; and again washing free 
 from acid (Thomsen, Th. 3, 391). According to 
 Kruss (B. 19, 2546), AU2O3.H2O is better prepared 
 from Au2CljAq by ppg. with magnesia alba, 
 boiling with dilute HN03Aq, washing with water, 
 and drying over P2O5. AujOj.HjO is easily 
 soluble in HBrAq and HClAq, with production 
 of much heat, and formation of AuOl^HAq and 
 AuBr,HAq respectively (v. Gold), M. M. P. M. 
 
 AITBINE V. Eosoiiio acid. 
 
 AUSTBALENE v. Tubpektine oUi. 
 
 AXIN V. AoE, p. 87. 
 
 AZAMMONIUM COMPOTTITDS. Compounds 
 obtained by oxidising mono-alkylated o-amido- 
 azo compounds, or by heating azimido-oom- 
 pounds with alkyl iodides followed by moist 
 Ag-^O (Zinoke a. Lawson, B. 20, 1173). Thus 
 C|5H5.N:N.C,|,Hu.NH.C„H5 gives, on oxidation - 
 with chromic acid, CjjHijNjO which might be 
 expected to have the formula : 
 
 .N(OH).CA 
 
 o,.H3<;i\ 
 
 \N-N.C,H3 
 Naphthalene - di - phenyl - azammonium hy- 
 drate 
 
 >N(0H).C3H. 
 C22H,3N3.0Hi.e. C,.h/|\ (?). 
 
 \n.n.c.H5 
 
 The chromate is obtained by the oxidation 
 of benzene - azo - phenyl - (/3) - naphthylamine 
 
 /N.CA 
 CjoHev I (?) with K2Cr20, and acetic 
 
 ^N.NHC„H5 
 acid. It is converted into the chloride by boil- 
 ing with alcohol and HCl till all the chromic 
 acid is reduced. The hydrate is obtained 
 from the chloride by AgjO. Its solution has a 
 greenish fluorescence, is strongly alkaline, and 
 tastes bitter ; it decomposes on evaporation. 
 
 Salts . — Like the base, they have a greenish 
 fluorescence in aqueous and alcoholic solution, 
 and a bitter taste. — 022H,jNsCl : glistening 
 prisms, v. sol. alcohol, less in water ; it forms 
 sparingly soluble double chlorides with SnOlj, 
 ZnClj, HgClj, &c.— (C22H,3N3Cl)2PtCl, : si. sol. 
 crystalline pp. — CjaHijNj.HSOj : glistening 
 transparent needles or prisms, v. sol. hot alco 
 hoi, si. sol. cold water. — C22H,5N3N03 : long 
 flat glistening needles, v. sol. hot alcohol, si. 
 sol. water. — (C22H,jN3)2Cr20, : long yellow 
 needles, sol. acetic acid, v. si. sol. water. — 
 ''(C22H,3N3)C,H2(N02)30: [243°]; small yellow 
 needles, v. si. sol. water (Zincke a. Lawson, B. 
 20, 1172). 
 
 AZABONE C.jH.eOs. [59°]. (296°). S.G. if 
 1-165 ; fg 1-0743. Obtained by distilling the 
 rhizomes of Azarum ewroptsum with steam 
 (Boutl6rofE a. Eizza, Bl. [2] 43, 114). White 
 crystalline body, si. sol. water, sol. alcohol, 
 ether CClj, and acetic acid. Combines with Br, 
 forming Gj^^^Br.fi,. 
 
 AZAUBOLIG ACIDS. 
 
 Ethyl-azaurolic acid CjH.NjO. [142°]. From 
 ethyl nitrolic acid (2 g.) by the action of water 
 and sodium amalgam. The yield (-25 g) is bad. 
 Formed also by reducing di-nitro-ethane 
 (V. Meyer a. Constam, A. 214, 330 ; B. 14, 1455). 
 
 Properties. — Orange-red prisms (from alco- 
 
804 
 
 A55AUKnLIC ACIDS. 
 
 hoi). M. sol. hot alcohol, si. sol. ether, v. si. sol. 
 water, chloroform, benzene or light petroleum. 
 Alkalis form a deep orange solution. At 142° it 
 melts, Nvith decomposition, leaving a liquid 
 which, after solidifying, melts again at 133°. 
 
 Reactions. — 1. Ammoniaoal solution gives 
 with AgNOj a brown pp., and with salts of Zn or 
 Pb, yellow pps. A solution of the ammonium salt 
 deposits, on evaporation, needles of the free acid. 
 2. Heat, dilute acids, nascent hydrogen, and 
 ammonia all convert it into ethyUeueazone : 
 2CjH,NjO + H^O = CjHjNaO + + NH3O the oxy- 
 gen converting another portion of ethyl-azaurolio 
 acid into acetic acid, N, and NjO. — 3. K2Cr20, 
 and H2SO4 give acetic acid and COj. 
 
 Constitution.— Its formation from ethyl, 
 
 nitrolic acid indicates the group MeC<^^, and 
 
 the presence of Me.C is shown by the production 
 of acetic acid on oxidation. Ethyl-azaurolic 
 
 acid would then be Me.CH^tJ^O or, more 
 
 probably, MeCH(NO).N:N.CH(NO)Me or perhaps 
 MeC{NO) :N.NH.CMe:NOH. 
 
 Ethyl-leucazone C,H,NsO. [158°]. Formed 
 together with nitrogen, Nfi, and hydroxylamine 
 by heating ethyl-azaurolic acid with dilute HCl 
 (M. a. C). Satiny needles. Eeddens litmus. 
 Combines with acids, bases, and salts. V. sol. 
 alcohol or water, insol. ether. Its aqueous solu- 
 tion is turned red by FcjClj and oxidised to 
 acetic acid by KjCrjO, and HjSOi. 
 
 Salts.— B'jHjSOi: [161-5°]; prisms, sol. 
 ordinary (90 per cent.) alcohol.— Ba(C4H5N30)2. 
 -0,H,N,0AgN03. 
 
 Propyl-azaurolic acid CaHsNjO. [127-5°]. 
 From propyl-nitrolic acid by sodium-amalgam. 
 
 AZELAIC ACIDS CbHijO^. 
 
 n-Azelaic acid 
 CO,H.OH2.CHj.CH2.CH2.CH2.CH2.CH2.C02H. 
 [118°]. Formed by reducing butyro-furonio 
 acid with HI and P (Tonnies, B. 12, 1200). 
 Slender needles (from chloroform). 
 
 Azelalc acid G,H,e04. Anchoic acid. Lep- 
 argylic acid. Mol. w. 188. [106°]. (above 
 860°). S. -108 at 12° ; S. (ether) 1-88 at 11°. 
 
 Formation. — 1. By the oxidising action of 
 HNO, upon Chinese wax (Buckton, O. J. 10, 
 166), cork, oleic acid (Laurent, A. Ch. [2] 66, 
 154), cocoa-nut oil (Wirz, A. 104, 265), castor 
 oil (Arppe, A. 120, 288; Ganttner a. Hell, B. 
 14, 560, 1545), and enninoio acid (Kraftt, B. 11, 
 1415).— 2. From oleic and KMnO^Aq (Saytzeff, 
 J.pr. [2] 33,301). 
 
 Preparation. — Castor oil is oxidised by HNO3 
 (S.G. 1-25). Heptoic acid is distilled off with 
 steam, and the hot residual liquor poured off 
 from a heavy nitrogenous oil. On cooling, 
 suberic and azelaio acids crystallise. Pure 
 suberic acid is got by washing the mixed acids 
 with ether, which dissolves azelaio acid as well 
 as oily impurities. The ether is evaporated, 
 the residue dissolved in boiling water and NaCl 
 added. Oily matter then separates and azelaic 
 acid crystallises from the brine (Dale a. Sohor- 
 lemmer, C. J. 85, 684 ; cf. Ganttner a. Hell, B. 
 14, 1545). 
 
 Properties. — Large thin plates, not volatile 
 with steam. Sol. water, alcohol, and ether. 
 Nitric acid oxidises it to succinic acid. It does 
 cot give a homologue of suberone when distilled 
 
 with slaked lime, hence its constitution is pro- 
 bably not analogous to that of the homologous 
 suberic acid. 
 
 Salts.— KjA": small plates.— K^"2aq: 
 needles.— KHA".—KH3Aj".—Na2A" aq : soluble 
 plates. — NajHA'V — {^'B.,)iA." : large plates. — 
 (NHJHA".— EaA"aq: S. -65 at 16°; -628 81 
 100°.— SrA"aq.— CaA": crystalline powder ; S. 
 •185 at 17° ; -193 at 100°.— MgA" 3aq.— MnA"3aq: 
 slender needles ; S. -206 at 14° ; -108 at 100°. 
 — NiA" 6aq. — CoA" 6aq. — ZnA": crystalline 
 pp.; S. -026 at 12°.— PbA": white pp.; S. -006 
 at 24°.— AgjA" : white pp. ; S. -0015 at 14°.— 
 CuA".— Fe(OH)A" 2aq.-0dA", 
 
 Ethyl eifterEt2A".(260°). Decomposedon 
 boiling, 
 
 AZIDINES. Compounds related to hydra- 
 zines {q. V.) in the same way that amidines are 
 related to Amines. Thus the hydrochloride of 
 phenyl-hydrazine acting on a solution of benz- 
 imido-ether in absolute alcohol produces dark 
 red needles of di - phenyl - benz - azidine, 
 Ph.C(NH.NPhH):N.NPhH ; while form-imido- 
 ether gives, when similarly treated, di-phenyl- 
 formazidine CH(NH.NPhH):N.NPhH [185°] 
 (Pinner, B. 17, 182, 2002). 
 
 AZIMIDO- COMPOUNDS. This term was 
 originally applied by Griess {B. 15, 1878) to the 
 coriipounds obtained by the action of nitrous 
 acid upon ortho-diamines, which are probably 
 
 of the form E'\ I >NH, and was extended by 
 
 Zincke (B. 18, 3134) to compounds, probably of 
 
 the form E"< | 
 
 I >NB', 
 
 got by oxidising o-amido- 
 
 azo- compounds (hydrazimido- compounds). The 
 
 first formula may also be written E"<^^jj ^N, 
 
 -NH2 
 ,C1 
 diazobenzene anilide stands to a mixture of 
 diazobenzeae chloride and aniline. 
 
 which stands to ^"<^^ pi in the relation that 
 
 Azimido-benzene CuH^Nj i.e. CjH^! 
 
 or C„H,<^j^>N. 
 
 l>H 
 
 [99°]. From aqueous 0- 
 
 phenylene-diamine sulphate and KNO2 (Laden- 
 burg, B. 9, 222). Needles (from benzene). 
 Azimido-nitro-benzene C^H^NjOj i.e. 
 
 C,H3(N02)< I >NH or C„H3(N02)< | [211°]. 
 
 Formed by passing nitrous acid into a solution 
 of nitro-o-phenylene diamine (Hofmann, Pr. 10, 
 496). Long white prisms, v. sol. alcohol and 
 ether, si. sol. cold water. Nitrous acid does not 
 affect it, hence it does not contain NH^. 
 
 Salts.— C„H,KN,0„.-C„H3AgN40j. Not 
 affected by boiling HCl', or KOH. 
 
 Azimido-toluene CjHjNj i.e. 
 N 
 CH3.C„H3<^|\nH or CH3.C3H3<™>N. 
 
 [83°]. (323°). From aqueous tolylene-o-diamine 
 sulphate and KNO^ (L.). Prisms containing 
 CjHj (from toluene). V. sol. alcohol, m. sol. 
 ether and boiling water. Not aiieoted by HClAq 
 
AZINES. 
 
 365 
 
 »tl60°. Salts,— B'HCl: decompoaed by water. 
 
 Acetyl derivative CjHjAoNj. [130°]. 
 From aoetyl-o-tolylene diamine, HOI, and NaNO^ 
 (Boessneck, B. 19, 1758). Needles. 
 
 (m.Azimido-benzolo acid GjHjKjO: i.e. 
 
 COjH.CbHj<' I \kH or COjH.CsHj*^ | . 
 
 From the hydrochloride oi di-amido-benzoio 
 acid, C0jH.0eHj(NHj)2 [1:3:4] and KNO^ (Griesa, 
 B. 2, 436). Also by the action of boiling potash 
 upon C,H3(C0jH)(N0J(NH.C0.NH,) [1:3:4] and 
 upon CsH,(C02H)(N02)(NH.CO.NH2) [1:4:3] 
 (Griess, B. 15, 1880). This seems to indicate 
 the symmetrical formula. Short needles, con- 
 taining water of crystallisation ; v. si. sol. water. 
 Not attacked by warm fuming HNOj. 
 
 (7)-Azimida-benzoic acid. Prepared similarly 
 from C02H.0jH3(NH2)j [1:2:3]. Long hair-like 
 needles (G.). 
 
 Azimido-benzene-i'-carboxylic ether CjHaNjOj 
 
 >Nv .N.CO.,Et 
 
 i.e. CfiiC I >N.CO,Et or O^X | 
 \n/ ^N^ 
 
 [73°]. From the hydrochloride of o-amido-phenyl 
 carbamio ether and KNOj (Eudolph, B. 12, 
 1295). 
 
 Fhenyl-azimido-uaphthalene 
 
 GioH8< I >N.-CsH5. [108°]. Fine white needles. 
 
 Soluble in hot acetic acid, sparingly in alcohol 
 and benzene. Formed by oxidation of benzene- 
 azo-(j3)-naphthylamine with CrOj in acetic acid 
 solution. It is not attacked by strong HjSO,, 
 acetic anhydride, or reducing agents (Zincke, B. 
 18, 3136). 
 
 o-Ozy-phenyl-azimido-naphthalene 
 
 C,oH.< I >N.CeH^(OH) [1:2] [140°]. White 
 
 silky needles. Easily soluble in alcohol and 
 benzene. Formed by oxidation of an alkaline 
 solution of o-oxy-benzene-azo-(/3)-naphthylamine 
 with lead peroxide. It is not attacked by strong 
 H2SO4, acetic anhydride, acetyl chloride, or re- 
 ducing agents (Z.). 
 
 ^-Ozy-phenyl-azimido-naphthaleue 
 
 yNv (1) (*) 
 
 C,oH.< I >N-C6H4(OH). [199°]. Thick crystals 
 
 or white needles. Soluble in hot alcohol and 
 hot acetic acid, sparingly in benzene. Formed 
 by oxidation of an alkaline solution of p-oxj- 
 benzene-azo-(;8)-naphthylamine with lead per- 
 oxide. It is not attacked by reducing agents. 
 Acetyl derivative 
 
 C,„H/|/>N.CaH,(OAc) [165°]; thin silky 
 
 plates {Z.). 
 
 Tolyl - azimido - toluene C^Hi^Nj i.e, 
 
 0,H,< I >NC,H,. [125°]. V.D. = 7-2a (for 8-32). 
 
 Formation. — 1. By oxidation of ^-toluene- 
 o-azo-|i-toluidine [1:4] CsHjMe.Nj.CsHjMefNHj) 
 [4:1:2].— 2. By heating the imide of o-diazo- 
 toluene-azo-toluene or by boiling its acetic acid 
 solution, N, being evolved.— 3, Together with »n 
 
 amido-phenol or diamine by reducing with SnOlj 
 the azo compounds obtained by combining 
 o-diazo -toluene-azo-toluene with phenols or 
 amines (Zincke a. Lawson, B. 19, 1455 ; 20, 
 1178). 
 
 Properties. — Thin colourless plates. Sol. 
 benzene, hot alcohol, and hot HOAc. Not 
 attacked by hot Ac^O, cold HjSO^, or reducing 
 agents. 
 
 AZINES. Compounds of the type 
 
 X'\ I >Y". Thus, phenazine may be repre- 
 
 sented by the formula 
 
 CH N CH 
 
 CH 
 
 HO 
 
 CH N CH 
 r/|\o„H„ 
 
 or C„Ha I /v 
 
 and the nomenclature of other azines may be 
 gathered from two examples (Hinsberg, B. 20, 21). 
 
 >N. 
 
 CijH,. 
 
 Phen-naphthazine O^H,' 
 
 Tolu-naphthazine C,H|iC | >C,„H, 
 
 Derivatives of quinoxaline 
 CH N 
 
 HOr"^^^- 
 
 HO 
 
 CH 
 
 are called quinoxalines, 
 ,N— CH 
 
 , and naphtho-ciuinoxaline, 
 >N— CH 
 
 /N-C 
 
 C,Hr I i 
 
 \N— C 
 
 tolu-quinoxaline 
 
 .N— CH 
 C,.H / I II 
 
 \n- 
 
 CH 
 
 Formation. — 1. From o-diamines and 0- 
 quinones or o-di-oxy- compounds. — 2. By oxida- 
 tion of a mixture of o-diamine and phenols (e.g. 
 (^)-naphthol). — 3. By boiling certain azo-dye- 
 stuffs, derived from secondary amines, with 
 dilute acids; e.g'.sulpho-benzene-azo-phenyl-(;8)- 
 naphthyl-amine yields naphtho-phenazine and 
 sulphanilio aoi4 05H^(S03H).N2.C,„Hs.NH0jH5 =. 
 
 C,.H,<^>CA + 06Hi(S03H).NH, (Witt, B. 
 
 20, 571).— 4. By fusing o-quinones with ammo- 
 nium acetate, or by heating them with alcoholic 
 NH3(Japp, O.J. 51, 100). 
 
 Properties. — Weak crystalline bases ; their 
 salts being decomposed by water. Eeduced by 
 
 SnClj to hydrides, K<;^^>R', whence Fe^Cl, 
 
 regenerates the original azine. 
 
 Azine-ammonium bases. Compounds of the 
 
 form X"< l/Y" . They have also been called 
 
 \nE(OH) 
 Azonium bases (Witt, B. 20, 1183), a term pre- 
 viously applied by Fischer to quaternary hydra- 
 aine derivative?. 
 
AZINSUOCINIC ACID. 
 
 AZINSUCCINIC ACID 
 
 (COjH)jC,H2:N.N:02H2(C02H),. Crystalline 
 
 solid. Very soluble in water and alcohol. Not 
 decomposed by acids or alkalis. The ethers of 
 this acid are obtained by the spontaneous de- 
 composition of the ethers of diazosuooinio acid 
 CjH2N2(C02E)2 on keeping, half the nitrogen 
 being evolved. A''Ba2: sparingly soluble yel- 
 lowish-white powder. 
 
 Tetra -methyl- ether A"Mei: [150°]; 
 silky white prisms ; easily soluble in hot water 
 and alcohol, sparingly in cold water, alcohol, 
 and hot ether ; not volatile with steam (Curtius 
 a. Koch, B. 18, 1299). 
 
 AZO-ANILINi; V. Amido-benzene-azo-aniline 
 under Azo- compounds. 
 
 AZO-BEIfZENE v. Benzene-azo-benzene 
 under Azo- compounds. 
 
 TBIAZO-BENZENE and its derivatives v. 
 DiAzo-BENZENE iMiDE and its derivatives. 
 
 AZO-BENZOIG ACID v. Carbozy-benzene- 
 azo-benzoio acid under Azo- compounds. 
 
 AZO- COLOnSING MATTEBS. 
 
 History. — The series of compounds comprised 
 under this class contains one or more diatomic 
 groups 'NtN- linking together acid or basic aro- 
 matic radicles. Of a very large number of azo- 
 oompounds known to science only a certain pro- 
 portion are of technical value, and these are 
 manufactured in large quantities owing to their 
 importance as colouring matters. The first 
 azo- compound introduced into commerce was 
 the oxalate of amidoazobenzene (' aniline yel- 
 low,' V. benzene-azo-aniline), CjHj.Nj.CjHj.NHj, 
 manufactured in 1863 by the firm of Simpson, 
 Maule & Nicholson, by the action of nitrous gas 
 on aniline dissolved in alcohol. Three years later 
 triamidoazobenzene, NHj.C5Hj.Nj.05Hs(NH2)2 
 {v. Amido - benzene - azo - phenylene - diamine 
 under Azo- compounds), was manufactured at 
 Manchester and introduced under the name of 
 ' Manchester brown ' (' Bismarck brown,' ' Pheny- 
 lene brown,' ' Vesuvine '). This compound was 
 prepared by the action of nitrous acid upon in- 
 phenylene-diamine. In 1875 diamidoazobenzene, 
 0jH5.Nj.0jH3(NH2)2 (v. Benzene-azo-phenylene- 
 diamine), was discovered independently by Caro 
 and Witt {B. 10, 213, 350) and introduced into 
 commerce by the latter under the name of 
 ' chrysoidine.' These basic colouring-matters 
 were soon foUowed by acid azo- compounds of 
 greater technical value {B. 10, 1378, 1509), and 
 numerous patents have since that time been 
 taken out, the general mode of preparation being 
 similar in principle to that first employed in 
 1870 by Kekul6 and Hidegh (B. 3, 233). These 
 are the chief points in the industrial history of 
 these compounds ; the chemical history will be 
 referred to under the individual compounds. 
 Azobenzene, C5Hs.N2.CuH5 {v. Benzene-azo-ben- 
 zene), which may be regarded as the prototype 
 of the azo- compounds, has been known since 
 1834 (Mitscherlich, A. 12, 311), but the industrial 
 development of these products is largely due to 
 the researches of Griess upon the diazo- com- 
 pounds {A. 106, 123 ; 113, 201 ; 117, 1 ; 120, 
 125 ; 121, 257 ; 137, 39). The theoretical views 
 which have led to the adoption of the formulis 
 at present generally received have been deve- 
 loped chiefly by KekuW {Z. 1866, 2, 309, 689). 
 
 Pormation,-~l. Comppunds of the azoben- 
 
 zene type are produced by the action of tmli 
 reducing agents, such as alcoholic potaeh, alco- 
 holic KOH and zinc dust, iron and acetic acid, 
 or sodium stannite, upon the corresponding nitro- 
 bodies : 2C6Hs.N02 + iS^ = CsH5.N2.CeH, -^ 4H2.O. 
 
 2. By the oxidation of the corresponding 
 amido-derivatives by potassium permanganate, 
 bleaching powder, chromic acid, hydric peroxide, 
 &c., thus : 2CSH5.NH2 -^ O2 = C5H5.N2.CcH5 + 2H2O 
 (Glaser, Z. [2] 2, 308). This method is applicable 
 to the Bulphonio acids and other derivatives of the 
 amido- compounds: 2C5H3(CH3)HS03.NH2 + 02= 
 N2(C5H3.CH3.HS03)2 + 2H20 [iUustrating the 
 production of azotoluenedisulphonic acid from 
 toluidinesulphonic acid ; Kornatzki, A. 221, 179]. 
 
 3. By the action of ethyldichloramine 
 (Tsoherniak, B. 9, 147) upon certain aromatio 
 amines(c.gr.2)-toluidine): 2C,H,.NH2 + C2H5.NCL = 
 C2H5.NH2HC1 + HC1 + C,H,.N2.C,H, (Pierson a. 
 Heumaun, B. 16, 1048). 
 
 4. By the action of nitroso- compounds upon 
 amines and ■ phenols : C3H5.NO + HjN.CjHj = 
 C5H5.N2.CBH5 + H2O (production of azobenzene 
 from nitrosobenzene and aniline ; Baeyer, B. 7, 
 1638). Similarly H0.C5H,.N0 + H2N.CsH5= 
 HO.OjH4.N2.C5H5 + H2O (production of benzene- 
 azophenol from nitrosophenol and aniline ; Ei- 
 mioh, B. 8, 1026). According to Henriques, 
 substituted amidoazo-oompounds are produced 
 by the action of ethyl-iS-naphthylnitrosamine 
 uponaniUne, &o.: N(C,„H,)Et.NO + H2N.CBH5= 
 N(C,„H,)Et.(N2.C5H5)+H20. The diazo- com- 
 pound immediately becomes transformed into 
 the isomeric benzeneazo-ethyl-;8-naphthyl-amine, 
 C5H5.N2.C,oH5.NH.Et (B. 17, 2668, v. also 0. N. 
 Witt, B. 10, 1309). Amidoazobenzene reacts 
 in a similar manner with the same nitrosamine 
 forming C5H5.N2.C5H,.N2.C,„H5.NH.Et. 
 
 5. From azoxy-compounds by intramolecular 
 transposition, such as the formation of oxy- 
 azobenzene (benzene-azo-phenol) by warming 
 azoxybenzene with strong sulphuric acid 
 
 ^«g=-|>0 = C6H5.N2.CjH,.0H (Wallach a. BeUi, 
 
 B. 13, 525). 
 
 6. By the action of phenylhydrazine upon the 
 naphthoquinones : OuHjOj + H2N.NH.C5H5 = 
 
 CioHs<^§_j;f2-CH ■'"■^i'O- The naphthoqui- 
 nonehydrazide then undergoes intramolecular 
 transposition with the formation of an azo- 
 compound: HO.CuHj.NiN.CjHs. The compound 
 thus obtained from (a) -naphthoquinone is iden- 
 tical with benzene-azo - (a) - naphthol, while 
 (/3) -naphthoquinone gives a compound which is 
 isomeric and not identical with benzene-azo-(/3). 
 naphthol (Zincke a. Bindewald, B. 17, 3026). 
 
 Preparation. — The method in general use for 
 the preparation of azo- colours is that depending 
 upon the readiness with which diazo- compounds 
 react with amines and phenols. In practice it 
 is not necessary to isolate the diazo- salt, but the 
 amido- compound which is to be converted into 
 a diazo- salt is treated with the necessary quan- 
 tity of sodium nitrite and acid to diazotise the 
 NHj group, and the solution of the diazo- salt is 
 then mixed with the solution of the amine in 
 acid or the phenol dissolved in alkali. During 
 the process of diazotising, the solution contain- 
 ing the amido-compound must be kept well 
 cooled, as the diazo- salts are very unstablSi 
 
AZO-COLOURTNG MATTERS. 
 
 367 
 
 especially in aqueous solution. Most aromatic 
 amido- compounds lend themselves to this re- 
 action, the azo- colours of commerce being pro- 
 duced by the action of diazotised amines, 
 amido-snlphonic acids, or amido-oarboxylio acids, 
 upon amines, phenols, amido-sulphonic and 
 oxy-sulphonic acids. A selection of typical re- 
 actions illustrating the formation of these com- 
 pounds by the present method may be here 
 conveniently discussed: 
 
 (a) When a salt of diazobenzene acts upon 
 aniline the first product of the reaction is 
 always diazobenzeneanilide(diazoamidobenzene): 
 C.H,.Nj.Cl + CeH,.NH, = CsH,.Nj.NH.0«H5 -i- HCl. 
 The latter compound was first produced by the 
 action of nitrous gas upon aniline dissolved in 
 cold alcohol (Griess, A. 121, 258). When allowed 
 to stand in the presence of aniline and aniline 
 hydrochloride, or when acted upon by hydro- 
 chloric acid or unstable metallic chlorides in 
 the cold, the diazobenzeneanilide is slowly 
 converted into the isomeric amidoazobenzene, 
 C5H5.N2.C8H,.NHj. This last compound is manu- 
 factured on a commercial scale for the prepa- 
 ration of other azo- colours and the indulines 
 (g. v.). In the case of other amines in which 
 the para- position with respect to the NH^ group 
 is open (or the ortho- position in the naphtha- 
 lene series), the transformation of diazo- into 
 amidoazo- compounds takes place with great 
 readiness. Thus, by the action of nitrous acid 
 upon o- and m- toluidine, m-xylidine and the 
 uaphthylamines, amidoazo- compounds are at 
 once formed. 
 
 (b) The salts of the aromatic diazo- com- 
 pounds react with primary and secondary mon- 
 amines, but not with tertiary monamines of the 
 fatty series. The resulting products are diazo- 
 compounds, such as CjHj.Nj.NH.CjHj (diazo- 
 benzene-ethylamide) and CjH5.N2.N(OH3)2 
 (diazobenzenedimethylamide). The diazo- com- 
 pounds of this class do not furnish isomeric 
 azo- compounds (Baeyer and Jager, B. 8, 148). 
 True azo- compounds of a mixed aromatic and 
 fatty type are produced by the action of diazo- 
 compounds upon the sodium derivatives of 
 nitro-hydrocarbons of the fatty series, e.g. 
 
 C^5.N2.N03 + NaC^Hj-NO^ = 
 
 C,H5.N2.C2H,.N02 -F NaNOa 
 
 (formation of benzeneazonitroethane, V, Meyer 
 
 and pupils, B. 8, 751, 1073, 1078 ; 9, 384 ; 12, 
 
 2285). 
 
 (c) Diazo- compounds always furnish true azo- 
 compounds with secondary and tertiary aro- 
 matic monamines, such as CjHj.Nj.CjH^.NMej 
 (benzene-azo-dimethylaniline) by the action of 
 diazobenzene upon dimethylaniline (Griess, B. 
 10,628),andC5H5.N2.C„H.,.NH.CjH5(benzene-azo- 
 diphenylamine) by the action of diazobenzene 
 upon diphenylamine (Witt, B. 12, 259, and C. J. 
 35, 185). 
 
 (d) The action of diazo- compounds upon 
 aromatic diamines is typified by the action of 
 diazobenzene-chloride upon w-diamidobenzene 
 to produce chrysoidine : C^H^.N^.d + C|jH4(NH2)2 
 = CeH5.N2.0sH3(NH2)2.HCl. Nitrous acid gives 
 with ortho-diamines a class of substances termed 
 by Griess azimido- compounds : 
 
 C.H,(NH,), -F HNO, = C,H,<|>NH + 20H, 
 
 (Hofmana, A. 115, 249 j Ladenburg, B. 11, 219 ; 
 
 Eudolph, B. 12, 1296; Griess, B. 15, 1878). 
 Metadiamines give under the same circum- 
 stances compounds of the type of triamidoazo- 
 benzene (Bismarck brown)2C5Hi(NH2)2 -I- HNOj = 
 (NH2)C„H4.N2.C„H3(NH2)2-i-2H20(Caro a. Griess 
 Z. 1867, 278). By acting with an excess of 
 HNO2 upon p- and m- CsHjCNHj)^ in acid 
 solution with suitable precautions both these 
 diamines can be diazotised and give azo- colours 
 when combined with phenols (Griess, B. 17, 607 
 and 19, 317). 
 
 (e) The formation of azo- colours from diazo- 
 compounds and phenols as illustrative of the 
 general method of technical production is shown 
 by the following typical examples : CuH^.Nj.NO, 
 + CjHs.ONa = C5H5.N2.CjH.,.OH + NaN03 
 (benzeneazophenol from diazobenzene nitrate 
 and sodium phenate: KekuU and Hidegh, B. 
 3, 233). By a similar reaction would be formed 
 such compounds as benzeneazoresorcin, 
 CA.N2.C,H3(OH)2 (Typke, B. 10, 1576), benzene- 
 azo-(o)-naphthol, CjHs.Nj.CijHj.OHa, &o. [ibid. 
 1580). Azosulphonio acids are formed by the 
 action of diazosulphonio acids upon phenols, or 
 by the action of diazo- salts uponphenolsulphonio 
 acids, thus, for example, p - sulphobenzene - 
 azo-/3-naphthol (Poirrier's 'Orange No. II.'), 
 HSO,.CeH,.N2.C,„H5.0Hi8 from diazo - benzene 
 sulphonic acid and sodium (/3)-naphtholate ; 
 benzene -azo- ((3) -naphthol disulphonio acid, 
 CeH5.N2.0,„H4(HS03)2.0Hj3 from diazo-benzene 
 and (fl)-naphthol sodium disnlphonate (' Orange 
 G,' Meister, Lucius a. Briining), or ^-sulpho- 
 benzene - azo - ($) - naphthol disulphonio acid, 
 HS03.CsH,.N2.C,oH4(HS03)2.0Hj3irom diazotised 
 sulphanilic acid and ()3) -naphtholdisulphonic acid 
 sodium salt (Meldola, B. 13, 942). 
 
 Classification and Nomenclature. — Azo- com- 
 pounds may be described as primary, secondary, 
 tertiary, Ac. according as they contain 1, 2, 3, 
 &o. Nj- groups. The modes of formation above 
 described have been illustrated by reference to 
 primary azo- compounds, all of which (with the 
 exception of the mixed aromatic and fatty com- 
 pounds) may be regarded as derivatives of 
 azobenzeue, CjHj.Nj.OsHs, benzeneazonaphtha- 
 lene, C3Hs.N2.C,gH, and azonaphthalene, 
 C,jHj.Nj.C,„Hj, or generally, in the case of 
 phenolic azo- compounds, as E.N^.Pl, where R 
 may stand for C^B.^, C|„H„ CsHi-HSOj, CsHi.NO^, 
 &c., and PI for CjHj.OH, C,„Hj.OH, 
 0,„H5(HS03)OH, &c. It will be found convenient 
 to write the formulse of azo- compounds so as to 
 represent the order of introduction of the 
 radicles. Thus, C3H5.Nj.C3Hj.OH indicates the 
 product from diazobenzene and phenol, and 
 would be described as benzene -azo-phenol; 
 CBHj(HSOs)N2.C,3H3.0Ha is ^J - sulphobenzene- 
 azo-(o)-naphthol, obtained by the action of 
 diazotised-sulphanilic acid upon (a)-naphthol; 
 while CsH5.N2.C,„H5(HS0s)0Ho is the isomeric 
 benzene-azo - (a) - naphtholmonosulphonic acid 
 obtained by the action of diazobenzene upon 
 (a) -naphtholmonosulphonic acid. The same 
 rules may be followed with the more complicated 
 types of azo- compounds ; thus, for instance 
 CjH5.N2.C3H,.N2.C5H3(0H)2, benzeneazobenzene- 
 azoresorcin obtained by the action of diazotised 
 amidoazobenzene upon resorcin ; in like manner 
 C3H5.N2.C,H8.N2.0,H5(0H)2maybe called benzene- 
 azotoluene-azoresorcin hj the action of di^zoti;^^ 
 
368 
 
 AZO- COLOURING MATTERS. 
 
 benzene-azoamidotoluene upon resorcin; and 
 0jH5.Nj.CjHj(0H)2.N2.CsH5, benzeneazodioxy- 
 benzeneazobenzene by tbe suooeesive introduction 
 of two diazobenzene-groups into resorcin. 
 Secondary and tertiary azo- compounds of the 
 types (E.N2)2P1", and (E.N2)3Pr" have been 
 termed by Wallach diisaso- and trisazo- com- 
 pounds {B. 15, 22 and 2812 ; v. also Heumann, 
 ibid. 813). 
 
 Secondary and tertiary azo- com/gounds. — The 
 typical secondary azo- compound of the type 
 (B.N2)2Pl"is the so-called ' phenolbidiazobenzene,' 
 {C5H5.Nj)2:C5Hs.OH, discovered by Griess (B. 10, 
 628). Compounds of this class are formed by 
 the successive introduction of two diazotised 
 radicles into a phenol. The resorcin secondary 
 azo- compounds have been especially studied by 
 Wallach {fi. 15, 22; Wallach a. B. Fischer, iUd. 
 2814), and the cresol compounds by Nolting a. 
 Kohn (B. 17, 351). Analogous amido- compounds 
 of the type (E.N2)j:0sH2(NH2)2 have been ob- 
 tained by the introduction of diazotised radicles 
 into ohrysoidine (Griess, B. 16, 2028). Secon- 
 dary azo- compounds of the type R"(N2.P1)2 have 
 been obtained by Wallach by acetylating one 
 amido- group in a diamine, diazotising the 
 aoetdiamido- compound, and combining with a 
 phenol so as to produce a compound of the type 
 
 ^""N^HAc* ^^® ^°®*y^ S™"P " *^®'^ ^^' 
 moved, the NHj-group diazotised, and the diazo- 
 
 oompound Ii"<rw^'rjl ^.gain combined with a 
 phenol (B. 15, 2825 and Wallach a. Sohulze, 
 %b%d. 3020). The metadiamines appear to lend 
 themselves most readily to this method. The 
 most direct method of preparing secondary azo- 
 compounds of this class is by diazotising both 
 amido- groups in a ^- or w-diamine, and then 
 acting with the product upon a phenol or phe- 
 nolsulphonic acid (Griess, B. 17, 607 and 19, 
 317). Another method of obtaining secondary 
 azo- compounds of these types is by diazotising 
 a p-nitramido- compound and combining with a 
 phenol or secondary or tertiary amine so as to 
 produce N02.B".N2.P1 or N02.R".N2.E".NR2. 
 The nitro- group is then reduced, the amido-azo- 
 compound diazotised and again combined with 
 a phenol, <fec., thus producing E"(N2.Pl)j, 
 
 ■^"'\n'''p1 ''"^'^'^ &c. (Meldola, C. J. 43, 425 ; 45, 
 106 and 47, 657). If the nitro-azo- compound 
 is combined with a monamine and the ilitro- 
 group reduced, a diamidoazo- compound of the 
 type NH2.E".N2.E".NH2 is produced in which 
 both amido- groups can be diazotised and com- 
 bined with phenols so as to form tertiary 
 azo- compounds, P1.N2.E".N2.E".N2.P1 i^iUd.). 
 Secondary azo- compounds of these types are 
 also formed by reducing ^-nitracetanilide, 
 diazotising and combining with a phenol or 
 amine so as to produce azo- compounds of the 
 
 ^NH Ac 
 type C8Hj<^j, p, ■. The acetyl group is then 
 
 removed, the amido-azo- compound diazotised 
 and again combined with a phenol (Nietzki, B. 
 17, 348 and 1350). 
 
 Secondary azo- compounds of the type 
 E'.N2.E".N2.PI are obtained by diazotising amido- 
 azo- compounds and combining the diazo-azo- 
 ?g,lt with phenols. Tbe typical compound, 
 
 CeHs.Nj.CsH1.N2.OBHj.OH, was first prepared 
 by Oaro and Sohraube (B. 10, 2230) and several 
 members of this group have since been intro- 
 duced into commerce under the names of 
 ' Biebrich scarlet,' ' Crooeine scarlet,' &e. These 
 scarlets are of considerable technical import- 
 ance, especially the latter, which are pre- 
 pared by the action of diazotised amidoazo- 
 benzene-sulphonic acid and its homologues 
 upon (3)-naphthol-(a)-sulphonio- acid. By the 
 action of diazotised amidoazobenzene upon 
 ohrysoidine a tertiary azo- compound of the type 
 
 ^'•'''''•■^/^2>C,H2(NH2)2 is formed (Griess, B. 
 
 16, 2036). Secondary azo- compounds of some 
 importance have recently been prepared by 
 diazotising diamidodiphenyl (benzidine) and 
 its homologues and combining the tetrazo- 
 salt with phenols, amines, and their sulphonio 
 acids ; of these colouring matters ' Congo red,' 
 CBH,.N2.0,„H.(HS03)NH2a , ,. , 
 c:H:.N:.0;X(HS0:)NH:a' "^^y ''^ mentioned 
 as a typical example. Tertiary azo- compounds 
 derived from triphenyl-carbinol are obtained by 
 diazotising the rosanilines and combining with 
 phenols (Meldola, 0. J". 47, 668). 
 
 Constitution of Aso- com/pounds. When a 
 diazo- compound combines with an amine or 
 phenol to form an azo- compound the N2-gronp 
 invariably takes up the para- position with 
 respect to the NH2, NHE, NEj, or HO, if this 
 position is open. The proof of the constitution 
 of azo- compounds is furnished by the products 
 which they yield on complete reduction. Thus, 
 amidoazobenzene, CjH5.N2.CsH4.NH2, gives on 
 reduction aniline and p-phenylene-diamine ; 
 ohrysoidine gives aniline and (1, 2, 4)- triamido- 
 benzene (Witt, B. 10, 658). The constitution 
 of some of the azo- compounds obtained by 
 combining diazosulphonio acids with phenols 
 has been established by Griess (B. 11, 2191). 
 The constitution of the azo-naphthol colours 
 has been determined chiefly by Liebermann and 
 his pupils {B. 14, 1310 and 1795; Jaoobson, 
 ibid. 1791 ; also Witt, O. J. 35, 179). When diazo- 
 compounds act upon substituted phenols, such 
 as salicylic acid, the N2-group also takes up the 
 para- position with respect to the HO-group 
 (P. P. Frankland, G. J. 37, 746); thus (a)- 
 naphthaleneazosalicylic acid gives on reduction 
 a-C,„H,.NH2 and CsH5(HO)(NH2)C02H [1:4:2] 
 When the para- position with respect to the 
 NHj or HO-group is already occupied the N,- 
 group enters the ortho- position (Nolting a. 
 Witt, B. 17, 77 ; Liebermann a. Kostaneoki, 
 ibid. 130, 876 ; Griess, ibid. 338 ; Nolting and 
 Kohn, iind. 351). This law holds good also 
 when the para- position is occupied by an azo- 
 group, as in the formation of (CjH5.N2)2:CjH3.0H 
 from benzeneazophenol by the introduction of 
 another CjHj.Nj-group (Nolting a. Kohn, B. 
 
 17, 868). In the case of the (is) -naphthalene 
 derivativestheNj-group also enters theortho-(a)- 
 position with respect to the hydroxyl or ami- 
 dogen group. Thus (/3) - naphthol orange, 
 HSO3.CeH4.N2.C10Hs.OH, gives on reduction 
 Bulphanilic acid and (o)-amido-(3)-naphthol,the 
 latter yielding (;8) -naphthoquinone on oxidation 
 (Liebermann, B. 14, 1310). Similarly the azo- 
 derivatives of (;8)-naphthylainine yield o-diamido- 
 naphthalene (NH2:NHj = Oi :/8,) on reduction 
 
AZO- COMPOUNDS. 
 
 369 
 
 (Lawson, B. 18, 796 and 2422). The fact that 
 Buch compounds as benzeneazo-(j8)-naphthol are 
 insoluble in cold aqueous alkalis has led Lieber- 
 mann to the suggestion that these oompounda 
 no longer contain HO, but possess the formula 
 
 C,H,.N<^^>C,„H5 {B. 16, 2858). A similar 
 
 conclusion has been suggested by Meldola with 
 respect to the (3)-naphthylamine derivatives, for 
 
 which he proposes the formula K.N<^-jj-g-])>0i„H5, 
 
 thus indicating a, relationship to the azimido- 
 compounds above referred to (C. J. 45, 117). 
 This conclusion is supported by the investiga- 
 tions of Ziucke and his pupils (B. 18, 3125, 
 3132 and 3142). This author has shown that 
 these (5) -naphthalene, as well as other ortho- 
 amidoazo- compounds, can be oxidised to com- 
 pounds of the azimido- type, E.N^ I ^C,.H,, and 
 
 be suggests for them the alternative formula 
 HNv 
 I >C,„H.. According to a recent 
 B.NH N / 
 
 paper by Nietzki a. Goll (B. 19, 1281) it 
 appears,however,thatamidoazo-(;8)-naphthalene 
 contains an NHj-group, or at any rate can be 
 diazotised under certain conditions. There can 
 be no doubt that the question of the constitution 
 of the azo- compounds is much more complicated 
 than was at first supposed, since by the action 
 of diazo- compounds upon phenols two isomeric 
 azo- compounds may be formed at the same time, 
 the isomerism probably depending upon the 
 position of the E.Nj-gronps with respect to the 
 HO as well as upon the formation of bodies of 
 the oximido- type. This appears to be the case 
 especially with the azo- derivatives of resoroinol 
 (WaUach, B. 15, 22 and 2814). 
 
 General properties and technology. — The indi- 
 vidual azo- colours will be described under their 
 respective headings, so that it will be only ne- 
 cessary here to give a brief account of the 
 general characters of these colouring matters. 
 The parent azo- compounds, CjH5.Nj.G5H5, 
 C,H5.Nj.C,„H„ C,„H,.N2.C,„H„ although pos- 
 sessed of colour are not of any value as dye- 
 stuffs : it is only when acid or basic radicles are 
 present in one or both aromatic nuclei that true 
 colouring matters are formed. The colours pro- 
 duced by these compounds are of various shades 
 of yellow, orange, brown, red, scarlet, indigo- 
 blue and violet. No pure blue or green azo- 
 compound is known. Of the basic primary azo- 
 eompounds, amidoazo-benzene, chrysoidine, and 
 ' phenylene brown,' show a gradation in shade 
 from yellow through orange to brown. The two 
 last compounds are now alone of technical 
 value. Among the acid azo- colours a regular 
 gradation of shade is also observed with the 
 increase in molecular weight. This is well seen 
 in the colours produced by the action of diazo- 
 benzene and its homologues upon the naphthol- 
 sulphonio acids, the lowest members of the series 
 being orange, and the highest members scarlet 
 of an increasing shade of blueuess. The acid 
 primary azo- compounds are dyed from acid 
 baths and have great aflSuity for silk and wool, 
 but do not readily dye cotton without the use of 
 mordants. Primary azo- colours as a rule dia- 
 
 VOL. I. 
 
 solve in strong sulphuric acid with a red or 
 orange colour. Azo- colours can be produced 
 directly in the fibre of cotton by impregnating the 
 latter with a phenol and a diazo- compound, and 
 then developing by means of an acid (T. Holli- 
 day, S. O. I. 4, 204). A similar process has 
 been described by Grassier {S. C. I. 4, 262) who 
 uses the nitrite in the form of an ammonium 
 salt or in combination with ammonium salts, 
 so that on heating the impregnated fabric the 
 nitrous acid is liberated in the presence of the 
 amine and phenol, and the colour is developed 
 without the use of acid. Oxyazo-oompounds, 
 which are not sulphonic acids, and which are in- 
 soluble, can be made soluble by warming them in 
 aqueous or alcoholic solutions of bisulphites. A 
 soluble double compound is thus formed which is 
 decomposed on heating with the liberation of the 
 colouring matter no that the process is especially 
 applicable for calico printing (Meister, Lucius 
 a. Brvining, B. 17, 452). The secondary azo- 
 colours derived from diazotised amidoazoben- 
 zene and its homologues in combination with 
 naphtholsulphouic acids are scarlets of greater 
 tinctorial power and purity than the primary 
 azo- scarlets, and possess a certain affinity for 
 cotton, especially the ' croceine scarlets ' already 
 referred to. The secondary azo- colours derived 
 from diazotised benzidine {' Congo red ' series) 
 and its homologues are reds or yellows which 
 also possess a certain affinity for cotton, but 
 many of these colours are too sensitive to acids 
 to be of much use technically. The stability of 
 these colours is increased, however, by using the 
 higher homologues of benzidine. It is only 
 among secondary azo- compounds that truo 
 shades of violet and indigo blue are found 
 (Nietzki, B. 17, 344 ; Meldola, C. J. 47, 665), 
 Some of these blue shades are now met with 
 in the market, a typical compound of the class 
 being a salt of ditolyltetrazo-(/3)-uaphtholdisul- 
 phonic acid, 
 
 C,Hs.N2.C,„H5(HS03)(0H),3 ,. ,, . _ 
 
 c:h:.N,.c;:h:(HS03)(0H);3 (^o-tlue of P.. 
 Bayer & Co.). ' Secondary azo- compounds dis- 
 solve as a rule in strong sulphuric acid with a 
 violet, blue, or green colour. The tertiary azo- 
 compounds have but little tinctorial value. Foi 
 observations on the absorption spectra of azo-" 
 colours see papers by H. W. Vogel {B. 11, 623), 
 Landaaer (B. 14, 391), and Stebbins {Am. 6, 117 
 and 149). E. M. 
 
 AZO- COMPOUNDS. (F. also Azo- ooloueinq 
 MATTEES and Di-Azo- COMPOUNDS.) The nomen- 
 clature of these compounds is based on the 
 following rules. Imagine N^ displaced by H^ and 
 the compound to break up accordingly, one H 
 going to one half and one to the other. If both 
 the resulting compounds are aromatic, name the 
 compound richest in carbon according to the 
 rules followed in this dictionary, and prefix azo- 
 to the name. Before azo- write the name of the 
 hydrocarbon from which the other half of the 
 molecule is derived. Then prefix all the sub- 
 stituents of the latter so that they may follow 
 one another in this order : chloro-, bromo-, iodo ■ 
 cyano-, nitro-, oxy-, amido-, sulpho-, and car' 
 boxy-. When both halves of the azo- compound 
 contain the same number of atoms of carbon 
 then the half which contains COjH is put last' 
 If neither contain COjH, the one oontainiog 
 
 BB 
 
870 
 
 AZO- COMPOUNDS. 
 
 SO,H comes last; if neither contain this, pre- 
 ference is given to OH, NH^, NO^, Br, or 01, 
 in succession. 
 
 If one half of an azo- compoand is derived 
 from a fatty hydrocarbon the name of this half 
 is written last. 
 
 The compounds obtained by the action of 
 ttiazo- compounds upon (/3)-naphthylamine, (3)- 
 naphthol, or more generally upon amido- or oxy- 
 compounds in which the p-position is already 
 occupied, are described as if they were ordinary 
 azo- compounds. It is, however, not improbable 
 that they may have a different constitution. 
 Thus the compounds obtained from diazo- com- 
 pounds and (0) - naphthylamine behave like 
 diazoamides in their decomposition by acids 
 into (;3) -naphthylamine, a phenol, and nitro- 
 gen ; but act on reduction like amido - azo- 
 derivatives giving (1:2) - naphthylene - diamine 
 and the amine. Three views may be taken with 
 regard to the constitution of these bodies : — 
 (I) That they are true diazoamides ; (2) that 
 they are o-amido-azo- derivatives ; (3) that they 
 are hydrazimido- compounds, i.e. dihydrides of 
 azimido- compounds. 
 
 The first hypothesis easily explains their de- 
 composition by acids ; and their reduction to 
 naphthylene - diamine might be accounted for 
 by assuming an intermediate change into the 
 amido-azo- compound. However, the fact that 
 a different isomeric body is formed by diazo- 
 tising (;8) -naphthylamine and combining it with 
 the otner amine does not agree with this view, 
 since compounds of the form X.Nj.NHY and 
 Y.N2.NHX are always found to be identical. The 
 other reactions of these bodies are also incon- 
 sistent with this hypothesis. The hypothesis 
 that the compounds are o-amido-azo- derivatives 
 does not readily account for their behaviour on 
 oxidation, which tends to show that they do 
 Qot contain an NH^ group. 
 
 The third hypothesis leads to the formula 
 JSB. „„ 
 
 C,.hZ I or C,A<^g>NR. 
 
 \n.nhr ^JNU/ 
 
 It is strongly supported by the fact that on 
 oxidation these bodies give rise to white crystal- 
 line azimido- compounds, which probably have 
 
 the constitution C,,HX I y^B> analogous to 
 
 \NH obtained 
 
 by the action of nitrous acid on o-phenylene- 
 diamine. The corresponding compounds from 
 (/3)-naphthol and diazo-salts may also be ob- 
 tained by the action of hydrazines upon {/3)- 
 Jiaphthoqninone, and hence may be represented 
 in a similar manner by the formula 
 
 C,„h/| or C,.H.<J^s,NE. 
 
 \k.nhr ^JNM/ 
 
 The formation of hydrazimido- compounds 
 from a diazo- salt and {/3) -naphthylamine can be 
 explained by assuming the intermediate forma- 
 tion of true diazo - amides C,„H,.NH.N:NB, 
 which by taking up HjO (or HCl) would form 
 C,„H,.NH.N(OH).NHBorC,„H,.NH.NH.N(OH)B, 
 and by again eliminating H^O it might give the 
 bydrazimido- compound. The decomposition by 
 
 Griess's azimidobenzene 
 
 
 acids might also be explained as a change inverse 
 to the above, resulting in the formation of the 
 diazo-amide, which would then be decomposed. 
 The ortfe)-amido-azo- derivatives of the benzene 
 series would also seem to be similarly constituted, 
 for on oxidation they also give colourless crystal- 
 line azimido- compounds. • 
 
 Apparently opposed to the hydrazimido- 
 hypothesis, is the behaviour of these bodies 
 towards nitrous acid, which converts them into 
 diazo- compounds. In many points, however, 
 these diazo-compounds greatly differ from the 
 ordinary diazo- compounds, and their constitu- 
 tion may possibly be expressed by the formula : 
 
 /N.N.OH 
 ^ v I I > ■which would represent their f orm- 
 
 \N.N.E' 
 ation from hydrazimido- compounds. By 
 SnClj or SO2 these diazo- compounds are not 
 reduced to hydrazines but to non-basic stable 
 bodies which probably have the constitution 
 
 /N— NH 
 E'\ I I . The o-diazo-imides readily lose 
 
 \N— N.E' 
 N2 on heating and are converted into azimido- 
 
 compounds B' 
 
 
 '|\n.B' i 
 
 identical with those 
 
 obtained by oxidation of the o-amido-azo- com- 
 pounds. On the hydrazimido- hypothesis the 
 body derived from diazo-benzene and phenyl- 
 (/3) -naphthylamine would be represented by the 
 
 /N.C,H, 
 formula C,oHeC | which agrees with its 
 
 \n^c,h, 
 
 reactions. Thus cone. HCl removes anihne, 
 
 forming an azine C,|,Hji 
 
 ^CA. 
 
 while oxi- 
 
 dising agents produce a powerful ammonium 
 base C,„HjN3(C8H5)20H (Meldola, C. J. 45, 107; 
 Nolting a. Wilt, B. 17, 77 ; Lawson, B. 18, 796, 
 2422 ; Sachs, B. 18, 3125 ; Zincke, B. 18, 3132, 
 3142 ; Zincke a. Lawson, B. 19, 1452). 
 
 Desoeiption or Azo- oompotindb. 
 
 Acetoplienone-azo-(/3)-naphtIiol [4:1] 
 C,H4(CO.CH3)— N2— C,„H,(OH). Formed by di- 
 azotising jj-amido-acetophenone and combining 
 the diazo- compound with (;8)-naphthol in alka- 
 line solution (Klingel, B. 18, 2695). Slender red 
 needles. V. sol. alcohol, si. sol. ether, insol. 
 water. Dyes silk a duU red. 
 
 o-Amido-benzene-azo-ace to-acetic acid 
 C,H,(NH2)— N3— CH(C0.CH3).C02H. [157°]. 
 Orange-red tables. BasUy soluble in acetic acid, 
 alcohol, ether and chloroform, sparingly in water. 
 Formed by reduction of o-nitro-benzene-azo-aoeto- 
 acetic acid with FeSO, and NH, (Bamberger, B. 17, 
 2420). 
 
 ^-Amido-benzene-^-aza-aniline 
 CsH,(NHj)— Nj— C5H,(NHj). p-Azo-anilim. Di- 
 amido-aeo-hemene. [235°]. Long flat yellow 
 needles. Easily soluble in alcohol, sparingly in 
 benzene and Ugroine. 
 
 Prepa/raUon. — 1. The mono-aoetyl derivative 
 of jp-phenylene-diamiue is diazotised and com- 
 bined with aniline, the aniUde thus obtained is ' 
 dissolved in aniline and warmed with aniline 
 hydrochloride by which it is converted into the 
 mono-acetyl derivative of amido-benzene-azo 
 
AZO- COMPOUNDS. 
 
 371 
 
 aniline, which is finally saponified. — 2. From 
 its di-acetyl derivative which is formed by the 
 action of zino and ammonia on aoetyl-^-nitro- 
 Bniline (Mixter, Am. 5, 282). 
 
 The mono-acid salts are green, the di-acid 
 red. B"H2Cl2: needles. 
 
 Mono-acetyl derwative Ci^^J^'R.^I^'B.k.c). 
 [212°], glistening golden yellow plates. Its salts 
 are red (Nietzki, B. 17, 345). 
 
 Di-acetyl derivative [282°] (M.). 
 
 Amido-benzene-azo-aniline 
 [4:1] CA(NH,)-N,-O.H,NH, [1:4]. [142°]. 
 Obtamed by reducing nitro-benzene-azo-nitro- 
 benzene [206°] with alcoholic ammonium sul- 
 phide (Janovsky, M. 6, 460). Minute plates 
 (from alcohol). Salt.— B"H2Cl2. This body is 
 probably identical with the preceding, the melting- 
 point having perhaps been misprinted. 
 
 m-Amldo-benzene-m-azo-aniline 
 [3:l]C,Hj(NHJ-Nj-OsH^(NH2) [1:3]. From the 
 nitro-compound by ammonium sulphide 
 (Janovsky, M. 6, 458). Minute flat yellow 
 needles with green lustre (from alcohol). 
 
 Amido-benzene-azo-benzene-jp-snlphonic acid 
 [4:1] C5H,(HS03)— N:N— C«H^.NH2 [1:4] S. -0144 
 at 22°. Yellowish-white microscopic needles 
 or scales (containing aq). Nearly insoluble in 
 water, alcohol, ether, and chloroform. Formed 
 by the action of diazo-benzene-p-sulphonic acid 
 on aniline (to extent of about 30 p.c). Pre- 
 pared from benzeue-azo-aniline and fuming 
 H^SO, at about 70°. • On reduction with tin and 
 HCl it gives ^-phenylene-diamine and sulpha- 
 nilic acid. 
 
 Salts. — A'NHj" : orange - yellow plates. — 
 A'2Ba6aq: sparingly soluble trimetric orange 
 needles— A'jCa 2aq (Griess, B. 15, 2184). _ 
 
 Amido-benzene-azo-benzene-jj-snlplionlc acid 
 [4:l]CsH^(S0,H)— N:N— CsHj.NH.[l:4]. S. -0196 
 at 22°. Pearly plates (containing aq). Formed 
 by reduction of the sparingly soluble nitro- 
 benzene-azo-benzene-p-snlphonic acid with am- 
 monium sulphide. On complete reduction with 
 tin and HCl it gives ^J-sulphanilio acid and p- 
 phenylene-diamine, and hence ought, according 
 to theory, to be identical with the preceding 
 compound; this, however, does not appear to be 
 the case. 
 
 ' Salts. — KA'aq: yellow trimetric plates.^ 
 »NaA': needles.— BaA'6aq : large glistening 
 monocUnic needles. — CaA'4aq: yellow pearly 
 plates.— PbA'2 : monoclinic plates (Janovsky, 
 B. 16, 1488 ; M. 4, 279, 652). 
 
 Si-amido-benzene - azo - benzene-2)-snlphonic 
 acid (NHj,)2CjH3— Nj- CjHj.SOsH. ChrysoUine 
 sulphonic acid. Brownish-red glistening needles. 
 SI. sol. water.' 
 
 Formation. — 1. By combination of ^-diazo- 
 benzene-sulphonic acid with m-phenylene di- 
 amine.— 2. By sulphonation of ohrysoidine. On 
 reduction it gives sulphanUic acid and (1:2:4)- 
 tri-amido-benzene (Griess, B. 15, 2196). 
 
 m-Aiaido-beiizeiie72)-azo-di-methyl-amline 
 [3:1] C,H,(NH,)-N,-C.H,NMe, [1:4]. [166°]. 
 Golden laminae, sol. alcohol. Formed by the 
 action of warm dilute H^SO^ on its acetyl deri- 
 vative [184°] which is obtained by mixing diazo- 
 tised aoetyl-TO-tolylene-diamine with dimethyl- 
 aniline (Wallach, A. 234, 263). 
 
 ^-Amido-benzene-aza-dimethylaniline 
 [4:1] NHj.C„Hj.N,.C,H,.NMej [1:4]. [188°]. By 
 
 warming the alcoholic solution of the nitro- 
 compound NOj.OjHi.Nj.OaHj.NMe^ withammonio 
 sulphide (Meldola, C. J. 45, 107). 
 
 Properties. — Briok-red needles (from dilute 
 alcohol). Insol. boiling water, but forms yellow 
 solutions in most solvents. Eeduced by zinc 
 dust and HCl it gives dimethyl-j>-phenylene-dia- 
 mine and ^-phenylene-diamine. On adding acetic 
 acid to an aloohoho solution, the liquid turns 
 green, on dilution with water it becomes red. 
 In cone. HjSO, the solution is orange. A very 
 dilute solution mixed with nitrous acid and 
 exposed to the air turns blue (test for nitrous 
 acid).— B"(HCl)2PtClj. 
 
 Methylo -iodide. — ^Insoluble brown scales. 
 Acetyl derivative. — Orange needles (from 
 alcohol). [217°]. 
 
 j2]-Amido-benzene-aza-(d)-iiaphtlioI 
 [4:1] NH,.C,H^.N:N.C,„H5.0H [a:0]. Formed by 
 reducing the corresponding nitro-compound with 
 ammonium sulphide and ammonia. Forms a 
 crimson solution in HjSO^ (Meldola, O. J. 47, 663). 
 
 jp-Amido-benzene-azo-(a)-naphthol 
 [4:1] NHj.CsH^.NrC,„H„.OH [a:i3]. Formed by 
 reducing para-nitro-benzene-azo-(o)-naphthol in 
 hot dilute NaHO with ammonium sulphide; ppd. 
 by HCl (Meldola, C. J. 47, 662). Dark brown 
 powder ; si. sol. hot water, v. sol. hot alcohol. 
 Forms a red solution in cone. H^SO,. 
 
 2j-Aniido-benzene-azo-(;3) - naphthol di-snl- 
 phonic acid. Acetyl derivative 
 CsHj(NHAc)-N2— C,„H,(OH)(S03H)2. Golden 
 glistening plates. Scarlet red dye-stuff. Formed 
 by diazotising the mono-acetyl derivative of p- 
 phenylene-diamine and combining it with {$)- 
 naphthol (E)-di-sulphonic acid (modification in- 
 soluble in alcohol). By saponification of th« 
 acetyl group it yields a bordeaux-red dye stuff. 
 By diazotising the latter and combining it with 
 (;8) -naphthol di-sulphonic acid a blue colouring 
 matter is produced (Nietzki, B. 17, 344). 
 
 p-Amido-benzene-aza-(a)-iiaphthylamine 
 [4:l]NH2.CjH,.Nj.C,„HeNH2[l:4]. [160°]. Formed 
 by reducing NOj.CjHj.Nj.CioHu.NHj with aqueous 
 ammonic sulphide (Meldola, C. J. 48, 432). 
 Ochreous needles. BeadUy soluble in alcohol, 
 acetone, benzene and chloroform. Its salts 
 form crimson aqueous solutions ; excess of acid 
 throws down the neutral salts.— -B"(HCl)2PtCl4. 
 
 p-Amido-benzene-azo-o-ozy-benzoic acid 
 [4:1] NH,.C,H,— N,-CeH3(0H)(C0^) [1:4:2]. 
 From the sodium salt of p-nitro-benzene-azo- 
 salicyHc acid by reduction with ammonium 
 sulphide. Colourless needles. SI. sol. boiling 
 water. Its alkaline solutions are yellow. Glacial 
 HOAo forms a crimson solution. Blackens at 
 219°-220° 0. (Meldola, C. J. 47 667). 
 
 m-Amido-benzene-azo-phenol 
 [8:1] C.H,(NH,)-N,-G,H,.OH [1:4]. 
 [168°]. Brownish yellow scales. Obtained by 
 saponification of the acetyl derivative. 
 
 Acetyl derivative 
 CeH,(NHAo).Nj.CeH,OH [0. 208°]. Prepared by 
 diazotising the mono-acetyl derivative of m- 
 phenylene-diamine and combining it with phenol. 
 (Wallach, B. 15, 3020). 
 
 j)-&mido-beiizene-azo-plienol 
 [4:1] NHj.C3H,.N:N.C„H^.0H [1:4]. [181°]. Oh- 
 tained by heating ^-nitro-benzene-azo-phenol 
 with ammonium sulphide. Brown scales (from 
 
 bb2 
 
873 
 
 AZO- COMPOUNDS. 
 
 water); v. sol. alcohol.— B'H„PtCL (Meldola, 
 C.J. 47, 658). 
 
 p-Amido-benzene-azo-diplieiiylainine 
 [4:1] NH,.CeH,.N2.C,H^NHC,H, [1:4] [c. 91°]. 
 Got by reducing the nitro- compound by ammonio 
 sulphide (Meldola, G. J. 43, 440). 
 
 Properties.— 81. sol. in boiling water, v. sol. 
 alcohol, acetone, chloroform and benzene, 
 forming yellow solutions. HCl added to the 
 alcoholic solution turns it first green, then red. 
 Solution in cone. H2SO4 is violet, turned red by 
 diluting. 
 
 Salts. — Form crimson aqueous solutions. 
 Dye wool orange. 
 
 m-Amido-benzene-azo-m-phenylene-diamine 
 [3:1] C.H,(NHJ-N,-0,H3(NH,), [1:2:4]. Bis- 
 marck brown. [137°]. Ppd. by adding NaNO^ 
 to a neutral solution of m-phenylene-diamine 
 hydrochloride (Caro a. Griess, Z. 1867, 278). 
 Brown plates. SI. sol. in hot water ; v. e. sol. 
 alcohol and ether. Dyes wool brown. Absorp- 
 tion spectrum (Hartley, C. J. 51, 180). 
 
 Salts .— B"2HC1.— B'-H^PtCle. 
 
 ^-Amido-benzene-azo-phenylene-diamine 
 "[4:1] C,H4(NH,)-N,— CeH,(NHJ, [l:2or3:4]. 
 From benzene-azo-benzene by nitration and re- 
 duction (Janovsky, M. 6, 466). 
 
 jj-Amido-benzene-azo-resorcin 
 [4:1] NH2.C,H,.N:N.CbH3(OH)j.[1:2:4]. _ By dis- 
 solving p-nitro-benzene-azo-resorcin in dilute 
 NaHO and warming with ammonium sulphide 
 (Meldola, C. J. 47, 661). Its alkaline solutions 
 are red ; its acid solutions are pale orange. — 
 B'jHjSO, : sHvery scales.— B'^H^PtClj. 
 
 jp-Amido-benzene-azo-m-xylidine 
 [4:1] NH2.CeH4.N2.CeH2Me2NH2 [1:8:5:2] [163°]. 
 Formed by reducing NO^.CsHi.Nj.CeH^Me^NH^ 
 with aqueous ammonio sulphide (Meldola, 0. J. 
 43, 482). Golden scales (from water). V. sol. 
 alcohol and benzene. 
 
 Salts. — The acid salts are very soluble in 
 water. Excess of HCl forms an amorphous 
 brown pp. of B"2HC1.— (B"2HCl)PtCli. 
 
 Amido-thiophene-azo-beuzene 
 C5H5.N2.C4SH2.NH2. Formed by adding diazo- 
 benzene chloride to a tolerably concentrated solu- 
 tion of thiophenine hydrochloride. — B'HCl |aq : 
 yellow needles, soluble in water and. alcohol 
 (Stadler, B. 18, 2817). 
 
 Amido - thiophene - azo - benzene -p - sulphonic 
 acid [4:1] CsH,(S03H).N2.C4SH2.NH2. Formed by 
 combination of diazo-benzene-p-sulphonic acid 
 with thiophenine. YeUow needles, red when dry. 
 SI. sol. water and alcohol. Dyes silk yellow. 
 (Stadler, B. 18, 2318). 
 
 Amido-thiopheue-azo-naphthalene 
 C,„H,.N2.CjSH2.NH2. Formed by adding (a), 
 diazo-naphthalene chloride to a solution of 
 thiophenine hydrochloride. The hydrochloride 
 forms microscopic red needles, sparingly soluble 
 in water and alcohol (Stadler, B. 18, 2318). 
 
 77z-Amido-toIneue-azo-aceto-acetic acid 
 [4:2:1] C„H3(CH3)(NH2).N2.CH(CO.CH3).C02H 
 [162°]. Bed glistening needles. Formed by re- 
 duction of m-nitro-toluene-azo-aceto-acetic acid 
 with FeSO, and NH3 (Bamberger, B. 17, 2421). 
 
 Amido-tolnene-azo-amido-cresol 
 [4:8:1] 0„H3(CH3)(NH2).N2.CsH2(CH3)(NH3)(OH). 
 Oxyaso-toluidine [212°]. Small dark - red 
 needles. V. sol. alcohol and ether, si. sol. water. 
 Formed from amido - toluene - azoxy - toluidiat 
 
 C3H3Me(NH2).N20.C3H3Me(NH,) by intramole- 
 cular change by heating it with H^SO^ at 110°. 
 It is reduced by SnClj to tolylene-diamiua 
 CsH3Me(NBL,)2 [1:2:4] together with di-amido- 
 oresol (Limpricht, B. 18, 1405).— B"H,S04.— 
 B"2HCl.-B"H3PtCl.. 
 
 Amido-toluene-azo-(j8)-naphthoI 
 
 [6:3:1] C„H3(CH3)(NH,)— N^- C,„H„OH [1:2]. 
 
 Acetyl derivative 
 C3H3(CH3)(NHAc)— Nj— CioH^OH [276°]. Insol. 
 water, si. sol. alcohol, m. sol. a mixture of 
 alcohol and chloroform. Bed colour. Formed 
 by diazotising the mono-aoetyl derivative of 
 (l:2:4)-tolylene-diamine and combining it with 
 ()3)-naphthol (Wallach, B. 15, 2830). 
 
 Amido-toluene-azo-nitro-ethane. 
 
 Acetyl derivative CuHuNjOj i.e. 
 [6:8:1] CsH3Me(NHAc).Nj,.CH(N02).CH3. [143°]. 
 From C3H3Me(NHAc).N3Br and NaCH(N02)C:^ 
 (Wallach, A. 235, 250). Bed needles (from alco- 
 hol-ether) ; v. si. sol. water, insol. ligroin. 
 
 Amido-toluene-azo-o-toluidine 
 [4:3:1] C3H3Me(NH,)-Nj-C3H3Me(NH,) [1:4:3] 
 [197°]. Formed by reducing nitro-o-toluidine 
 C3H3Me(N02)(NH3) [1:4:2], or the corresponding 
 azoxy-compound,by sodium amalgam in alcoholic 
 solution (Limpricht, B. 18, 1406; Graeff, A. 
 229, 350). Long red needles (from alcohol) or 
 small yellow needles (from water). Sparingly 
 soluble in water, easily in alcohol and ether. 
 
 Salts.— B"H2S0,: Slender reddish needles 
 — B"2HC1.— (B"2HCl)PtCl4.— B"2HBr. 
 
 Amido-toluene-azo-^-toliiidine 
 [6:3:1] CsH3Me(NH2)— Nj— C3H3Me(NHj) [1:6:3]. 
 [159°]. Bed needles. SI. sol. cold, v. sol. hot, 
 water ; v. sol. alcohol. Prepared together with 
 the hydrazo- compound by the prolonged action 
 of sodium amalgam on an alcoholic solution of 
 nitro-2)-toluidine (Buckney, B. 11, 1458). 
 
 Dl-amyl-amido-benzene-azo-di-amyl-aniline 
 [4:1] (C3H„),N.C,H,-N,-C;a,.N(C3H„), [1:4]. 
 Vi-amyl-ardline-azylme. [115°]. Bed pointed 
 crystals. Sol. hot alcohol. Formed by passing 
 NO through an aleohoUc solution of di-amyl- 
 aniUne. Salts. — B"(CjH2(N02)30H)2: small 
 yellow crystals. Periodide B",Is: small black 
 crystals with violet reflex (Lippmann a. Fleissner, 
 B. 15, 2142 and B. 16, 1419). 
 
 Beuzene-azo-aceto-acetic acid 
 CeHj- Nj— CHAcCOjH. [155°]. TeUowleaflc-ta 
 (from alcohol). Prepared by the action of a 
 solution of diazobeuzene nitrate on an alkaline 
 solution of acetaeetio ether (V. Meyer,B. 10, 2076).- 
 
 Salts. — A'K: yellow glistening leaflets. — 
 BaA'2, PbA'2, CuA'2, and AgA' are yellow pps. 
 
 Ethyl ether [75°]. Light yellow crystals ; 
 very readily saponified (Ziiblin, B. 11, 1417). 
 
 Beuzene-azo-acetone CijH5.N2.CH2.CO.CH, 
 [149°]. Glistening yellow prisms or needles. 
 Peculiar characteristic smell. Only slightly 
 soluble in hot water, and in aqueous alkalis. 
 
 Formation. — 1. By heating benzene-azo- 
 aoeto-acetic ether with a dilute alcoholic solution 
 of NaOH. — 2. By heating benzene-azo-aceto- 
 acetic acid to 170°-180°, COj being evolved 
 (Eichter a. Miinzer, B. 17, 1928). 
 
 Benzeue-azo-acetophenone 
 C„H5.N2.CH2.CO.C,H5. [129°]. Slender golden 
 needles. V. sol. hot alcohol and hot acetic acid. 
 Formed, together with benzene-azo-benzoyl- 
 acetic ether, by adding a solution of diazo- 
 
AZO- COMPOUNDS. 
 
 37» 
 
 benzene chloride to an iced alkaline solution of 
 benzoyl-aoetic ether (Bamberger a. Caiman, 
 B. 18, 2563). 
 
 Benzene-o-azo-aniline (?). 
 CjHs-Nj— CjH^NH^ (?). [123°]. Formed by 
 reducing benzene-o-azo-nitro-benzene with am- 
 monium sulphide (Janovsky, M. 8, 61 ; yellow 
 crystals with blue reflex (from dilute alcohol). 
 The salts are less soluble in water than those of 
 thejp-compound. 
 
 Benzene-azo-aniline Oi^H^N, i.e. 
 CjH^ — ^Nj — C5H4NH2 [1:4]. Amido-azo-benzene. 
 Mol. w. 197. [126°]. (above 360°). 
 
 Formation. — 1. By reducing benzene-azo- 
 nitro-benzene [137°] with ammonium sulphide 
 (G. Schmidt, Z. 5, 417 ; Janovsky a. Erb, B. 
 18, 1136).— 2. Together with bromo-aniline by 
 the action of bromine vapour upon aniline 
 (Kekul6, Z. [2] 1, 688).— 3. By action of mineral 
 acid (one molecule or less) upon diazo-benzene 
 anilide (v. Di-Azo- compounds) (Martins a. Griess, 
 Z. [2] 1, 132 ; FrisweU a. Green, C. J. 49, 746). 
 
 Preparation. — 1. Diazo-benzene -anilide is 
 dissolved in 2 or 8 times its weight of aniline, 
 jo'th its weight of aniline hydrochloride is added 
 at the ordinary temperature, and the mixture is 
 kept for an hour at 30° to 40° ; after standing 
 for twenty-four hours at the ordinary tempera- 
 ture, sufficient HOI is added to combine with 
 the free aniline and the amidoazo-benzene 
 base precipitates, or it can be obtained as 
 hydrochloride by adding more HCl. The yield 
 is nearly theoretical (Witt a. Thomas, O. J. 
 43, 113 ; Staedel a. Bauer, B. 19, 1953).— 2. A 
 cone, solution (of rather less than 1 mol.) of 
 NaNOj is added to (1 mol. of) aniline hydro- 
 chloride dissolved in (5 or 6 mols. of) aniline at 
 30°-40°, kept at 0. 40° for 1 or 2 hours, and 
 then at the ordirary temperature for 12 hours; 
 completed as above, the yield is nearly theo- 
 retical. 
 
 Properties. — YeUow crystals ; separates from 
 benzene vfith benzene of crystallisation (W. a. T.) ; 
 orange prisms with blue reflex (from alcohol). 
 v. si. sol. hot water, m. sol. ether and alcohol. 
 Its salts are decomposed by water; they dys 
 wool yeUow. Tin and HCl give aniline and p- 
 phenylene-diamine. Combines with EtI form- 
 ing the hydriodide of CsH,(NHJ.N2.C5H,NHEt. 
 Thediazo- compounds of benzene-azo-anilineand 
 its sulphonic acids are used for the preparation 
 of scarlets by combination with the naphthols 
 and their sulphonic acids. 
 
 Salts.— B'HCl: steel-blue needles or scales 
 (from boihng HClAq).— B'^H^PtCls.— B'HNOs. 
 — B'JLjSO,.— B'^H^C^O,. 
 
 Acetyl derivative CjH3.N2.C|iHj(NHAc). 
 [142°]. TeUow sUky crystals. On reduction 
 with alcoholic ammonium sulphide it gives 
 acetyl-amido-hydrazobenzene (Schultz, B. 17, 
 463 ; Berju, B. 17, 1400 ; C. C. 1884, 871). 
 
 BeacHons. — 1. By boiling benzene-azo-ani- 
 line with 10 pts. of HCl (S.G. 112) it is com- 
 pletely decomposed in a few hours with forma- 
 tion of ^-phenylene-diamine, aniline, chlori- 
 nated-hydroquinones, NH3, and colouring matters 
 (Wallaoh a. KoUiker, B. 17, 395).— 2. An alco- 
 holic solution of bromine forms a dibromo- 
 derivative [152°] which is reduced by tin and 
 HCl to aniline and ^-phenylene-diamine (Berju, 
 B. 17, 1400).— 3. With phenyl thio-oarbimide 
 
 it forms benzene-aeo-di-phenyl-thio-nrea (q.v.), 
 together with some benzene-azo-di-pheuyl-thio- 
 urea-azo-benzene (v. dis-Azo compounds). — 4, 
 Carbonyl chloride forms benzene-azo-di-phenyl' 
 urea-azo-benzene (Ph—Nj — C,Hj.NH)aCO(Berju, 
 B. 17, 1404). — 6. Benzene-azo-aniline hydrochlo- 
 ride (2 mols.) heated with acetone (1 mol.) at 
 150°-160° under pressure forms abase C„H,5N3, 
 [205°]. Yellow needles; v. sol. alcohol, ether, 
 and acids. By tin and HCl it is reduced to a 
 base of melting-point [185°]. Dilute solutions 
 of the salts have a blue fluorescence. Salts. — 
 B'HjSO, : slender soluble needles or small mono 
 clinic prisms. — B'H^Cr^Oirorange-yellowneedleB. 
 — B'HjCljPtCl, : flat yeUow needles, si. sol. cold 
 water (Engler a. Schestopal, B. 20, 480). 
 
 Benzene-azo-benzene C,2H,„N2 i.e. 
 C5H5— N2— CjHj. Azohemene. Mol. w. 182, 
 [68°]. (293°). V.D. 6-5 (calc. 6-3). S. (alcohol) 
 8-5 at 16° (Moltchanofisky, /. B. 1882, 224). 
 S.V. 220-4 (Eamsay). 
 
 Formation. — 1. By treating nitro-beuzena 
 with alcoholic potash (Mitscherlich, A. 12, 311 ; 
 Schmidt a. Schultz, ,4. 207, 328) , sodium-amalgam 
 in presence of alcohol and acetic acid (Werigo, 
 A. 135, 176 ; Alexejeff, Z. [2] 3, 33), iron (3 pts.) 
 and acetic acid (1 pt.) (Noble, A. 98, 253), or 
 with zinc-dust (Alexejeff, Bl. [2] 34, 684).— 
 2. By oxidising aniline with aqueous KMnO, 
 (Glaser, A. 142, 364), red-hot PbO (Schichuzky, 
 J. B. 6, 245), H^Oj (Leeds, C. N. 44, 210 ; B. 
 14, 1382) or bleaching powder (Schmitt, J. pr. 
 [2] 18, 195).— 3. It is the chief product of the 
 action of sodium on ^-bromo-aniline (Anschiitz 
 a. Schultz, B. 9, 1398; cf. Claus, B. 15, 315). 
 
 Preparation. — 1. By heating nitro-benzene 
 with a solution of sodium stannite prepared by 
 dissolving the theoretical quantity of SnCl^ in, 
 an excess of aqueous NaOH (Witt, B. 18, 2912). — 
 2. 400 grms. of NaOH (98 p.o. powdered) are 
 boiled with 2000 c.c. of ordinary alcohol till 
 most has dissolved ; 500 g. of nitrobenzene are 
 slowly added to the boiling solution, and the 
 formation of azoxybenzene completed by 2 or 3 
 hours' cohobation. 200 grms. of zinc-dust are 
 then slowly added and the boiling continued for 
 a day vrith occasional shaking. The alcohol is 
 distilled off on a, salt bath, warm water added, 
 the insoluble portion filtered off, washed, freed 
 from 2jn(OH)2 by HCl, and extracted with alco- 
 hol ; the filtrate on cooling deposits the azo- 
 benzene in splendid large plates ; good yield. 
 
 Properties. — Trimetric plates (Jeremejeff). 
 Crystallises with CjHj from benzene. Its absorp- 
 tion-spectrum has been descrtbed by Hartley 
 (C. /. 51, 176). 
 
 Beactions. — 1. Passed through a red-hot tube 
 it yields benzene and diphenyl (Ferko,B. 20,664). 
 2. Chromic acid in acetic acid at 200° forms 
 benzene-azoxy-benzene. — 3. Nitric acid forms 
 Ph.N,.C,H,(NO,) [1:4], Ph.N,.C«H,(N02) [1:2], 
 
 [4:1] CA(N0,).N,.C„H,(N0,) [1:4], 
 [1:3] C,H,(NO,).N2.CX(N02) [1:3], and a nitro- 
 benzene - azo - di - nitro - Ijenzene. — 4. Alcoholic 
 ammoniicm sulphide reduces it to hydrazo- 
 benzene (Hofmann, Pr. 12, 576). — 5. Hot cone. 
 HCl, HBr, or HI reduces it to benzidine, other 
 
 products being formed at the same time 
 
 6. Alcoholic SO2 produces benzidine. — 7. With 
 an ethereal solution of zinc ethyl it reacts form- 
 ing ethane (1 vol.), ethylene (8 vols.), and a 
 
374 
 
 AZO- COMPOUNDS. 
 
 product which, when treated with water, gives 
 aniline. 80 g. of azo-benzene gives 70 g. of 
 sniline. The reactions are probably : — 
 (a) PhNJPh + 2ZnEt2 = 2NPhH(ZnBt) + 2C2H, 
 (6) PhN2Ph + 4ZnEt2 = 
 
 2NPh(ZnEt)j + 2C^, + 2C,Hi. 
 And then, on adding water : 
 (a') NPhH(ZnEt) + H20 = NPhH2 + EtH + ZnO 
 (6') NPh(ZnEt)2 + 2B..fl = NPhH^ + 2EtH + 2ZnO 
 (Frankland a. Louis, O. J. 37, 560).— 8. Alde- 
 hyde at 200° forms a compound C^jH^^N^Oj 
 [164°]. In presence of chloride of zinc, alde- 
 hyde condenses with it to benzylidene-benzidine 
 Ph.CH:N.C,H,.CsHj.N:CH.Ph (?) [239°] (Barzi- 
 lovsky, /. B. 1885, 366).— 9. Bromine forms 
 mono-bromo- derivatives, a di-bromo- derivative, 
 [205°] {v. Bbomo-benzene-azo-beomo-benzene), 
 and a tetra-bromo- derivative, CijH^BrjNj, 
 [0. 320°] (Werigo, A. 165, 200). 
 
 Combinations. — C,jH|„N2,C^j [38°]. — 
 (CijHidNj)^ 8HC1 : unstable yellow crystals. — 
 (0,jH,jN2)2 3HBr : unstable red crystals, got by 
 passing HBr into a solution of azobenzene in 
 CS2. — CijHijNjBLBrj : crystals, formed by adding 
 bromine to a solution of the preceding body in 
 chloroform. — C,2H,„NjBrg: red prisms, got by. 
 adding excess of bromine to a solution of ben- 
 zene-azo-benzene in chloroform (Werigo, A. 
 165, 203). 
 
 Benzene-azo-benzene snlphonic acid 
 CeHs- Nj- CsH^SOsH [1:4]. [127°]. From ben- 
 zene-azo-benzene and fuming H^SO, (5 pts.) at 
 130° (Griess, A. 131, 89 ; 154, 208 ; Janovsky, 
 M. 2, 221; 3, 237; B. 15, 2576). Orange-red 
 plates (containing 3aq). SI. sol. alcohol and 
 ether. Potash-fusion converts it into E^SOj 
 and benzeue-azo-phenol. Ammonium sulphide 
 followed by mineral acid converts it into di- 
 amido-di-phenyl sulphonio acid. Nitric acid 
 forms mono-, di-, and tri- nitro- derivatives 
 (Janovsky, M. 3, 508). 
 
 Salts .—EA' 2aq.— BaAV— AgA'. 
 
 Chloride C.^HgN^SOjCl. [82°]. Orange 
 dumps (from ether). 
 
 Amide CijHjNjSO^NH^. Powder (Skanda- 
 toff, Z. [2] 6, 643). 
 
 Benzene-azo-benzene disulphonic acid 
 CsHs— Nj- C„H3(S03H)2 [1:2:4]. Formed, to- 
 gether with s-m,-, and s-p-, sulpho-benzene-azo- 
 benzene sulphonic acids by heating benzene- 
 azo-benzene (1 pt.) with pyrosulphuric acid 
 (4 pts.) at 150° (Janovsky, M. 3, 237). Very 
 deliquescent needles. Isomerides of this acid 
 are described as sulpho-benzene-azo-benzene 
 Bulphonic acid. 
 
 Benzene-azo-benzoic acid 
 C5Hs.N2.C,H^(C02H) [1:4]. Azo - benzene ■ p - 
 carboxylic acid. Obtained by saponification of 
 its nitrile by boiling with KOH. Long glisten- 
 ing brown prisms. Sol. alcohol, ether, and 
 warm benzene. Salts. — A'K: very soluble 
 brownish-yellow needles. — A'jBa : brownish-yel- 
 low needles ; sol. alcohol, si. sol. water (Mentha 
 a. Heumann, B. 19, 3023). 
 
 Nitrile C,H5.N2.C.H,(CN) [1:4]. p-Cyano- 
 azo-benzene. [101°]. Formed by diazotising 
 benzene-azo-aniline and allowing the solution 
 of diazo-benzeue-azo-benzene chloride to drop 
 into a hot solution of CuSO, and KCN. Brown 
 needles. V. sol. ether, benzene, and warm 
 cJoohol, insol. water. Sublimable (M. a. H.). 
 
 Benzene-azo-benzoyl-acetic acid 
 CsHj.N2.CH(CO.C„H5).C02H. [141°]. Long y el. 
 low needles. V. sol. alcohol, ether, and acetia 
 acid. Its ethyl-ether is formed, together with 
 benzene-azo-acetophenone, by adding a solution 
 of diazobenzene chloride to an iced alkaline 
 solution of benzoyl-acetic ether. By boiling 
 with dilute NaOH it is converted into benzene- 
 azo-acetophenone CsHs.N^.CHj.CO.CiiHs (Bam- 
 berger a. Caiman, B. 18, 2563). 
 
 Benzene-azo-benzylidene-auiline 
 CeHj- N2— C„Hj.N:CH.CjH5.B6M«2/M£Zene-amido- 
 azo-bemene. [125°]. Orange plates. Formed 
 by the action of benzaldehyde on benzene-azo- 
 anUine. By HCl it is resolved into its con- 
 stituents (Berju, B. 17, 1403). 
 
 Benzene-azo-o-bromo-benzene 
 C5H5 — N2— C^H^Br [1:2]. Bromo - azo - benzene. 
 [87°]. Glistening plates (from alcohol). SI. sol. 
 cold alcohol. By the action of bromine (1 mol.) 
 upon a warm acetic acid solution of benzene- 
 azo-benzene (1 mol.) a mixture of 0, m, and p, 
 mono-bromo-benzene-azo-benzene is obtained j 
 they can be separated by their different solubili- 
 ties in alcohol. By complete reduction they 
 give aniline and 0-, m-, or jp-bromaniline. 
 
 Benzene-azo-m-bromo-benzene 
 C5H5.N2.0.H.Br [1:3]. [56°]. Yellowish-green 
 pearly plates. V. sol. alcohol, ether and ace- 
 tone. On nitration it gives orange needles of 
 C,2H,Br(N02)N2 [123°] (Janovsky a. Erb, B. 
 20, 369). 
 
 Benzene-azo-^t-bromo-beuzeue 
 C„H5.N2.C,H,Br [1:4]. [82°]. Is the chief pro- 
 duct of the bromination of benzene-azo-benzene 
 in acetic acid. Orange yellow plates. Sub- 
 limable. V. sol. alcohol, ether, and acetone. 
 The corresponding hydrazo- compound forms 
 white needles. On nitration it gives orange 
 needles of C,2H^r(N02)N2 [108°] and also a 
 di-nitro- derivative [190°] (Janovsky a. Erb, B. 
 19, 2155 ; 20, 357 ; M. 8, 49 ; v. also Bbomo- 
 eenzene-azo-bkomo-benzene). 
 
 Benzene-azo-tri-bromo-resoTcin 
 Ph— Nj— CsBrs(0H)2. [186°]. Prom benzene- 
 azo-resorcin and bromine (Typke, B. 10, 1578). 
 
 Benzene-azo-p-chloro-benzene 
 Cells- N2 — CgHjCl [1:4]. Chloro-azobenzene. 
 [89°]. Yellowish-brown plates. Sublimes in 
 brown needles. Easily soluble in ether, benzene, 
 and hot alcohol, sparingly in cold alcohol. 
 
 Preparation. — 100 grms. of benzene-azo-ani- 
 line hydrochloride are suspended in 2 litres of 
 water and 220 c.c. of cone. HCl, and diazotised 
 by slow addition of a cone, solution of 20 grms. 
 sodium nitrite. After standing for some time 
 the diazo-azo-benzene solution is filtered and 
 slowly added to a boiling solution of 40 grms. 
 CujClj in 860 c.c. of cone. HOI, and boiled for 
 some time ; the greyish-black pp. is treated 
 with cone. HCl and then vrith dilute NaOH to 
 remove impurities, and extracted with hot al- 
 cohol ; the alcoholic solution after treatment 
 with animal charcoal deposits the benzene-azo- 
 chloro-benzene on cooling in glistening brown 
 plates ; the yield is 38 p.c. of the theoretical 
 (Heumann a. Mentha, B. 19, 1686). 
 
 Beactions. — When its alcoholic solution is 
 allowed to stand in the cold with SnClj and 
 2 drops of HjSOj it is converted into a chloro- 
 di-amido-diphenyl NHj.CjH^.CbH3C1.NH3. The 
 
AZO- COMPOUNDS. 
 
 375 
 
 latter liody is not formed, however, by heating 
 the hyirazo- oompound, previously prepared, 
 with i'HOl, but benzene-azo-ohloro-benzene, 
 ohlor(J-aniline, and aniline are formed instead. 
 On nitration with fuming HNOa benzene-azo- 
 chloro- benzene gives ^-ohloro-benzene-azo-^'- 
 nitro-benzene OsHiCl.N2.CsH,(N02). By treat- 
 ment with fuming Bulphurio aoid it is converted 
 into ^-chloro-benzene-azo-benzene ^'-sulphonio 
 acid CeH,Cl.N2.C„H^(S03H) (Mentha a. Heu- 
 mann, B. 19, 2970). 
 
 Benzene-azo-o-cresol 
 C,H,-N,-C,H3(CH3)(OH) [1:3:4]. [130°]. 
 Glistening yeUow plates. V. sol. alcohol, ether, 
 chloroform, and benzene ; si. sol. hot, insol. cold, 
 water. Dissolves in dilute alkalis with a 
 yellowish red colour. Obtained by the action of 
 diazobenzene chloride on an alkaline solution of 
 o-oresol. It readily gives a dis-azo- oompound 
 when treated in alkaline solution with a further 
 quantity of diazobenzene chloride. 
 
 Acetyl derivative: [82°]; yellow tahles, 
 T. sol. alcohol, ether, and benzene. 
 
 Benzoyl derivative: [111°]; small yellow 
 needles, v. sol. ether, acetone, and hot alcohol 
 (Liebermann a. Kostanecki, B. 17, 130 ; Nolting 
 a. Kohn, B. 17, 363). 
 
 Benzeue-azo-m-cresol 
 CeH,— N2-CeH3(CH3)(OH) [1:2:4]. [109°]. 
 
 Yellow needles. V. sol. alcohol, ether, chloro- 
 form and benzene. With alkalis it forms 
 yeUowish-red salts. Obtained by the action of 
 diazobenzene chloride on an alkaline solution 
 of m-cresol. It readily combines with another 
 mol. of a diazo- compound to form dis-azo- com- 
 pounds (Nolting a. Kohn, B. 17, 366). 
 
 Benzene-azo-p-cresol 
 0A-N,-0,H3(CH,)(0H) [1:5:2]. [109°]. 
 Orange yellow plates. Soluble in dilute alkalis. 
 Dyes a canary yellow. Formed by the action of 
 diazo-benzene chloride on an alkaline solution 
 of ^-cresol. It does not yield a dis-azo- compound. 
 
 Acetyl derivative Ph — N^ — C,Hs(OAc) : 
 [68°] ; yellow needles, v. sol. alcohol, ether, 
 chloroform, and acetone. 
 
 Benzoyl derivativeVh — N^ — C,H|j(OBz): 
 [113°] ; yellow needles, sol. ether, benzene, and 
 hot alcohol (Mazzara, G. 9, 425; Liebermann a. 
 Kostanecki, B. 17, 130 ; Nolting a. Kohn, B. 17, 
 352). 
 
 Benzene-azo-p-cresol-sulphonlc acid 
 CA-N,-C.H,(CH3)(OH)(S03H) [1:5:2:3]. 
 
 Small reddish brown tables or needles. Easily 
 soluble in water, sparingly in alcohol. Formed 
 by the action of diazobenzene chloride on an 
 alkaline solution of ^'-oresol-sulphonio acid 
 [1:4:2]. A'Na: soluble reddish brown plates, 
 dyes wool an orange yellow (Nolting a. Kohn, 
 B. 17, 357 ; cf. Stebbins, A. 0. J. 1, 465 ; 2, 263). 
 
 Benzene-azo-if'-camenol 
 0,H-N,-0,H(CH3)30H [1:3:5:6:2] [94°]. 
 Glistening brown prisms. In small quantities 
 it can be distilled undecomposed. Insoluble in 
 alkalis. Formed by combining diazo-benzene 
 chloride with t|(-cumenol [70°]. On reduction it 
 yields aniline and amido-i|'-cumenol [167°] 
 (Liebermann a. Kostanecki, B. 17, 886). 
 
 Benzene - azo - di - ethyl - amido - benzoic acid 
 0„H -N,-C,H3(NEt3)CO,H[l:4:2]. [125°]. From 
 diazo-benzene nitrate and di-ethyl-m-amido- 
 benzoic acid. Bed crystals with violet lustre 
 
 (from alcohol). Insol. water, si. sol. alcohol and 
 ether. Salts: BaA'^.— AgA' (Griess, B. 10, 526). 
 
 Benzene-azo-othyl-()3)-naphthyl-amine 
 C5H5— Nj— C,„H„.NHEt. [103°]. Bed needles. 
 Soluble in alcohol &c. with an orange-red colour, 
 insol. water. It forms bluish-violet salts with 
 acids. Formed by heating ethyl-(j3)-naphthyl- 
 nitrosamrne with an acetic acid solution of 
 aniline at 100°. Also produced by combining 
 diazo-benzene with ethyl- (/3)-naphthylamine. 
 
 Nitrosamine 0„H5.N2.C,„Hs.NEt(NO) : 
 [97°] ; red crystals (Henriques, B. 17, 2669). 
 
 Benzene-azo-ethyl-pheuylene-diamine 
 C3H5.N2.CsH3(NH2)NHEt. Ethyl - chrysc/idine. 
 Dyes a redder shade than ordinary chrysoidine. 
 Formed by combining ethyl-?»-phenylene- 
 diamine with diazo-benzene.— B"HC1: reddish- 
 brown needles with violet-blue reflection, soluble 
 in water and alcohol with an orange colour. — 
 W\n.fi\^V\,C\i; insoluble red pp. (Nolting a. 
 Strieker, B. 19, 547). 
 
 Benzene-azo-indoxyl 
 
 /C„H^-C(OH) 
 CA-N2-N< II (?) 
 
 \ CH 
 
 [236°]. Bed needles or thick orange prisms. 
 Sol. alcohol and alkalis, v. si. sol. water. 
 Formed by the action of diazo-benzene chloride 
 on indoxyl (Baeyer, B. 16, 2190). 
 
 Beuzene-azo-methane CgHj — N2 — CH3. Azo- 
 phenyl-methyl. (c. 150°). Yellow oil of pecu- 
 liar odour. Very volatile, and readily distils 
 with steam. Formed by oxidation of s-phenyl- 
 methyl-hydrazine CjHs.NH.NH.CH, with HgO 
 (Tafel, B. 18, 1742). 
 
 Benzene-azo-methazonic acid 
 Ph— N3- C3H3N2O3. [164°]. From diazo-ben- 
 zene nitrate and an aqueous solution of sodium 
 methazonate (Kimich, B. 10, 141). Orange 
 needles (from alcohol) ; insol. water. — NajA"2aq. 
 — BaA"aq. 
 
 Beuzene-azo-di-methyl-amido-benzoic acid 
 Ph— Nj— CsH3(NMe3)C02H [1:4:2]. Prom diazo- 
 benzene nitrate and di-methyl-m-amido-benzoio 
 acid (Griess, B. 10, 527). Orange nodules. 
 
 Benzene-azo-methyl-auiline 
 C5H5— Nj- OsHj.NHMe. Methyl-amido-azo-hen- 
 zene. [180°]. Bed needles. Sol. alcohol. Formed 
 by heating benzene - azo - aniline with Mel, — 
 B'HGl: violet needles. 
 
 Acetyl derivative CuHj.Nj.CjHi.NMeAc : 
 [139°] ; yellow silky needles (Berju, B. 17, 1401). 
 
 Benzene-azo-di-methyl-anLliue 
 CjHj.Nj. CsHj.NMej. JDi-meihyl-amido-azo-ben- 
 zene. [115°]. YeUow plates. 
 
 Preparation. — 1. A solution of 74 pts. of 
 NaNOj (100 p.c.) and 40 pts. of NaOH in 540 
 pts. of water is slowly added to a cooled solution 
 of 100 pts. of aniline, 130 pts. of dimethylaniUne, 
 and 230 pts. of HCl in 360 pts. of water (Griess, 
 B. 10, 525 : Mohlau, B. 17, 1490).— 2. By heat- 
 ing benzene-azo-aniline with Mel (Berju, B. 17, 
 1402 ; O. C. 1884, 871). 
 
 Methylo-iodideB'Mel. [174°]. Plates. 
 
 Benzene-azo-methyl-ketole 
 CeH,- Nj— OgHsN. [116°]. Yellow needles. 
 Formed by the action of diazo-benzene-chloride 
 upon methyl-ketole in aqueous alcoholic solution 
 in presence of sodium- acetate (Fischer, B. 19, 
 2990). 
 
876 
 
 azo- compounds. 
 
 Benzene-azo-methyl-phenylene-diamine 
 CjH5.Nj.C,H3(NH2)NHMe. Methyl-chryso'Cdine. 
 Minute orange prisms. Dyes a somewhat redder 
 shade than ordinary chrysoidine. Formed by 
 combining diazobenzene with methyl-m-phenyl- 
 ene diamine (Nolting a. Strieker, B. 19, 549). 
 
 Benzene ■azo-(a)-naphthol 
 CjHs— Nj — CioHj.OH. {a)-Naphthoqitinone- 
 
 phenyl-hydrazide. [206°]. Small needles with 
 blue reflection (from alcohol) or flat needles or 
 plates (from benzene). 
 
 Formation. — 1. By combining (a)-naphthol 
 with diazobenzene. — 2. By the action of phenyl- 
 hydrazine hydrochloride upon (a)-napthoqni- 
 none suspended in acetic acid. 
 
 Beactions. — Dissolves both in acids and 
 alkalis. Bromine forms two bromo- derivatives 
 [185°], and [196°] (Margary, G. 14, 271). 
 
 Salts. — A'K : crystalline pp. The hydro- 
 chloride, hydrobromide, and sulphate 
 form bluish or greenish glistening needles, 
 sparingly soluble in water, alcohol, and acetic 
 acid (Typke, B. 10, 1580). 
 
 Methyl ether X'Me: [83°]; brown crystals. 
 
 Ethyl ether A'Et : [100°]; long needles. 
 
 Acetyl derivative C,bH„N2(0Ac) [128°] ; 
 small brownish-red needles (Liebermann, B, 16, 
 2868 ; Zincke a. Bindewald, B. 17, 3026). 
 
 Benzene-o-azo-(a)-iiapIitliol 
 yOa. 
 
 [1:2]. (?) [138°]. (B.yNapUho- 
 
 C,.H / I 
 
 quirume-phenyl-hydrazide. Formed by the action 
 of phenylhydrazine hydrochloride upon (0)- 
 naphthoquinone. Long red needles ; sol. hot 
 alcohol and hot acetic acid. It does not combine 
 with acids or bases. By SnClj it is reduced to 
 (fl)-amido-(o)-naphthol. By treatment in hot 
 acetic acid solution with HNO, it gives di-nitro- 
 (ct)-naphthol. By the action of alkaline reducing 
 agents it is at once converted into ((8)-amido- 
 (a)-naphthol ; no intermediate product could be 
 detected (Zincke a. Bindewald, B. 17, 3030 ; 
 Zincke a. Eathgen, B. 19, 2482). 
 
 Bromo- derivative CuHjjNjBrjO ; 
 [216°-219°] : slender red needles. 
 
 Benzeue-azo-(/3)-naphthol C^^y^fl i.e. 
 
 C.H,.N2.C,„H„.0H or Ci„H, 
 
 y 
 
 m 
 
 \ 
 
 N2H.C,H50 
 
 [1:2]. 
 
 [134°]. 
 
 Formation. — By the action of a diazobenzene 
 salt on an alkaline solution of i8-naphthol. It 
 is not formed by the action of diazobenzene 
 hydrate on finely divided (/3)-naphthol (difference 
 from (a)-naphthol) (Liebermann, B. 16, 2858). 
 
 Properties. — Golden plates or long metallic 
 glistening needles. Soluble in ether, benzene, 
 ligroine and CSj. Dissolves in H^SO, with a 
 magenta-red colour. Is insoluble in caustic 
 alkalis. It has a slightly basic character, 
 dissolving in HCl with a red colour, and form- 
 ing an unstable hydrochloride crystallising in 
 needles. BySnClzit is reduced to (a)-amido- 
 (/3)-naphthol and aniline. The same reduction 
 products are also formed at once by treatment 
 with alkaline reducing agents (e.g. zinc-dust and 
 NaOH, ammonium sulphide, &c.) ; no inter- 
 mediate product was detected. When treated 
 in liot acetic acid solution with HNO3 it gives 
 
 ai-nitro-G3)-naphthol (Zincke a. Eathgein, B, 
 19, 2482). 
 
 Bromo- derivative CuHuBrN^O : [;.68°], 
 Brownish-red needles (Zincke a. Bindewaad, B 
 17, 3081). 
 
 Benzene-azo-(ii)-iiaphtlial sulphonic aCid 
 C^Hj— Nj— C,„H5(S03H)(OH). From Bodiinn (o). 
 naphthol sulphonate, aniline nitrate, and; KNOj 
 (Hofmann, B. 10, 1878). Slender brown needles 
 (from alcohol mixed with HClAq). Dyes orange, 
 — AgA'.— BaA'j. 
 
 Benzene-azo-(j3)-naphtliol sulphonic acid 
 CbHj— Nj— 0,„H5(HS0.,)0H. Brownneedles with 
 yellowish-green reflex. Difficultly soluble), in 
 water and alcohol. Prepared by the action of 
 an alkaline solution of (/3)-naphthol-sulphonio 
 acid on diazobenzene nitrate or chloride. — A'jBa. 
 Yellowish red microscopic leaflets. Slightly 
 soluble in water (Griess, B. 11, 2197). Its 
 absorption-spectrum has been examined by 
 Hartley {C. J. 51, 196). 
 
 Benzene-azo-(0)-naphthol disulphonic acid 
 CA— N^- C,oH,(S03H)j(OH). Fromsodium (/3)- 
 naphthol disulphonate and diazo-benzene nitrate. 
 Sol. water. Barium salt is si. sol. water 
 (Stebbins, jun., A. C. J. 2, 286). 
 
 Benzene-azo-(a)-naphtliylainine 
 C5H5 — N2— CioHjNH^. Prepared by the action 
 of diazobenzene sulphate on (o)-naphthyl- 
 amine (Griess, T. 1864, iii. 679 ; Weselsky a. 
 Benedikt, B. 12, 228).— B'jHjS0,4aq: micro- 
 scopic needles ; difiicultly soluble in water. 
 
 BenzeiLe-azo-(/3)-naplithylamine 
 
 .NH 
 C„H3-N,-C,.H3NH, or C,.H .< | 
 
 Benzene-hydrazimido-naphthaUne. [104°]. Bed 
 trimetric tables or long fine red needles. Easily 
 soluble in alcohol and acetic acid, insoluble in 
 water. Dissolves in strong HjSO, with a blue 
 colour. Its salts exist only in presence of a large 
 excess of acid. Formed by combination of 
 diazobenzene with (;3) -naphthylamine. By boiling 
 with 20 p.c. aqueous HjSOj it is slowly decom- 
 posed into (;8) -naphthylamine, phenol, and 
 nitrogen. On reduction it gives aniline and 
 (1, 2)-naphthylene diamine. On oxidation it 
 gives benzene-azimido-naphthalene {g[.v.). 
 
 Acetyl derivative C^HijAcNj. [153°]. 
 Small red needles, easily soluble in alcohol, in- 
 soluble in water. 
 
 Benzoyl derivative Cj^Rj^^zS,: [168°], 
 red crystals (Lawson, B. 18, 796). 
 
 Beuzene-o-azo-nitro-benzene 
 CsHs— Nj— CaHj(N02) [1:2]. Nitro-azobenzene. 
 [123°]. Formed by nitration of benzene-azo-ben- 
 zene in acetic acid at 100°. Orange-yellow 
 minute needles. V. sol. alcohol. Alcoholic 
 NaOH gives a beautiful emerald-green coloura- 
 tion ; by long boiling or by treatment with sodium- 
 amalgam it is further reduced to a compound 
 Cj^HisNjO. Tin and HCl or ammonium sulphide 
 first reduce it to benzene-o-azo-aniline and then 
 to aniline and o-phenylene-diamine. By bio- 
 mination in acetic acid it yields bromo-nitro- 
 benzene [123°] or [132°] (Janovsky a. Erb, B. 
 19 .2157 ; 20, 360 ; M. 8, 66). 
 
 Benzene-j)-azo-nitro-benzeae 
 C,H3.N2.CeH,.N02 [1:4]. [137°]. Small yellow 
 needles (from alcohol). Formed by nitration of 
 benzone-azo-benzene. By NHjHS it is reduced 
 
AZn. COMPOUNDS. 
 
 377 
 
 to ordinary benzbne-azo-aniline. Alcoholic 
 NH,HS produces red crystals of an intermediate 
 
 0,H,.N,.C,H,.NOH 
 nitrolio acid I (?) [134°], 
 
 C,H5.N2.CsH,.N0H 
 which forms a blue solution in NaOHAq. 
 KjFeCys reoxidises it to benzeue-azo-^-nitro- 
 benzene. By complete reduction it yields aniline 
 and ^-phenylene-diamine (Laurent a. Gerhardt, 
 
 A. 75, 73 ; Janovsky, B. 18, 1133 ; M. 6, 164, 455). 
 
 Benzene-azo-tri-nitro-benzene 
 O^Hj— N.,— C„H.(NO,),. [142°]. By action of 
 HgO on an alcoholic solution of the correspond- 
 ing hydrazo- compound (E. Fischer, A. 190, 133). 
 Slender red prisms (from alcohol). 
 
 Benzene-azo-nitro-iso-butane 
 C5H5 — N2 — CH(N02)?r. From diazobenzene ni- 
 trate and potassium nitro-iso-butane (Zublin, 
 
 B. 10, 2088). Oil. Forms an orange solution 
 in alkalis. 
 
 Benzene-azo-nitro-ethane CgHgNsOj i.e. 
 C.H^— Nj— CH(N02).CH3. [137°]. From diazo- 
 benzene nitrate and sodium nitroethane (V. 
 Meyer a. Ambiihl, B. 8, 751, 1073). Bectangular 
 orange crystals ; v. sol. alcohol and ether, insol. 
 cold water, sol. aqueous alkalis forming a blood- 
 red solution. Dyes silk yellow. Cone. fijSOj forms 
 a violet solution. It crystallises unaltered from 
 aqueous NH3 (Barbieri, B. 9, 386) but such a 
 solution gives pps. with metallic salts. 
 
 Salts.— C8H,K2Ns024aq.—0aH,Na2N302 7aq. 
 — CsH,ZnN30.,3a(i.— CsH,PbN30aPb02^aq. 
 
 Benzene-az i-nitro-methane 
 C^Hs— N2— CH2.NO2. [153°]. From diazoben- 
 zene nitrate and sodium nitromethane in very 
 dilute solution (Friese, B. 8, 1078). Slender red 
 needles (from alcohol). Cone. HjSO, gives a 
 purple solution. Decomposed by HGlAq only 
 after long boiling. 
 
 Benzene-az o-tri-nitTO-phenol 
 CsHs— Nj— CjH(N02)30H. Long brown prisms. 
 Insol. cold, si. sol. hot, water ; v. sol. alcohol. 
 Explodes at 70°. Dyes silk and wool orange- 
 yellow. Prepared by the action of a salt of 
 diazobenzene on an alcoholic solution of picric 
 acid (Stebbins, jun., A. C. J. 1, 465; 2,236; 
 
 C. Jf. 41, 117; B. 13,43). 
 Benzene-azo-nitro-propane 
 
 CaH— N2-CH(N02).0H2.CH3. [99°]. From po- 
 tassium nitropropane and diazobenzene nitrate 
 (V. Meyer, B. 9, 886). Orange needles; sol.alkalis. 
 
 Benzene-az o-iso-nitro-propane 
 C^H^— Nj— C(N0J(CHs)2. From aqueous diazo- 
 benzene nitrate and potassium nitro-isopropane. 
 Oil; insol. alkalis (V. Meyer a. Ambiihl, B. 
 8, 1076). 
 
 Benzene-azo-o-oxy-benzoic-acid 
 C.Hs— N2— CsH3(OH).C02H. From diazobenzene 
 nitrate and an alkaline solution of salicylic acid 
 (Stebbins, jun., A. 0. J. 1, 465; B. 13, 715; 
 C. N. 41, 117). Orange-red needles ; insol. water, 
 y. sol. alcohol or ether. Dyes wool orange. 
 
 Benzene-azo-di-ozy-naphthalene 
 
 C,H3-N2-0,„H,(OH)2 or C.oH,(OH) {^^hC,H,. 
 Oxy - (o) - naphthoquinone phenyl hydrazide. 
 [230°]. Formed by the action of phenyl- 
 hydrazine on oxy-naphthoquinone in aqueous- 
 alcoholic solution. Yellowish-red glistening 
 needles. V. sol. ether, hot alcohol, and hot 
 acetic acid. 
 
 Salts. — The alkali salts form slender oranga 
 needles, sol. alcohol. — A'^BalOaq: yellowisii- 
 brown plates or long red needles. — A'jCa 4aq : 
 slender orange needles. — A'Ag : reddish-brown 
 amorphous pp. 
 
 Acetyl derivative: [179°]; red needles. 
 
 Methyl ether A.'M.e: [175°]; red needles. 
 
 Ethyl ether A'Et ; [173°]; yellowish-red 
 needles, v. sol. hot alcohol and hot acetic acid. 
 
 Bromo-derivative OiaHiiBrO^Nj : [198°] ; 
 large red needles, si. sol. alcohol (Zincke a. 
 Thelen, B. 17, 180J). 
 
 Benzene-azo-phenolOsHj— N2— OjHj.OH[l:4]. 
 Oxy-azo-bemene. [154°]. 
 
 Formation. — 1. A product of the action of 
 BaCOj on diazobenzene nitrate in the cold 
 (Griess, A. 137, 84). — 2. From benzene-azo-ben- 
 zone sulphonic acid by potash fusion (Griess, A. 
 154, 211). — 3. From diazo-benzene nitrate and 
 CjEsOE (Kekul6 a. Heidegh, Z. [2] 6, 384).— 4. 
 By the action of ^-nitroso-phenol (20 pts.) on 
 aniline acetate (60 pts.) (Kimich, B. 8, 1499). — 
 5. By gently warming benzene-azoxy-benzene, 
 0,Hj— N2O— C^Hj, with H2SO, (Wallaoh, B. 13, 
 525 ; 14, 2617). 
 
 Properties. — Purple pyramidal plates. Insol. 
 cold water, sol. alkalis ; v. sol. alcohol. Bro- 
 mine in acetic acid gives a compound [139°]. 
 
 Salt.— AgA'. 
 
 Acetyl derivative. — Ph.Nj.OaHjOAo. 
 [85°]. (above 360°). Golden scales. 
 
 Methyl ether. — Fh.'S^.G^'afiUe [54°]. 
 Yellow scales. 
 
 Benzene-azo-phenol snlpbonic acid 
 CeHj- Nj- C„H3(OH)(S03H) [1:4:3]. From diazo- 
 benzene nitrate and an alkaline solution of 
 phenol o-sulphonic acid (Griess, B. 11, 2194), 
 Bed needles or tables ; sol. water and alcohol. — 
 K4.'. 
 
 Benzene-azo-pbenol sulphonic acid 
 0,2HsN2(OH)(S03H). From benzene-azo-phenol 
 and fuming HjSOi (Tschirvinsky, B. 6, 560). — 
 BaA'22aq.— CuA'j6aq.— MgA'26aq.— KA'. 
 
 Benzene-azo-phenol di-snlphonic acid 
 C,2H,N2(OH)(S03H)2. From azoxybenzene 
 (1 pt.) and fuming H2SO4 (10 pts.) by heating 
 for 3 hours at 150° (Limpricht a. Wilsiug, A. 
 215, 232 ; B. 15, 1297). Orange needles, v. e. 
 sol. water, v. sol. dilute acids. 
 
 Salts.— K2A"2aq: red needles, si. sol. oold 
 water; not attacked by Br. — BaA"aq: orange 
 crystalline pp. — AgjA" : red crystalline pp. 
 
 Benzene-azo-phenol tetra-sulphonic acid 
 '<C,2H5N2(OH)(S03H),. From azoxybenzene 
 and fuming HjSO^ (L. a. W.). Will not crystal- 
 lise. Salts.— C,2H5N2(0K)(S03K;),7|aq ; long 
 yellow needles. Gives with bromine-water a pp. 
 of tri-bromo-phenol [92°]. — ^Ba^A'^ 7aq : orange 
 crystalline pp. 
 
 Other benzene-azo-phenol sulphonic acids are 
 described as Oxy-bemene-Azo-bemene sulphonAo 
 acids, and sulpho-hemene-izo-phenol sulphon/ic 
 acids. 
 
 Benzene-azo-diphenylamine 
 C3H5-N2-CeH4.NH.C,H5. [82'] (0. N. Witt, 
 C. /. 35, 185 ; B. 12, 259). A solution of di- 
 phenylamine (17 g.) in alcohol (100 c.c.) is added 
 to a solution of diazo-benzene chloride (14 g.) in 
 alcohol (50 g.). The brown mixture is cooled 
 with ice, and alcohoUo NMe3 (used instead of 
 NH3 because NMe3HCl ia soluble in alcohol) is 
 
878 
 
 AZO- COMPOUNDS. 
 
 added from time to time to neutralise the liquid. 
 The oil which separates is purified by a lengthy 
 process, and finally crystaUised from benzoUne. 
 
 Properties. — Golden leaflets or needles. Sol. 
 benzene, alcohol, and ether. HCl turns its 
 alcoholic solution violet; steel-grey crystals of 
 the hydrochloride separating. The base forms 
 a green solution with HjSO, turned, by adding 
 water, into indigo, violet, and finally red. With 
 amylnitrite and acetic acid it forms a nitrosamine, 
 Ph.N(NO).0^HjNjPh, [120°], forming orange 
 needles, sparingly soluble in alcohol and acetic 
 acid, readily in benzene. 
 
 £euzeae-azb-m-plienylene diamine 
 CeHj— Nj— CaHalNHJj [1:2:4]. ChrysoUine. 
 
 [117-5°] (W.) ; [110°] (H.). From diazobenzene 
 salts and m-phenylene diamine (Witt, B. 10, 
 350, 654 ; Hofmann, B. 10, 213, 388 ; Griess, B. 
 10, 390). Slender yellow needles (from water) ; 
 si. sol. water, v. sol. alcohol. Reduced by am- 
 monium sulphide at 150° to aniline and (1,2, 4)- 
 tri-amido-benzeue. The absorption-spectrum has 
 been examined by Hartley (0. J. 51, 178). — 
 B"HC1 : black ootahedra or small red silky 
 crystals; its aqueous solution is orange, but 
 turned red by HCl— B"2H,PtCle.— B"HN03. 
 
 Di-acetyl derivative 
 Ph— Nj— CsH3(NHAc)2 [251°]. 
 
 Benzene-azo-m-phenylene-diamine snlphonic 
 acid O5H5— Nj— CjH3(NH2)2(S03H). ChrysoUine 
 sulphonic acid. Glistening spangles or needles. 
 SI. sol. water and alcohol. Prepared by the 
 action of diazobenzene-chloride on a salt of 
 m-phenylene-diamine sulphonic acid. A'Na : 
 soluble golden needles — A'^Ba : orange needles 
 (Euhemann, B. 14, 2655). By the sulphonation 
 of chrysoidine an isomeric acid is formed (v. 
 Di-amido-bemzene-azo-iensene sulphonic acid). 
 
 Benzene-azo - di- phenyl - methyl - pyrrol-car - 
 boxylic acid C^^ifi^^i.e. 
 HO„C.C:CMe. 
 
 .1 
 
 "X 
 
 ;N.C,H,.N2.0,H5. [195°]. Obtained 
 
 HC:CPh/ 
 
 by saponification of its ethyl ether, which is 
 formed from an acetic acid solution of aceto- 
 phenone-aceto-acetic ether (1 mol.) and benzene- 
 p-azo-aniHne (1 mol.) on standing for two days. 
 Large red crystals. V. sol. alcohol, ether, and 
 benzene ; si. sol. ligroin and acetic acid ; insol. 
 water, and cone, acids. Gives Laubenheimer's 
 reaction. 
 
 Ethyl ether EtA': [123°]; splendid red 
 crystals ; v. sol. benzene and ligroin, si. sol. 
 alcohol, ether, and acetic acid (Paal a. Schneider, 
 B. 19, 8162). 
 
 Benzeue-azo-phenyl-(i3)-naphthyl-amiue 
 C,,H„N, i.e. CeH,-N,-C„HeNHC,H, or 
 /N.CA 
 C,.H / 1 
 
 ^N^HC^H; 
 Benzene - phenyl - hyd/razimido - naphthalene. 
 [142°]. Obtained by combining diazo-benzene 
 chloride with phenyl-(3)-uaphthyl-amine in 
 alcoholic solution. It is also formed by the 
 action of an acetic acid solution of aniline upon 
 phenyl-(|8)-naphthyl-nitrosamine. Small red 
 glistening needles. 
 
 Reactions.— 1. By heating with cone. HCl it 
 
 yields naphthophenazine C^H,"; | >C,(,H. and 
 
 aniline. — 2. Bromine acting on the hot acetic 
 acid solution forms tetra-bromo-phenyl-(i8)- 
 naphthylamine with evolution of nitrogen. — 3. 
 It is redticed by SnClj to aniline and phenyl- 
 o-naphthylene diamine C„H|i(NH2)NHCjH5. — 4. 
 By oxidation with XjCvfi, in acetic acid solu- 
 tion the chromate of a powerful ammonimri- 
 base C22H15N3OH is formed ; the latter possibly 
 
 .N(0H).0„H5 
 has the constitution 0,fi^\ | \ 
 
 NN.N.CjHj 
 V. Naphthalene di-phenyl-^zusHo^nxsm-hydrate 
 (Heuriques, B. 17, 2671 ; Zincke a. Lawson, 
 B. 20, 1167). 
 
 Benzene-azo-di-phenyl-thio-nrea 
 C5H5— Nj— 0,H^.NH.CS.NHPh. [179°]. Plates. 
 Formed by combination of phenyl-mustard-oU 
 with benzene-azo-aniline (Berju, B. 17, 1405). 
 
 Benzene-azo-pyrogallol 
 C5H5 — Nj — CjH2(OH)3. Prepared by adding an 
 aqueous solution of diazobenzene nitrate to an 
 alkaUne solution of pyrogallol (Stebbins, jun., 
 
 A. G. J. 1, 465 ; 2, 236 ; B. 13, 44 ; C. N. 41, 
 117). Bed needles (from acetic acid). Insol. 
 water, sol. alcohol. Its alcoholic solution dyes 
 silk and wool orange. 
 
 Benzene-p-azo-resorcin 
 C.H3-N2-C3H3(0H)2 [1:2:4]. [161°] or [170°]. 
 From diazobenzene nitrate and resorciu (Typke, 
 
 B. 10, 1577 ; Wallach, B. 15, 2819 ; B. Meyer, 
 B. 16, 1329). Formed also by gently warming 
 diazobenzene auilide with resorcin, aniline being 
 eliminated (Heumann a. Oeconomides, B. 20, 
 905). Slender orange needles [170°] or short 
 red needles [161°], insol. water, sol. aqueous 
 alkalis, v. e. sol. alcohol. 
 
 Acetyl derivative [102°]. 
 
 Mono-ethyl etfeer [87°]. Scarlet needles. 
 
 Diethyl ether [70°]. Yellowish-redneedles. 
 
 Benzene-o-azo-resorcin CsH5.N2.CjH3(OH)2 
 [1:2:6]. Formed in small quantity (about 5 p.c.) 
 in the preparation of the ^-isomeride. 
 
 Mono-ethyl ether C8H5.N2.C8H3(OH)(OEt) 
 [150°]. Long fine scarlet needles ; v. e. sol. alco- 
 hol and ether, insol. water ; dissolves in aqueous 
 alkalis with a brownish-red colour. 
 
 Di-ethyl.etherG^B.^JS^.C^B^{(mi)^:{W\. 
 Large red glistening tables ; v. sol. ether, hot 
 alcohol and acetic acid, insol. water (Pukall, B. 
 20, 1145). 
 
 Benzene-azo-thymol 
 CeHj— Nj— CeH2MePr(0H) [1:2:5:4] [85°-90°]. 
 From diazobenzene chloride, and an alkaline 
 solution of thymol (Mazzara, Q. 15, 52, 228). 
 Eeddish-yellow needles. Eeduction followed by 
 oxidation gives thymoquinone. 
 
 Benzene-azo-thymol-sulphonic acid 
 CeH3-N2-C3H(CH3)(C3H,)(HS03)0H. [216°]. 
 Small yellow prisms. Yellow colouring matter. 
 Prepared by the action of diazobenzene chloride 
 on a salt of thymol-sulphonic acid. Salts. — 
 A'Na : small yellow crystals. — A'jBa : fine hair- 
 like needles (Stebbins, B. 14, 2793). 
 
 Benzene-^-azo-toluene O3H5 — N2— CjHj(CH3). 
 [63° corr.]. Formed by diazotising amido-ben- 
 zene-^-azo-toluene CsH4(CH3) — Nj — C3H4(NHj) 
 dissolved in alcohol and boiling the solution 
 (Schultz, B. 17, 466). Orange-red plates; v. sol. 
 alcohol. Volatile with steam. By treatment 
 with alcoholic SnCl^ and H2SO4 it is converted 
 into a base melting at [116°]. 
 
AZO- COMPOUNDS. 
 
 379 
 
 Benzene-azo-m-tolylene diamine 
 C8H5—Nj—CeH2Me(NH.j2.Tellowiieeaies. Easily 
 soluble in alcohol, sparingly in water. Prepared 
 by the action of diazobenzene chloride on (1, 2, 4) 
 toljlene- diamine, [99°]. — B'HOl : orange red 
 needles (Stebbins, jun., A. O. J. 1, 465 ; B. 13, 
 717 ; C. N. 41, 117). 
 
 Benzene - azo - xylenol CsHs.Na.CjHjMe^.OH 
 [1:3:5:2]. [175°]. Formed by combining diazo- 
 benzene chloride with m-xylenol CjHjMejfOH) 
 [1:3:4] (Grevingk, 5. 19, 148). Slender brownish- 
 red needles. V. sol. alcohol, ether, and benzene, 
 insol. water. On reduction it yields aniline and 
 o-amido-m-xylenol CBH2Me2(NH2)(OH) [5:3:2:1]. 
 
 Bromo-amido-benzeue-azo-^-bromo-aniline 
 
 Diacetyl derivative 
 [2:5:1] NHAo.CeHjBr— N^— C^HjBr.NHAc [1:5:2] 
 [282°]. Formed by warming aoetyl-bromo-nitro- 
 anilineCsH3(NHAc)Br(N0.J [2:5:1] with zino and 
 cone. NHjAq (C. H. Matthiesseu a. Mixter, Am. 8, 
 347). Pale red substance. 
 
 p - Bromo -benzene - azo - benzene -jp-snlphonic 
 acid [4:1] C^,Br - N, — C^,(S03H) [1:4]. 
 Formed by sulphonation of benzene-p-azo-bromo- 
 benzene or by brominatiou of benzene-azo-ben- 
 zene-2>-sulphonio acid. Flat needles (containing 
 3aq). 
 
 Salts. — KA.' : rhombic tables. — NaA' : 
 yellow silky needles, si. sol. water (Janoveky, M. 
 5, 162 ; B. 20, 358 ; if. 8, 53). 
 
 m - Bromo -benzene-azo-beuzene -^-sulphoiiic 
 acid [3:1] C,H^Br— N^— CeH,(S03H) [1:4]. 
 Formed by sulphonation of benzene-m-azo-bromo- 
 benzene with fuming sulphuric acid. Glistening 
 golden plates (containing If aq). 
 
 Salts. — EA': yellow pearly pp. of micro- 
 scopic needles. — NaA': pp. t. si. sol. water 
 (Janovsky a. Erb, B. 20, 359). 
 
 o-Bromo-benzene-o-azo-bromo-benzene 
 1.2:1] CsH^Br— Nj— C,H,Br [1:2]. [185°]. A 
 product of the bromination of benzene-azo- 
 benzene in HOAc (Janovsky, M. 8, 50 ; B. 20, 
 337). Golden plates, si. sol. alcohol. On nitra- 
 tion it gives a tri-nitro- derivative [135°]. 
 
 p-Bromo-benzene-2)-azo-bromo-1)8nzene 
 [4:1] C^H^Br— Nj— CXBr [1:4]. [205°]. Formed 
 by bromination of benzene-azo-benzene (Werigo, 
 A. 135, 178 ; 165, 189). Formed also by reduc- 
 tion of ^-bromo-nitro-benzene with zinc-dust 
 and alcohoUc KOH (Schultz, B. 17, 465). 
 Yellow needles. By alcoholic SnClu and H2SO4 
 it is converted into a di - bromo - di - amido- 
 diphenyl. Fuming H^SOj forms a sulphonic 
 acid C.-HiBraNaSOsH 3aq (W.). 
 
 m-Bromo-benzene-m-az6-bromo-benzene 
 [3:1] C^HjBr— Nj— C^H^Br [1:3]. [126°]. From 
 the corresponding hydrazo- compound by FojClj 
 (Gabriel, B. 9, 1407). 
 
 Tribromo-benzene-azo-dimethyl-auiline 
 OeHjBr,-Nj— CeH,(NMe2). [161°]. Formed by 
 adding an alcoholic solution of dimethylaniline 
 (2 mol.) to C„H2Br3N2.N03 (Imol.). Crystalline pp. 
 
 Bed plates (from glacial acetic acid). Insol. 
 water, hardly soluble in alcohol. It combines 
 with cone. HCl (SUberstein, Xpr. [2] 27, 124). 
 
 Tribromo - benzene - azo - methyl - diphenyl- 
 amine CeH^Br,— N^— C,H^NPhMe. [138°]. 
 From CsH^rjNjNOa and NPh^Me in alcohol. 
 Small brownish-red plates (from glacial acetic 
 acid). Insol. water, si. sol. alcohol. Does not 
 combine with HCl (Silberstein, /. pr. [2] 27, 126). 
 
 Broma-benzene-azo-(a)-naphthol 
 [4:1] C,H,Br— N^— C,„H„OH [1:4].- [196°]. From 
 ^-diazo-bromo-benzene and (o)-naphthol, or 
 by brominatiou of benzene-azo-(a)-naphthol 
 (Mazzara, G. 14, 271). 
 
 ^-Bromo - benzene - azo - (;3) - uaphthol 
 [4:1] C,H<Br— N,,— C,„H„OH [1:2]. [161°]. From 
 jp-diazo-bromo-benzene and (;8)-naphthol, or from 
 benzene-azo-(;8)-naphthol and bromine (Mazzara, 
 O. 13, 438). Orange needles. 
 
 ^-Bromo-benzene-p-azo-nitro-benzene 
 [4:1] CeH,Br-N,-C.H,(NO,) [1:4]. [108°]. 
 Formed by nitration of benzeue-^-azo-bromo- 
 benzene. Yellow needles. V. sol. alcohoJ 
 (Janovsky a. Erb, B. 20, 358). 
 
 Bromo-benzene-azo-di-nitro-benzene (?) 
 [4:1] C„H,Br-N,-OeH,(NO,), [1:2:4] (?). [190°]. 
 Formed by nitrating benzene-^J-azo-bromo-ben- 
 zene (Janovsky, M. 8, 52). 
 
 ^-Bromo-benzene-azo-mtro-ethane 
 [4:1] 0„H^Br-Nj— CH(N02).CHa. [0. 137°]. 
 From^-diazo-bromo-benzene nitrate and potas- 
 sium nitro-ethane (Wald, B. 9, 393). Brick-red 
 crystals (from dilute alcohol) ; sol. ether, glacial 
 HOAo, and chloroform. Salt.— OsHjENsO-^r. 
 
 Bi-bromo - di - imido-di-hydro-anthracene-azo- 
 di-bromo-di-imido-di-hydro-anthracene 
 CnHiEr^N, or 
 
 NJa: NH 
 
 CeH<g>C,3r,H-N,-Br,HC.<g>C3H,(?) 
 
 NH NH 
 
 [233°]. Prepared by heating dibromo - nitro- 
 anthraquinone with alcoholic NH3 (Claus a. 
 Diemfellner, B. 14, 1335). Bed needles. Sub- 
 limable. SI. sol. alcohol and ether, insol. water 
 or aqueous acids and alkalis. 
 
 Bromo ■ di - ozy - benzene - azo - bromo- 
 hydroqninone. Tetra-methyl derivative 
 C,HJBr(0Me)2— Nj— C,H2Br(OMe)2. [220°].. 
 
 Formed by bromination of the tetra-methyl 
 derivative of di-oxy-benzene-azo-hydroquinone 
 (Baessler, B. 17, 2125). Bed crystalline solid,. 
 V. sol. benzene, chloroform, and CS2, v. si. soL 
 alcohol, insol. water. 
 
 Bromo-sulpho-benzeue-azo-benzene suIpho> 
 nic acid 
 
 [6:3:l]C,H3Br(S03H)—Nj—C«H3Br[S03H) [1:6:3].. 
 Formed by oxidation of a neutral aqueous, 
 solution of bromo-amido-benzene sulphonic acid 
 CsH3Br(NH2)(S03H) [4:3:1] with KMnO^. 
 Salts. — K2A"2aq: glistening red tables (Lim- 
 pricht, B. 18, 1422). 
 
 Ci-bromo - sulpho - benzene-azo-di-bromo-ben- 
 zene sulphonic acid 
 
 r2:6:4:l]C.H2Br2(S03H).N2.C,H3Br2S03H[l:2:6:4]. 
 From potassio di - bromo - - amido - benzene 
 sulphonate and KMnO, (Eodatz, A. 215, 222). 
 Bed plates (containing 2aq). V. sol. water or 
 alcohol. Beduced by SnCl2 to the original 
 C8H2(NH3)Br2S03H. Salts. — K2A"2aq. ~ 
 BaA" 3aq.— CaA" 4aq.— PbA". 
 
 CTsZoriie.— [258°-262°]. Brown plates. 
 
 Amide. — Violet silky needles. 
 
 Si ■ bromo - sulpho - benzene - azo - di - biomo- 
 benzene snlphouic acid 
 
 [4:6:3:l]C,H2Br3(S03H).N2.C5H2Br2S03H[l:4:G:3].. 
 From potassic di-bromo-amido-benzene sulpho- 
 nate and KMnOj (Eodatz, A. 215, 216). Slender 
 red needles, containing If aq (from water). V, 
 sol. water, v. e. Bol. alcohol. Beduced by SnCl 
 
380 
 
 AZO- COMPOUNDS. 
 
 to the original CaHj(NH2)Br2.S0sH. Salts.— 
 iCjA"3aq.— BaA" aq.— OaA" 4aq.— PbA" 2iaq. 
 
 Chloride.— [2SS°2. Briok-red needles. 
 
 Amide. — Mioroscopio orange needles (from 
 alcohol). Does not melt. 
 
 An acid isomeric with the above may be got 
 by the action of KMnOj on the tetra-bromo- 
 hydrazo-benzene di-sulphonic acid of Jordan, 
 A. 202, 361. 
 
 Iri - bromo - sulpha - benzene • azo-tri - bromo- 
 benzene sulphonic acid [2:4:6:3:1] 
 C5HBr3(S03H)— Nj- CsHBrs(S03H) [1:2:4:6:3]. 
 From potassio tri-bromo-m-amido-benzoate by 
 KMnOj (Bodatz, A. 215, 225). Flat orange 
 needles. Eeduced by SnClj to the original 
 C„H(NHj)Br3.S03H. 
 
 KjA" 3aq.— BaA"2aq.— CaA" 7aq.— PbA"4aq. 
 
 Chloride.— {222''~22i°]. Dark violet tables. 
 
 Amide. — Brown crystals that do not melt. 
 
 Si-bromo - salpho -benzene - azo- (/3)- naphthol 
 ■C3H2Br2(S03H)— Nj— CioHjOH (Stebbins, O. N. 
 42, 44 ; A. C. J. 2, 236). From diazo-dibromo- 
 benzene sulphonic acid and an alkaline solution 
 ■of (i8)-naphthol. 
 
 Di-bromo - snipho -benzene- azo-di - ozy-naph- 
 thalene OsttiBrjfSOaH)— N^— C,„H5(OH)2. From 
 diazo-dibromo-benzene sulphonic acid and an 
 alkaline solution of dioxynaphthalene. Needles 
 <GrieBS, B. 11, 2199). 
 
 Bromo -snipho - tolneue -azo - bromo -toluene 
 sulphonic acid Nj{CsH2BrMe.S03H)2 [1:?:4:5]. 
 From potassio bromo-^-toluidine sulphonate (of 
 Jenssen) and KMnO, (Komatzki, A. 221, 186). 
 Eed tables with pointed ends. Salts. — 
 KjA" 4aq.— BaA" 5aq.— CaA" 4|aq.— PbA" 5aq. 
 
 Chloride. — [226°]. Groups of red prisms. 
 
 Amide. — [above 260°] : red powder. 
 
 Si - bromo • snipho - toluene - azo - di - bromo- 
 toluene sulphonic acid N2(C8HBr2Me.SOsH)2 
 [1:?:?:2:5]. From potassio dibromo-o-toluidine 
 ■sulphonate (of Hayduok) and KMnO^ (Komatzki, 
 
 A. 221, 188). Blood-red plates. Salts.— 
 K2A"2aq.— BaA" 9aq.— CaA" 8aq.-PbA" 9aq. 
 
 Chloride. [243°]. Eed swallow-tailed plates. 
 
 Amide.— [218°]. Powder. 
 
 Di - butyl -p - amido - benzene -azo-di - butyl - 
 anUine (C,H3)3N.C,H,-N2-C3H,N(C,H3)2. Di- 
 iutyl-anHine-azyUne. [158°]. Eed needles. 
 Formed by passing NO through an aloohoUc 
 solution of di-butyl-aniline. 
 
 Periodide. — ^B",!^: dark crystals with blue 
 reflection (Lippmanu a. Fleissner, B. 15, 2142 
 and B. 16, 1421 ; M. 3, 713). 
 
 m-Carbozy - benzene - azo - aceto - acetic acid 
 CeH^(COjH)— N^-CHAcCO^H. Formed by the 
 action of the sulphate of TO-diazo-beuzoio acid 
 ■apon acetoacetic ether in alkaline aqueous 
 solution (Griess, B. 18, 962). Small yellow 
 plates or needles. Soluble in alcohol, nearly 
 insoluble in water. Bitter taste. 
 
 o - Garbozy - benzene - o - azo - benzoic acid 
 [2:1] C3H4(C02H)-N2— CjHj.COjH [1:2]. 
 o-Azo-benzoic acid. [238^]. Mol. w. 270. From 
 o-nitro-benzoic acid and sodium-amalgam (Griess, 
 
 B. 30, 1868). Dark yellow hair-like needles. 
 Insol. water ; m. sol. alcohol. 
 
 S alts .—BaA" 7aq.— BaA" 9aq.— AgoA". 
 
 Ethyl ether 'Et^A". [139°]. From o-nitro- 
 benzoic ether by sodium-amalgam. Scarlet 
 needles (Fittioa, J. pr. [2] 17, 216). 
 
 m-Carbozy-benzene-m-azo-benzoic acid 
 Na(0eH4.C02H)2 [1:3]. m-Azobenzoic acid. From 
 m-nitro-benzoio acid by sodium-amalgam 
 (Streoker, A. 129, 134). Amorphous powder, 
 decomposed by heat, v. si. sol. water, alcohol, 
 and ether. Gives phenazine when distilled 
 with lime. Its copper salt gives azobenzene on 
 distillation. HgO and iodine gives an amor- 
 phous di-iodo-derivative, CnHgl2N204 (Benedikt 
 B. 8, 386). Salts.— BaA" 5aq.—Ag2A". 
 
 Ethyl ether EtjA". [99°]. By the action of 
 EtI on AgjA" Golubeff (B. 7, 1651) obtained two 
 bodies isomeric with this ether, one melting at 
 76°, the other being a monobasic acid. 
 
 ^-Carboxy-benzene-p-azo-benzoic acid 
 N2(C5Hj.C02H)2 [1:4]. From j3-nitro-benzoic acid 
 and sodium-amalgam (BeUstein a. Eeichenbach, 
 A. 129, 144 ; Bilfinger, A. 135, 154). Formed, 
 together with azoxybenzoic acid, by boiling 
 nitro-benzil with alcoholic KOH (Zinin, Z. 1868, 
 563). Flesh-coloured amorphous powder, insol. 
 water, alcohol, and ether. Gives phenazine 
 when distilled with lime. Salt s. — (NHJ jA"aq. — 
 NajA".- CaA" 3aq.— BaA".— AgjA''. 
 
 Ethyl ether Et^A". [88°] (Fittica, 
 J-. pr. [2] 17, 216). 
 
 m-Carbozy-benzene-azo-malonic acid 
 CsHj(C02H)— N2— CH(C02H)2. Formed by the 
 action of the nitrate of m-diazo-benzoic acid on 
 malonic ether in alkaline aqueous solution 
 (Griess, B. 18, 962). Microscopic orange needles 
 or plates. Easily soluble in alcohol. 
 
 Carbozy - benzene - azo - di-methyl-amido-ben- 
 zoic acid CjH,(C02H).N2.0,H3NMe2.CO2H. From 
 m-diazo-benzoio acid and dimethyl-m-amido- 
 benzoic acid (Griess, B. 10, 525). Brown pp. 
 
 m-Carbozy-benzene-azo-nitro-methane 
 CsHj(C02H).N2.CH2(N02). Formed by adding 
 the nitrate of m-cQazobenzoic acid to a dilute 
 aqueous alkaline solution of nitromethane 
 (Griess, B. 18, 961). YeUowish-red plates. Sol. 
 hot alcohol and ether, v. si. sol. water. 
 
 »t-Carboxy-benzene-azo-(i8)-naphthol 
 C5Hj(C02H)— N2— C,„H5(0H). [235°]. Prepared 
 by the action of m-diazo-benzoic acid on an 
 alkaline solution of (3)-naphthol (Griess, B. 14, 
 2035). Eeddish-yellow needles or plates. Sol. 
 hot alcohol, si. sol. cold alcohol and ether, insol. 
 water. 
 
 Salts : A'2Ba33aq : red microscopic needles. 
 A'K 2aq : easily soluble yellow needles or plates. 
 
 Ethyl ether A'Et. [104°]. Yellowish- 
 red needles or plates. Sol. ether, insol. water. 
 
 Amide. — Slender orange needles. SI. sol. 
 alcohol and ether, insol. water. 
 
 m ■ Carbozy - benzene-azo - (ff) - naphthol sul- 
 phonic acid C3Hj(C02H)— N2— C,„H3(OH)(HSOs). 
 Prepared by the action of TO-diazo-benzoic acid 
 on an alkaline solution of (;8)-naphthol sul- 
 phonic acid (Griess, JB. 14, 2036). Brown needles 
 or plates. Sol. hot water, si. sol. cold water and 
 alcohol, insol. ether. Dyes wool and silk a 
 splendid orange. — A"2H2Ba4aq : orange pp. of 
 slender needles. 
 
 TO-Carbozy-benzeue-aza-(/))-naphthol-dl-8ul- 
 phonic acid C3H,(C02H).N2.0,.H,(0H)(HS03)2. 
 Prepared by the action of m-diazobenzoio acid 
 on ()3)-naphthol-(a)-disulphonic acid in alkaline 
 solution (Griess, B. 14, 2037). Yellowish-red 
 microscopic needles. Dyes silk and wool aa 
 orange scarlet. 
 
AZO- COMPOUNDS. 
 
 3S1 
 
 Salts.— BaHA"'6aq: red crystalline pp. — 
 Ba3A"'2l2aq : red mioroscopio needles. 
 
 Carboxy-benzene-azo-phenol v. Oxy-benzene- 
 aio-bemoic acid. 
 
 I)i-oarbozy-1)enzene-azo-pIitlialic acid 
 CsH3(002H)2— N2- CsH3(C02H) J. Azo-phthalie 
 acid, [about 250°]. Prepared by reduction of 
 nitro-phthalio acid with sodium-amalgam (H. 
 Miiller; Glaus a. May, B. 14, 1330). Small 
 yeUow needles : si. sol. water, aloobol, and ether. 
 
 Salts. — A'^NajlOaq: yellow monoclinio 
 prisms, v. sol. water. — A'^K^Baq: long yellow 
 needles. — A''Mgjl8aq: large orange crystals. — 
 A''Ag4: yellow insoluble pp. — A'^Ba^: yellow 
 insoluble pp. 
 
 Di-carbozy-benzene-azo-tere-phtbalic acid 
 [5:2:1] C3H3(C03H),-Nj-C,H3(C02H)2 [1:5:2]. 
 A.eo-terephthalic acid. 
 
 Formation. — 1. By oxidation of hydrazo- 
 terepbthalic acid with nitrous acid. — 2. By 
 reduction of nitro-terephthalic acid with sodium- 
 amalgam (Homolka a. Low, B. 19, 1092). 
 
 YeUow needles. Sol. alcohol and ether, si. 
 Bol. water. Decomposes above 200°. 
 
 Carboxy-naplitlialene-azo-(j3)-napbtliolc acid 
 C,„H5(C02H)^N2— 0,„H3(C02H). From a nitro- 
 (t3) -naphthoic acid by ammonium sulphide 
 (Eakowsky, B. 5, 1022). 
 
 exo-Carboxy-toluene-azo-phenyl-acetic acid 
 C02H.CH2.C,H4— N^— C„H,.CHj.C02H. S. (cold 
 alcohol) 0-375; (hot alcohol) 1-57. Insol. hot 
 water, ether, and benzene. Does not melt below 
 300°- Formed by the action of sodium amalgam 
 on nitro-phenyl-acetio acid [151] (Wittenberg, 
 Bl. [2] 48, 111). 
 
 Carboxy - toluene - azo - toluio acid 
 [5:2:1] C3H3Me(C02H)—N2—C„H,MeC02H[l:5:2]. 
 Azo-p-toluic acid. [184°]. Prom nitro-p-toluio 
 acid by sodium amalgam (Fittica, B. 7, 1358). 
 Minute yeUow needles; m. sol. boiling water, 
 V. sol. alcohol. 
 
 p - Chloro - benzene - azo - benzene p-sulphonic 
 acid [4:1]0,H,01-N -C,H,{S03H) [1:4] [148°]. 
 Formed by warming ^-chloro -azo -benzene with 
 fuming sulphuric acid (10 p.c. SO,) at 60°-70°. 
 Brown needles ; v. e. sol. water and alcohol. It 
 is reduced by SnClj to fi-ohloro-aniline and p- 
 sulphanilio acid. 
 
 Salts. — A'Na: large orange-yellow pearly 
 plates or small needles; si. sol. cold water. — 
 A'jBa : glistening flesh-coloured needles. — The 
 K, Mg, Ca, Ag, Cr, and Fe, salts are white to 
 dark-yeUow needles; the Cu salt forms green 
 plates ; all are sparingly soluble. 
 
 Chloride Ofifil.^^.G^t.SOJDl: [130°]; 
 glistening red prisms, easily soluble in alcohol 
 and ether. 
 
 Amide C.H4Cl.Nj.C(;H,.S0,NHj, : [211°]; 
 yellowish - brown prisms ; sol. hot alcohol, 
 sparingly in ether and cold alcohol, insol. water 
 (Mentha a. Heumann, B. 19, 2972). 
 
 m-Chloro - benzene - m-azo - chloro - benzene 
 [1:3] OsH^Cl— Nj— CsH^Cl [1:3]. Azo-chloro- 
 hemene [101°]. Obtained by acting with 'Fefi\ 
 on m-di-chloro-hydrazo-benzene in alcoholic 
 solution (Laubenheimer, B. 8, 1025). Orange 
 needles (from alcohol). 
 
 p-Ghloro-benzene-^-azo-chloro-benzene 
 [4:1]0,H401— Nj-C,H,C1[1:4]. [184°]. Ytomp- 
 ohloro - benzene - p - azo - nitro - benzene and 
 alcoholic potash (WiUgerodt, B. 15, 1002) ; or 
 
 from di-chloro-azoxybenzene and fuming H^SOj 
 (Heumann, B. 5, 913, 918). Yellow needles. 
 
 p - Chloro - benzene - azo - chloro -benzene sul- 
 phonic acid [4:1] 0„H,C1.N2.C5H3C1.S03H [1:4:?]. 
 Prepared by sulphonation of the preceding body 
 (Calm a. Heumann, B. 13, 1183; 15, 2558). 
 Slender reddish-yellow needles. Sol. water and 
 alcohol. Salts. — A'Na : golden plates, si. sol. 
 cold water. — A'K : reddish-yellow glistening 
 plates, sol. hot water, and alcohol. — A'Ag. — 
 A'jBa : yellow crystalline pp. — ^A'^Ca : golden 
 yellow plates. — A'jPb : orange glistening plates. 
 
 Chloride C,.,B.,(\^^m^Cl : [161°]. Long 
 orange-red needles. 
 
 Chloro - benzene - azo - cMoro - phenol 
 [3:1] Cl.O.H,— N^— C„H3C1(0H) [1:3: ?]. [115°] 
 Formed by the action of fuming HjSO, on 
 m-di-chloro-azoxybenzene (Sohultz, B. 17, 465). 
 Brown plates. 
 
 Chloro-benzene-azo-chloro-nitro-benzeue 
 [4:1] C,H,C1-N,— C3H301(N0,) [1:4:?]. [210°]. 
 Prepared by reducing di - chloro - nitro - azoxy- 
 benzene with cold alcoholic NH^HS (Calm a. 
 Heumann, B. 13, 1184). Yellow needles. SI. 
 sol. alcohol. 
 
 m - Chloro -benzene - azo -di- methyl -aniline 
 [3:1] CsH.Cl— N^— C3H4NMej[l:4]. [98°]. YeUow 
 plates. Tolerably soluble in alcohol. Pre- 
 pared by adding sodium nitrite (1 mol.) to a 
 solution of m - chloraniUne (1 mol.) and di- 
 methylaniline (1 mol.) in dilute H2SO4 (Staedel 
 a. Bauer, B. 19, 1956). 
 
 ^-Chloro-benzene-p-azo-nitro-benzene 
 [1:4] C5H,Cl.Nj.C,H4(N02) [1:4]. [183°]. Formed 
 by nitration of ^-chloro-azo-benzene with fuming 
 HNO3. YeUow needles ; v. sol. acetic acid and 
 hot alcohol, si. sol. cold alcohol, insol. water. It 
 is reduced by SnCl^ to jp-chloro -aniline and p- 
 phenylene diamine (Mentha a. Heumann, B. 
 19, 2971). 
 
 ^-Chloro-benzene-azo-phenol 
 CsH^Cl— Nj— CsH,(OH). [152°]. Formed by 
 gently warming ^-chloro-diazo-benzene-chloro- 
 anilide with phenol, _p-ohloraniline being elimi- 
 nated. Eeddish-yeUow needles (Heumann a. 
 Oeoonomides, B. 20, 906). 
 
 Cumene-azo-cumene PrCjH, — Nj — OjHjPr. 
 Azo-cu/mene. [108°]. From nitro oumeue, [-35°], 
 by sodium-amalgam (Pospekhoff, J. B. 1886, 
 49). Thin yellow leaflets, si. sol. cold alcohol. 
 
 i|'-Cumene-azo-f-camenol 
 [2:4:5:1] C8H2(CH3)3.N2.C3H(CH3)3.0H [1:3:5:6:2]. 
 [148°]. Formed by combining di-azo-cumene 
 chloride (from iff-cumidine) with ifi-cumenol [70°] 
 (Liebermann a. Kostanecki, B. 17, 885). Orange 
 needles. Insol. alkalis. Dissolves in H^SO, 
 with an orange colour. No nitrogen is evolved 
 on boiling with HCl. 
 
 i^-Gumene-azo-t{/-cumidine 
 [2:4:5:1] CeHiMe3.N2.CsHMe3.NH2 [1:2:4:6:6]. 
 [189°]. Prepared by the action of cmnidine 
 hydrochloride upon diazo-cumene-cumide (di- 
 azo-amido-cumene) dissolved in cumidine (N61- 
 ting a. Baumann, B. 18, 1147 ; Bl. [2] 42, 335). 
 Orange plates (from alcohol). V. sol. ether. On 
 reduction with SnCl^ it yields cumidine and 
 cumylene-o-diamine. Salt. — B'HCl : yellow 
 crystalline powder; readily loses its HCl; dis- 
 solves in phenol with a yeUowish-brown colour. 
 
 Cumiuic-azo-cuminlc acid 
 Pr0eH3(C0jH)-N,— CeHjPr.COjH. [280°]. From 
 
S82 
 
 AZO- COMPOUNDS. 
 
 nitro - ouminic acid and sodium - amalgam 
 (AlexieS, Bl. [2] 38, 552 ; 42, 321 ; J. B. 1882, 
 198 ; Alex6eft a. Kissel, Bl. [2] 40, 72). 
 
 Ethers.— Me2A".[166°].—EtjA".[104°_108°]. 
 
 Cymene-azo-cymene 
 C^HjMePr— N^-CjHjMePr. [86°]. From nitro- 
 cymene by sodium-amalgam (Werigo, Z. 1864, 
 721). Cherry-coloured plates. 
 
 Ethyl - amido - benzene - azo - benzene - p - 
 sulphonio acid [4:1] CjH^(S03H).N2.0„Hj.NHEt 
 [1:4]. p - Sulpho - benzene - azo - ethyl - aniline. 
 [c. 244°]. Obtained by combining ^-diazo- 
 benzene-sulphonic acid with ethyl-aniline in 
 acid solution. Steel-blue needles. Nearly insol. 
 alcohol and cold water, si. sol. hot water. The 
 sodium salt (NaA') forms orange-red plates. On 
 reduction with (NHj)2S it yields mono-ethyl-p- 
 phenylene-diamine and ^-sulphaniUo acid 
 <Bernthsen a. Goske, B. 20, 929). 
 
 Si- ethyl -p - amido - benzene - azo- di- ethyl- 
 aniline C„Hj(NEtj)— Nj— C,H^(NEt,). Di-ethyl- 
 <tmUne-aeyline. [170°]. Prepared by passing 
 KO through an alcoholic solution of di-ethyl- 
 aniline ; yield 50 p.c. of the theoretical. Eed 
 monoclinio crystals, a:6:c = l:'7108:'9493. j8 = 
 90° 30'. V. Bol. chloroform, si. sol. cold alcohol. 
 
 Beactions. — 1. Nitrous acid acting on the 
 acetic solution gives ^-nitro-di-ethyl-auiline. — 
 2. On reduction it yields M-di-ethyl-^-phenylene- 
 diamine. — 3. Heated with ethyl iodide at 100° it 
 gives tetra-ethyl-p-phenylene-diamine. — 4. Mel 
 at 100° gives di-methyl-di-ethyl-^-phenylene- 
 diamine. 
 
 Salts. — B"H2Cl2PtCl, : small brownish-red 
 trimetric tables. — F errooyanide B"2H4PeCy5 : 
 brovm plates.— Picrate B"(CsH2(N02)30H)2 : 
 yellow sparingly soluble needles (Lippmann tu 
 Fleissner, JS. 15, 2136; 16, 1415; M. 8, 286, 
 788). 
 
 Si-ethyl-amido-benzene-azo-toluidine 
 Acetyl derivative 
 
 [4:1] C5H^(NEt2)— Nj— CjHjMefNHAo) [1:6:3]. 
 [159°]. Promdiazotised acetyl-tolylene-diamine 
 CjH3(NHj)Me(NHAo) [1:6:3] and di-ethyl-arnhne 
 <Wallach, A. 234, 359). 
 
 o-£tliyl-benzene-o-azo-ethyl-benzene 
 [2;l]C.H,(C^,)-N,-C,H,{C,H,)[l:2].[47°corr.]. 
 Formed by reduction of o-nitro-ethyl-benzene 
 with zinc dust and alcoholic NaOH (Schultz, B. 
 17, 473). Long red dimetric prisms, a:c = 1 : -3455. 
 V. sol. alcohol. By treatment with SnClj and 
 HCl in alcoholic solution it yields a di-amido-di- 
 ethyl-diphenyl. 
 
 p-Ethyl-benzene-p-azo-ethyl-benzene 
 [4:l]C,H,(C^,)-N,-C,H,(CA)[l:4].[63°oorr.]. 
 (above 340°). Formed by reduction of ^-nitro- 
 ethyl-benzene with zinc-dust and alcoholic 
 NaOH (Schultz, B. 17, 475). Orange-red plates 
 or thick prisms. V. sol. alcohol. By treatment 
 with SnClz and HjSO, in alcoholic solution it 
 yields a di-amido-di-ethyl-diphenyl. 
 
 p-£thyl-phenyl- amido-benzene-j) - azo - ethyl- 
 di-phenylamiue 
 
 [4:1] CeH,NEtPh— Nj— CjH^NEtPh [1:4]. [178°]. 
 From ethyl-di-phenyl-amine and NO (Lippmann 
 a. Fleissner, 11.4, 796). Monoclinic red crystals. 
 
 EthyI-pyrrol-azo-(;8)-naphthalene 
 C,„H,.N2.CjH.,NEt. [74°]. Obtained by adding 
 (/3)-diazo-naphtbalene chloride (1 mol.) to ethyl- 
 pyrrol (1 mol.) dissolved in alcohol containing 
 sodium acetate. Thick red tables. Sparingly 
 
 soluble in dilute HCl. Dissolves in oonc. HjSO^ 
 with a dark reddish-yellow colour. The platino- 
 chloride forms small sparingly soluble red 
 needles (0. Fischer a. Hepp, B. 19, 2258). 
 
 Ethyl-pyrrol-azo-p-toluene 
 
 C„H,Me.N2.g = CH 
 CsH,Me.N2.C,H3NEt probably NEti 
 
 HC = CH 
 [62°]. Formed by adding ^-diazo'toluene 
 chloride (1 mol.) to an alcoholic solution of 
 ethyl-pyrrol (1 mol.) containing sodium acetate. 
 Thick red prisms. Dissolves in cone. H^SO, with 
 a yellow colour, in dilute HCl with a reddish 
 yellow colour. The platino-chloride forms 
 sparingly soluble red needles (0. Fischer a. 
 Hepp, B. 19, 2257). 
 
 lodo-carbozy-benzene-azo-iodo-benzoic acid 
 C^H3l(C0^)— Nj- CbHJ(C02H). Aeo-iodo-ben- 
 zoic acid. From m-amido-benzoio acid, iodine, 
 and HgO (Benedikt, B. 8; 386). 
 
 Mesltylene-azo-mesitylene 
 C„Hj,(CH,)3 — Nj— C|iH2(CH3)3. Azo - mesitylem. 
 [75° corr.]. Prepared by oxidising an aqueous 
 solution of mesidine hydrochloride (5 pts.) with 
 a solution of 45 pts. of potassium ferricyanida 
 and 10 pts. of KOH (Schultz, B. 17, 476). Thin 
 red needles. Sol. hot alcohol. It does not 
 appear to yield a hexa-methyl-benzidine by 
 treatment with SnClj and HCl in alcoholio 
 solution. 
 
 Methyl - amido - benzene - azo - benzene - sul- 
 phonic acid[4:l] C„Hj(S03H).Nj.C,H^.NHMe [1:4]. 
 p-Sulpho-benzene-azo-methyl-anMiiei. Obtained 
 by combining ^-diazo-benzene sulphonic acid 
 with methyl-aniline in acid solution ; yield 30 
 p.c. of theoretical. Also formed by the action 
 of cold dUute acids upon p-sulpho-diazo-benzene- 
 methyl-aniUde CjH,(S03H).N2.NMeCsH5. Steel 
 blue needles, si. sol. water. The sodium-salt 
 (A'Na) forms large orange-red plates, v. sol. hot 
 water. On reduction with (NH4)2S it yields p- 
 Bulphanilic acid and mono-methyl-^-phenylene 
 diamine (Bernthsen a. Goske, B. 20, 925). 
 
 Si-methyl-amido-benzene-azo-benzene-salpli- 
 onic acid [4:1] C„H4(NMe2)— N^- C^,S03H 
 [1:4] HeliantJiin, or Orange III. 
 
 Preparation. — 1. From dimethylaniline and 
 ^-diazobenzene sulphonic acid (Griess, B. 10, 
 525). — 2. Dimethylamido-azobenzene (1 pt.) is 
 dissolved in 20 pts. cold sulphuric acid of 30 p.c. 
 anhydride value and allowed to stand for 24 
 hours (Mohlau, B. 17, 1491). The absorption 
 spectrum has been mapped by Hartley (C. /. 
 51, 192). 
 
 Si-methyl-amido-benzene-azo-benzoic acid 
 [4:1] CeH^NMe^- Nj,— C,Hj.C02H [1:3]. From 
 di-methyl-aniline and m-diazo-benzoio acid 
 (Griess, B. 10, 525). 
 
 Si - methyl - amido - benzene - azo-di-methyl- 
 anUine [1:4] CjH,(NMej)— N^- C^H^NMe^ [1:4] 
 [266°]. DimethylaniUne-azyline. Eed needles. 
 
 Formation. — 1. By diazotising p-amido-di- 
 methyl-aniline and combining the diazo-com- 
 pound C5H4(NMe2).Nj.Cl with dimethylanUine 
 (Nolting, B. 18, 1143).— 2. By passing NO 
 through an alcoholic solution of- di-methyl- 
 aniline for several days. 
 
 Beactions. — 1. Nitrous acid acting on the 
 acetic acid solution gives ^-nitro-cU-methyl- 
 aniline. — 2. On red/uction it gives M-di-methjl-^ 
 phenylene-diamine. 
 
AZO- COMPOUNDS. 
 
 383 
 
 SftltB.— B"H,Cl2PtCI,: diohroic crystalline 
 powder.— Piorat 6 B"CiH2(N02)30H + C^H^OH : 
 glistening green needles (Lippmann a. Pleissner, 
 23. 15, 2136; 16, 1415 ; M. 3, 708). 
 
 Di-metliyl-amido-benzene-azo-p-toluene 
 0,H,— Nj-CjHj.NMej. [168°]. Golden plates. 
 Easily soluble in alcohol and ether. 
 
 Preparation. — A solution of 65 pts.of NaNOj 
 (100 p.o.) and 35 pts. NaOH in 465 pts. of water 
 is slowly added to a cooled solution of 100 pts. 
 of ^'-toluidine, 113 pts. of dimethylaniline and 
 200 pts. of HCl in 300 pts. of water. 
 
 On reduction it yields ^-toluidine and di- 
 methyl-^-phenylene-diamine. The hydrochloride 
 and sulphate form violet prisms, giving a red 
 solution in alcohol (Mohlau, B. 17, 1492). 
 
 Bi-metliyl-amido-benzene-azo -p- toluene-suU 
 phonic acid C,H5(HS03).Nj.CjHj.NMej. Formed 
 by the combination of ji-diazo-toluene sulphonic 
 acid (Me:H803:Nj= 1:3:4) with dimethylaniline 
 (Mohlau, B. 17, 1493). Dark-violet prisms. 
 Soluble in water and alcohol with an orange 
 colour, insoluble in ether. The sodium salt 
 forms orange glistening plates. 
 
 Si-methyl-amido-benzene-azo-toluidine 
 [4:1] C,H4(NMe2)— Nj— CsH,Me(NH2) [1:6:3] 
 [145°]. From its acetyl derivative [200°] which 
 is formed by the action of diazotised-acetyl- 
 tolylene-diamine C5H3(NH2)Me(NHAo) [1:6:3] 
 upon di-methyl-aniline (Wallach, A. 234, 355). 
 
 Si-methyl-amido-benzene-azo-tolaidine 
 [4:1] OgH4(NMej)-Nj— C,H3Me(NH2) [1:4:3] 
 [215°]. From its acetyl derivative, [192°] which 
 is formed by the action of diazotised aoetyl- 
 tolylene-diamine CjH3(NH2)Me(NHAc) [1:4:3] 
 upon di-methyl-aniline (Wallach, A. 234, 359). 
 
 ^-Uethyl-phenyl-amido-benzene-azo-methyl- 
 dl-phenyl-amine 
 
 [4:1] C,HjNMePh.N2.C,H^NMePh [1:4] [150°]. 
 Yellow crystals, got by the action of NO on 
 methyl-diphenyl-amine (Lippmann a. Fleissner, 
 M. 4, 798). 
 
 (a)-Naphthalene-(a)-azo-naphthalene 
 [a] C,„H,.Nj.O„H, [a]. [190°]. Prepared by 
 boiling diazo-naphthalene-azo-naphthalene with 
 alcohol : 1 pt. of naphthalene-azo-naphthylamiae 
 is dissolved in 100 pts. of 95 p.o. alcohol and 
 6 pts. of HjSO, are added ; the still warm solution 
 is then treated with a saturated solution of (1 
 mol. of) NaN02 ; the fluid is heated and finally 
 boiled for a few hours, and the azonaphthalene 
 precipitated by water. It is recrystallised by dis- 
 solving it in hot aniline and adding alcohol 
 (Nietzki a. GoU, B. 18, 298, 8252). Steel-blue 
 crystals. Sublimes in thin yellow plates. Soluble 
 in aniline, sparingly in alcohol. It dissolves in 
 cold HjSO, with a blue colour, but on heating 
 the solution to about 180° it becomes violet and 
 exhibits a red fluorescence. By alcohoUo NH^HS, 
 or zinc-dust and alcoholic KOH, it is reduced to 
 hydrazonaphthalene. 
 
 (a) -naphthalene- (j3) -azo-uaphthalene 
 [a]C,pH,.Nj.C,„H,[e]. [136°]. Obtained by diazo- 
 tisation of (;8)-naphthalene-^-azo-(a)-naphthyl- 
 amiue and boiling with alcohol. Dark-brown 
 plates with steel-blue reflex. Sol. alcohol, acetic 
 acid, &c. Dissolves in cono. H^SOj with a violet 
 colour (Nietzki a. Gottig, B. 20, 612). Laurent's 
 naphthase [275°], got by heating nitro- 
 naphthalene with zinc dust, or (a)-naphthyl- 
 amine with PbO, has been regarded as naphtha- 
 
 lene-azo-naphthalene, but Witt has lately (B. 
 
 19, 2794) shown it to be an azine C^oHi^Nj v. 
 (a)3)-NAPHTHAziNB (Laurent, A. 109, 384 ; Doer, 
 B. 3, 291 ; Alex^eff , B. 3, 868 ; Schichuzky, B. 5, 
 365 ; Klobulowsky, B. 10, 670, 772, 873). 
 
 Naphthaleiie-^-azo-(a)-naphtliol 
 0,„H,— Nj— C,„HaOH. Formed by adding di- 
 azo-naphthalene chloride to a solution of (o)- 
 naphthol in NaOHAq ; it is ppd. by HCl. 
 Crimson powder. Soluble in alkalis forming 
 crimson solutions (P. F. Frankland, C. J. 37, 
 752). 
 
 Il'aphthalene-o-azo-(i8)-iiaphthol 
 C,„H,— Nj— CjoHeOH. [176°]. Formed by diazo- 
 tising (;8)-amido-azo-naphthalene and heating 
 the dlazo- compound with water (Nietzki a. Goll, 
 B. 19, 1282). Sublimes in glistening golden 
 needles. 
 
 (a)-ITaphthalene-(a)-azo-(a)-naphthylamine 
 C,„H,— N3— C,„H,.NH2. [180°]. Prepared by 
 adding ENO2 (1 mol.) to a dilute solution of (a)- 
 naphthylamine hydrochloride (2 mol.) and 
 making the mixture slightly alkaline with 
 Na^COa (Perkin a. Church, A. 129, 108 ; Nietzki 
 a. Goll, B. 18, 298). Hartley (C. J. 51, 190) has 
 mapped the absorption-spectrum. — B'iHCl. — 
 B'HCl.— B'2HC1.— B'jHjSOj. 
 
 (j3)-Naphthaleue-^-azo-(a)-naphthylamine 
 C,„H,.Nj.C„H,.NH;j [152°]. Formed by mixing 
 aquieous solutions of equal mols. of (S)-diazo- 
 naphthalene chloride (from (/3)-naphthylamine) 
 and (o)-naphthylamine hydrochloride. Yellowish- 
 brovm needles with green reflex (from alcohol). 
 The base and its salts are far more soluble than 
 the (o)-azo-(a)-naphthalene. H^SO, dissolves 
 it with a violet colour (Nietzki a. Gottig, B. 
 
 20, 612). 
 (j3)-ITaphthalene-azo-(i3)-naphthylamine 
 
 ,NH 
 C,„h/ I or 0,oH,.N2.C,„H,.NH2 [149°]. 
 
 \N2H.C,„H, 
 Eeddish-yellow needles. Easily soluble in ben- 
 zene and acetic acid, insoluble in water. Formed 
 by the action of amyl nitrite upon (S)-naphthyl- 
 amine. The absorption-spectrum has been 
 mapped by Hartley (C. J. 51, 191). 
 
 Meactions. — 1. By heating with dilute HjSO, 
 (20 p.c.) it is decomposed with evolution of 
 nitrogen. — 2. On reduction with SnCL it yields 
 (;3)-naphthylamine and (l:2)-naphthylenedia- 
 mine. — 3. Treated with bromine in alcoholic or 
 acetic acid solution it is converted into di-bromo- 
 (/3)-naphthylamine and a brominated ^-naphthol. 
 4. May be diazotised in the following manner : 
 15 grms. of the amidoazonaphthalene are finally 
 suspended in a mixture of 90 grms. H^SOj and 
 90 grms. of water, cooled with ice and slowly 
 treated with a concentrated solution of 5 grms. 
 sodium nitrite. The diazo- compound is very 
 unstable (Nietzki a. Goll, B. 19, 1281). 
 
 Acetyl derivative C2„H„NsAc [218°]; 
 prisms ; easily soluble in benzene, sparingly ia 
 alcohol and petroleum-spirit. 
 
 Benzoyl derivative Cj„H,4N,Bz [177°]; 
 silky red needles ; easily soluble in benzene, 
 sparingly in alcohol and petroleum-spirit (Law- 
 son, B. 18, 2422). 
 
 (a)-IJ'aphthalene-azo -peri - naphthylene - dia- 
 mine C,„H, — N2— C,„H5(NH2)2. Prepared by the 
 action of (a)-diazonaphthalene chloride on peri- 
 naphthylene-diamine (Stebbins, jun., B. 18, 
 
384 
 
 AZO- COMPOUNDS. 
 
 717 ; O. N. 41, 117 ; A. C. J. 1, 445). Sol. alco- 
 hol, insol. water. — B'HCl : si. sol. water, m. sol. 
 alooliol with a brown colour ; dissolves in strong 
 HjSO^ with a blue colour. 
 
 ()3)-ITaplitliol-azo-naphthalene snlphonic acid 
 C,„H„(0H)-N2— C^H^SOaH. From (;8)-naph- 
 thol and (a)-diazo-naphthalene sulphonic acid 
 (W. V. MiUer, B. 13, 268). 
 
 (a)-N'aphthol-2}-azo-diphenyl sulphonic acid 
 C,„H„(OH)— Nj— OjjHj.SOsH. From (a)-naph- 
 thol and ^'-diazo-diphenyl sulphonic acid (Car- 
 nelley a. Sohlevelmann, 0. /. 49, 383).— NaA' : 
 dyes wool brown — BaA'j. 
 
 (;3)-Naphthol-27-aza-diphenyl sulphonic acid 
 C,„Hs(OH)— Nj— CioHj.SOsH. From (3)-naph- 
 thol and ^-diazo-diphenyl sulphonic acid.— 
 NaA': bright red pp., si. sol. cold, v. sol. hot, 
 water; dyes wool red. — BaA'j (Caruelley a. 
 Schlevelmann, C. /. 49, 383). 
 
 o-Nitro-benzene-azo-aceto-aceticacid 
 C^H^NO^)— N2-CH(CO.CH3).C02H. [185°]. 
 Obtained by saponification of the ethyl-ether 
 which is prepared by the action of o-nitro-diazo- 
 henzene chloride on an alkaline solution of 
 aceto-acetic ether (Bamberger, B. 17, 2415). 
 Glistening brown plates. V. sol. acetic acid and 
 hot alcohol, v. si. sol. ether and cold alcohol. On 
 heating it evolves CO^ and yields o-nitro-ben- 
 zene - azo - acetone C5H,{N02).N2.CH2.CO.CH3. 
 The same decomposition is produced by heating 
 with alkalis. 
 
 Salts. — A'NH," : yellow needles. — A'Ag : 
 crystalUne pp. — A'jCu* : green pp., sol. hot 
 water. — A'jBa* : yellow needles. — A'^Hg : glis- 
 tening plates. 
 
 Ethyl ether A'Et [93°], glistening yel- 
 low plates or fine needles, sol. alcohol, ether, 
 acetic acid, and hot water. 
 
 o-Nitro-beuzene-azo-acetone 
 C,Hj(N02)— Nj— CH2.CO.CH3. [124°]. Formed 
 by heating o-nitro-benzene-azo-aceto-acetic acid 
 to its melting-point, or by boiling the acid or its 
 ether with alkalis. 
 
 Preparation. — o-Nitraniline dissolved in 
 absolute alcohol is diazotised by passing into 
 the well-cooled solution a stream of NjO,, the 
 product is poured into iced water, the solution 
 filtered and mixed without cooling with a dilute 
 solution of acetaoetic ether (1 mol.), and KOH 
 (1 mol.), after mixing the fluid must be acid, it 
 is digested at about 40° for 40 hours, the red pp. 
 is then filtered off and purified (Bamberger, B. 
 17, 2418). Long silky yellow needles. Easily 
 soluble in hot water, alcohol, ether, &c. 
 
 o-Nitro-benzene-azo-acetopheuone 
 [2:1] G,Hi(N02)— Nj— CH2.CO.C5H,. [141°]. 
 
 Formed together with o-nitro-benzene-azo-ben- 
 zoyl-acetic ether, by adding a solution of o-nitro- 
 diazo-benzene chloride to an iced alkaline solu- 
 tion of benzoyl-aeetic ether (Bamberger a,. Cai- 
 man, B. 18, 2565). GHstening yellow needles. 
 Easily soluble in ordinary solvents. 
 
 m-Nitro-benzene-azo-auiline 
 [3:1] N02.0aH„.N2.C,H4.NH2 [1:4]. [c. 210°]. 
 Prom diazotised m-nitraniline hydrochloride and 
 aniline hydrochloride (Meldola, G. J. 45, 112). 
 Orange fern-like leaflets (from alcohol). Insol. 
 water and dilute acids ; forms yellow solutions in 
 alcohol, acetone, and benzene (Meldola, C. J. 45, 
 113). On reduction it gives m- and^-phenylene- 
 diamine. Salt .— (B'HC^jPtOl,. 
 
 Kitro-benzene-azo-benzene sulphonic acid 
 [3:1] C,H^(N02)— Nj— CsH^SOaH [1:4]. Fron» 
 benzene-azo-benzene sulphonic acid by nitration: 
 (Janovsky, M. 3, 505; 8, 60).— KA-.— BaA',.— 
 PbAV 
 
 Nitro-benzene-azo-benzene sulphonic acid 
 [4:1] CsH^(N0J— Nj— OaH^.SOsH [1:4]. Formed, 
 together with the less soluble isomeride just de- 
 scribed, by heating benzene-azo-benzene ^-sul- 
 phonic acid with nitric acid (S.G. 1-41). Leaf- 
 lets.— KA' (Janovsky, M. 3, 506 ; 5, 157 ; B. 16, 
 1486). Animonium sulphide reduces it to an 
 amido - benzene - azo - benzene sulphonic acid 
 which is different from that formed from diazo- 
 tised sulphauilic acid and jp-phenylene-diamine, 
 although on complete reduction it gives sul- 
 phanilio acid and ^-phenylene-diamine. 
 
 Si-nitro-benzene-azo-benzene-Bulphonic acid 
 [3:4:1] 0,H3(N02)2— N^-C^H^.SOsH [1:4]. From, 
 either of the two preceding acids or from benzene- 
 azo-benzene sulphonic acid and nitric acid (S.G. 
 1-45). Orange leaflets.— KA'.—BaA'ji S. 7 at 
 68° (Janovsky, M. 3, 507 ; 5, 157). 
 
 o-Nitro-benzeue-azo-benzoyl-aceticacid 
 [2:1]C,H,(N02)-N2— CH(CO.C,H,).C02H.[177°] 
 Its ethyl-ether is formed, together with o-nitro- 
 benzene-azo-acetophenone, by adding a solution 
 of o-nitro-diazo-benzene chloride to an iced 
 alkaline solution of benzoyl-acetio ether (Bam- 
 berger a. Caiman, B. 18, 2565). Long, yellow 
 silky needles. SI. sol. alcohol and ether. By 
 long heating at its melting-point it loses COj 
 giving o-nitro-benzene-azo-aoetophenone. 
 
 Oxim C„H,„N2(N0j)(C0jH)N0H [142°]; 
 orange-yellow needles. 
 
 m - Nitro - benzene -azo-m-chloro -di-methyl. 
 aniline [3:1] CeH^(N02).Nj.C,H3Cl.NMe2 [1:2:4] 
 [156°]. Prepared by adding sodium nitrite (1 
 mol.) to a solution of m-nitraniline (1 mol.) and 
 m-chloro-di-methyl-aniline (1 mol.) in dilute 
 HjSOj (Staedel a Bauer, B. 19, 1956). Beddish- 
 yellow plates (from alcohol). 
 
 ^-Nitro-benzeue-azo-di-methylauiline 
 [4:1] N02.CeH^.N2.C,H^NMej, [1:4]. [230°]. The 
 hydrochloride is deposited as crystals with steel- 
 blue reflex when aqueous diazo-^-nitro-benzene 
 chloride is added to aqueous dimethylanihne 
 hydrochloride (Meldola, 0. J. 45, 107). 
 
 Properties, — Chocolate-brown powder, slightly 
 soluble in alcohol whence it separates as brown 
 needles. Solutions are orange in benzene and 
 in glacial acetic acid, orange in cone. H2SO4, 
 red on dilution. S alt.— (B'HCl)j,PtCl,. 
 
 m-Nitro-benzene-^-azo-dimethylaniline 
 [3:1] N03.C3Hj.Nj.C,H,NMej [1:4]. [159°]. From 
 N02.C5H^N,C1 and CsH^NMe^HCl (Meldola, 0. J. 
 45, 120 ; Staedel a. Bauer, S. 19, 1954). Orange 
 crystalline powder. Solutions in alcohol, ben- 
 zene, acetone, and glacial acetic acid, are 
 yellowish-orange ; in cone. H^SO, pale orange, 
 turned red by dilution. After reduction by HCl 
 and zinc-dust, Fe^Clg forms a blue dye. 
 
 m-Ifitro-benzene-azo-(a)-naphthol 
 [3:1] C3H,(N02)— Nj— CioHjOH [1:4]. From m- 
 diazo-nitro-benzene and (a)-naphthol (Stebbins, 
 jun., A. O. J. 2, 446). Brown pp., sol. water. 
 
 ^-Nitro-benzene-azo-(a)-naphthol 
 [4:1] CjH^(N02)— Nj— C,„H,OH [1:4]. From 
 ^-diazo-nitro-benzene chloride and an alkaline 
 solution of (o)-naphthol (Meldola, C. J. 47, 661). 
 Dull red powder, melts above 360°. V. si. sol 
 
AZO- COMPOUNDS. 
 
 S8JJ- 
 
 boiling alcohol. H2SOJ forms a violet solution ; 
 hot NaOHAq gives a blue colour. 
 m-II'itro-1>eiizene-azo-(£)-naphthol 
 -O.nH, 
 
 -N,- 
 
 .o^sOH [1:2] or 
 [194°]. From m-diazo- 
 
 [3:1] OA(NO, 
 
 
 C.,H.<| 
 
 nitro-benzene chloride and an alkaline solution 
 of (;8)-naphthol (Meldola, C. J. 47, 668). Lustrous 
 orange scales (from toluene). Insol. aqueous 
 alkalis ; sol. alcoholic KOH. H^SO, gives a 
 magenta red solution. It is not reduced by 
 ammonium sulphide. 
 
 ^-ITitro-1>enzene-azo-(;3)-naphthol 
 [4:1] O.H,(NO,)-N2-C,„H,OH (?) [1:2]. [249°]. 
 From p-diazo-nitro-benzene chloride and sodium 
 (|8)-naphthol (Meldola, O. J. 47, 663). Orange 
 needles. Insol. hot NaOHAq. Cone. HjSO, 
 gives a magenta-red solution. 
 
 m-ITitro-benzene-azo - (;S) -uaphthol-disulpho- 
 nie acid [3:l]C„H,(NOJ.N,.C,,H,.(S03H),(OH) (?). 
 Prepared by acting on di-azo-m-nitro-benzene 
 with (/3)-naphthol disulphonio acid in alkaline 
 solution. V. sol. water ; dyes an old gold colour 
 (Stebbins, jun., A. C. J. 2, 446). 
 
 m-NitTo-benzene-(a)-azo-(a)-naphthylamiue 
 [3:1] NOj.GeH^— N,-C,„H,.NH, [1:4]. [203°]. 
 From N02.CbHiN2C1 and CjoH^NH^HCl (Meldola, 
 C. J. 45, 114). 
 
 Properties. — Red needles. Solutions in al- 
 cohol, acetone, and benzene, are orange; in 
 acetic acid, red ; in cone. HjSO^ violet-red turned 
 red by dilution. Completely decomposed by 
 ammonic sulphide. 
 
 2)-Nitro-benzene-azo-(a)-naphthylamine 
 [4:1] NO,.C„H,.N,.0„H,NH, [1:4]. [252°]. 
 From aqueous ^-nitro-diazo-benzene chloride 
 and alcoholic (a)-naphthylamine hydrochloride 
 (Meldola, O. /. 43, 430). Brown needles (from 
 benzene). Forms a crimson alcoholic solution. 
 (B'HCy^PtOl^. Salts hardly soluble in alcohol. 
 
 JReactions. — ^Reduces to ^-phenylene-diamine 
 and {a,a) naphthylene-diamine. 
 
 m-Nitro-benzeue-azo-(j3)-naphthylamine 
 [3:1] 0^^(NOJ-N -C,„H,(NHj) or 
 NHv 
 
 I >C,„H,. [177°]. From 
 
 CeH^(NO,)-N^/ 
 
 NO2.CijH4.N2Cl and (|8) -naphthylamine. Splendid 
 orange needles. Solutions in toluene, chloro- 
 form, and glacial acetic acid, are orange ; in 
 alcohol and in acetone, orange but turned red 
 by HCl; in cone. H^SO,, violet (Meldola, C. J. 
 45, 117). 
 
 p-Nitro-benzene-azo-(i8)-naphthyIaiiune 
 [4:1] N02.C,H,— N2-C,„HeNH2 (?) [1:2]. [180°]. 
 From aqueous ^-nitro-diazo-benzene chloride 
 and aqueous (j8)-naphthylamine hydrochloride 
 (Meldola, G. J. 48, 420). Needles, with golden 
 lustre (from alcohol). Its solutions in alcohol, 
 acetone, and chloroform are red, in benzene and 
 toluene, orange, in cone. HjSO,, violet. Its 
 salts are readily soluble in alcohol.— 
 (B'HCl)2Pt01,. 
 
 ^-Ifitro-benzene-azo-p-uitro-benzene 
 [4:1] C,H,(N02)— N.— CbH,(N02) [1:4]. Di-niiro- 
 azo-bensene. [201°]. Formed by nitration of 
 benzeue-azo-benzene (Laurent a. Gerhardt, A. 
 75, 73; Janovsky, il/. 6, 159; 7, 135; B. 18, 
 1134). Bed crystals (from glacial HOAc). Gives, 
 when reduced by ammonium sulphide, a nitrolio 
 
 VnT. T 
 
 acid (C„H,(N0j)-N2— C„H3:NOH)2(?) [S18°] of 
 which the sodium salt is blue. It is re-oxidised by 
 KjFeCyj to ^-nitro-benzene-azo-p-nitro-benzene.. 
 
 m-Nitro-benzene-azo-m-nitro-benzene 
 [3:1] C.H4(NOj)-N2-C5Hj(N02) [1:3]. A red 
 oil, formed in the preparation of the preceding 
 (Janovsky, M. 6, 455). Ammonium sulphide 
 and NaOH give a violet colour. 
 
 o-Kltro-beuzene-p-azo-nitro-benzeue 
 [2:1] C,H,(N02)-N.-C„H,(N0,) [1:4]. [208°]. 
 From nitro - benzene - - azo - nitro - benzene- 
 (Janovsky, M. 7, 131). Orange laminae. Alcoholic 
 ammonium sulphide mixed with NaOHAq gives a 
 permanent blue. 
 
 Nitro-benzene-azo-nitro-benzene 
 C,H4(N02)— N2— C„H,(N02) [1:4]. [205°]. A 
 by-product in the nitration of benzene-azo-ben- 
 zene-p-sulphonio acid (Janovsky, M. 7, 132). 
 Orange laminae. Ammonium sulphide and NaOH 
 gives a permanent blue nitrolate. 
 
 Nitro-benzene-azo-nitro-benzene 
 OsH^jNOj)— N2— GA(N02). [180°]. A product 
 of nitration of benzeue-azo-benzene (Janovsky, 
 M. 7, 134). Pale, asbestos-like, needles. Ammo- 
 nium sulphide and NaOH give a blue nitrolate 
 changing to brown. 
 
 Nitro-benzene-azo-di-nitro-benzene 
 [4:1] OsH4(N02)— N2— C„H3(N02)2 [1 : 2 : 3 or 5 or 6] 
 or[l:3:5]. [112°]. Formed by nitration of benzene- 
 azo-benzene (PetriefE, Z. [2] 6, 564) or benzene- 
 azo -^ - nitro - benzene (Janovsky, M. 7, 125). 
 Yellow needles. Boiling with a mixture of 
 alcoholic NaOH and aqueous ammoniuai sul- 
 phide giv3s a green colour, changing to brown. 
 
 Nitro-benzene-azo-di-nitro-benzene 
 [3:1] C.H,(N02)-N2-0„H3(N02)2 [1:3:4]. [170°]. 
 Formed by nitration of benzene -p- azo -nitro- 
 benzene or m - nitro - benzene - m - azo - nitro- 
 benzene (Janovsky, M. 7, 126). Yellow tables. 
 Alcoholic ammonium sulphide and aqueous 
 NaOH give an oUve-green colour, turning brown. 
 
 Nitro - benzene - azo - di - nitro - benzene 
 [3:1]C,H4(N02)— N2— C„H3(N02)2[1 : 3 : 2 or 5 or 6]. 
 [124°]. Formed by nitrating m-nitro-benzene- 
 m - azo - nitro - benzene (J.). Yellow prisms. 
 Nitrohc reaction : emerald-green changing to 
 orange. 
 
 Nitro-benzeue-azo-di-nitro-benzene 
 [4:1] C,H,(N02)— N2-C„H3(N02)2 [l:4:3or2]. 
 [185°]. Formed by nitrating ^-nitro-benzene- 
 j)- azo -nitro -benzene or benzene - azo - benzene 
 (Janovsky, M. 6, 461 ; B. 18, 1135). Needles. 
 
 Nitro - benzene - azo - di - nitro • benzene 
 [4:1] 0„H.,(N02)-N2-0,H3(N02)2 [l:4:2or3]. 
 [160°] . Formed in the preparation of the preceding 
 substance (Janovsky, M. 6, 462 ; 7, 125 ; B. 18, 
 1134). Yellow needles (from alcohol). Nitrolic 
 reaction: green, turning blue. This body and' 
 the preceding, both give (1, 2, 4)-tri-amido- 
 benzene and ^-phenylene-diamine on reduction. 
 
 Nitro-benzene-azo-nitro-ethane 
 [3:l]C,Hj(N02)— N2— CH(N02).CH3.Frompota3- 
 sium nitro-ethane and m-diazo-nitro-benzene 
 nitrate(Hallmann,B.9,391). Yellowpowder. Ee- 
 duced by tin and HCl to the tin salt B"H2SnCl3 
 of an unstable base di-amido-phenyl-ethyl- 
 hydrazineC,H4(NH2)— N2H2— CH(NH2).0H3. 
 
 Nitro-benzene-azo-nitro-phenol 
 [3:l]0„H,(N02).N2.C3H3(N02)(OH)[l:3:4?].[173°]. 
 Formed by heating the isomeric di-m-nitro- 
 azoxy benzene CsH4(N02)— N^O— C|;H,(NO.,) 
 
 CO ■ 
 
363 
 
 AZO- COMPOUNDS. 
 
 with strong H^SOj for some time to about 140° 
 (Klinger a. Pitaolike, B. 18, 2552). Yellowish- 
 brown crystals. Dissolves in alkalis with an 
 orange colour. — A'Ag : red crystalline pp. 
 
 p-Nitro-1)eiizene-azo-o-ozy-benzoic acid 
 [4:1] CA(N0,)-N,-0,H3(C0,H)(0H) [1:3:4]. 
 Fromdiazotised^-nitro-aniline and a cooled alka- 
 line solution of salicylic acid (Meldola, 0. J. 
 47, 666). Brown needles (from dilute acetic 
 acid) ; sol. alkalis. H2SO4 gives an orange solu- 
 tion. Blackens at 225°. 
 
 ^-Nitro-benzene-azo-phenol 
 [4:1]0,H,(N0,)-N,-C„H,0H [1:4]. [184°]. 
 From diazotised p-nitro-aniline and sodium 
 phenol (Meldola, O. J. 47, 658). Golden scales ; 
 V. si. sol. water; sol. boiling dilute alkalis. 
 HjSOj gives an orange solution. 
 
 m-Nitro-beuzeue-p-azo-diphenylamiiLe 
 
 [3:1] (NO,)C,H.-N,-C,H,(NHC,H,) [1:4]. 
 [137°]. FromNOjCeHiNaCl andNH(CeH5)2 (Mel- 
 dola, O. J. 45, 118). Eeddish-brown scales 
 (from dilute alcohol). Solutions in alcohol, ace- 
 tone, glacial acetic acid, and benzene are orange. 
 On adding HCl to the alcoholic solution the 
 liquid turns crimson, and, if concentrated, a 
 brown gelatinous hydrochloride is ppd. Cone. 
 HjSO, forms a violet solution. After reduction 
 by Zn and HCl, Fefilg forms a blue dye. Its 
 salts are unstable. 
 
 Nitroso derivative [128°]. 
 
 jj-Nitro-benzene-azo-di-plieiiylamine 
 [4:l](NO,)0,H,-N,-CX(NH.G3H3)[l:4][151°]. 
 From aqueous diazotised p-nitraniline and 
 alcoholio diphenylamine. The pp. is treated 
 ■with ammonium carbonate, and the base crystal- 
 lised from dilute alcohol (Meldola, C. J. 43, 440). 
 Brown leaflets. Solutions are orange in 
 alcohol, turned violet by HCl; violet in cone. 
 H2SO4. The hydrochloride forms needles, with 
 violet reflex, but is very unstable. 
 
 2)-Nitro-benzene-azo-reBorcln 
 [4:1] C,Hj(N0,)-N,-0.H3(OH), [1:2:4]. From 
 jD-diazo-nitro-benzene nitrate and resorcin in 
 alkaline solution (Meldola, O. J. 47, 660). Brick- 
 red crystalline powder ; KOHAq forms a violet, 
 H2SO4 an orange, solution. 
 
 p-Nltro-benzene-azo-Tn-zylidine 
 ;[4:1] (N0,).C«H4-N,-CAMe,(NH,) [1:3:5:2]. 
 [141°]. From aqueous p-nitro-diazo-benzene 
 chloride and alcoholio m-xylidine hydrochloride 
 (Meldola, C. J. 43, 428). There results a bulky 
 reddish pp. of NOj.CsH^.Nz.NHCaHjMej which, 
 on standing, changes to the scarlet hydrochloride 
 of the azo- compound. 
 
 ProperUes. — Brick-red needles (from dilute 
 alcohol). Forms orange solutions in alcohol, 
 acetone, benzene, chloroform, and cone. HjSO^. 
 
 Salts. — The chloride, sulphate, and nitrate 
 form red needles with violet reflex, insoluble in 
 alcohol.— (B'HCl)jPtCl4. 
 
 Nitro-carboxy-beuzene-azo-nitro-beuzoicacid 
 N2(CjH3(N02).C02H)2(?). Formed by nitrating 
 earboxy-benzene-azo-benzoio acid (Golubeff, J. R. 
 6, 197). — Na,A". — K^A" 3aq. — BaA".— Et,A" : 
 [104°]. 
 
 Di-nitro-oxy-amido-benzene-azo-xylene 
 C.H(N0Jj(NH2)(0H)— N.-CAMe^. From 
 
 diazo-xylene chloride and di-uitro-amido-phenol 
 in alkaline solution (Stebbins, jun., A. C. J. 
 2, 236). Brown powder, si. sol. oold water. 
 
 Nitro-ozy-benzene-azo-benzene sulphonio 
 acid[3:4:l]CsH3(NOj)(OH)— Nj— C,H4.S03H[1:4], 
 From diazotised sulphanilic acid and o-niiro- 
 phenol (Griess, B. 11, 2195 ; E. Meyer a. Kreis, 
 B. 16, 1331). 
 
 Nitro - oxy - benzene - azo naphthalene 
 BulphonieacidC,H3(N02)(OH)— Nj— OioHj.SOjH. 
 From diazotised (a)-naphthylamine sulphonio 
 acid and o-nitro-phenol (Stebbins, jun., A. C. J. 
 2, 236). Red needles, v. sol. water. 
 
 Bi-nltro-oxy-benzene-azo-napthylamine sul- 
 phonio acid C„H,(N02)2(OH).N2.C,„H,(NH2).SO,H. 
 From diazo-di-nitro-phenol and (a)-naphthyl- 
 amine sulphonio acid (Stebbins, jun., A. C. J. 
 2, 446). Eeddish-brown dye ; sol. water. 
 
 Nitro-oxy-benzeae-azo-nitro-phenol. 
 
 Ethyl ether 
 [2:a;:l]C3H3(OEt)(NO,).N,.03H3(OBt)(NO,)[l:2:a!]. 
 [190°]. Formed by nitrating o-oxy-benzene-o- 
 azo-phenol ethyl ether, and separated from the 
 isomeric compound by alcohol, in which it dis- 
 solves (Andreae, /. pr. [2] 21, 322). Needles 
 (from alcohol). 
 
 Nitro-oxy-benzene-azo-nitro-phenol. 
 
 Ethyl ether 
 [2:a;:l]C,H3(OEt)(NO,).N,.C3H3(OEt)(NO,) [1:2:0)]. 
 [285°]. Formedtogether with the preceding (3. v.). 
 Brownish-red crystals (from chloroform). Insol. 
 alcohol. Dissolves without change in cone. 
 HjSO,. Eeduced by alcoholic ammonium sulphide 
 to the di-ethyl ether of dinitro-dioxy-di-phenyl- 
 hydrazine. 
 
 Bi-nitro-oxy-benzene-azo-phenol sulphonic 
 acid C,H,(N0,)2(0H)— N2- CjH3(OH).S03H. 
 From diazotised di-nitro-amido-phenol and an 
 alkaline solution of phenol o-sulphonio acid 
 (Stebbins, jun., A. C. J. 2, 236 ; C. N. 42, 44). 
 Brown lustrous needles, si. sol. hot water. 
 
 Nitro-diphenyl-azo-nitro-diphenyl (?) 
 [4:1] C3H4(NOJ.C.H4-N,-C.H,.C3H4(NO,) [1:4]. 
 [187°]. From ^-dinitro-diphenyl and sodium 
 amalgam (Wald, B. 10, 137). Yellow powder 
 (from alcohol). 
 
 m-Nitro-toluene-azo-aceto-acetic acid 
 [4:2:1] C8H3(CH3) (NO^)— Nj-CH(CO.CH3).C02H 
 [176°]. Obtained by saponification of the ethyl- 
 ether formed by the action of uitro-diazo- 
 toluene chloride (from nitro-^-toluidine [114°]) 
 on an alkaline solution of aceto-acetic ether 
 (Bamberger, B. 17, 2421). Long yellow silky 
 needles. V. sol. hot alcohol and HOAo. — ^A'^Ba. 
 
 m-ITitro-toluene-azo-acetone 
 [4:2:1]C,H3(CH3)(N02)— Nj— CH2.00.CH3.[134°]. 
 Formed by the action of a dilute solution of 
 aceto-acetic ether (1 mol.) and EOH (1 mol.) 
 on a solution of nitro-diazo-toluene nitrate (from 
 nitro-^-toluidine[114°]) (Bamberger, B. 17, 2421). 
 Orange-red prisms. V. sol. alcohol and ether. 
 
 m-Nitro-toluene-azo-acetophenoue 
 [4:2:1]C,H3(CH,)(N02)— Nj— CHj.CO.CsH5. 
 [168°]. Glistening yellow needles. Formed, 
 together with nitro-toluene-azo-benzoyl-aoetic 
 ether, by adding a solution of nitro-diazo- 
 toluene chloride (from -m- nitro -^-toluidine 
 [114°]) to an iced alkaline solution of benzoyl- 
 acetic ether. 
 
 £:eioa!imC,5H,3N2(N02):NOH:[174°];orange 
 needles (Bamberger a. Caiman, B. 18, 2566). 
 
 m-Nitro.j)-toluene-azo-benzoyl-aoetic acid 
 [4:2:1] C,H3(CH3)(NO2).N,.CH(CO.05H3).COjH. 
 [194°]. Its ethyl-ether is formed, together with 
 
AZO- COMPOUNDS. 
 
 387 
 
 m-nitro-^J-toluene-azo-aoetophenone, by adding a 
 solution o£ m-nitro-^-diazo-toluene chloride to 
 an ioed alkaline solution of benzoyl-aoetio ether 
 (Bamberger a. Caiman, B. 18, 2566). Silky 
 yellow needles. V. si. sol. cold alcohol and 
 acetic acid, more easily at the boiling-point. 
 
 p-Oxy-benzene-azo-benzene-m-sulphonio acid 
 [4:1] OeH,(OH)— Nj— OeHj.SOjH [1:3]. Prom 
 diazotised amido-benzene m-sulphonio acid and 
 an alkaline solution of phenol. Leaflets, with 
 violet reflex; insol. ether, v. sol. water and 
 alcohol.— KA' : long needles (Griess, B. 11, 2194). 
 
 p-Oxy-benzene-azo-benzene-p-suIplionio acid 
 [4:1] C,H,{HS03)-N,-CeH,(0H) [1:4]. Tro- 
 pcBoUne Y. Prepared by the action of an aqueous 
 alkaline solution of phenol on p-diazobenzene 
 sulphonio acid (Griess, B. 11, 2192). Yellowish 
 red prisms. V. sol. water and alcohol. 
 
 Salts. — BaA" : orange pp. — BaA'j 2aq. — 
 BaA'2 5aq : minute orange tables, si. sol. water. 
 — KA' : yellow rhombic leaflets, S. -26 at 15° 
 (Wilsiug, A. 215, 232). 
 
 ^-Oxy- benzene -azo- benzene sulphonio acid 
 [4:1] C5H,(0H)— N^-CsH^.SOjH. From azoxy- 
 benzeue (1 pt.) and fuming HsSOj (5 pts.) at 
 110° (Limprioht, B. 15, 1295; Wilsing, A. 215, 
 229) ; Tschirwinsky (J. B. 5, 217) considers this 
 acid to be identical with the preceding. Small 
 lustrous reddish plates, v. sol. water, m. sol. 
 dilute acids or alcohol. Br does not act on the 
 potassium salt. SnClj forms no aniline by re- 
 duction. Salts.— KA'aq: S.-85atl5°.-BaA'2.— 
 AgA .— MgA'j 6aq.— CuA's 6aq. 
 
 Chloride. [122°]. Orange 6- or 8-sided 
 plates. 
 
 Amide. [212°]. Plates. 
 
 Si-ozy-benzene-azo-benzene snlphouic acid 
 [4:2:1] OaHaCOH)^— N^— O^H^.SOsH [1:4]. Tro- 
 pcBoUn 0. ChrysoXne. Formed by sulphonating 
 benzene-azo-resorcin at 100° (Witt, O. /. 35, 
 183) or from diazotised amido-benzene p-sul- 
 phonic acid and resoroin dissolved in KOHAq 
 (Griess, B. 11, 2195). Bed leaflets with steel- 
 blue reflex ; v. si. sol. alcohol and cold water. — 
 KA'.— BaA'2 4aq. 
 
 The absorption-spectrum has been examined 
 by Hartley (C. J. 51, 182). 
 
 Si - oxy ■ benzene - azo - benzene m - snlphonic 
 acid [4:2:1] C,H3(OH),-N,-C,H4.S03H [1:3]. 
 From resorcin and diazotised amido-benzene 
 m-sulphonio acid. Orange needles. — KA': hy- 
 groscopic needles. 
 
 Tri-oxy-benzene-azo-benzene sulphonic acid 
 [2:4:6:1] ^(OH),— N^— 0,Hi.S03H [1:4]. From 
 diazotised amido-benzene ^-sulphonic acid and 
 an alkaline solution of phloroglucin (Stebbins, 
 C. N. 49, 44 ; A. C. J. 1, 465 ; 2, 236 ; B. 13, 
 716). Yellow leaflets with green lustre. — NaA' : 
 yellow leaflets, easily soluble in water. 
 
 ^-Oxy-benzene-m-azo-benzoic acid 
 [4:1] C5H^(0H) -N2— CsHj.CO^H [1:3]. [220°]. 
 
 Formation. — 1. From OT-diazo-benzoio acid 
 and phenol (Griess, B. 14, 2032).— 2. By gently 
 warming m - carboxy-diazo-benzene- m -oarboxy- 
 aniUde C5Hj(C02H).N2.NH.CeHj(C0,H) with 
 phenol, ?re-amido-benzoio acid being eliminated 
 (Heumann a. Oeoonomides, B. 20, 906). Bed 
 needles or plates ; sol. alcohol and ether, si. sol. 
 water. Dyes wool and sUk yellow. — BaA.'2 3 Jaq. 
 
 Di-oxy-benzene-m-azo-beuzoic acid 
 [4:2:1] 0,H3(OH)3— N^-O^H.-COjE [1:3]. Pre- 
 
 pared by the action of w-diazobenzoio acid on an 
 alkaline solution of resorcin (Griess, B. 14, 2034). 
 Brownish-red needles or brownish-yellow plates. 
 Sol. alcohol. Dyes wool and silk yellow. 
 
 Oxy-benzene-azo-jp-cresol. Ethyl ether 
 [4:1] C,Hj(0Et)-N2— C,H3(CH3)(OH) [1:5:2] 
 
 orOsHsMe/l . [104°]. Formed 
 
 \N2H.CsH3Me(0Et) 
 by combining ji-diazo-phenetol with ^-cresol 
 (Liebermann a. Kostaneoki, 'B. 17, 883). Golden 
 plates. Sol. alkalis. Dissolves in H2S0i with, a 
 brown colour. On reduction it gives ^-amido- 
 phenetol and amido-^-cresol. 
 
 o-Oxy-benzene-azo-o-cresol. Methyl ether 
 0,B.^{OUe)—N^—G,B.Me{OB.). [68°]. From 
 diazotised o-anisidine and o-cresol (Kanonnikoff, 
 J. B. 1885, 369). Di-methyl ether [103°]. 
 
 o-Oxy-benzene-azo-m-cresol. Methyl 
 ether. [161°]. Prepared like the preceding (K.). 
 
 Di-oxy-benzene-azo-if'-cnmene 
 [4:2:l]C„H3(OH)2— N2— CsH^Me, [199°]. Formed, 
 together with the disazo-oompound, by com- 
 bining diazo - oumene chloride (from amido- 
 pseudo-cumene [62°]) with resoroin (Liebermann 
 a. Kostanecki, B. 17, 131, 882). Small red needles. 
 Dissolves in alkalis with a brownish-yellow 
 colour. 
 
 Si - oxy - benzene - azo - hydroquinone 
 [5:2:1] C,H3(0H)3-N2-C,H3(0H)2 [1:2:5]. Azo- 
 hydroquinone. Tetra-methyl derivative 
 C3H3(0Me)2.N2.C3H3(0Me)2. [140°]. Formed by 
 reduction of nitro-di-methyl-hydroquinone in 
 alkaline solution (Baessler, B. 17, 2124 ; O. G. 
 1886, 671). Bed needles. V. sol. alcohol, ben- 
 zene, chloroform, and CSj, v. si. sol. water. 
 Dissolves in strong HCl with a blue colour. 
 
 Tetra-ethyl derivative [128°]. From 
 nitro-di-ethyl-hydroquinone, powdered zinc, and 
 alcoholic potash (Nietzki, B. 12, 39). 
 
 Si-oxy-benzene-azo-naphthaleue sulphonic 
 acid [4:2:1] C,H3(0H)2-N2-C,„H,.S03H [1:4]. 
 From diazotised (a)-naphthylamine sulphonio 
 acid and an alkaline solution of resorcin (Steb- 
 bins, jun., A. C. J. 2, 36 ; G. N. 42, 44). Dark- 
 brown needles, sol. water. 
 
 ^-Oxy-beuzene-azo-(a)-naplithylamine 
 [4:1] C3H,(0H)-N3-C,„H,.NH2 [1:4]. [170°]. 
 Prepared by the action of jp-diazophenol nitrate 
 on (ffl)-naplithylamine (Weselsky a. Benedikt, B. 
 12, 229). Orange needles (containing 3aq). — 
 B'jH^SOjeaq : green needles, insol. water. 
 
 o-Oxy-benzene-azo-(;3)-uaphthylamine 
 
 [2:1] C,H,(OH).N3G,„H3 or C.„H,<C| 
 
 .NH 
 
 \n3H.CsH,0H. 
 
 o-Oxy-bemene-hydrazimido-naphthalene. [193°]. 
 Formed by combining o-diazo-phenol with (/3)- 
 naphthylamine. Slender red needles (from alco- 
 hol or acetic acid), or dark red plates (from 
 benzene). It dissolves in aqueous or alcoholio 
 NaOH, but is insoluble in water. By heating 
 at 150° with HCl it is split up into (;8)-naph- 
 thylamine, pyrocatechin, and nitrogen. Bromine 
 in cold acetic acid solution gives di-bromo-(0)- 
 naphthylamine, a brominated pyrocatechin, and 
 nitrogen. On reduction with zinc dust and 
 acetic acid it yields (l:2)-naphthyleue-diainine. 
 
 Acetyl derivative [198°j. 
 
 Benzoyl derivative [183°]. 
 
 oc 2 
 
388 
 
 AZO- COMPOUNDS. 
 
 Methyl ether C,B.,(OUe).-S,C,,n, [133"^; 
 dark-red monoolinio prisms ; insoluble in water 
 (Sachs, B. 18, 3125). 
 
 jp-Oxy-benzene-azo-(/3)-naplithylainine 
 .NH 
 [4:1] CeH,(OH).N,C,„H,or C,„h/ | 
 
 \N2H.CjH,0H. 
 p-Oxy-bmizene-hydrazimido-naphthalene. [19S% 
 Formed by combining p-diazo-phenol with (P)- 
 naphthylamine. Plat red prisms. V. sol. benzene 
 and acetic acid, insol. water. By heating at 
 150'^ with HCl it is split up into (;3)-naphthyl- 
 amine, hydroquinone, and nitrogen. Bromine 
 in cold acetic acid solution gives di-bromo-(;8)- 
 napththylamine, a brominated hydroquinone, 
 and nitrogen. On reduction with zinc dust and 
 acetic acid it yields (l:2)-naphthylene-diamine 
 (Sachs, B. 18, 3125). 
 
 Mono-acetyl derivative [218°]. 
 
 Mono-benzoyl derivative [244°]. 
 
 Oxy-benzene-azo-orcin. Methyl ether 
 C„Hj(0Me).N,.C„H2(0H)„Me. Hair-like needles 
 (Stebbins, A. C. J. 5, 32). 
 
 o-Oxy-benzene-o-azo-phenoI 
 [2:1] C,H,(OH)— N^— CjH^fOH) [1:2]. o-Azo- 
 phenol. [171°]. S. (alcohol) -3 at 20°. Prepared 
 by fusing o-nitro-phenol with KOH (Weselsky 
 a. Benedikt, B. 11, 398 ; A. 196, 344). Golden 
 leaflets ; may be sublimed. Insol. water. 
 
 Reactions. — 1. Bromine added to an ethereal 
 solution forms a tetra-bromo-derivative.— 2. 
 Chlorine passed into an acetic acid solution 
 forms a tri-ohloro derivative CioHjClafOHj^Nj 
 [235°] (Bohn a. Heumann, B. 'l7, 275).— 3. 
 Nitric acid forms (1, 2, 4)-di-nitro-phenol 
 
 Ethyl ether {C,S.^{0'^i)]^.,. [131°]. 
 
 o-Nitro-phenyl-ethyl ether OsHj(OEt)(N02) 
 is dissolved in alcohol and reduced with sodium- 
 amalgam (5 per cent.), the liquid being allowed 
 to become hot. The product is poured into 
 water, and the pp. extracted by strong HCl which 
 dissolves the azo- compound. On pouring the 
 HCl solution into water, o-azo-phenetol is thrown 
 down (E. Schmitt a. Mohlau, J. pr. 126, 202). 
 Properties. — Long red prisms (from alcohol). 
 Melts under water, but insoluble therein and not 
 volatile with steam. It begins to boU at 240°, but 
 Buffers decomposition at the same time. Be- 
 actions. — 1. Beduced by alcoholic ammonium 
 sulphide to the corresponding hydrazo-compound 
 {q. v.). — 2. Cold fuming HNOj forms a nitre-, 
 and a di-nitro-, derivative. 
 
 OT-Oxy-benzene-m-azo-phenol Ethyl ether 
 /3:1] C„H,(0Et)-N3— C,Hj(OEt) [1:3]. m-Azo- 
 pheiietol. [91°]. Formed by reducing m-hitro- 
 phenetol in alcoholic solution with sodium 
 amalgam (M. Buchstab, /. pr. [2] 29, 299). 
 
 Properties. — Orange prisms (from alcohol). 
 Sol. ether. Insol. water and (difference from o- 
 eompound) in cone. HCl. Eeduced by H2S and 
 alcoholic ammonia to ?n-hydrazo-phenetol. 
 
 p-Oxy-benzene-p-azo-phenol 
 [4:1] C„H,(OH)— Nj— CsH,(OH) [1:4]. p-Azo- 
 ■phenol. [204']. 
 
 Formation. — 1. By potash-fusion from p- 
 nitroso-phenol (Jaegek', B. 8, 1499), j)-nitro- 
 phenol (Weselsky a. Benedikt, A. 196, 339), p- 
 oxy-benzene-azo-benzene p-sulphonic acid, or p- 
 Bulpho-benzene-azo-benzene p-sulphonic acid 
 (Bohn a. Heumann, B. 15, 3037).— 2. From p- 
 diazo-phenol nitrate and phenol potassium. 
 
 Properties, — Slender brown needles witil 
 blue reflex (containing aq) ; si. sol. water, y. 
 sol. alcohol. Bromine gives a tetra-bromo 
 derivative. Nitric acid (1, 2, 4)-di-mtro-phenol. 
 Chlorine gives tri-ohloro-phenol. 
 
 Salt .— BaCijHsNjOj 4aq. 
 
 Ethyl ether C,H<(OEt)— Nj— CeHj(OEt). 
 p-Azo-phenetol [160°] (S. a. M.) ; [158°] (A.). 
 Formed by adding sodium-amalgam (5 p.c.) to 
 an alcoholic solution of p-nitro-phenyl-ethyl 
 ether, precipitating the product with water, boil- 
 ing it with dilute HCl to remove amido-phenyl- 
 ethyl-ether, and crystallising from alcohol 
 (Schmitt a. Mohlau, J. pr. 126, 199 ; Hepp, B. 
 10, 1652 ; Andreae, J.pr. 129, 333). Properties.— 
 Glittering golden plates. M. sol. cold alcohol, v. 
 sol. ether and chloroform. Distils with difficulty. 
 Reactions. — 1. Fuming HNO3 forms the ethyl 
 ether of di-nitro-phenol (g. v.) and two isomeric 
 tri-nitro-azoxy-phenol ethyl ethers. — 2. HClAq 
 atl30°givesEtClandp-azo-phenolN2(CeH4OH)j, 
 but at 150° ohloro-p-amido- phenol is got 
 (Schmitt, J. pr. [2] 19, 313). 
 
 p-Oxy-benzene-azo-diphenyl sulphonic acid 
 [4:1] C,H^(OH)— Nj— C5H,.0,H4.S03H. From 
 diazotised ^J-amido-diphenyl sulphonio acid and 
 phenol (Carnelley a. Schlevelmann, C. J. 49, 
 380). Yellow dye. — BaA'^: insol. cold water. 
 
 m - Si - oxy -benzene-azo-diphenyl sulphonlc 
 acid [4:2:1] C,H3(0H),-N,-C,H,.CeH,.SO3H. 
 From diazotised p-amido-diphenyl sulphonio 
 acid and resoroin (Carnelley a. Schlevehnann, 
 C. /. 49, 382).— NaA'.— BaA'j. 
 
 p-Di-oxy-benzene-azo-diphenyl sulphonlc acid 
 [5:2:1] CsHs(OH)2.N2.C5H4.C,H4.SOsH. From 
 diazotised p-amido-diphenyl sulphonio acid and 
 hydroquinone (Carnelley a. Schlevelmann, 0. J. 
 49, 382). 
 
 p-Oxy-beuzeue-azo-phloroglucin 
 C,H^(OH)— Nj— CjH2(OH)3. Two modifications 
 appear to be formed by the action of p-diazo- 
 phenol nitrate on phloroglucin (Weselsky a. 
 Benedikt, B. 12, 227). (a) Bed crystalline pow- 
 der (containing 3aq), sol. alcohol. (j3) Green 
 amorphous mass, insol. alcohol. 
 
 p-Oxy-benzene-azo-resorcin. Ethyl -ether 
 [4:1] C„H,(OEt)-N,-C,H,(OH), [1:2:4]. [167°]. 
 Formed by the action of p-diazo-phenetol on 
 resoroin (Liebermann a. Kostanecki, B. 17, 883). 
 Bed plates. Sol. alkalis. Dissolves in HjSO, 
 with a brownish-red colour. 
 
 Dioxy-benzene-azo-resorcin 
 [2:6:1] C,H3(0H),— N^- CsH3(OH),[l:2:4]. TetrOr 
 oxy-azo-henzene. 
 
 Di-ethyl ether C,B.,{0^i)^:S2.0sB.3{0'R)^ 
 [182°]. Formed by combination of the di-ethyl 
 ether of o-diazo-resoroin C5H3(OEt)2N20H [6:2:1] 
 with resoroin. Light reddish-yeUow needles. 
 V. sol. alcohol and ether, insol. water. Dis- 
 solves in cone, alkali with a reddish yellow 
 colour, which becomes a splendid carmine-red 
 on dilution (Pukall, B.20, 1151). 
 
 Di-oxy-benzene-azo-resorcin 
 [2:4:1] C,H3(0H)2.N2.CsH3(0H)2 [1:4:2]. Tetra- 
 oxy-azo-benzene. 
 
 Di-ethyl ether 
 C,H3(0Et)2— N— C„H3(0H)2. [193°]. Formed 
 by combination of the di-ethyl ether of p-diazo- 
 resorcin C5H3(0Et)2.N20H [4:2:1] with resorcin. 
 Small brown needles or short prisms with green 
 reflex. V. sol. alcohol, ether, and aqueous 
 
AZO- COMPOUNDS. 
 
 389 
 
 Blkalig, insol. water. Carmine-red dyestuS 
 (Pnkall, B. 20, 1144}. 
 
 Oxy-benzene-azo-resoroin-di-sulphonic acid 
 
 Mono-methyl ether 
 OaH,(OMe).N,.C,H(OH),(S03H)2. YeUow plates 
 (Stebbins, A. C. J. 5, 55).— BaA"aq: needles. 
 
 jp-Oxy-benzene-p-azo- toluene 
 L4:l] C„H^Me-N,-C,H,(OH) [1:4]. [151°]. 
 Formed by gently warming y-diazo-toluene-^- 
 toluide with phenol, j)-toluidine being split off 
 (Heumann a. Oeconomides, B. 20, 905), or by 
 warming ^-nitroso-toluene with ^-toluidine ace- 
 tate (Kimioh, B. 8, 1030). Orange prisms, with 
 blue reflex. 
 
 7?i-Dl-oxy-benzene-o-azo-toluene 
 [2:1] CeH,(CH,)-N,-C„H3(0H), [1:2:4]. [195°]. 
 (W.); [178°] (F.). Formed by the action of o-diazo- 
 toluene on resorcin. Brownish-red felted needles. 
 
 Acetyl derivative [75°J. Orange-yellow 
 plates (Wallaoh, B. 15, 2825 ; of. Fischer, B. 20, 
 1579). 
 
 ??i-Di-oxy-benzene-2)-azo-toluene 
 [4:1] C,H,(CH3)-N,-CeH3(OH), [1:2:4] [184°]. 
 Prepared by the action of ^-diazo-toluene on 
 resorcin, or by gently warming ^-diazo-toluene- 
 p-toluide with resorcin, ^-toluidine being split 
 off (Heumann a. Oeconomides, B. 20, 906). 
 Eeddish-yellow needles : sol. alcohol, ether, and 
 aqueous alkalis. Acetyl derivative [98°]. 
 
 Oxy-benzeue-azo-tolnidine 
 [5:2:1] C,H3(CH3)(NH,)-N,-C,H,OH [1:4]. 
 [172°]. Formed by saponification of the acetyl 
 derivative. Slender brown needles. Sol. alcohol 
 and ether, v. si. sol. cold water. Dissolves in 
 aqueous acids and alkalis. 
 
 Acetyl derivative 
 
 C3H3(CH3)(NHAc) -Nj— CsH.OH. [253°]. 
 Prepared by diazotising the mono-acetyl deri- 
 vative of (l;2:4)-tolylene-diamine and combining 
 it with phenol (Wallach, B. 15, 2826). Yellow 
 plates. Sol. acetic acid and in aqueous alkalis, 
 b1. sol. alcohol. 
 
 Di - oxy- benzene -azo- xylene (Wallach, B. 
 15, 25). Formed by adding diazo-xylene chloride 
 to an alkaline solution of resorcin. 
 
 Si-ozy-benzene-azo-zylene sulphonic acid 
 [4:2:1] C3H3(OH)j— N^— CBH^Me^SOaH. Prepared 
 by the action of an alkaline solution of resorcin 
 upon diazo-xylene sulphonic acid. Slender 
 orange needles, si. sol. hot water ; m. sol. alcohol 
 (Griess, B. 11, 2197). 
 
 Oxy-carboxy-benzene-azo-naphthalene 
 0,oH-Nj-OeH,(OH)(CO,H) [1:4:3]. From 
 naphthylamine hydrochloride (9 g.), HCl, water 
 (500 g.), and NaNO^ (3-45 g.) at 0°, the filtrate 
 being poured into a solution of salicylic acid 
 (6'9_g.) and NaOH (6g.) in water (500 g.). The 
 liquid is filtered and the sodium salt ppd. by 
 NaCl (P. F. Frankland, 0. J. 37, 747). Salt.— 
 NaA'. S.'07 (cold). Dyes silk pale yellow. 
 Beduced by Sn and HCl to naphthylamine and 
 amido-salicylic acid, C,H3(NH2)(0H)C02H. 
 
 Oxy-carboxy-benzene-azo-(^)-naphthol 
 
 Mono-methyl derivative 
 C3H,(0Me)(C02H)— N^- C,„H„(OH). Prepared 
 by the action of diazo-anisic acid on an alkaline 
 solution of. (/3).naphthol (Griess, B. 14, 2039). 
 Small red needles or plates (containing l^aq). 
 SI. sol. alcohol. A'jBa 4aq : red minute needles. 
 
 Oxy-carboxy-benzene-azo-(/3) naphthol aul- 
 phonic acid. Methyl derivative 
 
 C„H3(0Me) (CO,H)— N,- C,„H3(0H) (S03H).From 
 diazo-anisic acid and (|8)-naphthol sulphonic 
 acid. Brown needles. Dyes wool scarlet. 
 BaA"2 8aq (Griess, B. 14, 2039). 
 
 Oxy-carboxy-benzene-azo-(/3)-naphthoI-(a)-di. 
 sulphonic acid Methyl derivative 
 C„H3(0Me) (COjH)— N — 0,„H^(0H) (S03H)j. Pre- 
 pared by the action of diazo-anisic acid on an 
 alkaline solution of (^)-naphthol-(a)-di-sulphonic 
 acid (Griess, B. 14, 2040). Small dark-red 
 needles (containing 8aq). Sol. water, and 
 alcohol, insol. ether. Dyes a blueish shade of 
 scarlet. A"'HK2 6aq: red crystals, sol. hot water. 
 
 Oxy-carboxy-benzene-azo-oxy-benzoio acid 
 
 Bi-methyl derivative 
 
 C„H,(0Me)(C0,H)— N3— C,H3(0M:e)(C0,H). 
 Formed by the action of sodium-amalgam on an 
 alkaline solution of nitro-anisic acid. Insol. 
 water.— BaA" aq (Alexejeff, C. B. 55, 472). 
 
 Dioxy- oarboxy - metbyi-phtbalide-azo-dioxy- 
 phthalide-acetio acid 
 
 Tetra-methyl derivativeC2t^''t^fii2 i-*- 
 
 ch.ch,.co,h'i 
 
 N2{0„H(0Me; 
 
 /^ 
 
 ;0 
 
 '\co- 
 
 Azo-meconic-acetic acid. [0. 257°]. Obtained 
 by reduction of nitro-di-methoxy-phthalide- 
 
 acetic acid C„H(0Me),(N0,)<^°7gjj (,q^jj 
 
 with zinc-dust and aqueous NH3. Yellow crystals. 
 Insol. water. Dissolves in cone. H^SO, with a 
 deep blueish-violet colour (Kleeman, B. 20, 880). 
 Tri - oxy - carboxy - toluene - azo-tri-oxy-toluio 
 acid. Anhydride of the tetra-methyl 
 derivative. 
 
 (6r5) (1) (4) (4) (6:5) (1) 
 
 C.H(0Me).(C0,H)<°'!i^^->0.H(0Me).(CO,H). 
 (3) (3) 
 
 [c. 245]. Formed by reduction of nitroso-opianio 
 acid CsH(0Me),(N0)(CH0)(C02H) with zinc- 
 dust and aqueous NH,. Dissolves in alkalis 
 with a yellow colour, in cone. H^SO, with an 
 intense purple colour. — AgA' : microscopic 
 needles (from hot water). — EtA': [101°], yellow 
 needles, v. sol. alcohol, ether, and benzene 
 (Kleemann, B. 20, 878). 
 
 (/3) -Oxy-naphthalene-azo-Mppuric acid 
 GO2H.CH2.NH.CO.CsH,— N,-C,„H„(OH). Pro- 
 pared by the action of diazo-hippurio acid on 
 an alkaline solution of (/3)-naphthol (Griess, B. 
 14, 2040). Eeddish-yellow needles. SI. sol 
 alcohol, V. si. sol. water and ether. 
 
 (a)-Oxy-(a)-naplithalene-(a)-azo-naphtliaIene- 
 (a) -sulphonic acid 
 
 [4:1] C,„H,fOH)-N2-C„H,.S03H [1:4]. From 
 diazotised (o) -naphthylamine sulphonic acid and 
 (a) -naphthol. The absorption-spectrum has been 
 examined by Hartley (0. /. 51, 198). 
 
 (;3) - Oxy - naphthalene - azo-naphthalene sul- 
 phonic acid Ci„H„(OH)— N2— CjoHjSOsH. From 
 diazotised (o) -naphthylamine sulphonic acid and 
 (j3)-naphthol (Caro ; Griess, B. 11, 2199). Bed- 
 dish-brown needles (from alcohol). Bed dye. — 
 BaA'j. The absorption-spectrum has been 
 examined by Hartley (0. J. 51, 197). 
 
 Oxy - propyl - carboxy - benzene - azo - oxy- 
 propyl-benzoic acid 
 
 C0,H.C„H3(C{0H)Me,)— K,— C.H3(C(0H)Me,)C0,H. 
 Formed by reduction of nitro-oxy-propyl-benzoio 
 acid with sodium - amalgam and water (Wid- 
 mann, JS. 15, 2550). Yellow plates. V. b1. soL 
 
390 
 
 AZO- COMPOUNDS. 
 
 most ordinary solvents, si. sol. acetic acid. — 
 NajA." lOaq : thin red rectangular tables. 
 
 Ozy-Buipho-benzene-aza-benzoic acid 
 [3:1] C,H,(CO^)-N,-C,H3(OH)(HS03) [1^:3]. 
 Prepared by the action of ))i-diazobenzoio acid 
 on an alkaline solution of phenol-o-sulphonio 
 acid (Griess, B. 14, 2033). Brownish-red crystals 
 (containing ^aq). Sol. water, alcohol and ether. 
 Yellow dye. Salts. — A"HKaq: yellow plates 
 or needles, si. sol. cold water. — A"jH2Ba : small 
 yellow needles or plates. — A"Ba aq : yellow crys- 
 talline pp. 
 
 Oxy ■ snlpho • benzene - azo • naphthalene snl- 
 phonic acid C5H3(OH)(S03H)— N^— C„H8.S03H. 
 From diazotised (o)-naphtnylamine sulphouio 
 acid and phenol sulphouic acid (Stebbins, A.C.J. 
 2, 446). 
 
 Ozy-tolnene-azo-toluene sulpbouic acid 
 [4:2:1] 0,H,(CH,)(SO,H)— N,— C.H,(CH,)(OH) [1:5:2]. 
 Formed by theaction of ^-diazo-toluenesulphonio 
 acid (by diazotisingp-toluidine-sulphonic acid) 
 on an alkaline selution of p-cresol (Nolting a. 
 Kohn, B. 17, 358). Beddish-brown crystals 
 with violet reflection. V. sol. water, si. sol. 
 alcohol. Salts. — A'Na: soluble yellow plates. — 
 A'^Ba 4aq : small reddish-brown needles, si. sol. 
 hot water. 
 
 Siphenyl-azo-diphenyl 
 C.H3.C,H,-N,-C,H,.C,H3. [250=]. Orange- 
 red plates. Sol. ether, insol. water, alcohol, and 
 acetic acid. Formed by reduction of j»-nitro- 
 diphenyl with sodium-amalgam, and by the dry 
 distillation of hydrazo-diphenyl. Prepared by 
 oxidising an alcoholic solution of hydrazo-di- 
 phenyl with Fe-^Clj (Zimmermanu, B. 13, 1962). 
 
 Phenyl - acetic - azo - phenyl - acetic acid v. 
 
 «a;o-CAEBOXY-TOLnENE-AZO-PHENTL-AOETIC ACID. 
 
 Phenyl - amido - benzene - azo - benzene - sal- 
 phonic acid 
 
 [4:1] CsH,(S03H)— Nj— CjH^NHPh [1:4]. Tro- 
 pcBoUne 0.0. Prepared by the action of ^-diazo- 
 benzene sulphonic acid on an alcohoUc solution 
 of diphenylamine (Witt, C. J. 35, 187 ; B. 13, 
 262). Steel-blue hair-like needles. SI. sol. water. 
 Salts. — A'K: flat yellow needles; si. sol. cold 
 water. — A'Na. — A'NH,.— A'NHMej: large yellow 
 leaflets. — ^A'JBa and A'jCa: insoluble yellow pps. 
 
 PhenyI-gIycolUc-0-azo-phenyl-glycollic acid 
 Nj(CeH^.O.CH,.C02H)2. [162°]. 
 
 Preparation. — o-NitrophenylglyooUio acid 
 (18-6 g.) water (140 g.) and Na^COa (5 g.) are 
 treated at 60° with sodium-amalgam (215 g. of 
 4 p.c. amalgam). The crystals which separate 
 on cooling are dissolved in very little water and 
 the acid is ppd. by acetic acid. The product 
 is reorystallised several times from alcohol 
 (A. Thate, J.pr. [2] 29, 161). 
 
 Properties. — Orange silky needles, contain- 
 ing 2aq (from water or dilute alcohol). When 
 dry (at 110°) it is brick-red. Sol. ether, alkalis 
 and strong acids. Its solutions are yellow or red. 
 
 Reactions. — 1. Aqueous solution is acid to 
 litmus and gives with AgNOj a red gelatinous 
 pp., and with Pb(0Ac)2 a flocculent yellow pp. — 
 2. Eeduced by alcoholic NH, and H^S to the 
 corresponding hydrazo- compound, the potas- 
 sium salt of which, l!i^Ta.,(G^,.O.CB..fiO.,K)^ 3aq, 
 crystallises from alcohol in rhombohedra. 
 
 Salts.— KjA"3aq. Orange plates. Its 
 solution gives with BaClj a red crystalline pp. ; 
 with Pb(0Ac)2 an orange flocculent pp.; with 
 
 AgNOj, a red flocculent pp. ; with PejCls an 
 orange pp. ; with CuSO^, a brownish-yellow pp. ; 
 with HgGlj, on boiling, a red pp. ; with MgSO, 
 after some time, an orange crystalline pp. — 
 Na^A" 3aq.— AgjA" 3aq.— BaA" 2aq.— CaA" 8aq. 
 
 Ethyl eiher. M^A.". [111°]. Bed crystals. 
 
 Phenyl-glyoxylic-azo-phenyl-glyoxylic acid 
 C02H.C0.CeH<— Nj— CsHj.CO.COjH. Ano-ben- 
 zoyl-formic acid. Orange needles (containing 
 2aq and melting at [135°]. When dry it melts 
 at about 151°. Prepared by reduction of m- 
 nitro-benzoyl-formio acid with FeSO, and KOH ; 
 yield, 60 p.o. (Thompson, B. 16, 1308). SI. sol. 
 ether and cold water, insol. acidulated water, 
 chloroform, or benzene. Very stable body. 
 A cold saturated aqueous solution of the acid 
 gives with BaClj or CaClu a micro-crystalline 
 pp., with AgN03 a yellow flocculent precipitate. — 
 A"Ba : orange crystalline pp., • insol. water. — 
 A"Ag2 : orange-yellow slightly soluble pp. 
 
 Fhenyl-pyrrol-azo-beuzene 
 
 C3H3.N2.C = CH 
 C A.N2.C<H3NPh probably NPh | . 
 
 HG = CH 
 [117°]. Prepared by adding diazobenzene chlo- 
 ride (1 mol.) to phenyl-pyrrol (1 mol.) dissolved 
 in alcohol containing AcONa. Brown prisms or 
 long reddish-yellow needles with blueish reflec- 
 tion. V. sol. alcohol. Dissolves in cone. H^SO, 
 with a reddish-violet colour, in alcoholic HOI 
 with a blood-red colour. Beduced by zinc-dust 
 and NH3 or NaOH to aniline and (probably) amido- 
 phenyl-pyrrol (0. Fischer a. Hepp, B. 19, 2256). 
 
 Si- propyl - amido - benzene - azo - di - propyl- 
 aniline CsH,N(C3H,)2— N^— C«H4N(03H,)3. Di- 
 propyl-aniline-azyline. [90°]. Formed bypassing 
 NO through an alcoholic solution of di-propyl- 
 aniline (Lippmann a. Fleissner, B. 15, 2140; 
 16, 1417). Large trimetrio crystals, a:b:c: = 
 1: -629: -913. Picrate B"(C3H2(NO.j30H)j : 
 orange-red insoluble crystals. — Periodida 
 B''^^ : violet glistening needles. 
 
 Pyrrol - azo - benzene CsHj— Nj— CjHjNH 
 C8H3.Nj.g = CH 
 probably NH| . [62°]. Prepared by 
 
 HC = CH 
 adding the calculated quantity of a moderately 
 cone, solution of diazo-benzene chloride to a well- 
 cooled solution of pyrrol (2 pts.) in alcohol 
 (100 pts.) with addition of sodium acetate (5 pts.) 
 (Fischer a. Hepp, JB. 19, 2251). Yellow needles. 
 V. sol. alcohol, ether, and petroleum spirit, si. 
 sol. water. It has basic properties. Easily 
 reduced {e.g., by zinc-dust and alkalis) to aniline 
 and (probably) amido-pyrrol. Eeadily combines 
 in alkaline or neutral solution with a further 
 quantity of diazo-compound, giving disazo-bodies. 
 Dissolves easily in dilute HCl with a reddish -yellow 
 colour. Dissolves in cono. HjSO^ with a yellow 
 colour. The platino-chloride forms small red 
 sparingly soluble needles. 
 
 Pyrrol-p-azo-di-methyl-aniline 
 C„H.,(NMeJ— Nj— C^HjNH. [159°]. Formed 
 by combining p-diazo-di-methyl-amido-benzena 
 with pyrrol in dilute alkaline solutien. Glitter- 
 ing green plates. Dissolves in very dilute HCl 
 with a grass-green colour, in cono. HCl with a 
 greenish-yellow colour. PtCl, gives a dark 
 green amorphous pp. (Fischer a. Hepp, B. 19, 
 2257). 
 
■ COMPOUNDS. 
 
 301 
 
 Fyrrol-(a).azo-naphthaleiieC„H,.Nj.C,H3NH 
 0,.H,.N2.C = 0H 
 probably NH I . [103°]. Formed by 
 
 H6 = CH 
 adding (a)-diazo-naphthalene chloride (1 mol.) 
 to pyrrol (1 mol.) dissolved in alcohol contain- 
 ing sodium acetate. Beddish-yellow plates. V. 
 sol. alcohol (0. Fischer a. Hepp, B. 19, 2255). 
 
 FyrTol-(i8)-azo-naphthaleue 
 
 C„H,.N,.Q = CH 
 0,„H,— Nj— 0,HsNH probably NH| 
 
 HC!=:CH 
 [101°]. Prepared by adding (/3)-diazo-naphthalene 
 chloride to an alcoholic solution of pyrrol con- 
 taining sodium acetate. Gold-bronzy plates 
 (0. Fischer a. Hepp, B. 19, 2255). 
 
 Pyrrol-2)-a20-toluene OeH^Me— N,— O4H3NH 
 C,H,.N2.Q = CH 
 probably NH | . [82°]. Prepared by 
 
 HC = CH 
 adding ^-diazo-toluene chloride (1 mol.) to pyrrol 
 (1 mol.) dissolved in alcohol containing sodium 
 acetate (Fischer a. Hepp, B. 19, 2254). 
 
 m-Salphi - benzene - azo - benzeue-m-sulphinic 
 acid C,H,{S02H)— Nj— CeH^(S02H). 
 Azo-bemene di-sulphimc acid. Obtained from 
 C8H,(S0,SH).Nj.C,H^(S0,SH) by treatment 
 with sodium amalgam (Limpricht, B. 18, 1473 ; 
 Bauer, A. 229, 363). Tellowish amorphous 
 mass, si. sol. cold water, insol. ether. 
 
 Salt s.— NajA" a:aq. — CaA" liaq. — BaA".— 
 PbA". These salts are readily oxidised (e.g. by 
 KMnOj or I in KI) to the corresponding di- 
 sulphonates. Cone, ammonic sulphide converts 
 them into the di-thio-di-sulphonates. They are 
 not reduced by sodium amalgam. Boiled with 
 HCl the acid clots together, but cone. HCl. at 
 110° forms (2 p.o. of) an isomeric hose. 
 
 f -Sulphi - benzene - azo - benzene -p- sulphiuic 
 acid SOjH.CsH,— Nj— CeHj.SO^H. 
 Aao-bemene p-di-suVphimic acid. Prepared from 
 SO^CLO^H,— Nj-CbH^.SOjCI and Ba(SH)j, or 
 from NaS.SO2.CeH4.N2.O5Hj.SO2.SNa by sodium 
 amalgam (Limpricht, B. 18, 1475; Bauer, A. 
 229, 369). The free acid is ppd. by HCl from 
 its salts as a bulky yellow mass, sparingly soluble 
 in water or alcohol. Clots together when heated 
 with acids. Salts. — NajA" 4aq. — BaA". 
 
 Sulpho-benzene-azo-amido-ethane v. Sulpho- 
 
 BENZENE-AZO-ETHTLAMIHB. 
 
 f-Sulpho-benzene-azo-di-amido-benzoic acid 
 [4:l]0„H,(SO,H)-N2— C,H2(NH2)2C02H[1:4:2:6]. 
 Formed by the action of p-diazo-benzene- 
 Bulphonic acid on s-di-amido-benzoio acid 
 (Griess, B. 15, 2199). Needles or plates. SI. sol. 
 water, cold alcohol, and ether. Very unstable. 
 Decomposes by boiling with water. On reduction 
 it gives sulphanUio acid and (5:3:2:l)-tri-amido- 
 benzoic acid. 
 
 Sulpho-benzene-azo-aniline-sulphonic acid 
 [4:1] C5H,(HS03)— N2-CeH3(HS03)NH2 [1:?:4]. 
 Amido-azo-benzene disulphonic acid. Formed 
 by sulphonation of ^-amido-benzene-azo-ben- 
 zene-^-sulphonio acid (Griess, B. 15, 2187). 
 Violet glistening needles. Sol. hot water. _ Dyes 
 silk and wool yeUow. On reduction with tin and 
 HCl it gives sulphanilio acid and p-phenylene- 
 diamine-sulphonio acid. BaA" 7385 : orange 
 needles, sol. hot water. 
 
 m-Snlpho-benzene-azo - benzene-m - snlphonio 
 acid [3:1] S03H.C,H,— N.,— CeH^.SOaH [1:3]. 
 
 Formation. — 1. From nitro-benzene jre-sul- 
 phonic acid by treatment with sodium-amalgam 
 (Glaus a. Moser, B. 11, 762) or, better, with 
 powdered zinc and KOH (Mahrenholtz a. Gilbert, 
 A. 202, 332).— 2. One of the acids got by sul- 
 phonating benzene - azo - benzene at 150° 
 (Janovsky, M. 3, 244). — 3. From potassium m- 
 amido-benzene sulphonate and KMnO^. 
 
 Monoclinio prisms, si. sol. water and alcohol, 
 insol. ether. 
 
 Salts. — Na2A"3iaq: monoclinic crystals. — 
 (NHj2A"2aq. — CaA"4aq. — BaA"5aq. — 
 PbA"4laq. 
 
 Amide [290°]. Prisms, si. sol. water. 
 
 Ethyl ether BtjA". [100°]. 
 
 Chloride C.H4(S0201).N2.CeH4(S0201). 
 [166°]. Acts upon cold cone, aqueous Ba(SH), 
 thus: 0„H4(S02C1).N2.C3H,(S02C1) + 2BaH2S2= 
 N2(C8H4.S02.S)^a + BaCl2-i-2H2S forming thio- 
 sulpho-beuzene-azo-benzene-thio-sulphonioacid, 
 part of which then decomposes according to the 
 following equation: N2(CjH4.S02.S)2Ba + H2S = 
 H2N2(C„H4.S02.S)2Ba + S forming the barium 
 salt of hydrazobenzene di-thio-di-sulphonio acid 
 (Bauer, A. 229, 363). 
 
 m-Sulpho-benzene-azo - benzene -p - snlphonic 
 acid [4:1] 0.Hj(HS03)-N2-0.H,(HS03) [1:3]. 
 Formed, together with the p-p-aiaia, by heating 
 benzene-azo-benzene with HjSO, at 160° (Iiim- 
 pricht, B. 14, 1356; Bodatz, A. 215, 216), and 
 by the oxidation of a mixture of m- and p- 
 potassium amido - benzene sulphonate with 
 KMnOj. UncrystaUised syrup. On heating 
 with dilute HCl to 150° it gives p- and vi- 
 amido-benzeue-sulphonio acids (Limpricht, B. 
 15, 1155). 
 
 Salts. — K2A"2|aq: yellow needles, v. Bol. 
 water. — AgjA". 
 
 Chloride [125°]: red needles. 
 
 Amide [258°] : slender yellow needles. - 
 
 jjj-sulpho-benzene-azo-benzene - p- sidphonie 
 acid. [4:1] SOjH.C^H,— Nj-CjH^.SOjH [1:4]. 
 
 Formation. — 1. By oxidising amido-benzene- 
 ^-sulphonic acid with KMnO, (Laar, B. 14, 
 1928 ; Limpricht, B. 18, 1414).— 2. Among the 
 products of the sulphonation of benzene-azo- 
 benzene at 160° (Limpricht, B. 14, 1356 ; 15, 
 1155 ; Janovsky, M. 3, 242). 
 
 Properties. — Euby-red needles containing 2 
 or 3 aq (J.), or aq (L.). Melts at about 60° or, 
 when dry, at about 150°. HClAq at 150° giveg 
 sulphanilic acid and other products. 
 
 Salts : K2A"2^aq: si. sol. water.— NajA".— 
 (NHJjA".- Ag2A".-.CaA".— PbA"aq.— CuA"6aq. 
 
 Chloride [222°]. Bed needles. 
 
 Amide [above 300°]; orange plates or 
 needles, si. sol. hot water. 
 
 Si-sulpho-benzene - azo-benzene - disnlphonie 
 acid [5:3:1] CeH,(S03H)2.N2.CeHa(S03H)2 [1:3:5]. 
 From nitro-benzene-di-sulphonic acid, zinc dust, 
 and baryta (Eeiohe, A. 203, 64). Very deliques- 
 cent crystals. — K^A'' 3aq. — ^BajA'' 5aq. 
 
 Si-sulpho-benzeue-azo-benzene - di-sulphonie 
 acid [4:3:1] CeH,(S03H)2.N2.C,H3(S03H)2 [1:3:4]. 
 From the corresponding nitro-benzene di-sul- 
 phonio acid, zinc dust, and baryta- water (Eeiche, 
 A. 203, 70). Salts.-KjA" 3aq.— BajA" 4aq. 
 
 Chloride [58°]; radiating needles. 
 
 Amide [222°] ; white needles. 
 
 j>-Sulpho-benzene-azo-o-cresol. 
 [4:1] C3H,(S03H)-N,-C.H3(CH3)(0H) [1:8:4]. 
 
SOS 
 
 AZO- COMPOUNDS. 
 
 Formed by the action of diazo-benzene-^-aul- 
 phonio acid (by diazotising sulpbanilio acid) on 
 an alkaline solution of o-oresol (Nolting a. Eohn, 
 B. 17, 364). Small reddish-brown needles. Sol. 
 hot water. V. si. sol. alcohol. On redaction 
 with tin and HCl it gives sulphanilic acid and 
 amido-o-cresol C,H3(CH3)(NH2)(OH) [1:5:2]. 
 
 Salts. — A'Na2aq: yellow soluble plates. 
 A'jBa 3aq : yeUow tables, si. sol. hot water. 
 
 jp-Sulpho-benzene-azo-m-cresol 
 [4:1] C,H,(SO,H)-N,-C„H3(CH3)(OH) [1:2:4]. 
 Formed by the action of diazobenzene-^-sul- 
 phonio acid on an alkaline solution of m-cresol 
 (Nolting a. Kohn, B. 17, 366). Small reddish- 
 brown crystals with violet reflex. V. sol. 
 water and hot alcohol. Orange-yellow dye stuff. 
 On reduction it gives sulphanilic acid and 
 amido-m-cresol CsHs(CH3)(NH2)(OH) [1:2:5]. 
 
 Salts : A'Na : small yellow soluble needles. 
 A'jBa : yellow plates, v. si. sol. cold water. 
 
 Sulpho-benzene-azo-ji-cresol 
 [4:1] C,H,(S03H)-N,-CeH3(CH3)(OH) [1:6:2]. 
 
 
 or I ^CeHjCHj. 
 
 CeH,(SO,H)— N,h/ 
 
 Formation. — 1. By the action of j>-diazo- 
 benzene-sulphonio acid on an alkaline solution 
 of ^-cresol. — 2. By sulphonation of benzene- 
 azo-^-oresol (Nolting a. Kohn, B. 17, 355). 
 Tellowish-brown plates with violet reflex. V. 
 sol. water and hot alcohol. Dyes silk and wool 
 orange-yellow. On reduction with tin and HCl 
 it yields sulphanilic acid and amido-p-oresol 
 0,H3(CH3)(NH,)(OH) [1:3:4]. 
 
 Salts: A'Na: soluble yellow plates. 
 A'K 3aq.— A'^Mg 5aq. — A'^Ba : yellowish-brown 
 tables, si. sol. hot water. 
 
 ^-Sulpho-benzene-azo-i((-oumenol 
 [4:1] C.H^(HS03)— N^— C,H(CH3)30H [1:3:5:6:2]. 
 Formed by combining diazo-benzene-j)-sulphouic 
 acid with ilz-oumenol [70']. — KA' 2aq : orange 
 needles (Liebermann a. Kostauecki, B. 17, 887). 
 
 Snlpho -benzene - azo - ethylamiue. Potas- 
 sium salt. C„H,(SOsK)— N^— CH(NH2).CH3. 
 From the potassium salt of the correspond- 
 ing nitro-oompound by reducing with ammonium 
 sulphide (Kappeler, B. 12, 2285). Silvery plates 
 (from water) ; si. sol. water, insol. NajCOjAq. 
 NaOHAq dissolves it with crimson colour. 
 
 m-Sulpho-beazene-azo-(a)-napbthol 
 [3:1] 0,H,(HS03)-N,-C,„He.0H [1:4], Pre- 
 pared by the action of an alkaline solution of 
 («)-naphthol on m-diazobenzene sulphonic acid 
 (Griess, B. 11, 2197). Small greenish leaflets. 
 SI. sol. cold water and cold alcohol. 
 
 m-Sttlpbo-benzene-azo- (;3) -naphthol 
 [3:1] C„H,(HS03)-N,-C„H.(0H) [1:2] or 
 0\ 
 
 I >C,|,H.. Prepared by the 
 C.H,(HS03)-Hn/ 
 
 action of an alkaline solution of (/3)-naphthol 
 on j»-diazobenzene sulphonic acid (Griesa, B. 
 11, 2197). Slender red needles. V. sol. alcohol 
 and water. BaA'^ 5aq : yellowish-red scales. 
 SI. sol. water. 
 
 2)-Sulpbo-benzene-azo-(a)-naphthol 
 [4:1] 0,H,(S03H)— N — C,„H„(OH) [1:4]. Tropm- 
 o'line 000, No. 1. Prom^-diazobenzene sulphonic 
 acid and an alkaline solution of (a) -naphthol 
 (Liebermann a. Jaoobsen, A, 211, 61). Orange- 
 
 dye. Its absorption spectrum ia given bj 
 Hartley (0. J. 51, 184). 
 
 p-Sulpho-ben.zene-azo-(;8)-naplithol 
 [4:1] 0„H,(S03H)-N,-C,.H,(0H) [1:2] or 
 
 I yGtfipTropcBolimeOOONo.'i 
 C5Hj(S03H)— HN/ 
 
 From j3-diazo-benzene sulphonic acid and {$-) 
 naphthol (W. v. MUler, B. 13, 268 ; Hofmann, 
 B. 10, 1378 ; Griess, B. 11, 2198). The absorp- 
 tion spectrum has been examined by Hartley 
 (O. /. 51, 185). 
 
 2)-Sulpho-benzene-azo-(/8)-naphthol sulphonic 
 acid [4:1] C„H,(HSO3)-N2-0,„H5(HSO3)0H. 
 Prepared by the action of ^-diazobenzena 
 sulphonic acid on an alkaline solution of (6)- 
 naphthol sulphonic acid (Griess, B. 11, 2198; 
 Stebbins, A. G. J. 2, 236). Yellowish red crys- 
 tals. Excessively soluble in water. BaA" 7|aq : 
 difficultly soluble orange microscopic needles. 
 
 ^-Sulpbo-benzene-azo-(a)-naphthylainine 
 [4:1] C,Hj(HS03)— Nj— C,„H,.NH2 [1:4]. From 
 diazotised sulphanilic acidand(a)-naphthylamine 
 (Griess, B. 12, 427). Brownish-violet needles, 
 V. si. sol. boiling water. Its acid solutions have 
 a deep magenta colour (Griess's test for nitrous 
 acid) ; its alkaline solutions are orange.. On 
 reduction with tin and HCl it gives sulphanilic 
 acid and (l,4)-naphthylene-diamine. 
 
 Salts: KA'Saq: brownish-yellow plates, 
 sol. hot water. — BaA'j 3aq : sparingly soluble 
 brown needles (Griess, B. 15, 2190). 
 
 p-SaIpho-benzene-azo-(/3)-naphthylaiuine 
 [4:1] C,H,(HS03)— N,-C„H,.NH, [1:2] or 
 HNv 
 
 I >C,oHj. Formed by tha 
 C„H^(HS03)— HN/ 
 action of ^-diazo-benzeue-sulphonic acid on 
 (;8)-naphthylamine hydrochloride (Griess, B. 
 15, 2191). Small yellowish-red needles. SI. soL 
 water, v. sol. hot alcohol, insol. ether. On 
 reduction with tin and HCl it gives sulphanilio 
 acid and (1, 2)-naphthylene-diamine. — Kk'l^aq: 
 orange plates, sol. hot water. 
 
 Sttlpho-benzene-azo-(o)-naphthylamine sulph- 
 onic acid C5H,(S03H).N2.C,„H,(S03H).NH2 [1:4:2]. 
 Formed by the action of ^-diazo-benzene-sulpho- 
 nic acid on (o)-uaphthylamine-sulphouic acid 
 (Griess, B. 15, 2194). Needles or plates. Sol. 
 water and alcohol, insol. ether, dyes silk and 
 wool orange.— BaA" T^aq : red needles or plates, 
 sol. hot water. — BaH2A"2 8aq : sparingly soluble 
 violet-brown needles. 
 
 ^-Sulpho -benzene - azo-(/3)-naphthyl - phenyl - 
 amine CsH^(S03H)— N^— C,„H8.NHC^, or 
 C,H,(S03H).HN2.C,.H, 
 
 \y' . Prepared by slowly 
 N.CA 
 adding dryjp-diazobenzene-sulphonio acid (18 g.) 
 to a solution of phenyl-(;8)-naphthylamine (22 g.) 
 in glacial acetic acid (100 c.c.) at c. 50°, followed 
 by finely powdered dry KjCOj (7 g.) ; the com- 
 pound separates out in glistening red needles of 
 the potassium salt. It is a splendid scarlet 
 dyestuff, but is very fugitive in light. The 
 potassium salt is easily soluble in water ; when 
 cold its solution solidifies to a transparent red 
 jelly. HOI precipitates the free acid. By SnOl, 
 it is reduced to phenyl-o-naphthylene-diamine 
 and sulphanilio acid. By boiling with dilute 
 
AZO- COMPOUNDS. 
 
 393 
 
 mineral acids it is converted into naphthophea- 
 azine and sulphanilia acid : 
 
 eH,(S03H).N,.0,„H,.NHC.H, = 
 
 0,oH,<^>G,H, + 0,H^(NH,)S03H. The Ba and 
 
 Ca salts are orystalline insoluble pps. (Witt, B. 
 20, 572). 
 
 p-Snlpho-'benzen.e-azo-nitro-isoliatane 
 CjHj(HS03)— Nj- 04Hs(N02). Prepared by the 
 action of ^-diazobenzene-sulphonio acid on an 
 alkaline solution of nitro-iso-butane. — KA' aq : 
 orange-yellow needles. Soluble in alkalis to a 
 red solution. Dyes silk orange (Kappeler, B. 
 12, 2288). 
 
 ^-Salpho-benzene-azo-nitro-ethane 
 C,H,(HS03)— Nj— C.,Hj(N02). Prepared by the 
 action of ^'-diazobenzene-sulphonio acid on an 
 alkaline solution of nitro-ethane. A'K : golden 
 yellow leaflets, sparingly soluble in cold water, 
 soluble in alkalis to a blood-red solution 
 (Kappeler, B. 12, 2286). 
 
 p-Snlpho-beuzene-azo-nitro-methaue 
 OjH,(HS03)— Nj— CH2(N02). Prepared by the 
 action of ^-diazobenzeue-sulphonic acid on an 
 alkaHne solution of nitro-methane. — KA' Saq : 
 orange needles. Dyes silk orange (Kappeler, 
 B. 12, 2286). 
 
 p-Salpho-benzene-azo-nltro-propane 
 C,H,(HS03)— Nj— C(NOJ(CH3)2. Prepared by 
 the action of ^-diazobenzene-sulphonic acid 
 on an alkaline solution of nitro-isopropane. 
 A'K: light-yellow leaflets. Has no dyeing 
 power. Insoluble in alkalis (Kappeler, B. 12, 
 2287). 
 
 p-Sulphobenzene-azo-orcin 
 [4:1] C„H.(HS03)— N2-C,H,(GH3)(OH),. Small 
 yellowish-red needles. Difficultly soluble in 
 water. Prepared by the action of an alkaline 
 solution of orcin upon j)-diazobenzene-sulphonic 
 acid.— KA'2aq (Griess, B. 11, 2196). 
 
 jj-Sulpho-benzene-azo-o-oxy-benzoic acid 
 [4:1] C,H,(S03H)-N,-C^3(qH)(CO,,H) [1:4:5]. 
 I'rom diazotised sulphanilio acid and an alkaline 
 solution of salicylic acid. Golden needles; si. 
 sol. hot water (Griess, B. 11, 2196 ; Stebbins, 
 a ID, 716).— BaH^A",. 
 
 ^-Sulpho-benzene-azo-oxy-quinoline 
 
 (JS.l) 
 
 (B. 4) /CHiCH 
 
 
 Formed 
 
 0sH,(HS03)-Nj-0sH2(0H) 
 
 ^N : OH 
 
 by the combination of ^-diazo-benzene-sulphonio 
 acid with (B. 4)-oxy-quinoline (Fischer a. 
 Eenouf,B. 17, 1642). Small needles. Orange dye. 
 
 p-Sulpho-benzene-azo-phenol disulphonic acid 
 C,H,(S03H)-N,-C3H,(S03H),(OH). _ Formed 
 by heating azoxybenzene with fuming HjSOj. 
 Small soluble flat red needles with green lustre. 
 On reduction it gives ^-amido-benzene-sulphonio 
 acid and amido-phenol-di-sulphonio acid. 
 
 Salt s.— A"'K3 3aq : yeUow microscopic 
 jieedles, easily soluble. Bromine-water gives tri- 
 bromo -phenol. — A'''Ag : unstable red pp. — 
 A"'jBa3 7aq: brown orystalline pp.— A"'2Pb3 l^aq. 
 
 Chloride: red orystalline powder [220°]. 
 
 Amide: yellow plates [260°], sparingly 
 soluble in alcohol (Limpricht, B. 15, 1297; 
 Wilsing, A. 215, 234), 
 
 p-Sulpho-benzene-azo-xylenol 
 [4:1] C.H,(SO.,H)-N— C^H^Me^.OH [1:3:5:2]. 
 Formed by combining diazobenzene-^-sulphonio 
 aoid with w-xylenol C3H3Me3(OH) [1:3:4] 
 
 (Grevingk, B. 19, 148,. Dyes wool and silk a 
 brownish yellow from an acid bath. On reduc- 
 tion it yields sulphanilic aoid and o-amido-»i- 
 xylenol C„H2Me2(NHjj)(OH) [5:3:1:2]. 
 
 Sulpho ■ carboxy - benzene -azo -(;3)-nap}ithol- 
 (a)-di-siilphanic acid 
 
 C„H3(C0^) (S03H)-N,-C,„H,(0H) (SO3H),. 
 Prepared by the action of m-diazo-sulpho- 
 benzoio aoid on an alkaline solution of (/3)- 
 naphthol-(a)-di-sulphonic aoid (Griess, B. 
 14, 2038). Orange needles or prisms. V. sol. 
 water and alcohol, insol. ether. Salts. — 
 A''2H2Ba3 3aq : slightly soluble yellow needles. 
 A'''Ba2 5aq : nearly insoluble red crystalline pp. 
 
 Sulpho-carboxy-benzene - azo - oxy - naphthoic 
 acid 0,H3(S03H) {CO.,H)— N^— G,„H5(0H) (CO^H). 
 Prepared by the action of diazosulphobenzoio 
 acid on an alkaline solution of (a)-oxy-naphthoic 
 acid (Griess, B. 11, 2199). Brown microscopic 
 needles or leaflets. SI. sol. water. 
 
 Sulpho-naphthalene-azo-(;S)-naphtliol- disul- 
 phonic acid C,„H„(S03H).N2.C,„H,(OH)(S03H)j. 
 Crimson dye (Stebbins, A. C. J. 2, 446). 
 
 Sulpho-to'.uene-azo-toluene-sulphonio acid 
 [2:4:1] C,H3Me(S03H).N.,.C„H3Me(SO,H) [1:2:4]. 
 From potassium o-toluidine sulphonate (of 
 Gerver) and KMuOj (Kornatzki, A. 221, 183). 
 Small red prisms, grouped in tables, very soluble in 
 water and in alcohol. E2A" : red plates grouped 
 in clumps. — BaA"aq. — CaA"3aq. — PbA" aq. 
 
 Chloride. [218°]. Bed needles (from ObH„). 
 
 Amide. [250']. Tables (from aqueous NH3). 
 
 Sulpho-tolusne-azo-toluene-sulphonic acid 
 [2:5:1] C3H3Me(S03H).N2.C,H3Me(S03H) [1:2:5]. 
 
 Azo-tohoene-disulphonic acid. From o-nitro- 
 toluene sulphonic acid, zinc dust, and KOHAq 
 (Noale, A. 203, 74) ; or from o-toluidine sul- 
 phonic acid of Hayduck and KMnO, (Kornatzki, 
 A. 221, 181). Salt s.— BaA" 4aq.— K^A" 2iaq.— 
 CaA"5aq.— PbA"4aq. 
 
 Chloride. [220°]. Bed prisms. 
 
 Amide. [800°]. Bed powder. 
 
 Sulpho-toluene - azo - toluene - sulphonic acid 
 [4:6:1] 0sH3Me(SO3H).N2.C„H3Me(SO3H) [1:4:6]. 
 From potassium jj-toluidine sulphonate and 
 KMnOj (Kornatzki, A. 221, 182). 
 
 Salt.— BaA" 3aq. 
 
 Sulpho-toluene-azo-toluene-sulphonic acid 
 [4:5:1] C„H3Me(S03H).N3.CeH3Me(S03H) [1:4:5]. 
 From _p-nitro-toluene o-sulphonic aoid, KOHAq, 
 and zinc dust (Neale, A. 203, 80) ; or from 
 potassio i)-toluidine sulphonate and EMnO,. 
 
 KjA" 3aq.— CaA" 3aq. —BaA" aq.— PbA" 2aq. 
 
 Chloride. [194°]. Bed crystals. 
 
 Amide. [270°]. Yellow. 
 
 Exo - Sulpho - toluene - azo - toluene - exo - sul - 
 phonic acid S03H.CH2.C,H,.N3.C,H,.GH2.S03H. 
 
 Formation.— 1. From C,H,(N02).CH3.S03H 
 by boiling with zinc dust and KOH or Bai(0H)2. — 
 2. From C5H,(NH3).CH,.S03K and KMnO, (Mohr, 
 4.221,223). Salts.— K2A"^aq: orange plates.— 
 BaA" l^aq'.- Ag^A" aq. 
 
 Chloride. [149°]. , 
 
 Sulpho-xylene-azo-di-bromo-naphthol 
 C3H2Me2(S03H)— N3— C,„H,Br3(0H). From p. 
 diazo-xylene sulphonic acid and di-bromo-(a)- 
 naphthol (Stebbins, jun., A. C. J. 2, 446). Sol. 
 hot water, forming a scarlet solution. 
 
 Sulpho.xylene-azo-(a)-naphthol 
 03H2Mei,(S03H)— Nj— C,oH„OH. From ^j-diazo- 
 
S94 
 
 AZO- COMPOUNDS. 
 
 xylene sulphonio acid and (a)-naphthol (Stebbina, 
 jun,, A. C. J. 2, 446). Brown dye ; sol. water. 
 
 Sulpho-m-xylene-azo-(iS)-naphthol 
 [1:3:6:4] C,H,Me,{S03H)-N,-C,„H,(0H). 
 Formed by the action of diazo-OT-xylene sulpho- 
 nio acid (from m-xylidine sulphonio acid) upon 
 an alkaline solution of {j3)-naphthol (Nolting a. 
 Kohn, B. 19, 139). Metallio green crystals. SI. 
 sol. cold water. Dyes wool and silk from an 
 acid bath a yellowish shade of scarlet. 
 
 Salts. — A'Na" : red soluble plates. — ^A'^Ba: 
 si. sol. hot water. 
 
 Sulpho-xyleiie-azo-(;8)-phenant]irol. From p- 
 diazo-xylene sulphonio acid and (;8)-pheuanthrol 
 (Stebbius, A. G. J. 2, 446). Eeddish-brown dye. 
 
 Sulpho-xylene-azo-resorcin v. Di-oxt-ben- 
 
 ZENE-AZO-XYLENE SULPHONIO ACID. 
 
 Snlpho-xylene-azo-zylene sulphonio acid 
 
 [2:4:5:1] CsH^Me^CSOaH)— N^— C,H,Me2(S03H) 
 [1:2:4:5]. Formed by oxidising (1, 3, 6, 4)- 
 xylidine sulphonio acid with dilute KMnO^ 
 (Jaoobsen a. Ledderboge, B. 16, 194) ; or by 
 reducing (6, 1, 3, 4)-nitro-xylene sulphonio acid 
 with zinc-dust and NaOH (Limpricht, B. 18, 
 2191). Orange plates; v. sol. water; si. sol. acids. 
 
 Salts.— K2A"4aq.—KEIA."4aq. 
 
 Chloride. [86°] ; red crystals. 
 
 Amide. [174°]. 
 
 m-Thio-gulpho-benzene-azo-benzene - sulpM- 
 nic acid [3:1] (HS.SOJ0.H^.N2.C8H,(SO2H) [1:3]. 
 [below 100°]. A solution of the barium thio- 
 Bulpho-benzene-azo- (or hydrazo-) benzene-thio- 
 Bulphonate gives, on evaporation, S and the salt 
 of the present acid. This salt forms red crusts 
 which are sparingly soluble in water, but are 
 converted by boiling Na2C03 into the soluble 
 Na salt, whence HOI separates the free acid as a 
 bulky flocculent pp. hardly soluble in water, but 
 resinified by boiling with it. It is soluble in 
 alcohol. Oxidised by KMnO, to N2(CsH4S03K)2. 
 
 Salts.— BaA" (dried at 140°).— K^A".- 
 NajA" icaa.— PbA" (dried at 130°). 
 
 Isomer. — Ammonia converts the acid into a 
 brown amorphous base, isomeric with it (Lim- 
 pricht, B. 18, 1472 ; Bauer, A. 229, 360). 
 
 m-Thio-suIpho-benzene -azo-beuzene -m-thio- 
 snlphonic acid 
 
 [3:1] HS.S02.CeHj.N2.CeH,.S02.SH [1:3]. 
 [91°-93°]. From its salts by adding glacial 
 acetic acid. A voluminous yellow pp. insol. 
 water or alcohol, and resinified whei. boiled 
 with them (Limpricht, B. 18, 1471 ; Bauer, A. 
 229, 358). 
 
 Barium salt. — ^BaA"5aq. One of the pro- 
 ducts of the action of baric sulphydrate upon 
 the chloride of sulpho-benzene-azo-benzene- 
 sulphonic acid {q. v.). V. sol. hot water, si. sol. 
 cold water, nearly insoluble in alcohol. Yellow 
 ammonic sulphide slowly converts it into the 
 corresponding hydrazo- compound. 
 
 Ka2A"a;aq. Its solutions give amorphous 
 pps. with salts of Cu, Pb, Ag and Fe'". 
 
 ^-Ihio-Bulpho -benzene-azo- benzene - thiosul- 
 phonic acid 
 
 [4:1] C,H,(S02SH)-N2— C,H,(S02SH) [1:4]. 
 Yellow amorphous solid. SI. sol. water and 
 alcohol. Formed by the action of a saturated 
 aqueous solution of Ba(SH)2 upon the chloride 
 of sulpho-benzene-azo-benzene-sulphonic acid. 
 Na2A"a;aq: very soluble yeUow warty crystals. 
 
 — BaA" : yellow warty crystals, sol. hot watee 
 (Limpricht, B. 18, 1474 ; Bauer, ^. 229, 368). 
 
 «-ToIuene-azo-aceto-acetic acid 
 [4:1] C,H,(0H3)-N2- CH(CO.CH3).C02H. [188°]. 
 
 Ethyl ether A'Bt: [70°]; yellow needles. 
 Formed by the action of ^-diazo-toluene chlo- 
 ride on an alcoholic solution of sodio-acetacetio 
 ether (Ziiblin, B. 11, 1419 ; Kiohter a. MUnzer, 
 B. 17, 1929). 
 
 »-Ioluene-azo-acetone 
 [4:1] C,H,(CH3)-N2-CH2.CO.CH3. [115»]. 
 
 Formation. — 1. By heating ^-toluene-azo- 
 aceto-acetio ether with a dilute alcoholic solution 
 of NaOH. — 2. By heating 2>-toluene-azo-aceto- 
 acetic acid above its melting-point, COj being 
 evolved (Eichter a. Munzer, B. 17, 1929). Yel- 
 low needles. SI. sol. water. 
 
 Toluene-azo-bromo-toluene 
 CjHjMe — Nj — CeHjBrMe. Bromo-azo-ioluene. 
 [136°] (P.); [138-5°] (J. a. E.). Formed by 
 brominating p-toluene-^-azo-toluene (Petrieff, 
 B. 6, 557 ; Janovsky a. Erb, B. 20, 363). Golden 
 plates or needles. Keduces to a hydrazo- com- 
 pound [119°]. 
 
 Tolnene-azo-chloro-tolaene 
 [4:1] CeH,Me.N2.C„H3MeCl [1:5:2]. [97°]. Formed 
 by the action of cuprous chloride upon diazotised 
 2)-toluene-^-azo-toluidine (from ^-toluidine) ; 
 yield, 20 p.c. of theoretical. Brown plates. V. sol. 
 alcohol, ether, and benzene (Mentha, B.19, 8026). 
 
 p-Toluene-azo-^i-cresol 
 [4:1] C,H,(0H3)-N2-C3H3(CH3)(0H) [1:5:2] 
 [113°]. Obtained by the action of ^-diazo- 
 toluene chloride on an alkaline solution of p- 
 cresol. It is also formed by diazotising ^-toluene- 
 azo-i)-toluidineO„H4(CH3)— Nj— CsH3(CH3)(NH2) 
 and boiling the product with water (Nolting a. 
 Kohn, B. 17, 354). Eeddish needles or yellow 
 tables. V. sol. ether, benzene, and hot alcohol. 
 
 Acetyl derivative [91°], yellow needles. 
 
 Benzoyl derivative [95°], small yeUow 
 needles. 
 
 o-ToIuene-azo-etIiyl-(;3)-naphthyl-amine 
 [2:1] 03H,(CH3)-N2-0,.H„(NHEt) [1:2]. [132°]. 
 Formed by heating ethyl-(/3)-naphthyl-nitros- 
 amine with an acetic acid solution of o-toluidina 
 (Henriques, B. 17, 2670). 
 
 ^-ToIuene-azo-ethyl-(/3)-napIithyl-ainine 
 [4:1] C,H,(GH3).N2.C,„H,(NHBt) [1:2]. [113°]. 
 Formed by heating ethyl-(j3)-naphthyl-nitros- 
 amine with an acetic acid solution of ^ -toluidine 
 (Henriques, B. 17, 2670). 
 
 o-Tolnene-p-azo-(a) -naphthol 
 [2:1] C3H,Me.Ns.C,„H3(0H) [1:4]. {a).NapMho- 
 qmnone-o-tolyl-hydraeide. [146°]. 
 
 Formation. — 1. From o-diazo-toluene and 
 (o)-naphthol. — 2. From (a)-naphthoquinone and 
 o-tolyl-hydrazine. 
 
 Properties. — Bed glistening needles. V. sol. 
 alcohol, acetic acid, and benzene, less readily in 
 benzoUne. HNO3 converts it into di-mtro-(a). 
 naphthol. With HCl and HBr it gives dark 
 blue metallic-glistening salts. Dissolves in di- 
 lute NaOH. 
 
 Methyl e < ^ler 0„H,3N2(OMe) [93°] ; reddish, 
 brown glistening needles ; easily soluble in ordi- 
 nary solvents. 
 
 Ethyl ether C„H,,N2(0Et) [94°]; red 
 plates or dark thick needles (Zincke a. Bathgen, 
 B. 19, 2488). 
 
AZO- COMPOUNDS. 
 
 396 
 
 j>-Tolueiie-p-azo-(a)-naplitlioI 
 
 [4:1] OeH,Me.Nj.C,„H5(OH) [li4]. [a).Naphtho- 
 quinone-p-tolyl-hydrazide. [208°]. 
 
 Formation. — 1. From ^-diazo-toluene and 
 (o)-naplithol. — 2. From (a)-naphthoqumone and 
 p-tolyl-hydrazine. 
 
 Properties. — Metallic - glistening dark -red 
 apangles. Y. sol. acetone, aniline, and liot 
 nitrobenzene, si. sol. alcohol, acetic acid, and 
 benzene. Dissolves in dilute NaOH. HNOj 
 converts it into di-nitro-(o)-naphthol. Not at- 
 tacked by bromine in acetic acid solution. With 
 mineral acids it forms salts which separate in 
 bluish-green metallic-glistening plates. By 
 heating with baryta-water it is rendered in- 
 soluble in alkaUs.— B'HCl.— B'HBr. 
 
 Methyl ether 0„H,3N2(0Me) [104°]. 
 
 Ethyl ether C„Hi3Nj(0Et) [127°], large 
 red crystals or red needles. 
 
 Acetyl derivative 0„H,sNj(OAc) [102°], 
 fine yellowish needles (from benzoUne) (Zincke 
 a. Bathgen, B. 19, 2486). 
 
 o-Toluene-o-azo-(a)-naphthol 
 [2:1] C,H,Me.N,.C,.H5(0H) [2:1] or 
 O. 
 
 I >C,„H.. {fi)-Naphtho-quinone-o- 
 CsH^Me-HN,/ 
 
 tolyl-hydrazide. [156°]. Formed by the action 
 of o-tolyl-hydrazine upon (i3)-naphthoquinone. 
 Glistening red plates. Easily soluble in ordinary 
 solvents. HNO3 converts it into di-nitro-(o)- 
 naphthol. Bromine gives a di-bromo-derivative 
 [254°] (Zincke a. Eathgen, B. 19, 2492). 
 
 ^-Tolnene-o-azo-(a)-naplithal 
 [4:1] OeH,Me.N,.0,„H,(OH) [2:1] or 
 
 C,HiMe.N. H-^ \ Ci,H,. ((i)-Na^htho-gumone- 
 p-tolyl-hydraiide. [145°]. Formed by the 
 action of ^-tolyl-hydrazine upon (j3) -naphtho- 
 quinone. Bed slender glistening needles. V. 
 sol. alcohol, benzene, and acetic acid, sparingly 
 in benzoline. By SnCl^ it is reduced to (18). 
 amido-(o)-naphthol and ^-toluidine. HNO3 con- 
 verts it into di-nitro-(a)-naphthol. Bromine 
 gives a di-bromo-derivative [236°] (Zincke a. 
 Bathgen, B. 19, 2491]. 
 
 p-Toliiene-o-azo-(;8)-naplithol 
 [4:1] C,H,Me.N,.0,„H3(0H) [1:2] or 
 
 CjH,Me.NjH/-Ac,oH5. [135°]. Formed by 
 combination of p-diazo-toluene with (i8)-naph- 
 thol. Thick red needles or tables. V. sol. alcohol, 
 benzene, acetic acid, and acetone. Insoluble in 
 cold dilute NaOH. With acids it forms unstable 
 salts. Bromine in acetic acid converts it into a 
 di-bromo-derivative [190°]. HNO3 gives di-nitro- 
 (/3)-naphthol (Zincke a. Eathgen, B. 19, 2490). 
 
 o-Ioluene-o-azo- (fl) -naphthol 
 [2:1] OeH,Me.N,.C,„H,(OH) [1:2] or 
 
 C,H,Me.N2H/l-\c,„Hs. [131°]. Formed by 
 combination of o-diazo-toluene with(/3)-naphthol. 
 Fine red needles or plates. Insol. cold dilute 
 NaOH. With acids it forms unstable salts. 
 HNO3 converts it into di-nitro-(;3)-naphthol. Bro- 
 mine forms a mono-bromo-derivative [167°]. 
 (Zincke a. Bathgen, B. 19, 2491; Fischer, B. 20, 
 1680). 
 
 ^-Talnene-azo-(;8)-naphthol disalphonlc acid 
 C^H^Me— Nj— C,„H,(0H)(S03H)j. From sodium- 
 (/3)-naphthol disulphonate and f-diazo-toluene 
 
 nitrate (Stebbins, A. C. J. 2. 236 ; C. N. 42, 44). 
 Eed leaflets, v. sol. water. Scarlet dye. The 
 corresponding 0- compound dyes yellower, the 
 m- compound, redder. 
 
 p-Toluene-azo-(a)-naphthyIamine 
 [4:1] C,H.,(CH3)— N,— 0,3H3.NH, [1:4]. [145°]. 
 Prepared by the action of j3-diazo-toluene sul- 
 phate on (a)-naphthylamine (Weselsky a. Bene- 
 dikt, B. 12, 229). Eed leaflets ; insol. water.— 
 B'jH^SO, Baq : steel-blue needles. 
 
 o-Toluene-azo-nitro-ethane 
 [2:1] CeH^Me— Nj-CH(N02).0H3. [88°]. From 
 o-diazo-toluene nitrate and potassium nitro- 
 ethane (Barbieri, B. 9, 387). Unstable orange 
 needles. — NaA' : golden spangles. 
 
 ^-Toluene-azo-nitro-etliane. [133°]. Prepared 
 like the preceding (B.). Orange prisms with 
 steel-blue lustre. Its alkaUne solutions are 
 deep red. 
 
 Tolueue-azo-nitro-toluene 
 C5H,Me — N2 — CjH3(N02)Me. Nitro-azo-toluene 
 [114°]. Among the products of the nitration 
 of toluene-azo-toluene dissolved in glacial acetic 
 acid (Janowsky a. Erb, B. 20, 363). Orange 
 monoclinic needles (from 90 p.c. alcohol). 
 
 Toluene-azo-nitro-tolnene.[76°] .From toluene- 
 azo-toluene and HNO3 (S.G. 1-4) (Petrieff, B. 6, 
 557). 
 
 o-Tolnene-azo-orcin 
 CsH^Me— Nj— C,H3Me(0H)2 [203°— 206°]. From 
 o-diazo-toluene and orcin (Scichilone, Q. 12, 
 223). Eed-brown crystals. 
 
 ^-Xoluene-azo-thymol sulphonic acid 
 C,H,(CH3)-N,-C„H(CH3)(C3H,)(HS03)0H. 
 Prepared by the action of ^-diazo-toluene- 
 chloride on sodium thymol-sulphonate. — A'Na: 
 slender yellow needles; sol. alcohol and hot 
 water, almost insoluble in cold water (Stebbins, 
 B. 14, 2795). 
 
 o-Toluene-o-azo-toluene 
 [2:1] Me.CsH,— Nj— CsHj-Me [1:2]. o-Azo-tolume 
 [55°]. 
 
 Preparation. — 1. By distilling o-nitro-toluene 
 with alcoholic potash; or by reducing it with 
 zinc-dust and alcoholic NaOH (Schultz, jB. 17, 
 497). Carmot be prepared by reducing o-nitro- 
 toluene in alcoholic solution with sodium-amal- 
 gam (Perkin). — 2. From o-toluidine and KMnOi 
 (Hoogewerff a. van Dorp, B. 11, 1203). 
 
 Properties. — Dark red trimetrio prisms; 
 a:6:c = 2-225:l:l-708. Volatile with steam. Gives 
 a mono-nitro- derivative [0. 67°], a di-nitro- 
 derivative, [142°], and a tri-nitro- derivative that 
 decomposes before melting (PetrieS). 
 
 m-Toluene-m-azo-toluene 
 [3:1] McCsHj— Nj— CjH^Me [1:3]. m-Azo-toluerM 
 [51°] (G.); [55°] (B.). From m-nitro-toluene 
 by boiling with alcoholic KOH (Goldschmidt, 
 JB. 11, 1624), or by treatment with zinc-dust and 
 alcoholic KOH (Barsilowsky, B. 10, 2097; A. 
 207, 114). Orange-red trimetric tables, a;6;c = 
 •85:1: -54. V. sol. alcohol. 
 
 D-Tolnene-p-azo-tolnene. p-Azo-toluene 
 [4:1] Me.C„H,— Nj— CsHjMe [1:4]. [144°]. 
 
 Formation. — From ^-toluidine and CrO, in 
 glacial acetic acid ; or by treating a solution of 
 ^-toluidine in chloroform with bleaching-powder 
 (E. Schmitt, J. pr. [2] 18, 198). Or by oxidising 
 p-toluidine with H^O, (Leeds, B. 14, 1382), 01 
 benzoyl peroxide. Cannot be prepared by dis- 
 tilling ^-nitro-toluene with alcoholic potash 
 
306 
 
 AZO- COMPOUNDS. 
 
 (Periin), for by such treatment a red condensa- 
 tion product is obtained which on further reduc- 
 tion gives di-amiJo-di-phenyl-ethylene [227°]. 
 (Bender a. Schultz, B. 19, 3237). 
 
 Preparation.^p-Wiiro-iolnene (20g.) in alco- 
 hol is treated with sodium-amalgam added gradu- 
 ally, the mixture being frequently cooled. The 
 brown solid that separates is crystallised from 
 glacial acetic acid (Perkin, G. J. 37, 554, cf. 
 Jaworsky, J. pr. 94, 283 ; Werigo, Z. 1864, 640 ; 
 Alexejeff, Z. 1866, 269; Melms, B. 3, 649; 
 Schultz, B. 17, 472). 
 
 Properties. — Eed trimetric needles. V. sol. 
 alcohol and ligroin, si. sol. alcohol. Slowly re- 
 duced to hydrazo-toluene by ammonium sul- 
 phide. In alcoholic solution it is reduced by 
 SnClj and HCl to tolidine [91°]. (S.). Nitric 
 acid forms a mono-nitro- derivative, [76°], a 
 dinitro- derivative [110°], and a tri-nitro- deriva- 
 tive [201°] (Petriefi). 
 
 o-Toluene-m-azo-toluene 
 [2:1] CeH^(CH3)-N2— C5H,(CH,) [1:3]. Obtained 
 by diazotising o-toluene-azo-o-toluidine (from o- 
 toluidine) and treating the diazo- compound with 
 alcohol (Schultz, B. 17, 470). Eed oil. Volatile 
 with steam. V. sol. alcohol and ether. By 
 SnClj and HCl in alcoholic solution it is con- 
 verted into an uusymmetrioal tolidine. 
 
 m-Tolueae-p-azo-toluene 
 [4:1] C.H,(CH3)-N,-C,H,(CH,) [1:3]. [58°]. 
 
 Formation. — 1. By the action of zinc-dust 
 and alcohol upon o-diazo-toluene-azo-toluene. — 
 2. By the action of Ag,0 and alcohol upon the 
 compound C^H^N, the reduction-product of 
 o-diazo-toluene-azo-toluene (Zincke a. Lawson, 
 B. 19, 1458). Brownish-red plates. V. sol. alco- 
 hol, ether and benzene. 
 
 o-Toluene-azo-o-toluidine 
 [2:1] C,H,(CH3)-N,-C,H3(CH3)(NH,) [1:3:4] 
 [100°]. Formed by passing nitrous acid gas 
 into o-toluidine (Nietzki, B. 10, 662). Tri- 
 metric crystals, o:6:c = l-0416:l:l-3268. Heated 
 with aniline hydrochloride and alcohol at 160° it 
 forms a red dye resembling saffranin. 
 
 Salts .— B'HCl : orange tables.— B'^HaPtCle. 
 
 Acetyl derivative 
 C,H,— Nj— C,H„(NHAc). [185°]. Slender red 
 needles, v. sol. alcohol (Schultz, B. 17, 469). 
 
 m-Toluene-azo-m-toluidine 
 [3:1] C,H,Me— N^— C,H3Me(NH2) [1:2:4]. [80°]. 
 Pormed by treating an alcoholic solution of 
 m-toluidine with nitrous acid gas (Nietzki, 
 B. 10, 1155). Golden needles. — B'HCl. — 
 B'jHjPtClj. Gives ^-tolylene diamine, [64°], on 
 reduction. 
 
 ^-Tolueue-azo-o-toluidine 
 [4:1] CsHjMe— N — C^HjMelNHj) [1:3:4]. [128°]. 
 From ^-diazo-toluene toluide and o-toluidine 
 hydrochloride (Nietzki, B. 10, 832). Gives 
 y-tolylene-diamine, [64°], on reduction. Heated 
 with aniline hydrochloride it forms a violet dye. 
 Salt s.— B'HCL— B'^H^PtCle. 
 
 ^-Toluene-azo-m-toluidine 
 [4:1] C„HjMe— N,— C„H3Me(NH,) [1:2:4]. [127°]. 
 From ^-diazo-toluene toluide and m-toluidine 
 hydrochloride in alcoholic solution (Nietzki, B. 
 10,1156). Large yellow plates. Gives 2)-tolylene- 
 fli amine [64°] on reduction. 
 
 Salt s.— B'HCl.— B'jH,PtCla. 
 
 p-Toluene-azo-p-toluidine 
 [4:1] CsH,Me— Nj— CeH3Me(NH2) [1:5:2] oi 
 NHv 
 
 I >OsHsMe. [119°]. o-Amido-azo- 
 CsH^McN^h/ 
 
 toluene. Toluene-hydrazimido-toluene. Pre- 
 pared by heating ^ -diazo- toluene -p- toluide 
 (diazo-amido-toluene), dissolved in 5 or 6 times 
 its weight of melted p-toluidine, with 2)-toluidlne 
 hydrochloride (1 mol.) at 65° for 12 hours. 
 Orange-red glistening needles. V. sol. hot alco- 
 hol, acetic ether, and benzene. On reduction 
 it gives ^J-toluidine and tolylene-o-diamine. CrO, 
 oxidises it in acetic acid solution to toluene- 
 azimido-toluene C,H, — Nj — CjHe (Zincke, B. 18, 
 3142). Heated with jp-toluidine hydrochloride 
 andp-toluidine at 100° it gives a body C^^HjiN, 
 analogous to azophenine which forms flat red 
 needles. Heated to a higher temperature dye- 
 stuffs of the induline series are formed. It is 
 converted into eurhodine C„H,3N3 by heating 
 with (a)-naphthylamine hydrochloride (Witt, 
 C. J. 49, 393). The salts of o-amido-azo-^- 
 toluene are yellow in the solid state, but dissolve 
 to green solutions. — B'HCl : slender light-yellow 
 needles. 
 
 Acetyl derivative. [157°] ; yeUow felted 
 needles. 
 
 Benzoyl derivative. [135°]; orange- 
 yellow needles (Witt a. Nolting, B. 17, 77). 
 
 Disulphonic acid Ci4H,3N3(S03H)2. 
 Formed by sulphonating with fuming HjSO, 
 (N. a. W.). Greyish white needles. Is a yellow 
 dyestuff of redder shade than ' acid yellow.' — 
 BaA" 4aq : brownish-red crystalline powder. 
 
 p-Toluene-azo-tolylene-diftmine 
 [4:1] CsH.Me- Nj— C„H2Me(NHj2 [1:3:4:6]. 
 [183°]. From ;p-diazo-toluene nitrate and toly- 
 lene-m-diamine (Hofmann, B. 10, 218). Orange 
 needles, v. sol. alcohol, insol. water. — B"HC1. — 
 
 Xylene-azo-(;3)-naplitliol-(/3)-siilphoiiic acid, 
 Diazo-xylene does not combine with Eumpf 's ' a '- 
 sulphonic acid of (;8)-naphthol in dilute alkaline 
 solution, although some other diazo- compounds 
 (such as diazo-benzene) do combine with it under 
 the same conditions. If, however, the solution 
 is very concentrated, the combination with 
 diazo-xylene takes place. The product forms 
 red needles, dissolves in HjSO, with a red 
 colour, and dyes wool a somewhat yellower shade 
 than the compound from Schaf er's ' |8 '-acid 
 (Schultz, B. 17, 461). 
 
 Xylene-azo-thymol-Bulphonic aeid 
 C,H3(CH3),-N,-C^(CH3)(C3H,)(HS03)OH. 
 Slender yellow needles. Prepared by the action 
 of diazo-xylene chloride on sodium thymol- 
 sulphonate. — A'jBa: small yellow needles or 
 plates (Stebbins, B. 14, 2795). 
 
 Xylene-azo-xylene 
 CeH3(CH3),— N^- CeH3(CH3)2. Azo-xylem [126° 
 corr.] Formed by reduction of nitro-m-xyleno 
 with sodium-amalgam or with zinc-dust and alco- 
 holic NaOH ; very small yield. A better yield 
 is obtained by oxidation of xylidine with alkaline 
 potassium ferricyanide (Werigo, Z. 1864, 723 ; 
 1865, 312; Samonoff, Bl. [2] 39, 597; J. B. 
 1882, 327 ; Schultz, B. 17, 476). Eed needles. 
 Sol. hot alcohol. It does not appear to give a 
 dixylyl base by treatment with SnOlj and HCl 
 in alcoholic solution. 
 
DIAZO- COMPOUNDS. 
 
 307 
 
 ni-Xylene-o-azo-m-zylidine 
 [2:4:1] C,U,-^e,—-N,—O^B^UeMU^) [1:3:5:6] 
 NHv 
 
 or I \OMMe,. o-Amido-azo- 
 
 0,H,Me,-N^/ 
 xylene. [78°] 
 
 Preparation. — Diazo-ro-xylene-w-xylide, pre- 
 pared by adding a solution of 1 mol. of sodium 
 nitrite to a mixture of 1 mol. of TO-xylidine 
 0,H3Me2.NH2[l:3:4] and 1 mol. of its hydro- 
 chloride, is dissolved in m-xylidine and gently 
 warmed for a long time with about 5 p.o. of 
 nt-xyUdine hydrochloride. The mixture is then 
 acidified with dilute HCl, the precipitated hydro- 
 chloride is filtered off, washed with water, 
 alcohol, and ether, basified, and crystallised 
 from alcohol or benzene ; the yield is 70 p.c. to 
 80 p.c. of theoretical. Orange plates. V. sol. 
 benzene, and hot alcohol, v. si. sol. water. 
 
 Reactions. — On reduction it yields m-xylidine 
 and TO-xylylene-o-diamine CjHjMezfUHj)^ 
 [1:3:5:6]. 
 
 Salts. — BTICl : yellow crystalline powder, 
 dissolves sparingly in alcohol with a green 
 colour, soluble in phenol with a splendid green 
 colour (Nolting a. Forel, B. 18, 2682). 
 
 m-Xylene-^-azo-m-xylidine 
 [2:6:1] CeHsMe^— Nj— C^H^Me^CNHi,) [1:3:5:4] 
 [78°]. Yellow plates. EasUy soluble in alcohol 
 and benzene. Prepared from ?n-xylidine 
 CjH3Me2.NH2[l:3:2] by the same method as that 
 described under m-xylene-o-azo-m-xyhdine. 
 
 Salt s. — ^B'aHjCl^PtClj : red crystallinepowder. 
 The hydrochloride dissolves in phenol or alcohol 
 with a red colour (Nolting a. Forel, B. 18, 2684). 
 
 7re-Xylene-p-azo-m-xylidine 
 [3:5:1] C^HaMej— N^— OeHjMe2(NHJ [1:2:6:4]. 
 [95°]. Prepared from m-xyUdiue CjHjMejNHj 
 [1:3:5] by the same method as that described for 
 j»-xylene-o-azo-«i-xylidine. Yellow plates. On 
 reduction it gives symmetrical jre-xylidine and 
 m-xylylene-j)-diamine CsH2Me2(NH2)j [1:3:2:5]. 
 The hydrochloride dissolves in phenol with a 
 violet-red colour (Nolting a. Forel, B. 18, 2684). 
 
 o-Xylene-p-azo-o-zylidine 
 [2:3:1J OjHjMej— N^— CsHjMe2(NH2) [1:2:3:4]. 
 [111°]. Prepared from o-xylidine CsHjMej.NHj 
 [1:2:3] by the same method as that described 
 under j?i-xylene-o-azo-OT-xyUdene (Nolting a. 
 Forel, B. 18, 2684). Glistening yellow plates 
 (from alcohol or benzene). On reduction it 
 yields o-xylidiue and o-xylylene-;p- diamine 
 CsHJS/!.e2(SH,)ll:2:3:6]. The hydrochloride 
 dissolves in phenol with a red colour. 
 
 jra-Xylene-^-azo-p-xyUdine 
 [2:4:1] CjEsMe^— N^— CeH2Me,(NHj) [1:2:5:4]. 
 [111°]. Eed plates. 
 
 Preparation : 50 c.o. of a solution of sodium 
 nitrite Containing 227 grms. NaNOj per Utre are 
 added to a mixture of 20 grms. of j)-xylidine 
 and 26 grms. of hydrochloride of m-xylidine 
 C5H3Me2(NH2) [1:3:4] ; the diazoamide so formed 
 is dissolved in 20 grms. of 51-xylidine and gently 
 warmed with 4 grms. of p-xyhdene hydrochloride. 
 
 Beactions. — On reduction it yields m-xyUdine 
 and^-xylylene-p-diamineCeH2Me2(NH2)2[l:4:2:5]. 
 The hydrochloride dissolves in phenol with a 
 red colour (Nietzki, B. 13, 470; Nolting a. 
 Forel, B. 18, 2686). 
 
 p-Xylene-^ azo-p-xylidine 
 [2:5:1] CBHjMe,— Nj— C,H2Me2(NH2) [1:2:5:4]. 
 
 [150°]. Eed plates (from alcohol). Prepared 
 from jp-xylidine C„HsMe2(NH2) [1:4:5] by the 
 same method as that described under m-xyleue- 
 o-azo-m-xylidine. On reduction it yields p. 
 xylidine andp-xylylene-p-diamine 08H2Me2(NH2)j 
 [1:4:2:5]. The hydrochloride is red, and dissolves 
 in phenol with a violet-red colour (Nolting a. 
 Forel, B. 18, 2685). 
 
 o-Xylene-o-azo-o-xylidine 
 [3:4:1] 05HjMe2— N2— CsH2Me2(NH2) [1:3:4:6] or 
 NHv 
 
 I >05H2Me2. [179°]. Yellow 
 CsH,Me2— NjH-^ 
 
 plates. SI. sol. alcohol. Prepared from o-xylidine 
 CjH3Me2(NH2) [1:2:4] by the same method as that 
 described under m-xylene-o-azo-m-xylidine. On 
 reduction it gives rise to o-xylidine and o- 
 xylylene-o-diamine C|iH2Me2(NH2)2 [1:2:4:5]. Its 
 hydrochloride dissolves in phenol with a green 
 colour (Nolting a. Forel, B. 18, 2685). 
 
 DIAZO- COMPOTTNDS. A class of bodies 
 formed by the action of nitrous acid upon 
 primary amido- compounds : X.NjHj + OjN.OH = 
 X.N2.OH + H2O. They contain a pair of nitrogen 
 atoms (Fr. azote) which are united to only one 
 hydrocarbon radicle, whilst in the azo- compounds 
 the N2 group is united to two hydrocarbon 
 radicles X.N2.Y. The diazo-radicles X.N'j can- 
 not of course exist in the free state, but they 
 occur as hydrates X.Nj.OH, chlorides X.N^.Cl, 
 amides X.Nj.NHB, &c. For the sake of con- 
 venience reactions will usually be represented 
 in this article as taking place with the hydrates. 
 
 The diazo- salts X.N2A may be regarded as 
 derived from the salts of amines X.NHjA by 
 the displacement of H3 by N. This may take 
 place in two ways. According to Kekul^'s 
 view, which is that most generally adopted, both 
 nitrogen atoms are trivalent : X.N:N.A. On the 
 other hand, Blomstrand (Ghemie der Jetztzeit, 
 p. 272, and B. 8, 51) assumes that the nitrogen 
 attached to the carbon is pentavalent : X.N.A ; 
 
 N 
 Strecker [B. 4, 786) and Erlenmeyer (B. 7, 1110) 
 also concur in this view. The reduction of 
 diazo- compounds to hydrazines, which have the 
 undoubted constitution X.NH.NHj, E. Fischer 
 {A. 190, 67) regards as a proof of the correct- 
 ness of Kekul6's formula, since a body of the 
 constitution X.N.A would, he considers, give on 
 
 N 
 reduction X.NH2. Crum Brown, however, has 
 
 NH 
 pointed out in a private communication that 
 this argument is fallacious, since the product 
 of the reduction is not a hydrazine itseli but a 
 hydrazine-salt, and X.N.A, by adding Hjto each 
 
 N 
 N, would give the hydrazine salt X.NH,A. He 
 
 NHj' 
 considers the pentad N in the salts of hydra- 
 zines is most probably that connected to the 
 hydrocarbon nucleus, in which case to explain 
 their formation by adoption of Eekul6's formula 
 would necessitate a shifting of the acid from 
 one N to the other. The strongest argument 
 against KekuU's formula is that it represents 
 diazo- salts, by not containing pentad nitrogen, 
 as differently constituted to the salts of all 
 other nitrogen bases. On the other hand, the- 
 
SOS 
 
 DIAZO- COMPOUNDS. 
 
 formula X.JJ.A would necessitate a rearrange- 
 
 N 
 ment of the molecule in the formation of azo- 
 tompounds which undoubtedly have the con- 
 stitution X.N:N.Y. 
 
 The simplest member of the series H.Nj.OH 
 ■should be formed by the action of nitrous acid 
 upon NHjj but it has not yet been obtained, 
 probably by reason of its extreme instability. 
 The best-known diazo- compounds are those 
 derived from aromatic amines and amido- com- 
 pounds, some of which are tolerably stable bodies. 
 No diazo- compounds have at present been ob- 
 tained from fatty amines, for, like the first 
 member of the series, H.Nj.OH, they are so un- 
 stable that they are probably scarcely capable of 
 existence, and at once break up into the alcohol 
 sad Nj. The only known fatty diazo- compounds 
 are a few which have lately been prepared from 
 fatty amido-ethers (e.g. glyoocoU). In their con- 
 stitution they differ from the aromatic diazo- 
 hydrates by containing a molecule of water 
 less : (Et02C)OH2.Nj.OH-H20 = (Et02C)CH:Nj, 
 
 A. Aromatic diazo- componnds. The dis- 
 covery of these bodies, and a large portion of 
 6ur knowledge concerning them, are due to P. 
 Griess (A. 106, 123; 113, 201 ; 117, 1 ; 120, 125 ; 
 121, 257 ; 137, 89 ; &o.), who, in a series of 
 classical researches, opened up a field of in- 
 vestigation which in a few years has produced 
 more discoveries of scientific interest and prac- 
 tical utility than almost any other branch of 
 organic chemistry. 
 
 Formation. — 1. By the action of nitrous 
 ftcid, or any compound readily forming nitrous 
 acid {e.g. NOCl, NOBr, S02(0H)(N02), zinc-dust 
 and HNO3, &o.) upon salts of primary amines. — 
 2. By oxidation of primary hydrazines (E. Fischer, 
 A. 190, 97). 
 
 Preparation. — The details vary very much 
 with individual cases and the purposes for 
 which the diazo- compounds are required. The 
 amine can be dissolved in water, alcohol, acetic 
 acid, HOI, HjSO,, &c., and can then be treated 
 with nitrous acid gas, sodium nitrite, or a 
 nitrous ether. When required in the solid form, 
 a common method is to mix the nitrate of the 
 amine with a little water, cool in a freezing- 
 mixture, and saturate with N^Oj gas ; the diazo- 
 nitrate is then ppd. by addition of alcohol and 
 ether. Diazo- compounds can also be isolated 
 from their aqueous solutions by ppn. as platino- 
 chlorides, perbromides, picrates, sulphites, &o. 
 When the diazo- compound is required for a 
 subsequent reaction it is seldom necessary to 
 isolate it, but the compound can be prepared 
 tinder the conditions suitable to the second re- 
 action. For instance, when the diazo- compound 
 is to be conjugated with an amine or phenol to 
 form an azo- compound, the amine is usually 
 ■dissolved in water containing 2 mol. of HGl for 
 each NHj group, cooled by addition of ice, and 
 mixed with an aqueous solution of sodium 
 nitrite (1 mol. to each NH2). The solution of 
 the diazo-ohloride thus prepared can be at once 
 treated with a solution of the phenol or amine. 
 
 The diazotisation of simple amines, in not 
 too dilute solutions, usually takes place quanti- 
 tatively, and the reaction is tolerably rapid. 
 For instance, the diazotisation of aniline in a 
 10 p.o. solution is so complete within an hour 
 
 that it forms the most accurate method of eati. 
 mating nitrous acid or aniline (Green a. Eideal, 
 G. N. 49, 173 ; Green a. Evershed, 8. O. I. 1886, 
 633). The greater the molecular weight of th« 
 amine the slower and less complete is the diazo- 
 tisation. The diazotisation of heavy amido- 
 bodies is facilitated by the presence of a very 
 large excess of mineral acid, using as little 
 water as possible. Alcohol in many cases 
 appears to have a contrary effect. Amido- groups 
 cannot be diazotised unless combined with an 
 acid : thus if the ordinary hydrochloride of p-' 
 phenylene diamine C|iH,(NH2)(NH3Cl) is treated 
 with HNOj only one NH^ group is diazotised ; 
 but if a large excess of HCl is employed so that 
 CsH4(NH3Cl)2 is present, both NH2 groups are 
 diazotised. The final products of the action of 
 nitrous acid upon the mono-acid salts of di- 
 amines vary with the constitution of the latter. 
 Thus o-phenylene diamine gives azimido- 
 benzene : 
 
 C„H,(NH2).N2.0H-H20 = C„h/ I \nh. 
 
 m - Phenylene diamine gives tri - amido - azo- 
 benzene,thus: OsH4(NH2).Nj.OH + CjH4(NHj)2= . 
 CsH4(NH2).Nj.C5H3(NH2)2 + H^O. Whilst the 
 diazo - compound 0|,Hj(NH2).N2.0H [1:4], from 
 ^-phenylene diamine, does not undergo any 
 further transformation. The di-amido-benzoio 
 acids react with nitrous acid in an exactly 
 similar manner according as the NH^ groups 
 are 6, m, or p to each other (Griess, B. 17, 607). 
 Properties. — The diazo- salts are in general 
 very unstable crystalline solids. When dry they 
 often decompose with detonation, by heat or per- 
 cussion. Their solutions slowly decompose at 
 the ordinary temperature, more quickly on heat- 
 ing, with evolution of nitrogen. The hydrates 
 are even more unstable than the salts, and have 
 scarcely ever been isolated. The stability is 
 increased by substitution in the nucleus ; thus 
 diazo-benzene-sulphonic acid is more stable 
 than diazo-benzene. The diazo- derivatives of 
 substituted phenols and of o- and p- sulphonio 
 acids usually occur in the form of anhydro- com- 
 pounds, e.g. 
 
 N 
 C,H2Br2<^|°^-H20 = 0eH2Br/|', and 
 
 ^«s<so*^-^^o=°«^'<^l 
 
 .N, 
 
 '\so," 
 
 In a similar 
 
 manner o-amido-diazo- compounds form inner 
 amides (e.g. azimido-benzene, v. supra). 
 
 BeacUcms. — The diazo- compounds are ex- 
 tremely prone to undergo reactions ; they play a 
 most important part in organic syntheses and 
 the determination of the constitution of isomeric 
 aromatic compounds, by serving as an inter- 
 mediate stage by means of which NH^ groups 
 can be replaced by H, OH, 01, Br, I, F, ON, 
 SH, NO2, &a. Their power of combining with 
 amines and phenols to form azo- compounds 
 renders thsm of great technical importance 
 for the production of colouring-matters, for 
 which purpose they are prepared in large quan- 
 tities. The majority of their reactions consist 
 in the evolution of Nj, and its replacement by 
 the atom or group (01, OH, &o.) previously 
 united to it. 
 
DIAZO- COMPOUNDS. 
 
 398 
 
 1. By heating the aqueous solution nitrogen 
 Is evolved, with formation of the corresponding 
 phenol: X.Nj.OH = X.OH + N^. The best method 
 is to dissolve the amine in a considerable excess 
 of dilute HjSO,, diazotise by adding NaNOj to 
 the iced solution, and finally heat to boiling. 
 
 2. When heated with strong alcohol the 
 normal reaction appears to be the replacement 
 of the N2 group by OEt, with formation of 
 ethoxy- compounds (Wroblewski, Z. 6, 164 ; B. 
 17, 2703; Haller, B. 17, 1887; Hofmann, B. 17, 
 1917; Eemsen, 4m. 8,243; B. 18, 65; Hayduck, 
 A. 172, 212; Zander, A. 198, 25; Heffter, A. 
 221, 352 ; Paysan, A. 221, 212, 363 ; Mohr, A. 
 221, 222 ; Hesse, A. 230, 293). 
 
 3. tinder certain circumstances, at present 
 nndetermined, the reaction with alcohol takes a 
 different course, resulting in the substitution of 
 H for the Nj group, with production of the cor- 
 responding hydrocarbon together with aldehyde : 
 
 X.Nj.OH + O^HjO =X.H + CjHiO + Nj + H^O 
 (Griess). (a) The amido- compound is treated 
 with a solution of nitrous acid in absolute alcohol, 
 warmed till nitrogen comes ofi freely, allowed 
 to cool, resaturated with NjO,, and the opera- 
 tion repeated until but little gas is evolved on 
 heating (Neville a. Winther, C. J. 37, 452). 
 (b) The amido-compound is dissolved in a con- 
 siderable excess of cone. HjSOj, the solution 
 diluted with a small quantity of water is cooled 
 in a freezing-mixture, and the necessary quan- 
 tity of solid sodium nitrite added. When diazo- 
 tised the solution is poured in a thin stream 
 into two or three times its bulk of alcohol ; the 
 mixture becomes warm enough to complete the 
 reaction without further heating (Meldola, C. J. 
 1885, 507). 
 
 4. Mercaptan, when heated with diazo- com- 
 pounds at 170°, behaves similarly to alcohol in 
 reaction 3, causing the displacement of Nj by 
 hydrogen with simultaneous formation of di- 
 ethyl-di-sulphide (Sohmitt a. Mittenzwey, J. jor. 
 126, 192). 
 
 5. The displacement of the N^ group by H is 
 also effected by reduction to the corresponding 
 hydrazine (j. v.), and treatment of this with 
 CuSO, or FejClj (B. 18, 90). 
 
 6. Eeduotion of a diazo-chloride with excess 
 of SnClj also effects the displacement of Nj by H: 
 X.NjCl + SnCl, + H^O = X.H + SnOCl^ + HCl + Nj. 
 A dilute aqueous solution of the diazo-chloride 
 is treated with an excess of SnClj at 0°, and 
 finally heated for two hours with an inverted 
 condenser ; the yield is good (Effront, B. 17, 
 2329; Gasiorowski a. Wayss, B. 18, 337). 
 
 7. By treatment of a cold solution of a diazo- 
 compound in cone. HCl with (2 mols. of) SnClj, 
 the corresponding hydrazine (q. v.) is produced : 
 X-Nj-Cl + 2SnCl2 + 3HC1 = X.NH.NHj + 2SnCl,. 
 
 8. The reduction of the sulphites of diazo- 
 compounda with SOj, or with zino-dust and 
 acetic acid, also gives rise to hydrazines. 
 
 9. By heating with dilute HNO., nitrated 
 phenols are obtained (Nolting a. Wild, B. 18, 
 1338). 
 
 10. The platino-chlorides on distillation with 
 dry NajCO, yield the corresponding chloro-deri- 
 ▼atives : (X.N2.Cl)2PtCl, = 2X.C1 -f 2N2 -t- PtCl,. 
 
 11. The replacement of Nj by CI is also 
 effected by boiling the diazo- compound with 
 fuming HCl in large excess ; X.Nj.Cl = X.Cl-l-Nj 
 
 (Griess, B. 18, 960; Gasiorowski a. Wayss, B. 
 18, 1936). 
 
 12. The same replacement is most readily 
 effected by treating the aqueous solution of the 
 diazo-chloride with cuprous chloride, which 
 appears to act by intermediate formation of an 
 addition product B.Nj.Cl, Cu^Cl^. (a) A 10 p.c. 
 solution of CujClj is prepared by adding 100 pts. 
 of cone. HCl and 13 pts. of copper turnings to a 
 hot solution of 25 pts. of crystallised CuSOj and 
 12 pts. of NaCl, boiling till decolourised, and 
 making up the weight to 203 pts. with cone. HCl. 
 A dilute HOI solution of the diazo- compound is 
 allowed to run slowly into the above solution 
 (about 5 times the weight of the amine used) 
 heated nearly to boiling ; the product, if volatile, 
 is distilled with steam, or it is separated and 
 purified by crystallisation. (6) In most cases 
 instead of separately diazotising the amine, its 
 solution in dilute HCl can be mixed with about 
 5 pts. of the 10 p.c. CUjClj solution, and a solu- 
 tion of the calculated quantity of NaNO^ run 
 into the nearly boiling mixture (Sandmeyer, B. 
 17, 1638, 2650; LeUmann, B. 19, 810). 
 
 13. The perbromides {q. v.) of diazo- com- 
 pounds, on heating by themselves, or vrith dry 
 Na^COa, or best by boiling with glacial acetic 
 acid, yield bromo - derivatives : X-Nj-Br, = 
 X.Br + Br^ + N^ (Neville a. Winther, 0. J. 87, 452). 
 
 14. The replacement of Nj by Br is also 
 effected by boiling the diazo- compound with 
 fuming HBr in large excess : X.Nj.Br = X.Br + N^ 
 (Griess, B. 18, 960 ; Gasiorowski a. Wayss, B. 
 18, 1936). 
 
 15. The same replacement in most con- 
 veniently effected by means of cuprous bromide 
 (cf. reaction 12). A solution of 125 pts. of 
 crystallised CuSO, (\ mol.), 860 pts. of KBr (3 
 mols.), 800 pts. of water, and 110 pts. of cone. 
 HjSO, (1 mol.), is boiled with 200 pts. of copper- 
 turnings tiU decolourised. The amine (1 mol.) 
 is then added, and into the mixture, heated 
 nearly to boUing, is slowly run a solution of 
 70 pts. NaNOj (1 mol.) in 400 pts. of water 
 (Sandmeyer, B. 17, 2650 ; 18, 1492). 
 
 16. By boiling diazo- compounds with aqueous 
 HI the Nj group is replaced by I forming iodo- 
 compounds: X.Nj.I= XI-i-Nj (Griess, B. 18, 
 960). 
 
 17. By boiling with HF the Nj group is re- 
 placed by F giving fluoro- compounds : X.Nj.!" = 
 XJP + Nj (Griess, B. 18, 960; Paterno a. Oliveri, 
 G. 12, 85 ; 18, 533 ; Wallaoh, A. 285, 255). 
 
 18. By heating diazo- salts with Cu2(CN)2 the 
 Nj group is replaced by CN (cf. reactions 12 and 
 15). The nitrUes so formed can be converted 
 into carboxylic acids by saponification, so that 
 by means of this reaction an NHj group can be 
 replaced by CO^H. 28 pts. of KCN (96 p.c.) are 
 added to a hot solution of 25 pts. of crystallised 
 CuSOj in 150 pts. of water ; into this solution, 
 heated to about 90°, is slowly run an aqueous 
 solution of the diazo-chloride. If the nitrile is 
 required for conversion into the acid, it is not 
 always necessary to isolate it, but the crude pro- 
 duct of the reaction can be at once saponified 
 (Sandmeyer, B. 17, 2650 ; 18, 1492, 1496). 
 
 19. By the action of a warm alcoholic solution 
 of KjS the Nj group is replaced by SH, thus : 
 X.Nj.SH = X.SH + Nj. The mercaptaus so formed 
 can be converted into sulphonic acids by oxida- 
 
400 
 
 DIAZO- COMPOUNDS. 
 
 tion with cold KMnO,; bo that by means of 
 this reaction an NH^ group can be replaced by 
 SOjH (Elason, B. 20, 349). 
 
 20. Hydric sulphide converts diazo-benzene 
 into phenyl sulphide (CjHsJjS (Graebe a. Maun, 
 B. 15, 1683). 
 
 21. Diazo- compounds combine with ethyl 
 mercapian to form unstable bodies X.Nj.SEt, 
 which when boiled with alcohol yield sulphides : 
 X.N2.SEt = X.SEt + N2 (Stadler, B. 17, 2075). 
 
 22. By heating with acetic anhydride, aoetyl- 
 ated phenols are formed: X.Nj.OH + Ac^O = 
 X.OAo + N5, + AoOH (Wallaoh, A. 235, 234). 
 
 23. SO2 in presence of boiling alcohol con- 
 verts some diazo- compounds into the corre- 
 sponding sulphonio acids: X.N^.OH -H SO2 = 
 X-SO^-OH + Nj (Hubner, B. 10, 1715). 
 
 24. Alkalis give insoluble pps. of complex 
 constitution (Frankland, C. J. 37, 750). 
 
 25. Action of cyanogen compounds (v. Griess, 
 B. 9, 132 ; 12, 2119 ; Gabriel, B. 12, 1637). 
 
 26. Ciiprous nitrite replaces the diazo- group 
 by NOj. The amine (1 mol.) is dissolved in 
 exactly 2 mols. of dilute HNO3 (or 1 mol. of 
 dilute H2SO4) and the iced solution treated with 
 one half of a solution of 2 mols. of NaNOj, the 
 other half being added when the diazotisation 
 is complete. The solution of the diazo-nitrite 
 is added to a paste of 1 mol. of Cu^O (obtained 
 by reducing CuSO, with glucose and NaOH) 
 and the decomposition allowed to proceed in 
 the cold. The yield of nitrobenzene from ani- 
 line is 42 p.c. of the theoretical, but with other 
 bases it is smaller (Sandmeyer, B. 20, 1494). 
 
 27. Primary and secondary amines, react at 
 (mce with diazo- compounds forming diazo-amides 
 fe. V.) : X.N2.OH + HjN. Y = X.N2.NHY + H^O. In 
 these bodies the diazo- radicle replaces H united 
 to N, and on treatment with excess of acid they 
 readily regenerate the diazo- compound and 
 amine. When diazo- compounds act upon salts 
 of aromatic amines, the diazo- residue may re- 
 place H in the carbon-nucleus, with formation of 
 amido-azo- compounds : X.Nj.OH + HY".NH2 = 
 X.N^.Y".'SB.^ + B.fi. In the case of tertiary 
 aromatic amines the latter reaction is the only 
 one possible, but with primary and secondary 
 aromatic amines the replacement in the nucleus 
 may be preceded by the formation of a diazo- 
 amide, when there is no large excess of mineral 
 acid present. The readiness with which amido- 
 azo- compounds are formed varies greatly with 
 the amine : in some cases (e.g. (o)- and (;S)-naph- 
 thylamine, phenylene diamine, &c.) the replace- 
 ment in the nucleus appears to take place almost 
 instantly; in others {e.g. aniline) the reaction, at 
 the ordinary temperature, takes several hours 
 for its completion, allowing the intermediate 
 formation of the diazo-amide CFriswell a. Green, 
 O. J. 1885, 917; Proceedings 1887, 26). In 
 many cases the formation of an amido-azo- 
 compound wiU take place in presence of a large 
 excess of acid, under which conditions the forma- 
 tion of a, diazo-amide is precluded. In the for- 
 mation of amido-azo- compounds of the benzene 
 series the diazo-residue enters in the para- posi- 
 tion to the NHj group ; but when this place is 
 already occupied it takes the ortho- position. 
 The ortho-amido-azo- compounds appear to be 
 differently constituted to the para-amido-azo- 
 oompounds {v. Azo- com; oundb). If the amine 
 
 does not contain any free para- or ortho- position 
 the formation from it of an amido-azo- compound 
 does not appear to be possible. When a diamine 
 contains displaceable H atoms para to each NH, 
 group, it is capable of reacting with 2 mols. of a 
 diazo- compound to form a disazo- compound : 
 2X.N„.0H + H,.Y"{NH2)2 = 
 {X.NJ,Y"(NH2)2-i-2H,0. 
 
 28. Diazo - compounds readily react upon 
 phenols and their sulphonio and earboxylio acids 
 in alkaline solution, forming oxy- azo -com- 
 pounds X.N2.OH + H.Y".OH = X.N2.Y".0H + H^O. 
 Compounds of the form X.N2.OY' analogous to 
 the diazo-amides have never been obtained. The 
 above remarks (reaction 24) with regard to the 
 position taken by the diazo- group in the benzene- 
 nucleus apply equally to oxy- and to amido-azo- 
 oompounds. Also, the di-oxy- compounds, simi- 
 larly to diamines, can give rise to disazo- 
 compounds (X.N2)2Y''(OH)2 when they contain 
 displaceable H atoms para to each OH group. 
 
 29. Diazo- compounds readily react with 
 pyrrol, with formation of azo- and disazo-bodies, 
 X.N2.C,H3NH and (X-NJ^CiH^NH, but no com- 
 pounds analogous to diazo-amides (O. Fischer a. 
 Hepp, B. 19, 2251). 
 
 30. Piperidine, on the other hand, gives rise 
 to piperidides X.N^.NCsH,, (0. Wallaoh, A. 235, 
 233). 
 
 31. Amido-thiophene, unlike aniline, does not 
 appear to form diazo-amides when treated with 
 diazo- compounds, but gives at once amido-azo- 
 compounds X.Nj.C^SHj.NHj (Stadler, B. 18, 
 2318). This is no doubt due to the tendency to 
 replacement of the hydrogen being greater in the 
 thiophene ring than in the benzene ring. 
 
 32. Diazo- compounds react with those-bodies 
 of the fatty series which contain H Hnited to C, 
 replaceable by sodium, e.g. nitro-methane, nitro- 
 ethane, malonio ether, aceto-acetio ether, other 
 ketonic ethers, &o. The products are mixed 
 azo- compounds : those from nitro-methane, for 
 instance, have the constitution X.N2.CH2(N0j) 
 (Meyer, B. 8, 751, 1073 ; 9, 384 ; Zublin, B. 11, 
 1417; Kappeler, B. 12, 2286; Bichter a. 
 Miinzer, B. 17, 1926; Griess, B. 18, 961; 
 Bamberger, B. 17, 2415 ; 18, 2563). 
 
 Salts. — The diazo- salts have the general 
 formula X.N2.A. They are mostly white crys- 
 talline solids, very easily soluble in water, but 
 sparingly in alcohol and ether. They are 
 usually very unstable, and in the dry state are 
 often very explosive, especially the nitrates 
 and piorates. By the action of KjSOj upon 
 diazo- chlorides, sulphites are formed of 
 the constitution X.N^.SOjK. Stannic and 
 cuprous salts give double compounds of 
 the formula (X.N^.C^aSnOl,, (X.N^.C^Cu^Clj, 
 (X.N2.Br)Cu2Br2, &o. (Griess, B. 18, 965; 
 Lellmann, B. 19, 810). The platino-chlorides 
 (X.Nj.C^jPtCl^ are sparingly soluble pps. An 
 excess of bromine produces yeUow or red pps. 
 of the per-bromides X.NjBr,. The diazo- 
 sulphonic and earboxylio acids form salts 
 X"(S03M).N2.0H with bases, as well as 
 X"{S03H).N2.A with acids. 
 
 Amides. As already mentioned [reaction 
 27), the action of primary and secondary amines 
 upon diazo- compounds gives rise to diazo- 
 amides of the general formula X.Nj.NIIY, or 
 X.Nj.NYiYj. Thus diazo-benzene and anihus 
 
DIAZO- COMPOUNDS. 
 
 401 
 
 yield diazo-benzene-aiiilide(diazoainidobenzene); 
 
 C^nj.Nj.OH + C^Hs.NHj = C,ft.Nj.NH.CeH5. 
 These bodies are in general yellow crystalline 
 Bolids, stable below 100° when free from acid. 
 By treatment with an excess of mineral acid 
 they are resolved, even in the cold, into the 
 diazo- salt and amine. When the amine is 
 aromatic the resolution products again slowly 
 recombine, if the conditions are favourable, to 
 produce an amido-azo- compound X.N^.y'.NHj 
 isomeric with the original diazo- amide. The 
 resolution and recombination take place con- 
 currently when the diazo-amide is treated with 
 1 mol. of cold dilute HCl, or with unstable 
 salts, such as ZnClj, CaCl:, aniline chloride, &a., 
 in alcoholic or aniline solution (Friswell a. 
 Green, C. J. 1885, 917 ; WaUach, A. 235, 233). 
 When a diazo-amide is treated with a salt of a 
 base different from that of which it is a com- 
 pound, the diazo- salt generated will react upon 
 that base of the two whose nucleal hydrogen is 
 most readily replaced. Thus diazo-benzene-di- 
 methyl-amide CjHj.Nj.KMOj treated with aniline 
 chloride gives amido - azo - benzene and di- 
 methyl-amine ; similarly, diazobenzene-anilide 
 CJH5.N2.NHCJH5 treated with m-phenylene- 
 diamine hydrochloride yields di-amido-azo- 
 beuzene C5H5.N2.C5H3(NH2)2, whilst aniline is 
 set free ; but diazo-benzene-anilide treated 
 with jj-toluidine hydrochloride gives amido-azo- 
 benzene and jp-toluidine, because the para H of 
 the aniline is more readily replaced than the 
 ortho H of the ^-toluidine. Even very weak 
 acids, such as acetic acid and phenols, are capable 
 of resolving most diazo-amides. In the latter 
 case the diazo- compounds produced immediately 
 combine with the phenol to form oxy-azo- com- 
 pounds, for diazo- residues replace the hydrogen 
 of the nucleus more readily in phenols than 
 in amines (Heumann a. Oeconomides, B. 20, 
 904). 
 
 In general it may be said that the reactions 
 of the diazo-amides towards reagents in presence 
 of acids, are simply the reactions of the free 
 diazo- salts ; thus SnClj and HCl reduce them 
 to hydrazines (c/. reaction 7) ; heating with 
 strong halogen acids gives haloid derivatives of 
 the hydrocarbons (c/. reactions 11, 14, 16, and 
 17); &c. 
 
 It appears to be proved (Griess, B. 7, 1619 ; 
 Nolting a. Binder, Bl. 42, 336 ; Meldola a. Streat- 
 feild, O. J. 1887, 102, 434) that the diazo-amides 
 of the types X.N^.NHY and T.Nj.NHX are iden- 
 tical—that is, the same body is obtained which- 
 ever of the two amines is diazotised and com- 
 bined with the other. The resolution of these 
 nnsymmetrioal diazo-amides quite corresponds 
 to their formation, for they yield a mixture of 
 both diazo- compounds X.N^OH and Y.N2OH, 
 and both amines X.NHj and Y.NHj. For in- 
 stance, the compound CjHj.NjH.CjH, is obtained 
 by combining either diazo-benzene vrith ^-tolui- 
 dine, or ^-diazo-toluene with aniline ; and on 
 treatment with HCl it splits up equally into 
 diazo-benzene, _p-diazo-toluene, aniline, and jp- 
 toluidine. When only 1 mol. of HCl is present 
 these resolution products will recombine to form 
 one or more amido-azo- compounds according to 
 circumstances. 
 
 Alkalis, even in boiling aqueous or alcoholic 
 solution, usually have no action upon diazo- 
 
 Yoi,. I. 
 
 amides. The H of the NH group of the primary 
 diazo-amides appears to have slightly acid pro- 
 perties, and by introduction of NO^ groups into 
 the nuclei the diazo-amide becomes sufficiently 
 acid to dissolve in aqueous alkalis and form 
 tolerably stable salts X"(N02).N2.NM'.Y(N02) 
 (Meldola a. Streatfeild, O. J. 1886, 624 ; 1887, 
 102, 434). 
 
 By the action of alkyl haloids upon the- 
 primary diazo-amidos dissolved in an alcoholic 
 solution of (1 mol. of) sodium ethylate secondary 
 diazo-amides are obtained (M. a. S. ; Friswell a. 
 Green, B. 19, 2034 ; O. J. 1886, 746). When the 
 two aromatic nuclei are the same the secondary 
 diazo-amides obtained by alkylation are identical 
 with those got by direct combination of the 
 diazo- compounds with secondary amines. But 
 according to Meldola and Streatfeild (C J. 1887, 
 434) the compound obtained by ethylating 
 the unsymmetrical m-nitro-diazo-benzene-p- 
 nitranilide [3:1] 0,H4{NOJ.N3H.C8H4(N02) [1:4] 
 (which is obtained either from TO-nitro-diazo- 
 benzene and ^'-nitraniline, or from ^-nitro- 
 diazo-benzene and m-nitraniline) is different 
 from either of the two ethyl-derivatives 
 [3:1] C„Hj(N02).N,.NEt.C„H,(N02) [1:4] and 
 [4:1] C„Hj(N02).N2.NEt.CjHj(N02) [1:3], obtained 
 by combining to- and_p-nitro-diazo-benzene with 
 ethyl-p- and to- nitranilines respectively. The tv.o 
 latter ethyl derivatives are split up by acids into 
 TO-nitro-diazo-benzene and ethyl-^J-nitraniline, 
 and j)-nitro-diazo-benzene and ethyl-TO-nitranil- 
 ine respectively ; but the former ethyl derivative 
 (obtained by ethylation) yields both diazo-com- 
 pounds and both ethyl-nitranilines in about 
 equal amounts. 
 
 Constitution of diazo-amides. — Although a 
 considerable amount of work has been done on 
 this subject, the matter is still far from settled. 
 The formula X.N — N.Y is disproved by the 
 
 resolution of the alkyl derivatives into diazo- 
 compound and alkylated amine, since the latter 
 could not be obtained fov m a compound of that 
 structure (Friswell a. Green, C. J. 1886, 746, and 
 B. 19, 2034). The formula X.N.NHY does not 
 
 N 
 appear to have much probability, since one- 
 would expect a body of the constitution 
 CjHj.N.NHCjHj to give on reduction NH3 andt 
 
 N 
 hydrazobenzene ; these bodies, however, are not 
 formed from diazo-benzene-anilide, even by 
 adding sodium to its boiling alcoholic solution 
 (F. a. G.). Neither the latter formula nor that 
 usually assumed X.N:N.NHY is capable of ex- 
 plaining the existence of more than two isomeric 
 alkyl derivatives. 
 
 For further references concerning the diazo- 
 amides see Bayer a. Jager, B. 8, 148, 893; 
 Sarauw, B. 14, 2442 ; 15, 42 ; Nolting a. Bau- 
 maun, B. 18, 1147; Staedel a. Bauer, B. 19, 
 1952; WaUach, 4. 235, 233; Bernthsen a. Goske, 
 B. 20, 926. 
 
 Imides. — Obtained by the action of NH, 
 upon the per-bromides : 
 
 X.N2Br,-^NH3 = X.N< ll-hSHBr (Griess, A, 
 
 \n 
 
 137, 65 ; B. 18, 963). They are also formed by 
 
402 
 
 DIAZO- COMPOUNDS. 
 
 the decomposition of 
 
 X 
 
 •-a: 
 
 NO 
 
 = X.N< ||+H,0 
 
 nitroso-hydrazines : 
 (Fischer, A. 190, 
 
 
 92, 96). They are usually yellowish oily liquids, 
 insoluble in water, exploding when heated. 
 When heated with cone. HCl they are converted 
 into ohloro-amido- compounds : HX".N3 + HCl = 
 X"C1(NH2) + Nj. Diazo-benzene-imide heated 
 ■with H2SO4 diluted with an equal volume of 
 water is converted into ji-amido-phenol : 
 C„H5.N3 + H,0 = C,Hj(0H)NH2 + N2 (Griess, B. 
 19, 313; Fischer, A. 190, 67; 282, 236; 
 Silbersteiu, /. pr, [2] 27, 116). Diazo-benzoio 
 aeid reacts with phenyl-hydrazine, forming the 
 imides of diazo-benzoic acid and of diazo-ben- 
 eene together with amido-benzoio acid and aui- 
 
 /CO, 
 line, thus : 2C,H,< | + 2G„H5NH.NHj = 
 
 C.H,(CO,H).N<^ + C,H,.N<§ + 
 
 C5H,(NH,)C0aH + CsH5.NH2. This equation is 
 general (Griess, B. 20, 1528). 
 
 Diazo - compounds derived from 
 o-amido-azo- compounds. — Although the so- 
 called o-amido-azo- compounds probably do not 
 contain an NH, group, but are hydrazimido- 
 
 NTT NH 
 
 bodies X'— N<:SS:>Y" or | 
 
 \NH/ X'-NH.N 
 
 they are, nevertheless, slowly attacked by nitrous 
 (tcid, with production of diazo- compounds. The 
 only member of this class of diazo- compounds 
 at present examined is that obtained by diazo- 
 tising o-amido-azo-toluene. In some of its 
 Teactions it behaves like an ordinary diazo- 
 compound, in others quite differently. On 
 heating with water or alcohol it is decomposed 
 with evolution of nitrogen. By zinc-dust and 
 alcohol it is converted into »n-^-azotoluene and 
 Nj. It is not reduced by SnCLj or SO^ to a 
 •hydrazine, but gives a stable compound C,4H,jNj 
 which probably has the constitution 
 
 N— NH 
 C8H,(CHj)<' I I This body is re- 
 
 ^-N.C,H,(CH3). 
 converted by bromine into the per-bromide of 
 the original diazo-compound. The diazo-imide 
 loses nitrogen on heating, and yields tolyl- 
 
 y^\ 
 
 azimido-toluene CsH5(CH3)< | >N.CjH4(CHs) 
 
 identical with that obtained by oxidation of 
 o-amido-azo-toluene (tolyl-hydrazimido-toluene). 
 Hence the constitution of this peculiar diazo- 
 compound is probably 
 
 .N— N.OH 
 C„H3(CH3)<; I I (Zincke a. Law- 
 
 \N-N.C,H,(CH3) 
 «)n, B. 19, 1452 ; 20, 1176). 
 
 TB. Fatty diazo- compounds X' 
 
 '<: 
 
 As 
 
 "ailready stated, the fatty diazo- compounds con- 
 tain a molecule of water leas than the aromatic 
 diazo-hydrates. Their discovery is quite recent, 
 and is due to Curtius. At present only a few 
 members of the group are known ; these are 
 obtained by the action of NaNO, upon the 
 hydrochlorides of amido-f atty-ethers X"'Hj.COjK, 
 
 and hence have the constitution X"'(N.JC()jR- 
 They are unstable oily bodies, which exhibit 
 the following reactions : — 1. By boiling with 
 water or dilute acids, they are usually con- 
 verted into oxy-ethers, e.g. CH2(0H)C0jEt, 
 with evolution of nitrogen; however, diazo- 
 
 C(N2).C02Bt 
 succinic ether I by this treatment 
 
 CHj.C0j,Et, 
 gives fumaric ether. — 2. With alcohols they 
 yield alkyl-oxy-ethers, e.g. CH2(0Et).C02Et.— 
 3. With organic acids they yield alkoyl-oxy- 
 ethers, e.g'. CH2(OAc).C02Et.— 4. With aldehydes 
 they yield alkoyl-ethers, e.g. CHjAc.COaEt. — 5. 
 With zinc-dust and acetic acid, they are reduced 
 first to hydrazines, and then to the original 
 amido-ethers. — 6. Iodine in ethereal solution con- 
 verts them into di-iodo-ethers, e.g. CHIj.COaEt ;, 
 bromine and chlorine act similarly. — 7. By long 
 boiling with aromatic hydrocarbons, nitrogen ia 
 evolved, and condensation-products are formed. — 
 8. By treatment with cone, halogen acids they 
 yield haloid ethers, e.g. CH^Cl.COjEt.— 9. By 
 treatment of the diazo-ethers with NHj they are 
 converted into the corresponding amides, e.g. 
 CH(N2).CO.NH2, whose reactions are similar to 
 those of the ethers. The free diazo-acids, e.g. 
 CHINjj.COjH, and their salts, have not yet been 
 isolated, on account of their instability (Curtius, 
 B. 17, 953; B. 18, 1283; Buchner a. Curtius, 
 B. 18, 2371 ; 19, 850 ; Curtius a. Koch, B, 
 18, 1293 ; 19, 2460). A. G. G. 
 
 DESCRIPTION OP DIAZO- COMPOUNDS. 
 
 A large number of diazo- compounds are 
 mentioned under the amido- compounds from 
 which they are formed. 
 
 Pseudo-diazo-aeetamide CjHjNsO,. Formed, 
 together with diazoacetamide, by prolonged 
 action of strong aqueous NH, in the cold upon 
 the methyl ether of diazoacetic acid CHNj.COjMe 
 (Curtius, B. 18, 1287). Fine crystalline yellow 
 powder, consisting of microscopic quadratic 
 plates. SI. sol. cold water, dilute HCl, and 
 acetic acid. Insol. alcohol, ether, and benzene. 
 Dibasic acid. On warming with water it evolves 
 nitrogen. Aqueous alkalis evolve nitrogen and 
 ammonia. It gives a green colouration with 
 Fehling's solution ; on boiling a black pp. is 
 formed. Silver and mercury salts are reduced 
 on boiling. 
 
 Salts. — A"(NH4)2: small yellow tables; si. 
 sol. cold water [c. 155°]. — A"Ag2 IJaq : yellow 
 microcrystalline pp., v. si. sol. water. Ex- 
 plodes on heating. — A'Hg : yellow pp. — A"Cu'' : 
 sparingly soluble reddish -brown pp. — A"Pb: 
 yeUow pp. 
 
 Diazo-acetic acid CHNj.COjH. The free 
 acid and its salts have not been isolated on 
 account of their instability. The alkaline salts 
 are obtained in solution by treating the methyl 
 ether with cold aqueous alkalis. 
 
 Methyl ether MeA'. (129°) at 721 mm. 
 S.G. 2i 1-139. 
 
 Ethyl ether MA'. [-24°]. (144°) at 721 
 mm. S.G. 22 1-078. Formed by the action of 
 NaNOjOn a concentrated solution of the hydro* 
 chloride of amido-aoetio ether. Yellow oil. V. si. 
 sol. water ; miscible with alcohol, ether, "Benzene, 
 and light petroleum. Explodes when corio. 
 
DIAZO- COMPOUNDS. 
 
 403 
 
 H2SO4 is poured upon it. Reactions. — 1. Boil- 
 ing water gives glycoUio ether, nitrogen, and 
 alcohol.— 2.BoilingaZco;ioigivesCH2(OEt).C02Et 
 and nitrogen. — 3. Benzoic acid gives rise to 
 CH2(0Bz).C02Et.— 4. Eeduces AgNOj in cold 
 aqueous solution. — 5. Eeduces hot Fehling's 
 solution. — 6." Zinc-diist and acetic acid form an 
 unstable hydrazo- derivative NHj.NHOHj.COjEt, 
 which is further reduced to ammonia and 
 NH2.CH2.C02Et. The hydrazo- derivative re- 
 duces cold Fehling's solution. — 7. Combines 
 with aldehydes, thus: Ph.CHO + CHN^.COjEt = 
 Ph.CO.CH2.C02Et + Nj.— 8. Changes on stand- 
 ingiuto ' azin-suocinio ' ether, OBHiNjOjEtj [245°]. 
 
 9. Boiling aniline produces NPhH.CHj.COjEt. — 
 
 10. Cono. HCl gives CH2Cl.C0,Et.— 11. Hotoono. 
 KOH forms a crystalline pseudo-diazo-salt 
 whence boiling dilute HjSOj liberates hydrazine, 
 NoHj (Curtius, B. 20, 1632). -12. Boihng aro- 
 matic hydrocarbons produce condensation pro- 
 ducts ; thus benzene gives C,H,CO,Et (Buohner 
 a. Curtius, B. 18, 2371). 
 
 Iso-amyl-ether CsH^A'. (160°) at 720 mm. 
 
 Amide CHN^-CONHj [114°]; yellow tables 
 or prisms ; v. sol. cold water or alcohol. Formed 
 by the action of strong aqueous NH3 upon the 
 methyl-ether. The aqueous solution decom- 
 poses on boiling with evolution of nitrogen and 
 formation of glyooUamide. By treatment in 
 alcoholic solution with iodine it is converted into 
 di-iodo-acetamide CHIj.CONH^ with evolution 
 of nitrogen. It gives a blood-red colouration 
 with AgNOj, and in a few moments a reduction 
 to metallic silver. It also reduces Hg(N0s)2 
 and Cu(0Ac)2. With Fehling's solution it pro- 
 duces a red colouration, which becomes green on 
 boiUng (Curtius, B. 17, 953 ; 18, 1283). 
 
 Biazo-amido-benzolc acid 
 (3)_ /CO.O(i) 
 
 ,)\ I . Obtained by adding 
 
 ■ \ N:N (6) 
 
 sodium nitrite to a solution of (6:3:l)-p-di- 
 amido-benzoio acid containing barely sufficient 
 HCl to dissolve it. Long slender needles, or 
 four-sided plates. Yellow colour. Bitter taste. 
 V. sol. hot water, si. sol. hot alcohol, insol. 
 ether. Has no acid properties, but is a weak 
 base. When dry it explodes on heating. It is 
 decomposed by long boiling with water. It com- 
 bines with amines and phenols to form azo- 
 compounds. 
 
 Salts. — BjHCl: white six-sided plates 
 
 B.H^CljPtClj : sparingly soluble small yellow 
 trimetrio plates. —BaAuClj.HCl : yellow insolu- 
 ble needles (Griess, B. 17, 603). 
 
 ^j-Diazo-aniline salts are formed by diazo- 
 tising salts of p-phenylene-diamine (Griess, JS. 
 17, 607).— CjHj(NHj)N201HClAujCl5 is an in- 
 soluble pp. 
 
 /^ 
 
 m-Siazo-aniline imide C.H4(NH2).NC || 
 
 m-AnUdo-diazo-bemene imide. Yellowish oil. 
 Volatile with steam. Easily soluble in alcohol 
 and ether. 
 
 Preparation. — ?re-Amido-phenyl-oxamio acid 
 CjHj(NH2).NH.C202.0His diazotised and conver- 
 ted into the tribromide C,H,(N2Br3).NH.C202.0H. 
 By treatment with NH, this yields the imide 
 C|,Hj(N3).NH.C202.0H, which on boiling with 
 aqueous KOH splits off the oxalyl group with 
 
 C,H3(NH2)< 
 
 production of w-diazo-aniline imide. On diazo- 
 tisation it gives a diazo- compound which com- 
 bines with phenols and amines to form azo- 
 dyestuffs. Decomposes explosively on heating. 
 
 Salts.— B'HOl: white soluble trimetric 
 plates. — B'jHjCljPtCl, : yellow needles (Griess, 
 B. 18, 963). 
 
 m-Siazo-aniline plperidide. 
 
 Acetyl derivative 
 C„H,(NHAo).N2.NC5H,„. [101°]. From acetyl- 
 m-tolylene-diamine hydrochloride by diazotisa- 
 tion and treatment with piperidine (WaUaoh, A. 
 235, 266). 
 
 (ci)-I)iazo-anthraquinone nitrate 
 CnHjOj.N.^NOj. Formed by passing nitrous acid 
 gas into a solution of (a)-amido-anthraquinone 
 in dry ether (Bottger a. Petersen, A. 166, 150). 
 Powder, m. sol. water, v. sol. alcohol, insol. 
 ether. When heated with water it gives Nj and 
 m-oxy-anthraquinone. 
 
 Diazo-benzene. References : Griess, Tr. 1864, 
 iii. 667 ; A. 113, 201 ; 137, 39. 
 
 Hydroxide Ph.N2-0H(?). On addingaoetio 
 acid to an aqueous solution of Ph.N^.OK a thick 
 yellow oil is ppd. ; this may be diazo-benzene 
 hydroxide. It is very unstable. 
 
 Salts. — Ph.Nj.OK. A crystalline substance 
 obtained by adding excess of cone, aqueous KOH 
 to a saturated solution of diazo-benzene nitrate, 
 and evaporating at 100°. Detonates feebly at 
 130°. V. sol. water and alcohol, insol. ether. — 
 Ph.Nj.OAg : obtained as a greyish-white pp. on 
 adding AgNOj to an aqueous solution of the 
 preceding ; explodes when heated. — (Ph.N^. 0)2Hg : 
 white pp. got by adding HgCl^ to the potassium 
 salt (Griess, A. 137, 57). 
 
 Jfiiraie. — Ph.N2.NO3. S.G.1-37. H.F. 
 -47,400 (Berthelot a. Vieille, O. R. 92, 1074). 
 Prepared by passing nitrous fumes at 0° into 
 an aqueous solution of aniline nitrate contain- 
 ing undissolved aniline nitrate in suspension; 
 ppd. by adding alcohol and ether. Needles; 
 V. e. sol. water, m. sol. alcohol, insol. ether and 
 benzene. Stable in dry air in the dark, but 
 decomposed in moist air. Explodes at 90° 
 forming CO, CH^, N, HON, CH^, and C. The 
 decomposition may be roughly represented thus : 
 C3H5.N2.NO3 = 3C0 + 30 + 5H -H 3N. 
 
 Reactions. — 1. Barium carbonate added to 
 its aqueous solution produces Ph.N2.CjH4.OH and 
 CisHhNjO [131°]. This ' benzene-di-azo-phenol ' 
 is perhaps CsHs.N2.C5H3(OH).N2.C,H5 for it 
 may be reduced by HI to di-amido-phenol 
 (P. F. Franklaud, O. J. 37, 751). It is soluble in 
 NaOHAq. — 2. Aqueous NaOH, added to neutral- 
 isation, gives the ' benzene-di-azo-phenol ' and a 
 brown substance, C3|,H23N50, insol. NaOHAq. — 
 3. Aqueous ammonia produces diazo-benzene- 
 aniHde and two amorphous brown substances, 
 C,bH24N20 and C,2H,3N50. The latter is very 
 explosive and is decomposed by boiling HCl into 
 phenol, aniline, and Nj. — 4. Boiling dilute HNO, 
 (1 mol.) forms 0- and p- nitro-phenol (Nolting a. 
 Wnd, B. 18, 1338).— 5. Aqueous K^FeCys forms 
 a compound CuHhNj, [150°] (Griess, B. 9, 132). 
 6.PotassicferricyanzdegiveB{C^fT^2)3(H^FeCjg)2. 
 
 7. Sodium, nitroprusside gives the compound 
 CBH,N2H2FeOy5(NO)aq (Griess, B. 12, 2120).— 
 
 8. Nitro-henzyl cyardde and alcoholic KOH give 
 a pp. of O^H^N^Oj [202°] (Perkin, O.J. 43, 111). 
 
 Chloride, — ^Ph.Na.Cl. Formed in solution 
 
 D d2 
 
404 
 
 DIAZO- COMPOUNDS. 
 
 by diazotising aniline hydrochloride. Oomiina- 
 tioJis. — (CjHs.Ns.CljjSnClj : white plates, sol. 
 water, v. si. sol. alcohol and ether (Griess, B. 18, 
 965).— (PhN^C^jPtCl, : yellow prisms, v. si. sol. 
 water, insol. alcohol and ether. — PhN^ClAuCl,, : 
 golden plates, insol. water, m. sol. warm alcohol. 
 
 Bromide. — Ph-Nj-Br. Formed by adding 
 bromine to an ethereal solution of diazo-benzene 
 anilide, or by washing the perbromide for a long 
 time with ether. Pearly plates, v. e. sol. water, 
 insol. ether. 
 
 Perbromide. — Ph.Nj,.Br3. Formed by 
 adding bromine dissolved in HCLiq to an 
 aqueous solution of a diazobenzene salt. Large 
 yeUow plates, insol. water and ether, m. sol. cold 
 alcohol. Gives bromo-benzene when distilled 
 with Na^COs or when heated with alcohol. 
 
 Sulphate.— FKia,. SO ^K. Ppd. by adding 
 alcohol (3 vols.) and ether to a solution of 
 diazobenzene nitrate mixed with an equivalent 
 quantity of H^SOj. Prisms, v. e. sol. water, 
 V. si. sol. alcohol, insol. ether. Explodes at 100°. 
 
 Z)ic2/o?iide.— CgHsN, or CsHs.N^.CN.HCN. 
 [69°]. Formed by the action of a diazo-benzene 
 salt on a solution of KCN. Eeadily decomposes 
 (Gabriel, B. 12, 1637). 
 
 Picrate. — Ph.Nj.O.OjH^fNOj),. Yellow 
 needles, obtained by mixing solutions of diazo- 
 benzene nitrate and sodium picrate. Very ex- 
 plosive (Baeyer a. Jager, B. 8, 984). 
 
 Sulphite. — The potassium salt, 
 CjHs.Nj.SOjK, called also potassium diazobenzene 
 sulphonate is ppd. by adding KOH to a mixture 
 of diazobenzene nitrate and K^SOjAq (E. Fischer, 
 
 A. 190, 73). It forms explosive yellow crystals. 
 Bromioe in cone. HBrAq pps. diazobenzene 
 perbromide. 2ino-dust and acetic acid reduce 
 it to the corresponding hydrazo- compound. 
 
 Nitrite. — Converted by Cu^O into nitro-ben- 
 zene (Bandmeyer, B. 20, 1407). 
 
 Benzene - sulphinate Ph.N2.SO2.C5H5. 
 [76°]. From sodium benzene sulphinate and 
 diazobenzene nitrate (Konigs, B. 10, 1532). 
 Orange tables (from alcohol) ; insol. cold water, 
 V. sol. alcohol and ether. 
 
 OT-Tetr-azo-benzene CsHj(N2.0H)2 [1:3]. 
 Formed by the action of a large excess of 
 nitrous acid upon ?re-phenylene-diamine in pre- 
 sence of a large excess of HCl. It combines 
 with 2 mols. of an amine or phenol. 
 
 Salts. — C,H,(N2Cl)2PtCl^: small yellow 
 plates; nearly insoluble in cold water and 
 alcohol ; heated with dry NajCOj it yields di- 
 chloro-benzene. — C5H4(N2Cl)2Au2Cl8 : pp. of 
 yellow microscopic needles, explosive (Griess, 
 
 B. 19, 317). 
 
 p-Tetr-azo-benzene C8H4(N2.0H)2 [1:4]. 
 Formed by the action of an excess of nitrous 
 acid upon ^-phenylene-diamine in presence of 
 a large excess of acid. — CsH4(N2Cl)2PtCl4 : yellow 
 crystalline explosive pp. ; by heating with dry 
 Na^COj it yields ^'-di-chloro-benzene (Griess, 
 B. 19, 319). 
 
 Siazo-benzene-m-amido-benzoic acid 
 C5H-.N2.NH.C|iH.,C02H. Formed by mixing so- 
 lutions of diazo-benzene nitrate and ni-amido- 
 benzoic acid (Griess, A. 137, 62). Small yellow 
 plates (from ether). SI. sol. alcohol, v. e. sol. 
 ether.— C,3H„N302n2PtCl„. 
 
 Ethyl ether. — EtA': yellow crystals, v. e. 
 Ml. alcohol and ether.— CuHisNjOaH.rtCl,. 
 
 The above diazo-benzene-amido-benzoio acid 
 OBH5.N2.NH.CjH4.CO2H is identical with diazo- 
 benzoio-acid-anilide, CeH5.NH.N2.CsH4.CO2H 
 (Griess, B. 7, 1619; cf. Meldola, C. /. 51, 
 485). 
 
 Diazo-benzene-anllide Ph.Nj.NHPh. Diazo- 
 amidobenzene. Mol. w. 197. [96°]. 
 
 Formation. — By passing nitrous acid gas 
 into an alcohoho solution of aniline (Griess, A, 
 121, 258). 
 
 Preparation. — A solution of 18 pts. of sodium 
 nitrite is added to a solution 50 pts. aniline, 
 15 pts. cone. H2SO4 in about 1,500 pts. of water, 
 the temperature of the mixture is kept for 15 
 mins. between 25° and 30°, the pp. then filtered 
 off, washed, and dried ; the yield is 98 p.c. of 
 the theoretical (Staedel a. Bauer, B. 19, 1952). 
 
 Properties. — Golden plates (from alcohol), or 
 large flat prisms (from benzene). Explodes 
 between 150° and 200°. Insol. water, and dilute 
 acids, m. sol. cold alcohol, v. sol. hot alcohol, v. 
 sol. ether and benzene. 
 
 Reactions. — 1. Hot cone. HClAq splits it up 
 into phenol, nitrogen, and aniline ; cold HClAq 
 gives aniline and diazobenzene chloride, which, 
 if an excess (more than 1 mol.) of HCl is not 
 present, recombine forming benzene-azo-aniline 
 (g. v.). Unstable chlorides such as aniline 
 hydrochloride or ZuClj also effect the conver- 
 sion into benzene-azo-aniUne. — 2. Bromine in 
 HBrAq gives diazobenzene bromide and tribromo- 
 aniUne. — 3. The hydrogen atom of the NH-group 
 can be readily replaced by alkyl radicles by 
 treatment with alcoholic haloids, and sodium 
 ethylate. The alkylated diazobenzene-anilides 
 thus obtained are split up by acids into diazo- 
 benzene and the corresponding mono-alkyl-ani- 
 line. A proof is thus afforded of the unsym- 
 metrioal structure of the anilide, and since the 
 only other possible formula CjHj.N.NH.CjHs is 
 
 N 
 excluded by the fact that the body is not reduced 
 by alkaline reducing agents to hydrazobenzene 
 and NH3, the formula Ph.Nj.NHPh is probably 
 correct (FrisweU a. Green, O. /. 49, 746 ; B. 
 19, 2034).— 4. Phenol at 100° gives benzene-^- 
 azo-phenol. Besorcin and the naphthols act 
 similarly (Heumaim a. Oeconomides, B, 20, 
 372). 
 
 Salts. — Ph.Nj.NAgPh: orange needles. — 
 (Ph.N2.NHPhHCl)2PtCl4: unstable crystals. 
 
 Di-sulphonamide 
 C5H,(S02NHj).N2.NH.CeH4.S02NH2. [183°]. 
 
 Yellow needles. From C,H4(S02NH2)NH2, HNO, 
 and nitrous acid gas (Hybbeneth, A. 221, 206). 
 Cone. HCl converts it into CsHiOl.SOjNH,, 
 CeH4(NH2)S02NH2 and N2. 
 
 Siazo-benzene-azo-beuzene-p-sulphonic acid 
 C5H4(S03)— N2— C,H4— Nj. Small yeUowneedlea. 
 
 Nearly insoluble in most solvents. Formed by 
 long action of nitrous acid on amido-benzene- 
 azo-benzene-sulphonic acid. Boiled with water 
 it gives oxy-benzene-azo-benzene-sulphonic acid; 
 with alcohol it gives benzene-azo-benzene-sul- 
 phonic acid (Griess, B. 15, 2186). 
 
 Siazo-benzene-benzyl-anilide 
 0jH5.N2.N(C,H,).C,H5. Benzyl ■ diazo - amido- 
 benzene. [81°]. Yellow needles. V. sol. acetone, 
 m. sol. alcohol, insol. water. 
 
 Preparation. — 30 k. of sodium are dissolved 
 
DIAZO- COMPOUNDS. 
 
 405 
 
 in 300 CO. of alcohol, a hot solution of 200 g. of 
 diazo-benzene-anilide in 500 o.o. of absol. alcohol 
 added, and the mixture heated with 140 g. of 
 benzyl chloride for 1 or 2 hours ; the product ia 
 precipitated by water and recrystallised from 
 alcohol ; yield, 200 g. 
 
 BeacUons. — On heating it decomposes ex- 
 plosively. By excess of Hpl it is resolved into 
 diazobenzene and benzyl-aniline (FriswelL a. 
 Green, B. 19, 2036). 
 
 Siazo-benzene-broma-anilide v. Diazo-bbomo- 
 
 BKNZENE-ANILIDE. 
 
 Diazo - benzene-^ -chloro- anilide. Formed 
 from ^-chloro-diazo-benzene and aniline. By 
 warming with phenol it gives oxy-azo-benzeue 
 and p chloraniline (Heumann a. Oeconomides, 
 B. 20, 908). 
 
 Siazo - benzene - ethylamide Fh.N,.NHEt. 
 From diazo-benzene nitrate and ethylamine. 
 Picrate C,H„N30,H,(NOj)30H. 
 
 Diazo-benzene othyl-hydrazidePh.Nj.NjHjEt. 
 From diazo-benzene nitrate and ethyl hydrazine 
 (E. Fischer, A. 190, 306). Very unstable oil. 
 Beduced in alcoholic solution by zinc-dust and 
 acetic acid to ethyl-hydrazine and phenyl- 
 hydrazine. 
 
 Biazo-benzene-imide CjHyNj. Tri-azo-hen- 
 zene. 
 
 Formation. — 1. Diazobenzene perbromide is 
 treated with aqueous NH, and the product 
 distilled with steam, dried over CaClj, and 
 rectified under diminished pressure (Griess, Tr. 
 1864, iii. 700). — 2. By warming nitroso-phenyl- 
 hydrazme with dilute KOH (Fischer, 4. 190, 92).— 
 3. By adding NajCOj to a mixture of diazo- 
 benzene sulphate and hydroxylamine. 
 
 Properties. — A heavy oil; insol. water, m. 
 Bol. alcohol and ether. Detonates when distilled 
 under atmospheric pressure. Not attacked by 
 KOH. 
 
 Beaciiojis. — 1. Eeduced in alcoholic solution 
 by Zn and H^SOj to aniline and NHj. — 2. By 
 heating with strong HCl it is converted into a 
 mixture of o and^-chloro-aniline: 
 
 OjH5.Na -F 2HC1 = CA-NHj + 01, + Nj = 
 CsH^CLNHj-hHCl + Nj. 
 3. By heating with H^SO, diluted with an equal 
 volume of water it is converted into ^-amido- 
 phenol : GsH^.N, -i- H^O = CjHs.NHj + -t- Nj = 
 CjHj(OH)NH2-fN2 (Griess, B. 19, 313). 
 
 Diazo - benzene - dimethylamide Fh.Nj.NMe^. 
 From diazobenzene nitrate and aqueous di- 
 methylamine (Baeyer a. Jager, B. 8, 893). 
 Yellowish oil; explodes when large quantities 
 are heated ; volatile with steam ; insol. water 
 and alkalis, v. e. sol. alcohol, ether, and acids. 
 Decomposed by acids into diazobenzene salts 
 and dimethylamine. Aniline hydrochloride 
 forms diazo-benzene-anilide and NMejH hydro- 
 chloride. Picrate Ph.Nj.NMe20»H2(NO2)3(OH) : 
 yellow needles. 
 
 Siazo-benzene-methyl-anilide 
 CjH5.N2.NMeOjH5. Methyl-diazo-amido-bensene. 
 Heavy deep-yellow oil. Not volatile with steam. 
 Misoible with. alcohol, insol. water. 
 
 PreparaUon. — 30 g. of sodium are dissolved 
 in 300 c.c. of absolute alcohol and mixed with 
 a hot solution of 200 g. diazobenzene-aniUde in 
 600 c.c. of absolute alcohol ; when nearly cold 
 170 g. of methyl iodide are added ; a vigorous 
 reaction soon sets in and is completed by 1 or 3 
 
 hours' cohobation; half the alcohol is then 
 distilled oft and the residue precipitated by 
 water, the oil separated and dried over CaClj ; 
 the yield is 200 grms. 
 
 Beactions. — On heating it decomposes ex- 
 plosively. By excess of HCl it is resolved into 
 diazobenzene chloride and methylaniliue 
 (Friswell a. Green, O. J. 49, 748 ; B. 19, 2035). 
 
 Diazo-benzene phosphonic acid nitrate (?). 
 N03.N2.CsHj.PO(OH),3aq. [188°]. S. 58 at 18° ; 
 59 at 80°. Formed by passing nitrous acid gas 
 into a boiling solution of amido-benzene phos- 
 phonic acid in HNOjAq (Michaelis a. Benzinger, 
 A. 188, 288). Long white prisms (from HNOjAq). 
 Explodes above 190°. V. sol. alcohol, si. sol. 
 ether. Not affected by boiling water, even in 
 presence of S2SO4; sUghtly decomposed by 
 boiling NaOHAq. 
 
 Salt s.— Na.,A" 2aq.— KjA" aq.— BaA" 3aq.— 
 Ag2A".-PbA". 
 
 Diazo-benzene-piperidide PhN^NCsHu. [43°] 
 (Baeyer a. Jager, B. 8, 898 ; WaUach, A. 235, 
 241). 
 
 Preparation. — Aniline (lOOg.) is dissolved in 
 aqueous HCl (210 0.0.) and the solution at 0° is 
 diazotised with NaNOj (74 g.) and then poured 
 into a dilute aqueous solution of piperidine 
 (100 g.) containing KOH (60 g.) cooled with ice. 
 
 Properties. — Crystals (from ether or petro- 
 leum-ether). 
 
 Beactions. — 1. HCl passed into an ethereal 
 solution gives diazobenzene chloride and piperi- 
 dine hydrochloride. Aqueous HCl acts simi- 
 larly. — 2. Warm HCl forms N^, ohlorobenzene 
 and piperidine hydrochloride ; phenol is a by- 
 product. HBr and HI act similarly.— 3. Hot 
 dilute H^jSOj forms phenol. — 4. An ethereal 
 solution of picric acid gives diazo-benzene 
 picrate. 
 
 o-Diazo-benzene sulphonic acid 
 
 Cii'Bii<^ J- '^Yellowish tables, obtained by pass. 
 
 ing nitrous acid gas into water containing o-amido- 
 benzene sulphonic acid in suspension (Berndsen 
 a. Limprioht, A. 177, 101). 
 
 m-Diazo-benzene sulphonic acid 
 
 C|jH4<^ jj '^. Prepared by passing nitrous acid 
 
 gas into a concentrated solution of TO-amido- 
 benzene sulphonic acid, containing the free acid 
 in suspension (Meyer a. Stiiber, A. 165, 165 ; 
 Berndsen, A. 177, 88). Small columns (from 
 water). Very explosive when dry. V. sol. water 
 and decomposed by it at 60°. Boiling HBr gives 
 m-bromo-benzene sulphonic acid. Boiling alco- 
 hol has no action. 
 
 m-diazo-bemene sulphamide nitrate 
 N03.N,.CsH,.S0j.NHj. From C,H4(NH,JS0,NHj 
 by mixing with HNO, and passing in nitrous 
 acid gas (Hybbeneth, A. 221, 205). Minute 
 orange needles. 
 
 p-Diazo-benzene sulphonic acid 
 
 SO N. 
 
 CbH4<^X, 'j>. Formed by diazotising p-amido- 
 
 benzene sulphonic acid (Schmitt, A. 120, 144 ; 
 Fischer, A. 190, 76). Small needles (from water). 
 Insol. cold water, v. sol. water at 60°. Boiling 
 water forms phenol ^-sulphonic acid. An alka- 
 line solution gives a red colour with aldehydes 
 (Petri, B. 8, 291; Zahn, B. 17, Eef. 290), but 
 this is not a characteristic test for aldehydes, as 
 
406 
 
 DIAZO- COMPOUNDS. 
 
 it is given also by many other bodies {E. Fisober, 
 e. 16, 657; O. Loew, J.pr. [2] 31, 136). 
 
 Beactions. — 1. BoiUng alcohol forms ben- 
 zene sulpbonio acid.— 2. PCI5 at 100° bas no 
 action (Laar, J.pr. [2] 20, 263). 
 
 Ethyl mercaptide CsH^(S03H).N2.SEt. 
 Formed by oombining^-diazo-benzene-sulphonio 
 acid witb an alisaline solution of etbyl meroaptan. 
 The sodium salt (A'Na) forms yeUow glistening 
 needles, v. sol. water. It is very unstable, readily 
 decomposing with evolution of nitrogen. When 
 boiled with alcohol it yields etbyl-phenyl-sul- 
 pbide p-sulphonio acid C2H..S.0.H,(S0,H) 
 (Stadler, B. 17, 2075). 
 
 Methyl anilide CpHj(S03H).N,.NMeC5H,. 
 Formed by combination of ^'-diazo-benzene- 
 sulphonio acid with mono-methyl-aniline in 
 nearly neutral solution. The sodium-salt (NaA') 
 forms large colourless plates, v. sol. water, from 
 which it is precipitated in white felted needles 
 by alkali; nearly insol. alcohol. Not affected 
 by boiling with dilute caustic soda. Acids 
 resolve it into its constituents p-diazo-benzene- 
 Bulphonic acid and methyl-aniline, which when 
 the acid is dilute recombine to form methyl- 
 amido- benzene -azo- benzene sulpbonio acid 
 C,H^(S03H).Nj.CsHj.NHMe (Bernthsen a. Goske, 
 B. 20, 926). 
 
 Piperidide 0,'H.,{SO,B.).-N^.-^G,K,„ (Wal- 
 laeh, A. 235, 270). From sulphanilic acid by 
 diazotisation and treatment with piperidine (1 
 mol.) and aqueous NaOH (1 mol.). Salt. — 
 NaA' : satiny plates. — AgA'. Stable in neutral or 
 alkaline solutions. 
 
 Imide C„H,(S03H).N<;|^ [1:4]. 
 
 Triazobenzene-p-sulphonic acid. Formed by 
 the action of phenyl-hydrazine upon diazoben- 
 zene-^i-sulphonio acid suspended in cold water; 
 diazobenzene-imide, sulphanilic acid, and ani- 
 line, are formed simultaneously : 
 
 20,H / I -f2C,H5NH.NH2 = 
 
 ■'\S03 
 
 C„H,(N,)S03H + CeH,N3 + C„H,(NH,)S03H + 
 CjHj.NHj. White deliquescent needles. V. s. 
 sol. alcohol and water. Salts. — BaA'2 2aq: 
 white six-sided plates, m. sol. hot water. 
 Phenyl-hydrazine salt CjHjN^H^A'aq: long 
 white glistening plates, m. sol. hot water and 
 alcohol, less in the cold, nearly insol. ether and 
 chloroform ; decomposed by alkalis, but not by 
 HCl even when boiling (Griess, B. 20, 1528). 
 Siazo-benzene disulphouic acid 
 
 CsH3(S03H)<|^j^''\. The salts are formed by 
 
 passing nitrous acid gas at 0° into a solution of 
 the acid salts of C3H3(NH2)(S03H)2 [1:3:4 ?]. The 
 free acid is unstable (Zander, A. 198, 24). — 
 KA'.— BaA'3 2aq. 
 
 Siazo-benzene disnlphonic acid 
 C,H3(SO,H)(S03N2)". Formed by diazotising 
 CaH3(NHj)(S03H)2 [1:3:5]. Slender needles ; v. 
 Bol. water and alcohol. Decomposed by NaOH 
 or BaCOj. The salts are formed by diazotising 
 salts of the amido-benzene disulphonic acid 
 (Heinzelmann, A. 188, 174 ; 190, 223).— ZA',.— 
 BaA'j 3aq.— PbA'j 3aq. 
 
 Siazo-benzene disulphonic acid 
 C,H3(S03H)(S03N2)". Formed by diazotising 
 C.H3(NH3)(S03H), [1:2:4]. 
 
 Salts. — NHjA'. - KA'. — CaA', 2aq. — 
 BaA'2 2aq. — PbA'jSaq (Heinzelmann a. Zander, 
 A. 198, 5). 
 
 Siazo-benzene ^-toluide is identical witb 
 diazo-toluene anilide (q, v.). 
 
 o-Siazo-beuzoic acid. 
 
 Nitrate NOs.Nj.C^H^.COjH. By diazotisa- 
 tion of o-amido-benzoic acid suspended in dilute 
 HNO3 (Griess, B. 9, 1653). Colourless tables or 
 prisms, v. e. sol. water, m. sol. alcohol. Explodes 
 when heated. Boiling water converts it into 
 salicylic acid. Bepeated solution in water and 
 ppn. with alcohol converts it into the so-called 
 semi-nitrate : 
 
 (CO^H.C^Hj/ I I \C,H3.COj,H)HN03(?). This 
 
 ^N — N^ 
 substance is also formed by passing nitrous acid 
 gas into an alcoholic solution of o-amido-benzoio 
 acid (Griess, A. 117, 39 ; Hand, A. 234, 146). 
 Perbromide 0,H5N202Br3. 
 Imide N3.05H,.C02H. Triazo-benzoicacid. 
 [145°]. From the perbromide and ammonia 
 (Griess, Z. [2] 3, 165). Long needles. M. sol. 
 boiling water. 
 
 m-Siazo-benzoic acid. 
 
 Sulphate SOjH.Nj.CjHj.COjH. Formed 
 by passing nitrous acid gas into a thin paste of 
 the sulphate of m-amido-benzoic acid ; ppd. by 
 alcohol and ether. Long white laminse, v. e. 
 sol. water; detonates when heated. Treatment 
 with dilute alcohol gives rises to a ' basio 
 sulphate' CjH^NjO^fHjSOj (?), or more pro- 
 bably iN,(C,H3C02H)2}H2SO,. 
 
 Nitrate N03.N2.C„H,.C02H (Griess, A. 
 120, 126). Its aqueous solution left in contact 
 with BaCOj forms carboxy-benzene-azo-oxy- 
 benzoio acid. With aqueous NajCOa it forms an 
 acid CjiHuN^O,. 
 
 Hydroxide HO.N^.CjHj.COjH. Unstable 
 yellow oil. 
 
 Chloride Cl.T^^.G^S.^.CO^B.. Combina- 
 tions.— {Gm^.GsH,.COJI]jetGlt:yeIlowpnsms.— 
 (ClN2.CsH,.C02H)AuCl3. This salt suspended in 
 alcohol and treated with HjS gives benzoic acid, 
 chloro-benzoic acid, and sulphydro-benzoio acid, 
 HS.OjHj.COjH (Griess, J.pr. [2] 1, 102). 
 
 Perbromide Br3N2.OBH4.CO2H. OUy pp. 
 Converted by boiling alcohol into ?ra-bromo- 
 benzoio acid (Griess, A. 135, 121; Cunze a. 
 Hubner, A. 135, 106). 
 
 Ethyl ether; nitrate. N03.N2.C8Hi.C02Et. 
 Formed by diazotising m-amido-benzoic ether 
 dissolved in nitric acid (Griess, A. 120, 127). — 
 Aurochloride (Cl.N2.C3H,.C02Et)Au01, : 
 
 golden prisms (from alcohol). 
 
 Amide; nitrate. NOa.Nj.CjH^.CONHj. 
 Formed by the action of nitrous acid gas ou a 
 solution of m-amido-benzamide in alcohol mixed 
 with ether (Griess, A. 120, 127). Needles. 
 Platinoohloride (Cl.N2.C3H,.C0NH2)2PtCl4. 
 
 Imide N3.CiiH4.CO2H. Triazobenzoic acid. 
 
 [160°]. From the perbromide and NH3 (Griess, 
 
 Z. 1867, 164). Thin lamiuie. Y. sol. alcohol 
 
 and ether, m. sol. boiling water. By heating 
 
 with HCl it is converted into two isomeric 
 
 chloro-amido-benzoio acids, (4, 3,1) and (2, 3,1): 
 
 N3.C3H4.C02H + 2HC1 = 
 
 HjN.C^H^.COjH + CI2 -F N, = 
 
 H2N.CBH3Cl.CO2H + HCl + N2 
 
 (Griess, B. 19, 315). Salt.— N3.C,H4.COaAg. 
 
DIAZO- COMPOUNDS. 
 
 407 
 
 Anilide v. Diazo-benzene-auxdo-benzoic 
 
 ICID. 
 
 Bromo-anilide v. Diazo-bbomobenzene-amido- 
 
 BENZOIC ACID. 
 
 Nitrilc. Nitrate N03.Nj.C„H,.CN. From 
 »»-amido-benzonitrile (Griess, B. 2, 370). 
 Explosive crystals ; m. sol. cold wivter. — 
 Perbromida BrjNu.CjHj.CN. Crystals. — 
 tmide N3.0sH,.0N. [57°]. Needles, y. si. sol. 
 water. 
 
 ^-Siazo-benzoio acid. 
 
 Nitrate NO3.N2.CjH4.COjH. Explosive 
 white prisms (Griess, J". 1864, 353). 
 
 Amide. Nitrate. N03.N,.C„H4.CONH2 
 (Griess, Z. 1866, 1). 
 
 Imide Nj.CuHj.CO^H. Xriazohensoic aoid. 
 [185°]. Thin lamina (Griess, Z. 1867, 164). 
 
 m-Diazo-benzoic-m-amido-benzoic acid 
 [3:1] COjH.0,Hj.N2.NH.C,H4.CO,H [1:3]. 
 Formed by passing nitrous aoid gas into an 
 alcoholic solution of m-amido-benzoio acid, or 
 by mixing aqueous solutions of m-amido-benzoio 
 acid and the nitrate of m-diazo-benzoic acid 
 (Griess, A. 117, 2; Z. 1864, 353). Orange 
 grains. Explodes at 180°. V. si. sol. water, 
 alcohol, and ether. Sol. alkalis and reppd. by 
 acids. Boiling HCl forms m-amido-benzoic acid 
 and TO-ohloro-benzoio aoid. Bromine water 
 gives bromo-, and tri-bromo-, benzoic acid. 
 Boiling water and iodine form iodo-oxy-benzoic 
 acid. Nitrous acid passed into a boiling aqueous 
 solution forms nitro-oxy-beuzoio acid ; nitrous 
 acid passed into a boiling alcoholic solution 
 forms benzoic acid. Fuming HNO3 gives tri- 
 nitro-oxy-benzoic acid. 
 
 Salts.— (NH,),A".—K,A".—Ag2A". 
 
 Methyl ether Me^A". [160°].Yellowneedles. 
 
 Ethyl ether m^A". [144°]. Golden needles. 
 
 ji-Biazo-benzoic-p-amido-benzoic acid 
 [4:1] C02H.C.H4.N3.NH.O„H,.CO,H[l:4]. Orange 
 powder, v. si. sol. boiling alcohol. Formed by 
 passing nitrous acid gas into an alcoholic solu- 
 tion of jp-amido-beuzoio acid (Beilstein a. Wil- 
 brand, A. 128, 269). 
 
 m-Diazo-benzoic.^-amido-benzoic acid 
 [3:1] C0.,H.C,H,.N2.NH.C„H,.C02H [1:4]. From 
 the nitrate of m-diazo-benzoic acid and p-amido- 
 benzoic acid (Griess, /. 1864, 363). An isomeric 
 (?) acid is got from the nitrate of ^-diazo- 
 benzoic acid and m-amido-benzoic acid. 
 
 m-Diazo-bromo-benzene. 
 
 Perhromide CjHjBr.NjBrj (Wurster, A. 
 176, 173). 
 
 ^-Diazo-bromo-benzene. 
 
 Nitrate OjHjBr.Nj.NOj. Formed by pass- 
 ing nitrous acid gas into an aqueous solution of 
 y-bromo-aniline nitrate (Griess, Tr. 1864, iii. 
 695). Ppd. by alcohol and ether. 
 
 Hydroxide CjHjBr.Nj.OH : bright yellow 
 needles. Very explosive.— CjHjBr.Nj.OK. From the 
 nitrate and strong KOH ; gives the preceding body 
 when treated with acetic acid. — CjH^Br.NjOAg. 
 
 Bromide CjHjBr.NjBr: scales; v. sol. water, 
 m. sol. alcohol.insol. ether.— - (CsH4Br.N2Br)2PtBr4. 
 
 Perhromide CsHjBr.N^Brj : monoclinio 
 prisms (from alcohol), v. si. sol. ether, insol. 
 water. 
 
 Chloride C^^TcTSjul: from the bromide 
 tndmoist silver chloride.— (CeHjBr.NjC^AuCl,. — 
 (C,H,Br.N,Cl),PtClj. 
 
 Sulphate CjH^Br.Nj.SO.H: slender prisms. 
 
 Imide CsH,Br.Nj. Tria20-brofru>-bemen&. 
 [20°]. Insol. water, m. sol. alcohol, v. sol. ethei 
 and benzene. Reduced by Zn and H^SOj to 
 bromo-aniliue and NH3. 
 
 Cyanide C„H,Br.N^CNHCN.[128°]. From 
 p-diazo-bromo-benzene nitrate and aqueous KCH 
 (Gabriel, B. 12, 1638). 
 
 Anilide CjHiBr.Nj.NH.CjHs or, alterna- 
 tively CsHj.Na.NH.CjHiBr. Formed either from 
 diazo benzene nitrate and |)-bromo-aniline o» 
 from ^-diazo-bromo-benzene nitrate and aniline 
 (Griess, B. 7, 1618). Tellow plates ; v. e. sol, 
 ether, m. sol. alcohol.— (Ci^HioBrNsHC^^PtClj. 
 
 p- Bromo -anilide CjHjBr.Nj.NH.CuHjBr. 
 [145°]. Obtained from p - bromo - aniline. — 
 (C,2H3Br,N3)^,PtCl3. 
 
 Siazo-di-bromo-benzene. 
 
 Nitrate C^B.^Br^.'S^.NOa [2:4:1]. Obtainea 
 by passing nitrous aoid into an aqueous solution 
 of the nitrate of di-bromo-aniline (Griess, 2V. 
 1864, iii. 704). Needles or plates. 
 
 Platinochloride (OjHjBrj.NjCl) jPtCl, : 
 orange plates. 
 
 P e r 6 r om i<J c CjHaBr^.NjBrj : slender needles. 
 
 Imide Cs'H.^'Bi^.^,. [62°]: needles. 
 
 Di -bra mo -anilide 
 C„H3Br2.N2.NHC„H3Brj. [168°]. From (2,4,1)- 
 di-bromo-aniline. Golden needles, v. b1. soL 
 alcohol and ether. 
 
 Siazo-tri-bromo-benzene, 
 
 Nitrate C5HjBr3.N2.NOs [2:4:6:1]. Forme* 
 when a rapid current of nitrous acid gas is passed 
 into alcohol containing tri-bromo-aniline in sus- 
 pension together with excess of HNO3. As. 
 soon as everything is dissolved, ether ia added 
 and a bright yellow crystalline pp. of the diazo- 
 nitrate is formed (H. SUberstein, J. pr, [2] 27^ 
 102). 
 
 Prqperites.-Yellowtrimetricplates. Explodes 
 at 85°. Sol. water and HCl. V. si. sol. alcohol, 
 ether, and benzene. 
 
 Beactions. — 1. Boiled with alcohol it gives 
 tri-bromo-benzene, N^, HNO3 and aldehyde. — 
 
 2. Boiled with water, gives off no nitrogen but 
 forms undetermined compounds. — 3. Heated 
 with glacial acetic acid gives oS Nj and nitrous 
 fumes and leaves tri-bromo-benzene. — 4. Heated 
 with hensene (4 pts.) it decomposes at 45° forming 
 a diazo-di-bromo-phenol (q. v.), tetra-bromo- 
 benzene [98°], and nitrobenzene. — 5. Heated with 
 CHCI3 it gives diazo-di-bromo-phenol and tetra- 
 bromo-benzene.— 6. Heated with concentrated 
 HCl it forms crystals of iAiB perhromide of diaao- 
 tri-bromo - benzene chloride, CjHjBrsNjClBrj. 
 Probably chlorine, liberated in this reaction,, 
 turns out bromine from some of the tri-bromo- 
 compound, which bromine then unites with 
 the diazo-chloride. The perhromide explodes 
 at 100°, forming ohloro-tri-bromo-benzeue. — 
 
 7. With HBr it gives the bromide (q. v.).-- 
 
 8. With HI it gives tri-bromo-iodo-benzene. 
 
 Sulphate CjH^BrsN^.SOiH. 
 
 Properties. — Colourless prisms. SoL water, 
 si. sol. alcohol, insol. ether and benzene. 
 
 Beactions. — 1. Decomposed by osZco/ioZ intotri. 
 bromo-benzene, HjSOj and Nj.— 2. Boiled with 
 acidulated water it forms no tri-bromo-phenol. — 
 
 3. Heated with glacial acetic acid it forms tri- 
 bromo-benzene. — 4. Not affected by boiling hery- 
 zene. 
 
 Bromide C^H.^Br^NjEr. Small golden ni- 
 
108 
 
 DIAZO- COMPOUNDS. 
 
 metric tablets, got by adding dilute HBr to a 
 solution of the nitrate. Decomposed by sun- 
 light into Nj and CaHiBr^. SI. sol. water, insol. 
 alcohol and ether. Heated with glacial acetic 
 acid it gives unsymmetrical CjHjBrj. 
 
 Perbromide CjH^BrjNjBrj. jPormed by 
 adding cone. HBr to a solution of the nitrate, 
 C HjBrjNjNOs '. tte liquid is filtered from 
 C^HjBrjNjBr and evaporated to crystallisation. 
 It forms orange prisms and behaves very much 
 like CsH^BrsN^CIBrj (g. v.). 
 
 Ghloro -per bromide CBHjBrjNjCl.Brj. 
 Krom tri-bromo-diazo-benzene nitrate (q. v.) and 
 HCl. It explodes at 100° forming chloro-tri- 
 bromo-benzene. Beactions. — 1. With NHj gives 
 tri-bromo-diazo-benzene imide (q.v.). — 2. With 
 alcoholic dimethylaniline forms tri-bromo-beu- 
 zene-azo-dimethylaniliue CsHjBrj.Nj.CjH^NMej. 
 3. With alcoholic methyl-di-phenylamine it 
 forms tri-bromo-benzene-azo - methyl-di-phenyl- 
 amine OsHjBraNj.CjHjNMePh. — i.'With.mercuric 
 diphenyl it forms chloro-tri-bromo-benzene and 
 nitrogen (Silberstein, J.pr. [2] 27, 117). 
 
 Imide CiiS^rs-N,. [59°]. Formed by adding 
 dilute ammonia to CjHjBraNjClBr^. Colour- 
 less needles. May be distilled with steam. 
 Insol. water, sol. warm alcohol, ether, and CHOI.,. 
 Unlike diazo-benzene-imide, it is not reduced by 
 Zn and H-^SOj to NH, and tri-bromo-aniline 
 (Silberstein, J.pr. [2] 27, 116). 
 
 Anilide CoH^BrsK^NHPh. [104°]. From 
 alcoholic aniline (2 mols.) and CsH^rjNjNOj 
 (1 mol.). The pp. is crystallised from alcohol 
 (Silberstein, J.pr. [2] 27, 121). Yellow, glitter- 
 ing, triclinio prisms. Insol. water, sol. hot alco- 
 hol, ether, and benzene. Boiled with glacial acetic 
 acid it gives nitrogen and tri-bromo-aniline. 
 
 Tri-bromo- anilide 
 CjHjBrj.Nj.NH.CjHJBrj. Obtained by passing 
 NjO, slowly into a cold alcoholic solution of tri- 
 bromaniline. Some CjH^BrsNjNOj is formed at 
 the same time. The product is washed with 
 water and hot alcohol and crystallised from 
 benzene. The yield is bad (Silberstein, J. pr. 
 [2] 27, 120). Insol. water and alcohol, v. si. sol. 
 ether. V. sol. CHCI3 and benzene. Not attacked 
 by cold acids, but decomposed by boUing with 
 acids with evolution of Nj. 
 
 Diazo-p-bromo-benzene-amido-benzoic acid 
 C,H,Br.N2.NH.CBH4.C02H. Diazo-benzoic acid 
 p-bromo-anilide. From ;p-diazo-bromo-benzene 
 nitrate and m-amido-benzoio acid (Griess, J. 
 1866, 453). Clusters of needles. 
 
 Siazo-bromo-beuzene sulphonic acid 
 
 O^K^Bt^f^^y [4 f]. From the corresponding 
 
 bromo-amido-sulphonic acid (Borns, A. 187, 
 371). Small yellow needles, v. sol. water, m. 
 sol. alcohol ; explodes when struck or when 
 heated. Heated with alcohol, it gives 7»-bromo- 
 benzene sulphonic acid. Cone. HBr gives 
 CeH,Br2(S03H) [4:1:2]. 
 
 Siazo-bromo-benzene disulphonic acid 
 
 C.H^r(S03H)<S^°»>. 
 
 From C,H,(NHJ(S03H)2Br [1:4:6:2]. Minute 
 plates ; v. sol. water and alcohol. Does not 
 explode when struck (Zander, A. 193, 15).- 
 KA'Saq. 
 
 Siazo-di-bromo-benzene sulphonic acid 
 
 C„H^r.,<^^»>. From C„H2(NH,)Br,(S03H) 
 
 [1:2:6:4]. Yellowish scales; explodes above 
 100°. V. si. sol. cold water, v. sol. hot water 
 Boiling water gives di-bromo-phenol sulphonic 
 acid. Heated with alcohol it gives di-bromo- 
 benzene sulphonic acid. 
 
 Siazo - di - bromo-benzene-snlphonic-acid- di- 
 bromo-sulphanilid e 
 
 C.H^r,(S03H).N,.NH.C„H^r,(S03H). 
 [70°-80°]. From CeH,Br,(NH2)S0,H [2:4:1:5] 
 by warming with alcohol and KNO,. Needles 
 (from water). Insol. alcohol (Baessmann, A 
 191, 229). 
 
 Diazo-di-bromo-benzene-disulphonic acid 
 
 CsHBr2(S03H)<^^»^. From the nitro-ben- 
 
 zene disulphonio acid [1:3:5] ? whose chloride 
 melts at 96°, by reduction, bromination, and 
 diazotisation (Heinzelmann, A. 188, 183). 
 Diazo-tri-bromo-beuzene sulphonic acid 
 
 C|iHBr3.^^'^. From tri - bromo - aniline, 
 
 CjH2(NH2JBr3 [1:3:4:5] by snlphonation and 
 diazotisation (Spiegelberg, A. 197, 291). Minute 
 needles. 
 
 Diazo-tetra-bromo-benzene p-sulphonic acid 
 
 CjBrj<^ jj '^. Crystalline powder not decom- 
 posed by boiling alcohol (Beckurts, A. 131, 225). 
 
 Siazo-bromo-nitro-toluene sulphonic acid 
 CBHMeBr(N02)<;g^2 y^ Formed by projecting 
 
 m-bromo-p-amido-toluene o-sulphonic acid into 
 fuming HNO3 (Weckwarth, A. 172, 203). 
 
 Siazo-di-bromo-nitro-tolnene sulphonic acid 
 
 CsBr2Me(N02Xg^2 ^. Formed by projecting 
 
 di-bromo-o-amido-tolueue ^-sulphonic acid into 
 fuming HNO3 (Hayduck, A. 174, 855). 
 Siazo-di-bromo-phenol 
 
 C,H,Br,<g^ [0:N, = 1:2]. 
 
 Preparation. — Bromine water is added to 
 an aqueous solution of o-diazo-phenol chloride 
 and the pp. is dissolved in fuming HCl, filtered 
 through asbestos and ppd. by water. 
 
 Properties. — Orange crystalline powder, much 
 less stable than the p- compound. When heated 
 it explodes at 128°- It is more soluble in cold 
 water than the p- compound ; on warming the 
 solution a resin is formed. The solution gives 
 an amorphous grey pp. with silver nitrate. It 
 is almost insoluble in alcohol, ether and CSj, 
 but readily dissolves in CHCI3, hot benzene, and 
 benzoline. It does not reduce Fehling's solu- 
 tion, nor form a crystalline body with NaHSOj. 
 CoH2Br2(OH)N2Brl^aq : decomposed by water. 
 
 Ethyl ether, nitrate of. 
 C„H.,Br,(OEt).N2NOs. Got by passing N^O, into 
 alcohol containing HNO3 and di-bromo-o-amido- 
 phenetol in suspension, and pouring it into dry 
 ether at 0°. Properties. — Prisms. Explodes at 
 102°. If its alcoholic solution be diluted 
 with water (10 vols.) and boiled as long as Nj 
 escapes, it is converted into di-bromo-phenetol, 
 bromine being replaced by hydrogen, not by 
 hydroxyl (Mohlau a. Oehmiohen, J. pr. [2] 24, 
 482). 
 
DIAZO- COMPOUNDS. 
 
 409 
 
 Dlazo-di-bromo-phei) ol 
 
 C,H,Br,<°^>. [0:N, = 1:4]. 
 
 Formation. — 1. Obtainea by adding bro- 
 mine water to an aqueous solution of any salt 
 of ^ - diazo-phenol : 0„H^(OH)N2Cl + 2Br2 = 
 
 C,H2Br2<;§ +HCl + 2HBr.— 2. From HBr and 
 
 diazophenol nitrate (j. v.). 
 
 Properties. — A flooculent yellow pp. re- 
 sembling sulphide of arsenic. Dissolves in 
 boiling water, without decomposition, and 
 crystallises in yellow prisms as the solution 
 cools. Almost insolable in cold water, ether, 
 and CSu, somewhat more soluble in CHGI3. 
 Soluble in alcohol and in amyl alcohol. May 
 be kept for months in closed bottles in the dark, 
 but, when exposed to air and light, it soon turns 
 brown. Heated to 137° it explodes. 
 
 Salts. — Unstable, decomposed by water 
 and by alcohol. CjH2Br2(OH)N2Br,act. — 
 {CsHjBr2(0H)N2Br}jPtClj: triclinio plates, 
 decomposed by water. — CsHjBr2(OH)N„S04H 
 (Bohmer, /.pr. 132, 458). 
 
 Reactions. — 1. Boiled with water of which 
 the boiling-point, by addition of calcic chloride, 
 has been raised to 120°, it gives off nitrogen 
 and forms di-bromo-hydroquinone : 
 
 C,H^r,<g^ + H,0 = 0,H,Br,<Og + N, 
 
 (Bohmer, J. pr. 132, 464). — 2. Dissolves in a 
 hot solution of NaHSOjj and as the solution 
 cools, yellownefedles of 05H2Br2(OH)N2SOsNa2aq 
 are formed. These crystals dissolve in ether, 
 benzene and CS2 ; do not explode when heated ; 
 show Liebermann's reaction; do not reduce 
 Fehling's solution ; and give with BaClj golden 
 scales of {CsH2Br2(OH)N2SOs|2Ba5aq.— 3. Ee- 
 duced by Sn and HCl to di-bromo-^J-amido- 
 phenol. 
 
 Diazo - di - bromo - phenol. (?) Identical with 
 the preceding diazo-di-bromo-phenol just de- 
 scribed may be converted into this isomeride 
 by first reducing it to dibromo-^-amido-phenol 
 hydrochloride and again diazotising. 
 
 Properties. — Explodes at 145°, has a greyish- 
 yellow colour, is insoluble in water. Crystallises 
 from alcohol in much thinner needles than the 
 preceding. With NaHSOa it forms small plates, 
 whereas the sulphonate of its parent-isomeride 
 crystallises in needles (Bohmer, J.pr. 132,471). 
 
 Diazo-di-bromo-phenol 
 
 C,HjBr2<^=!>. [Br:Br:N:0 = 1:5:6:3]. Formed 
 
 by heating tri-bromo-diazo-benzene nitrate with 
 benzene at 45° (Silberstein, J.pr. [2] 27, 107). 
 
 Properties. — Oblique prisms, from water. 
 Crystallises from alcohol. Explodes at 142°. 
 Soluble in hot alcohol. Nearly insoluble in 
 chloroform and ether. 
 
 Salts. — These are very unstable ; they are 
 formed by warming with rather strong solutions 
 of acids, but are saponified by water. 
 
 ReacUons. — 1. Not attacked by boiling water. 
 2. Heated with strong HBr forms tri-bromo- 
 phenol and N^. — 3. Beduced by Sn and HCl to 
 di-bromo-amido-phenol and NH3. 
 
 Constitution. — The hydrochloride of the di- 
 bromo-amido-phenol obtained by reduction, gives 
 Schmitt's reaction upon the gradual addition of 
 dilute bleaching powder, viz.: a violet colour 
 
 followed by a white pp. As this reaction ia 
 characteristic of ^-amido-phenols, this body 
 must be di-bromo-^-araido-phenol, and since it 
 is formed from 0„H2(NH2)Br8 [1:2:4:6] its con- 
 stitution is as given above. It appears to be 
 different from Bohmer's compound, oxplodins 
 at 137°. 
 
 Siazo-tri-bromo-phenol. 
 
 Ethyl ether, nitiate of. 
 C,HBr,(OEt)N,N03[OEt:N2 = 1:2]. Triclinio 
 
 plates, prepared by bromination of o-diazo- 
 phenetol. Does not explode when struck. In 
 melting-point tubes it explodes at 92°. It is 
 decomposed by boiling water into tri-bromo- 
 phenetol, the N^NO, being displaced by H, not 
 by OH (Mohlau a. Oehmichen, J. pr. 132, 484) : 
 20„HBr3(OEt)N2N03 + 2H.0 = 
 2C,HBr3(OEt)H -1- 2N^ + 0^+ 2HN0a. 
 
 Diazo-bromo-toluene sulphonic acids 
 
 CH3.C,H3Br<;^^ >. Five are known : 
 
 p-diazo-m - bromo - toluene o-sulphonic acid 
 (Weckwarth, 4. 172, 196). Bed crystals. Heated 
 with alcohol under pressure it gives bromo- 
 toluene sulphonic acid. 
 
 p-diazo - bromo - toluene m - sulphonic acid 
 (Peohmann, A. 178, 211). Heated with alcohol 
 under pressure it gives bromo-toluene m-sul- 
 phonic acid. 
 
 dlazo-o-bromo-tolnena m-snlphouic acid 
 (Sohafer, A. 174, 360). 
 
 diazo-p-bromo-toluene m-sulphonic acid (S.). 
 
 diazo-^-bromo-toluene o-snlphonic acid (S.). 
 
 o-Diazo-di-bromo-toluene p-solphonic acid 
 (Hayduck, A. 174, 352). 
 
 Siazo-camphor v. Camphor. 
 
 Diazo-^-chloro-benzene [1:4] OsHjCl.N^.OH. 
 Yellow explosive powder, ppd. from its salts by 
 HOAc. Salts.— OBH4Cl.N2.NOs: whiteplates.— 
 C,H,Cl.NjBr3 : yeUow prisms.— CsH^CLNs.— 
 (OsHjClNjC^PtCl^ (Griess, Tr. 1864, iii. 705). 
 
 Anilide v. Diazo-benzene ^-ohloro-anilide. 
 
 p- Chloro-anilide CbH,C1.N2.NH.C.H,01 
 [125°]. 
 
 Siazo-di-chloro-benzene. 
 
 Salts.— CBH3CI2.N2NO3. — C3H3Cl2.NjBr3.— 
 (C.H3Cl3.N3Cl)3PtCl, (G.). 
 
 Di-chloro-anilide CsHsCIj.Nj.NH.CbHsCI, 
 [127°]. Needles, v. sl. sol. alcohol and ether. 
 
 Diazo-chloro-nitro-phenol 
 
 CjH2C1(N02) <q2-^. From chloro-nitro-amido- 
 
 pheuol (Griess, A. 113, 215). Brownish-red 
 columns (from alcohol). 
 
 Diazo-di-chloro-phenol C^H2012<[q''^. From 
 
 C3H2(OH)Cl2(NH3) [1:3:5:2] (Sohmitt a. Glutz, 
 B. 2, 52). Brown flocoulent powder. 
 
 Diazo-tri-chloro-phenol C8HCl3<^?^">. From 
 
 tri-chloro-2)-amido-phenol (Lampert, J. pr. [2] 
 33, 375). Golden needles, explodes at 137°- SI. 
 sol. hot alcohol or benzene, insol. ether. 
 
 Reactions. — 1. Boiling alcohol gives a tri- 
 chloro-phenol [54°] (253°).— 2. Cone. Na3S03Aq 
 forms C3HCl3(ONa).N2S03Na, of which the 
 acid C3HGl3(0H).N2.S03H, explodes at 200°, and 
 forms an orange crystalline barium salt. — 3. HI 
 forms C5HCI3I.OH. 
 
 Diazo-chloro-thymol cbloride 
 UsHClMePr(OH).N,CI. By the action of NjO, on 
 
410 
 
 DIAZO- COMPOUNDS, 
 
 a cold alcoholic solution of hydrochloride of 
 cliloro-amido-thymol (Andresen, /. pr. 131, 180). 
 Precipitated by ether. Colourless needles, often 
 grouped in fans. 
 
 o-Diazo-cinnamie acid. Prom amido-cinna- 
 mio acid (10 pts.), HCl (9 pts. of S.G. 1-19), 
 water (70 pts.), and NaNO^. The chloride 
 separates as a yellow powder (Fischer a. Kuzel, 
 B. U, 478; A. 221, 272). The nitrate 
 C.H,(N2N03).CH:CH.C02H forms clear prisms. 
 Both salts may be boiled with potash without 
 giving ofl nitrogen, but they are decomposed by 
 boiling water, forming o-ooumaric acid. With 
 NajSOs they form C„H^(N2SOsNa).CH:CH.C02H, 
 whence, by reducing with zinc and HOI, 
 CA(NH.NH.S03Na).CH:CH.C02H. The latter 
 forms slender needles. It reduces HgO in 
 the cold, and Fehling's solution. HCl in the 
 cold converts it into hydrazido-cinnamic acid 
 (2.D.). 
 
 ^-Siazo-cinnamic acid. The chloride 
 C„H,(N:N.C1).CH;CH.C02H is prepared by the 
 action of NaNO^ on ^-amido-cinnamic acid 
 suspended in HCl (Gabriel, B. 15, 2300). Long 
 needles (containing aq). M. sol. water. Can be 
 dried at a gentle heat without decomposition. 
 
 j2>-Diazo-cresol M.e.G^Ilj<^Q''^. Formed by 
 
 diazotising CsH3Me(NH2)(OH) [1:3:4] (Wagner, 
 B. 7, 1270)— (MeOjH3(OH)N,Cl),PtCl, : powder, 
 m. sol. water. 
 
 Biazo-f-camene-sulpliite. 
 
 Salt.— C„H2(CH3)3.N2.S03Na [1:3:4:6]. Trans- 
 parent prisms (containing 2|aq). Not explosive 
 (Haller, B. 18, 90). 
 
 Diazo-iJ'-ciimene-eiiniide. Diasoamidocivmene. 
 [1:3:4:6] CeH2Me3.N:N.NH.CsH,Me3 [6:1:3:4]. 
 [131°]. Formed by the combination of diazo- 
 oumene with cumidine (Nolting a. Baumann, B. 
 18, 1147). Yellow tables (from ether). V. sol. 
 benzene, ether, and acetone, m. sol. alcohol. 
 
 Diazo-ouminic-amido-cuminlc acid 
 Pr.C3H3(C02H) .N,.NH.C„H3i'r.C0,H. Formed 
 by passing nitrous acid into an alcoholic solution 
 of amido-cuminio acid at 0°. Minute prisms or 
 leaflets (Griess, A. 117, 62). 
 
 Diazo-ethane sulphite C2H5.N2.SO8H. Diazo- 
 ethane sulphonic acid. 
 
 Salt. — KA'. Formed by the action of HgO 
 on the corresponding hydrazo- derivative 
 C2H5.NH.NH.SO3K (Fischer, A. 199, 302). 
 V. sol. water ; ppd. by alcohol. Explodes when 
 heated. Decomposed by boiling acids, Nj and 
 SO2 coming off. Eeduoed by zinc-dust and 
 acetic acid to C^Hj.NH.NH.SOjK. 
 
 Diazo-ethoxane C^Hj.O— Nj— CC^Hj (?) 
 V.D. 4-02 (oalo. 4'08). Prepared by the action 
 of silver hyponitrite, AgNO, on EtI (Zorn, B, 
 11, 1630). Neutral liquid. Exceedingly ex- 
 plosive. Is decomposed by water with production 
 of aldehyde and alcohol : {02^^)20^^^ + B..fl 
 = Nj + CH3.COH + CjHjOH + H^O. By tin and 
 acetic acid it is reduced to nitrogen and alcohol : 
 (C^HJjOjNj + H, = 20.,H,0H + Nj. 
 
 o-Siazo-hemipic acid 
 
 0jH(0Me)2(C0jH) <\c6'^°" ^iO'^o-di-methoxy- 
 phthalic acid. Formed by the action of nitrous 
 acid upon o-amido-hemipic acid. YeUow micro- 
 crystalline powder. SI. sol. ordinary solvents. 
 Kzplodes on percussi(m or when heated to 
 
 140''-150°. Converted into hemipic acid by 
 boiling with alcohol. 
 
 HydrochlorideC^B.{Oyie).i{CO^B.)^.'i!ifi\ii.q,l 
 long colourless needles. 
 
 The sulphate forms small prisms (Griine, 
 B. 19, 2302). 
 
 Diazo-hipparlc acid. 
 
 The nitrate COjH.CHj.NH.CO.CjHj.N^.NO, 
 is formed by diazotising the nitrate of »i-amido- 
 hippuric acid (Griess, Z. 1867, 165). — Per- 
 bromide CjHjNOs.NaBrs : yellow prisms, 
 Imide CjHgNOs.Na: tables or needles. 
 
 Siazo-leucaniline v. Hexa-azo-tri-phenyl- 
 methane (infra). 
 
 p-Diazo-iodo-benzene C^H^LN^OH: yellowpp. 
 
 Salt s.— (C„H^I.N2Cl)2PtCl^.- CeH J.NjNOj.— 
 CjHjI.NjSO^H : small plates, v. sol. water, si. 
 sol. alcohol.— CsH^LN^Brs.— Imide C„HJ.N, 
 (Griess, 2V. 1864, iii. 706). 
 
 (o)-Diazo-naphthalene (Griess, J. 1866, 459). 
 Nitrate 0,„H,.N2.N03 : formed by diazotising 
 a-naphthylamine nitrate. — Perbromide 
 CjuH-.N^Brj : orange crystals. — Platino- 
 chloride (d.^.-'H^G^^ViGl^.- Imide C,„H,.Na: 
 yellowish oU (0/. Fischer, A. 232, 242). 
 
 A solution of the chloride neutralised by 
 NajCOj gives a brown pp. Part of this dissolves 
 in alkalis and appears to be OjjHjNO, the rest 
 is ppd. as minute crystals by adding alcohol 
 to its benzene solution. Analysis indicates 
 C5„H33N502. Both form crimson solutions in 
 alcohol, ether, benzene, and glacial acetic acid 
 (P. F. Frankland, 0. J. 37, 750). 
 
 (j3)-Diazo-naphthalene. Obtained by diazo- 
 tising (;8)-naphthylamine (Liebermann a. Palm, 
 A. 183, 267). The sulphate forms pale yellow 
 needles, and the perbromide orange needles. 
 
 (C,oH,.N2.Cl)Cu2Cl2'' : very unstable yellow 
 pp. which is formed on adding CujClj to a cold 
 solution of ;8-diazo - naphthalene - chloride. 
 (C,„H,.Nj.Br)CujBr2 : red pp. ; on boiling with 
 water it evolves nitrogen yielding (j8)-bromo- 
 naphthalene (Lellmann, B. 19, 810). 
 
 (a) ■ Siazo - naphthalene - (a) - naphthylamide. 
 [100°]. Formed by action of nitrous acid on 
 fo)-naphthylamine, or by ppg. a solution of 
 (o)-diazo-naphthalene chloride with (o)-naph- 
 thylamine. Brown laminae (from alcohol). 
 Acids resolve it into naphthylamine and diazo- 
 naphthalene (Martins, Z. [2] 2, 137). 
 
 (a)-Diazo-naphthalene sulphonic acid 
 
 •N*N-v 
 "CidHj-C^^^oq p.. [1:4]. Got bypassing nitrous 
 
 acid gas into (o) -naphthylamine sulphonic acid 
 (formed by sulphonating (a) -naphthylamine) 
 suspended in water (CUve, Bl. [2] 26, 241; Nevile 
 a. Winther, C. J. 37, 632). Powder, nearly in- 
 soluble in cold water. Boiling water converts it 
 into a crimson dye, forming very little naphthol 
 sulphonic acid. Heated with dilute H^SOj (ir)- 
 naphthol p-sulphonie acid is formed. By heat- 
 ing with strong H^SO^, or with water at 160°, 
 (a)-naphthol is produced. Dilute HNO3 (7 to 
 15 p.c. HNO3) forms di-nitro-naphthol, [138°]. 
 Cone. HCl forms a chloro-naphthalene sul- 
 phonic acid, whence PCI5 forms dichloro- 
 naphthalene [68°]. 
 
 Imide C„H„(S03H).N<|{ [1:4]. 
 
 Triazo-naphthalene-p-sulphordc acid. Formed 
 by the action of phenyl-hydrazine upon tha 
 
DIAZO- COMPOUNDS. 
 
 411 
 
 acid ; diazo-benzene-imide, (a)-naphthylamine- 
 p-sulphonio acid, and aniline are formed simul- 
 
 taneously: 2C,„H| 
 
 \S0, 
 
 + 2C„H,NH.NH, 
 
 C,„H,(N3)S03H + CAN, + C,„H,(NHj)S03H + 
 C^Hj.NHj. Wtite needles. V. sol. water and 
 alcohol. 
 
 Salt.— BaA'^: white silvery plates, v. si. sol. 
 boiling water. Phenyl-hydrazine salt 
 CjHsNiiHjA' : long plates ; v. sol. alcohol, nearly 
 insol. ether and chloroform (Griess, B. 20, 1530). 
 
 (a)-Diazo-naphtIialene sulphonic acid 
 
 CioH8<^g^^^. [1:1' or 41. Similarly prepared 
 
 from the product of the reduction of (o)-uitro- 
 (o) -naphthalene sulphonio acid formed by sul- 
 phonating nitro-naphthalene (CUve, Bl. [2] 24, 
 512). TeUow crystalline powder. Boiling water 
 gives (a)-naphthol (a)-sulphonic acid. 
 (j3)-Diazo-uaphthalene sulphonio acid 
 
 CijHj<^^S ]>• Microorystalline powder. 
 
 Formed by diazotising (0)-naphthylamine sul- 
 phonio acid (formed by sulphouating (;8)-naph- 
 thylamine). By boiling with HCl, converting 
 into the K salt and heating with PCI5 it yields 
 chloro-naphthalene-sulphonio chloride [129°] 
 (Porsling, B. 19, 1715). 
 
 (j3)-Siazo-napIithalene sulphonio aoid 
 
 C,oH,<^>. Formed by diazotising (?j8,j3j- 
 
 naphthylamine sulphouic acid, itself got by 
 the action of NH, upon Schaffer's (/3)-naphthol 
 Bulphonic acid at 180°. Minute crystals. Con- 
 verted by treatment with cuprous chloride into 
 (0) chloro naphthalene sulphonio aoid, whose 
 chloride melts at 110°, and, by distiUatiou with 
 PCI5 is converted into (e)-di-chloro-naphthalene, 
 [136°] (ForsUng, B. 20, 80). 
 
 Tetrazo-ainaphthylHO.Nj.C,„H5.Ci„Hj.N20H. 
 Formed by diazotising naphthidine. It gives 
 violet dye-stuffs when combined with the sul- 
 phonio acids of (j8)-naphthol. By boiling with 
 alcohol it yields (oo)-dmaphthyl. 
 
 Salts. — CjjHi^NjSOi" : yellowish plates. — 
 (CjoHjjNiCyPtCli : sparingly soluble yellow 
 needles (Nietzki a. GoU, B. 18, 3256). 
 
 Diazo-nitro-benzaldozim chloride 
 CsH3(N02)(N:N01)(CH:N0H) [3:4:1]. Formed 
 by the action of amyl nitrite and HCl on (3:4:1)- 
 nitro-amido-phenyl-acetic acid (Gabriel, B. 15, 
 837). Plates or needles. Explodes on heating. 
 On heating with alcohol it gives m-nitro-benz- 
 aldoxim CeH<(N02)(GH:N0H). 
 
 jp-Diazo-o-nitro-benzaldoxim chloride 
 C,H3(N0j)(Nj.Cl)(CH:N0H) [2:4:1]. Formed, 
 with evolution of CO2, by the action of amyl 
 nitrite on a HCl solution of o-nitro-^-amido- 
 phenyl-acetio acid (Gabriel a. E. Meyer, B. 14, 
 826 ; C. C. 1885, 516). Long red needles. Ex- 
 plosive. By the action of HBr it gives o-nitro- 
 p-bromo-benzaldoxim. By hot alcohol it gives 
 o-nitro-benzaldoxim CsHj(N02)(CH:N0H). On 
 oxidation it gives o-nitro-benzaldehyde. Ammo- 
 nium sulphide reduces it to o-amido-benzaldoxim 
 C.H,(NHj,).CH:NOH [133°]. 
 
 m-Slazo-nitro-benzene. Formed by diazo- 
 tising 7»-nitro-aniline. 
 
 Nitrate C.Hj(N0.,).N..N03 : cubes.— 
 
 (O.H,(NO,).N,Cl),PtCl,.-0„H,(NO,).N^r, 
 (Griess, Tr. 1864, iii. 708). « »" « 
 
 Imide C„H4(N02).N3. [52°]. 
 
 p Diazo-nitro-benzene. Formed by diazo- 
 tising ^-nitro-aniliue. 
 
 Nitrate C^B.,{iiO^).N^.NO^: slender needles. 
 Gives no pp. with PtCli, 
 
 Imide 0,H,(N0J.N3. [71°]. 
 
 m-Diazo-nitro-benzens-p-ethyl-toluide 
 [3:1] CsH^NOJ— N,-NEt.C„H,Me [1:4]. [55°]. 
 From m-diazo-nitro-benzeue chloride and ethyl- 
 p-toluidine (Gastiger, Bl. [2] 42, 342). Eesolved 
 by dilute HCl into its generators. 
 
 p-Diazo-nitro-benzene-^-ethyl-toluide 
 [4:1] C,H,(N02)-Nj-NEt.C.H^Me [1:4]. [105°]. 
 Yellow needles (Gastiger, Bl. [2] 42, 342). Re- 
 solved by HCl into |i-diazo-nitro-benzene chloride 
 and ethyl-p-toluidiue. 
 
 TO-Diazo-nitro-benzene-TO-nitro-anilide 
 [3:1] C3H,(N0,).N,.NH.C.H,(N0,) [1:3]. [195°]. 
 Formed by the action of nitrous acid (1 mol.) on 
 m-nitro-aniline (2 mols.). Small red prisms, v. 
 si. sol. alcohol (Griess, A. 121, 272; Meldola a. 
 StreatfeUd, C. J. 51, 107). Insol. hot aqueous 
 KOH ; but the potassium salt separates as brown 
 crystals from a solution in alcoholic KOH. Cold 
 HClAq gives m-nitro-aniline and m-diazo-nitro- 
 benzene chloride. 
 
 jp-Siazo-nitro-benzene-p-nitro-anilide 
 [4:1] C„H4(N0J.N2.NH.C„H^(N02) [1:4]. [223°]. 
 Formed by the action of nitrous aoid (1 mol.) on 
 p-nitro-aniline (2 mols.) (Griess, A. 121, 271 ; 
 Meldola a. Streatfeild, C. J. 49, 624). Small 
 yellow needles, m. sol. boiling alcohol. Possesses 
 distinctly acid properties, decomposing NajCOj. 
 Cold alcoholic KOH or boiling aqueous KOH 
 form a magenta-coloured solution of the potas- 
 sium salt. It forms ^-nitro-aniline when heated 
 with dilute HjSO, or with water in sealed tubes 
 at 230°. Cone. HCl at 20° gives p-diazo-nitro- 
 benzeue chloride and p-nitro-aniline. 
 
 S alts .— C„H4(N02).N2.NNa.C,H4NOj : forms 
 steel-blue needles, soluble only in excess of 
 alkaU.-{C,H,(N0,).N3.(C,H,N0,)},Cu.— 
 {C3H,(N0,).N3.(C,H,N0,)},Cd.- 
 {C.H,(NO,).N3.(C,H,NO,)},Co. 
 
 ira-Diazo-nitro-benzene-p-uitro-anilide 
 [3 or 4 : 1] CeH^(N0j).N,.NH.C,H,(N02) [1 : 4 or 3]. 
 [211°]. From diazotised TO-nitro-aniline hydro- 
 chloride and ^-nitro-aniline ; or from diazotised 
 ^-nitro-aniline hydrochloride and m-uitro-auiline 
 (Meldola a. Streatfeild, G. J. 51, 103, 439). Yel- 
 low needles (from alcohol). Dissolves in NaOHAq, 
 forming a red solution. Cold aqueous HC} 
 gives TO- and p-diazo-nitro-benzeue chlorides 
 and m- and ^-nitro-aniline. 
 
 m - Siazo - nitro - benzene - to - nitro - benzyl . 
 anilide [3:1] C3Hj(N02).N2.NC,H,.CeH,(N02) [1:3]. 
 [142°]. From ni-diazo-nitro-benzene-TO-nitro- 
 aniHde, alcoholic KOH, and benzyl chloride 
 (M. a. S.). HClAq at 100° gives TO-chloro-nitro- 
 benzene and w-nitro-benzyl-aniline. 
 
 ^-Diazo-nitro-benzene -p-nitro-benzyl-anilide 
 [4:1] C3H,(N0,).N,.NC,H,.C,H,(N0,) [1:4]. [190°]. 
 From 2'-'i'azo-nitro-benzene-^-nitro-benzyl-ani. 
 lide, alcoholic KOH, and C,H,C1 (Meldola a. 
 Streatfeild, 0. J. 51, 112). Minute yellow 
 needles. Cone. HCl decomposes it at 100° into 
 ji-nitro-benzyl-aniline and ^-chloro-nitro-ben. 
 
412 
 
 DIAZO- COMPOUNDS. 
 
 p- Diazo - nitro - benzene - m - nitro-benzyl - ani- 
 lide [4:1] CeH,(N0,).N3.C,H,.C„H,(N0,) [1:3]. 
 [180°]. From ??i-diazo-nitro-benzene -^-nitro- 
 »uilide alcoholic KOH, and benzyl chloride 
 ^Meldola a. Streatfeild, C. J. 51, 114). 
 
 m-Biazo-nitro-benzene-m-nitTo-ethyl-anilide 
 1.3:1] CeH,(NOJ.N,.NEt.CA(NOj) [1:3]. [119°]. 
 From m-diazo-nitro-benzene-m-nitro-anilide by 
 treatment -with KOH and EtI. Also from 
 >re- diazo -j3-mtro-benzene and m-nitro-ethyl- 
 aniline. Needles. Cold cone. HCl forms m- 
 diazo-nitro-benzene chloride and m-nitro-ethyl- 
 jiniUne (Meldola a. Streatfeild, C. J. 51, 108, 
 441). 
 
 p-Diazo-nitro-benzene-p-nitro-ethyl-anilide 
 [4:1] CeH,(N0j).N2.NEt.C„H4(N02) [1:4]. [192°]. 
 i'ormed by the action of EtI and KOH upon 
 p - diazo -nitro - benzene -p ■ nitro - ethyl - anilide 
 (Meldola a. Streatfeild, C. J. 49, 631). Or from 
 -diazotised ^-nitro-aniline and jj-nitro-ethyl- 
 .uniKne (M. a. S., O. J. 51, 111, 442). YeUow 
 needles, v. si. sol. alcohol, insol. alkalis. De- 
 composed by cold HCl into j)-diazo-nitro-benzene 
 •chloride and p-nitro-ethyl-aniline. 
 
 p-Diazo-nitro-benzene-m-nitro-ethyl-anilide 
 [4:1] C,H,(N02).N2,NEt.CsH4(N02) [1:3]. [187°]. 
 From diazotised p-nitro-aniline and m-nitro- 
 -ethyl-aniline (Meldola a. Streatfeild, C. J. 51, 
 111, 442). Orange needles (from alcohol). V. 
 -si. sol. alcohol. Cold cone. HCl gives m-nitro- 
 •cthyl-aniline andp-diazo-nitro-benzene chloride. 
 
 m - Diazo - nitro - benzene -p- nitro - ethyl- 
 ^anilide (?). 
 
 [3:1] CeH,(N0,).N3.Et.C,H,(N0,) [1:4]. [148°]. 
 Prepared by digesting the potassium salt of m- 
 diazo - nitro - benzeue-p-nitro-anilide dissolved in 
 alcohol with EtI (Meldola a. Streatfeild, G. J. 
 51, 105). Small yellow needles. Heated with 
 HCl at 100° it gives m-audp-nitro-ethyl-anilines 
 ^nd m- and p- chloro-nitro-benzenes. By cold 
 HCl it is resolved into m- and p- diazo-nitro-ben- 
 zene chlorides and m- andjp- nitro-ethyl-anilines. 
 
 m-Diazo-nitro-benzene -p-nitro - ethyl-anilide 
 .[3:1] C,H^(Nq2).N2.NEt.CsH,(N02) [1:4]. [175°]. 
 i'rom diazotised m-nitro-aniline and p-nitro- 
 ^thyl-anUine (Meldola a. Streatfeild, C. J. 51, 
 110). Yellow needles (from alcohol). V. si. sol. 
 alcohol. With cone. HClAq it forms ^-nitro- 
 •aniline and m-diazo-nitro-benzene chloride. 
 
 jp-Siazo-nitro-benzene-piperidide 
 [4:1] CeH,(N02).Nj.N05H„,. [97°] (Wallaoh, A. 
 235, 264). 
 
 m-Diazo-nitro-benzene sulphouic acid 
 
 (3) JSi (1) 
 ■CjH3(N02)C I . Formed by diazotisation 
 
 ^S0,(6) 
 ■of m-nitro-aniline sulphonic acid (1:3.6). White 
 Tniorosoopic tables. By heating with absolute 
 alcohol under an extra pressure of 400 mm. it 
 is converted into p-nitro-benzeue sulphonic acid 
 (Limpricht, B. 18, 2186). 
 
 Diazo-nitro-benzeue disulphonic acid 
 
 -CsHj(S0aH)(N02)<g'^^>. Formed by diazo- 
 
 tising m-nitro-aniliue disulphonic acid (Lim- 
 pricht, B. 8, 289). Boiling alcohol forms m- 
 ■nitro-benzene disulphonic acid. 
 Diazo-nitro-benzoic acid 
 
 C|jH3(N0j)<^„^ ^. Explosive yellow laminss 
 
 <Sattowski, A. 173, 63). 
 
 Diazo-nitro-di-ozy-quinone. The salts are 
 formed by diazotising nitro-amido-tetra-oxy- 
 benzene (Nietzki a. Benkiser, B. 18, 501). — 
 Ce(N02)(N20H)(OH)(OKa)02aq : long yellow ex- 
 plosive needles.— Cs(NOj)(N20H)(OH)(OAg)0» : 
 yellow explosive plates. 
 
 Diazo-nitro-phenol C^B.^(;^0^<^^'^. From 
 
 C„H3(OH)(NH2)(NO.J [1:2:4] by diazotisation 
 (Griess, A. 113, 212). Brownish-yellow granular 
 mass ; v. si. sol. hot water, v. sol. alcohol. Ex- 
 plodes at 100°. 
 
 Methyl ether. 
 Nitrate CsH,(N02)(0Me).N2.N0j. Formed by 
 diazotising nitro-anisidine (Griess, J. 1866, 459). 
 Platinochloride|C5Hs(N02)(OMe)N2Cl}jPtCl4 
 Perbromide CeH3(N0J(0Mej.NjBrj. 
 Imide C,H3(NOj)(OMe)N3 : needles. 
 Methoxy-nitranilide 
 
 CsH3(NO,)(OMe).Nj.NH.CBH3(NO,)(OMe). 
 Formed by passing nitrous acid into an alcohol 
 solution of nitro-anisidine (Griess, A. 121, 278). 
 
 Diazo - di - nitro - phenol CsH2(N0 )2<^'y. 
 
 Formed by passing nitrous acid into an alco- 
 holic solution of di-nitro-amido-phenol (piora- 
 mic acid (Griess, A. 113, 205). Yellow plates 
 (from alcohol). 
 
 Diazo-nitro-iS-pIienyl-propionie acid 
 [3:4:1] CeH3(NOj)(N2.0H)CjH4.CO,H. Mtro- 
 diazo - hydrocmnamic acid. The nitrate is 
 formed by the action of ethyl nitrite and HNO, 
 on (3:4:l)-nitro-amido-i8-phenyl-propionio acid. 
 It forms short colourless needles which explode 
 feebly on heating. Heated with alcohol it 
 gives m- nitro -hydrooinnamio acid (Gabriel, B. 
 15, 845). 
 
 Diaza-nitroso-methyl-nitro-benzene v. Diazo- 
 
 NIIBO-BENZUDOXIItl. 
 
 jp-Diazo-nitroso-ozindole chloride 
 C^H^N.O.Cl or C„H3(N:N.C1)<'^(^--^^)>C0. 
 
 p-Diazo-dioxindole-oxim chloride. Small 
 yellow needles. Prepared by the action of amyl 
 nitrite on a solution of amido-oxindole in HCl. 
 Is only shghtly attacked by boiling alcohol 
 (Gabriel a. E. Meyer, B. 14, 832 ; C. C. 1885, 
 516). 
 
 o-Diazo-j}-nitro-tolnene-piperidide 
 C,,H,3N,0, i.e. [1:4:2] C,H3Me(N0,).N,.NC,H„. 
 [51°]. From^-nitro-o-toluidine [107°] by diazo- 
 tisation of its hydrochloride and subsequent 
 addition of piperidine (WaUach, A. 235, 248). 
 
 o-Diazo-nitro- toluene ^-sulphonic acid 
 
 C8HjMe(N02)<^j^^^. Formed by dissolving 
 
 o-toluidine ^-sulphonic acid in fuming HNO, 
 and ppg. with ice-water (Hayduck, A. 172, 117). 
 Boiling alcohol under 1160 mm. pressure does 
 not attack it. 
 
 p - Diazo - nitro - toluene o ■ sulphonic acid. 
 Formed by dissolving ji-toluidine o-sulphonio 
 acid in cold fuming HNO3 (Weokwarth, A. 172, 
 202). Large dark-red prisma. Alcohol heated 
 with it under 1,000 mm. pressure gives nitro- 
 toluene sulphonic acid (Pagel, A. 176, 304). 
 
 j2}-Diazo-nitro-toluene m-sulphonic acid 
 C„HjMe(N02)N2S03 [1:2:4:5]. Formed by dis- 
 solving p-toluidine m-sulphonio acid in fuming 
 HNO3 (Pechmann, A. 173, 214), and also from 
 CBH2Me(N02)(NHj)SO,H [1:2:4:5] and nitrous 
 
DIAZO- COMPOUNDS. 
 
 413 
 
 Acid. Insol. cold water ; on boiling with water 
 only f of the theoretical quantity of nitrogen 
 comes off ; when boiled with FOjClj all comes off. 
 Boiling alcohol does not affect it, but in a 
 sealed tube at 100° it is converted into o-nitro- 
 toluene m-sulphonio acid. 
 
 p-Diazo-di-nitro-toluene o-sulphonic acid 
 
 C5HMe(NO,)2 <^^2 y_ pj-om i)-toluidine o- 
 
 sulphonio acid and fuming HNO3 (Pagel, A. 
 176, 306). Yellowish needles. Not affected by 
 alcohol boUing under 1,000 mm. pressure. 
 
 Diazo-ozy-acrylic ether (?) 
 C,HsNA i-e- CN,:C(0H).C02Et (?). (142°) at 
 717 mm. V.D. = 50 (obs.). Yellow oU of strong 
 peculiar odour. Volatile with steam. 
 
 Formation. — Gelatine, swollen with water, 
 is warmed with absolute alcohol whilst HCl gas 
 is passed in, it soon dissolves and after dis- 
 laUing off the alcohol a thick brown syrup is 
 left ; the latter, which appears to be the 
 hydrochloride of amido-oxy-acryHc ether 
 CH(NHj):C(0H).C02Et yields the diazo-ether 
 when its concentrated aqueous solution is treated 
 with NaNOj ; it is purified by distillation with 
 steam ; the yield is 150 grms. from 400 grms. 
 of gelatine. 
 
 Eeactions. — Acids eliminate its nitrogen, but 
 it is very stable towards alkalis, with the ex- 
 ception of NH3, which even in the cold soon 
 splits off GO2 and alcohol. By zinc-dust and 
 acetic acid it is reduced first to a hydrazine and 
 finally to an amido-aoid. An ethereal solution 
 of iodine converts it into di-iodo-oxy-acrylio 
 ether Cl2:C(0H).C02Et which on treatment with 
 cold aqueous NH, loses COj and alcohol and 
 yields di-iodo-vinyl-amine Cl2:CH(NH2). It 
 reduces AgNOj in the cold (Buchner a. Ourtius, 
 
 B. 19, 850). 
 Siazo-o-oxy-benzoic acid 
 
 CeH3(C02H)<^^ [C02H:0:N = 1:6:3]. 
 
 Diazo-salicylic acid. Formed by passing NjOj 
 into an aqueous or alcoholic solution of hydio- 
 chloride of amido-sahoylic acid and concentrating. 
 CrystaUised from water (Schmitt, J. 1864, 384 ; 
 Goldberg, 7. 2)r. [2] 19, 362; P. F. Frankland, 
 
 C. J. 37, 749). Slender needles. 
 
 Reactions. — 1. Boiled with cone. HI it gives 
 iodo-saUoylic acid [196°] {q. v.). — 2. Mereaptan 
 at 170° gives salicylic acid (Schmitt a. Mitten- 
 zviej.J.pr. [2] 18, 193). 
 
 Chloride. — CeH3C0jH)(0H)NjCl. — Pla- 
 tino-chloride{C,H3(C02H)(OH)NjCl}jPtClj. 
 
 Siazo-p-ozy-benzoic-amido-ozy-benzoic acid. 
 Dimethyl derivative. 
 
 Diazo-amido-anisic acid 
 CsH3(OMe)(COjH).N3.NH.CsH3(OMe)(C03H). 
 Formed by passing nitrous acid gas into a cold 
 alcoholic solution of amido-anisic acid (Griess, 
 A. 118, 337; 117, 45). Amorphous powder, 
 insol. water, alcohol, and ether. Warm cone. 
 HCl converts it into a red acid C^^'B.^fl,. — 
 Na2A"4aq.— KjA"2aq.— EtjA" : narrow leaflets. 
 
 Siazo-ozy-cinnamic acid. Methyl deriva- 
 tive C,H3(N,0H)(0Me).CH:CH.C0,H [5:2:1]. 
 Formed by diazotising methoxy-amido-cinnamio 
 acid. The chloride forms yellow crystals, 
 which decompose at about 102°. The nitrate 
 C.H3(N:N.N03)(OMe)(C2Hj.C02H) orystaUises in 
 yellow needles, which explode at 152°, nearly 
 
 insoluble in cold water, alcohol, and ether 
 (Schnell, B. 17, 1385). 
 
 o-diazo-phenol. Chloride C3Hj(0H)NjCl. 
 By passing NjOj into an alcoholic solution of 
 the hydrochloride of o-amido-phenol, and then 
 adding ether (Schmitt, B. 1, 67 ; Bohiner, /. pr. 
 132, 460). Bhombohedra. Bromine-water added 
 to its aqueous solution forms a yellow pp. of 
 diazo-dibromo-phenol {q. v.). 
 
 Sulphite C„Hj(OH).N2.S03K aq. Golden 
 scales, got by adding KHSO3 to C3H4(0H).N2C1 
 (Schmitz a. Glutz, B. 2, 51 ; Beisenegger, A. 
 221,314). 
 
 Platino chloride {C^B.,{OB.)l>ifil)J?tCl,. 
 
 m-Diazo-phenol. Ethyl derivative (Wag- 
 ner, J. pr. [2] 32, 70). 
 
 iJ-Diazo-phenol. Nitrate C„H,(OH).N2N03. 
 Formed by passing nitrous acid gas into a cold 
 ethereal solution of phenol (Weselsky, Sitz. B. 
 1875, 9 ; B. 8, 895), or of jp-nitroso-phenol 
 (Jager, B. 8, 894). 
 
 Preparation. — By passing NjOj into alooholio 
 solution of hydrochloride of jj-amido-phenol, 
 adding strong HNO3 and cooling strongly (Boh- 
 mer, /.pr. 132,450). 
 
 Reactions. — 1. By warming with dilute 
 HBr (15 per cent, solution) it does not give off 
 nitrogen, as diazo-benzene nitrate would do, 
 but forms di-azo-di-bromo-benzene in accordance 
 with the equation : 
 
 3C.H,Br„<g^+3O.H.<^^^j+3NO,+3N0 + 9H,O. 
 
 Chloride C3H,(0H).N2C1. Formed by 
 diazotising p-amido -phenol hydrochloride. 
 Converted into hydroquinone by boiling cone. 
 HCl or dilute HjSO^ (Schuler, B. 9, 1160). 
 Heated vrith mercaptan it gives phenol and 
 (C^^Si (Schmitt a. Mittenzwey, J. pr. [2] 18, 
 194).— (C,H,,(OH).N3Cl)2Pt01,. 
 
 Bromide CBHj(OH)NjBr. Formed by pass- 
 ing N2O3 into an alooholio solution of the hydro- 
 bromide of jp-amido-phenol (C. Bohmer, /. pr. 
 132, 451). Precipitated by ether. 
 
 Platinobromide (C8H4(OH)N2Br)2PtBr^. 
 Needles grouped in spherical segments. Got by 
 adding an aqueous solution of PtBrj (prepared 
 like PtClj by dissolving spongy platinum in HBr 
 mixed with HNO3 and evaporating) to one of 
 diazo-phenol hydrobromide. If left for several 
 days in contact vfith their mother liquor, the 
 crystals absorb eight molecules of water of 
 crystallisation changing to blood-red twin 
 crystals resembling gypsum. These are in- 
 soluble in ether, OS^ and CHClj, difficultly soluble 
 in water. The salt heated with 10 pts. ol 
 Na2C03 does not yield bromophenol. 
 
 Sulphate C3H,(OH)N2.S04H. Obtained 
 by adding dilute HjSO, to an alcoholic solution 
 of the hydrochloride of p-amido-phenol, passing 
 in N2O3 and adding ether. Needles. Does not 
 explode when heated. Converted by boiling 
 HBr into the bromo-phenyl ether of hydro- 
 quinone (q. v.). 
 
 Sulphite HO.C3H,.Nj.S03K. Fromp-amido- 
 phenol, HCl, NaNO^, and KjSOj (Beisenegger, A. 
 221, 316). Yellowish plates. 
 
 Ethyl derivative ''C3H4(OEt)N20H. Salts.— 
 C3H4(0Et)N2Cl. Fromp-amido-phenetol hydro, 
 chloride by solution in alcohol and treatmeni 
 with NjOj. Precipitated by ether as an oil. 
 
414 
 
 DIAZO- COMPOUNDS. 
 
 Crystallises when cooled to - 18°. But if H^SO, 
 be added to the alcoholic solution of the chloride, 
 avoiding rise of temperature, crystals of the 
 sulphate C5Hj(OEt)N2.S04H separate. Boiled 
 with water this forms C5H:j(0Et)(0H:), hydro- 
 quinone mono-ethylic ether (g. v.) (Hantzsoh, 
 J.pr. 130,461). 
 
 Methyl derivative. The salts are formed 
 by diazotising p-anisidine (Salkowski, B. 7, 
 10D9) : C,H,(OMe).N2N03.— C,H^(OMe).NrSO^H. 
 
 Slazo-phenol-carbamic ether. Ethyl deri- 
 vative 
 
 .N ^CO,Et. 
 C,H3(0Et)/ \ 
 
 Preparation. — ^By passing N^Oj into a solu- 
 tion of the hydrochloride of ethoxy-amido- 
 phenyl-urethane, 0,H,{0Et)(NH2).NH.C0^t, 
 HCl (Kohler, J.pr. [2] 29,273). 
 
 Properties. — Slender, silvery-white matted 
 needles. Insol. water, sol. alcohol, ether, and 
 glacial acetic acid. Decomposes below 100°. 
 
 Beactions. — 1. Does not explode. — 2. Not 
 affected by boiling alcohol. — 3. Boiled with soda, 
 it is decomposed with evolution of nitrogen. 
 
 Diazo-pheuol sulphonlc acids 
 C!„H,(NjOH)(OH)(S03H) [1:4:3] and [3:4:1] are 
 unstable crystalline acids obtained by diazo- 
 tising the corresponding amido-phenol sulphonic 
 acids (Beunewitz, J. pr. [2] 8, 52). 
 
 Diazo-phenol disulphonic acid 
 
 C.H2(S03H)2^ I . From ^-amido-phenol di- 
 
 \o 
 
 Bulphonic acid (q^.v.) (Wilsing, A. 215, 238). 
 
 Salt. — K2A"aq. Small sulphur - yellow 
 needles. Warmed with water it forms hydro- 
 •quinone disulphonic acid. 
 
 ^-p-Tetra-azo-diphenyl 
 
 Nitrate NOj.Nj.CsH^.CjHj.N^NOa. Formed 
 by passing nitrous acid gas into an aloohoHc 
 solution of nitrate of benzidine, and ppg. with 
 «ther (Griess, Tr. 1864, iii. 719). White needles, 
 V. sol. water, m. sol. alcohol, insol. ether. 
 Explodes when heated. Boiling water forms 
 p-^-di-oxy-diphenyl. 
 
 PerbromideBi^'i^f^-OaB.yCJB.i.Tif^'Brs. 
 
 iTOifieNa.CjHj.CjHj.Ns. [127^]. Whiteplates. 
 
 Platinochloride 
 {ClN2.CsH,.C,H,.N2Cl)PtCl, : yellow plates. 
 
 Sulphate 
 (HSO A-C6H..C8H^.Ni,SO,H)HjSO^ : white 
 
 ucsdlGs* 
 
 Anilide PhNH.N2.C,H,.C,H,.N2.NHPh : 
 lance-shaped crystals, insol. water. Explosive. 
 
 Piperidide 
 C,,H,„N.N2.C„Hj.C,H,.N3.NC5H„. From benzi- 
 dine by diazotisation and treatment with piperi- 
 dine. Insol. water, si. sol. alcohol, v. sol. ether 
 {Wallach, A. 235, 271). 
 
 m-m-Tetra-azo-diphenyl (Brunner a. Witt, 
 B. 20, 1028). 
 
 Diazo-pheuyl-carbamic ether 
 
 c„h/ } 
 
 ^N— COjEt. Formed by diazotising o- 
 amido-phenyl-carbamic ether (Rudolph, B. 12, 
 1296). 
 
 Heza-azo-tri-phenyl-carbinol 
 
 Chloride { CjHjfNjCl) } 3COH. Diazo-p- 
 rcsaniline chloride. Formed by diazotising p- 
 
 rosaniline hydrochloride (E. a. O. Fischer, A, 
 194, 274).— C,5H,3N„Cls3AuCl5. 
 
 Hexa-azo-tri-phenyl-carbinyl cyanide 
 
 Chloride {CsH^(NjCl)|sC.CN2aq. From 
 hydroeyano-^-rosaniline hydrochloride by diazo- 
 tisation. Slender needles, v. sol. water. Gives, 
 with boiUng water, (0sHiOH)30.CN (Fischer, A. 
 194, 275). 
 
 Hexa-azo-tri-phenyl-methane chloride 
 (C5HjN2Cl)3CH. Diazo-p-Uucaniline. Formed 
 by diazotising tri-amido-tri- phenyl -methane- 
 hydrochloride (E. a. 0. Fischer, A. 194, 269). 
 Gives ^-rosolic acid (aurin) when boiled with 
 water. 
 
 Si-azo-phenyl methyl ketone snlphite of 
 sodium CH3.CO.CjHj.N2.SO3K. Formed by di- 
 azotising - amido - aoetophenone and treating 
 the product with K2SO3. On reduction it gives 
 the hydrazine salt: CH3.CO.G,H,.NH.NHS03K 
 whence HCl forms methyl-indazol, 
 
 >CMe 
 C.H.^ |\ (v. Indazol). The aqueous solu- 
 
 \n-nh 
 
 tion of the hydrazine salt changes to 
 
 .CMe 
 CoH/ |\ 
 
 ^N — N.S03Na methyl-indazol sulphonate 
 of sodium (Fischer a. Tafel, A. 227, 305). 
 
 Heza-azo-di-pheuyl-tolyl-carbinol. 
 
 Chloride {G^n,'Sfi\)fi(OB.).C^M.aSjSL 
 Diaeo-rosaniline. Formed by diazotising rosani- 
 line hydrochloride (Caro a. Wahklyn, Z. 1866, 
 511 ; E. a. 0. Fischer, A. 194, 279). Gives 
 rise to rosolie acid when boiled with water. — 
 (02oH„N,Cl3).,3PtCl,6aq.-C2,H,3N,Cl33AuCl,. 
 
 Hexa-azo-di-pheuyl-tolyl - carbinyl cyanide. 
 
 Chloride (CsH^N^Cl) j:C(CN) .CsH3MeN2Cl. 
 Diazohydrocyan - rosaniline. — Gold salt. — 
 C2.H„(CN)N,Cl33AuCl,. 
 
 Siazo-resorcin chloride. Diethyl ether 
 C5H3(0Et)2N2Cl. From the amido- compound 
 (PukaU, B. 20, 1136). Unstable crystals. 
 
 Siazo-rosaniline (v. sv/pra). 
 
 Diazo-salicylic acid v. Diazo-oxy-benzoio 
 
 ACID. 
 
 Siazo-Bnccinamic acid 
 
 CO2H.CH2.CN2.CONHJ. 
 
 Methyl ether A'Me: [84°]; long yellow 
 prisms (from alcohol). Formed by the action 
 of aqueous NH, upon methyl diazo-succinate. 
 By decomposition with cold slightly acidified 
 water it yields methyl f umaramate and methyl 
 malamate. Heated with benzoic acid at 140°- 
 150° it gives methyl benzoyl-malamate. Iodine 
 in ethereal solution converts it into methyl 
 di - iodo - succinamate — C02Me.CHj.CIj.C0NHj 
 (Curtius a. Koch, B. 19, 2460). 
 
 Ethyl ether C^B.^TA^(COl^'B^(CO^t — 
 [112°] ; long thin yellow prisms ; easily soluble 
 in hot water and alcohol, sparingly in cold 
 water and ether. It is not altered by boiling 
 with pure water, but by acids and alkalis is at 
 once decomposed with evolution of nitrogen. 
 Eeduced to aspartio ether by zinc-dust and 
 acetic acid (Curtius a. Koch, B. 18, 1293). 
 
 Diazo-Buccinic acid CjH2N2(C02H)2. The 
 di-methyl and di-ethyl ethers of this acid 
 are obtained by mixing iced solutions of 
 the hydrochlorides of the aspartio ethers 
 C02E.CH(NH3C1).CH2.C02E and sodium nitrite, 
 and adding a few drops of dilute HaSO^, after 
 
DIAZO- COMPOUNDS. 
 
 418 
 
 'vhich the product is shaken out with ether. 
 The ethers form dark-yellow oils which have 
 not yet been obtained in a pure state. By boil- 
 ing with water or aqueous acids they are decom- 
 posed with evolution of nitrogen and formation 
 of the corresponding fnmario ether. They 
 decompose spontaneously on keeping, evolving 
 nitrogen and forming azinsuccinio ethers 
 (C02E)3CjH2:N.N:C2H2(C02R)2. Strong aqueous 
 NHj converts them into diazo-sucoinamic ethers. 
 
 2)-Diazo-toluene. 
 
 Salts. — The preparation and properties of 
 these salts resemble those of the corresponding 
 diazo-benzene salts (Griess, C. /. 20, 86). — 
 OjHjMe.Nj.NOj : long slender white needles. — 
 (CjHjMe.NjC^jPtClj: yellow prismatic crystals. 
 C„H,Me.NjSO,H.— CjHiMe.N,Br3. 
 
 Dicyanide CsH^N^ or CsHiMe.Nj.CN.HCN. 
 [78°]. Needles or leaflets. Formed by the action 
 of a diazo-toluene salt on a solution of KCN 
 (B. 12, 1638). 
 
 Anilide CjHjMe.N^.NHPh or, alternatively, 
 Ph.N2.NH.C8HjMe. From p-toluidine and di- 
 azobenzene nitrate or from aniline and ^-diazo- 
 toluene nitrate (Griess, A. 137, 60; B. 7, 1619). 
 Narrow yellow leaflets. By warming with phenol 
 it gives a mixture of aniline,2)-toluidine, benzene- 
 azo-phenol andp-toluene-azo-pheuol; similarly 
 with resorcin (Heumann a. Oeconomidea, B. 20, 
 907). 
 
 p-Ohloro-anilide. Formed from p- 
 chloro-diazo-benzene and ^-toluidine. By heat- 
 ing with phenol it gives ^-toluene-azo-phenol 
 and ^-ohloranUine {Heumann a. Oeoonomides, 
 B. 20, 909). 
 
 Piperidide Ci^HjjNa i.e. CjHj.Nj.NCjH,, 
 [41°]. From CHj.CjH^.NjOl and piperidine. 
 Prisms (from alcohol or ether). Insol. water. 
 Dry HCl passed into its solution in petroleum- 
 ether appears to form an unstable hydrochloride, 
 quickly decomposing into diazotoluene chloride 
 and piperidine hydrochloride (WaUach, A. 235, 
 244). 
 
 p-Toluide CjHjMe.Nj.NH.CeH^Me. [116°]. 
 Formed by passing nitrous acid gas into a solu- 
 tion of ^-toluidine in alcohol and ether (Griess, 
 A. 121, 277 ; when pure (by digestion with 
 alcoholic {NH4)2S) it forms nearly colourless 
 large thin prisms (Bemthsen a. Goske, B. 20, 
 928). 
 
 p-Ethyl-toluide CoHjMe.Nj.NBt.CsHjMe. 
 Decomposed by acids into ethyl-^-toluidine and 
 p-diazo-toluene chloride (Gastiger, BL [2] 42, 
 342). 
 
 o-Diazo-tolneue-o-toluide 
 [2:1] C5H4Me.N2.NH.C,H4Me [1:2]. [51°]. 
 Orange-yellow powder of microscopic needles. 
 Prepared by adding sodium nitrite (1 mol.) to 
 an aqueous solution of o-toluidine (2 mols.) and 
 HCl (B mols.) and then neutralising the HCl 
 with sodium acetate, the temperature being 
 kept below — 5° during the whole reaction. It 
 is crystallised by dissolving in cold alcohol and 
 adding ice (Fischer a. Wimmer, B. 20, 1582). 
 
 o-Diazo-toInene-azo-tolueue CjjHisNj.OH i.e. 
 .N— N.OH 
 CMjC II • (?) Obtained by diazotising 
 
 \N— N.C,H, 
 toluene-azo-o-toluidine ; the salts crystallise out 
 when a stream of nitrous acid gas is passed 
 into an alcoholic solution of toluene-o-azo- 
 
 toluidine and an excess of acid, or upon 
 subsequent addition of a little ether. On 
 heating with water or alcohol it decomposes, 
 evolving nitrogen like ordinary diazo-compounds. 
 By SnClj or SO2 it is not reduced to a hydrazine 
 but gives a stable compound CuHuN^ which 
 
 .N— NH 
 
 probably has the constitution C.H, 
 
 / 
 
 I 
 
 \N— NC,H, 
 by bromine this body is reconverted into the 
 diazo-perbromide. By zinc-dust and alcohol it 
 is converted into m-toluene-jp-azo-toluene [58°] 
 with evolution of nitrogen. The diazo-imide 
 loses nitrogen on heating and yields tolyl- 
 
 azimido- toluene C,HX | >N.C,H,identicalwith 
 
 that obtained by oxidation of toluene-azo-o-tolui- 
 dine. o-Diazo-toluene-azo-toluene reacts with 
 amines and phenols like an ordinary diazo- 
 compound ; the products, however, reduce to a 
 diamine or amido-phenol and tolyl-azimido- 
 toluene. All the salts have a deep orange-yellow 
 colour and are tolerably stable. — CjjHijNj.Cl" : 
 red granular crystals. — (CnHigNj-Clj^PtClj: yel- 
 low aoicular crystals. — CnHuNj.NO," : slender 
 red pointed crystals. — CuHiaNj-SO^H" : red in- 
 terwoven needles. — C,iH,3N4.Br3: [125°], long 
 glistening red needles or compact crystals. 
 
 Imide CnHi^Nj: [85°], thick yellowish red 
 crystals ; formed by the action of alcoholic NH, 
 upon the perbromide (Zincke a. Lawson, B. 
 19, 1452). 
 
 Product of Reduction OnHuN, probably 
 
 r/ 
 
 .N— NH 
 C,HZ I I [168°]. Long colourless 
 
 \N— N.C,H, 
 needles. V. sol. hot alcohol, si. sol. ether 
 and chloroform, insol. water. It has no 
 basic properties. It is not aiieoted by 
 reducing agents. Bromine in alcoholic or acetic 
 acid solution readily converts it into o-diazo- 
 toluene-azo-toluene perbromide. On addition of 
 AgjO to its alcoholic solution nitrogen is evolved 
 and ?7t-^-azotoluene [58°] is formed. 
 
 Acetyl derivative CnHijN^Ac [134°] : 
 glistening white plates (Zincke a. Lawson, B. 
 19, 1457). 
 
 p-Siazo-toluene-azo-toIueue 
 [2:1] C,H,(CH3)-N,-C,H3(CH3).N,OH [1:3:4]. 
 Prepared by dissolving toluene-azo-^-toluidine 
 in alcohol, adding an excess of HCl, diazotising 
 by passing N2O3 into the well-cooled solution, 
 and precipitating the diazo-salt with ether. By 
 reduction with SnClj or zinc-dust and acetic 
 acid in cold dilute aqueous solution it is split 
 up (without formation of a hydrazine) inta 
 o-toluidine and tolylene-p-diamine. 
 
 Salts. — ''C,jH,3Nj.N03: slender brownish- 
 yellow needles, m. sol. water and alcohol. — 
 CnH|3N4.Br3: yellow crystalline pp. which 
 changes on standing to small violet needles. — 
 0„H|3N.|.S03Na : glistening scales (from alcohol), 
 V. sol. hot. alcohol, si. sol. water. 
 
 Imide C,4H,3N5: [60°]; long plates; sol. 
 alcohol and acetic acid (Zincke a. Lawson, B. 
 20, 1181). 
 
 o-Siazo-toluene m-sulphouic acid 
 
 »MeCsH3<g^'''> [1^]. Precipitated as a 
 white powder when nitrous gas is pasced into a 
 
410 
 
 DIAZO- COMPOUxVDS. 
 
 cold solution ol o-toluidine sulphonio acid. 
 Explodes feebly at 100° (Nevile a. Winther, C. J. 
 37, 628). 
 
 o-Siazo-toluene p-sulphouic acid. 
 
 Minute monocliuio prisms (Hayduok, A. 
 172, 213; 174, 344). Boiling alcohol produces 
 Me.CeH3(OEt).S03H [1:2:4]. 
 
 j)-Diazo-tolueiie o-sulphouic acid. Yellow 
 or brown needles (Asoher, A. 161, 8 ; Jensen, A. 
 172, 235). Heated with alcohol under pressure 
 it gives MeCsH3(OEt)(S03H) Kemsen a. Palmer, 
 Am. 8, 243). 
 
 jj-Diazo-toIaene m-sulphonic acid 
 
 '<MeC5H3<^gj^> [l|]. More soluble than 
 
 the corresponding o-oompound (Nevile a. Win- 
 ther, 0. J. 37, 631). Prepared by passing 
 nitrous acid gas into p-toluidine sulphonio acid 
 suspended in alcohol. Hot alcohol gives toluene 
 m-sulphonic acid (Petermann, A. 173, 201). 
 ^-Siazo-tolaene exo-sulphonic acid 
 
 CsH,<^J^ ^SOj. Heated with alcohol under 
 
 1,100 mm. pressure it gives CeHj(0Et).CHa.S03H 
 (Mohr, A. 221, 219). 
 
 p - Diazo - toluene - snlphonic - amide - toluene 
 snlphonic acid. Amide 
 
 [1:4:2] C,H,Me(SO^NHa)N,.NH.C,H,Me.SO^NH, [2:1:4]. 
 From 03H3Me(NH2)S02NH2 [1:2:4], alcohol, and 
 nitrous acid gas (Paysan, A. 221, 211). Decom- 
 posed by HCl into N^, OsHjClMe.SOjNH^, and 
 OjH3(NH2)Me.SOjNHj. 
 
 o-Siazo-tolnene disulphonic acid 
 
 C.H,Me(S03H)< | 
 
 aqueous o-toluidine disulphonic acid at 0° (Lim- 
 prioht, B. 18, 2176 ; Hasse, A. 230, 291). Micro- 
 scopic needles. Explosive. Heated with alcohol 
 under pressure it gives CBH2Me(OEt)(S03H)2. 
 With HI it forms CBH^MelfSOsH)^. 
 Salt s.— KA'.— BaA'j 4aq.— PbAV 
 r)-I)iazo-toluene di-sulphonic acid 
 .N, 
 
 [-=!]. 
 
 From N.O. and 
 
 SO, 
 
 Formed by diazotisation 
 
 0,H2Me(S03H)/l 
 
 of ^-toluidine- di- sulphonio acid. Yellowish 
 crystals. By heating with HI it yields p-iodo- 
 toluene-di-sulphonio acid; with HBr it yields 
 p-bromo-toluene-di-sulphonic acid. 
 
 Salts. — A'K: large yellow prisms. — A'jBa : 
 yellowish white needles. — A'^Pb : small red 
 prisms (Limpricht, B. 18, 2178). 
 
 Siazo-toluic-amido-toluic acid 
 C3H3Me(COjH).N2.NH.C3H3Me.C02H. From 
 
 amido-toluio acid and nitrous ether (Griess, 
 A. 117, 59). Minute yellow prisms (containing 
 I aq) ; insol. water, alcohol, and ether. 
 
 o-Siazo-^-toIuidine bromide, 
 
 Acetyl derivative 
 
 C„H3Me(NHAc).NjBr [1:4:2]. 
 From C8H,,Me(NHAo)(NHJ [1:4:2], cone. HBr 
 and cone. NaNO^ at 0° (Wallaoh, A. 235, 249). 
 
 Beactions. — 1. Hot ACjO converts it into 
 C„H3Me(NHAc)(0Ac) [132-5°].— 2. Nitro-ethane 
 and NaOBt give C„H,Me(NHAo).N2.0HMe(N02). 
 [143°].— a. HNEt^ gives 03H3Me(NHAc)N2.NEt2. 
 [108°]. — 4. Fiperidine gives the piperidide: 
 CsH3Me(NHAo).Nj.NC5H,„. [154°]. HOI passed 
 into an alcoholic solution of this base gives a 
 
 pp. of OeH3Me(NHAo)N201. Boiling HOlAq 
 gives C3H3Me(NHAo)Cl. 
 
 Siazo-m-zylene-sulphoaic acid 
 
 C3H2Me2<|^^>. [1:3:4:6]. White pp. Sparingly 
 
 soluble in water. Decomposes at 60°- 70°. 
 Combines with phenols and amines. Formed 
 by diazotisation of m-xylidine-sulphonic acid 
 (Nolting a. Kohn, B. 19, 138). 
 Diazo-^-xylene-sulphonlc acid 
 
 OsHjMej-c;;^ ^ [l:4 ^] . YeUowish white plates. 
 
 Stable at ordinary temperature, decomposes on 
 heating with water at 60°-70°. Formed by 
 the diazotisation of p-xylidiue-sulphonic acid 
 C<iH2Me2(NH2)(S08H) [1:4:2:5] (Nolting a. Kohn, 
 B. 19, 141). 
 
 DISAZO- COMPOUNDS, Secondary aso- com- 
 pounds. Compounds containing two azo- groups 
 of the form C — N^ — 0. The general methods by 
 which they may be prepared are given in the 
 article on azo- colouring matters (p. 368). Thft 
 nomenclature here used is like that used for 
 azo- compounds. To find the name of a disazo- 
 compound, write down the formula, strike out 
 everything between the two N^ groups, remove 
 one of the Nj groups, and join the remaining 
 parts of the formula together and name the 
 resulting azo- compound as directed on p. 369. 
 Then insert after the word ' azo ' the name of 
 the central hydrocarbon, preceded by prefixes, 
 representing its substituents and followed by 
 ' azo.' 
 
 Si-amido -benzene -azo-benzene-azo-benzen» 
 snlphonic acid 
 
 [4:1]C3H,(S03H)-N,-C,H,-N,-03H3(NH3), 
 [1:2:4]. Formed by the combination of diazo- 
 benzene-azo-benzene-^-sulphonio acid with m- 
 pheuylene diamine. Bed microscopic needles. 
 V. si. sol. alcohol and ether. In HjSOj it dis- 
 solves with a violet-blue colour. — KA'2aq:red 
 glistening plates, si. sol. hot, v. si. sol. cold, 
 water, dyes silk, wool, and cotton a brownish- 
 red (Griess, B. 16, 2035). 
 
 Amido-sulpho-naphthaleue-azo-diphenyl-azo- 
 naphtbylamine snlphonic acid 
 
 [1:4:2] C,„H,(NH,)(S03H)-N,-CA. 
 
 [1:4:2] C,„H,(NH,)(S03H)-N,-C3H3. 
 Formed by combining diazotised benzidine with 
 (a)-napEthylamine jp-sulphonic acid. Dyes 
 cotton from an alkaline bath scarlet, turned 
 blue by a trace of acid. The aqueous solution 
 is readily reduced by NH3 and zinc-dust, giving 
 benzidine and naphthylene-o-di-amine sulphonio 
 acid (Witt, B. 19, 1719). 
 
 Benzene-azo-m-diamido-benzene-azo-benzens 
 C,H3-N,-C3H,(NH),-N,-C3H3. [250°]. 
 
 Formed by the combination of diazobenzene 
 with chrysoidine. Dark red needles or six- 
 sided plates. Sol. hot chloroform and benzene, 
 V. si. sol. alcohol and ether, insol. water. Weak 
 base. Salt s. — B'HCl : violet-brown amorphous 
 solid.— B'jHjCljPtClj : violet-brown amorphous 
 pp. (Griess, B. 16, 2028). 
 
 Benzene-azo-m-diamido - benzene-azo-benzene 
 2>-sulphonic acid 
 
 C.H,(S03H)-N,-C3H,(NH,),-N,-CeH5. 
 Formed by the action of ^-diazo-benzene-sul- 
 phonic acid on chrysoidine. Dark-brown mi- 
 croscopic crystals. V, si. sol. alcohol, insol. 
 
DISAZO- COMPOUNDS. 
 
 417 
 
 ether. A'K : reddish-brown plates, sol. hot, si. 
 ■ol. cold, water (Grriess, B. 16, 2032). 
 
 Benzene -azo - di-amido -benzene-azo-benzoio 
 acid OA(aO,;E)-N,-0,H,(NH,),-N,-OeH,. 
 Formed by combining m-diazo-benzoio aoid 
 with chrysoidine (Griess,B.16,2032). Brownish- 
 red powder. Insoluble or nearly insoluble in 
 til ordinary solvents. Soluble in alkalis with a 
 brownish-red colour. 
 
 (a)-Benzene-azo-m-di-amido-benzene-azo-toIu- 
 ene 0,Hj— N,,— 0,Hj{NHj)2— N^— C,H,. [192°]. 
 Formed together with a small quantity of the 
 (3)-isomeride by the combination ot p-diazo- 
 benzene with p-toluene-azo-phenylene-diamiue. 
 Dark-red glistening needles. Sol. ether, chloro- 
 form and hot benzene, insol. water and alcohol. 
 
 (i3) - Benzene - azo-m - di - amido - benzene - azo- 
 tolnene C,H,-Nj— C„H,(NHJ,-N,— C,H,. 
 [225°]. Slender yellow needles. Sol. alcohol and 
 ether, t. si. sol. chloroform, sol. in water (Griess, 
 B. 16, 2029). 
 
 Benzene - azo - m - di- amido -benzene • ^ - azo - 
 toluene C,H,— Nj— 06H2(NHj)2— N^— CeH,. 
 [214°]. Formed by the combination of Jj-diazo- 
 toluene with chrysoidine (Griess, B. 16, 2030). 
 Dark-red glistening needles. SI. sol. chloroform, 
 ether, and benzene. 
 
 Benzene-azo-benzene-azo-27-cresol 
 
 (4) (1) (6) (2) 
 
 C,H,-N,-C,H-N,-CA(CH3)(0H). [160°]. 
 Obtained by the action of diazo-benzene-azo- 
 benzene chloride (by diazotising benzeue-azo- 
 aniline) on an alkaline solution of p-oresol 
 (Noltiug a. Kohn, B. 17, 354). Small brown 
 needles. SI. sol. alcohol, m. sol. chloroform, 
 benzene, and acetic acid. Dissolves in H^SOj 
 with a reddish violet colour. 
 
 Benzene-azo-benzene-azo-ethyl-(;8)-naphthyI- 
 amine CsHj— N^— CeH,— N^— 0,(,Hj.NHEt. 
 [142°]. Small red needles. Formed by heating 
 ethyl-(i8)-naphthyl-nitrosamine with an acetic 
 acid solution of benzene-azo-aniline (Henriques, 
 B. 17, 2670). 
 
 Benzene -azo-benzene-azo-(i3)-naphthol 
 CeHs— Nj— CbH4— Nj— C,„Hs.OH. From diazo- 
 tised benzene-azo-aniline and (j3)-naphthol 
 (Nietzki, B. 13, 1838). Brick-red powder. 
 
 Benzene-azo-benzene-azo-resorcin 
 CsH,— Nj— CsHj— Nj— CsH3(0H)j. By the action 
 of diazotised benzene-azo-aniline on resorcinol 
 two isomerides are formed which are separated 
 by their different solubilities in aqueous alkalis. 
 
 (a)-Compound [184°]. Brownish red 
 powder consisting of microscopic tables. Dis- 
 solves with a carmine red colour in aqueous 
 NaOH and in HjSOj. Sol. alcohol, ether, and 
 chloroform. 
 
 {p)-Gompound [215°]. Brown powder. Dis- 
 solves in alcoholic NaOH with a violet-blue 
 colour and in H^SO, with a pure blue colour, 
 V. si. sol. alcohol, ether, and chloroform, insol. 
 aqueous NaOH (Wallach, B. 15, 2817). 
 
 Eenzene-azo-metbyl-pyrrol-azo-benzene 
 C,H,-N,-0,H,NMe-N,-C,H, 
 C5H5.Nj.C=CH 
 probably NMe| [196°]. Formed by 
 
 C5H3N2.0=CH 
 the methylation of benzene-azo-pyrrol-benzene. 
 Eed plates (O. Fischer a. Hepp, B. 19, 2253). 
 
 Vol. I. 
 
 Benzene-azo-ozy-benzene-azo-benzene 
 
 (1) (4) (3) 
 
 O5H5— Nj— OeH3(OH)— Nj— O^Hj. Benzene, 
 
 disazo-phenol. Phenol-bi-diazo-benzene. [131°]. 
 Formed, together with benzene-azo-phenol, by 
 treating diazo-benzene nitrate with BaCO, in" 
 the cold, or by the action of diazo-benzene 
 nitrate upon a solution of benzene-azo-phenol 
 in KOHAq (Griess, A. 137, 86; B. 9, 628). 
 Brown lustrous needles or plates (from alcohol). 
 V. si. sol. water, v. sol. KOHAq, v. si. sol. NHjAq, 
 insol. Na^COjAq. 
 
 Methyl ether C,8H,3N,(OMe) [110°], smaU 
 yellow crystals, v. sol. ether, benzene, acetone, 
 and hot alcohol. 
 
 Acetyl derivative C,8H|3N4(OAc) [116°], 
 small yellow needles, sol. alcohol, ether, and 
 benzene. 
 
 Benzoyl derivative 0,8H,3N4(OBz) 
 [139°], small yellow needles, si. sol. cold alcohol 
 (Nolting a. Kohn, B. 17, 368). 
 
 Benzene-azo-di-ozy-beuzene-azo-benzene 
 C.Hj— N2-C.H,(0H),— N,— C^Hj. By the 
 action of diazo-benzene chloride on an alkaline 
 solution of benzene-azo-resoroin two isomerides 
 are formed which are separated by their solu- 
 bility in aqueous alkalis. A third isomeride (7)- 
 is formed, together with beuzene-azo-resorcin, 
 by the action of diazo-benzene chloride on res- 
 orcin treated with KOH (1 mol.) in dilute 
 aqueous solution. 
 
 {a)-Compound [215°]. Brown felted needles. 
 Dissolves easily with a red colour in aqueous 
 NaOH and in H^SO,. SI. sol. alcohol and ether, 
 m. sol. chloroform. Its di-aoetyl derivative 
 forms brown glistening needles, [184°] (WaUaoh). 
 
 {0)-Oompound [220°]. Microscopic needles. 
 SI. sol, alcohol and chloroform, insol. aqueous 
 NaOH. Dissolves in H2SO4 with an indigo-blue 
 colour, and in alcoholic NaOH with a red colour 
 (WaUaoh, B. 15, 2816). 
 
 (■y)-Oompound [222°]. Large red needles 
 Sol. chloroform, v. si. sol. alcohol. It dissolves 
 in strong alkalis with a brownish-yellow colour; 
 in H2SO4 with the same colour. By tin and 
 HOI it is reduced to aniline and di-amido- 
 resorein. 
 
 Di-acetyl-derivative 
 C,8H,2N,(OAc)2 [138°], orange needles (Liebei- 
 mann a. Kostaneoki, B. 17, 880). 
 
 Benzene-azo-triozybenzene-azo-benzene 
 CjHs— N2— a5H(OH)3— Nj— CsHj. Phloroglucin. 
 H-diazo-hemene. Yellowish-brown leaflets. Pre- 
 pared by the action of diazobenzene nitrate on 
 phloroglucin (Weselsky a. Benedikt, B. 12, 226). 
 
 Benzene-azo-diozy-benzene-azo - naphthalene 
 CsHj— N2-C8H2(0H)j— Nj— C,„H,. [155°]. From 
 diazo-benzene chloride and an alkaline solution 
 of w-di-oxy-benzene-azo-naphthalene (Wallach, 
 B. 15, 22). 
 
 Benzene-azo-di-ozy-benzene-azo-tolnene 
 C3H3-N,-C,H,(OH),-N,-C,H4(OH3) [1:4]. 
 Prepared by the action of diazo-benzene chloride 
 on an alkaline solution of m-dioxy-benzene-azo- 
 toluene, or of diazo-toluene chloride on an alka- 
 line solution of benzene-azo-resorcin ; in either 
 case the same three isomerides are simultane- 
 ously produced and are separated by means ol 
 their different solubilities. 
 
 (a)-Compound [196°]. Golden brown needles. 
 Dissolves with a red colour in H^SO, and NaOH. 
 
418 
 
 DISAZO- COMPOUNDS. 
 
 Sol. alcohol and ohloroform. Its di-aoetyl- 
 derivative forms yellow needles, [176°]. 
 
 (a')-Gompound [241°]. Dissolves with a red 
 oolour in H^SO, and in aqueous NaOH. Its 
 di-aoetyl-derivative £orms yellow needles, 
 [196°]. 
 
 (P)-Compound [206°]. Brownish - black 
 miorosoopio crystals. Insol. aqueous NaOH, dis- 
 solves in HjSO, to a blue solution. SI. sol. alco- 
 hol, m. sol. ohloroform (Wallach, B. 15, 2821). 
 
 Beuzene-azo-oxy-cymene-azo-i>euzene 
 (2) (i)(4) (3) (6) 
 
 0,H5— Nj— C5HMePr(0H)— Nj— C^H,. Thymol- 
 bi-diazo-hemene. [168°]. Formed, together with 
 benzene-azo-thymol, by the action of diazo- 
 benzene on thymol (Mazzara, G. 15, 52, 228). 
 Silky needles, sol. chloroform. By reduction 
 with tin and HCl, and subsequent treatment with 
 PejCl,, it is converted into oxy-thymoquinone. 
 
 Benzene-azo-o-ozy-toluene-azo-benzene 
 
 (1) (3) (4) (5) 
 
 CA-N,-O.H,Me(OH)-N,-C,H,. [115°]. Ob- 
 tained by the action of (2 mols. of) diazo- 
 benzene chloride on an alkaline solution of 
 o-oresol (Nolting, B. 17, 364). Eeddish-brown 
 plates. V. si. sol. cold alcohol. Dissolves in 
 alkalis with a yellowish red colour. 
 
 Acetyl derivative [121°], yellow needles, 
 V. sol. alcohol, ether, and benzene. 
 
 Beuzeue-azo-TO-ozy-tolueue-azo-beuzeue 
 
 (1) (2) (4) (3) 
 
 CeHs— Nj— C5H2Me(OH)-Nj— CeH^. [149°]. Ob- 
 tained by the action of (2 mols. of) diazo- 
 benzene chloride on an alkaline solution of 
 wi-oresol. Eeddish-brown plates. Sol. ether, 
 benzene, and hot alcohol, si. sol. cold alcohol. 
 
 Acetyl derivative [157°], small yellow- 
 ish-brown needles (Nolting a. Kohn, B. 17, 367). 
 
 Benzene-azo-di-phenyl-urea-azo-benzene 
 05H.-Nj-C,H,.NH.C0.NH.C,H,— N,— CeH,. 
 [270°]. Formed by the action of carbonyl 
 ehloride on benzene-azo-aniline (Berju, B. 17, 
 1404; C. C. 1884, 871). Small plates. Sol. 
 chloroform and benzene, si. sol. alcohol. 
 
 Benzene-azo-di-phenyl-thio-urea-azo-benzene 
 O^Hj— Nj— C„Hi.NH.CS.NH.C„H,— Nj— CjHs. 
 [199°]. Formed as a by-product of the action 
 of phenyl-mustard oil on benzene-azo-aniline 
 (Berju, B. 17, 1405). SI. sol. hot chloroform, 
 xylene, and acetic acid, v. si. sol. alcohol, ben- 
 zene, and CSj. 
 
 Benzeue-azo-pyrrol-azo-benzene 
 
 0.H— N,-0,H3N-Nj-C„H„ 
 OeH5.N2.C = CH 
 probably NH | . [131°]. Obtained 
 
 0»H5.N2.0 = CH 
 by combining (2 mols. of) diazo-benzene chloride 
 with (1 mol. of) pyrrol in alkaline solution. 
 Bed crystalline solid. Sublimable. M. sol. 
 ether and benzene, si. sol. alcohol, nearly insol. 
 water. Possesses basic properties. Dissolves 
 in dilute HCl with a reddish-yeUow colour ; in 
 cone. H2SO4 with a splendid blue colour. Its 
 alcoholic solution is turned magenta-red by 
 NaOH, reddish-violet by cone. HCl (0. Fischer 
 a. Hepp, B. 19, 2251). 
 
 Benzeue-azo-pyrrol-(/3)-azo-naphthalene 
 C.H.-N,-CAN-N,-0,oH, 
 CjH5.N2.C = CH 
 probably NH | . [151°]. Formed 
 
 C,,H,.N2C = CH 
 
 by the combination of diazo-benzene ohloridi 
 with pyrrol-(/3)-azo-naphthalene or of (/3)-diazo- 
 naphthalene dhloride with pyrrol-azo-benzene, 
 in alkaline alcoholic solution. Bed plates, with 
 bluish reflection. SI. sol. alcohol (0. Fischer a. 
 Hepp, B. 19, 2256). 
 
 Tri - bromo - benzene - azo - di - phenyl ■ di. 
 isoindole-azo-trl-bromo-benzene 
 
 O.H.— Nj— CjHjBr, 
 
 CijHjiNeBrj or 
 
 N 
 C.H..C-bH 
 
 HC-CC.H. 
 
 \/ 
 
 N 
 
 C,H.— Nj— C,HjBr, 
 [150°]. Orange yellow prisms. Soluble in most 
 ordinary solvents except water. Formed by the 
 action of tri-bromo-diazo-benzene chloride on 
 di-phenyl-di-iso-indole. — B"H2Cl2: slender 
 yellowish-brown needles (Mohlau, B. 15, 2490). 
 Si - bromo - oxy ■ benzene - azo - di - phenyl- di- 
 isoiudole-azo-dl-bromo-phenol. 
 
 C,H,-N.-O.H^r,(OH) 
 
 N 
 
 CAC OH 
 
 C„H,5N,Br,0j0r | | 
 
 HO CO„H. 
 
 V 
 
 CsH,— Nj— C,H2Br2(0H) 
 
 [198°]. Tellowish-green prisms. Soluble in 
 alcohol, dyes wool orange and silk yellow. 
 Formed by the action of di-bromo-diazo-phenol 
 on di-phenyl-di-isoindole. — B"H2Clj: short 
 metallic glistening prisms, insol. water (Mohlau, 
 B. 15, 2492). 
 
 ■i/ - Cumene - azo - m - di - oxy -benzene • azo - ^- 
 cnmene 
 
 CsHjMe,— Nj— CsHj(0H)2— Nj— CeH^Me,. 
 Formed, together with cumene-azo-resorcin, 
 by combining diazo-cumene chloride (from 
 amido-pseudo-cumene [62°]) with resorcin 
 (Liebermann a. Kostaneoki, B. 17, 882). Small 
 red needles. Dissolves in H2S04 with a red 
 colour. Insoluble in alkalis. 
 
 ^-Si-methyl - amido - benzene -^-azo ■ benzene- 
 azo-(;3)-naphtliol 
 
 HO.C,„H-N,-0eH,-N,-0,H,.NMe,. [210°]. 
 Got by pouring a diazotised solution of ^J-amido- 
 benzeue-azo-dimethylaniline hydrochloride into 
 a solution of (j8)-naphthol in NaOH (Meldola, 
 G. J. 45, 109) Bronzy green needles. SI. sol. 
 alcohol, V. sol. hot C2H402, benzene, and chloro- 
 form. Solutions in the above solvents are red ; 
 in alcoholic NaOH, red ; in cone. H^SO, green, 
 turned blue by dilution. An alcoholic solution 
 is turned blue by HCl. 
 
 p - Si-methyl - amido-benzene -p - azo .benzene- 
 azo-(a)-naplithol 
 
 HO.C,oH„.Nj.CsH4.N2.CsH4NMe2. Prepared like 
 its (;3) isomeride (M.). Its properties are similar, 
 except that the solution in alcoholic EOH is 
 violet. It decomposes below 200°. 
 
DISAZO- COMPOUNDS. 
 
 419 
 
 Di-methyl - amido - benzene - azo - benzene-azo- 
 resoroin 
 
 (HO)jO.H3— Nj— OeH^— Nj— OjH^.NMej. Brown 
 powder. Decomposed before melting. SI. sol. 
 boiling alcohol, the solution being reddish- 
 orange and turned first violet, then blue by 
 adding HCl. SI. sol. glacial acetic acid, the 
 solution being red when hot, violet when cold. 
 Insoluble in toluene. Solution in alcoholic 
 KOH is reddish-violet. Solution in cone. HjSOj 
 is violet, becoming blue on dilution (Meldola, 
 C. J. 45, 110). 
 
 Di-metIiyi-amido-benzene-2)-azo-benzene-azo- 
 phenol 
 
 HO.OjH^— Nj— 0,H,— Nj— CjE^NMej. Brown 
 powder, forming a brown solution in aqueous 
 KOH, and a red solution in alcoholic KOH. 
 Besembles the analogous di-methyl-amido- 
 benzene - ^ - azo - benzene - azo - resoroin (j. v.) 
 (Meldola, G. J. 45, 111). 
 
 Di-methyl -amido -benzene - azo - toluene - azo- 
 (/5)-naplithol (2) (i) (4) 
 
 C,H,(NMe,)-N,-CeH3Me-N,-C,oH,.OH. 
 From diazotised di-methyl-amido-benzene-azo- 
 p-toluidine and (j3)-naphthol CWallaoh, A. 234, 
 358). Bed needles (from chloroform), insol. 
 water. 
 
 Ol-methyl-amido -benzene - azo - toluene - azo - 
 phenol (3) (1) (4) 
 
 CeH,(NMeJ-N,-CeH3Me-N,-CeH,OH.[160°]. 
 From diazotised OaH4(NMe2)— Nj— CaHjMeNHj 
 and phenol (Wallaoh, A. 234, 357). Orange 
 needles. 
 
 (a) • naphthalene - azo - pyrrol - (o) - azo - 
 naphthalene 0„H,— N^— O^H^NH— Nj— 0,„H„ 
 0,„H,.N2.C=CH 
 probably 'SSU \ . 
 
 C;oH,.N2.C=CH 
 Formed by adding (o)-diazo-naphthalene chloride 
 (2 mols.) to an alkaline solution of pyrrol (1 mol.). 
 MetaUio-gUstening needles. Sol. alcohol with a 
 dark yellowish-red colour. Dissolves in cone. 
 HjSOi with a blue colour (0. Fischer a. Hepp, 
 B. 19, 2255). 
 
 (/3)-Naphthalene-azo-pyrrol-(;3)-azo-naphthal- 
 ene 0,<,H,— N^-O^H^NH— N^— 0,„H,. 
 
 C,„H,.Nj.C=CH 
 probably J^fH | . [288°]. Formed by 
 
 0,„H,.N,.0=CH 
 adding ()3)-diazo-naphthalene chloride (2 mols.) 
 to an alkaline solution of pyrrol (1 mol.). 
 Glistening coppery plates. SI. sol. alcohol. 
 The alcoholic solution is turned reddish-violet 
 by cone. HCl. Dissolves in eonc. H^SOj with a 
 blue colour (0. Fischer a. Hepp, B. 19, 2255). 
 
 wi-BTitro-benzene-^-azo-benzene - (o) - azo - (0) - 
 naphthol NOAHi-Nj-O.Hi— N,— Ci.H^.OH. 
 [0.218°]. From diazotised NOj.OsH^.Nj.OsH^.NH^ 
 and (/3)-naphthol. Small yield (Meldola, 0. /. 
 45, 113). Orange crystals with green lustre. 
 Solutions in CjHjOj and in toluene are orange ; 
 in alcoholic NaOH, violet ; in cone. HjSO^ green, 
 turned blue on dilution. 
 
 m-Xitro-benzene-(a)-azo-naphthalene-(a)-azo- 
 (a)-naphthol 
 
 N02.0,H<— Nj— C,„H,— N2-C,„He.0H. A dark 
 amorphous powder. Solutions in toluene, chloro- 
 form and glacial acetic acid are red ; in oono. 
 H2SO4 dark indigo violet, becoming blue on 
 dilution; in alcoholic potash, greenish-blue 
 (Meldola, C. J. 45. 116). 
 
 m-nitro-benzene-(a)-azo-naphthaIene-(a)-azo- 
 (|3)-naphthol 
 
 N02.CeH,-N,-0,oH,— N,-C,„H..OH. 
 From m-nitro - benzene - (a) - azo-(o) - naphthyl - 
 amine by diazotising and treating with (iS)- 
 naphthol (Meldola, G. J. 45, 115). Minute 
 bronzy needles (from toluene). Blackens at 
 245°. Insol. alcohol or glacial aoetic acid. Solu- 
 tions in chloroform and in hot aniline are violet ; 
 in toluene red when hot, reddish-violet when 
 cold ; in boiling alcoholic KOH, blue ; in cone. 
 H2SO4, olive colour, on dilution, blue and then 
 violet. 
 
 m-nltro - benzene- (a) - azo - naphthalene - azo - 
 resoroin N02.C5H4—N2—0,„H5—N2—C|,H3(OH)2. 
 Bronzy powder, not very soluble. Solutions in 
 boiling alcohol are reddish ; in glacial acetio 
 acid, toluene and chloroform, orange ; in aqueous 
 or alcoholic KOH, blue ; in cone. HjSO,, green, 
 changing to bluish-green on dilution (Meldola, 
 G. J. 45, 116). 
 
 p-lJ'itro-benzene-azo-m-xylene-azo-(a)-naph- 
 thol NOj-CsH^-N,— O^H^Me^— N,— 0,oH„.OH. 
 Preparation and properties are similar to those 
 of the preceding (j8) -compound. 
 
 Sulphonic acid 
 NOAH4-N2— OsH^Me^— Nj-C,„H3(S0,H)(0H) 
 Similar to the corresponding (/3) -compound, but 
 dyes reddish-brown. 
 
 p - Nitro - benzene - azo -m- xylene - azo - i3 - 
 naphthol 
 
 N0,.C,H4— N^— C^H^Mej— Nj— 0,„H„.OH.[278°]. 
 From N02.CsH,— Nj— OeHjMe^NHj by diazo- 
 tising and treating with sodium (i8)-naphthoI 
 (Meldola, G. J. 43, 434). Green scales (from 
 toluene). Scarcely soluble in alcohol or glacial 
 acetio acid. Forms a crimson solution in boil- 
 ing aniline or nitrobenzene, and a green solution 
 in cone. HjSOi, turned violet by dilution. 
 
 Sulphonic acid 
 N02.C3H,.N2.C„H,Mej.N,.C„H,(0H)S03H. Gotby 
 using C,„Hs(OH)SOsH. Dyes claret-red. 
 
 ^-Mtro-oenzene-azo-m-zylene-azo-phenol 
 N02.C,H4—N2-C3H2Mej-Nj—0aH4.0H. Orange 
 powder. SI. sol. alcohol and benzene, v. sol. 
 hot amline. Solutions are orange. Solution in 
 alcoholic NaOH is reddish-violet. Solution in 
 cone. HjSO, is blue (Meldola, G. J. 43, 436). 
 
 ^-Nitro-benzene-azo-m-zylene-azo-resorcin 
 
 NO„.CeH,-N,-C«H,Me2-Nj-03H3(OH)j. 
 [231°]. Brown powder. Forms orange solutions 
 in boiling alcohol, toluene, and glacial acetio 
 acid. Solution in alcoholic NaOH is red, turned 
 violet by excess of NaOH. Cone. HjSO^ forms 
 a blue solution (Meldola, 0. /. 43, 436). 
 
 j}-0zy-benzene-j7-aza-benzene-(a)-aza-(a)-naph- 
 tholO,H4(OH)-N2— CoH^-Nj— C,„H5.0H. 
 From diazotised p-amido-benzene-azo-(o)- 
 naphthol and an alkaline solution of phenol 
 (Meldola, O. J. 47, 665). Dark amorphoua 
 powder. Its solution in cone. HjSOj is indigo- 
 blue; in boiling toluene, orange; in alcohol, 
 red ; in KOHAq, duU red ; and in alcoholio 
 NaOH, deep claret colour. 
 
 p - Ozy- benzene -p - azo - benzene-(a)-azo-(i3)- 
 naphthol HO-C^Hi— N^— C.H^— N^— C,„H„(OH). 
 [225°]. From ^-amido-benzene-azo (fl)-naphthol 
 by diazotising and mixing with an alkaline 
 solution of phenol (Meldola, 0. J. 47, 666). Bed 
 warty concretions. Its solution in cone. H^SO^ 
 is bluish-green, and becomes violet on dilution. 
 
 K B 2 
 
420 
 
 DISAZO- COMPOUNDS. 
 
 Us solution in boiling toluene, or boiling alcohol, 
 is red. Its solution in KOHAq is reddish- violet. 
 
 m-Si-ozy -benzene -p-azo-benzene-(a)-azo-(a)- 
 naphthol 
 
 [4:2:1] CsH,(OH),-N,-0,H^-N,-C,„He(OH). 
 Formed by mixing diazotised ^J-amido-benzene- 
 azo-(o)-naphthol with a solution of resoroin in 
 dilute NaOH (Meldola, C. J. 47, 665). Bronzy- 
 green powder; Sl. sol. toluene and aoetio acid, 
 forming a red solution. Its solution in KOHAq 
 is blue ; its solution in NHjAq is violet. It is 
 decomposed by heat without fusion. 
 
 m-I>i-oxy-benzene-2)-azo-benzene-(a)-azo-(j3)- 
 naphthol 
 
 [4:2:1] C8H3(OH),-N,-C,H^-N2-C,„H,.OH. 
 From diazotised ^-amido-ben^ene-azo-(;8)-naph- 
 thol and an alkaline solution of resorcin (Meldola, 
 C.J. 47, 666). Bronzy-green powder. Its solu- 
 tion in cone. H2S04 is deep bluish-green; in 
 dilute aqueous alkalis, violet. SI. sol. toluene 
 forming a red solution. 
 
 m-Oxy-benzene-azo-benzene-n-azo-plienol 
 [3:1] HO.CjH^— N^— C5H4— N,— C^H^.OH [1:4]. 
 Dark powder. BasUy soluble in alkalis. Formed 
 by diazotising amido-benzene-TO-azo-phenol 
 (ObH4(OH)— Nj— C5H4.NH2) and combining it 
 with phenol (WaUaoh a. Sohulze, B. 15, 3021). 
 
 p-Oxy-benzeue-azo-benzene-jp-azo-phenol 
 [4:1] HO.C„H,-N,-C,H -N2-C„H,.0H [1:4]. 
 [c. 207°]. From diazotised amido-benzene-^)- 
 azo-phenol and a solution of phenol in dilute 
 alkali (Meldola, C. /. 47, 660). Amorphous 
 brown powder. Its solution in eonc. H2SO4 is 
 violet, unchanged on considerable dilution ; v. 
 sol. NHjAq and KOHAq forming a red solution; 
 insol. boiling toluene ; forms an orange solution 
 in hot phenol or aniline. 
 
 m - Bi - oxy - benzene -p - azo -benzene - azo - re- 
 sorcin 
 
 [4:2:1] O.H.(OH),-N.-C.H.-N,-C.H.(OH), [1:2:4]. 
 From diazotised ^-amido-benzene-azo-resorcin 
 and an alkaline solution of resoroin (Meldola, 
 C. J. 47, 661). Dull bronze-like powder, v. sl. 
 sol. alcohol, insol. toluene. Its solutions in 
 cono. H2SO4 and in alkalis are violet, 
 
 Oxy - carboxy - benzene - azo - benzeue-(a)-azo- 
 (;3)-naphtliol 
 
 (4) (3) (1) (4)(a) (/3) 
 
 C,H3(0O,H)(0H)-N,-0,H4-N:N-C,„H,(OH). 
 [above 255°]. From diazotised ^-amido-benz- 
 ene-azo-salicylic acid and an alkaline solution 
 of (;8)-naphthol (Meldola, C. /. 47, 668). Minute 
 brown needles (from boiling aniline). V. sl. 
 sol. boiling toluene, sl. sol. alcohol and glacial 
 HOAo. Its solution in cone. H^SOj is greenish- 
 blue, changing to violet on dilution. Its solu- 
 tion in KOHAq is reddish-violet. 
 
 Oxy- oymene - azo - tri - phenyl - methane - azo- 
 thjmol 
 
 [6:3:4;l]C.H,MePrrOH)-N,-O.H..^p„p. 
 [6:3:4:1] 0,H,MePr(OH j— N.— O.H.-^ oara. 
 [170°]. Formed by mixing diazotised diamido- 
 ti'i-phenyl-methane hydrochloride with an alka- 
 line solution of thymol (Mazzara, G. 15, 44). 
 Amorphous black powder. After reduction and 
 oxidation it gives thymoquinone. 
 
 (o) - Oxy - naphthalene -jp - azo - benzene - (a) - 
 naphthol 
 
 (a) (aK4) (l)(a) (a) 
 
 C,„H3(0H)— N:N— CeH^— N:N— C,„He(OH). 
 Formed by diazotising ^ - amido-benzeue-azo- 
 (o)-naphthol and mixing the product with an 
 
 alkaline solution of (o)-naphthol (Meldola, C. /. 
 47, 664). Green lustrous powder; v. sl. sol. 
 glacial HOAo, alcohol, and toluene, m. sol. 
 boiling aniline, forming a red solution. Its 
 solution in NaOHAq is blue, in cono. H^SOj 
 blue, turned violet on dilution. With AojO and 
 NaOAc it forms on heating a di -acetyl 
 derivative. 
 
 (;3)-0zy-(a)-naphthalene •'p - azo - beuzeue-(a)- 
 azo-(J3)-naphtliol 
 
 O) (<l)(1) (4)(a) (/3) 
 
 C,.H.(0H)-N:N-C,H4— N:N-0,„H„(OH). 
 [over 275°]. From diazotised 2>-amido-benzene- 
 azo-(i3)-naphtholand an alkaline solution of (/3)- 
 naphthol (Meldola, O. J. 47, 664). Dull bronzy 
 powder, or green needles (from hot aniline). 
 Insol. boiling alcohol, or NaOHAq; sol. cold 
 alcoholic NaOH, forming a violet solution. Sl. 
 sol. hot toluene forming a magenta solution. 
 Cone. H2SO4 forms a bine solution, turned 
 violet on dilution. 
 
 (a) ■Ozy-naphthalene-2)-azo -benzene-azo-(S)- 
 naphthol 
 
 (a) (a)(1) {4)(a) O) 
 
 C,„H,(OH)-N:N-O.H4-N:N-0,oH,(OH). 
 [236°]. From diazotised ji-amido-benzene-azo- 
 (a)-naphthol and an alkaline solution of (/3)- 
 naphthol (Meldola, 0. 3. 47, 665). Dull bronzy 
 powder, v. sl. sol. boiling alcohol ; m. sol. boil- 
 ing toluene and glacial acetio acid forming 
 violet solutions ; cone. H2SO4 forms a blue solu- 
 tion, becoming violet on dilution. 
 
 (a) -Oxy-naphthalene-^-azo -benzene - azo-(/3)- 
 naphthoI-di-BoIphonic acid 
 
 (a) (a)(1) (4) Vf, 
 
 0,.H.(OH)-N:N-C.H.-JS:K-0,^.(SO.H),(bH). 
 From diazotised p - amido - benzene - azo - (o)- 
 naphthol and an alkaline solution of (j8)-naphthol 
 di-sulphonic acid. Its sodium salt is violet and 
 gelatinous; it is an indigo-blue dye (Meldola, 
 C. /. 47, 665). 
 
 ()3) - Oxy - naphthalene - azo - benzene - azo (jS) - 
 naphthol dl-sulphonic acid. Is similar to the 
 last body, but of greater stability (M.). 
 
 Oxy-di-snlpho-naphthalene-azo-benzene-azo- 
 (/3) -naphthol di-suIphonic acid 
 C,.H.(S0,H),(OH)-N,-O.H.-N,-0„H.(SO.H),(0H). 
 Glistening greenish needles. Dyes wool and 
 silk a deep indigo-blue, which, however, is very 
 unstable to light. Is prepared by diazotising 
 the mono-acetyl derivative of ^i-phenylene-di- 
 amine and combining it with (;8)-naphthol-di- 
 sulphonio acid (modification insoluble in spirit), 
 the product C,H4(NHAo).Nj.C,oH,(OH)(SOsH)j, 
 which is a scarlet colouring matter, is saponified, 
 diazotised, and again combined with (j3)-naph- 
 thol-di-sulphonic acid (Nietzki, B. 17, 344; 1350). 
 
 Phenyl - amido - benzene -p - azo - benzene-azo- 
 (;3) -naphthol 
 
 HO.C,„Hs— N^-CeH.— N,— OANHCeHj. 
 [204°]. From ^-amido-benzene-azo-di-phenyl- 
 amine by diazotising and adding sodium (^)- 
 naphthol (Meldola, G. J. 43, 442). Warty scalei 
 with bronze lustre. Sl. sol. boiling alcohol, v. 
 sol. benzene. The solutions are red. In glacial 
 acetio acid the solution is red when hot, violet 
 when cold. Solution in cono. H^SO, is greenish- 
 blue, solution in alcoholic KOH is red but 
 turned blue by HCl (characteristic). 
 
 Phenyl - ethyl - amido - benzene - azo-beuzene< 
 azo- (;3) -naphthol 
 
 HO.O,„H.-Nj— 0,H4— N,-C„H4.NEt.C,H,. 
 
DISAZO- COMPOUNDS. 
 
 421 
 
 From p-diazo-nitro-benzene by combining with 
 ethyl-cU-phenyl-amine, reducing with ammo- 
 nium sulphide, diazotising the product and 
 treating with (/3) • naphthol. Bronzy powder. 
 Solutions in alooholio KOH, alcohol, and ben- 
 zene are red; in cone. H,SO, indigo-blue, turned 
 bright blue on diluting. HCl turns the alcoholic 
 solution blue (Meldola, O. J. 45, 111). 
 
 ^ - Sulpho - benzene - azo - benzene - azo - (|3)- 
 naplithol-(;3)-Biilphonic acid 
 
 (4) {y(l) (4)(a) (a) (3) 
 
 C.H.(SO.H)-N:N-O.H.-N:N— 0,,H.(SO,H)(0H). 
 From diazotised ^-amido-benzene-azo-benzene 
 Bulphonio acid and an ammoniaoal solution of 
 sodium (j3)-naphthol ' a '-sulphonic acid (Bayer 
 a. Co., B. IS, 1351). The sodium salt is a scarlet 
 dye (oroceine scarlet). Cone. E2SO4 forms a 
 blue solution. The absorption spectrum has 
 been studied by Hartley (C J. 51, 195). 
 
 ^-Sulpho -benzeue-azo-benzene - azo -tolylene 
 diamine 
 
 C.H,(S03H)— Nj— C„Hj— Nj— C,H5(NH2)2. Eed- 
 dish-brown microscopic needles. Formed by 
 combining diazo-benzene-azo-benzene-^-sul- 
 phonic acid with tolylene-diamine (Griess, B. 
 16, 2036). 
 
 Sulpho -benzene-azo- di-phenyl-di-isoiudole- 
 azo-benzene sulphonic acid 
 
 C„H,-K,-C,H,(S03H) 
 
 A 
 
 CsHjO — CH 
 
 Hd - CC,H, 
 
 \/ 
 
 C,H,-N,-0eH,(SO,H) 
 Formed by the action of diazo-benzene-sulphonio 
 acid on di-phenyl-di-isoindole. Metallic glisten- 
 ing brown scales. Very slightly soluble in all 
 solvents. Dyes silk and wool nearly the same 
 shade as chrysoidine. On reduction it gives 
 EulphaniUc acid and di-amido-di-phenyl-di-iso- 
 indole. 
 
 Salts. — A"Najaq: yellow plates. — A"Agj: 
 red prisms (Mohlan, B. 15, 2495). 
 
 Sulpho - oeuzene-azo- sTilpho-beuze]ie-(a)-azo- 
 (/3)-naphthol 
 
 O.H,(SO^)-N,-CA(SO,H)— N,-C,.H„.OH. 
 From diazo-sulpho-benzene-azo-benzene sul- 
 phonic acid and an alkaline solution of (fi)- 
 naphthol (NietzM, B. 13, 800). The sodium salt 
 is a red dye (Biebrich scarlet). Cono. HjSO, 
 forms a green solution. Its absorption spectrum 
 has been studied by Hartley (C J. 51, 194). 
 
 Sulpho - benzene - azo-sulpho - benzene - (;3) ■ 
 azo-naphthyl-f -tolyl-amine (' Wool-black ') 
 0,H,(SO,H).N,.CeH3(S03H).N2.G,„H,.NHO,H,. 
 The coml. product is a bronzy powder. V. sol. 
 hot water with a violet-blue colour. Dissolves 
 in cone. HjSO^ with a deep indigo-blue colour. 
 Formed by combination of diazotised amido- 
 sulpho-benzene-azo-benzene-sulphonic acid with 
 p-tolyl - (0) - naphthylamine. By boiling with 
 moderately dilute H^SO^ it is decomposed into 
 tolu-(ai3)-naphthazine [169°] and amidoazo-benz- 
 ene-di-sulphonic acid : 
 
 OA(SO.H)-ir.-OA(SO.H)— ]!r,-0,A-NHO,H,= 
 
 0„H.<^ I \!,H.+0»H.(SO.H)-N,-O.H.(NH,)(SO.H). 
 
 The Ga and Ba salts are insoluble black pps. 
 (Witt, B.^20, 579). 
 
 2)-ToIuene - azo-m - dlamido - benzene - azo - {$)• 
 naphthalene C,H,— Nj— G8Hj(NHj)2— Nj- Gi„H,. 
 Formed by the combination of p-diazo-toluene 
 with (j3)-naphthalene-azo-m-phenylene-diamine 
 (Oriess, B. 16, 2031). Small red glistening 
 plates, y. sol. chloroform. 
 
 ^-loluene-azo-ethyl-pyrrol-p-azo-tolueue 
 
 0,H,-Nj— C^H^NEt— Na— C,H„ 
 
 G,H4Me.N2.g=GH 
 
 probably NEtl [180°]. 
 
 C,H4Me.N2.0=CH 
 
 Formed by ethylation of toluene-azo-pyrrol-azo- 
 
 toluene ; or by combining diazo -p - toluene 
 
 chloride (2 mol.) with ethyl-pyrrol (1 mol.) in 
 
 alkaline solution. Steel-blue needles. SI. sol. 
 
 alcohol (0. Fischer a. Hepp, B. 19, 2254). 
 
 Toluene-azo-diozy-benzene-azo-toluene 
 C,H,— N2— CjH2(0H)2— Nj— G,H,. By the action 
 of p-diazotoluene chloride on an alkaline solu- 
 tion of ^-toluene-azo-resoroin two isomerides 
 are formed which are separated by theii; dif- 
 ferent solubilities in alkalis. 
 
 (aj-Compound [256°]. Yellow felted needles. 
 Sparingly soluble in alcohol and cold chloroform. 
 
 (B)- Compound [203°]. Brownish - black 
 microscopic needles (WaUach, B. 15, 2825). 
 
 Toluene-azo-trioxybenzene-azo-toluene 
 C^H^Me— N2— C3H(OH)3— Nj— GjHiMe. Long 
 red needles. Prepared by the action of diazo- 
 toluene nitrate on phloroglucin (Weselsky a. 
 Benedikt, B. 12, 227). 
 
 loluene-azo-pyrrol-azo-toluene 
 
 G,H— Nj— CANH-N,— G,H„ 
 CsH4Me.Nj.Q=CH 
 probably IJtH | . [179°]. 
 
 CsH,Me.Nj.C=CH 
 Formed by adding (2 mols.) diazo-^-toluene chlo- 
 ride to an alkaUne solution of pyrrol (1 mol.). 
 Bed prisms with steel-blue reflex. SI. sol. 
 alcohol. Its alcoholic solution is turned reddish- 
 violet by cone. HCl. Dissolves in cone. H^SO, 
 with a blue colour (0. Fischer a. Hepp, B. 19, 
 2254). 
 
 Tolueiie-o-azo-toluene-azo-(a)-naphthol 
 
 (4) (1) (6) (2) (a) 
 
 C^,(CH3-N,-G3H3(GH3)-N,-C„H3(0H), 
 N-N-0,oH3(OH) 
 or C3H3(GH3)< I I . [210°]. 
 
 \n-N-C3H,(GH3) 
 Formed by combination of o-diazo-azo-toluene 
 with (a) -naphthol. Brownish-red needles (from 
 aniline). SI. sol. ordinary solvents. Insol. 
 aqueous NaOH, sol. alcoholic NaOH with a 
 violet-red colour. By SnClj it is slowly reduced 
 to amido-{o)-naphthol and tolyl-azimido-toluene 
 G,H5:N3.G,H„ together with small quantities of 
 ^-toluidine and tolylene-o-diamine (Zincke a. 
 Lawson, B. 20, 1178). 
 
 Taluene-o-aza-toluene-azo-(;3)-naphthol 
 
 (4) (1) (6) (2) (/3) 
 
 C3H,(CH3)-N2-0,H3(CH3)-N,-C„H,(OH),or 
 
 N-N-C,„H3(0H) 
 C3H3(CH3)< I I . [177°]. Formed 
 
 \N-N-C3H4(CH3) 
 by combination of o-diazo-azo-toluene with 
 (/3)-naphthol. Long dark-red four-sided prisms, 
 with green reflex. V. sol. benzene, and chloro- 
 form, «1. sol. alcohol, acetone, and petroleum- 
 spirit. Dissolves in alcoholic NaOH oiUy slightly. 
 
4S2 
 
 ■DISAZO- COMPOUNDS. 
 
 By SnCL it is reduced to {a).amido-(fl)-naplithol 
 and tolyl-azimido-toluene 0,H|j:N3.C,Hj, together 
 with small quantities of ^-toluidineand tolylene- 
 o-diamine (Miucie a. Lawson, B. 20, 1179). 
 Ioliiene-^-azo-tolueue-azo-;3-naplithal 
 
 f2) (1) (3) (4) (P) 
 
 C,H,(CH,)-N,-C,H3(CH3)-N,-C,„H,(OH). 
 [186°]. Formed by combination of jp-diazo-azo- 
 toluene with (^)-naphthol. Deep-red needles. 
 v. sol. hot alcohol and benzene. By SnClj 
 it is easily reduced, giving (o)-amido-(/3)-naph- 
 thol, o-toluidine, and tolylene - ^ - diamine 
 CsHjMe^NHj)^ [1:2:5] (Zinoke a. Lawson, B. 20, 
 U82). 
 
 lolueue-o - azo - toluene -azo- (j3) -naphthyl- 
 
 (4) (1) (5) (2) (3) 
 
 amineC,H,(CHJ.K,.C,H3(CH3).N,.C,„H„(NH,),or 
 the corresponding hydrazimido- formula. [203°]. 
 Formed by combination of o-diazo-toluene-azo- 
 toluene with (;8) - naphthylamine. Deep-red 
 glistening plates. V. sol. benzene and chloro- 
 form. By SnClj it is reduced to tolyl-azimido- 
 toluene C,H8:NjC,H, and (probably) naphthyl- 
 ene-o-'diamine (Zincie a. Lawson, B. 20, 1180). 
 
 AZO- COMPOUNDS, TEBTIAHY. 
 
 Ozy-1]eiizeue-^-azo-beuzene-(a)-azo-naplithal- 
 ene-azo-phenol 
 
 HO.C.H.— N,— CeH.— Na— 0,„H,— N,— O.H..OH. 
 From NHj.CjHj— Nj— CijHs.NHj by diazotising 
 and adding sodio phenate (Meldola, 0. J. 43, 
 489). Dull bronzy-green powder. Forms 
 orange solutions with boiling aniline or toluene. 
 Solution in alcoholic KOH is violet; in cone. 
 H2SO4, indigo-blue. 
 
 Di-oxy-benzene-p-azo-benzene-(a)-azo-napli- 
 thalene-azo-resorcin 
 
 (HO),O.H.— N,— C.H.— N— CoH.— N,— C.H,(OH\._ 
 Brown powder. Its solutions are dull red in 
 alcohol, violet in alcoholic KOH, bluish-green 
 in cone. H^SOj. 
 
 (;8).oxy-naphthalene-^-azo-benzene-(o)-azo- 
 naplithalene-azo-(;8)-naphthol 
 
 HO.O„H,— N— C.H.-N^— C,„H,— N,-€,„H,.OH. 
 Formed by diazotising amido-benzene-azo-(/3). 
 naphthylamine NHj.CjHi.Nj.CioHj.NHj and 
 treating with an alkaline solution of (y8)-naphthol 
 (Meldola, C. /. 43, 437). The pp. may be 
 separated by crystallisation from hot aniline 
 into two modifications, one remaining in solu- 
 tion, the other separating as needles with green 
 lustre. 
 
 Crystalline form [c. 295°]. Insoluble 
 in boiling alcohol, acetone, or glacial acetic acid, 
 hardly soluble in chloroform or benzene. Forms 
 violet solutions with aniline or nitrobenzene. 
 Solution in cone. HzSO, is deep inky blue. 
 Alcoholic KOH forms, with difficulty, a blue 
 solution. 
 
 Soluble form. — Soluble in the above 
 liquids. Its solution in boiling glacial acetic acid 
 is violet when hot, blue when cold. Solution in 
 cone. H2SO4 is clear indigo-blue. Alcoholic 
 potash forms a violet solution. 
 
 Di-sulphonic acid. — From (j8)-naphthol- 
 Bulphonic acid and diazotised 
 NH,.C„H,.N,.C,„H3.NH3. 
 
 (a) -Oxy-naphthalene.j)-azo - benzene - (o) -azo- 
 naphthalene-azo-(a)-naphthol. Similar to the 
 preceding. Bronzy powder, forming a blue solu- 
 tion in alcoholic KOH, and an indigo-blue solu- 
 tion with cone. H^SO,. 
 
 (/3)-0xy-naphtlialene -p - azo - benzeue-azo-m- 
 zylene-azo-(;3)-naphthol 
 
 HO.O,„H.— N,— O.H.— N,— C.H.Me.— N,— CoH.OH. 
 
 From NH^.CjHj.Nj.CjHjMe^NHj by diazotising 
 and adding sodium (j3)-naphthol (Meldola, C. J, 
 43, 439). Small green needles (from xylene). 
 Its solution in aniline is reddish-violet; in 
 xylene, violet ; in hot alcoholic KOH, bluish- 
 violet ; in cone. HjS04 greenish-blue, becoming 
 blue on dilution. It is insoluble in alcohol and 
 in glacial acetic acid. Its sulphonic acid dyes 
 silk and wool dull violet. 
 
 Tri-oxy-tri-naphtlialene-hexa-azo-tri-plienyl- 
 earbinol UO.GiG^B.^—'Si—C^^B.fi'H.),'^. From 
 diazotised para-rosaniline and (o)- or (;8). naph- 
 thol in alkaline solution (Meldola, C. J. 47, 
 668). Orange amorphous powders. Similar 
 compounds may be got from ordinary rosaniline. 
 They dye silk and wool orange. 
 
 AZO- COTTON DYES. The azo- dye-stufla 
 obtained from benzidine and its homologues 
 (Congo-red, benzopurpurine, deltapurpurine, 
 benzaurine, chrysamine, benzazurine, &c.) have 
 the special characteristic of dyeing cotton with- 
 out a mordant. This property depends upon 
 the constitution of the diphenyl molecule, for 
 benzidine itself (and other diphenyl bases) 
 readily combines vrith the cotton fibre. This is 
 easily shown by allowing cotton to soak for 24 
 hours in a cold solution of benzidine hydro- 
 chloride, wringing, drying at the ordinary tem- 
 perature, and washing thoroughly with hot and 
 cold water ; if the cotton thus mordanted with 
 benzidine is now passed through a dilute solu- 
 tion of nitrons acid, and finally treated with a 
 solution of (a)-naphthylamine-sulphonic acid it 
 becomes dyed with Congo-red (Mohlau, B. 19, 
 2014). 
 
 Tetrazo-diphenyl (diazotised benzidine) 
 forms red dye-stuffs by combination with (a), 
 and (;8)-mono-sulphonio acids of (3)-naphtnol 
 or vrith the G di-sulphonio acid. The E di- 
 sulphonic acid (Na salt insoluble in spirit) 
 however exhibits a very peculiar reaction. One 
 mol. of tetrazo-diphenyl combines with one mol. 
 of the E di-sulphonate forming a dye-stuff which 
 is red. If two mols. of the sulphonate are taken 
 one mol. remains in solution unused. If now the 
 ppd. red colouring matter is heated with the 
 mother-liquor, the second mol. of di-sulphonate 
 is taken up and a blue colouring matter is pro- 
 duced. A similar reaction has been observed 
 with many other di-amido- bodies (Sohultz, B. 
 17, 461). 
 
 In general, the tetrazo- derivatives of diphe- 
 nyl, ditolyl, &c. (obtained by diazotising benz- 
 idine and its homologues) can combine with 
 either one or two mols. of a phenol, amine, 
 or their sulphonic and carboxylio acids. The 
 
 compounds with one mol., viz., E"<Cii'"r' ' ^™ 
 tolerably stable, and sparingly soluble; by 
 boiling with water or with alcohol the unoom- 
 bined diazo- group is replaced by OH or by 
 hydrogen. These half-conjugated diazo- com- 
 pounds readily combine with a second mol. 
 of phenol or amine, so that mixed azo- compounds 
 can be thus obtained. The latter bodies are 
 colouring-matters of various shades, and dye 
 cotton direct without a mordant (Lange, B, 19| 
 1697 ; Martius, B. 19, 1755). 
 
AZOXIMS. 
 
 423 
 
 The azo- compounds (Hessian yellow, Hessian 
 purple, curcumine, &o.) obtained by combining 
 two mols. of a phenol, amine or respeotiye 
 sulphonio acid, or one mol. of one amine or 
 phenol and one mol. of another, with the tetrazo- 
 oompound derived from di-p-amido-di-phenyl- 
 ethyleneorits sulphonio acids, have the property 
 of dyeing umnordanted cotton from a soap-bath. 
 The compound from {a)-naphthol-su]phonio acid 
 dyes cotton a bluish -violet, (i3)-naphthol-B-di- 
 sulphonio acid a blue, (a)-naphthylamine-sul- 
 phonio acid a red salicylic acid a yellow, &o. 
 (Bender a. Schultz, B. 19, 3234). The di-amido- 
 derivatives of fluorene also give colouring 
 matters which dye cotton. To the class of 
 cotton colours also belongs the compound which 
 has recently been introduced under the name 
 of ' PrimuUne.' This body dyes unmordanted 
 cotton from an alkaline bath a greenish yellow. 
 It is an amido- compound and may be diazo- 
 tised upon the fibre. By treatment of the 
 cotton thus prepared with solutions of amines 
 or phenols, fast colours (red, orange, and brown) 
 may be produced {Ofceen,prw. com.). 
 
 IBIAZOL. A name given to the hypo- 
 HN N 
 
 I II 
 
 theticalCANjorHC CH 
 
 (Bladin, B. 19, 2598) {v. PHENTL-METHyi-TEiAzoL 
 and Cyano-phenyl-methtl-tbiazoi;). 
 
 AZO -MECONIC- ACETIC ACID v. Dioxy- 
 tarboxy - methyl-phthalide - kzo-dioxy -phthalide- 
 acetic acid. 
 
 AZO-DI-METHYI-HYDKOQXriirONE v. Di- 
 vxy-benzene-Azo-hydroguinone. 
 
 AZO-NAFHIHALENE v. Naphthalem-Axo- 
 na/phthalene. 
 
 TEIBAZONES. Compounds of the form 
 E2:N.N:N.N:Ej obtained by oxidising unsym- 
 metrical di-alkylated hydrazines {q^. ii.). 
 
 AZONITTU BASES. Compounds of the form 
 NH2.NBB'B"(0H) (Fischer). The name has been 
 also applied by Witt (B. 20, 1183) to compounds 
 .NB'(OH) 
 
 AZO-OFIANIC ACID is amido-hemipic anhy- 
 dride, V. Hemific acid. 
 
 AZOPHENINE 0,,^,^^. [237°]. Is formed 
 by the action of a variety of azo- and nitroso- 
 compounds (eg. benzene-azo-aniline, toluene- 
 azo-toluidine, phenyl-amido-benzene-azo-benz- 
 ene, chrysoidine, diphenyl-nitrosamine, nitroso- 
 di-methyl-aniline, &o.) upon aniline (Kimich, B. 
 8, 1026). The best method of preparation con- 
 sists in warming an acetic acid solution of ani- 
 line with a nitroso- compound (e.g. nitroso-di- 
 methyl-aniline) filtering off the crystals of azo- 
 phenine, washing them with alcohol and re- 
 crystallising from aniline or nitro-benzene. If 
 the anUine is replaced by its homologues, the 
 homologues of azophenine are obtained. It 
 forms unstable salts of violet colour. It cannot 
 be acetylated. Cone. HjSOi at 100° yields a 
 Bulphonic acid crystallising in violet needles, 
 which form brown crystalline salts. By heat- 
 ing with aniline hydrochloride it is converted 
 into iuduline (q. v.). By heating alone at .S60° 
 it is converted into aniline, a violet inter- 
 
 of the form X"<^ 
 
 mediate body, and fluorindine. The latter is a 
 splendid blue crystalline colouring-matter, the 
 solutions ofwhiohhaveabeautifulred fluorescence 
 and a characteristic absorption spectrum. By 
 reduction with SnCl^ azophenine yields aniline 
 and a sparingly soluble hydrochloride of an 
 unstable base. The latter, when set free by 
 alkalis, rapidly absorbs oxygen from the air, and 
 changes into a new colouring-matter, the salts 
 of which are indigo-blue (Witt, B. 20, 1538; 
 Witt a. Thomas, O. /. 43, 112). 
 
 AZO-PHENTL ACETIC ACID v. Exo-car- 
 hoxy-tolttene-izo-phen/yl-acetic acid. 
 
 AZO-DIPHENYL BLUE v. Induhnb, 
 
 AZO-PHENYLENE, now called Phenazink 
 (2- "•)• 
 
 AZO-PHTHALIC ACID v. Di-carboxy- 
 bemene-Azo-phthalic acid. 
 
 AZO-PYKOMELLITIC ACID C8Nj(C02H),. 
 
 Tetra-ethyl ether A'^Mt [134°]; glis- 
 tening red trimetric tables ; easUy soluble in 
 alcohol, ether, and acetic acid, insoluble in 
 water; sublimable. Formed by reduction of 
 di-nitro-mellitic ether with zinc-dust and acetic 
 acid. It forms an unstable colourless hydro- 
 chloride (Nef, B. 18, 2805). 
 
 AZO-BESOBCIN v. Besobcin. 
 
 AZO-BESOBTTFIN v. Besoboin. 
 
 AZO-TOLTJENE v. Tohiene-izo-tolwne. 
 
 AZO-TOLTJIDIITE v. Arrddo-tolmne-Jiieo. 
 tolmdme. 
 
 AZOXIMS. Amidoxims, E.C(N0H).NH2, are 
 produced by the union of hydroxylamine with 
 nitriles; these react with acid chlorides, 
 B'.CO.Cl, or anhydrides, (E'COj^O, with formation 
 of alkoyl derivatives, B.C(N0.C0.B').NH2, which 
 under suitable conditions (application of heat, 
 or boiling with water) split oS water and change 
 
 into azoxims B.C^ -^ ^C.E'. The azoxims 
 
 are very volatile in the vapour of other liquids 
 or in air ; many of those boiling above 200° ara 
 volatile even in vapour of ether. They sublime 
 at the ordinary temperature of the air (Tiemanu, 
 B. 18, 1060; 19,1475). 
 
 Chloroformic ether acting upon benzamid- 
 oxim produces an azoxim which has the 
 
 character of a lactam, C^^. C.^^g^CO. 
 
 Phenyl-acet-amidoxim, 
 
 Ph.CH2.C(NOH).NH2, 
 does notproduce azoxims so readUy asbenz-amid- 
 oxim, Ph.C(N0H).NH2, but phenyl-acryl-amid- 
 oxim (cinnamidoxim), Ph.CH:CH.C(NOH).NHj, 
 produces them with great ease. 
 
 m-Amido-benzenyl-azozim-benzenyl 
 
 OsH,(NH2).C.^^j;°^C.CA. [143°]. Formed by 
 
 reduction of »i-nitro-benzenyl-azoxim-benzenyl 
 with alcoholic ammonium sulphide. Crystal- 
 lises from alcohol or sublimes in long needles, 
 v. sol. alcohol, ether, benzene, and chloroform, 
 insol. ligroin and water. By nitrous acid it is 
 diazotised. 
 
 Salts. — B'HCl: very sparingly soluble. — 
 B'jHjCljPtCI, : sparingly soluble pp. 
 
 Benzoyl derivative OnH,ON2(NHBz) : 
 [213°] ; needles ; sol. boiling alcohol, ether, and 
 benzene, insol. water and ligroin (Schapfl, B. 
 18,2473). 
 
134 
 
 AZOXJMS. 
 
 Benzenyl-azozim-benzeayl CnH,„Ni,0 i.e. 
 
 C„H5.C<^^^^^C.C.H,. [108°]. (290°). YolatUe 
 
 with steam. Sublimes in long white needles. 
 V.D. (H = l) 113-3. V. sol. alcohol, ether, and 
 benzene ; v. si. sol. water. 
 
 Formation. — 1. By heating the benzoyl deri- 
 vative of benz-amidoxim— 0|jH5.C(NH2);N.OBz. 
 2. By heating benz-amidozim with benzoic acid, 
 or with benzotrichloride. 
 
 JReactions. — It is an extremely stable sub- 
 stance, being unattacked even by strong HNO, 
 or HjSOj. Long boiling with tin and HCl 
 reduces it to benzonitrile (Tiemann a. Kruger, 
 B. 17, 1694). 
 
 Benzenyl-azozim-benzenyl-o-carboxylic acid 
 
 C^B.,.C<^.^'^C.CsEt.COiBi. [151°]. Formed 
 
 by melting together benz-amidoxim and phthalic 
 anhydride. White glistening needles. V. sol. 
 alcohol, ether, and benzene, v. si. sol. water 
 and ligrom. 
 
 Salts. — A'Ag: white crystalline pp. — 
 A'jBalaq: plates or microscopic needles. — 
 A'jCu : bluish-green pp. — A'PbOH : white 
 granular pp. 
 
 Ethyl ether. — A'Et : heavy yellow oil. 
 
 Amide.— C,tB.,0N2.G0^B.^: [160°], mioro- 
 Bcopio needles (Schulz, B. 18, 2463). 
 
 Benzenyl-azoxim-benzenyl-m-carboxylicacid 
 
 C„H5.C<^^jJ;P^C.C,H4.COjH. [218°]. Formed 
 
 by heating benzamidoxim m-oarboxylic acid 
 with BzCl (a. MuUer, B. 19, 1497). White 
 crystalline powder ; sol. alcohol, insol. water. 
 Benzenyl-azozim-butenyl 
 
 C^n^O-^.^'^C.O^B.,. (265°). Oily fluid. Vola- 
 tile with steam. Formed by the action of butyric 
 anhydride upon benz-amidoxim, or by elimi- 
 nating HjO from the butyryl derivative of the 
 latter (Schulz, B. 18, 1085). 
 Benzenyl-imldozim-carbonyl 
 
 C,H,NA i-e. C,H,.0<^-°>CO and 
 
 CjHj.C'^ -1^^0(011). Benzenyl-azoxim-carbi- 
 
 not [198°]. Carbonises at about 300°. Solu- 
 ble in alcohol, ether, chloroform, benzene, and 
 hot water, sparingly in cold water. The aqueous 
 solution reacts strongly acid to litmus. It de- 
 composes carbonates. Not attacked by PClj or 
 by HCl. Formed by elimidatiou of alcohol 
 from benzenyl-amidoxim-carbonic ether or, 
 directly, by heating benzenyl-amidoxim with 
 chloroformic ether. 
 
 Salts. — A'Ag: white pp. — A'^Cu: green pp. 
 
 Ethyl derivative C^U^'Kmfii [36°]; 
 soluble in alcohol, ether, &c., nearly insoluble 
 in water ; indifferent body (Falck, B. 18, 2468 ; 
 19, 1481). 
 
 Benzenyl-azozim-etlLenyl C,HsN20 i.e. 
 
 O.H,.C<^jf ^CCHj. [41°]. (244°). Formed by 
 
 boiling benzenyl-amidoxim with acetic anhy- 
 dride (Tiemann a. Kruger, B. 17, 1696 ; 18, 
 1059 ; Schulz, B. 18, 1084). Flat prisms. Easily 
 volatile with steam. Sublimes at the ordinary 
 temperature in white needles. V. sol. alcohol, 
 ether, and benzene, si. sol. water. 
 
 Benzenyl-azozlm-propenyl 
 
 O.H,.C<^^j;;P^O.CjH5. (255°). Colourless oil. 
 
 Volatile with steam. Formed by the action of 
 propionic anhydride upon benz - amidoxim 
 (Schulz, B. 18, 1085). 
 
 Beuzenyl-azoxim-propeuyl-w-carbozylic acid 
 
 0„H5.C<^j;°^C.OH,.CH2.COjH. [120°]. Formed 
 
 by fusing benz-amidoxim with succinic anhy- 
 dride. White trimetric plates or prisms. V. 
 sol. alcohol, ether, hot water and benzene, insol. 
 ligroin. It is not decomposed by warming with 
 H,SO,. 
 
 Salts. — A'Ag: white crystalline pp. — 
 A'2Ca35aq: long glistening soluble needles. — 
 A'jBa aq : short prisms, or monoclinic crystals, 
 — A'jCu : bluish-green granular powder. — 
 A'PbOH : granular pp. 
 
 Ethyl ether A'Et: (255°), yellowish oil. 
 
 Amide G,„HsONj.CONH2 : [168°], slender 
 needles (Schulz, B. 18, 2459). 
 
 m-Carbozy-benzenyl-azozim-benzenyl 
 
 C,B.,(CO^-H.).0'^.^'^C.0,-E,. [218°]. Formed 
 
 by heating benzamidoxim-w-carboxylic acid with 
 benzoyl chloride. White crystalline powder. 
 Soluble in acetic acid, alcohol, and ether, insolu- 
 ble in water and benzene. The aqueous solution 
 of the ammonium salt gives pps. with AgNO. and 
 CuSO, (MiiUer, B. 19, 1497). 
 
 TO-Carbozy-benzenyl-azozim-etbenyl 
 
 CsH,(CO,H).C<^^j^°^0.CH3. [217°]. Formed 
 
 by heating benzamidoxim - to - carboxylic acid 
 with acetic anhydride. White crystalline pow- 
 der. Sol. alcohol and ether, si. sol. water and 
 benzene. The aqueous solution of the ammo- 
 nium salt gives pps. with AgNO,, CuSO„ 
 Pb(0Ac)2, and ZnSO, (Muller, B. 19, 1496). 
 jp-Oarbozy-benzenyl-azozlm-ethenyl 
 
 C,„H,NA i.e. C,H,(CO,H).C<^j;°^C.0H,. 
 
 [218°]. Formed by boiling benzamidoxim-^)- 
 carboxylic acid with acetic anhydride. Crystal- 
 line solid. Soluble in hot water and alcohol, 
 more sparingly in ether and chloroform. The 
 dilute solution of the ammonium salt gives 
 pps. with AgNOa, Pb(OAc), and CuSO, (MOUer, 
 B. 19, 1492). 
 
 TO- Carboxy - benzenyl - azoxim - propenyl - a- 
 carboxylic acid 
 
 C,H,(CO,H{.C<^jf>C.CH,.CH,.CO,H. [213°]. 
 
 Formed by heating benzamidoxim-m-carboxylio 
 acid with succinic anhydride. Needles. Sol. 
 hot water, v. sol. alcohol and ether, si. sol. 
 chloroform, insol. benzene. The aqueous solu- 
 tion of the ammonium salt gives sparingly 
 soluble pps. with AgNOj, CuSO,, and Pb(OAo)2 
 (Miiller, B. 19, 1496). ' 
 
 p - Carboxy . benzenyl - azoxim - propenyl - w- 
 carboxylic acid 
 
 C„H,(CoiH)?C<^°^0.CH2.CH2.CO2H. Formed 
 
 by heating benzamidoxim-^J-oarboxylic acid 
 with an excess of succinic anhydride. Sol. 
 alcohol, si. sol. water, v. si. sol. ether, insol. 
 benzene and chloroform. Carbonises at a high 
 temperature without melting. The dilute aqueoui 
 
AZOXY- COMPOTJNDa 
 
 425 
 
 solution of the ammonium salt gives insoluble 
 pps. with CnSO, and Pb(OAo)2, pps. soluble in 
 hot water with ZnSO^ and AgNOj (MuUer, B. 19, 
 1493). 
 
 Ethenyl-azoxim-benzenyl 
 
 OHs.C^'^j^j^^O.C.Hs. [57°]. Long white 
 
 needles. Begins to sublime at 70°-60°. Easily 
 volatile with steam. V. sol. alcohol, ether, and 
 benzene, si. sol. hot water, insol. cold water and 
 ligroiin, Formed by heating ethenyl-amidoxim 
 hydrochloride with benzoyl chloride (Nordmann, 
 B. 17, 2754). 
 
 m-Nitro-benzeuyl-azoxim-benzeuyl 
 
 C.H^(N0J.C<^j^°^C.C«H5. [160°]. Formed by 
 
 the action of benzoyl chloride upon m-nitro- 
 benz-amidoximCeH,(NOJ.C(NHj):NOH(Schopff, 
 S. 18, 1067). White needles. Subhmable. Sol. alco- 
 hol, ether, and benzene, insol. water and ligrom. 
 m-ITitra-benzenyl-azozlm-ethenyl 
 
 C.H,(NOj).0<''^^^>C.CH3. [109°]. White 
 
 needles. Sublimable. Formed by the action of 
 acetic anhydride upon m-nitro-benz-amidoxim 
 C5H,(N03).0(NH2):NOH (Schopff, B. 18, 1066). 
 m-Ozy-benzenyl-azoxim-benzenyl 
 
 C,H,(OH).C<^jf>0.0»H5. [163°]. Formed by 
 
 diazotising m-amido-benzenyl-azoxim-benzenyl 
 and heating the aqueous solution. Yellow 
 needles. Sublimable. Sol. alcohol, ether, and 
 benzene, scarcely sol. water, insol. ligrom. 
 
 Ethyl ether C,^fiS^{(im): [71°] ; fine 
 felted crystals; soluble in alcohol (Schopff, B. 
 18, 2475). 
 
 Fhenyl-allenyl-azoxim-benzenyl 
 
 C,H5.CH:0H.0<^^^°^C.C5H5. [102°]. Cinna- 
 
 mewyl-asoxim-benzenyl. Formed by elimination 
 of HjO from the benzoyl derivative of phenyl- 
 acryl-amidoxim by heating it above its melting- 
 point or by boiling it with water (Wolff, B. 19, 
 1509). Very slender white needles. V. sol. 
 alcohol, ether, chloroform, and benzene, v. si. 
 sol, cold water. Sparingly volatile with steam. 
 Fhenyl-allenyl-azoxim-etlienyl 
 
 C,H^.CI1:C11.C<^^'^C.0I[,. [78°]. Sublimable. 
 
 Colourless crystals. Formed by heating phenyl- 
 acryl-amidoxim with acetic anhydride (Wolff, B. 
 19, 1509). 
 
 Phenyl - allenyl - azozim - propenyl - a - car- 
 bozylic acid 
 
 OeH5.CH:0H.0.^j^°^C.CH2.CHj.CO2H. [114°]. 
 
 Formed by heating phenyl-acryl-amidoxim with 
 succinic anhydride (Wolff, B. 19, 1511). Long 
 white glistening prisms. - Sol. alcohol, ether, 
 benzene, and hot water, si. sol. ligroin. — ^A'Ag : 
 white powder. 
 
 Fhenyl-ethenyl-azoxim-benzenyl 
 
 C.H5.CH,.0<^^j^°^C.C,H5. [82°]. Formed by 
 
 boiling the benzoyl derivative of phenyl-acet- 
 amidoxim with water for a long time (Enudsen, 
 B. 18, 1070). White needles. Volatile with 
 steam. V. sol. alcohol, ether, and benzene, 
 insol. water. 
 
 Fhenyl-ethenyl-azoxim-ethenyl 
 
 C„H,.CHa.0<^j;°^C.CH3. (262°). Oil. Volatile 
 
 with steam. Formed by boiling the acetyl 
 derivative of phenyl-aoet-amidoxim with water 
 for a long time (Enudsen, B. 18, 1070). 
 
 Phenyl - ethenyl - azoxim - propenyl ■ u>- 
 carboxylic acid 
 
 0„H3.0H,.C<^j^°>0.0H,.0H,.CO,H. [60°]. 
 
 Formed by fusing together phenyl-acet-amidoxim 
 C„H5.CH2.C(NH2):NOH and succinic anhydride. 
 Prismatic plates. V. sol. alcohol and ether, si. 
 sol. cold, water, m. sol. hot. It is a strong acid. 
 
 Salts. — A'Ag : white pp. — A'^Cu: bluish 
 green pp. (Enudsen, B. 18, 2483). 
 
 Phenyl-oxy-ethenyl-azoxim-ethenyl 
 
 C,H5.CH(OH).0<^^j;f°^O.CH3. [65°]. Formed 
 
 by heating the acetyl derivative of phenyl-oxy- 
 acet-amidoxim CsH5.CH(OH).C(NH2):NOAc with 
 water for some time. Transparent needles. 
 Distils undecomposed, and is volatile with 
 steam. V. sol. alcohol, ether, and benzene, si. 
 sol. cold water. 
 
 Acetyl derivative 
 
 OeH,.CH(OAo).C<^^j^°^C.CH3. [52°]; fine white 
 
 needles; volatile with steam; sol. alcohol, 
 ether, and hot water, nearly insol. cold water 
 (Gross, B. 18, 1076). 
 
 ^-loluenyl-azoxim-benzenyl CgjHijNjO i.e. 
 
 C„H,Me.C<^^°>C.C8H,. [103°]. Formed by 
 
 heating the benzoyl derivative of p-tolu- 
 amidoxim, HjO being split off (Sohubart, B. 
 19, 1490). Long slender white needles. V. sol. 
 ether, benzene, and chloroform, si. sol. hot 
 water, insol. cold. 
 
 AZOXINES. — Compounds whose molecular 
 
 formulae may be written X"<^ q ^T", such aa 
 Phenazoxine O^t^ q ^CjHj and 
 
 Naphthazoline C,jH|i<;[ q ^C,„Ha. 
 
 They may be formed: — (1) By heating aro- 
 matic imido-sulphidea with copper oxide : 
 
 C..H,<^^>0,oH, + CuO = 
 
 C..H„<^(f>C,^. + CuS; 
 (2) By heating o-amido-phenols with o-di-oxy. 
 compounds: C3H,<^^=-H°^>C8H,= 
 
 C3H,<™>03H, + 2H,0 
 
 (Bernthsen, B. 20, 942). 
 
 AZOXY- COMFOUNSS, compounds whose 
 molecular formula may be represented by 
 O 
 
 X — N — N — X. They are formed by treating 
 nitro- compounds with alcoholic potash or 
 sodium amalgam. They may be reduced to 
 hydrazo- compounds, X — NH — NH — X, and 
 finally to two molecules of an amine, X — NH^. 
 The products of nitration of azoxy- compounds 
 
 
 
 are often unsymmetrlcal, X— N— N— T. 
 
496 
 
 AZOXY- COMPOUNDS. 
 
 p ■ Aldehydo -benzoic azozy - 21 ■ aldehydo-ben- 
 Eoic acid 
 
 W (1) (2) (*) 0) 
 
 C.H3(CHO)(C02H).N . N.C,H3(0H0)(C0jH). 
 
 Formed by reduction of nitro-^-aldehydo-benzoio 
 acid with aqueous KCN. Colourless needles. 
 v. sol. ether, alcohol, and chloroform, si. sol. 
 ligroin, nearly insol. water. Decomposes at 
 about 280°. It gives the ordinary reactions of 
 an aldehyde. 
 
 Phenyl hydrazide: small golden yellow 
 prisms (Homolka a. Low, B. 19, 1090). 
 
 o-Amido-benzeue-o-azozy-aniline 
 
 Di-benzoyl d erivative 
 (OjHjNHBzjjNjO. [195°]. Prepared by acting 
 on benzoyl-o-nitranilide dissolved in alcohol 
 with zinc-dust and adding ammonia and pla- 
 tinic chloride. Bright yellow mass, insol. water, 
 b1. sol. boiling alcohol (Mixter, Am. 6, 26). 
 
 m-Amido-benzeue-m-azozy-auiline [0. 272°]. 
 
 Di-benzoyl derivative. — Prepared by 
 dissolving m-nitro-benzanilide in boiling alcohol 
 and adding alcoholic ammonia and powdered 
 zinc together with a trace of platinum. Very 
 light powder with pale yellow colour. Insol. 
 alcohol, ether, and benzene (Mixter, Am. 5, 5). 
 
 ^■Amido-benzene'^-azozy-aniUne 
 (CjH,NH2)N20. [182°-184°]. Prepared by the 
 action of potassio ethylate on its diacetyl de- 
 rivative. Sol. alcohol, giving a red solution. 
 SI. sol. boiling water, from which it separates on 
 cooling as a fibrous yellow mass (Mixter, Am. 5,4). 
 
 Di-acetyl derivative (C|jH4NHAo)2NjO 
 [275°-278°]. Prepared by the action of pow- 
 dered zinc and ammonia on ^-nitro-acetanilide 
 in alcohoUo solution. Hair-like particles vrith 
 light golden-yellow colour. SI. sol. boiling 
 alcohol. 
 
 Di-benzoyl derivative 
 (CjHj.NHBz)jN20. [310°]. Prepared by the 
 action of zinc and ammonia on ^i-nitro-benz- 
 anilide. Light yellow colour. Insol. alcohol 
 and water (Mixter, Am. 5, 284). 
 
 o-Amido-toluene-azozy-o-toluidine 
 [1:2:4] CBH,Me(NHj).N20.CsH3Me(NH2) [4:1:2] 
 Azoxy-o-tolwMne. [168°]. Fromnitro-o-toluidine 
 in alcoholic solution by sodium amalgam (Lim- 
 pricht, B. 18, 1405 ; Graeff, A. 229, 344). Long 
 orange silky needles (from alcohol), or yellow 
 needles (from water). V. sol. alcohol, si. sol. 
 water. Converted by cone. H2SO4, by molecular 
 change, into amido-tolueue-azo-amido-oresol. 
 
 Salts .— B"H,SO, iaq : needles.— B"2H0L— 
 B"H2CljPtCl4.— B"2HBr. 
 
 j)-Amido-tolnene-azozy-p-tolnidine 
 [1:4:2] CBH3Me(NH2).NjO.C8H3Me(NHj) [2:1:4]. 
 [148°]. Yellow needles. Sol. alcohol and hot 
 water. Prepared by the action of sodium 
 amalgam on an alcoholic solution of nitro- 
 B - toluidine. — B"(HC1)2 : si. sol. water. — 
 B"HjCl2PtCl4 (Buokney, B. 11, 1451). 
 
 Benzoyl derivative 
 C,H3Me(NHBz).N20.CaH3Me(NHBz). [290°]. 
 From C„H3Me(NHBz)(N02) [1:4:2] by treatment 
 with zinc and ammonia (Mixter, Am. 5, 285). 
 Light yellow substance, insol. water and alcohol. 
 
 Benzene-j}-azozy-aniline 
 C„H,(NH2).NjO.C3H5. [139°]. S. 4-27 at 21°. 
 Formed, together with benzene-azo-aniline, by 
 
 the action of ammonium sulphide on an 
 alcoholic solution of benzene-azoxy-nitro-benz- 
 ene {Or. Schmidt, A. 122, 174 ; Z. [2] 5, 419). 
 Large pale-yellow tables (from dilute alcohol). 
 SI. sol. hot water, v. sol. alcohol and ether. 
 Beduced by tin and ECl to aniline and p- 
 phenylene-diamine. 
 
 Salts. — ^B'HCl: silvery laminae, saponified 
 by water.— B'jHjPtCls. 
 
 Benzene-azozy-benzene CJS.y'Sfi.C^'H.y Mol. 
 w. 198. [36°], S. (alcohol) 17-5 at 16°. 
 
 Formation. — 1. From nitro-benzene by the 
 action of alcoholic KOH (Zinin, J. pr. 36, 93 ; 
 Basenack, B. 5, 364 ; Schmidt a. Schultz, A. 
 207, 828 ; Wilsing, A. 215, 228), or sodium-amal- 
 gam (Alexejeff, J. 1864, 525 ; Moltchanoffsky, 
 J. B. 1882, 350).— 2. From aniline by oxidising 
 with KMnOi (Glaser, Z. [2] 2, 308).— 3. From 
 benzene-azo-benzene by oxidising with CrO, 
 (Petrieff, B. 6, 577). 
 
 Preparation. — 1. By reduoingnitro-benzene in 
 alcoholic solution by means of sodium-amalgam. 
 The yield is 87 p.c. of the theoretical (Mol- 
 tchanoffsky, J. B. 1882, 224 ; Bl. [2] 38, 551).— 
 2. By boiling nitro-benzene with sodium methyl- 
 ate, prepared from methyl alcohol (250g.) and 
 sodium (10 g.), the reaction being as follows : 
 4PhNOj, + 3CH30Na = 
 2PhjN20 + BHCOjNa -1- BHjO 
 (Klinger, B. 15, 865). 
 
 Properties. — Pale yellow trimetric needles; 
 insol. water, sol. alcohol, and ether. Small 
 quantities may be volatilised with steam. 
 
 Beactions. — 1. When mixed with neutral 
 substances {e.g. NaCl) and distilled it gives 
 aniline, azo-benzene, and other products. — 
 2. Ammonium sulphide has hardly any action 
 upon it in the cold, but on warming it reduces it 
 to hydrazo-benzene. — 3. SnClj and HCl reduce 
 it to aniline, very little benzidine being formed 
 (Schmidt a. Schultz, B. 12, 484).— 4. Warm 
 cone. HjSO, converts it into benzene-p-azo- 
 phenol (Wallacha. Belli, B. 13, 525).— 5. Aniline 
 hydrochloride at 230° gives violaniline (v. 
 Dechend a.Wichelhaus, B. 8,1614). — G.Diphenyl- 
 amine hydrochloride heated with it gives tri- 
 phenyl-violaniline (Girard a. Caventou, B. 12, 
 290).— 7. Cone. HBr at 250° gives di-bromo- 
 anilme (Sendzink, Z. [2] 6, 266) ; HI gives 
 benzidine. — 8. PBr^ gives yellow crystals of 
 Ci^HiiNaBr, which are converted by aqueous 
 AgN03 into benzene-azo-benzene (Werigo, Z. [2] 
 6, 387). — 9. POI5 added to an ethereal solution 
 gives benzene-azo-benzene (Werigo, A. 165,202). 
 
 10. Sodium amalgam gives hydrazo-benzene. — 
 
 11. Sulphurous acid forms benzidine sulphate. — 
 
 12. Nitric acid forms three benzene-azoxy-nitro- 
 benzenea (g. v.) and also a tri-nitro- derivative 
 C,2H,(N04sNi,0, [152°] (G. Schmidt, Z. [2] 5, 
 421). This is converted by CrOj mixed with 
 cone. HNO3 at 200° into C,2H,(NOj)3NA. [102°], 
 and C,jH,(N02)3N203. [52°] (Petrieff, B. 6, 558). 
 
 Benzene-azozy-benzene-m-snlphonic acid 
 C,H3.NjO.C,H,(S03H). [60°-70°]. Very deli- 
 quescent reddish-brown tables. Formed as a by. 
 product in the oxidation of m-amido-benzene- 
 Bulphonio acid by KMnOj. — KA'aq: long soluble 
 tables (Limpricht, B. 18, 1420). 
 
 Benzene-azozy-beuzene-p-snlplioiiio acid 
 CaH,.N,0.CsH,(S03H). [below 100°]. Red scales. 
 V. sol. water. Formed as a by-product in the 
 
AZOXY- COMPOUNDS. 
 
 427 
 
 oxidation of sulplianilio acid by KMnO,; the 
 yield is about 2 p.o. — KA'2aq: small yellow 
 crystals (Limpricht, B. 18, 1420). 
 
 Benzene-azoxy-bromo-benzene sulphonlc acid 
 C5H5.N20.05H3Br(S03H). Formed as a by- 
 product of the oxidation of bromo-amido-benz- 
 ene-sulphonio acid C8H3Br(NH2)(S03H) [4:3:1] 
 with KMnOj. — KA'2aq: small red six-sided 
 tables (Limpricht, B. 18, 1423). V. sol. water 
 and alcohol. 
 
 Benzene-^i-azcxy-iiitro-beiizene 
 C,H5.N30.CeH,NOj [1:4]. [153°]. Formed together 
 with the following body by the action of HNO3 
 (S.G. 1-45) on benzene-azoxy-benzene (Zinin, .4. 
 114, 218). Hair-like yellow needles. Reduced 
 by alcoholic ammonium sulphide to benzene-^- 
 azoxy-aniline. 
 
 Benzene-azoxy-nitro-benzene 
 C„Hj.N20.0eH^.N0j. [49°]. Needles or prisms ; 
 prepared as above. Alcoholic ammonium sul- 
 phide forms a compound Ci2H3N30(?) [85°]. 
 
 Benzene-azoxy-nitro-beuzene 
 C,ft.N,0.08Hj(N02) [1:2J. [127°]. Formed by 
 adding fuming HNO3 (25-30 c.c.) to a solution 
 of benzene-azo-benzene (20 g.) in glacial acetic 
 acid (100 c.c.) at 75°. Bed rhombic plates. Sol. 
 alcohol, ether, and acetone. Alcoholic KOH 
 gives an emerald-green colouration ; by long 
 boUing or by treatment with sodium-amalgam 
 it is reduced to a compound CjiHuNeO (Janovsky 
 a. Erb, B. 20, 361). 
 
 Benzoic o-azoxy-benzoic acid 
 [2:1] C,H,(00,H)-N,0-CeH,(CO,H). [1:2]. 
 Mol. w. 286. [237°-242°]. 
 
 Formation. — 1. By the action of KCN on o- 
 nitro-benzaldehyde (Homolka, B. 17, 1902).— 
 2. From o-nitro-benzoic acid by treatment with 
 sodium-amalgam or aleohoUo KOH (Griess, B. 7, 
 1611).— 3. Together with o-nitro-toluene by boil- 
 ing o-nitro-benzyl alcohol with aqueous KOH 
 (Jaff6, H. 2, 57). 
 
 Properties. — Small colourless prisms ; m. 
 Bol. hot alcohol, si. sol. ether and boiling water. 
 Beduoed by sodium-amalgam to carboxy-benz- 
 ene-azo-benzoic acid, and finally to hydrazo- 
 benzoic acid. 
 
 Salt.— BaA"4aq. 
 
 Benzoic m-azoxy-benzoic acid 
 [3:1] C„H^(C02H).N20.C,H,(C02H) [1:3]. Formed 
 by boiling m-nitro-benzoic acid with alcoholic 
 KOH (Griess, A. 131, 92). Minute needles or 
 plates. Insol. water, si. sol. alcohol and ether. 
 Beduced by tin and HCl to di-amido-diphenic 
 acid. 
 
 Siazoxy-benzoic acid 
 
 N 
 
 C,H,NA or C0,H.C,H3/ I ^0 [ 1 ^] {?). 
 
 Formed by reducing di-nitro-benzoic acid dis- 
 solved in NaOHAq with sodium-amalgam (V. 
 Meyer a. Miohler, B. 6, 746; Miehler, B. 7, 
 420 ; A. 175, 150). An amorphous black powder, 
 insol. alcohol, ether, benzene, chloroform, and 
 glacial acetic acid. Eeduced by tin and HOI to 
 diamido-benzoic acid. HNO5 gives an amorphous 
 nitro- derivative. 
 
 Salts.— AgA': black pp. sol. NHjAq.— 
 BaA'2 : black pp.— ZnA'^ : brownish-black pp. 
 
 An isomeric acid, resembling the above, is 
 formed from (1, 2, 4)-di-nitro-benzoio acid. It 
 is not attacked by tin and HCl. 
 
 «i-Bromo-benzene-ni-aioxy-bromo-benzene 
 [3:1] C„HiBr.N20.C„H,Br [1:3]. [112°]. From 
 ?re -bromo- nitro -benzene and alcoholic KOH 
 (Gabriel, B. 9, 1405). Bright yellow prisms ; v. 
 si. sol. alcohol. 
 
 ^-Bromo-benzene-p-azoxy-bromo-benzene 
 [4:1] C„H,Br.N,0.03H,Br [1:4], [172°] (Hof- 
 mann a. Geyger, B. 5, 919) ; [175°] (Werigo, 
 
 A. 165, 198). From ^-bromo-nitro-benzene by 
 treatment with alcoholic KOH or sodium-amal- 
 gam. Yellow leaflets, v. sol. hot alcohol. Nitric 
 acid forms a tri-nitro- derivative [174°]. 
 
 Bromo - benzene - azoxy - bromo -benzene sul- 
 phonic acid 
 
 OjH^Br.NjO.CsHaBrJSOjH). Formed as a by- 
 product of the oxidation of di-bromo-amido- 
 benzene-sulphonic acid CjH2Brj(NH2)(S03H) 
 [1:3:6:4] by KMn04.—KA'2aq: very small yellow 
 scales (Limpricht, B. 18, 1425). 
 
 m-Chloro-benzene-m-azoxy-chloro-benzene 
 [3:1] C5HJCI.N2O.GSH4CI [1:3]. [97°]. Formed 
 by boiling OT-ohloro-nitro-benzene with alcoholic 
 KOH (Laubenheimer a. Winther, B. 8, 1623). 
 YeUowish-brown flat needles. V. si. sol. alcohol. 
 Treated with fuming H2SO4 it is chiefly con- 
 verted into m-chloro-benzene-azo-chloro-phenol, 
 only a very small quantity of m-chloro-benzene- 
 azo-chloro-benzene being formed (Schultz, B. 
 17, 464). 
 
 p-Chloro-benzene-azoxy-chloro-beszene 
 [4:1] 0,H,C1.N,0.0,H,C1 [1:4]. [155°]. From 
 ^-chloro-nitro-benzene by treatment with alco- 
 holic KOH (Heumann, B. 5, 910; cf. Willgerodt, 
 
 B. 15, 1002), sodium-amalgam (Alexejeff, Z. 
 1866, 269), or (in ethereal solution) with sodium 
 (Hofmunn a. Geyger, B. 5, 916). Pale yellow 
 needles, si. sol. cold alcohol. Treated with 
 fuming H2SO4 it is chiefly converted into j3-ohloro- 
 benzene-azo-chloro-benzene only forming traces 
 of a chlorinated benzene-azo-phenol (Schultz, B. 
 17, 464). 
 
 Di-chloro-benzene-azoxy-di-chloro-benzene 
 [8:5:1] C8H3CI2.N2O.CJH3CI2 [1:3:5]. [172°]. Prom 
 (3,5,1) - di - chloro - nitro-benzene and alcoholic 
 KHS (Beilstein a. Kurbatow, A. 197, 84). 
 
 Di-chloro-benzene-azoxy-di-chloro-benzene 
 [2:5:1] 0,H3Cl2.N20.CsH3Cl2[l:2:5]. [112°]. From 
 ^-di - chloro - nitro - benzene and alcoholic KOH 
 (Laubenheimer, B. 7, 1600; 8, 1623). Small 
 bright yellow needles. 
 
 p-Ghloro-benzene-azoxy-chloro-nitro-benzeue 
 [4:1] C,H,Cl.N20.CsH3Gl(NO,) [1:4:?). [134°]. 
 Prom ^-chloro-beuzene-^-azoxy-chloro-benzene 
 and HNO3 (Heumann, B. 5, 912; 13, 1185). 
 Bright yellow flooculent substance. V. si. sol. 
 boiling alcohol ; reduced by alcoholic ammo- 
 nium sulphide to ^-chloro-benzene-azo-ohloro- 
 nitro-benzene. 
 
 Chloro-tolneue-azozy-chloro-tolaene 
 [6:3:1] OeHjMeCl.N^O.CsHjMeCl [1:6:3]. [128°] 
 Formed by the action of Na on an ethereal 
 solution of ohloro-nitro-toluene (Hofmann a, 
 Geyger, B. 5, 919). Small needles. 
 
 m-Iodo-beuzene-m-azoxy-iodo-benzene 
 [3:1] 08H,I.Nj0.0,HjI [1:3]. From m-iodo-nilro- 
 benzeno and alcoholic KOH (Gabriel, B. 9, 1408). 
 Flat yellow needles ; si. sol. cold alcohol. 
 
 ^-lodo-benzene-p-azoxy-iodo-benzene 
 [4:1] 0„HJ.NjO.O,H,I [1:4]. [200°]. From p. 
 iodo - nitro - benzene and alcoholic KOH (G.). 
 I Light yellow plates or scales. SI. sol. hot alcohol. 
 
428 
 
 AZOXY- COMPOUNDS. 
 
 SI - methyl - amido-benzene-azozy-di-methyl- 
 anilino _ [4:1] CjH^NMej.NjO.OsHiNMej [1:4]. 
 From i)-nitroso-di-methyl-aniline and alcoholic 
 KOH (Schraube, B. 8, 619). Glittering brown 
 crystals ; si. sol. water, m. sol. hot alcohol and 
 benzene. The salts are decomposed by water. 
 -B"HjPt01saq. 
 
 m-Nitro-benzene-m-azoxy-nitro-beuzene 
 [3:1] 0,H,(N0,).N,O.0,H,(NO,). [1:3] [142°]. 
 
 Prepwration. — A solution of 2 or 3 pts. of 
 Bi-di-nitrobenzene in about 15 pts. of methyl 
 alcohol is mixed with a solution of sodium 
 methylate prepared by dissolving 1 pt. of sodium 
 in 20 pts. of methyl alcohol. A vigorous reac- 
 tion sets in, which is completed by 48 hrs. 
 cohobation ; large yield. Long needles. V. sol. 
 benzene, m. sol. ether and CS^, v. si. sol. cold 
 alcohol. By heating to about 140° with strong 
 HjSOi it is converted into the isomeric di-nitro- 
 oxy-azo-beuzene CbH^(N02).Nj.CsH5(N02)(0H) 
 (Klinger a. Pitsohke, B. 18, 2551). 
 
 ^-Nitro-diphenyl-p-azoxy-nitro-diphenyl 
 CsH<(N02).C,Hi.N20.05H^.C5H,N02. [225°]. From 
 y-di-nitro-diphenyl by acting on its alcoholic 
 solution with sodium-amalgam (Wald, B. 10, 
 137). Brick-red crystalline powder; forms a 
 red solution in cone. HjSOj. Insol. most 
 solvents. Eedueed by alcoholic ammonium 
 sulphide to benzidine. 
 
 Xitro-oxy-benzene-azoxy-di-nitro-phenol 
 
 Diethyl ether 
 CeH3(N02)(0Et).N20.C,H;,(N02)20Et. [168°]. 
 From HNOs and the diethyl ether of ^-oxy-ben- 
 zene-^-azo-phenol : the product is exhausted 
 with water, and then treated with alcohol. On 
 cooling, the alcohol deposits the body in long 
 yellow needles grouped in stars. Sol. ether, 
 CHCI3, CgHg and glacial acetic acid (Andreae, 
 J.pr. 129, 337). 
 
 An isomeric tody. [187°]. Thisformsthe 
 greater part of the product of the nitration, and 
 is left undissolved when the former body is 
 extracted with alcohol. It is crystallised from 
 acetic ether, in which it is very soluble. 
 
 o-Oxy-benzeue-o-azoxy-pheaol 
 
 CeH,(OH).N,O.C.H,.OH. 
 
 Ethyl ether {C^i{a&i)}^fi. Azoxy- 
 phenetol. [102°]. By reducing a cold (0°) solu- 
 tion of o-nitro-phenetol (1 pt.) in alcohol (7 pts.) 
 by adding sodium amalgam ; on adding water a 
 pp. is got; this is freed from azo-phenetol by 
 washing with strong HCl as long as the latter 
 is coloured (Schmitt a. Mohlau, J.pr. 126, 201). 
 
 Properties. — Colourless triolinic plates. In- 
 soluble in water, but melts in boiling water. 
 Slightly soluble in cold alcohol, insoluble in hot 
 alcohol. Not volatile with steam. 
 
 Diphenyl-azoxy-dipheuyl 
 CeH5.CsH^.NjO.O,H,.OeH5. [205°]. Small 
 yellow plates. Insol. water and alcohol, si. sol. 
 acetic acid. Prepared by the action of alcoholic 
 KOH on^-nitro-di-phenyl (Zimmermann, B. 13, 
 1961). 
 
 Phenyl - glycollic -o-azoxy- j,lienyl - gly eoUic 
 acid ON2{CsH,O.0H2.CO2H)2. [187°]. 
 
 Preparation. — o-Nitro-phenyl glycollic acid 
 (18'6 g.), water (140 g.) and NajCOs (5 g.) are 
 treated at 65° with sodium-amalgam (165 g. of 
 4 per cent, sodium), added in small portions. 
 On cooling, crystals separate. These are 
 dissolved in water and decomposed by HCl. 
 
 The precipitated acids are recrystallised from 
 alcohol. If the mixed acids now ihelt above 
 162°, they are etherified by alcohol and HCl. 
 The ether of the azoxy- acid is less soluble 
 in alcohol than that of the azo- acid, it ia 
 crystaUised from alcohol and then saponified 
 (A. Thate, J.pr. [2] 29, 152). 
 
 Properties. — Crystallises, from aqueous or 
 dilute alcoholic solutions, with aq as short 
 prisms or as soalenohedra ; but if left in con- 
 tact with the mother hquor these change to 
 rhombohedra, taking up ^aq. Both these forms 
 are sulphur-yellow. At 130° they become white 
 and anhydrous. . Dissolves in alialis, HCl and 
 glacial acetic acid. The solutions are yellow. 
 Forms red solutions with HNO, and HjSO^. 
 Insoluble in ether and in benzene. 
 
 Beactions. — 1. Lead acetate, a yellowish- 
 white flocoulent pp. — 2. AgNO, and BaClj, no 
 pp. in hot solutions, on cooling a crystalline pp. 
 
 Salts. — (NHJjA" : obtained, as a yellow 
 micro-crystalline pp., by passing NH3 into a 
 solution of the acid in absolute alcohol. Its 
 aqueous solution gives yellowish-white pps. 
 withBaClj andPb(0Ac)2, yellowpps. with AgNOj 
 and FejClj, and a green pp. with CUSO4. — AgjA". 
 — AgHA" : more soluble than the neutral salt. 
 BaA" 2aq. 
 
 Ethyl eifeer.— EtjA"; [114°]. Whitesilky 
 needles. 
 
 m - Snlpho -benzeue-m-azoxy- benzene snl - 
 phonic acid [3:1] CsH,(HSOs).NjO.CeH,(HSOs) 
 [1:3]. [125°]. Prepared by the reduction of 
 w-nitro-benzene-sulphonic acid with alcoholic 
 KOH (Brunnemann, B. 11, 1048 ; A. 202, 240). 
 Yellow needles. V. sol. water and spirit. 
 A"K2 4aq: needles. — A"(NHj22Jaq: rhombic 
 pillars. — A"Baaq: difficultly soluble prisms. 
 A"Ca 3 Jaq : difficultly soluble needles. — A"Pb aq. 
 
 Chloride [138°]. Yellowish-red pillars. 
 
 Amide [273°] : si. sol. hot water. 
 
 Sulpho-naphthalene-azoxy-uaphthalene sul- 
 phonicacid 0,„H8(S03H).NjO.C,„Hs.S03H. From 
 (a)-nitro-naphthalene-(a)-sulphonic acid and 
 alcohoKc KOH (Alen, Bl. [2] 45, 184). V. sol. 
 water ; cone. H^SOi forms a violet solution. 
 
 Salts . — KjA" aq : trimetric tabular crystals. 
 Na^A" 2aq : tables. — BaA'aq. — CaA' 2aq. — 
 PbA'2aq. 
 
 Terephthalic-azoxy-terephthalic acid 
 [6:3:1] C3H3(C02H).N20.CeH3(COj,H), [1:6:3]. 
 Yellowish plates. Sol. hot, si. sol. cold, water, 
 V. sol. alcohol and ether. Decomposes between 
 250° and 280°. Obtained by oxidation of 
 aldehydo-benzoic-azoxy-aldehydo-benzoic acid 
 N20(03H3(CH0)C03H)j with alkaline KMnO,. 
 
 Salts. — A''(NHj)j'' : long yellowish prisms. 
 A'^Agj : yellow pp. (Homolka a. L5w, B. 19, 1091). 
 
 Toluene-azoxy-bromo-toluene 
 C3H4Me.N20.C8H3BrMe. [74°]. From p-iolxism- 
 p-azoxy-toluene and bromine. Bright yellow 
 tables ; v. sol. alcohol and ether (Helms, B. 8, 551). 
 
 loluene-azoxy-nitro-toluene 
 
 C,H4Me.N20.CeH8(N0j)Me. [84°]. Formed by 
 nitration of j3-toluene-^-azoxy-toluene (Petrieff, 
 B. 6, 557). Yellow needles. 
 
 loluene-o-azoxy-toluene 
 CsH,(0H3).N20.C3H4(CH3). [60°]. Formed by 
 passing CI3O into an ethereal solution of 0- 
 hydrazo-toluene (Petrieff, B. 6, 557). 
 
 Preparation. — 10 pts. of o-nitro-toluene are 
 
BACTERIA. 
 
 430 
 
 added gradually to a solution of 6 pts. of sodium 
 in 60 pts. by volume of methyl alcohol, the 
 mixture being finally cohobated on the water- 
 bath for 3 or 4 hours. 
 
 Properties. — ^Large yellow needles or plates ; 
 the crystals belong to the dimetrio system, 
 o:6 = '8416:1. 
 
 Reactions. — By distillation with iron powder 
 it yields o-azotolueue and a little toluidiae. It 
 also yields o-azotoluene by heating with H^SO^ 
 (Klinger a. Pitsohke, B. 18, 2553). 
 
 p-Tolnene-p-azoxy-toluene 
 0^jMe.NjO.Cja^Me. [70°] (M.); [59=] (P.). 
 From ^-nitro-toluene by reducing it in alcoholic 
 solution with sodium amalgam (Melms, B. 8, 
 551; Petrieff, Z. [2] 5, 264 ; [2] 6, 30; B. 6, 557). 
 V. sol. alcohol and ether. 
 
 Bromine gives a bromo- derivative, [74°], and 
 a di-bromo- derivative [138°]. 
 
 Nitric acid gives a nitro- derivative [84°], a 
 di-nitro- derivative [145°], and a tri-nitro- deri- 
 vative [201°]. 
 
 AZOXYLENE V. Xylene-kzo-xylene. 
 
 AZOXY-ITAPHTHALENE v. Naphthalene- 
 AzoxT-naphthalene. 
 
 AZOXY-PHENOL v. Oxy-benzene-AzoxY- 
 phenol. 
 
 AZOXY-DIPHENYL v. Diphenyl-AZOXY- 
 diphenyl. 
 
 AZOXY-TOLTTENE v. Toluene-Azoxx-toluene. 
 
 AZTTLENE or Az]ilin. Blue colouring matter 
 present in essential oils of chamomile, worm- 
 wood, and millefolium. Causes these and other 
 oils to give an absorption-spectrum, viz., three 
 bands in red and orange (Hook, Ar. Ph. [3] 
 21, 17). 
 
 AZTTLMIC ACID C^H^NjO. Floooulent 
 brown pp. formed together with oxamide and 
 oxamio acid by passing cyanogen into aqueous 
 ammonia. SI. sol. pure water, with violet 
 fluorescence ; acid or alkaline solutions fluoresce 
 green. Boiling water slowly converts It into 
 mycomelio acid CjHjNjOj. Nitric acid orKMnO, 
 oxidises it to azulmoxin C4H3N5O2, an orange 
 powder, insol. water, sol. cone. HjSOj, the 
 solution having a deep-green fluorescence. 
 
 Hydrazulmin C^HjNj is formed by mixing 
 dry cyanogen with dry NH3. It forms black 
 leaflets, converted by water at once into NH, 
 and azulmic acid (Emmerling a. Jacobsen, B. 4, 
 927). By the spontaneous decomposition of an 
 aqueous solution of HON containing a little NH, 
 a brown pp. is produced which, according to 
 Gautier {A. Ch. [4] 17, 158), contains an azulmio 
 acid of the formula C3H3N9O. 
 
 AZURIN OasHjjN^Os. [250-5°]. Small colour- 
 less tables forming solutions which have a 
 splendid blue fluorescence. Prepared by heating 
 salicylic aldehyde with o-tolylene-diamine 
 (Ladenburg, B. 11, 596). 
 
 AZYLINES. Azo- compounds of the form 
 E2N.05Hj.N:N.CsH4.NE2 prepared by passing 
 nitric oxide into alcoholic solutions of tertiary 
 aromatic amines; thus, di-methyl-aniline-azyl- 
 ine is described as di-metbyl-amldo-benzene- 
 azo-di-methyl-aniline, di-amyl-aniUne-azyline is 
 described as di-amyl-amido-benzene-azo-di-amyl- 
 aniline ; and di-ethyl-aniline-azyline as di-ethyl- 
 amido-benzene-azo-di-ethyl-aniiine (Lippmann 
 a. Fleissner, M. 3, 705; 4, 284, 788; B. 15, 
 2136 ; 16, 1421 ; Nolting, B. 18, 1143). 
 
 B 
 
 BABLAH. The fruit of several species of 
 Acacia. The seeds and husks are rich in 
 tannin. 
 
 BACCABIIfE. An alkaloid in Baccharis 
 cordifoUa or ' Mio-Mio.' Needles, si. sol. water, 
 Bol. alcohol, amyl alcohol, and ether. Its aqueous 
 solution is neutral to litmus (Arata, Ph. [3] 
 10, 6). 
 
 BACTEEIA. — The name given originally to a 
 common rod-like form which is assumed in the 
 course of growth by the minute plants to which 
 Nageli (6) in 1857 applied the term Schizomycetes : 
 hence the term ' Bacteria ' is very frequently 
 used to designate the whole of this group of 
 organisms. 
 
 The Bacteria, Bacteriacese, or Schizomycetes 
 are a group of plants of extreme simplicity of 
 structure and very minute in size. Like larger 
 fungi, they are destitute of chlorophyll, and ac- 
 cordingly are unable to decompose carbonic acid 
 in the presence of sunlight ; as a consequence 
 their nutrition resembles in some resj^cts that 
 of animals, since they are dependent on the 
 complex chemical substances produced by other 
 organisms. The variety of substances contain- 
 ing either C or N, or both, which they can 
 attack and make contributory to their sus- 
 
 tenance is very great, whilst the chemical 
 changes which they bring about in these sub- 
 stances are no less varied and remarkable. The 
 exact nature of these changes and the relation 
 of the Bacteria themselves to the substances 
 upon which they feed form an enormous field 
 of inquiry which has only recently been looked 
 at by chemists, and that, as yet, very cursorily. 
 The study of the forms presented by different 
 kinds of Bacteria in the course of their growth 
 is also as yet in an incomplete state, and whilst 
 it is certain that there are kinds of Bacteria 
 characterised each by its particular forms, its 
 particular pabulum or chemical food, and by its 
 particular chemical operations resulting in the 
 formation of definite chemical products from the 
 breaking up of the appropriate pabulum, we do 
 not yet know in any large number of cases 
 whether a particular form is constantly asso- 
 ciated with particular chemical conditions and 
 results, or whether it is possible under modified 
 conditions for a given form to change its chemical 
 and physiological activities. In a certain number 
 of cases we do know that modified chemical and 
 physical conditions will cause a given form in 
 the course of its growth to acquire a very marked 
 modification of form. Hence it is at present iu- 
 
430 
 
 BACTERIA. 
 
 possible to discriminate with assurance different 
 ' species ' of Bacteria, although botanists use par- 
 ticular names to designate those wMch, so far as 
 our information yet goes, are characterised by 
 the constancy of a certain range of form, or in 
 addition to this," by the constancy of chemical 
 and physiological activity. By ' species ' the 
 naturalist understands a group of organic forms 
 the members of which may present very little 
 or very great differences of form and even of 
 activities as compared one with another, but of 
 which it is true, either that they actually are 
 connected with one another by natural processes 
 of reproduction which have occurred within 
 human experience and observation, or that there 
 is good reason to suppose that they might be so 
 connected within human experience. Forms 
 which are separated from one another by an 
 interval the passage of which has not been 
 witnessed and recorded by observers in the past, 
 or defies experiment at the present day, are dis- 
 tinct species. We have not by experimental 
 breeding produced a horse from an ass or an ass 
 from a horse, or both from a third form, and 
 we have no record of observations leading to 
 the inference that such a passage has occurred 
 within human experience, hence the horse and 
 the ass are distinct species. On the other hand, 
 we have traditional and experimental evidence 
 of the production of the varieties of fancy pigeons 
 from the Eock Pigeon, and conversely we know 
 that from the most fantastic of fancy pigeons the 
 Eock Pigeon can be produced in the course of a 
 few generations : hence the Eock Pigeon and the 
 Tumbler, Pouter, Fantail, Carrier, &o., are all 
 variously modified members of one species. 
 
 It is necessary to allude to the question of 
 species here because the progress of our know- 
 ledge of Bacteria in the immediate past has con- 
 sisted in an important degree in the recognition 
 of the fact that a great variety of microscopic 
 forms may belong to one and the same species 
 of Bacterium, and because we have to expect the 
 most important advances in the future from the 
 endeavours of bacteriologists experimentally to 
 breed by change of conditions one kind of Bac- 
 terium from another, and even to create experi- 
 mentally new kinds; and this in spite of the 
 fact that it has been unjustifiably assumed that 
 the forms of Bacteria at present recognised are 
 of the nature of species and immutable. 
 
 Classificatory position of Bacteria. — The 
 nearest allies of the Bacteria among chlorophyll- 
 bearing plants are the Osoillatorise and certain 
 green-coloured organisms (the so-called B. chlo- 
 rinum, B. virens, B. viride) which, whilst iden- 
 tical in form with some of the Bacteria, differ 
 physiologically from them in possessing chloro- 
 phyll. The distinction between these plants and 
 the Bacteria is not by any means a wide one, 
 and there can be no doubt of the close genetic 
 relationship of the green and the greenless 
 Sohizophyta, the Bacteria having, as is the ease 
 in other groups of plants, lost their chlorophyll 
 and acquired parasitic or saprophytic (refuse- 
 eating) hahitB pari passu. 
 
 rorms of Bacteria The Bacteria present 
 
 themselves either as swarming accumulations of 
 detached cells or as linear aggregates (filaments 
 or chains) of cells. Frequently the cells or 
 plastids are loosely packed side by side and 
 
 embedded in a jelly so as to form sheets or 
 massive aggregations. The individual cells are 
 usually extremely minute, being only •001 mm. 
 or even less in diameter, though they may be 
 larger. The cells consist of a homogeneous pro- 
 toplasm in which no nucleus can be detected ; a 
 cell wall, sometimes extremely deUcate, bounds 
 the surface of the cell, consisting of ' myoopro- 
 tein,' rarely of cellulose. When the cell-wall 
 swells up, imbibing water, a jelly is formed in 
 which the cells are set at intervals (' zooglcea' 
 condition). The ultimate shape of the cells of 
 the Bacteria varies: it may be spherical (coccus- 
 form or micrococcus), biscuit-shaped or lieyhole- 
 shaped, like two spheres partially fused (cli- 
 thridium-form or bacterium sfiJisMsiricfei), cuboid, 
 varying from a cube to a short prism (mioro- 
 baoiUus form), rod-shaped (baciUus-form), curved 
 like a bent rod (comma-form), twisted like a 
 fraction of a corkscrew (spirillum-forrn ; if the 
 spiral is not strongly marked, vibrio-form). 
 The most characteristic feature of these cells 
 is their power of rapid growth and multi- 
 plication by fission into two equal portions. 
 Brefeld has observed a Bacterium, formed by 
 fission, grow to the size of the parent cell and 
 itself divide into two in the course of half an 
 hour, each of the daughter cells repeating the 
 process in half an hour. In the course of 24 
 hours there are thus produced from a single 
 Bacterium more than a billion individuals like 
 itself. The constant and rapid process of binary 
 fission is what has led to the use of the names 
 Schizophyta and Schizomycetes. All the forms 
 of cells which we have enumerated as being 
 assumed by Bacteria exhibit this phenomenon. 
 But it is not necessary that the results of the 
 fission should separate entirely from one another. 
 Frequently such separation occurs, and in 
 the forms known as cUthHMum (or bacterium 
 sensu stricto) bacillus, vibrio, and spirillum, 
 a filament of naked protoplasm is frequently 
 observed hanging from each end of the fission- 
 product, and by its lashing movements causes 
 an active ' swarming ' movement, or darting 
 progression of the separate cells. Contrasted 
 with this locomotive swarming phase we have 
 to note the phase of aggregation or continuous 
 growth. As the result of variation in their 
 pabulum. Bacteria which were at one hour 
 separating from one another after fission — may 
 remain in the next hour of growth in contact— 
 held by their unruptured cell-walls. Thus are 
 produced, in place of motile swarming individual 
 cells, aggregates or colonies which may be (1) 
 linear ; (2) tessellate ; (3) branched ; (4) reti- 
 form ; (5) massive. Any of these forms of 
 aggregation may be exhibited by any of the 
 different forms of cells. Linear aggregates of 
 micrococci are called rosary-chains or strepto- 
 coccus ; linear aggregates of micro-bacUli form 
 longer baciUi and so-called leptothrix filaments ; 
 linear aggregates of comma-shaped segments 
 form spirilla ; and small spirilla and vibrios 
 when aggregated end to end form larger spirilla. 
 Branched aggregation is seen in the so-called 
 Cladothrix dichotoma, where a leptothrix fila- 
 ment breaks so as to allow a new line of growth 
 to start at the broken surface, but without sepa- 
 ration of the original continuation of the filament, 
 which takes up a lateral position as a ' false ' 
 
BACTERIA 
 
 431 
 
 branch (fig. s). Similarly mesh-works (resem- 
 bling those of the green hydrodictyon) are pro- 
 duced (fig. r), and very regular tessellate aggre- 
 gates (fig. q). In the latter, bacillus or olithri- 
 dium forms may be arranged with absolute sym- 
 metry forming little plates of twenty or more 
 cells, in rows of five or more (merismopedia 
 form). In the sarcina form the grouping is 
 cuboid, ' packets ' being produced instead of 
 
 Forms of Bacteria, a. Micrococcus; ft. DIploooccus; 
 e. Olithridium or biscuit (with Sagella) ; d. Micro- 
 bacillus ; e. Bacillus (built up of microbacilli) ; /. 
 Leptothrix or filamenlibus form, homogeneous at one 
 end, divided intb bacilli in the middle and into micro- 
 bacilli at the other end ; g. Spirillum (vibrio) ; A. 
 SpitlUum (close spiral) with fiagella ; i. Comma (seg- 
 ment of spirillum) ; k. Homogeneous bacillus with 
 flagella ; I. Ovoid or double-cone form ; m. Large irre- 
 gular form ; these may occur of great size and various 
 shapes, as flat discs (macroplasts) in Bact. rubescens. — 
 Lant. ; n. Bacillus with monillCorm protoplasm, not 
 spores (B. tuberculosis) ; o, Sporobacillus, with endo- 
 spores ; p. Kosary-chain ; linear aggregate of micro- 
 cocci; 9. Merismopedia-formor tablet; tesselate aggre- 
 gate of clithridia ; r, Hydrodiotyon-form : retitorm 
 aggregate of bacilli ; >. Oladothrix-f orm : false-branch- 
 ing linear aggregate of bacilli; t, Nostocoid linear ag- 
 gregate ; larger cocci occur at intervals in a chain of 
 smaller cocci (observed in cultivations of B. anthracis); 
 «. Two micrococci embedded in jelly-like envelope ; 
 w. Lenconostoc-form : a spirillum with jelly-like en- 
 velope ; X, Zooglcea of clithridia : clithridia embedded 
 in jelly-like matrix. 
 
 •plates.' Lastly, where the cell-wall swells up 
 and forms a jeUy, we may have the bacterian 
 cells of any one shape adhering by the jelly to 
 one another (fig. x), and forming spherical or 
 irregular misses of jeUy (zooglcea). These 
 masses often are as large as the hand of a man, 
 and are founi on putrefying liquids and solids. 
 There is no doubt that all the forms of cell 
 tnd of cell-aggregates which hava been above 
 
 described, and others to boot, may be exhibited 
 by one and the same species of Bacterium. The 
 Bacterium rubescens of Lankester [Ij forms port- 
 wine coloured pellicles on decaying organic 
 matter in fresh-water ponds and in salt-marshes, 
 the protoplasm of the cells being coloured by a 
 peculiar insoluble pigment ' bacterio-purpurin.' 
 Lanlzester found all the varieties of aggregation 
 and of cell-form (except spirilla, since observed 
 by Warming [2] and by Giard [3]), in a small 
 tank in which this organism was flourishing ; 
 their connection with one another was proved 
 by their all containing the peculiar colouring 
 matter and by transition-forms of growth. The 
 accuracy of these observations has been con- 
 firmed by Zopf [4], and Lankeater's conclusions 
 adopted by him as well as by De Bary [5]. The 
 species of Bacteria are said to be 'pleo- 
 morphic ' or in Lankester's phraseology ' pro- 
 tean.' Nevertheless it is exceedingly probable 
 that not all bacterian species exhibit so vdde a 
 range of form as does B. rubescens. Some seem 
 to be limited to the micrococcus and clithridium 
 cell-forms, and to exist either as free swarming 
 cells of those shapes, or as Linear aggregates of 
 the same. Others again are possibly limited to 
 the micrococcus form, though it is necessarily 
 extremely difficult to be sure that under appro- 
 priate conditions of cultivation the cell-form 
 and aggregation-form will not change altogether, 
 and, untU experiments have been very carefully 
 made in each case with the object of breaking 
 down the limitation of form usual to this or 
 that species of Bacterium, it will not be justifiable 
 to dogmatically characterise a species of Bacte- 
 rium by reference to its shape. 
 
 Spore-formation. The Bacteria reproduce 
 with enormous rapidity by fission, but some few 
 are known to produce special reproductive bodies 
 which have the property of resisting the inju- 
 rious effects of desiccation and heat. 
 
 In one sense of the word ' spore,' every seg- 
 ment into which a previously unbroken plastid 
 or cell of a Bacterium divides is a spore. A 
 more special justification of the use of the term 
 is found when occasionally one of the products 
 of division is larger or more refringent than its 
 fellows. Such ' spores ' are recognised in the 
 cultivations of Bacterium (Bacillus) tuberculosis. 
 None of these are sufficiently specialised as 
 reproductive particles to justify thoroughly the 
 use of the term ' spore ' in regard to them. In 
 certain species, however, e.g. Bacterium subtile. 
 Bacterium anthracis, and B. megaterium— the 
 formation of well-defined endospores is charac- 
 teristic. The protoplasm within each member 
 of a linear aggregate of bacillus-forms separates 
 centrally from itself an ovoid mass (fig. 0), on 
 the surface of which a coat of dense mycoprotein 
 is produced. The bacilli themselves die away 
 and decompose, but the ovoid spores remain, and 
 have the power when dried of resisting an ex- 
 posure to boiling water for as much as fifteen 
 minutes. This property in the spores of B. 
 subtile, which are common in old hay, has led 
 to erroneous inferences as to the ' spontaneous 
 generation,' or ' abiogenesis,' of Bacteria. It is 
 possible, as suggested by De Bary [5], that the 
 Bacteria which produce endospores are widely 
 separate (as to their origin from green algss) 
 from the other Bacteria which have no special- 
 
BACTERIA. 
 
 ised spores. He divides the Bacteria into 
 Endosporea and Arthrosporea. 
 
 Classification and nomenclature of Bacteria. 
 For the present De Bary's division of the Bac- 
 teria into Endosporea and Arthrosporea may be 
 accepted. The various generic names in use, 
 tuoh as Streptococcus, Ascococous, Cladothrix, 
 Beggiatoa, Myconostoc, Leuconostoo, have no 
 logical basis, and produce a good deal of confusion 
 by a false appearance of order. It is probably 
 sufficient at present to limit generic distinctions 
 to the three terms Micrococcus, Bacterium, and 
 Sporobacterium. The genus Micrococcus com- 
 prises those BacteriacesB which are not at pre- 
 sent known to exhibit any form of plastid or cell 
 other than that of minute spheres; the genus 
 Bacterium contains only those Bacteriaceffl which 
 are known to exhibit in the course of growth 
 rod-like forms of plastids, as well as in many 
 cases micrococcus-forms and spiral and straight 
 filamentous forms ; the genus Sporobacterium 
 includes only those forms which produce endo- 
 spores, the so-called Bacterium (Bacillus) an- 
 thracis, B. subtile, and B. megaterium. Ad- 
 hering to this nomenclature, we still make use 
 of the terms vibrio, spirillum, bacillus, clithri- 
 dium, asooeoccus, zoogloea, &c., &c., to describe 
 conditions of growth or varieties of cell-form. 
 
 With regard to the use of specific names, it is 
 well that every form or group of forms of Bao- 
 teriacese which definitely recurs in certain con- 
 ditions, and seems to be, so far as observation 
 has gone, distinct from other known forms or 
 groups of forms, should receive a name. Seeing 
 that many of these names are probably but of 
 temporary significance, it would be well that 
 they should be as definitely descriptive of some 
 feature of the supposed species as possible. The 
 BacteriacesB should be named according to their 
 chief properties, place of occurrence, or character 
 of growth, and not after persons. 
 
 The following is a list of some of the chief 
 supposed species of Bacteriacese which have been 
 described, with an indication of the mode of oc- 
 currence. It is by no means an exhaustive list, 
 and it is quite certain that some of the few sup- 
 . posed species here enumerated will, on further 
 inquiry, be found to be phases of growth of other 
 species. 
 
 Section A. : Endosporea. 
 
 Genus SpoBOBAOTERinn. 
 
 Species : 8. subtile, common in hay ; S. an- 
 thracis, in the blood of cattle, sheep, and man, 
 causes the disease known as splenic fever; S. me- 
 gaterium, observed on boiled cabbage ; S. buty- 
 ricwm, the butyric ferment, occurs in cheese- 
 making, and has been confused with S. subtile. 
 
 Section B. : Arthrosporea. 
 
 Genus Baoiekium. 
 
 Species : B. termo, the commonest form in 
 putrefying vegetable infusions, but not yet iso- 
 lated and characterised; B. lineola, a larger 
 form occurring in foul ponds and sewage ; B. 
 rubescens, the protoplasm is wine-red in colour, 
 the plastids and aggregates are of the most 
 varied forms, occurs in ponds on vegetable 
 refuse ; B. dichoUyma, forming branched aggre- 
 gates (cladothrix) and straight and spiral fila- 
 ments, common in riVer water on dead leaves ; 
 S. Kuhmana, in wells and drain-pipes (Creno- 
 thrix); B, mesenteroides, forming masses like 
 
 frog-spawn on the beet-root juica of sugar re- 
 fineries ; B. tuberculosis (fig. n), in the diseased 
 growths of men and animals suffering from tuber- 
 cular consumption or phthisis ; JB. leprce, in the 
 diseased skin of persons suffering from leprosy ; 
 B. mallei, in men and horses affected with 
 glanders ; B. typhosum, in the spleen and intes- 
 tinal glands in fatal cases of typhoid fever ; B. 
 acidi lactioi, in sour milk, the manufacturer of 
 lactic acid ; B. cyanogenvmi, in milk, causing it to 
 turn deep blue ; B. pyocyaneum, in pus in badly 
 dressed wounds, producing an emerald-green 
 colouring matter ; B. ahiei, causing a disease 
 in bee-larv8B known as foul-brood ; B. v/reee, in 
 urinals, causing the ammoniacal fermentation 
 of urea ; B. aceti, the vinegar ferment, causing 
 the conversion of ethylio alcohol into acetio 
 acid, occurs in vinegar factories; B. prodi- 
 giosum, causing blood-red staining of bread, milk, 
 &c., leading to public alarm, and regarded as 
 a portent; B. ovatmn, causing the silk- worm 
 disease known as ' pebrine ; ' B. cuniculicidum, 
 causing a specific septicaemia in mice and birds : 
 B. cholercB galUna/rum, in the blood and in the 
 intestines of fowls suffering from chicken 
 cholera ; B. pneumonice crouposce, in the exuda- 
 tion in croupous pneumonia of man ; B. Koctm, 
 Koch's comma-bacillus, found in the intestines 
 of persons dead of Asiatic cholera (this is a 
 spiriUum form which breaks into comma-shaped 
 segments ; it is not proved to have any causal 
 relation to cholera) ; B. Finkleri, similar to the 
 last but larger, occurs in ordinary diarrhoea ; 
 B. buceale and B. ZewisU, spiral and filamen- 
 tous forms breaking into commas which occur 
 in the healthy human mouth. 
 
 Genus MioKooocons. 
 
 Species: M. pyogenes, in acute abscesses; 
 M. erysipelatosus, the cause of erysipelas in 
 man ; M. va/riolce, in the pustules of small-pox ; 
 M. gonorrhcecB, probably the cause of gonorrhoea ; 
 M. bombycis, causing the disease in silk-worms 
 known as flaccidezza; M. ventriculi, in the 
 human stomach, observed in vomit, the ' sarcina 
 ventriculi ' of Goodsir ; M. scarlatinee, probably 
 the cause of scarlet fever in man, and of a disease 
 of the udder in cows ; M. raHdorum, the cause 
 of rabies, not satisfactorily isolated as yet ; be- 
 sides a list of twenty or thirty more causing 
 special kinds of pyssmia in such animals as 
 rabbits and mice, or producing well-marked 
 colouring matters in colourless vegetable or ani- 
 mal infusions, green, blue, red, yellow, purple. 
 
 For a complete enumeration of the supposed 
 ' species ' of Bacteriacese which have been de • 
 scribed, together with a description of each 
 species and many illustrative figures, the reader 
 is referred to the extremely useful and trust- 
 worthy treatise by Dr. Edgar Crookshank, en- 
 titled A Manual of Bacteriology, published by 
 H. K. Lewis, London, 1887. Dr. Crookshank 
 gives complete references to the original de- 
 scription of every known species and to the 
 subsequent literature. 
 
 Chemical relations of the Bacteriacese. — The 
 above incomplete list gives some idea of the im- 
 portance attaching to these minute organisms. 
 It is an importance entirely depending on the 
 variety and peculiarity of the chemical decom- 
 positions and reconstructions which they excite 
 in the organic compounds forming either the 
 
BACTERIA. 
 
 433 
 
 living or dead bodies o( higher plants and 
 animals. Without Bacteria there would be no 
 such thing as putrefaction, and therefore no 
 circulation of the organic elements from their 
 more stable compounds to the condition of albu- 
 mens, fats, and sugars, and back again to the 
 stable results of putrescence. The earth's sur- 
 face would be cumbered with the dead bodies 
 of former generations in which the carbon and 
 nitrogen now serving as the food of plants would 
 be permanently locked up. All the evil smells 
 which are not directly due to the chemist, are, 
 with few exceptions, due to the action of Bac- 
 teria. Many valuable commercial products, 
 sach as acetic acid, lactic acid, and flavouring 
 compounds such as butyric acid, are obtained 
 through their agency. The pungent fumes of 
 stable refuse are caused by their action on urea. 
 It is almost certain that they too are the agents 
 of nitrification in the soil — one species of Bac- 
 terium (or Micrococcus ?) converting the am- 
 monia produced by another, into nitrates and 
 nitrites. Some Bacteria produce highly poison- 
 ous bodies by their action on the albumens of 
 dead animals and plants ; amongst these poisons 
 are the ptomaines, which have recently excited the 
 attention of chemists [6]. Other Bacteria make 
 their way into living animals and plants and 
 there produce poisonous decomposition-products 
 from the albuminous constituents of the organ- 
 ism, which are recognised in their effects under 
 such names as splenic fever, scarlet fever, 
 phthisis, rabies, &c. It appears that there are 
 many kinds of Bacteria which are parasitic in 
 and on the bodies of men and of other animals, 
 the results of whose chemical activity is not 
 injurious, whilst other kinds (or possibly the 
 same kinds under changed conditions) produce 
 deadly results. Other kinds again, it now seems 
 certain, are not merely iimocuous but actually 
 necessary to the healthy life of the animal they 
 inhabit. The digestion of food in the alimentary 
 canal of man and other animals is largely aided 
 by the Bacteria which are present in the intes- 
 tine in countless myriads, and it appears that 
 the products of digestion owe their chemical 
 characteristics in no small degeee to the Bac- 
 teria. In the absence of the normal parasitic 
 Bacteria the products of digestion in the human 
 intestine would, it appears highly probable, be 
 of such a nature as to act poisonously when 
 absorbed into the blood. When to these con- 
 siderations we add the fact that the Bacteria 
 are ubiquitous, abounding in the dust of the air, 
 in aU natural waters, and upon all surfaces 
 whether of animate or inanimate objects which 
 hare not been chemically cleansed within a 
 few seconds of their examination, some idea 
 may be formed of the immense importance 
 which belongs to the study of the Bacteria in 
 the immediate future. 
 
 Methods of Study. — ^At present the state 
 of knowledge of the chemical relations of the 
 Bacteria is extremely fragmentary. They were 
 originally discovered by Leeuwenhoek [7], the 
 Dutch naturalist, in the fluids of the mouth, 
 and various forms were subsequently seen with 
 the microscope in natural waters, ponds, &o., 
 and described by Ehrenberg [8] and others. It 
 was Theodore Schwann [9], however, who, in 
 18.S8, demonstrated by a simple experiment that 
 
 Vol. I. 
 
 the Bacteria cause the putrefaction of organio 
 substances, and that without them there is no 
 putrefaction. Later, Pasteur [10], in opposi- 
 tion to Liebig, extended Schwann's observations 
 and conclusions, and established the doctrine of 
 organised ferments, which has proved of immense 
 practical importance, and is as yet only at the 
 commencement of its history. The foundation 
 of the experimental demonstrations of Schwann 
 and of Pasteur lies in the fact that the living 
 protoplasm of the Bacteria is destroyed — that 
 is to say, undergoes an irrevocable chemical 
 change — when subjected to a temperature below 
 or about that of boiling water. Consequently 
 it is possible, by the action of heat, to destroy 
 the Bacteria present in an experimental vessel 
 and its contents, and to protect the contents 
 from the further accession of Bacteria. By this 
 method, and by this method alone, it has been 
 possible to prepare organic infusions, as well as 
 solid gelatine, albumen, &c., which, whilst 
 capable of supporting the life of Bacteria, are 
 yet free from their presence for the time being. 
 Such substances are said to be ' sterilised.' 
 They can be inoculated at pleasure with Bacteria 
 and the effects of the inoculation studied. In 
 order to procure the Bacteria for inoculation in 
 a state of purity, special methods have been 
 devised. So abundant and varied are the kinds 
 of Bacteria present in nearly all natural organio 
 material, that any rough process of inocula- 
 tion will introduce many kinds of Bacteria 
 simultaneously into a sterilised medium. To 
 separate the various kinds of Bacteria for the 
 purpose of study of each in its isolated con- 
 dition, three principal methods are employed. 
 The first applies, as far as is knovm, to but one 
 kind, the Sporobacterium (Bacillus) subtile. The 
 dry spores of this Bacterium resist the destruc- 
 tive effect of boiling water for as much as 
 fifteen minutes, whilst all other known Bacteria 
 are destroyed by it. Hence we have only to 
 boil old hay in water for a few minutes in. 
 order to obtain i pure cultivation of B. subtile. 
 The second method (due to Nageli [11]) is that of 
 fractional dilution. Given a liquid swarming 
 with a mixture of various Bacteria, of which it 
 is estimated by inspection that one individual 
 in twenty is of the kind it is desired to cultivate. 
 Dilute the liquid to such an extent that ona 
 drop of it should contain but a single bacterium. 
 Then it is probable that every twentieth drop, 
 will contain a single isolated individual of the 
 desired Bacterium. Fifty tubes of sterilised 
 nutrient material are prepared, and into each a. 
 single drop of the diluted Bacterium-holding 
 fluid is introduced. One, or possibly more, of 
 the tubes will thus be inoculated with an isor, 
 lated example of the desired Bacterium, which 
 wiU multiply in the sterilised nutrient material 
 and thus yield a pure cultivation, and can be 
 recognised by the microscope. The third method 
 is due to Brefeld, of Berlin. By streaking with 
 a needle point a minute drop of fluid containing 
 various Bacteria, over a surface of solid sterilised 
 gelatine, the various Bacteria will be locally 
 isolated along the course of the streak. They 
 will remain thus separated from one another 
 and commence to multiply in situ. With a low 
 power of the microscope and a fine needle 
 samples can be now removed from the various 
 
 FF 
 
434 
 
 BACTEIIIA. 
 
 patches of growth and placed in the pure con- 
 aition in tubes of sterilised nutrient material for 
 further cultivation and study. Similar isolation 
 is effected by mixing liquid gelatine with a 
 dilute infected liquid ; when the gelatine solidi- 
 fies, the various bacteria are embedded apart 
 from one another, and grow in isolated patches, 
 which can then be removed and separately 
 studied by further cultivation. 
 
 Conditions of life required by Bacteria. — 
 General results, (a) 
 
 1. The first general result of these methods of 
 study has been to determine the ubiquity of a 
 large number of different kinds of Bacteria, and 
 the comparative rarity of others. More will be 
 said below as to the study of the distribution of 
 Bacteria in air and water. 
 
 2. The Bacteria are found to differ from one 
 another in their relation to free oxygen ; the 
 aerobic (Pasteur) will only multiply in the 
 presence of free oxygen ; the anaerobic will not 
 flourish except in the absence of free oxygen, 
 or at any rate are indifferent to its presence. 
 Thus B. authracis is eminently aerobic, whilst 
 the Bacterium of malignant oedema is anaerobic. 
 The hay-bacillua (B. subtile) is aerobic, the 
 butyric bacillus of cheese (very similar to the 
 former in appearance) is anaerobic. 
 
 3. The source of nitrogen required by Bac- 
 teria for buUding up their protoplasm is various. 
 Very many can take it in as low a form of com- 
 bination as ammonia. Others require it in 
 higher combination, and some either regvAre it 
 in the form of albumen or at any rate can take 
 it from albumens. It is from albumens that 
 some of the most remarkable products formed by 
 Bacteria result. There can be little doubt that 
 the first steps in this process are comparable to 
 the digestion of albumen by animal cells. It is 
 not ascertained that all and any Bacteria can 
 attack albumens. The exact range of the chemi- 
 cal quaUty of the nitrogenous food possible to 
 each species of Bacterium has yet to be deter- 
 mined. 
 
 4. The carbon required by Bacteria may be 
 taken in as low a form as acetic acid by cer- 
 tain species ; others can take it from tartaric 
 acid ; others can do with nothing lower than a 
 sugar ; others again require glycerin or a simi- 
 lar body, and others apparently require their 
 carbon as well as their nitrogen to be presented 
 in the form of a proteid. Thus it results that 
 many Bacteria can be nourished by solutions of 
 ammonium tartrate alone, whilst the limits of 
 complexity of necessary food-compounds has 
 various ranges in other species, aU of which 
 require accurate determination by the chemist. 
 Little has as yet been ascertained in this 
 direction, but recently Dr. Boux [12] of the 
 Pasteur Institute, has made an extremely im- 
 portant observation showing the necessity for 
 extended research of the kind. It was found by 
 Koch extremely difiScult to cultivate the Bacte- 
 rium tuberculosis, even upon blood-serum kept 
 at the normal temperature of the body. Bonx 
 found that the addition of a minute quantity of 
 glycerin to the serum led to the rapid and 
 abundant growth of the B. tuberculosis suppKed 
 with that mixture; and further, that an ordinary 
 meat broth which alone cannot serve as pabulum 
 for the B. tuberculosis, when mixed with a 
 
 minute quantity of glycerin acts as a moBl 
 efficient nutrient medium for this species. It is 
 highly probable that other such special require- 
 ments in regard to the chemical nature of their 
 food, exist in respect of other species of Bacteria, 
 whilst others again are more catholic in their 
 nutrition. 
 
 6. Water is necessary for the growth of 
 Bacteria as of all living things. Most Bacteria 
 will flourish in the presence of that small amount 
 of water in proportion to solid matter which 
 suffices to constitute mere dampness or moist- 
 ness. Bacteria are not killed by partial desicca- 
 tion, but none resist thorough desiccation. In 
 this respect important variations have been 
 determined in different kinds. The spores of 
 the Bndosporea have a special power of resisting 
 desiccation. 
 
 6. There is an optimum temperature favour- 
 ing the growth of Bacteria, which ranges in 
 various species from 10° to blood heat. Ex- 
 periments have been made proving that certain 
 species of Bacteria are killed by extreme cold, 
 whilst all are arrested in growth during expo- 
 sure to the freezing temperature of water. The 
 most careful observations have been made in 
 regard to the effects of exposure to high tempera- 
 ture. Exposure to a temperature of 100° for 
 five minutes kills all Bacteria except those be- 
 longing to the Eudosporea, the spores of which 
 can resist the effects of this exposure for half- 
 an-iiour, and possibly longer. Many Bacteria 
 are killed at lower temperatures (e.g. 80°), but 
 careful experiments are wanting. ^ 
 
 7. Experiments as to the effects of diminution 
 and increase of atmospheric pressure upon the 
 life of Bacteria have been made, but without 
 reference to particular species. Diminution of 
 pressure is not known to have any influence, 
 whilst experiments made by the writer show 
 that a pressure of thirty atmospheres does not 
 hinder the development of putrefactive Bacteria 
 appreciably, though modifying the chemical 
 results of their life - processes. Extremely 
 high pressures are stated to be destructive of 
 Bacteria. 
 
 8. The influence of light is, according to the 
 experiments of Downes [13], inhibitory to the 
 growth of certain Bacteria, but the species so 
 affected have not been determined. This is in 
 accordance with the absence of protective pig- 
 ment in most species, and the general fact of 
 their growth within turbid liquids and beneath 
 the surface of solid bodies away from the light. 
 
 9. Like the yeast-plant, which creates a 
 poison (alcohol) in the nutrient fluids in which 
 it grows, which after reaching a certain per- 
 centage causes the arrest of growth and the 
 subsidence of the yeast-cells — so the Bacteria 
 are limited in their growth by the existence of 
 products of their own formation. These pro- 
 ducts have not been investigated by chemists. 
 But it appears to be established that putre- 
 factive Bacteria grovring in a nutrient medium 
 flourish for a time abundantly, then suddenly 
 cease their growth and sink to the bottom of the 
 vessel in which they have been growing, although 
 the nov/rishmg material is not exhausted. A 
 further and exact investigation of this pheno- 
 menon by the chemist in regard to various 
 species of Bacteria must lead to results of the 
 
BAOTERIA, 
 
 436 
 
 greatest value in relation to the practice of 
 preventive inoculation for disease. 
 
 10. A condition of the life of a given species 
 of Bacterium is found in the presence of other 
 species of Bacteria. Frequently one species of 
 Bacterium is the indispensable friend and 
 associate of a second — preparing by its chemical 
 activity the pabulum on which alone the second 
 can thrive. An association of the kind is seen 
 in what is called the vinegar plant, where 
 Hycoderma prepares from starch the alcohol 
 which the Bacterium aceti converts into acetic 
 acid. So, too, the Bacterium of ammoniaoal 
 fermentation is the antecedent of the Bacterium 
 which converts ammonia into nitrites and 
 nitrates. Equally important is the inhibition 
 and possibly the destruction of one species of 
 Bacterium by another. Very little has been 
 ascertained on this important matter, but it 
 appears that the presence of certain putrefactive 
 Bacteria in a nourishing medium will actually 
 prevent the development and growth of certain 
 pathogenic species of Bacteria, although these 
 are present in small numbers. Apart from the 
 question of possible specific incompatibility of 
 two Bacteria, it appears that the question of 
 quantity (v. Cheyne [14]) is important. A species 
 of Bacterium which is at the commencement 
 of an inoculation experiment one hundred times 
 more numerous than a second species, may by 
 its rapid development and numbers prevent 
 altogether the growth of the second species. 
 
 11. The question of the conditions of life of 
 the Bacteria involves the very important one of 
 their tolerance of the presence of various che- 
 mical substances in the liquids in which they 
 grow, those substances the presence of which 
 is not tolerated by the Bacterium being called 
 'germicides' or 'antiseptics.' On account of the 
 practical importance of destroying or inhibiting 
 the development of putrefactive and pathogenic 
 Bacteria, a good deal of attention has been given 
 to this subject by chemists, but unfortunately 
 it is only recently in the laboratory of Koch 
 [15] that experiments to determine the germi- 
 cidal action of chemical substances have been 
 made with the necessary discrimination of the 
 species of Bacteria which were the subject of ex- 
 periment. The fact is now definitely established 
 that some species of Bacteria are killed by che- 
 mical substances which do not injuriously affect 
 others, and that the amount of such substances 
 which is effective varies in the case of different 
 species. The inquiry has only as yet been com- 
 menced, but it is of immense practical impor- 
 taiioe, since it may be possible to discover ' ger- 
 micides ' of a generally innocuous character 
 which are specific poisons for certain disease- 
 producing Bacteria, whilst harmless to other 
 Bacteria and harmless to the higher animals in 
 whose tissues the pathogenic Bacteria flourish. 
 Thus weak solutions of quinine sulphate are 
 poisonous to the Bacterium uretz, whilst not in- 
 jurious to putrefactive Bacteria. Such a solu- 
 tion can be injected into the human bladder 
 without causing irritation, and thus the inflam- 
 mation resulting from the ammoniacal decom- 
 position of the urine in the bladder by Bac- 
 terium urefB, which sometimes gains access 
 thereto, can be entirely arrested. In this 
 inquiry the diSerenoe between actual destruc- 
 
 tion of the Ufe of the Bacteria, and mere arrest 
 or inhibition of growth due to the presence of 
 the antiseptic chemical, have to be distinguished. 
 It is also needful to inquire how far such ' anti- 
 septics,' without killing or inhibiting Bacteria, 
 may modify the physiological processes and 
 chemical results brought about by the latter. 
 The most powerful and generally effective 
 poison for Bacteria appears to be corrosive sub- 
 limate. The presence of as little as 1 in 10,000 
 of this salt in a nutrient fluid has been found to 
 kill Bacteria present. Phenol is also a general 
 and powerful germicide. Boracic acid also and 
 common salt in large quantities are effective. 
 The nature of their action and their effectiveness 
 in regard to different species of Bacteria have yet 
 to be accurately determined. Antiseptic surgery, 
 the future treatment of zymotic disease, and the 
 preservation of perishable articles of food, depend 
 upon the further discoveries of chemists in regard 
 to this matter. It is not improbable that the 
 most effective and useful germicides will be 
 found in chemical substances which, like quin- 
 ine, resemble those inhibitory products which 
 are produced by the Bacteria themselves and act 
 as the natural obstacles to their excessive mul- 
 tiplication. The more general question of the 
 tolerance of or necessity for the presence on the 
 one hand of free acid, on the other of free alkali 
 in the nutrient fluids suited to different Bacteria, 
 belongs here. It has been studied in regard to 
 many Bacteria in a rough and ready way. Some 
 Bacteria will not flourish in acid media, others 
 will; but accurate quantitative investigation* 
 are stiU wanting. 
 
 The prodncts of the activity of Bacteria, — 
 When a species of Bacterium grows in a nutrient 
 fluid of known chemical composition with access 
 to a definite and limited volume of atmospheric 
 oxygen — under given conditions of temperature, 
 pressure, and illumination — certain chemical 
 interchanges occur in the materials contained 
 in the apparatus. These can be accurately de- 
 termined in certain instances, and the variation 
 of the quantity of change in relation to time can 
 be stated. Various factors of the process, such 
 as temperature, presence or absence of initial 
 chemical substances, &o., can be varied, and the 
 results stated and compared. In no case has such 
 an experiment as yet been accurately made by a 
 chemist. Nevertheless, we know roughly that, 
 in the supposed experimental apparatus above 
 indicated, there wiU be after a certain time an 
 increase in the weight of mycoprotein and albu- 
 mens existing in the form of Bacteria, and a 
 corresponding diminution in the C, H, N, and 
 of the other material in the apparatus. Not 
 only this, but we find certain new chemical com- 
 pounds present outside the actual substance of 
 the multiplied Bacteria which result from and 
 aocompany the growth and Ufe of the particular 
 species experimented upon. The same general 
 statement is true of any higher organism in 
 relation to its necessary pabulum ; but whereas 
 in large multicellular organisms the resulting 
 products of the life of the organism are tem- 
 porarily or permanently held within the mass 
 of the body, in the minute unicellular Bacteria 
 there is no taking in or envelopment of tha 
 materials to be acted upon by the living thing, 
 but the organism gets into its food instead of 
 
 ff8 
 
«5G 
 
 BACTERIA. 
 
 the food getting into it : consequently processes 
 comparable to the digestive and even to the more 
 deep-seated metabolic processes of higher organ- 
 isms take place in the nutrient liquid in which 
 the Bacterium lives, being initiated at the sur- 
 face of the swarming ceUs constituting the colo- 
 nies of these minute plants, and serving their 
 economy equally as well as though they occurred 
 in an alimentary canal or in a series of blood- 
 vessels and tissue-spaces. The chemical changes 
 induced by Bacteria should be studied from the 
 same point of view as that taken by the physio- 
 logist in regard to the activities of the various 
 cells of the tissues with their diverse and specific 
 functions. We are not yet in a position to treat 
 the subject from this standpoint, but we can dis- 
 tinguish with more or less certainty results 
 traceable to respiration, digestion, assimilation, 
 secretion and excretion ; the chemical correla- 
 tives of these processes are changes described as 
 de-oxidation, oxidation, specific fermentations, 
 specific syntheses. 
 
 The obvious results of the activity of Bacteria 
 (setting aside the probably universal evolution 
 of CO2 and consumption of free O, common to 
 the Bacteria and all living protoplasm) though 
 by no means necessarily the most important in 
 regard to their own physiology, are the produc- 
 tion in the liquids in which they grow of (1) 
 substances having distinctive smells and fla- 
 vours ; (2) substances having brilliant colours ; 
 (3) substances having eminently poisonous pro- 
 perties ; to these may be added such remarkable 
 results of oxidation as the manufacture of ni- 
 trates in soil, of acetic acid in vinegar factories, 
 and the manifestation of light — the phosphores- 
 cence — of decayingfish,bones, and other organic 
 refuse. 
 
 The chemical nature of the substances which 
 are thus produced, the by-products which ac- 
 company them, and the nature of the processes 
 by which they are originated, havenot yet formed 
 the subject of chemical investigation to any 
 large extent. Such knowledge as we have is 
 due to Pasteur [16], to Fitz [17], and one or two 
 others. 
 
 It seems probable that we may distinguish 
 amongst these results those which are due to 
 synthesis, by the Bacterium acting on lower 
 compounds taken into its substance, and those 
 which are due to analysis resulting from the 
 action of ferments and other agents secreted by 
 the Bacteria and acting on surrounding material 
 of a high degree of chemical complexity. Of 
 the nature of these ferments we know nothing ; 
 their existence is hypothetical but highly pro- 
 bable. To the first category belong certainly 
 many of the brilliant pigments which the Bac- 
 teria produce ; in most oases these pigments are 
 soluble and pass out from the protoplasm into 
 the surrounding water, la Bacterium rubeseens 
 the wine-red pigment is not soluble, and remains 
 where it is manufactured in the cells of the 
 plant. The remarkable smelling substances 
 formed by putrescent Bacteria also belong to 
 this group of built-up products, and it is pro- 
 bable that the poisonous products of some 
 pathogenous Bacteria, though not of all, are thus 
 elaborated. The chief experimental reason 
 which we have for concluding that these bodies 
 ttre built up by the Bacterium from lower com- 
 
 pounds is this, that they are formed when the 
 Bacterium is cultivated in a pure solution of 
 ammonium tartrate (with traces of mineral salts) 
 often called Pasteur's or Cohn's solution. Thus 
 the Bacterium of blue milk can be grown and 
 made to produce its blue colour from ammonium 
 tartrate, the Bacterium of green pus similarly, 
 and many of the chromogenic Micrococci, whilst 
 some of the specially active putrefactive Bacteria 
 manufacture foul-smelling products from the 
 same salt when experimentally nourished with 
 it. 
 
 In regard to the second group, that of sub- 
 stances resulting from a breaking down of higher 
 chemical bodies brought into relation with the 
 Bacterium (and that probably by the action of a 
 secreted ferment which may be minute in 
 amount and possibly never separated from the 
 surface of the Bacterium-ceU), we have to note 
 first of all that the ferment itself belongs to the 
 previous group. Secondly, that various species 
 of Bacteria have been shown to produce ethylio 
 and other alcohols in this way — from sugar 
 and similar bodies — as does the yeast-plant 
 (Saccharomyces). Fitz [17] has shown that 
 a certain Bacterium converts glycerin into ethyl 
 alcohol, whilst another converts it into butyl 
 alcohol. Other Bacteria have been shown to 
 convert sugar into gum or into mannite, pro- 
 ducing the so-called ' ropy fermentation ' of 
 syrups, wine, and beer. Urea is converted into 
 carbonate of ammonia, hippurio acid into 
 benzoic acid and glycocoU. Albumens are 
 broken down into bodies which have not been 
 determined in many cases, but include the 
 ptomaines, neuridine, and trimethylvinyl-am- 
 monium hydrate. Various Bacteria as well as 
 the specific B. lactici, produce small quantities 
 of lactic acid from various substances, such as 
 grape-sugar, milk sugar, and glycerin, whilst 
 possessing other ferment-producing action also. 
 Butyric acid is frequently produced in these 
 processes by other Bacteria as well as by the 
 B. butyricnm of cheese-factories. Exact know- 
 ledge is, however, sadly deficient in these 
 matters, owing to the fact that hitherto chemists 
 have not been careful to ascertain what species 
 of Bacterium is present in the fermentations 
 studied by them. Owing to this we do not yet 
 know whether in different nourishing fluids and 
 under different conditions of access of oxygen 
 and of temperature, the same Bacterium can 
 produce different fermentations. Such know- 
 ledge as we have tends to a positive answer to 
 the above question. One of the best researches 
 with a known species of Bacterium is that of 
 Vandevelde [18], on the hay bacillus (B. subtile). 
 
 Since it is probable that there is this change 
 of chemical activity under changed conditions, 
 it is also probable that a Bacterium which is 
 harmless under ordinary conditions of growth 
 may, when specially cultivated in albuminous 
 media, acquire the property of living in the 
 animal body as a parasite, and there cause 
 deadly disease by its fermentative action, or by the 
 secretion of poisonous products. Buohner [19], 
 starting from this theoretical consideration, has 
 endeavoured to produce the deadly B. anthracis 
 of splenic fever from the hay bacillus [B. subtile), 
 and conversely to restore the parasitic form by 
 cultivation to the primitive state. His experi- 
 
BACTERIA. 
 
 437 
 
 ments, though of extreme interest, are not oou- 
 elusive. 
 
 It is di£Boult to hazard a guess as to whether 
 the poisonous effects of any given Bacterium 
 proved to be concerned in the production of 
 disease, are due to the secretion of a poison by 
 the Bacterium or to the production of one by its 
 fermentative action upon the constituents of the 
 blood, tissues, or intestinal contents. The che- 
 mical theory of the antidotal action of inoculation 
 with various ' vaccine ' cultivations, which is 
 that favoured by their chief discoverer and in- 
 vestigator, M. Pasteur, would seem to involve 
 the hypothesis that whilst the effective poison 
 is a secretion of the Bacterium, the antidotal 
 material is a chemical compound resulting from 
 the fermentative action of the Bacterium, quite 
 distinct from the poison. This fermentation- 
 product by its accumulation inhibits the de- 
 velopment of the Bacterium as alcohol inhibits 
 the further growth of the yeast plant by the 
 fermentative action of which it has been formed. 
 The phagocyte theory of Metschnikow [20] in re- 
 lation to preventive inoculation does not involve 
 this distinction (see below). 
 
 The oxidising action of Bacteria must be 
 considered merely as a special form of their 
 fermentative action. By the latter they produce 
 intermediate chemical substances which are 
 readily oxidised by the free atmospheric oxygen. 
 It is probably thus that acetification proceeds 
 when B. aceti converts ethylio alcohol into 
 vinegar or when organic nitrogenous bodies and 
 ammonia in the soil are converted into nitrites 
 and nitrates. There is no evidence of a specific 
 oxidising action on the part of the Bacterium. 
 The phosphorescent substance produced in stale 
 fish, old bones, meat, &c., under certain con- 
 ditions by certain Bacteria (as yet not precisely 
 determined) may be regarded as an example of 
 one of these intermediate oxidisable substances. 
 The oxidation in this case is accompanied by the 
 evolution of light. 
 
 Special Study of the Occurrence and Dis- 
 tribution of Bacteria in the Atmosphere and in 
 Potable Waters. — The ubiquity of Bacteria has 
 been demonstrated by the use of sterilised nutri- 
 ent fluids. If such u fluid be touched by a glass 
 rod or by the finger or by any surface not chemi- 
 callycleansed,Bacteria are conveyed into the fluid 
 and multiply there with enormous rapidity. 
 Gelatin has been used as a means of studying 
 the number of Bacteria present in the atmosphere 
 or in a sample of water (v. Percy Frankland's re- 
 searches [21]). However modified, the process is 
 essentially this : a given volume of air is passed 
 through a liquid so as to arrest all Bacteria pre- 
 viously floating in the air. The liquid is then 
 mixed with gelatin, warmed to liquefy the gela- 
 tin, and rapidly cooled as a thin layer on a plate. 
 The Bacteria develop at various separate points 
 in the gelatin, giving rise to spherical growths 
 or nests. These are then counted, and the 
 species present may be discriminated by further 
 cultivation.- Where water is the subject of in- 
 vestigation the gelatin is directly mixed with a 
 given volume of the water. The results thus 
 obtained have only a subordinate value from the 
 point of view of the hygienist. The majority 
 of Bacteria are perfectly innocuous, and their 
 presence is not— as has been too readily as- 
 
 sumed — an indication of the probable presence 
 of pathogenic Bacteria. No such natural asso- 
 ciation of pathogenic and innocuous Bacteria in 
 definite proportions has been ascertained, and 
 its assumption is not warranted. It is necessary 
 in all cases, if the results are to have hygienic 
 value, to distinguish the kinds or species of 
 Bacteria present and to ascertain their proper- 
 ties. Further, it is quite certain that all species 
 of Bacteria will not flourish in gelatin even 
 when mixed with peptone or such bodies. For 
 instance, one of the most important pathogenic 
 Bacteria — that concerned in tubercular consump- 
 tion — will not do so. A special pabulum is needed 
 for this Bacterium, and its presence would not 
 be indicated by the ordinary gelatin cultiva- 
 tion of the contents of a given volume of air. 
 Hence it seems necessary that in addition to 
 careful discrimination of the Bacteria obtained 
 by such experiments on atmospheric and aquatic 
 distribution, there should be a systematic use of 
 various cultivating media for the purpose of 
 demonstrating the presence of various kinds of 
 Bacteria. No doubt many kinds can be secured 
 by the peptonised gelatin method, but if the 
 results of such studies are to have any qualitative 
 hygienic significance, other cultivating media 
 must be simultaneously made use of. All the 
 work at present done on this subject requires 
 doing afresh from this point of view. 
 
 Special Study of Pathogenic Bacteria. — A 
 large number of most important observations 
 have been made of late years by pathologists — 
 especially by Lister, Pasteur, Koch, Klein, and 
 their pupils — demonstrating not only the 
 presence of Bacteria in the blood and tissues of 
 man and other animals when in a state of 
 disease, but also proving in a certain number of 
 cases that the Bacteria are the cause of specific 
 disease. The proof, which is sufficient, and has 
 been furnished in a limited number of instances, 
 consists in — 1. The constant presence of a 
 definite form of Bacterium in the diseased 
 animal and in the specially-diseased parts of it. 
 2. Its successful removal from the diseased 
 animal, and its pure cultivation on media free 
 from all contamination by particles of the dis- 
 eased animal. — 3. The experimental introduction 
 of the cultivated Bacterium into the body of a 
 healthy animal liable to the disease in question 
 but free from it. — 4. The subsequent develop- 
 ment of the disease in the inoculated animal. 
 This proof has been furnished in regard to the 
 connection of B. anthracis with splenic fever 
 in cattle and sheep, and malignant pustule in 
 man ; in regard to B. tuberculosis and consump- 
 tion or phthisis in man and animals ; in regard 
 to B. cholera gallium and the cholera of fowls ; 
 in regard to Micrococcus erysipelatosus and ery- 
 sipelas of man ; in regard to certain Bacteria and 
 septiosemic and pyiemic conditions in rats, mice, 
 rabbits, and birds ; and in regard to some other 
 diseases of animals. Such a connection is 
 strongly suspected, but not yet proved in the 
 complete manner formulated above in regard to 
 certain observed Bacteria or Micrococci, and the 
 following diseases, viz. small-pox, scarlatina, diph- 
 theria, typhoid fever, cholera asiatica, malaria, 
 yellow-fever, gonorrhoeaj &c. The first definite 
 researches in this direction, which were immedi- 
 ately accompanied by piacticai results of eaor- 
 
433 
 
 BACTERIA. 
 
 mous value, were those of Sir Joseph Lister, 
 who showed that the blood-poisoning so frequent 
 in crowded hospitals after surgical operations 
 was due to the access of Bacteria to the wounds 
 where they multiplied and manufactured poison- 
 ous products (sepsine, ptomaines ?) which were 
 absorbed into the blood. Lister adopted mea- 
 sures for preventing the access of these Bacteria, 
 chiefly by the use of phenol and great cleanliness 
 in instruments, dressings, &o., and thus estab- 
 lished the antiseptic system of surgery. 
 
 It is remarkable that the researches which 
 have been made on the relation of Bacteria to 
 disease have been mostly of a purely empirical 
 character. Almost the only investigator who has 
 carried the matter further (and with the most 
 brilliant results) is the French chemist Pasteur. 
 The fact is that the question as to what the 
 Bacteria do after entering an animal body is, 
 like the question of their action on substances 
 external to the body, essentially a chemical one. 
 Following up the observations of Toussaint, 
 Pasteur [22] was led to the discovery that the 
 Bacterium anthracis when cultivated in broth 
 could be made to assume a condition in which 
 its virulence was greatly diminished. Neverthe- 
 less when introduced into the tissues of a sheep, 
 the cultivated Bacterium multiplied, and as a 
 consequence of its growth rendered the sheep 
 BO treated resistant to the attacks of the virulent 
 Bacterium anthracis taken from another animal's 
 blood. 
 
 It was known that an animal which had 
 survived an attack of the virulent B. anthracis 
 was thereby rendered ' immune ' to subsequent 
 attacks, just as one attack of small-pox renders 
 its survivor ' immune ' in regard to that disease. 
 Pasteur conceived the theory that the Bacterium 
 causing the disease in all such cases produces 
 as a by-product^ndependent of its specific 
 poison — a chemical substance which inhibits its 
 further growth (as in the case of the alcohol 
 produced by the yeast-plant) and that this 
 substance remaining in the animal body pro- 
 tects it from being the seat of further growth 
 of the pathogenic Bacterium. The modified cul- 
 tivated variety of B. anthracis equally produces 
 this substance, and consequently acts as a pro- 
 tective against the incursions of the virulent 
 form. Similarly cow-pox is to be regarded as 
 the result of the growth of a modified small-pox 
 Micrococcus, and thus the protective effects of 
 inoculation with cow-pox are to be explained. 
 Applying this conception Pasteur has success- 
 fully protected fowls against fowl-cholera, and 
 has been led to his greatest triumph, the pro- 
 tection by inoculation against rabies and the 
 successful treatment of persons bitten by rabid 
 dogs. 
 
 It is extremely interesting and important to 
 observe that the discoveries which have been 
 made in this subject are due to chemical con- 
 ceptions. Nevertheless there is much proba- 
 bility in the view put forward by Metschnikow 
 (a distinguished zoologist, now director of the 
 Bacteriological Institute of Odessa) to the effect 
 that protective inoculation does not depend upon 
 the development within the inoculated animal 
 of a germicidal poison, resulting from the growth 
 of the very germ which is killed or inhibited by 
 that poison, but is rather due to the education 
 
 of the living tissues, and especially of the whiti 
 corpuscles of the blood, which, he has proved, 
 attack and feed upon Bacteria which are multi- 
 plying in the blood and tissues. This property 
 of the white corpuscles leads Metschnikow to 
 term them ' phagocytes,' and, according to him, 
 preventive inoculation depends for its efficacy 
 on the fact that, having learnt to resist and 
 destroy a weaker modification of a pathogenous 
 Bacterium, they are able to deal subsequently 
 with the more virulent variety; whilst it has 
 been suggested that in the struggle between the 
 phagocytes and the inoculated modified Bacteria, 
 there must be a survival of the fittest and a 
 consequent strengthening of the later generations 
 of phagocytes in the protected animal. 
 
 However this may be, it is obvious that both 
 the direct study of the chemical history of 
 pathogenic Bacteria and the indirect suggestions 
 derived from further knowledge of the chemical 
 history of Bacteria of all kinds, are of an im- 
 portance to human life and health which cannot 
 be over-estimated. 
 
 In connection with the study of the patho- 
 genic Bacteria which attack man, it is necessary 
 to insist that at present no one has attempted 
 to determine the various kinds of Bacteria 
 which are normally present on the surface of 
 the human body, in the mouth, stomach, and 
 intestines. There appear to be twelve or more 
 present in the healthy human mouth {v. Vignal, 
 [23]). So strangely has this matter been neg- 
 lected that Koch of Berlin was ignorant, when 
 he discovered the so-called ' comma-baciUus ' in 
 the intestines of choleraic subjects in India, 
 that an identical form occurs in the healthy 
 human mouth, as shown by Lewis [24]. 
 
 Spontaneous generation or abiogenesis. — 
 Twenty years ago experiments and observations 
 were brought forward by various more or less 
 competent observers [25] which were interpreted 
 as proving the sudden formation of Bacteria as 
 living things in fluids containing the elements ol 
 protoplasm where no germ or living thing pre- 
 viously existed. It is suificient to say here that 
 these views had a valuable effect in stimulating 
 the investigation of the life-conditions and acti- 
 vities of the Bacteria, but have been definitely 
 proved to be erroneous and to have arisen from 
 the imperfect state of knowledge as to the 
 ubiquity of Bacteria and the power to resist 
 the destructive effect of boiling water possessed 
 by the spores of Bacterium subtile — the hay 
 bacillus. 
 
 Conclusion. — An endless field of investiga- 
 tion is open in connection with the Bacteria. 
 It seems certain that in the near future we shall 
 be able to control the disease-producing forms, 
 whilst the suggestion presses itself that it may 
 be possible to cultivate and intensify the activi- 
 ties of those which act as scavengers and even 
 to lead some by appropriate methods to the 
 acquirement of new powers, or to the develop- 
 ment of activities at present scarcely recognised. 
 There is no reason, from the point of view of the 
 biologist, why these lowest plants should not be 
 cultivated and specialised as breeds and varieties 
 for the service of mankind, as the peach and the 
 strawberry, the wheat and the cabbage have 
 beeo, 
 
 E.B. Ik 
 
BACTERIA. 
 
 4sa 
 
 iiibliography (referred to by numerals in 
 brackets in the preceding article). 
 
 1. Lankester, B. Bay. ' On a Peach-coloured 
 Bacterium,' Qtiart. Joum. Micr. Sci. Vol. xiii. 
 (1873) and Vol. xvi. (1876) ; also ' On the Pleo- 
 morphism of Bacteria,' ibid. vol. xxvi. (1886). 
 
 2. Warming. Om nogleved Danmarks Kyster 
 levende Bacierier, 1876. 
 
 3. Giard. ' Etude sur nne bact^rie ohromo- 
 gtae dea eaux de rouissage du lin,' Bevue des 
 Sci. Nat. tome v. (1877). 
 
 4. Zopf. Zur Morphologie der Spaltpflanzen, 
 Leipzig, 1882; also Die SpaltpiUe, Breslau. 
 3rd edition, 1885. 
 
 5. De Bary. Vergleichende Morphologic und 
 Siologie der PiUe, Mycetozoen und Bacterien, 
 Leipzig, 1884, p. 490. 
 
 6. Brieger. Zur Kermtniss der Faulniss- 
 Alkaloide. H. 7, 274 ; B. 17, 515, 1137. 
 
 7. Leeuwenhoek. T., a.d. 1683. 
 
 8. Ehrenberg. Die InfusionstMerchen, Leip- 
 zig, 1838. 
 
 9. Schwann, P. 41, 184. 
 
 10. Pasteur. A. Oh. [3] 68, 328. 'Animal- 
 cules infusoires,' &o. O. B. 52, 1142 (1861). 
 Etudes sur la Biire, 1876. 
 
 11. Nageli. Untersuchungen Uber niedere 
 Pilze, 1882. 
 
 12. Eoux. Annales de I'InsUtut Pasteur. 
 No. 1, 1887. 
 
 13. Downes and Blunt. 'Influence of Lighten 
 Bacteria,' Trans. Boy. Soc. of Victoria, vol. xx. 
 
 14. W. Watson a. Cheyne. British Medical 
 Journal, 1887. 
 
 15. Koch. Mitiheilungendeskaiserl.Oesund- 
 heitsamtes, 1881, et seg. 
 
 16. Pasteur. A. Ch. a.d. 1858. 
 
 17. Fitz. B. 9 (1876), 1348 ; 10, 276 ; 11, 
 42, 1890 ; 12, 474 ; 13, 1309 ; 15, 867 ; 16, 844 ; 
 17 (1884), 1188. 
 
 18. Vandevelde. Studien zur Chemie des 
 Bacillus subtilis. H. 8 (1884), 867. 
 
 19. Buchner in Nageli's Untersuchungen 
 Uber nied. Pilze, 1882. 
 
 20. Metschnikow. Yirchow's Archiv, vol. 
 xevi. (1884), p. 50% 
 
 21. Percy Franlland. Pr. A.D. 1885-6-7. 
 
 22. Pasteur (B. anthracis). La vaccination 
 charbonneiose. C. B, 1883. 
 
 23. Vignal. Journal de I'Anatomie et de la 
 Physiologic, 1887. 
 
 24. Lewis, T. E. Beport of the Commission 
 on Cholera, 1885. 
 
 25. Bastiau. The Beginnings of Life, 1868. 
 Roberts. Tr. a.d. 1874. Tyndall. Floating 
 Matter of the Air, 1881. 
 
 BALANCE V. Analysis. 
 
 BALATA. A substance resembling caoutchouc 
 and gutta-percha, obtained from the dried milky 
 juice of the Bully-tree {Sapota Muelleri) (Sper- 
 ling, Z. [2] 6, 480). 
 
 BALSAU. This term was originally con- 
 fined to a single substance called Balm of Grilead 
 or Balsam of Judea, but is now employed gene- 
 rally to denote any liquid resin with aromatic 
 odour. They are composed of solid resins 
 mixed with essential oUs. Balsams of Peru, 
 Tolu. Liquidambar, and Storax, contain cinna- 
 mic acid ; Copaiba balsam, Mecca balsam, and 
 turpeiiDine, do not. 
 
 FARABAKIC AGIO v. Pakabanic acid. 
 
 BAPHIIN (C„H,„Oj)„. Extracted by etliut 
 from barwood {Baphia nitida). Plates or 
 needles (from ether), insol. water, v. si. sol. 
 benzene. Its alcoholic solution is turned red 
 by air. Boiling aqueous KOH converts it into 
 baphio acid O^^Hj^On (?), baphnitin (OjH^O)., 
 and baphnitoue, C^gS^gOg. The latter gives a 
 tri-bromo- derivative CjuHosBrjOj. 
 
 BAPTISIA TINCTORIA. The root of this 
 plant contains a orystallins alkaloid (Greene, 
 Ph. [3] 10, 584). 
 
 BARBALOiN v. Aloin, p. 140. 
 
 BAEBATIC ACID C,„Hj„0,. [186°]. Occurs, 
 together with usnic acid, in a lichen, Usnea 
 barbata (Stenhouse a. Groves, C. J. 37, 405 ; A. 
 203, 302). Needles or plates (from benzene). 
 Decomposed by boiling milk of lime into CO, 
 and (3)-orcin. 
 
 BARBITTJBIC ACID 
 
 C,H,N,03 i.c. CH,<^°;^g>CO. 
 
 Malonyl-urea. Formed by heating malonic acid 
 with urea and POCl,, at 100° (Grimaux, C. B. 
 88, 85 ; A. Ch. [5] 17, 276), or by reducing di- 
 bromo-barbiturio acid with sodium amalgam or 
 HI. Prepared by heating alloxantin (1 pt.) with 
 H2SO, (3 or 4 pts.) at 100° as long as SOj comes 
 off. The product is poured into water. 
 
 Properties. — Trimetrio prisms (containing 
 2aq) from water. SI. sol. cold, v. sol. hot, 
 ■water. 
 
 Beactions. — 1. Boiling aqueous potash forma 
 malonic acid and urea (CO^andNH,). — 2. HNOj 
 forms nitro-barbiturio (dilituric) acid. — 3. KNO.j 
 forms nitroso-barbituric (violurio) aoid.^4. Br 
 forms di-bromo-barbituric acid. — 5. Heated with 
 glycerin it forms dibarbiturio acid, urea, and 
 ammonium malobiurate. — 6. Cyanogen forms a 
 compound C4H,Nj05(CN)2 aq, whence potash 
 forms ' cyanuromalio acid.' 
 
 Salts. — NH^HA": needles, v. si. sol. cold 
 ■water. — Na^A" 2aq. — KHA". — BaH^A" 2aq.— 
 PbA".— CuHjA''^ 8aq.— AgHA".— AgjA". 
 
 Acetyl derivative CiHaAcNjO,. A by- 
 product in the preparation of barbituric acid 
 from urea, malonic acid, and POCI3. Po^wder, 
 sol. hot water. 
 
 Di-methyl derivatives. — I. Malonyl- 
 
 dimethyl-urea CO<^^g-^Q>OHj. [123°]. 
 
 From malonic acid, di-methyl-urea and PCI5, or 
 from di-methyl-urea and cyano-acetyl chloride, 
 CN.CH2.CO.CI (Mulder, B. 12, 466). Flat 
 needles, v. sol. water. Forms a di-bromo-deri- 
 vative [175°-180°]. 
 
 II. Di-nzethyl-malonyl-urea 
 
 C0<^g;^^>CMe2. [265°]. From silver bar- 
 
 biturate and Mel (Conrad a. Guthzeit, B. 14, 
 1643) or from di-methyl-malonic acid, urea, and 
 POCI3 (Thome, C. J. 39, 545). Plates (from 
 water). V. si. sol. cold water. Boiling KOH 
 forms di-methyl-malonic acid. 
 Salt.— Ag2A"iaq. 
 
 Ethyl derivative CO<|^g^Q\.CHEt. 
 
 [190°]. From ethyl-malonio acid, POCl,, and 
 urea. Gives a bromo-derivative. 
 
 Di-ethyl derivative CO^^g^^^CEt. 
 
 [182°]. From silver barbiturate and EtI. 
 
440 
 
 Bemyl derivative 
 
 BARIUM. 
 
 From 
 
 [206°]. 
 benzyl-malonio acid, POClj, and urea. 
 
 Additional Beferences.—Fmok, A. 132, 304 ; 
 Baeyer, A. 130, 136 ; Conrad a. Guthzeit, B. 
 U, 1643 ; 15, 2844. 
 
 Di-barbituric acid CsHgNjOs. The ammo- 
 nium salt is formed by heating barbituric acid 
 with glycerin at 150°. The acid is an insoluble 
 powder ; it gives a di-bromo- derivative. 
 
 Salts .— NH^HA".— Na^A" 2aq. — KHA" xaq 
 (Baeyer, A. 130, 145). 
 
 BARIUM. Ba. At. w. 136-8. Mol. w. un- 
 known, as V.D. not determined. Very little 
 known of properties ; doubtful if approximately 
 pure Ba has yet been obtained. S.G. abt. 3-5-4 
 (sinks in H^SOJ. S.V.S. abt. 36-5. Chief 
 lines in spectrum are 5850, 6538, 4934, 4553, 
 3140 (Huggins, T. 154, 139). 
 
 Occurrence. — Not as metal ; chiefly as sul- 
 phate (heamy sjpwr), and carbonate (witherile) ; 
 also as silicate in combination with sUioates of 
 Sr, K, or Al, and as oxide in combination with 
 oxide of Mn. Ba compounds occur in many 
 mineral waters ; in the ashes of certain plants 
 (Eckart, A. 100, 294) ; and in small quantities 
 in sea water (Dieulafait, A. Oh. [5] 15, 540). 
 
 Formation. — ^An amalgam of Ba and Hg is 
 prepared in several ways : — (a) by electrolysing 
 BaClj mixed with a little very dilute HClAq, 
 using an amalgamated Pt wire as negative 
 electrode (Bunsen, A. 92, 248) ; (6) by electro- 
 lysing moist BaO using Hg and Pt as electrodes 
 (Davy, T. 1808. 303) ; (c) by bringing hot BaO 
 or BaClu into contact with vapour of K, and 
 treating the product with Hg, or by heating BaO 
 with Na and treating with Hg (Kern, 0. N. 31, 
 244) ; {d) by the action of Na amalgam on cone, 
 warm BaCl^Aq (Orookes, 0. N. 6, 194). By 
 heating Ba amalgam in an atmosphere of H, or 
 of hydrocarbon vapours, metallic Ba was sup- 
 posed to be obtained ; but Donath (B. 12, 745) 
 asserts that it is impossible to remove all the 
 Hg even at a white heat, and that the residue 
 contains as much as 62 to 77 p.o. Hg. 
 
 Preparation. — By electrolysis of fused BaCl^ 
 mixed with NH^Cl, in a porcelain crucible in an 
 atmosphere of H ; the positive electrode con- 
 sisting of a cylinder of coke, the negative of an 
 iron wire (Matthiessen, 0. J. 8, 294). 
 
 Properties and Reactions. — It is very doubt- 
 ful whether the properties enumerated by 
 differ&nt chemists as characteristic of Ba were 
 determined by experiments made on even 
 approximately pure metal. Davy described Ba 
 as silver-white ; Bunsen and Matthiessen as a 
 golden yellow, slightly lustrous, somewhat 
 malleable, metal, which melts at a red heat, but 
 cannot be distilled. It is very easily oxidised, 
 decomposes cold HjO readily, and burns in the 
 oxyhydrogen flame. As no gaseous compounds 
 of Ba have as yet been obtained, and as the 
 spec, heat of the metal has not been determined, 
 the value to be given to its atomic weight, the 
 combining weight or equivalent having been 
 determined, is arrived at chiefly by considering 
 the analogies between the compounds of Ba and 
 those of other allied elements, chiefly Ca, Sr, 
 Mg, Zn, and Cd. These analogies lead to the 
 lormulffl BaX and BaYj for the compounds of 
 
 Ba, where X = 0, S, S0„ 00„ &o., and T = C1, 
 NO3, CIO., &o. ; these compounds belong to one 
 series. The valency of the atom of Ba in gaseous 
 molecules is unknown. That the atomic weight 
 of Ba is represented by a number the most 
 probable value of which is about 136-8, provided 
 the composition of the Ba compounds is ex- 
 pressed by the general formula BaX^, where X = 
 a monovalent atom or group of atoms, was estab- 
 lished chiefly by analyses of barium chloride con- 
 ducted by Marignao {A. 68, 215 ; 106, 165) and 
 Dumas {A. Oh. [3] 55, 137). Ba reacts asastrongly 
 positive metal ; the salts obtained by replacing 
 H of acids by Ba are stable and well marked ; 
 BaO and BaOjHj, BaS and BaS^H^, exhibit no 
 acidic characters ; BaOjHj is distinctly alkaline, 
 its heat of neutralisation is the same as that of 
 sodaand potash {Th.l, 332) rBaO'H^Aq.H-'SO 'Aq] 
 = 31,150; [BaO'ffAq, 2HGlAq] = 27,640. Ba 
 combines with and the halogens with produc- 
 tion of much heat and formation of very stable 
 compounds :—[Ba,0] = abt. 124,000; [Ba,ClT 
 = 194,700; [Ba,Br2J = 170,000 (Th. 3, 266); 
 these numbers are approximate only ; they were 
 determined indirectly, except that for BaO, but 
 the Ba used was not free from Hg. Barium is 
 very closely related to Ca and Sr, and less closely 
 to Mg (v. art. AlkaijIne Eakths, metals or the). 
 
 Baryta was obtained by Scheele in 1774 from 
 heavy spar ; Davy in 1808 decomposed baryta 
 by electrolysis ; the metal was obtained approxi- 
 mately pure in 1855 by Bunsen and Matthiessen. 
 
 Oombinations. — Very few compounds of Ba 
 have been formed directly from the metal. It 
 forms alloys with a few metals ; that with 
 mercury (v. supra. Formation) is a silver-white 
 body whichrapidly decomposes water and cannot 
 be separated into Ba and Hg by heat alone. 
 Beketoff (A. 110, 375) obtained an alloy with 
 aluminium, as a greyish sohd with a, tinge of 
 yellow, by heating Al with Ba02H2 and a little 
 BaClj ; it decomposed H^O rapidly, but the water 
 did not acquire an alkaline reaction. Caron 
 described aUoys of Ba with lead, bismuth, anti- 
 mony, &c., obtained by the action of alloys of 
 these metals with Na on molten BaCl, (A. Ill, 
 114). 
 
 Detection. — Many salts of Ba are soluble 
 in water; some are insoluble; aqueous solutions 
 of Ba salts are ppd. by cone. HClAq or cone. 
 HNOjAq. Insoluble Ba salts are decomposed 
 by fusion with alkaline carbonates, giving BaCO, 
 which dissolves in dilute acids. Fusible salts 
 of Ba impart a pale yellowish-green colour to 
 the non-luminous flame ; the colour appears 
 blue-green through a green glass. The emission- 
 spectrum of Ba is characteristic ; it contains very 
 many lines in the green ; about ^gjj mgm. Ba 
 may be detected by the spectroscope. Dilute 
 sulphuric acid, or a dilute aqueotis solution of 
 sulphates, ppt. white BaSOj, insoluble in 
 alkalis and dilute acids; 1 part Ba.2N03 in 
 100,000 parts of water gives an immediate 
 pp. ; one part in 400,000 gives a cloudiness on 
 standing. By this reaction Ba salts are dis- 
 tinguished from Ca salts, and to some extent 
 from salts of Sr. 
 
 Estimation. — 1. Ba is usually determined as 
 BaSOj, which is ppd. from fairly oonc. solutions, 
 containing a little HOI or HNOj, by dilute 
 HjSO^Aq; the pp. is coUeoled, well washed, 
 
BARIUM. 
 
 441 
 
 and strongly heated, before weighing. If salts 
 of Oa are present, CaSOj may be removed from 
 the pp. by long washing with very dilute HClAq, 
 or by digesting with Na2S20sA.q (Diehl, J.j^. 79, 
 30) which dissolves CaSO^ but not BaSOj. 
 PbSO„ if present, may be removed from the 
 pp. by washing with solution of potash, or of 
 ammonium tartrate. — 2. In presence of salts of 
 Ca and Sr, Ba is best estimated as BaSiPj, which 
 is ppd. by freshly prepared H^SiFjAq, followed 
 by alcohol ; after standing 12 hours, the pp. is 
 collected, washed with a mixture of equal 
 volumes of alcohol and water, dried at 100°, and 
 weighed {v. also Eose, P. 95, 286, 299, 427). 
 
 Barium, alloys of, v. BABruM ; Combina- 
 tions. 
 
 Barium, antimonates of, v. aniimonaies, 
 under Amtimont, acids op. 
 
 Barium, arsenates of, v. abse^nates, under 
 Absenic, Acms oe. 
 
 Barium, arsenites of, v. abseniies, under 
 Absenic, acids oe. 
 
 Barium, bromide of. BaBr,. Mol. w. un- 
 known, as compound has not been gasified. 
 [abt. 812°] (Carnelley, 0. J. 33, 280). S.G. 4-23 
 (Schiff, A. 108, 21). H.F. [Ba.Br^ = 169,960 ; 
 [Ba,Br-,Aq] = 174,940 (rfc. 3, 266). 
 
 FcyrmaHon. — 1. By acting on BaOjH, or 
 BaS, with HBrAq. — 2. By adding BaS to an 
 aqueous solution of Br. — 8. Along with BaBrO,, 
 by the action of Br on BaO^H^Aq. 
 
 Preparation. — ^Aqueous BDBr is neutralised 
 by pure BaOO,, the liquid is boiled down and 
 allowed to crystallise, and the crystals of 
 BaBr2.2H20 are heated in a stream of dry air to 
 100°. 
 
 Properties and Reactions. — Crystallises with 
 2H2O in white trimetric plates (Bammelsberg, P. 
 55, 237) ; according to Hauer (J.pr. 80, 230) and 
 Werther {ibid. 91, 167) the crystals are mono- 
 olinio ; the hydrated salt is perhaps dimorphous. 
 HJ. [BaBr2,2H'0] = 9,110. [Ba,Br^2H20] = 
 179,070 (Th. 3, 266). Heated to 75°. 
 BaBr^-H^O remains, and at 100° BaBr^ is 
 obtained. The hydrate Ba6r2.2H20 is soluble 
 in water. S. (0°) 98; (20°) 104; (40°) 114; 
 (60°) 123 ; (80°) 135 ; (100°) 149. It is also 
 easUy soluble in alcohol. S.G. 3-69 (Schiff, A. 
 108, 21). BaBr^ is completely decomposed by 
 heating to redness in dry (Sohulze, /. pr. [2] 
 21, 407). When cone, aqueous solutions of 
 BakBr^ and BaO are mixed so that the salts are 
 present in the ratio BaBr^iBaO, crystals of 
 BaBrj.Ba0.5H,0 ( = BaBrOH.2H20) separate 
 out (Bechmann, J.pr. [2] 26, 388 and 474). 
 
 Barium bromide, hydrated, v. Baeiuih, ebo- 
 MTDE or ; Preparation. 
 
 Barium, chloride of. BaClj. Mol. w. un- 
 known, as compound has not been gasified, 
 [abt. 860°, Carnelley]. S.G. 3-75-3-89 (Schroder, 
 P. 107, 113). S.H. (16°-47°) -0902 (Kopp, T. 
 165, 71) ; (14°-98°) -0896 (Eegnault, A. Ch. [3] 
 1, 129). S. (5°) 32'2 ; (30°) 38-2 ; (50°) 43-6 ; 
 (80°) 52-4 ; (100°) 58-8 (Mulder ; v. Michaelis' 
 Lehrbuch der Anorgan. Chem. 3, 660). S. (al- 
 cohol 99 p.c. : 14°) -01 ; (alcohol at B.P.) -06 
 (Fresenius, A. 59, 127). H.P. [Ba,Cl=] = 
 194,740; [Ba,CP,Aq] = 196,810 (Thomsen). The 
 following data apply to the hydrate BaCl2.2H20 : 
 S.G. 3-052 (Schifi, A. 108, 21). S.H. (18°-40°) 
 
 •171 (Kopp, T. 155, 71). S. (15°) 43-5; (105°) 78. 
 H.P. [Ba,CP;2H''0] = 201,740 ; [Ba,0R2H'i01 = 
 7,000 (Th. 3, 266). O.E. (cub. abt. 15°-200°i 
 •0000548 (Playfair a. Joule, C. J. 1, 121). 
 
 Formation.— 1. By the action oi CI on hot 
 BaO (Weber, P. 112, 619).— 2. By passing HCl 
 over hot BaO ; light is evolved as well as heat : 
 or by adding cone. HClAq to BaO, boiling down, 
 and drying at 100^—3. By dissolving BaS in 
 cone. HCIAq; boiling down, and drying at 100°. 
 Preparation. — 1. Powdered witherite (BaCOj) 
 is added little by little to HClAq ; the solution 
 is digested in absence of air with more BaCO, 
 (to remove iron, &o.), and is then poured off, 
 evaporated to dryness, and the residue heated to 
 100° for some time. — 2. Two parts of finely 
 powdered heavy spar (BaSOJ are heated in a, 
 crucible to redness with 1 part dry CaClj and 2 
 parts iron filings; the fused mass is digested 
 for a short time with 6-8 parts boiling water 
 (by long digestion BaSO, and CaClj are re- 
 formed), the liquid is filtered from FeS, CaS, and 
 undecomposed BaSO^, made slightly acid by 
 HClAq, and evaporated to dryness at 100°. — 
 3. The solution of MuClj which is obtained in 
 making 01 from MnOa is neutralised by BaCOj 
 or CaCO, and evaporated to dryness ; the residue 
 is heated with heavy spar and coal ; the mass is 
 lixiviated (MnS, FeS, and some BaSOj remain), 
 the liquid is treated with a little MnCljfAq to 
 decompose any BaS present, HClAq is added, 
 and the whole is evaporated to dryness (Kuhl- 
 mann, 0. B. 47, 403, 464, 674). 
 
 Properties. — White salt, easily soluble in 
 water, [BaCP,Aq] = 2,070 {Th. 3, 266); slightly 
 soluble in alcohol {v. supra) ; solution has a 
 bitter taste and is poisonous. Melts at red heat 
 and cools to an opaque mass. 
 
 Reactions. — 1. Heated in steam, HCl ia 
 evolved, and residue has an alkaline reaction. — 
 2. Partly oxidised by fusion with potassium 
 chlorate, but unchanged by heating in dry 
 oxygen (Schulze, J.pr. [2] 21, 407). — 3. Com- 
 pletely decomposed by fusion with silicates. 
 
 Combinations. — 1. Cone, solution of BaOl^ 
 mixed with cone. BaOAq pps. thin transparent 
 plates of BaCl2.BaO.5H2O ( = BaC10H.2H20) 
 (Bechmann, /. pr. [2] 26, 388, 474).— 2. Com- 
 bines with water with production of heat, 
 [BaC1^2H=0] = 7,000, to form the hydrate 
 BaCL,.2H20. This hydrate crystallises in white 
 flat trimetric plates, which are not efflorescent ; 
 they lose 2H2O at 100°, but take it up again ia 
 moist air. A cone, solution is decomposed to 
 Ba.2N03 and NaCl by heating with NaNOj. 
 
 Barium chloride, hydrated, v. Baeium, 
 OHLOEiDE OF ; Comhinatiofis, No. 2. 
 
 Barium, cyanide of. Ba(CN)2. Obtained 
 
 by action of HCNAq on BaO.,H, [v. Cyanides). 
 
 Barium, fluochloride of. JBaFCl {v. Babium, 
 
 FLUOKIDE Oe). 
 
 Barium, fluoride of. BaP2. Mol. w. un- 
 known, as compound has not been gasified 
 [abt. 908°] (Carnelley, C. J. 33, 280). S.G. 
 ia 4-58 (Bodeker). . / . 
 
 Preparation.—!. By ppg. Ba2N0aAq by 
 NaFAq.— 2. By the action of HFAq on BaOA<i, 
 or on freshly ppd. BaCO,, and evaporating. The 
 former action is attended with the production of 
 much heat; Guntz {A. Ch. [6] 3, 5) gives 
 the values [BaOAq, 2HFAql = 34,800 ; and 
 
443 
 
 BARIUM. 
 
 [BaO'ff, 2HF1 = 71,400 (solid BaF, is produced 
 by action of gaseous HP on solid BaOjHj). 
 
 Properties and Reactions White, finely 
 
 granular, crystals ; scarcely soluble in water, 
 but easily in HNOaAq, HCU.q, and KPAq. Not 
 decomposed by heat alone. 
 
 Combinations. — 1. With BaClj to form 
 BaP2.BaCl2( = BaFCl); obtained by adding 
 NHjAq to a solution of BaPj in HCLAq ; also by 
 fusing 1 part NaP with 6-8 parts BaClj, and 
 digesting with water ; also by adding KPAq to 
 BaCljAq and evaporating. Porms white granular 
 crystals, more soluble in water than BaP^; 
 partly decomposed, with loss of BaCl2, by long- 
 continued washing with water.— 2. With BPj tc 
 form BaPj.2BP3.2H2O ( = Ba(BP,)2.2H,0); ob- 
 tained by acting on BaCOa with HBP,Aq, and 
 evaporating; boric acid separates, and afterwards 
 the double salt (v. bobofluokides under Bobon, 
 FLnoKiDE or).— 3. With SiP^ to form BaPj.SiP, 
 ( = BaSiP„) ; obtained by adding H^SiFjAq to a 
 solution of a Ba salt. White solid, very slightly 
 soluble in cold water— S. (17°) •03— and only 
 slightly soluble in HClAq. S.G. 4-28. Leaves 
 BaPj when heated; heated with NH^Cl gives 
 residue of BaCl^ (Stolba, J. pr. 96, 22) {v. 
 BiLioorLUOBiDES, Under Silicon, fluoride op). 
 
 Barium, hydroxide of. BaOJS.^ {Caustic 
 baryta). Mol. w. unknown, as compound 
 has not been gasified. S.G. 4-495 (Pilhol, 
 A.Ch.[S-\ 21,415). S.(0°)l-5,(5°)l-75, (10°)2-22, 
 (15°) 2-89,(20°) 3-48,(25°) 4-19, (80°) 5-0,(85°) 6-17, 
 (40°) 7-36, (45°) 9-12, (50°) 11-75, (55°) 14-71, 
 (60° 18-76, (65°) 24-67, (70°) 31-9, (75°) 56-85, 
 (80°) 90-77 (Eosensthiel a. Euhlmann, J. 
 1870. 314). H.P. [Ba, 0, H^O] = 146,500, value 
 only . approximate ; [BaO, H^O] = 22,260 
 (Th. 3, 266). 
 
 Formation.— 1. By heating heavy spar with 
 carbon, dissolving BaS formed in hot water, 
 filtering, adding CuO or ZnO to decompose the 
 BaS, filtering, evaporating to dryness, and 
 heating to redness (Miiller, J. pr. 82, 52 ; 
 Stahlsohmidt, X». P. X 182, 30 ; Nicklds, W. J. 
 1869. 274).— 2. By heating Pe with Ba.2N03 to 
 redness, dissolving in water, filtering, evapo- 
 rating, and heating the residue. — 3. By the 
 action of steam on BaOO, (Lenoir, W. J. 1867. 
 256). 
 
 Preparation. — 1. Water is added little by 
 little to BaO (q. v.) ; the product is heated to 
 dull redness in a silver dish. — 2. Aqueous 
 solution of pure NaOH, S.G. about 1-1 to 1-15, 
 the quantity of NaOH in which is accurately 
 known, is heated to boiling, a quantity of 
 powdered Ba2N03 is added equivalent to the 
 NaOH used, the liquid is boiled for a little, if 
 solution is not complete water is added, the hot 
 liquid is filtered quickly and allowed to cool in a 
 closed vessel when crystals of Ba02H2.8H20 are 
 deposited ; these crystals are separated, reorys- 
 taUised from boiling water, and heated gradually 
 to redness in a silver dish (Mohr, Ar. Ph. [2] 
 88, 38). 
 
 Properties and Beactions. — A white powder, 
 dissolving in water {v. supra) to form an alkaline, 
 caustic, liquid ; melts at a full red heat and 
 eryBtallises on cooling ; not decomposed by heat 
 alone, but by heating in a stream of air BaO 
 and HjO are produced. Aqueous solution is 
 \iiavkedJy alkaline, and neutralises acids with 
 
 production ol same quantity of heat as KOHAq 
 and NaOHAq (Th. 1, 332). Does not absorb 
 CI, except in presence of H^O ; action is then pro- 
 bably 6BaOAq + 601^ = SBaCl^Aq + Ba(C103)jAq 
 (Weisberg, B. 12, 346). Is not acted on by 
 CO2 (Soheibler, JS. 19, 1973). 
 
 Combinations. — With water with production 
 of heat [Ba02H^8H20] = 27,470 {Th. 3, 266) to 
 form crystals of BaOjHj.SHjO (Beckmann, J.pr. 
 [2] 26, 388, and 474 ; Filhol found TBfl, Noad 
 and others 9H2O). (For preparation of these 
 crystals v. supra.) These crystals lose 7H2O 
 over H^SOj in vacuo, or by heating to 75°, and 
 the eighth H^O at a red heat ; they dissolve in 
 about 3 parts boiling water, and 20 parts water 
 at 15°- The solution is attended with disap- 
 pearance of heat [BaO-'H2.8H20,Aq]= -15,207 
 {Th. 3, 263). Crystals of BaO^H^.H^O melt at 
 88°-85° (Veley, C. J. 49, 371). According to 
 Bechmann {J. pr. [2] 26, 388 and 474) pure 
 BaO is obtained by heating Ba02H2.8H20 in a 
 stream of 0. 
 
 Barium, iodide of. Bal^. Mol. w. un- 
 known, as compound has not been gasified. 
 S.G. 4-92 (Pilhol, A. Ch. [3] 21, 415). 
 H.P. [Ba,I^Aq] = 144,520 {Th. 3, 266). 
 
 Formation and Preparation. — Similar to 
 methods for BaBr2 {q. v.) : also by action of 
 gaseous HI on BaO. 
 
 Properties and Reactions. — A white, non- 
 deliquescent, solid ; easily soluble in water or 
 alcohol ; not decomposed by heat in absence of 
 air, in presence of air BaO is formed and I 
 evolved ; wholly decomposed by heating in 
 (Sohulze, J. pr. [2] 21, 407) ; aqueous solution 
 absorbs CO^ from air. 
 
 Combinations. — 1. With water to form 
 BaIj,.7H20 (Croft, /. pr. 68, 402 ; Thomsen, B. 
 10, 1343 ; Werther, J. pr. 91, 331, says the 
 crystals are Bal2.2H20). This hydrate forms 
 needle-shaped crystals which deliquesce, with 
 partial separation of I, in moist air, and melt 
 on heating ; heated in absence of air Bal, 
 remains, one TLfl is lost at 100°, 5H2O at 
 125° and the seventh H^O at 150°. Thom- 
 sen gives these data [Ba, F, 7H20] = 151,370 ; 
 [BaP.7H20,Aq] = -6,850.— 2. With baryta to 
 form BaO.BaL,.5H20(=BaIOH.2H.p) (Beck- 
 mann, J. pr. [2] 26, 388 and 474) ; this salt 
 crystallises from a mixture of cone, solutions of 
 its constituents, in the ratio BaOiBal,. 
 
 Barium iodide, hydrated, v. Babium, iodidb 
 OP, Combinations, No. 1. 
 
 Barium, oxides of. Ba forms two oxides, 
 BaO and BaOj ; the former is produced by the 
 action of dry air, or 0, on Ba ; BaO heated to 
 about 450° combines with and forms BaO,, 
 which is again reduced to BaO at a higher 
 temperature, or by reducing the pressure at 
 450°. Dry BaO, is stable, but the presence of 
 water brings about slow decomposition to 
 BaOjHj + O; Berthelot (A. Ch. [5] 14, 433; 
 comp. C.B. 85, 880) gives these data [BaO,0] = 
 - 6,050 ; [BaO^H20] = 2,760 (givingBaO^Hj + 0). 
 BaO is a strongly basic oxide ; BaO, evolves 
 (or H2O2) and forms the same salts as BaO 
 when acted on by acids. 
 
 I. Babidm monoxide {Baryta) BaO. Mol. w. 
 unknown as compound has not been gasified. 
 S.G. 4-85 (Playfair a. Joule, 0. S. Mem. 3, 84); 
 S.G. crystals 5-722 (Brugelmann, W. 2, 466 ; 
 
BARIUM. 
 
 443 
 
 4, 277) ; 5-456 (Filhol, A. Ch. [3] 21, 415). H.F. 
 [Ba,0] = 124, 240; [Ba.O.Aq] = 158, 760 {Th. 
 
 3, 266 ; values approximate only, as Ba used 
 was not pure). 
 
 Soheele distinguished baryta from lime in 
 1774; Gahn recognised the presence of this 
 earth in heavy spar ; Bergmann called the earth 
 tmra ponderosa ; Eirwan gave the name baryta ; 
 Davy, in 1808, proved it to be a metallic oxide. 
 
 Formation. — 1. By the action of dry air on 
 Ba. — 2. By strongly heating BaCOj, best with 
 A,-ith of carbon whereby CO is formed which 
 does not again combine with the BaO. — 3. By 
 strongly heating Ba.2N0j ; Bammelsberg (B. 7, 
 542) says that an oxide with the composition 
 Ba30,( = 2BaO.Ba02) is thus produced; Brugel- 
 mann {W. 2, 466 ; 4, 277) obtained hexagonal 
 crystals of BaO by this method. — 3. By strongly 
 heating BaCl,, or BaSO,, to white heat, in a 
 current of steam. 
 
 Preparation. — 1. By strongly heating BapOj), 
 in a porcelain crucible until all I is removed. — 
 2. By heating dry Ba.2N03 in a capacious 
 porcelain vessel (best a retort), gradually raising 
 the temperature when the salt melts, again 
 raising the temperature to full redness when 
 the residue in the vessel re-soUdifies ; the 
 heating must be continued until all nitrate is 
 decomposed, but no longer, as on long-continued 
 heating CO^ is absorbed; the portions in con- 
 tact with the porcelain take up a little SiOj and 
 
 AlA- 
 
 Properties.— A. grey-white powder, very 
 poisonous ; melts at white-heat ; takes up H^O 
 and CO2 from the air ; dissolves in water to 
 form a caustic alkaline solution (v. BABroii, 
 
 EYDBOXIDE Oe). 
 
 Reactions. — 1. Beduced by heating with 
 potassium. — 2. Decomposed to Ba-l-0 ^j electro- 
 lysis. — 3. Heated in chlorine, BaCl^ and are 
 formed. — 4. Heated with sulphv/r, BaS and 
 BaSOj are produced. — 5. Heated in carbon 
 disulphide vapour, the products are BaS along 
 with BaCOj. — 6. Heated in phosphorus vapowr, 
 in presence of H, barium phosphide BaPj (j. v.) 
 and Ba^PjO, are formed (Dumas, A. Ch. [2] 32, 
 364). — 7. Heated with arsenic vapour barium 
 arsenite (g.v. under Absenites) is said to be 
 produced. 
 
 Combinations. — 1. Combines with water to 
 form BaOjHj (j. v.) with production of much 
 heat, and increase of volume : [BaO, H^'O] = 
 22,260; [BaO, 9H=0]=49, 730 (Th. 8,266).— 
 2. With carbonic anhydride, to form BaCO, 
 (dry BaO has no action on CO^ ; Soheibler, B. 
 19, 1973) ; with sulphuric anhydride to form 
 BaSO,; [BaO, 00^=62, 220; [BaO, 801 = 
 110, 590 (Th. 3, 266).— 3. Heated in air or 
 oxygen to about 450°, forms BaOj (j. v.). — 
 
 4. With methylic or ethylic alcohol, forms 
 Ba0.2CH^0 or Ba0.2C2H„0. 
 
 11. Baeium dioxide. BaO^. Mol. w. unknown. 
 S.G. 4-96 (Playfair a. Joule, C. 8. Mem. 3, 84). 
 Discovered by Thenard (A. Ch. 8, 308). 
 
 Formation.— 1. BaO, or a mixture of BaOjH^ 
 and CaO or MgO, is heated in nearly dry air, 
 or 0, to dull redness in a glass or porcelain 
 tube. 
 
 Preparation. — A mixture of 4 parts finely 
 powdered KCIO, and 1 part BaO is thrown 
 little by little into a porcelain crucible heated 
 
 just to redness ; the KCl formed is dissolved out 
 by cold water (Liebig a. Wohler, P. 26, 172) ; 
 the impure hydrated BaOj containing BaO 
 (Berthelot, A. Ch. [5] 6, 207, says the residue is 
 nearly BaCBaO^) is rubbed in a mortar with 
 water, and added little by little to very dilute 
 HOlAq, but not in quantity sufficient to neu- 
 tralise the acid; the solution (which contains 
 HjOg) is filtered, made slightly alkaline by 
 addition of dilute BaOAq, whereby alumina and 
 iron oxide are ppd., the liquid is again filtered 
 through linen, and an excess of BaOAq is added j 
 lustrous plates of Ba02.8H20 are ppd. : (the 
 filtrate must contain HjOj, proved by the pro- 
 duction of a blue colour in ether when shaken 
 with ether after acidifying and adding dilute 
 KjCrjOjAq) ; the pp. is washed with cold water, 
 pressed between filter paper, and placed over 
 H2SO4 until all water is removed and BaOj 
 remains (Berthelot, A. Ch. [2] 6, 207). Or.HjOjAq 
 is added to BaOAq, the pp. of BaOj.SH^O is 
 washed with cold water, pressed between filter 
 paper, and heated in dry air free from CO2 to 
 100°-120° (Schone, B. 6, 1172).— 2. Pure BaO 
 is heated to low redness in a stream of O (Brodie, 
 T. 1850. 775). 
 
 Properties. — A white powder, resembling 
 MgO ; insoluble in, and combines with, water ; 
 melts at full red heat with evolution of 0. 
 
 Reactions. — 1. Decomposed by heat to BaO 
 and 0; at slightly reduced pressures (750 to 
 730 mm.) decomposition begins at about 450° ; 
 at ordinary pressure at a higher temperature 
 than this ; it the BaO produced is allowed to 
 cool to 450° in presence of under reduced 
 pressure BaO^ is re-formed (Boussingault, A. Ch. 
 [5] 19, 464). — 2. Decomposed very slowly by 
 cold, quickly by hot, water, forming BaOjH^ + 6 
 [BaOS ffO] = 2,760 (giving BaO^H^H-O, Ber- 
 thelot, A. Ch. [5] 14, 433).— 3. Cone, sulphuric 
 acid forms BaSO,, and evolves at temperatures 
 above 60°-70°, but mixed with ozone at 
 lower temperatures (Houzeau, C. B. 40, 949). — 
 4. Heated in dij carbonic anhydride, BaCO, and 
 are produced.— 5. Heated with carbon mon- 
 oxide, or sulphurous OMMjdride, light and heat 
 are produced, and BaCO,, or BaSO,, is formed 
 (Wohler, A. 78, 125).— 6. Acts as a powerful 
 oxidiser towards carbon, phosphorus, &c., &o. 
 (comp. Slater, J. pr. 65, 253; and Brodie, T. 
 1862. 837).— 7. With dilute acids forms salts of 
 Ba, and H^Oj or 0. 
 
 Combinations. — 1. With water, combines to 
 form BaOj.SHjO (produced also by action of 
 BaOAq on HjO^Aq ; v. Preparation) ; prismatic 
 dimetric crystals, which lose 8H2O in vacuo, or 
 by heating in absence of COj to 100°-120°. 
 Berthelot gives the formula BaO2.10H2O to the 
 hydrate (A. Ch. [5] 21, 157) ; he also describes 
 another hydrate with 7H2O (l.c. [5] 6, 207) ; he 
 gives the data [BaO^ 10H'=O] = 9,100 (l.c. [5] 
 14, 433). — 2. With hydrogen peroxide forms 
 very unstable, monoclinic, crystals, Ba02.H20, ; 
 produced by adding excess of HjOjAq to BaOAq, 
 or by adding NHjAq to the solution of a Ba salt 
 mixed with H2O2 (Schone, A. 192, 257). 
 
 Barium, oxysulphidea of, v. Barium, 
 Sulphides of ; monosulphide. Reactions. 
 
 Barium, phosphide of. Described as a 
 grey mass, having the composition BaP„ 
 produced by passing H charged with P vapour 
 
444 
 
 BARIUM. 
 
 over hot BaO ; decomposed by H.O, giving PH. 
 and BaHPOj (Dumas, A. Oh. 32, 364). 
 
 Barium, salts of. Salts produced by 
 replacing H of acids by Ba ; they form one series 
 belonging to the form BaX, where X = C1, &o., 
 O, SO,, COj, ^ . 
 
 2 2 2 """^^ °^ these salts has 
 
 been gasified we do not know the molecular 
 weight of any of them ; the spec, heat of Ba is 
 undetermined; the formulas are, therefore, 
 based on analogies between these salts and those 
 of similar metals which form gasifiable com- 
 pounds, especially Zn and Cd, and also on 
 analogies between the salts of Ba and Ca, the 
 atomic weight of the latter metal having been 
 settled by the spec, heat method. Barium forms 
 salts with most, if not all, the acids ; very few 
 basic salts are known, and those which have 
 been prepared are generally salts of the weaker 
 acids, e.g. boric, tungstic, molybdic, &o. The 
 haloid salts are very stable; the carbonate, 
 nitrate, iodate, chlorate, &a., are decomposed by 
 heat ; Ba salts of the oxyacids are reduced by 
 heating with C, H, or CS^. Most Ba salts are 
 isomorphous with the corresponding salts of Ca 
 and Sr ; many with the corresponding salts of 
 Pb. A few Ba salts are soluble in water ; the 
 greater number are slightly soluble only, or 
 insoluble (v. Eoeates, Careokates, Phosphates, 
 Sulphates, &c., &c.). 
 
 Barium, selenide of. BaSe. Mol. w. 
 unknown. White solid, changing in air, obtained 
 by heating BaSeO, in H to dull redness (Fabre, 
 C. B. 102, 1469). 
 
 Barium, selenocyanide of. BaSe2(CN)2(?). 
 Prepared by Crookes {J. pr. 53, 161). Data 
 very meagre. 
 
 Barium, silicofluoride of. BaSiFj, v. Babium 
 TLUOP-iBE OF, Combinations, No. 3. 
 
 Barium, sulphides and hydrosulphide (or 
 sulphydrate) of. Three sulphides of Ba 
 are known; a fourth probably exists in 
 solution. The monosulphide BaS is obtained 
 by heating BaO in a stream of HjS ; by 
 heating BaS + 2S to 360°, the trisnlphide BaSg is 
 formed ; by boiling BaSAq with 3S and crystal- 
 lising, BaSj may be prepared ; and if BaSAq is 
 boiled with considerable excess of S the solution 
 reacts as if it contained a pentasulphide BaS;. 
 Only one hydrosulphide or sulphydrate, BaSoH^, 
 is known. The sulphides and the hydrosulphide 
 are fairly stable compounds ; they are soluble in, 
 and partly decomposed by, water ; they resemble 
 the sulphides of the alkali metals in their 
 reactions, e.g. BaS^H^Aq reacts with ASjSj to 
 form barium thio-arsenite Ba^ASzEj (q. v.). 
 Sabatier {A. Ch.) [5] 22, 1) gives the thermal 
 data :— [BaO, H-S] = 22,100 ; [BaS, 0'] = 236,600 ; 
 [BaS, AqJ = 7,000. 
 
 I. MoNCBULPHIDE. BaS. 
 
 Formation. — 1. BaO is heated in a stream of 
 HjS. — 2. BaSO, is reduced by heating in H or 
 coal gas. 
 
 Preparation. — 1. A stream of CO^ is passed 
 through CS2 and then over red-hot BaCOj; CSj 
 must be in excess as BaS is decomposed by COj ; 
 the product is freed from higher sulphides by 
 heating in H (Schone, P. 112, 193).— 2. 
 BaO.Hj.H^O (prepared by heating BaO.,Hj.8H20 
 to 80° in H) is acted on by dry H^S ; the 
 rroluciB are EaS and H^O (Veley, C. J, 
 
 49, 369).— 8. Crude BaS (which is the starting, 
 point in the preparation of many Ba compounds) 
 is prepared by miixing 8 parts heavy spar with 
 2 parts wood charcoal and 1 part rye meal, all 
 in fine powder, making into a stiff paste with 
 water, rolling into small cylinders, drying, 
 packing in a crucible in alternate layers with 
 charcoal, and gradually heating to full redness 
 (Liebig, A. 35, 115 ; -o. also Griineberg, J. pr. 
 60, 168 ; Buchholz, Ar. Ph. 36, 275 ; Kuczinsky, 
 D. P. J. 135, 455). 
 
 Properties. — A white amorphous solid; soluble 
 in water ; exposed to sunUght and then placed in 
 the dark, it gives off light ; oxidised in moist 
 air. 
 
 Beacfions. — 1. In moist air decomposes to 
 BaCOj and BaS^O, with evolution of H^S. — 2. 
 Seated in air is slowly oxidised. — 3. Heated in 
 steam, BaSO, is formed and H evolved (Lauth, 
 C. C. 1863. 880).— 4. Chlorine, bromine, and 
 iodine, decompose BaS, forming BaXj 
 (X = 01, Br, or I) and S.— 5. Dilute acids form Ba 
 salts and evolve HjS. — 6. Water brings about 
 partial decomposition into BaSjHj, BaOjH2, 
 polysulphides and oxysulphides of Ba (v. Veley, 
 0. J. 49, 369). The action of water on crude 
 BaS has been examined in detail by H. Eose (P. 
 55, 415). If hot water is added in quantity just 
 sufficient for solution, the liquid gives a pp. of 
 MnS, without evolution of H^S, on addition of 
 an aqueous solution of a neutral manganous 
 salt ; the solution, therefore, contains either 
 BaS or hydroxide and hydrosulphide in the ratio 
 BaOjHjrBaSjHj ; 
 
 (?Ba02H5,Aq + BaS^HjAq + 2MnCl2Aq= 
 2MnS -I- 2BaCl5,Aq + 2H2O). If cold water is 
 added to crude BaS in an open vessel, in quantity 
 rather less than sufficient for complete solution, 
 and the liquid is evaporated, BaO^H^ separates 
 out, then various oxysulphides (v. infra), then, on 
 evaporating the mother liquor in a retort, 
 crystals of BaS.6H20 (v. infra, Combinations) 
 separate, and finally on evaporating to dryness 
 BaSjH, remains. 
 
 The oxysulphides prepared as above de- 
 scribed, or by cooling the solution obtained by 
 acting on crude BaS vrith boihng water in a 
 closed vessel, seem to be three : 
 Ba,0,S3.58HjO[=4(BaOjHj.9HjO).3(BaS.6H20)], 
 Ba^OS-lOHjO [ = (BaO,H2.8H20)(BaS.H20)], and 
 Ba4S30.28H20[ = (Ba02Hj.9H20).3(BaS.6H20)]. 
 The compositions of these bodies are, however, far 
 from settled ; the compounds are very unstable and 
 are separated by recry stallisation into BaO^Hj and 
 BaSjHj. If successive quantities of cold water, 
 each less than sufficient for complete solution, 
 are shaken with crude BaS in a closed vessel 
 for some hours, the first solution contains 
 BaSjHj along with a little of the higher sul- 
 phides of Ba (the solution gives MnS and also 
 HjS on addition of MnCljAq) ; the next solution 
 contains either BaS or BaOjHj and BaSjHj in 
 the ratio BaOjHjiBaSjHj (with MnClj it gives 
 MnS without evolving HjS) ; the following solu- 
 tions contain BaOjH^, as they give more and 
 more MnOjHj on addition of MnCLAq and less 
 and less MnS. 
 
 Combinations. — With water BaS forms 
 BaS.CHjO ; prepared as above described, also 
 by evaporating in vacuo a solution of BaS after 
 addition of a little S (Schone, P. 112, 193) ; or 
 
BASE. 
 
 445 
 
 fcy evapOTatingBaSsAq {q.v.) mvaetio. BaS.eH^O 
 crystallises in white six-sided plates; slightly 
 soluble in cold, easily in hot, water ; insoluble 
 in alcohol ; loses GH^O between 100° and 350° 
 vith partial decomposition. 
 
 II. TbistjiiPhlde. BaSa. Prepared by heat- 
 ing 2 parts BaS with 1 part S, and removing 
 excess of S by distilling it ofi at 360° (Sohone, 
 P. 112, 193). Forms a yellowish-green mass, 
 soluble in hot water ; heated to redness in 
 absence of air gives BaS + 28. A solution 
 of BaSa in much boiling water evaporated 
 in vaciio deposits (1) BaS.GHjO {v. stipra), 
 then (2) a mixture of BaS,.!^^© (v. infra) 
 and orange dichroio monoolinic prisms of 
 3(BaS.6H20).(BaS4.HjO).6H20 (Sohone, I.e.). 
 
 III. Tetbasuuhedb. Known only in combi- 
 nation with H.;0 as BaSj.HjO. By evaporating a 
 solution of BaS, in hot water in vacuo, or by 
 evaporating BaSAq with 3S, trimetrio, diohroic, 
 needles separate ; yellow by transmitted, red by 
 reflected, light ; soluble in water, may be re- 
 crystaUised from hot water ; insoluble in alco- 
 hol ; at 300° lose H^O with decomposition into 
 HoS, S, and BaSj (Sch5ne, Z.c). A more 
 hydrated salt, probably BaS,.2H20, was obtained 
 by Veley by dissolving S in BaSjHjAq (C. J. 
 49, 378). 
 
 IV. PENiASuiPHrDB. BaSs. Not known in 
 definite form. BaSAq or BaSjH^Aq boiled with 
 excess of S, yields a yeUow alkaline solution, 
 from which on cooling S and BaS, separate out ; 
 the mother liquor contains Ba and S in ratio 
 BaiSs, on evaporation crystals of S separate 
 out, and BaSj remains in solution (Sohone, l.c. 
 confirming older observations of Berzelius). 
 
 V. HvDKOsuLPHiDE or ScIjPHTDkate. BaSjHj. 
 Formation. — By action of H^O on BaS 
 
 (v. MoNosTjLPHiDE ; BeocUons, No. 6). 
 
 Preparation. — BaOAq (saturated at 100°) is 
 saturated with H^S at 60°-70° ; the liquid is 
 decanted in absence of air, and is cooled to 
 about 10° ; the crystals of BaS2H2.4H20 which 
 separate are dried between paper out of contact 
 with air, and then heated in a stream of H 
 («. Veley, C. J. 49, 369). 
 
 Properties and Reactions. — With 4H2O forms 
 white aoicular crystals, which effloresce in air, 
 and gradually absorb 0, forming BaSjO, and 
 BaS04 ; these crystals are soluble in water but 
 insoluble in alcohol ; aqueous solution evolves 
 H2S when boiled ; heated to redness out of con- 
 tact with air, H2S is removed and BaS remains 
 (for details, v. Veley, Z.c). BaS2H2 is strongly 
 basic in its reactions ; e.g. with AsjSg it forms 
 Ba thio-arsenite. 
 
 Barium, snlphocyanide of. Ba(SCN)2. Ob- 
 tained by decomposing NH^.SCNAq by BaOAq 
 {v. STjLPHOCTANiBES, Under Cyanides). 
 
 Barium, thio-antimonate of. Ba3(SbS4)2. Ob- 
 tained by the action of BaCljAq on NajSbS^Aq 
 (compare thio-autimonates under Antimony, 
 THio-Acms of). 
 
 Barium, thio-arsenite of. Ba2As2S5. Obtained 
 by digesting BaS2H2Aq with AB2S3; and Barium 
 thio-arsenates Baa^AsSJj and Ba(AsS3)2, ob- 
 tained by the action of H2S on BaHAsO^Aq 
 (v. THio-ABSBNiTEs and THio-ABSENATES Under 
 Aksenic, ihio-acids or). 
 
 M. M. p. M. 
 
 BABTTA. Oxide of Barium, v. Baeidm, 
 
 OXIDE OF. 
 
 BASE. — The characteristic reaction of an 
 acid is that the whole, or a portion, of the hy- 
 drogen of an acid can be displaced by a metal, 
 with production of a new body, called a salt, 
 composed of the metal and the elements of the 
 acid, excepting the displaced hydrogen (v. 
 Acids). If the oxide of a metal reacts with an 
 acid to form a salt, the hydrogen displaced from 
 the acid combines with the oxygen of the oxide 
 to form water ; the products of the reaction are 
 a salt and water. The salt is not characterised 
 by the properties either of the acid, the metal, 
 or the metalHo oxide; it has been built upon 
 the metal or metallic oxide by combining this 
 with the acid. The name base was given by 
 Bouelle in 1744 to those bodies which reacted 
 with acids to form salts. The name has some- 
 times been applied to metals, as well as to oxides 
 and hydroxides of metals ; at other times it has 
 been confined to compounds of metals with H 
 and ; at all times the conception underlying 
 the name has been that of a substance which, 
 while chemically very unlike an acid, reacts 
 with acids to form salts. The dual origin of a 
 salt is implied in the statement that for its pro- 
 duction there is required the interaction of an 
 acid and a base. A definition of any one of 
 the terms, acid, base, salt, implies a definition 
 of the other two. The chemical reaction cha- 
 racteristic of bases, as the term is now used, is 
 the production of salts by the mutual reaction 
 of a base and an acid ; in some cases water is 
 also formed, in other cases the salt is the sola 
 product. Typical reactions are as follows : 
 KjOAq + HSOM = E„S04Aq + }l.fl 
 2K0HAq + H2S04Aq =' K.SO^Aq + 2H2O 
 2NHsAq + HjSO^Aq = (NH4)2SO,Aq. 
 A base may then be (i.) a metaUio oxide, (ii.) a 
 metallic hydroxide or an allied compound such 
 as NEt^.OH, PMe^.OH, SEtj.OH, &o., (iii.) am- 
 monia or a derivative thereof, e.j.NHjEt, NMcj, 
 &c. The terms strong and weak may be applied 
 to bases with meanings similar to those given 
 to the terms when applied to acids ; a strong 
 base, in this sense, is one which, when it reacts 
 in aqueous solution with another base and an 
 acid — all being present in equivalent quantities, 
 and all possible products being soluble in water 
 — combines with a large proportion of the acid 
 and leaves only a smaU proportion for the other 
 base to combine with. The hydroxides MOH, 
 where M= an alkali metal or Tl, are strong 
 bases ; NH3 is a weak base ; NHjEt and NH2Me 
 are stronger bases than NH3 ; NMcjOH and 
 SEtjOH are nearly as strong bases as the 
 alkalis (v. Appihity). By the term a strong 
 base is sometimes meant a base which reacts 
 with various acids to form very stable salts ; 
 e.g. salts which are not changed by water, hot 
 or cold. In this meaning of the term Ba02H2 
 is a strong base, but BiOjHj or Sn02H2 is a 
 weak base. The oxides and hydroxides of poly- 
 valent metals appear to be weaker bases than 
 the corresponding compounds of the monova- 
 lent metals. The more positive a metal is, the 
 more basic are its oxides and hydroxides. 
 Sometimes a metallic oxide, or hydrated oxide, 
 may react towards strong acids as a base, and 
 towards strong bases as an acidic oxide; thus 
 
446 
 
 BASE. 
 
 k\Os.xSfi reacts with H^SOjAq to form 
 Alj03-3S03( = A1,.3S0,), but M^O^.xB.fi re- 
 acts with much KOHAq to form K^O-AljOj 
 ( = K^AljOJ. In some cases the basic and acidic 
 functions of a compound may be nearly equal ; 
 thus amido-acetic acid (? CH^.NHj.COOH) forms 
 salts by its reactions with bases as other acids 
 do, but it also combines with acids, as NHj 
 does, to form salts. The hydroxides of certain 
 metals which in some of their reactions behave 
 as non-metals react as bases towards most 
 acids, but if oxygen is added to these hydroxides 
 compounds are formed which react as bases 
 only towards the stronger acids and at the same 
 time react as acids towards the stronger bases ; 
 such compounds are SnO^H^, and SnO.OjHj, 
 respectively. Bases are sometimes divided into 
 mono-acid, di-acid, iri-acid, &e., according as 
 one reacting weightinteractswith one, two, three, 
 &o., reacting weights, of a monobasic acid, to 
 form a salt. The poly-acid bases are weaker 
 than the mono-acid bases. As examples of 
 mono-acid bases may be given KOH, NHj, NH^Et, 
 &C. ; of di-acid bases, CaOjHj, BaOaHj, ZnOjHj, 
 NHjC2H^, &c. ; of tri-acid bases, FeOaHj, 
 C5H2{NH2)30H, &o. ; of tetra-acid bases, ZrOjH,, 
 &o. (comp. Acms and Salts). M. M. P. M. 
 
 BASES, ORGANIC, v. ALKAioms, Amines, 
 Amides, Azines, Pyeidinb, Quinolinb, &o. 
 
 The nomenclature of bases containing carbon 
 and nitrogen in one ring is as follows : 
 
 Pyrrol 
 CH:CH. 
 
 CH:CH^ 
 
 Pyrazol 
 CH:N V 
 I >NH 
 
 CH:CH/ 
 
 Triazol 
 N:CHv 
 I >H 
 N:Ch/ 
 
 Pyridine Pyrasine (Ketines) Pyrimidine 
 
 HC:CH.CH HC:N.CH HC:N.CH 
 
 I II I II I II 
 HO:N.CH HC:N.CH 
 
 0«H,< 
 
 / 
 
 CH:CH 
 
 N:CH.CH 
 
 Iso^uinoline 
 .CH:CH 
 
 \n. 
 
 N:CH 
 
 CH:N 
 
 ^\, 
 
 QuinazoUne Quinoxaline CinnoUne 
 
 ^CH:N ^N:CH ,CH:CH 
 
 0^/ I chZ I c^h/ I 
 
 \N : CH \N:CH \n : N 
 
 Indasine 
 
 .CHv CH. 
 
 C^H^I )>NHorC.H/| V 
 
 Phenazi/ne 
 
 
 CgH^ 
 
 Olyoxaline 
 .NH-CH 
 
 CH<: 
 
 "^, 
 
 CH-N 
 
 BASIC OXIDES. Oxides which react with 
 acids to produce salts. The greater number of the 
 metallic oxides are basic ; oxides of well-marked 
 non-metals are never basic. The correlative 
 term is acidic oxides {v. Bases, Acids, SaiiTs). 
 
 M. M. P. M. 
 BASICITY OF ACIDS v. Acids, EisiciTY of. 
 _ BASILICUm, OIL OF. The essential oil ob- 
 tained by distilling the leaves of Ooymum basili- 
 cum with water contains C,„H,s3H20 which orya- 
 talhses in prisms (Dumas a. Peligot, A. 14, 75). 
 _ BASSIA LATIFOLIA. The seeds of this 
 Himalayan plant yield by pressure a buttery 
 
 substance, [27°-30°], containing olein and stearin 
 (Hardwick, O. J. 2, 231). 
 
 BASSOBIN. The insoluble gum acid, pro. 
 bably meta-arabio acid, or at least a meta- acid 
 allied thereto (v. Abaein) of gummi bassorae, 
 G. Toritonense, or Q. Kutera. These gums 
 consist of a part (the meta- acid) that swells up 
 to a jeUy when they are treated with water, and 
 of a soluble part, the alkaline or earthy salt of 
 the acid. 0. O'S. 
 
 BASTOSi! V. Cellulose. 
 
 BASYLOTTS. A name sometimes applied to 
 the more positive, usually oxygen-containing, 
 radicles, or groups of atoms, which combine 
 with more negative, or chlorous, groups to form 
 
 + - + - + - 
 salts ; e.g. K3O.SO3, K20.Cr03, Crj03.3S03, &c. 
 The name is sometimes also applied to the 
 elements which displace H from acids with 
 formation of salts. The correlative term is 
 chlorous. M. M. P. M. 
 
 BDELLIUM. A gum-resin (Johnston, J. pr. 
 26, 145). 
 
 BEBEERINE C^HjiNOj. Bebirine. [180°]. 
 Occurs, together with a resin (sepirin) and an 
 acid (bebirio acid) in the bark of the bebeeru 
 tree of Demerara (Bodie ; Maclagan, A. 48, 106 ; 
 Maclagan a. TiUey, P. M. 27, 186 ; v. Planta, A. 
 77, 333). It is an amorphous powder, v. si. sol. 
 water, v. e. sol. alcohol, v. sol. ether.— B'jHjPtCl,: 
 orange amorphous pp. Buxine has been con- 
 sidered to be identical with bebeerine (Walz, 
 N. J. P. 14, 15). 
 
 BEE'S WAX V. Wax. 
 
 BEHENIC ACID O^JE^Oj. Benic acid. 
 [76°]. Occurs as glyceride in oil of ben and in 
 the fatty oil of black mustard seed. Needles, 
 resembling stearic acid. — NaA'. — BaA'g. — 
 PbA'j.— EtA' [49°] (Voelcker ; Strecker, A. 64, 
 346). 
 
 BEHENOLIC ACID CjjH^Oj. Benolic acid. 
 [57'5°]. Formed by the action of alcoholic 
 potash on di-bromo-behenio acid (Hausskneoht, 
 A. 143, 41). White needles (from alcohol) ; v. 
 sol. alcohol and ether, insol. water. Not re- 
 duced by sodium-amalgam, but combines with 
 Br^, forming Cj^Hj^r^Oj [47°], and with Br„ 
 forming C^K^Brfi, [78°]. 
 
 Salt s.— MgA'2 3aq.— AgA'.— BaA'j. 
 
 BELLADONNINE. An alkaloid occurring in 
 the mother-liquor from which sulphate of atro- 
 pine {c[.v.) has been crystallised (Hiibschmann , 
 Schweiz. Z. PJiarm. 1858, 128 ; Kraut, A. 148, 
 236 ; B. 13, 165 ; Ladenburg a. Eouth, B. 17, 
 152 ; Merling, B. 17, 381). Amorphous, v. si. 
 Bol. water, v. sol. alcohol, ether, and chloroform. 
 It is but slightly attacked by boiling baryta- 
 water, but is split up by alkalis into tropic acid 
 and oxy-tropine CjHjsNOa. This would indi- 
 cate that belladonnine is oxy-atropine C„Hj3N0, 
 (L.). According to Merling, beUadonuiue is 
 CijHjiNOj and gives tropine, atropic acid, and 
 iso-atropio acid when boiled with baryta-water. 
 Salts: B'jHjPtClj.— B'HAuCl^. 
 
 BEN, OIL OF. A fatty oil expressed from 
 the fruits of Moringa nux behen. It contains 
 glyceryl palmitate, stearate, oleate, and behenate 
 (v. Behenic acid). 
 
 BENIC ACID V. Behenio acid. 
 
 BENYLENE C^H^s (223°-228°). S.G. 2-911. 
 Formed by the action of alcohoho potash on 
 
BENZ-AMIDOXIM. 
 
 447 
 
 tri-amylene bromide C,,H.„Br. (Bauer a. Verson, 
 4.147,252). 
 
 BENZACIN CjAjNaO. [150°]. A neutral 
 crystalline substance obtained by extracting 
 with alcohol the product of the action of ZnEtj 
 on phenyl-aoetonitrile (Erankland a. Tompkins, 
 C. J. 37, 569). 
 
 S£NZAL- V. Benztlidene-. 
 
 BENZALDEHYDE v. Bbnzoio aldehyde. 
 
 BENZALDOXIM CsHj.CHiN.OH. Oxim of 
 benzoic aldehyde, (o. 220° with decomposition). 
 Colourless oil, formed by the action of hydroxyl- 
 amine on benzoic aldehyde (Petraozek, B. 15, 
 2735). Formed also by reducing benzamidoxim 
 with sodium-amalgam (Tiemann a. Kriiger, B. 
 17, 1692). By heating with HCl it is split up 
 into hydroxylamine and benzaldehyde. Ae^O 
 converts it into benzonitrile (Laoh, B. 17, 1571). 
 
 Sodium salt 0,Hs:N(ONa) aq : white easily 
 soluble plates, formed by the action of sodium 
 ethylate on benzaldoxim in alcohoUo solution ; 
 gives characteristic pps. with the salts of the 
 heavy metals. 
 
 Hydrochloride C,Hs:N(OH),H01 : white 
 glistening scales, rotates on water. 
 
 Methyl ether C,H5:N(0Me): (191° un- 
 corr.) ; colourless oil, lighter than water and 
 slightly soluble ; formed by the action of methyl 
 iodide and sodium ethylate on benzaldoxim; 
 by HCl it is split up into benzaldehyde and 
 methyl-hydroxylamine. 
 
 Ethyl ether C,H8:N(0Et) : (208° uncorr.); 
 colourless oil, split up by HCl into ethyl- 
 hydroxylamine and benzaldehyde. 
 
 Propyl ether C,H5:N(0C3H,): (225° un- 
 corr.), colourless oil. 
 
 Iso-hutyl ether C,H8:N(0C,H,) : (238° 
 uncorr.), colourless oil. 
 
 Amyl ether C,H5:N(OC5H„) : (161° un- 
 corr.), colourless oil (Petraczek, B. 16, 823). 
 
 BENZAMIDE C,H,NO i.e. CeH5.CO.NH2. 
 Amide of benzoic acid. Mol. w. 121. [130°] 
 (Ciamician a. Magnaghi, B. 18, 1828). S.G. * 1-34 
 (Schroder, B. 12, 1612). 
 
 Formation. — 1. Prom BzCl and NH, — 2. 
 Together with NHjOBz, by the action of Bz^O 
 on NH,.— 3. From EtOBz and NH3.— 4. By 
 boiling hippuric acid with water and PbOj, or by 
 heating hippuric acid in a current of dry HCl. 
 
 Properties. — Monoclinio tables : a:b:a = 
 •228:1:1-068; ;3 = 89° 22' (Klein, A 166,184); 
 V. si. sol. cold water, m. sol. hot water, especially 
 if it contain NH3 ; v. sol. alcohol and ether. 
 
 Reactions. — 1. It splits up into water and 
 benzonitrile when heated with dehydrating agents 
 (P2O5, PjSj, or H2SO4) and to some extent when 
 heated alone at 290°. — 2. Boiling aqueous potash 
 forms KOBz. — 3. Boiling acids form benzoic 
 aoid.— 4. BzCl or Bz^O form benzonitrile and 
 benzoic acid.— 5. Beduced in aoid solution by 
 sodium-amalgam to benzyl alcohol. — 6. Boiling 
 phenol gives benzoyl-phenol (PhOBz) and NHj. — 
 7. PCI5 forms an unstable substance which 
 rapidly splits up into HCl and benzonitrile 
 (Wallach, A. 184, 19).— 8. COCL, gives benzo- 
 nitrile, cyaphenine, anddi-benzoyl-urea (Schmidt, 
 J. pr. [2] 5, 35).— 9. CSClj gives benzonitrile, 
 COS, and HCl (Bathke a. Sohafer, A. 169, 107).— 
 10. With chloral it combines forming CgHgCljNO 
 [151°] (Wallach, B. 5, 251).— 11. With ethyl 
 nitrite it forms N^, benzoic ether, and H^O 
 
 (Meyer a. Stuber, B. i, 962).— 12. Converted by 
 bromine in alkaline solution into aniline 
 (Hofmann, B. 18, 2737).— 13. A solution of 
 benzamide in bromine deposits crystals of 
 unstable BzNHjBrj. 
 
 Combinations.— BziiB.^B.Cl : long prisms, 
 formed by saturating a mixture of benzamide 
 and HClAq with HCl (Dessaignes, A. Ch. [3] 
 34, 146 ; Pinner a. Klein, B. 10, 1897). When 
 exposed to the air it gives off all its HCl. — 
 BzNHj fHCl. [178°] (B. v. Meyer, J. pr. [2] 
 
 Salts.— (BzNH)2Hg [224°]. Formed by 
 boiling benzamide with water and HgO. Laminae 
 (from alcohol) ; v. sol. alcohol and ether. — 
 BzNHTl : slender needles (Church a. Crookes, 
 C. J. 17, 151). 
 
 Additional References. — Liebig a. Wohler, 
 A. 3, 268; FehUng, A. 28, 48; Schwarz, A. 
 75, 195 ; Laurent, Beime Scient. 16, 391 ; 
 Henry, Z. [2] 5, 446; Brauns, Ar. Ph. [2] 
 126, 214; Oppenheim a. Czarnomsky, B. 
 6, 1392; Guaresohi, G. 4, 465; A. 171, 141; 
 Kekul6, B. 6, 113; Schift a. Tassinari, B. 
 10, 1785 ; Friedburg, A. 158, 26. 
 
 Benz-chloro-amide ObHs.OO.NHCI. Pre- 
 pared by gradually adding a cone, solution of 
 chloride of lime to a cold cone, solution of 
 benzamide acidified with AcOH, the product 
 being shaken out by ether as it is formed. Long 
 colourless prisms (from water) (Bender, B. 
 19, 2274). 
 
 Dibenzamide 0„H„N02 i.e. NHBZj [148°]. 
 S. '12 at 15°- Formed, together with benzamide, 
 by the action of KNHj on BzOl dissolved in 
 ether (Baumert a. Landolt, A. Ill, 1) ; and 
 from benzonitrile (10 g.) and fuming H^SO, (7 g.) 
 (Barth a. Senhofer, B. 9, 975 ; Gumpert, J. pr. 
 [2] 30, 87). Trimetric crystals, a:6:c = 
 •931:1:1-069. SI. sol. boiling water, v. sol. alcohol, 
 ether, and benzene. 
 
 Salts. — NaNBzjIaq: small prisms, sol. 
 ether. — AgNBzj. 
 
 BENZAMIDINE C,n^S,i.e. 0eH5.C(NH).NH, 
 [75°-80°]. 
 
 Preparation. — ^Benzonitrile is converted by 
 treatment with isobutyl alcohol and HCl into 
 the hydrochloride of CsH5.C(NH).OC,H5, whence 
 ammonia produces benzamidine (Pinner a. Klein, 
 B. 10, 1880; 11,4). 
 
 Properties. — M. sol. water, si. sol. ether, v. e. 
 sol. alcohol; deliquescent; very volatile. De- 
 composed by heat into NH, and cyaphenine. 
 
 Salts.— B'HOl: flat needles.— B'H,PtCL.— 
 AgC,H,N2. 
 
 BENZAMIDO- v. Benzoyl-AmDO-. 
 BENZAMIDO-ACEXIC ACID v. Hippceio 
 
 ACID. 
 
 BENZ-AMIDOXIM CjHjNjO i.e. 
 PhC(NH2).N0H. Benzenyl-oxamidine. Ben- 
 zenyl-amidoxim. Isomtroso-benzylamine. [80°]. 
 
 Formation. — 1. By the action of hydroxyl- 
 amine on an alcoholic solution of benzonitrile 
 (Tiemann, B. 17, 128).— 2. By the action of 
 hydroxylamine on the hydrochloride of benz- 
 amidine. — 3. As a, by-product in the action of 
 hydroxylamine hydrochloride upon benzimido- 
 ethyl-ether. — 4. By digesting thio-benzamide 
 with an alcoholic solution of hydroxylamine 
 (Tiemann, B. 19, 1668). Long flat monosym- 
 metrical prisms a:b:c = 2-502:l:l-077. Volatilises 
 
448 
 
 BENZ-AMIDOXIM, 
 
 undeeomposed. V. sol. alcohol, ether, benzene, 
 and hot water, si. sol. cold water. It is poi- 
 sonous. It dissolves both in acids and alkalis. 
 FejCl, gives a red colouration. The ammo- 
 niacal solution gives white crystalline pps. with 
 BaClj, AgNOj, Pb(OAo)j, and ZnSO^. The silver 
 pp. on heating in the solution in which it is 
 formed gives a Splendid silver mirror. 
 
 Beactions. — 1. Gives- the carbamine reac- 
 tion with chloroform and alcoholic potash. — 
 2. Nitrovs acid forms benzamide. — 3. Sodium 
 amalgam reduces it to benzaldoxim and NH3 
 (Tiemann a. Nageli, B. 18, 1086).— 4. When 
 quickly heated at 170° it splits up into benzo- 
 nitrile and NH3. — 5. By heating with acetic 
 anhydride it yields benzenyl-azoxim-ethenyl 
 
 Salts.— A'Na: white crystalline solid, de- 
 composed by water. — A'K : crystals. — A'Ag : 
 unstable white crystalline pp. — A'(CaOH) : 
 amorphous dark green pp. — A'H,HC1 : large flat 
 plates or concentric needles. — A'H.HjSOj : large 
 prisms. — (A'H)2H2S04 ; amorphous solid. 
 
 Methyl ether.— MMs: [57°]; (-230° un- 
 corr.) ; prisms ; v. sol. alcohol, ether, and benz- 
 ene, si. sol. water. By HCl and NaNOj it is 
 converted into benzenyl - methoxim chloride 
 CsH3.CCl(N0Me). 
 
 Ethyl ether. — A'M: [67°]; trimetrio 
 plates. By dilute H^SOj and sodium nitrite 
 it is converted into benzbydroximio - ethyl - 
 ether (benzoyl - hydroxylam,ine ethyl ether) 
 C,H5.C(0H)N0Et. With HGl and NaNO^ it 
 yields benzenyl-ethoxim-chloride. 
 
 Benzyl ether. — A'CjHj : [91°]; scales. 
 
 Benzoyl derivative. — ■ 
 CsH5.C(NHJ:N0Bz : [140°]; slender white 
 needles ; v. sol. alcohol, ether, and aqueous 
 acids, insol. water. On heating it readily splits 
 off HjO, giving rise to benzenyl-azoxim-benzenyl 
 
 C,H,.G<NjjO>C.C,H,. 
 
 Acetyl derivative G^yGl^^^-^Oko. 
 [96°] ; thin plates or flat prisms, sol. alcohol, 
 b1. sol. ether, v. si. sol. water. By boUing 
 with water it loses HjO and is converted into 
 benzenyl-azoxim-ethenyl. 
 
 Butyryl derivative 
 CsH5.C(NH2):NO.CO.C3H,. [94°] : fine needles. 
 
 Ethylene ether (Vla..C(^'R.^):'SO).fi^B.^. 
 [156°]. White plates. Sol. alcohol, ether, 
 benzene, and ligroin, insol. water. Formed by 
 heating an alcoholic solution of benz-amidoxim 
 (2 mols.) and sodium ethylate (2 mols.) with 
 ethylene bromide (1 moL). 
 
 Compound with chloral CjHjNjCljOj. [135°]. 
 Obtained by mixing the constituents. White 
 crystalline powder. V. sol. alcohol and ether, 
 insol. water. By treatment with H^SOj or by 
 long boiling with water it is resolved into its 
 components (Falck, B. 19, 1485). 
 
 References. — Pinner, B. 17, 184 ; Tiemann 
 a. Kriiger, B. 17, 1685 ; 18, 731, 1053 ; Tiemann, 
 B. 19, 1479, 1668 ; Schulz, B. 18, 1080 ; Falck, 
 B. 19, 1484 (v. also Azoxims). 
 
 Benz-amidoxim-carbonic ether 
 C.H,.C(NHJ:N.O.CO,Et. [127°]. Formed by the 
 action of ohloroformic ether upon benz- 
 amidoxim (Falck, B. 18, 2467). Long glisten- 
 ing needles. V. sol. alcohol, ether and 
 
 benzene, less in ligroin. On heating it splits 
 ofE alcohol, forming benzenyl-azoxim-carbinol 
 
 C,H3.C<Njf>C(0H). 
 
 Oarbouyl-di-beuz-amidozim CisHgjOjN,, i.e. 
 
 c:H::ciNHJ:NC>^o- [129°]- ^°>^-edi'yti'« 
 
 action of carbonyl chloride upon benz-amidoxim 
 dissolved in benzene (Falck, B. 18, 2470). 
 White plates. Sol. alcohol and ether, v. si. sol. 
 benzene, insol. water. 
 
 BENZ-AMIDOXIM-m-CASBOyTLIC ACID 
 CHsNA i-e- [3:1] CeH^(002H).C(N0H)NH2. 
 [200°]. CrystalUne solid. Sol. hot water and 
 alcohol, si. sol. ether, nearly insol. chloroform 
 and benzene. 
 
 Formation. — 1. By saponification of the 
 ethyl ether which is obtained by combination of 
 m-cyano-benzoio ether with hydroxylamine. — 
 2. By digesting a mixture of equivalent quan- 
 tities of m-cyano-benzoic acid, hydroxylamine 
 hydrochloride, and sodium carbonate, in dilute 
 alcoholic solution for 12 hours at 80°-100°. 
 
 Beactions. — The aqueous solution of the 
 ammonium salt gives sparingly pps. with CuSOj, 
 Pb(OAo)2, AgNOj, and ZnSOj. Heated with 
 acetic anhydride it is converted into m-carboxy- 
 benzenyl-azoxim -ethenyl 
 
 C3H,(CO,H).C<^jf>C.CH3. 
 
 Ethyl ether A'Et [118°]; needles; v.sol. 
 alcohol, si. sol. water (Miiller, B. 19, 1495). 
 
 Benz-amidoxim-p-carboxylic acid 
 [4:1] C,Hj(C0jH).C(N0H)NH, [above 330°]. 
 Formed by digesting ^-oyanobenzoio acid (1 
 mol.) hydroxylamine hydrochloride (1 mol.), and 
 sodium carbonate (1 mol.) in dilute alcoholic 
 solution for 18 hours. Sol. dilute alcohol, si 
 sol. water, nearly insol. absol. alcohol, ether, 
 and benzene. A dUute aqueous solution of the 
 ammonium salt gives pps. with CuSOj and with 
 AgN03. By boiling -ivith acetic anhydride it is con- 
 verted into ^-carboxy-benzenyl-azoxim-ethenyl 
 
 C^K,[GO^B.).C-^^~^C.GR, (MuUer, B. 19, 
 
 1491). 
 
 Ethyl ether A'Et: [135°]; obtained by 
 heating the ethyl ether of ^-cyanobenzoic acid 
 with hydroxylamine in alcoholic solution (Miil- 
 ler, B. 18, 2485). Colourless crystals; sol. 
 boiling water. 
 
 BENZAM-MAIONIC ACID v. Cabboxy- 
 
 PHENyL-HALONAMIC ACID. 
 
 BENZAM-OXALIC ACID v. Oakboxy-phentl- 
 
 OXAMIC AOID. 
 
 BENZ AM-SEBACIC ACID v. Oaeboxy-phenyl- 
 
 BEBAOAMIO AOm. 
 
 BENZAM-SITCCINIC ACID v. Cabboxy- 
 
 PHENYIi-SnOCINAinC AOID. 
 
 BENZ-ANHYDEO- v. Benzenyl- or as deri- 
 vatives of Benzamidine. 
 
 BENZABSEN- v. Absenio, okganio deeiva- 
 
 IIVES OF. 
 
 BENZAKSENIC ACID v. Absenio, obganio 
 
 DEEIVATIVES OE. 
 
 BENZ-BROMO-auINOLINE i). (B.)-Bbomo- 
 
 QUINOLINE. 
 
 BENZ-CHLOEO-AMIDE v. Benzamide. 
 BEHZ-CHLOEO-QTJINOLINE v. (B.)-CHi,ono- 
 
 quinoline. 
 
BENZEJTE. 
 
 449 
 
 BE»Z-CKEATIN 
 
 Benz-(a)-iDetliyI-glyoo(!yainiiie 
 NH,.C(NH).NMe.C„H,.CO,H. From benzglyoo- 
 cyamine, cono. EOH, methyl alcohol, and 
 Mel (Griess, B. 8, 324). Narrow laminse (con- 
 taining 1| aq), si. sol. water and alcohol. De- 
 composed by baryta into urea and' methyl- 
 amido-benzoio acid. — B'HCl aq.— B'^H^PtCle 2aq. 
 
 Benz- (|8) -methyl-glyoocy amine 
 NHMe.C(NH).NH.C,Hj.CO.,H. From 'ethoxy- 
 carbimidamido-benzoio acid ' and cold cono. 
 NMeHj solution. Lamime, v. si. sol. cold water. 
 Boiling baryta forms methyl-urea and amido- 
 benzoio acid.— B'HCl.— B'^F^PtCL 2aq. 
 
 BENZCEEATININE 
 
 o-Benz-(«)-metliyl-glyoooyamidine C.HaNaO 
 /N(CH3)-C,H, 
 t.e. HN = C< I . Prepared by the 
 
 \NH CO 
 
 action of Mel on o-benzglycooyamidine (Griess, 
 B. 13, 978). White needles. Sol. alcohol, si. 
 sol. ether and hot water. Insol. caustic alkalis. 
 
 Salts. — B'HCl aq : soluble 
 (B'HCl)jPtCl,. 
 
 o-Benz-(i8)-methyl-glycooyamidine 
 
 .NH — C,.H, 
 
 CjH,N30i.e. HN = C- 
 
 /^' 
 
 \n(CH3)— CO 
 Prepared by the action of methylamine on 
 ' ethoxy - cyan-amido - benzoyl ' (CuHioNjOj) 
 (Griess, B. 13, 978). White needles. Sol. 
 caustic alkalis. Weak base. 
 
 Salts. — B'HCl: small tables or prisms, 
 decomposed by water. — (B'HCl) jPtCl, : sparingly 
 soluble yellow plates. 
 
 BENZCYAITIDINE v. Benzoyl cyanide. 
 
 BENZEINS. These bodies, which much re- 
 semble the phthaleins, are hydroxylated aromatic 
 carbinols, such as di-oxy-tri-phenyl-carbinol 
 CsH5.C(CeH40H)2(OH). Prepared by heating 
 phenols with benzotriohloride. The compound 
 from resorcin is yellow, those from cresols, 
 pyrocatechin, hydroquinone, orcin, and ($)- 
 naphthol are yellow or yellowish-red, pyrogallol 
 gives a blue, and (a)-naphthol a green dye. On 
 reduction they give the corresponding deriva- 
 tives of methane (Doebner, B. 13, 610 ; A. 217, 
 227). 
 
 BENZENE CsHj. Mol. w. 78. [6°]. (80-1°) 
 (B. Schiff, A. 220, 91). S.G. if -8839 (S.) ; 
 f -8799 (Bruhl). V.D. 2-74 (calo. 2-70) (S.). 
 S.H. -3834 -I- -001043* at «° (E. Schiff, A. 234, 
 320). H.C.p. (liquid) 776,000 (Berthelot, A. Ch. 
 [5] 28, 193); 779,530 (Stohmann, Eodatz a. 
 Herzberg, J. pr. [2] 88, 258) ; (gaseous) 
 799,350 at 18" {Th) ; 787,488 (S. B. a. H.). 
 H.F.p. (as vapour) - 12,510 (Thomsen, Th. 4, 61) ; 
 H.P.V.- 13,670 (r/s.). O.E. (14-2 to 80'1) -00136 
 (S.). S.V. 95-94 (S.); 95-8 (Eamsay, G. J. 35, 
 469). lif 1-5184 (B.) ; /^d 1-5062 at 14° (Negreano, 
 0. B. 104, 428) ; 1-5050 (Gladstone, C. J. [2] 7, 
 101). B 00 42-16 (B.) ; 44-02 (Kanonnikoff, /. jjr. 
 [2] 81, 352). Dielectric constant2-2'd2 at 14° (N.). 
 
 Formation. — 1. By heating benzoic acid with 
 lime (Mitscherlich, A. 9, 39 ; Peligot, A. 9, 48, 
 257 ; 11, 277 ; 12, 39), or by passing the vapour 
 of benzoic acid over red-hot iron (Daroet, A. 
 Ch. [2] 66, 99).— 2. By heating phthalic acid 
 with lime (Marignac, A. 42, 217).— 3. By dry 
 distillation of quinio acid (Wohler, A. 51, 146). — 
 Vol. I. 
 
 4. By passing oil of bergamot over red-hot 
 lime (Ohme, A. 31, 318).— 5. Together with 
 naphthalene, styrene, retene, &o., by heating 
 acetylene to a red heat (Berthelot, A. Ch. [4] 9, 
 469). Benzene is among the products obtained 
 by passing toluene, xylene, ^-oumene, or styrene 
 through a red-hot tube. — 6. Metallic suooinatea 
 give on dry distillation a liquid (hydroquinone 
 dihydride ?) which yields benzene when distilled 
 with zinc-dust (v. Bichter, /. pr. [2] 20, 206).— 
 7. From benzene sulphonio acid by passing 
 steam through its solution in diluted H2SO4 at 
 175° (Armstrong a. Miller, 0. J. 45, 148).— 8. 
 From phenol (70 g.) by distilling with P^Sj. 
 The yield is small (16 g.) : SC.H.OH + P^S, 
 = 2(C8H,)3PO,-H3H,S + 2C«H5 (A. Geuther, ^. 
 221, 55). — 9. The homologues of benzene when 
 treated at their boiling-points with a current of 
 HCl gas in presence of Al^Clj evolve MeCl and 
 yield lower homologues, but at the same time 
 part of the MeCl attacks other portions of the 
 hydrocarbon with production of higher homo- 
 logues. Thus if HCl is passed into boiling m- 
 xylene containing AljClj, benzene, toluene, 
 pseudooumene, mesitylene, and durene are 
 obtained (Jacobsen, B. 18, 338 ; AnsohUtz a. 
 Inmiendorif, B. 18, 657). — 10. Benzene is pro- 
 duced when benzylideue chloride, PhCHCl^, or 
 benzotriohloride, PhCCl^ is heated with soda- 
 lime (Limprioht, A. 189, 303). — 11. From diazo- 
 benzene nitrate or sulphate by heating with 
 alcohol or alcoholic KOH. 
 
 Preparation. — 1. Coal tar is distilled and the 
 fraction boiling below 150° is freed from 
 phenols by shaking with NaOHAq and from 
 bases by shaking with H2SO4. It is then recti- 
 fied. It is convenient to keep the still-head 
 at 100° : toluene is then condensed while 
 benzene passes over (Faraday, T. 1825, 440 ^ 
 Hofmann a. Mansfield, 0. J. 1, 244). On the' 
 large scale the distillation is performed in an. 
 iron boiler, to which is attached a tall vertical 
 column divided into compartments ; the fire is- 
 regulated so that pure benzene passes over, 
 while its homologues condense and run back tO' 
 the boiler. Benzene is completely freed from 
 its homologues by cooling with ice and salt, 
 when it solidifies and the homologues which 
 remain fluid may be pressed out. It is freed! 
 from thiophene by shaking with cono. H2SO4. — 
 2. A mixture of benzoic acid (1 pt.) and slatecS 
 lime (3 pts.) is distilled from an iron tube : the 
 product is shaken with KOHAq, distilled with 
 steam, dried with CaCl2 and Na and rectified. 
 Diphenyl and benzophenone are by-products. 
 The benzoic acid used must not be prepared from 
 toluene, otherwise it will contain thiophenio 
 acid, and the benzene will contain thiophene. 
 
 Properties. — Colourless, mobile, strongly re- 
 fracting liquid. Volatile with steam. Scarcely 
 soluble in water, v. e. sol. alcohol, ether, glacial 
 acetic acid, acetone, and chloroform. Crystal- 
 lises in trimetric pyramids, a:6:o = -891:1: -779 
 (Groth, Z. [2] 6, 553). It dissolves S, P, I, fats, 
 resins, oils, and many alkaloids. It burns with 
 a luminous flame ; Ig. burnt with excess of 
 hydrogen giving out a light equal to 5-8 g. of 
 spermaceti. When burnt with CO, and CH4, 
 the light equals that of 6-1 g., and 7-8 g., of 
 spermaceti respectively (Frankland a. Thprnn, 
 C. J. 38, 98). There are four bands in the 
 
 GG 
 
450 
 
 BENZENE. 
 
 ultra-violet absorption-gpeotrum of benzene 
 {Hartley, C. J. 39, 162 ; 47, 694). 
 
 Detection. — Benzene is converted by fuming 
 HNOj into nitro-benzene ; this is washed with 
 water and reduced by tin and HCl to aniline ; 
 caustic soda is added and the aniline extracted 
 with ether ; the ether is evaporated and the 
 aniline dissolved in much water ; the aqueous 
 solution gives a violet colour with bleaching- 
 powder. A mixture of HNOs and H.^SOj forms 
 di-nitro-benzene, which, after crystallising from 
 dilute alcohol, melts at 89°. 
 
 Detection of Thiophene in Benzene. — Thio- 
 phene, which is usually present in small quanti- 
 ties in commercial benzene, is indicated by the 
 blue colour produced by shaking with cone. 
 HjSO, and isatin (V. Meyer, B. 16, 1465 ; Baeyer, 
 B. 12, 1309). 
 
 Impurities. — Crude benzene may contain 
 traces of toluene, xylene, thiophene, CSj, amyl- 
 ene, orotonylene, alcohol, and acetonitrile. 
 
 Reactions. — 1. Benzene when passed through 
 a red-hot tube forms hydrogen, a little acetylene, 
 diphenyl, benzerythrene Cj^H^g, _p-di-phenyl- 
 benzene, iso-di-phenyl-benzene, and triphenyl- 
 ene (Berthelot, Bl. [2] 6, 272, 279 ; G. Schultz, 
 A. 174, 201 ; H. Schmidt a. G. Schultz, A. 203, 
 118). — 2. A mixture of benzene vapour and 
 ethylene passed through a red-hot tube gives 
 diphenyl and small quantities of anthracene, 
 Btyrene, and phenanthrene (Berthelot, Bl. [2] 
 7, 113, 274 ; Ferko, B. 20, 660).— 3. A mixture 
 ol equivalents of benzene and toluene dropped 
 at the rate of 80 g. per hour from a tap funnel 
 into the turned-up end of an iron tube kept at 
 low red heat is converted, to the extent of about 
 10 per cent., into gases, naphthalene, diphenyl, 
 p-tolyl-di-phenyl, o-^-di-tolyl, (7) and (5) di- 
 phenylene-methane, phenanthrene, anthracene, 
 ^-di-phenyl-benzene, a hydrocarbon C32H25, a 
 hydrocarbon [18°] (293°-316°) and two liquid 
 hydrocarbons (359°-38B°) and (404°_427°) (Car- 
 nelley, C. J. 37, 701).— 4. Induction sparks 
 passing through liquid benzene produce a gas 
 that contains 42 p.c. acetylene and 57 p.c. 
 hydrogen (Destrem, Bl. [2] 42, 267).— 5. Alu- 
 minium chloride {v. p. 147) acting upon a mixture 
 of benzene and an alkyl chloride causes HCl to 
 escape with the resulting formation of an alkyl- 
 benzene (Friedel a. Crafts, O. B. 84, 1392, 1450 ; 
 85, 74 ; A. Ch. [6] 1, 449). (a) Thus methyl 
 chloride passed into a mixture of benzene and 
 AljCls gives toluene, o-, m-, and jp-xylene, iff- 
 caniene, mesitylene, durene, isodurene, penta- 
 methyl-benzene, and hexa-methyl-benzene (Ador 
 a. Killiet, B. 12, 329 ; Jacobseu, B. 14, 2624). 
 (6) Chloral is converted by benzene in presence 
 of Al.Clj into CPhCLj.CH(OH)Cl, the hydro- 
 chloride of ao-dtchloro-phenyl-acetio aldehyde 
 (Combes, O. R. 98, 678; Bl. [2] 41, 382). 
 (c) Methylene chloride in presence of AljClj 
 gives di-phenyl-methane, anthracene, and tolu- 
 ene (Friedel t. Crafts, Bl. [2] 41, 322). (d) 
 Chloropicrin, AljClj, and benzene form CHPh, 
 and PhaCOH (Elbs, B. 16, 1274). (e) Allyl 
 chloride, Al^Clj, and benzene give di -phenyl - 
 propane and w-jwopyl-benzene (Wispek a. Zuber, 
 
 A. 218, 374). (/) Vimyl bromide, Al^Cl^, and 
 benzene give ethyl-benzene, M-di-phenyl-ethane, 
 ond di-methyl-anthraoene dihydride (Angeblis 
 
 B. Ansohiitz, B. 17, 167). Vinyl tribromide, 
 
 CHjBr.CHBrj, gives di-benzyl. (g) Oxygen -pahsei 
 into boiling benzene containing Al^Clo forma 
 phenol (Friedel a. Crafts, C. B. 86, 884, cf. 
 Senff, A. 220, 232). (h) Sulphur mixed with 
 boiling benzene and AljOlj forms phenyl mer- 
 captan, di-phenyl sulphide and ' diphenylene 
 disulphide' (C^HJ.S^ (Friedel a. Crafts, G. B. 
 86, 884). (i) Sulphurous acid, Al^Clj, and benz- 
 ene give di-phenyl-sulphoxide, Ph^SO (Colby a. 
 McLoughlin, B. 20, 195). (J) Acetylene in pre- 
 sence of AI2CI5 forms styrene, di-phenyl-ethane, 
 and di-tolyls (Varet a. Vienne, Bl. [2] 47, 917).— 
 
 6. Heated with Al^Clj (2 pts.) at 200° in sealed 
 tubes benzene gives toluene, ethyl-benzene, and 
 diphenyl (Friedel a. Crafts, C. R. 100, 692).— 
 
 7. Phenol is among the products of oxidation 
 of benzene by H^O^ (Leeds, Ph. [3] 11, 1068 ; 
 cf. Kingzett, 0. N. 44, 229). Phenol is also 
 formed when benzene is digested for some days 
 at 40° with cuprous chloride and dilute HCl, 
 atmospheric oxygen attacking benzene and 
 CU2CI2 simultaneously (Nencki a. Sieber, J. pr. 
 [2] 26, 25). In the animal body it is oxidised 
 to hydroquinone and pyrooateohin (Nencki a. 
 Giacosa, H. 4, 325 ; cf. Schultzen a. Naunyn, 
 C. G. 1867, 705). Oxidation with MnO^ and 
 dilute HjSOj produces formic, benzoic, and 
 phthalic acids (Carius, Z. 4, 505 ; A. 148, 
 50). The formation of benzoic acid is per- 
 haps preceded by that of diphenyl (Kekul6). 
 PbOj and H^SO^ give benzoic acid; PbO^ and 
 boiling dilute HNOj give only oxalic acid ; CrO, 
 gives only CO^ (Holder, Am. 7, 114).— 8. PCI, at 
 a red heat forms PhPClj, diphenyl, and P 
 (Michaelis, A. 181, 265 ; Kohler, B. 13, 1623).— 
 9. S.Clj at 250° forms ohloro-benzene, HCl, and 
 S (Schmidt, B. 11, 1168).— 10. Iodic acid and 
 H2SO4 on heating slowly form iodo-benzene 
 (Peltzer, A. 136, 194).— 11. SOjCl^ at 150° gives 
 chloro-benzene (Dubois, Z. [2] 2, 705).— 12. 
 CI.SO2.OH forms PhS02Ph, PhS02Cl, and 
 PhSOjH (Knapp, Z. [2] 5, 41).— 13. HCIO forms 
 CaH|i(OH)3Cl3 the trichlorhydrin of phenose 
 (Carius, A. 136, 323).— 14. Aqueous HClOj forms 
 trichloro-phenomaHc acid, chloro-benzene, and 
 diohloro-quinone (Carius, A. 142, 129). — 15. 
 CrOjClj acting upon benzene diluted with HOAo 
 (1 vol.) gives triohloro-quinone (Carstanjen, J. 
 pr. 107, 331). When benzene is heated with 
 CrOjClj there is formed a brown pp. of 
 C5H4(Cr02Cl)2 which is converted into quinone 
 by water (Etard, A. Gh. [5] 22, 269).— 16. Con- 
 denses with sulphuric acid and aldehydes, XCHO 
 to XCHPh2. Thus chloral forms CCl^.CHPhj; 
 bromal forms CBrjCHPh2; chloro-aldehyde forms 
 CHjCLCHPhj-, formic aldehyde forms CHjPh; 
 (Goldschmiedt, B. 6, 985 ; Hepp, B. 6, 1439).— 
 17. Benzene is not attacked by HIAq and P 
 at 250°, but at 280° it gives hexahydro-benzene 
 (Wreden a. Znatowicz, A. 187, 163; cf. Ber- 
 thelot, A. Gh. [3] 15, 150).— 18. When chlorine 
 is passed into benzene containing thiophene 
 HCl is evolved and the benzene then no longer 
 gives the indopheniue reaction (Willgerodt, J. 
 pr. [2] 33, 480). Pure benzene is not attacked 
 by chlorine in the cold and in the dark, but at 
 80° or in sunlight benzene hexachlorideis formed. 
 In presence of carriers, i.e. substances capable 
 of combining with chlorine in more than one 
 Ijroportion, chloro-beuzenes are produced. — 19. 
 Nitric acid forms nitro- and di-nitro-benzenes. 
 
BENZENE. 
 
 451 
 
 Cc»»5i?uiiious.— (CjHJjAlCla. [3°]. Decom- 
 posed by water into benzene and alumina ; with 
 Br it gives C^Bvg (Gustavson, B. 11, 2151). — 
 (OsHsJaAIBrs.— (C,H„)j3SbCls: monoolinic tables, 
 formed by warming SbClj with benzene 
 (Watson Smith a. Davis, O. /. 41, 411). 
 
 FotaBBlum-benzeue CuHsK mixed with 
 C^HjK;. Formed by heating benzene with K at 
 250° (Abeljanz, B. 5, 1027 ; 9, 10). Blue-blaok 
 crystalline mass, insol. benzene. Takes fire in 
 air. Converted by water into di-phenyl-benz- 
 ene, hydrogen, and di-phenyl. 
 
 Constitution of Benzene. — That the molecu- 
 lar formula of benzene is CjHj, and not any 
 multiple or submultiple of this, is settled, not 
 only by its vapour density, but also by the exis- 
 tence of the following series : CjHsCl, CbH^OIj, 
 C^HsClj, CJ1,C\^, CJS.G\, C.Cl,. We may call 
 the six atoms of hydrogen in the molecule of 
 benzene, a, 6, c, d, e, f. The first question is : 
 are these six atoms of equal value, or could we, 
 by displacing a by an element or radicle E, get 
 a product different from that which would be 
 produced by displacing 6 by B ? 
 
 PnoposiTioN I. — Four, at least, of the hydrogen 
 atoms are of equal value. 
 
 Ordinary phenol contains hydroxyl in place 
 of one hydrogen : call this hydrogen a. Bromine 
 and phosphorus convert phenol into CjHjBr. 
 Sodium and carbonic acid convert this bromo- 
 phenol into sodio benzoate, O^Hj.COjNa. Hence 
 the carboxyl of benzoic acid has taken the 
 place of the hydrogen atom a. Now, there exist 
 three oa;2/-benzoio acids, CuH^(0H)(C02H), and 
 since in these the carboxyl is in position a, the 
 three hydroxyls must have displaced three other 
 atoms of hydrogen, say 6, o, and d. When dis- 
 tilled with lime, these three acids, instead of 
 giving three phenols, the hydroxyl being in places 
 6, c, d, give the same phenol which is identical 
 with the original phenol. Hence, the four hy- 
 drogen atoms which we have called a, 6, c, and 
 d, are of equal value (Ladenburg, B. 7, 1684). 
 
 Pboposition II. — To every hydrogen atom in 
 the molecule of benzene there are two pairs of 
 hydrogen atoms similarly related. Benzoic acid, 
 
 a 
 CjH5(C0jH) gives bromo-benzoic acid, which 
 
 c a 
 we may call C8H4Br(C02H). This, when acted 
 upon by nitric acid, produces two isomeric 
 nitrobromo-benzoic acids. We may call these 
 
 CeH3{N0.JBr(C0"H), and 
 
 C,H3(NOJBr(CotH). 
 
 But by reduction these lose their bromine, and 
 give rise to amido-benzoio acids : 
 
 C.H,(NH2)(C0,H), C^,(NH2)(C02H). These 
 are found to be identical, being anthranilic acid. 
 Hence, h and / are symmetrically related with 
 regard to a (Hubner a. Petermann, A. 149, 129). 
 Again, ordinary nitro-benzoic acid may be con- 
 verted into the above bromo-benzoic acid by the 
 
 c a 
 
 diazo- reaction, hence it is C|iHj(N02)(C02H). 
 On nitration it gives a di-nitro-benzoic acid 
 
 which we may call C,H3(N02)(N02)(C0,H), 
 
 which may be reduced to C,H3(N02)(NH,)(C0,H), 
 
 whence we may successively prepare 
 
 0,H3(N0.,)C1(C02H), CeH3{NHJCl(Co"H), and 
 
 e a 
 OeH^ClfCO^). The last acid is found to be 
 identical with the chloro-benzoic acid 
 
 c a 
 
 C5H401(C03H) obtained by the diazo- reaction 
 
 c a 
 from C,H4(N02;(C02H). Hence c and e are 
 similarly related with regard to a. Therefore 
 we have a second pair of hydrogen atoms simi- 
 larly related with regard to a (Hubner, A. 222, 
 94, cf. Wroblewsky, A. 192, 206). 
 
 Proposition III. — The six atoms of hydrogen 
 in the molecule of benzene are of equal value. 
 Since a, h, c, and d are of equal value, and the 
 situations of / and e are similar to those of 6 
 and respectively, all six atoms of hydrogen 
 are similarly placed and of equal value. This 
 conclusion might also be deduced from the fact 
 that no instance of isomerism among the mono- 
 substitution products of benzene has been 
 proved. 
 
 Isomerism ainong di-suhstitution products. 
 Since two pairs of hydrogen atoms are symme- 
 trical to any fifth, it follows, that only three di- 
 derivatives of benzene can exist with a given 
 formula. Using our former notation, these are — 
 
 db~af, ac=ae, and ad. 
 This is confirmed by experiment. 
 
 Structural formula, — Since the atom . of 
 carbon is assumed to be tetravalent, all the 
 hydrogen atoms of benzene cannot be attached 
 to the same atom of carbon, and symmetry re- 
 quires that they must be either each attached 
 to one carbon, or else three must be attached 
 to one, and three to another ; or, finally, two 
 must be attached to one carbon, two to another, 
 and the remaining two to a third. The two 
 latter hypotheses do not account for more than 
 two di- substitution products ; hence the former 
 is established. The carbon atoms must be united 
 amongst themselves in a symmetrical fashion. 
 Each atom of carbon must be united with at 
 least two other atoms, or the group would not 
 hold together ; but it may be united with three 
 other atoms. The former hypothesis results in 
 the formula ; 
 
 HC 
 
 HC. 
 
 CH 
 
 ,CH 
 
 This is the ring-formula of Kekul^, which is 
 one of the two formulae originally put forward 
 by him {A. 137, 160). If we number the posi- 
 tions occupied by the atoms of hydrogen thus, 
 
 6C 
 
 I 
 
 6G. 
 
 I I 
 
 / 
 
 ca 
 
 1 
 
 C3 
 
 oo2 
 
453 
 
 BENZENE. 
 
 we see that the formula shows the possible 
 existence of fawr di-substitution products — viz. 
 1:4, 1:3, 1:2 and 1:6. To get over this diffi- 
 culty, Kekul6 resorts to a peculiar mechanical 
 hypothesis. He supposes that what we repre- 
 sent by straight lines in a formula really indi- 
 cates that two atoms vibrate with reference to 
 each other so that the above formula would 
 mean that, in a given unit of time, 1 approaches 
 6 twice as often as it approaches 2 ; and so for 
 the other atoms. Now, if this were the case, 
 the di- substitution product 1 : 2 would differ 
 from 1:6; but he assumes that the motions of 
 1 are as follows : first, it approaches 6 twice ; 
 then it approaches 2 once ; next it approaches 
 6 onci ; then it approaches 2 t/wici ; then 6 
 twice ; 2 once ; and so on. This is equivalent 
 to saying that the above formula for benzene 
 ia true for one instant, after which it changes to 
 
 «C' 
 
 I 
 
 5C, 
 
 I I 
 
 Cs 
 
 I 
 
 ,C3 
 
 C 
 
 4 
 
 and the next instant it changes back again, and 
 so on. This assumption leads to the deduction 
 that only three di- derivatives can exist, and, if 
 we could devise no other formula for benzene, 
 we should be obliged to accept it. As a matter 
 of fact, it is now almost universally adopted ; 
 not so much on its intrinsic merits, as on account 
 of the enormous service which it has rendered 
 to chemistry. 
 
 There remains, however, a second hypothesis 
 possible, which is that every atom of carbon is 
 united to three other atoms. The following 
 mechanical construction may help to elucidate 
 this hypothesis. 
 
 Let three rods be driven into the ground at 
 the angles of an equilateral triangle, and let the 
 top of each rod be joined by elastic string with 
 the bottom of each of the two adjacent rods. 
 A figure somewhat resembling a coronet is 
 obtained, and we may suppose the six atoms 
 of carbon in the benzene molecule situated at 
 the two extremities of each of the three rods. 
 At first sight it might appear that this repre- 
 sentation of the benzene molecule would indicate 
 the existence of three di- derivatives — namely, 
 
 (1) when the substituted hydrogens are attached 
 to two carbon atoms at opposite ends of one rod ; 
 
 (2) when they are attached to carbon atoms which 
 are both on the upper or both on the lower 
 ends of two different rods ; (3) when one carbon 
 atom is on the upper end of one rod and the 
 other is on the lower end of another rod. But 
 if we assume that formulse and other mechanical 
 symbols represent not actual position in space, 
 but merely modes of combination of atoms, 
 especially showing -ffhioh atoms are directly and 
 which indirectly united, (3) is identical with 
 (1), for it can be converted into (1) by simply 
 holding the string, at the opposite ends of 
 which the carbon atoms have been placed, up- 
 right, and doing the aame with the two corre- 
 
 sponding strings. The rods will now take posi- 
 tions formerly occupied by the strings now 
 held upright, and the figure will be the same 
 as before. Hence this figure for benzene gives 
 only two di- derivations, and accordingly it 
 must be discarded. When the figure we have 
 just considered is projected on a plane it assumes 
 the form : 
 
 This figure, by simply twisting the central rod, 
 is converted into 
 
 and il the central rod be now elongated we 
 get: 
 
 CH(S» 
 
 This symbol, which has been a favourite 
 with some chemists, must, of course, be aban- 
 doned along with the solid figure from which it 
 is derived ; but it is also very easy to see that 1 : 2 
 and 1:4 di- derivatives, are identical, since if 
 we pick up the carbon atom (4) and place it 
 upon (2), and then take up (2) and place it 
 where (4) was, supposing all the while that the 
 connections, which we may imagine to bo elastic, 
 are not broken, the figure will be whoUy un- 
 altered. 
 
 There remains one other benzene formula : 
 it is obtained by joining the ends of the three 
 rods placed vertically by six strings as before, 
 but with this difference, that whereas in the 
 previous formula the top of one rod is joined to 
 the bottom of the others, in this formula the 
 top of each rod is joined with the top of each of 
 the others, and the bottom of each rod is joined 
 with the bottom of each of the others. We 
 thus obtain a right-angled prism on a triangular 
 base. This formula, defended by Ladenburg . 
 {Theorie der aromaUschen VerbiTtdungeniBums- 
 wick, 1876), is capable of explaining most of the 
 reactions of benzene, and the objections that 
 have been brought against it are chiefly the 
 
BENZENE. 
 
 453 
 
 result ol miBconception of its nature. Projected 
 npon a plane this formula becomes : 
 
 0HC 
 
 ^HC 
 
 CH® 
 
 CH® 
 
 ©HC 
 
 If the upper triangle be rotated through 180°, 
 and then the figure be projected upon a hori- 
 zontal plane, we obtain a figure which resembles 
 a star: 
 
 The two former figures are not symmetrical, 
 but the latter is clearly so, and it has this 
 advantage over the prism formula, that, if the 
 atoms of carbon are numbered consecutively, 
 they correspond to the atoms of carbon in 
 EekuU's formula, also numbered consecutively ; 
 whereas this would not be the case with the 
 second of the three f ormulse here given, which is 
 that used by Ladenburg. 
 
 For most purposes it will not be necessary 
 to decide which formula we adopt, for both the 
 star-formula and the formula of KekuU : 
 
 4SHC 
 
 «HC 
 
 CHCd 
 
 CH(S 
 
 may be represented by the simple hexagon : 
 H(l> 
 
 <«" 
 
 The numbering of the carbon atoms here given 
 is used throughout this dictionary. Thus, the 
 expression CsH^Brj [1 : 5] must be taken to 
 mean that one bromine atom has displaced the 
 hydrogen atom numbered (1) and the other the 
 hydrogen atom numbered (5). 
 
 Physicists have tried to decide between the 
 formulae of KekuIS and Ladenburg. Thomsen 
 
 {Th. iv. 272 ; A. 205, 133) considers that thermo- 
 ohemical data favour Ladenburg's formula, but 
 the assumptions he makes in the course of his 
 argument lead him in other cases to impossible 
 conclusions. The specific volume of benzene 
 is 96 ; whereas that calculated on the assumption 
 that the S.V. of = 11, and that of H = 5-5 is 
 99: this would merely show that the relation 
 between the carbon atoms in the benzene mole- 
 cule is different from that in saturated paraffins. 
 If we compare the specific volumes of hexane, 
 diallyl, and benzene, we find that : 
 
 Hexane, C„H„ has a S.Y. 140-0 
 Diallyl, C.H„ „ „ 125-7 
 Benzene, CjH, „ „ 95-9. 
 We see that the difference between the first and 
 second (14-3) is less than that between the 
 second and third (29-8) and that when hexane 
 is converted into benzene by the removal of 
 8H the S.V. is lowered by 8 x 5-6, while the 
 removal of 4H, in converting hexane into diallyl, 
 lowers S.V. by only 4 x 3-6. That is to say the 
 want of saturation of diaUyl is accompanied by 
 an unusually large specific volume, whereas this 
 is not observed in the case of benzene. This 
 would indicate that benzene is not unsaturated 
 in the ordinary sense, and can be used as an 
 argument in favour of Ladenburg's formula for 
 benzene (Lessen, A. 214, 129 ; E. SchifE, A. 220, 
 BOB). 
 
 On the other hand, the S.V. of hexahydro- 
 toluene (141-8) differs iiom that of toluene (118) 
 by 23-8. This is about three times the difference 
 (7-2) between the S.V. of pentane (117-2) and 
 amylene (110). Hence it would appear that the 
 change in the state of saturation in passing 
 from hexahydro-toluene to toluene is of a 
 similar character to the change in passing from 
 pentane to amylene : the removal of H^ in both 
 cases producing a diminution of between 7 and 
 8 units in the S.V. This supports KekuU's 
 formula for benzene (Lessen, A. 225, 119 ; 
 Horstmann, B. 20, 766). 
 
 The refractive power of benzene is about 
 equal to that calculated on the assumption that 
 Kekul6's formula is correct, provided that cer- 
 tain assumptions are made regarding the con- 
 nection between the refractive powers of com- 
 pound molecules and the refractive powers of 
 the constituent atoms (Briihl, A. 200, 228; 
 Kanonnikoff, J. B. 15, 473). 
 
 Passing from physical to chemical consider- 
 ations, we note first that the behaviour of 
 benzene towards halogens is, on the whole, 
 more like that of a saturated than an unsatu- 
 rated compound. The following special argu- 
 ments have also been employed. Sodium acting 
 upon succinic ether gives succinyl-suocinic ether, 
 which loses H^ on oxidation, changing to di-oxy- 
 terephthalic ether. The formula of suooinyl- 
 succinic ether may be written in one of the 
 following ways : 
 
 (I.) COjEt.CH.CO.CHj 
 
 CH2.00.CH.C0jEt 
 (II.) C0jEt.GH.C(0H):CH 
 
 CHj.C(0H):C.C0,Et 
 (in.) C0jEt.CH.C(0H):0H 
 
 CH:C(0H).0H.C0^t 
 
464 
 
 BENZENE. 
 
 (IV.) 00jEt.C : C(0H).CH2 
 
 (V.) 
 
 I 
 
 CH2.C(0H):C.C0.Et 
 CO2Et.CH.CO— OHj 
 
 CO2Et.CH.CO . CHj. 
 H the first correctly represents succinyl-succinio 
 ether, it must be supposed to change into (II.), 
 (in.), or (IV.) during the oxidation. The third 
 formula would naturally lead to the formula 
 .C(OH) = CH. 
 
 COjEtC^- 3C.C0JEt and therefore 
 
 \CH=0(OH)/ 
 
 .CH = CHv 
 to the benzene formula H0<- ^CH 
 
 \ch=ch/ 
 
 proposed by Wislicenus, a formula which would 
 indicate the existence of two ohloro-benzenes. 
 The second formula 
 
 C02Et.CH<^g^^) "^^j^C.COjEt, would give 
 
 CO^Et.C'^^^^bQ'^^C.COjEt on oxidation, 
 
 a formula based upon KekuU's ring. The fourth 
 formula, like the third, leads to the benzene 
 ring of WisHcenus. The fifth formula would 
 lead to Kekuld's or Wishcenus' ring, but with 
 the carboxyls in the ortho- position, whereas in 
 terephthaUo acid they are in the para- position. 
 Ladenburg's formula for dioxy-terephthaUc acid is 
 
 CH CH V 
 
 COjEt-C^l-} ; \c.COjEt, the forma- 
 
 \C(0H)— C(OH)/ 
 tion of which from formulse I., II., III. or IV. 
 requires the improbable assumption of a wander- 
 ing of hydroxyl such as takes place when salicylic 
 acid changes to ^-oxy-benzoic acid. Laden- 
 burg's formula can be derived from V, but only 
 by assuming a rearrangement of the unsaturated 
 unions. 
 
 By the action of sodium upon malonio ether 
 a tricarboxylic ether, 
 COjEt 
 
 I 
 CH 
 
 / \ 
 
 OC CO 
 
 , is formed. This 
 
 COjEt.CH CH-CO^Et 
 
 ^CO' 
 
 is found to be phlorogluoin tri-oarboxylio ether, 
 COjEt 
 
 \y 
 
 // \ 
 
 HOC C(OH), and this nndonbtedly 
 
 I II 
 
 COjEt.C C.CO^Et 
 
 '^ / 
 
 C(OH) 
 favours EekuU's hypothesis, especially when it 
 is remembered that phlorogluoin, 
 C(OH) forms a tri-oxim C(NOH) 
 
 // \ / \ 
 
 CH CH H,C OH, 
 
 C(OH) C(OH) 
 CH 
 
 (HON)C C(NOH) 
 CH, 
 
 It will thus be seen that, in spite of the great 
 number of researches carried out on the benzene 
 derivatives, the constitution of benzene itself 
 still remains unsettled. 
 
 'B&centdisaxiss'ums on the Benzene formula. — 
 Ladenburg, B. 19, 971; 20, 62; Baeyer, B. 
 19, 1797 ; A. E. Miller, C. J:51, 208; Thomsen, 
 B. 19, 2944 ; Claus, B. 20, 1422. 
 
 Orientation. 
 Benzene gives rise to only one mono- substi- 
 tution product. It gives three di- substitution 
 products, and these, assuming either Kekul6's or 
 Xadenburg's formula, are named as follows : 
 1, 2 = 1, 6 is called ortho, 
 
 1. 3 = 1, 5 „ „ meta. 
 
 1.4 „ „ $ara. 
 When we come to tri- substitution products 
 
 we must distinguish several oases. — 1. Com- 
 pounds of the formula C5H3A3, that is to say, 
 where the three substituting elements or radicles 
 are aU alike. There are three such eompoundi . 
 
 1, 2, 3 is caUed consecutive. 
 
 1, 3, 5 „ „ symmetrical. 
 
 1, 2, 4 „ „ irregular. 
 2. Compounds of the formula CoHjABj. There 
 are six such compoimds. — 3. There are ten 
 compounds of the formula C5H3ABC. 
 
 In the case of tetra- derivatives of benzene : 
 
 1. There are three compounds of the formula 
 C,HA: 
 
 1, 2, 3, 4 is called consecutive. 
 1, 2, 4, 5 „ „ symmetrical. 
 1, 2, 3, 5 „ „ irregular. 
 
 2. There are seven compounds of the formula 
 C5H2AB3. — 3. There are thirteen compounds of 
 the formula CjHjAjBj. — 4. There are sixteen 
 compounds of the formula CjH^ABCj. — 5. There 
 are thirty compounds of the formula GgH^ABCD. 
 
 There is only one penta- derivative of the 
 formula C^HAj, and only one compound of the 
 formula C^Aj. 
 
 The next question is how to determine, in 
 a given case, the position of substituting radicles 
 in the benzene ring. In isolated cases it is 
 frequently found that this may be settled by 
 special considerations, but the only general 
 method known is that which was thoroughly 
 worked out, by KekuU's pupil Korner, in a 
 most laborious research, in the course of which 
 he discovered no less than 126 new compounds 
 (G. 4, 805). This research has done more than 
 anything else towards establishing the ring for- 
 mula for benzene. 
 
 Suppose we convert CuHiBr^ into CjHjBrj : 
 by reference to a figure it wiU be found that we 
 can introduce a bromine atom in place of an 
 atom of hydrogen in ortto-dibromobenzeue in 
 such a way as to produce either a consecutive 
 or an irregular tribromobenzene, but not so as 
 to produce a symmetrical product. 
 
 Afeto-dibromobenzene can give rise to con- 
 secutive, irregular, or symmetrical, tribromo- 
 benzene, while pasra-dibromobenzene can only 
 give rise to an irregular tribromobenzene. 
 
 An unknown dibromobenzene is therefore 
 para-, ortho- or meta-, according as wo can got 
 one, two, or three tribromobeuzenes by treating 
 it with bromine. Thus the dibromobenzene 
 from dibromoaniline gives rise to three tribromo- 
 
BENZENE IIEXACHLORIDE. 
 
 455 
 
 benzenes ; therefore it is a meta- compound. 
 Again, the chief product of the action of two 
 molecules of bromine upon benzene gives rise 
 to only one tribromobeuzene on further treat- 
 ment with bromine; hence this product is 
 para-dibromobenzene. On the other hand, the 
 minor product of the dibromination of benzene 
 gives rise to two, and only two, tribromo- 
 benzenes ; therefore it is ortho-dibromobenzene. 
 
 In order to investigate the constitution of a 
 given tribromobeuzene, two methods may be 
 followed : either introduce another atom of 
 bromine in place of hydrogen and see how many 
 tetrabromobenzenes result, or displace an atom 
 of bromine by hydrogen and carefully examine 
 how many dibromobenzenes are formed. It can 
 easily be seen by reference to the formula that 
 consecutive tribromobeuzene produces two di- 
 bromobenzenes and also two tetrabromobenzenes, 
 while symmetrical tribromobenzene produces 
 one dibromo- and one tetrabromo- benzene, and 
 irregular tribromobenzene gives rise to all three 
 dibromobenzenes and aU three tetrabromo- 
 benzenes. 
 
 The follovring are the melting and boiling 
 points of the bodies described : 
 
 Dibromobenzenes. 
 Ortho. . . . [-1°](224°) 
 Meta .... liquid (220°) 
 Para .... [89°] (219°) 
 
 Tribromobemenes. 
 Consecutive . . [ 87°] 
 Symmetrical . . [120°] (278°) 
 Irregular . . . [ 44°] (276°) 
 
 Tetrabromobenzenes. 
 Consecutive (1, 2, 3, 4) [160°] 
 Symmetrical (1, 2, 4, 5) [137°-140°] 
 Irregular (1, 2, 3, 5) am. [ 99°] (329) 
 
 It will be observed that the isomerides differ 
 widely in melting-points, but very slightly in 
 boiling-points, and this is usually the case 
 where isomerism is due to difference of position 
 of substituents in the benzene nucleus. 
 
 The orientation of any given benzene deriva- 
 tive must be determined either by preparing it 
 from one of the three bromobenzenes, or else by 
 preparing a bromobenzene from it. 
 
 Examples. 
 
 Para-dibromobenzene when treated with 
 sodium and methyl iodide gives a dimethyl- 
 benzene or xylene : C^H^Brj + 2CH3.I + 4Na = 
 2NaI + 2NaBr + CjHj(CH3)2. By oxidation this is 
 converted first into toluic acid, C5Hj(CH3}C02B[, 
 and next into terephthalic acid, 0^^(00.^}.^. 
 It is therefore evident that the xylene, the toluic 
 acid, and terephthalic acid, are all pa,ra-coia.- 
 pounds. Also since a certain bromotoluene, 
 CsH^Br(CH3), when treated with sodium and 
 methyl iodide gives the above para-xy\ene, it 
 must be the ^ara-bromotoluene, and the bromo- 
 benzoio acid derived from it by oxidation — 
 CjHjBrOHa + O3 = CjH.Br.COjH + HjO— must be 
 para-bromobenzoic acid. 
 
 As another example we may take the ortho- 
 series. A certain bromoaniline, CjH^Br.NHj, is 
 known to be ortho- because when the amidogen 
 is displaced by bromine the product is ortho- 
 dibromobenzene. Now, this ortTio-bromoaniline 
 
 may be got by reducing a bromonitrobenzene 
 0„HjBr(N02), which may be formed by diazo- 
 reaction from a nitroaniline C|jHj(NH2)(N02), 
 and this may be got by acting on a nitroanisol 
 CbHj(OCH3)(N02) by ammonia, and this nitro- 
 anisol may be obtained from a nitrophenol 
 C„Hj(OH)(NOj), and this nitrophenol may be 
 itself reduced to an amidopheuol C|iHj(0H)(NH2), 
 and this amidophenol may be converted by 
 diazo- reaction into a chlorophenol CjHj(OH)Cl, 
 and this chlorophenol may be converted by 
 cautious fusion with potash into a dioxybenzene 
 C„Hj(0H)2. AU the compounds here enumerated 
 are clearly ortho- compounds, and as the dioxy- 
 benzene is found to be pyrocateohin, we have 
 proved that pyrocatechin is ori/io-dioxybenzene. 
 
 In the para- series we may trace, in the same 
 way, the connection between ^-dibromobenz- 
 ene and ^-nitroanisol CjHj(OCH3)N02. Thence 
 we proceed by the following steps : reduce 
 to CsHj(OCH,)(NHJ, convert this into 
 CjHj(0CH3)(0H) by nitrous acid, and treat with 
 hydrio iodide. In this way we get a second 
 dioxybenzene, which is found to be hydro- 
 guinone, and this body is therefore a para- 
 compound. The remaining dioxybenzene ia 
 resorcin, which must be the meta- compound. 
 
 The rules governing substitution in the benz- 
 ene molecule are discussed in the article Aro- 
 MATio Seeies. Derivatives of benzene are de- 
 scribed, as Aniline, Phenol, Bkomo-, Bromo- 
 NITRO-, Chloko-, Chloko-niteo-, Iodo-, Methtel-, 
 
 N1TKO-, OXT- BENZENE, CtC. 
 
 BENZENE HEXABROMIDE C,H,BrB. 
 Bromine is dropped into boiling benzene exposed 
 to direct sunlight ; the hexabromide crystallises 
 out on cooling ; it is separated from tri-bromo- 
 benzene by sublimation, and finally crystallised 
 from a mixture of alcohol and benzene 
 (Mitscherlich, P. 35, 374 ; Meunier, C. B., 101, 
 378 ; A. Ch. [6] 10, 269). Prisms, isomorphous 
 with the (a)-hexaohloride; not attacked by HNO3 
 or HjSOj. Alcoholic KOH splits it up into HBr 
 and M-tri-bromo-benzene. If the product of the 
 action of ZnEtj upon benzene hexabromide 
 dissolved in benzene be oxidised with chromic- 
 mixture, benzoic, isophthalio, terephthalic, and 
 di-bromobenzoio acids are formed (Ador a. 
 Killiet, Bl. [2] 24, 485). 
 
 BENZENE CARBOXYIIC ACIDS v. Benzoic, 
 Phthalic, 2Vi-MELLiTio, 2Vi-MESio, Henii- 
 MELLiTio, Peehnitio, Ptbomellitic, Mellophanio, 
 and Melliiio acids. 
 
 Benzene penta-carboxylic acid 0„HjO,, t.«. 
 C|;H(C02H)5. Formed by oxidation of penta- 
 methyl benzene (Friedel a. Crafts, A. Ch. [6] 
 1, 474). Amorphous (containing Gaq). The 
 K salt forms small deliquescent prisms ; the 
 salts of Ag, Pb, Ba, Fe, Cu, and Al form 
 insoluble pps. 
 
 BENZENE (a)-HEXACHLOBIDE C^UJSi^ 
 Mol. w. 291. [157°]. S.G. 1-87. Prepared by 
 chlorinating benzene in direct sunlight (Faraday, 
 A. Ch. [2] 30, 275; Mitscherhch, P. 35, 370; 
 Lesimple, Bl. [2] 6, 161): 350 g. may be got 
 from 600 g. benzene (Leeds a. Everhart, A. C. J. 
 2, 205). It may be freed from C^HClji and 
 OsHjClj by treatment with H^SO^ or HNOj 
 (Meunier, A. Ch. [6] 10, 223). Monoolinic 
 crystals; may be sublimed. At 288° it boils, 
 splitting up into HCl and (1, 2, 4)-tri-chloro- 
 
456 
 
 BENZENE HEXAOHLORIDE. 
 
 benzene. The same decomposition is effected 
 by heating with alcoholic KOH. 
 
 Beactimis. — 1. Zmc reduces it, in alcoholic 
 solution, to benzene (Zinin, Z. 1871, 284). — 
 
 2. Fuming nitric acid has no action. — 3. Silver 
 acetate forms crystalline 0„HjCl3(OAo)3C8HsCl3. 
 
 Benzene (S).hexacliloride CsHsCls. [310°]. 
 V.D. 9'28. Formed at the same time as the (a)- 
 compound ; when the mixture is sublimed, the 
 (3)- compound sublimes last. I£ the mixture 
 (4 pts.) be boiled with KCN (3 pts.) and alcohol, 
 the (j8)- compound is left while the (a)- compound 
 is decomposed. Kegular ootahedra, cubes, tetra- 
 hedra, or tetrakis-tetrahedra. Alcoholic potash 
 splits it up into HCl and (1, 2, 4)-tri-ohloro- 
 benzene, but more slowly than the (a). compound 
 (J. Meunier, C. B. 98, 436; 100, 358). 
 
 BENZENE.HYDEA.ZIMIDO- v. pp. 369, 370. 
 
 BENZENE - PHENYL - HYDRAZIMIDO - 
 NAPHTHALENE v. Bemene-xzo-phenyl-{$)- 
 naphthylamine. 
 
 BENZENE-PYKOGALLOL-PHTHALElN v. 
 
 Tri - OXY - TKI - PHENYIi - CAREINOL - OAKEOXYLIC 
 ANHTDKIDE. 
 
 BENZENE-TRI.QTTINONE C,0e4aq. So- 
 called ' oxy-carboxylic acid ' of Lerch. [c. 95°]. 
 
 Formation. — 1. By the action of HNO3 upon 
 the hydrochloride of tetra-oxy-di-amido-benzene ; 
 the yield is 65 p.c. — 2. By the action of HNO3 
 upon di-imido-di-oxy-quinone Cb(NH).^(0H)202. — 
 
 3. By oxidation of hexa-oxy-benzene Cj(0H)5. 
 Properties. — Colourless microscopic needles. 
 
 Nearly insoluble in cold water, alcohol, and ether. 
 
 Beactions. — By reducing agents it is con- 
 verted successively into di-oxy-benzene-di- 
 quinone 05(011)20^, tetra-oxy-benzene-quinone 
 05(011)402, and finally hexa-oxy-benzene 
 Cj(OH)s. On heating to 100° or on boiling 
 with water it evolves COj and yields eroconio 
 acid C5H2O5 (Nietzki a. Benckiser, B. 18, 504). 
 
 BENZENE-RESOECIN PHTHALElN v. Di- 
 
 OXT - TEIPHENYL - CAKBINOL - CARBOXyLIO AN- 
 
 HYDKIDE. 
 
 BENZENE - SULPH . AHIDO ■ ANILISE v. 
 
 Benzene-sdlphonio acid. 
 
 BENZENE - SnLPH - AMIDO - TOLUIDE v. 
 Benzene-suiiPhonic acid. 
 
 BENZENE STJLPHINIC ACID CsH^SO^ i.e. 
 CeHjSOjH. [84°]. 
 
 Formation. — 1. By adding zinc-dust to a 
 cooled alcoholic solution of the chloride of 
 benzene sulphouic acid ; the resulting zinc salt 
 is very slightly soluble in water ; it is treated 
 with Na2C03; the filtrate is concentrated and 
 the acid ppd. by HCl (Schiller a. Otto, B. 
 9, 1584). — 2. From the phenyl-hydrazide of 
 benzene sulphonic acid PhSOjNjHjPh, called 
 also di-phenyl-sulphazide, by boiling with 
 baryta-water (Limpricht, B. 20, 1239).— 3. By 
 passing SOj into a warm mixture of benzene 
 and AI2CI5 (Friedel a. Crafts, G. B. 86, 1368 ; 
 Adrianowsky, B. 12, 853). — 4. By the action of 
 ZnEtj on C.H5S02C1 (Kalle, A. 119, 156).— 
 6. From CaH^SOjCl and Pb(SEt)2, thus : 
 2PhS0201 + 2Pb(SEt)2 = 
 (PhS02)2Pb + PbClj -f SjEtj 
 (Schiller a. Otto, B. 9, 1636).— 6. Fromdiphenyl 
 disulphide and alcohol potash : 2Ph2S2 + 4K0H 
 = PhS02K+ 3PhSK + 2H2O (S. a. 0.). 
 
 Properties. — Long radiating prisms. SI. sol. 
 cold, V. sol. hot, water; v. sol. alcohol and 
 
 ether ; acid to test-paper. Above 100° it 
 decomposes. 
 
 Beactions.— 1. Water at 130° gives benzene 
 sulphonic acid and phenyl benzene -thiosul- 
 phonate (Otto, A. 145, 317) ; the same reaction 
 takes place slowly in the cold, especially in pre- 
 sence of HCl (Pauly a. Otto, B. 10, 2181).— 
 2. Ethyl mercaptan at 100° gives di-ethyl di- 
 sulphide and phenyl-ethyl di-sulphide (Otto a. 
 Eossing, B. 19, 3136).— 3. Phosphorus penta- 
 chloride reacts thus : PhS02H + PCI, 
 = PCl3 + HCl-(-PhS02Cl. — 4. Potash fusion 
 gives benzene and K2SOS. — 5. Sodium chloro- 
 acetate gives phenyl - sulphonyl - acetic acid, 
 Ph.SO2.CH2.CO2H. — 6. Sodium di-chloro-acetate 
 gives phenyl chloro - methyl sulphone 
 Ph.SOj.CHjCl. — 7. Methylene iodide reacts 
 thus : CH2I2 + Ph.SOjNa = Nal + Ph.SOj.CHjI.- 
 
 8. Sodium aa-di-chloro-propionate acting upon 
 sodium benzene sulphinate gives di-phenyl 
 ethylene di-sulphone, Ph.SO2.C2H4.SO2.Ph — 
 
 9. Phenyl-hydrazine in presence of cone. 
 HClAq forms phenyl benzene-thiosulphonate 
 and the phenyl hydrazide of benzene sulphonic 
 acid (2. v.). — 10. When HjSO^ is added to a 
 solution of Ph.SOjNa and N02Na a pp. is got 
 which may be crystallised from alcohoj. It 
 is perhaps (PhS02)2NOH. It is si. sol. cold 
 water, CSj or ligroin, but v. sol. alcohol and 
 ether. At 100° it evolves nitrous acid gas. 
 Boiling water, alkalis, or acids, decompose it 
 into PhSOjH and nitrous acid (Konigs, B. 
 11, 615). — 11. Fuming nitric acid forms 
 CisH^NSjO, which may be (Ph.S02)3NO. It 
 forms crystals, [98-5°], insol. alkalis, si. sol. 
 alcohol, m. sol. benzene (Otto a. Gruber, A. 
 141, 370 ; Konigs, B. 11, 615, 1590). 
 
 Salts. — BaA'j: clumps. — ZnA'2 : tablets, si. 
 sol. alcohol and ether, si. sol. water (Kalle). — 
 ZnA'2 2aq: insol. cold water (S. a. 0.). — AgA'. 
 
 Ethyl ether EtA'. — Formed by means of 
 EtOH and HCl, or, together with COj, by heat- 
 ing Ph.S02Na with G1.002Et. Non-volatile oil. 
 KMnO, in acetic acid solution oxidises it to 
 Ph.S03Et (Otto a. Eossing, B. 18, 2495 ; 19, 
 1225). 
 
 Benzene di-sulphinic acid CbH4(S02H)2 [1:3]. 
 From [1:3] C„Hj(S02Cl)2, and zinc-dust (Pauly, 
 B. 9, 1595). Oil.— BaA". 
 
 BENZENE-SULPH-NITR-ANILIDE v. Benz- 
 
 ENE-SULPHONIO ACID. 
 
 BENZENE SULPHONE v. Di-phenyl-sul- 
 
 PHONE. 
 
 BENZENE SULPHONIC ACID C5H„S03 i.e. 
 CjHj.SOjH. Phenyl-sulphurous acid. Sulpha- 
 bemoUc acid. [42°]. 
 
 Formation, — 1. From benzene and fuming 
 HjSO, (Mitsoherlich, P. 31, 283, 634; Sten- 
 house, Pr. 14, 351; Wurtz, C. B. 64, 749).— 
 2. By the oxidation of benzene sulphinic acid 
 (Otto a. Ostrop, A. 141, 369).— 3. By the oxida- 
 tion of phenyl mercaptan : PhSH + 03 = PhSOjH 
 (Vogt, A. 119, 151).— 4. By boiling ^-diazo- 
 benzene sulphonic acid with alcohol under 
 pressure (E. Schmitt, A. 120, 129).— 5. Together 
 with phenyl benzene-thiosulphonate by heating 
 benzene sulphinic acid with water at 130° 
 (Otto, A. 145, 317) : 
 
 3Ph.S02H = PhSOjH + Ph.SO2.SPh + B.fi. 
 
 Preparation. — Benzene (2 pts.) is shaken 
 with fuming H.,S04 (3 pts.) with gentle warm- 
 
BENZENE SULPHONIC ACID. 
 
 457 
 
 ing. The aoid is separated from undissolved 
 benzene, diluted, and neutralised with BaCOj 
 or lead carbonate. In the filtrate the Ba, or 
 Pb, salt is decomposed by H^SO^ or H^S re- 
 spectively. 
 
 Properiies. —SmaXl, four-sided, deliquescent 
 plates (containing Ijaq). 
 
 BeacHons. — 1. By fusion with potash, soda, 
 or a mixture of the two, it is converted into 
 phenol. The percentage of phenol obtained in- 
 creases with the amount of alkali and with the 
 temperature of the fusion. The percentage of 
 phenol is given in this table ; one equivalent of 
 acid being used : 
 
 KOH NaOH Temperature Phenol 
 
 2 
 
 
 
 253° 
 
 23 
 
 3 
 
 — 
 
 210° 
 
 7 
 
 3 
 
 — 
 
 267° 
 
 79 
 
 — 
 
 3 
 
 209° 
 
 1 
 
 — 
 
 3 
 
 280° 
 
 26 
 
 3 
 
 3 
 
 211° 
 
 2 
 
 3 
 
 3 
 
 277° 
 
 39 
 
 3 
 
 3 
 
 360° 
 
 64 
 
 7 
 
 — 
 
 252° 
 
 96 
 
 (P. Degener, J. pr. 125, 401).— 2. The potassium 
 salt distilled with KCN or K,FeCyj gives benzo- 
 nitrile (Merz, Z. [2] 5, 33).— 3. Dry distillation 
 gives H2SO4, benzene, SOj, and di-phenyl-sul- 
 phone. — 4. Dry distillation of the ammonium 
 salt gives benzene and small quantities of ben- 
 zene sulphamide, diphenyl, di-phenyl sulphoue, 
 phenyl meroaptan, and (traces of) quinoline 
 (Egli, B. 18, 575).— 5. The potassium salt dis- 
 tilled with NaNHj gives aniline (Jaolcson a. Wing, 
 Am. 9, 75). — 6. Distillation of the Na salt gives 
 di-phenyl sulphide, di-phenyl di-sulphide, phenyl 
 meroaptan, COj.and SO^ (Stenhouse). — 7. A mix- 
 ture of H^SOj and water boiling at 175° converts 
 it into benzene and H^SO^ (Armstrong, 0. J. 45, 
 151). — 8. Fusion with potassium formate gives 
 potassium benzoate. 
 
 Salts fFreund, A. 120, 76; Kalle, .4. 119, 
 161). — ^BaA 2 aq : pearly plates, si. sol. "alcohol. 
 — CuA'j6aq: large blue tables, sol. alcohol. — 
 AgA'Saq: tables. — ZnA'2 6aq: six-sided tables. 
 
 Methyl ether MeA.'. S.G. 1^ 1-27. Formed 
 by action of NaOMe upon Ph.SOjCl in ether (R. 
 Ilubner, A. 223, 235). Oil. 
 
 Ethyl ether EtA'. S.G. 1^ 1-22. From 
 NaOEt and PhSOjCl in ether. Formed also by 
 oxidising PhSO^t (Otto a. Bossing, B. 19, 1225). 
 Oil, miscible with alcohol, ether, and benzene. 
 Saponified by boiling water. 
 
 Propyl ether PrA'. S.G. ii M79 (H.). 
 
 Phenyl ether PhA'. [35°]. Formed by 
 acting upon Ph.SO^Cl dissolved in benzene with 
 sodium-phenol. Formed also by action of zinc- 
 dust on a mixture of phenol and PhSO^Cl. 
 Trimetric crystals, a:b:c = -6847:1: -8076. V. sol. 
 benzene, ether, and alcohol, insol. water. 
 Slowly saponified by boiling aqueous KOH; 
 alcoholic NH3 even at 200° does not affect it. 
 On nitration it gives the nitro-phenyl ether, and 
 also a tri-nitro- derivative [116°] (Sohiaparelli, 
 G. 11, 66 ; B. Otto, B. 19, 1832). 
 
 p-Nilr -phenyl ether C.B.ySOs.C.H.tC^O^). 
 [82="]. Formed by nitrating the preceding; or 
 from p-nitro-phenol, ZnCl^, and PhSO^Cl (Sohia- 
 parelli, a. 11, 70). SI. sol. cold alcohol. 
 
 Chloride Ph.SOjCl. — Benzeiie sulphochlo- 
 
 ride. (247°). S.G. 33. 1-378. Formed by the 
 action of PCI5 on a salt of benzene sulphonio 
 acid (Gerhardt a. Chancel, C. R. 35, 690), or by 
 passing chlorine into an aqueous solution of 
 PhSOjH (Otto a. Ostrop). Oil ; v. sol. alcohol and 
 ether. Slowly solidifies at 0° forming large 
 rhombic crystals. May be distilled in vacuo, but 
 is much decomposed on boiling under atmospheric 
 pressure. Hardly attacked by water. 
 
 Reactions.— 1. Tin and HCl form phenyl 
 meroaptan. — 2. Sodium amalgam or Tii^E^t^toTcas 
 a benzene sulphinate.— 3. PCI5 at 210° gives 
 CeHjCl, phosphorus oxychloride, and SOjOl, 
 (Kekul6 a. Barbaglia, B. 5, 876).— 4. PbO, gives 
 at 180° PbSO^ and C^H^Cl (Wallach, A. 214, 
 219). — 5. Phenol (1 mol.) and zinc-dust gives 
 Ph.SOjPh; phenol (J mol.) and ZnCl^ gives 
 Ph.S02.C„H..O.S02.Ph (?) [123°] (Sohiaparelli, 
 0. 11, 66). 
 
 Bromide Ph.SOaBr. From PhSO.H and 
 Br (Otto, A. 141, 372). Oil. 
 
 Amide Ph.SO.^NH,. Benzene sulphamide. 
 Benzene sulphonamide. [156°] (Hybbeneth, A. 
 221, 206). S. -43 at 16°. Formed by the action 
 of NH, on the chloride or bromide (Otto a. 
 Ostrop, A. 141, 365), or, in small quantities, by 
 heating the ammonium salt at 200° (Stenhouse, 
 Pr. 14, 351). Needles (from water) or plates 
 (from alcohol). V. si. sol. water, sol. hot NH,Aq, 
 v. sol. alcohol and ether. Ammoniacal AgNO, 
 gives a pp. of Ph.SO^.NHAg. With PCI5 the 
 amide gives Ph.SO^.NH.PClj [131°] (Wichelhaus, 
 B. 2, 502). Sucoinyl chloride gives rise to 
 PhS02N:(C.,OJC2Hj, [160°], whence cone. NHjAq 
 produces Ph.SO.,.N.CO.CjHj.COjNHj, [165°] 
 (Gerhardt a. Chancel, C. R. 35, 690 ; Gerhardt 
 a. Chiozza, A. Ch. [3] 47, 129). 
 
 Benzoyl derivative'Ph.SO.^SB.'Bz. [147°]. 
 From benzene sulphonamide and BzCl at 145° 
 (Gerhardt, A. 108, 214 ; WaUach, A. 214, 210). 
 Prisms (from alcohol). Salt.— PhSO.^NNaBz. 
 Silky needles (from alcohol). Reactions. — 1. 
 PCI5 gives the imido-chloride Ph.S02.N:CCl.Ph 
 [80°]. This forms tricUnic plates (from benzo- 
 line) a:6:c = -862:1: ?,o = 87° 59', j8 = 94° 31', 7 = 
 08° 24'. When this imido-chloride is heated 
 it splits up into benzonitrile and benzene 
 sulpho - chloride (Wallach a. Gossmann, A. 
 214, 210). Aniline converts the imido-chlor- 
 ide into phenyl-sulphonyl-phenyl-benzamidine 
 (PhSOjN):C(NHPH).Ph.— 2. The Pb and Ag de- 
 rivatives are converted by EtI at 100° into the 
 original amide (Bemsen a. Palmer, Am. 8, 235). 
 Di-benzoylderivativeFhSO^}!iBz2.(l05°]. 
 Methylamide Ph.SO2.NHMe. An oil, 
 formed by treating the chloride with aqueous 
 methylamine (Eomburgh, R. 3, 16). 
 
 Methyl-nitro-amide Ph.S02.NMe(N02). 
 [44°]. From the preceding and HNO, (S.G. 1-48). 
 Ethylamide'Ph..S0^.1AM'B.. [68°]. From 
 the chloride and NEtHj (Bomburgh, R. 3, 13). 
 
 Ethyl-nitro-amide Ph.S02.NEt(N02), 
 [44°]. Formed by the action of HNO3 on the 
 preceding or on the succeeding compound. 
 Needles (from alcohol) ; volatile with steam. 
 Di-methylamide OeH^.SOoNMej. [48°]. 
 Di-ethylamide Ph.SO^.NEtj. [42°]. 
 Anilide Ph.SO^NHPh. [102°] (Wallach, 
 A. 214, 221). S. 4-3 at 16°. From the chloride 
 and anUine (Biffi, A. 91, 107 ; Gericke, A. 100, 
 217 ; Meyer a. Ascher, B. 4, 326). 
 
458 
 
 BENZENE SULPHONIC ACID. 
 
 p-Chhro-anilide PhS03.NH.C^HiCl. [122°]. 
 From the preceding and PCI5, or from PhSO^Cl 
 and jp-ohloro-aniline (Wallaoh a. Huth, JS. 9, 
 425). 
 
 o-Nitro-anilide Pli.SOj.NH.0,H,(NOj) 
 [1:2]. [104°]. From o-nitro-aniline and PhSOjCl 
 (Lellman, A. 221, 1%;B. 16, 594). YeUow 
 plates, sol. alcohol, glacial HOAo, and CHCI3. 
 
 m-Nitro-anilide Ph.S02.NH.C5Hj(N0.,) 
 [1:3]. [132°]. Fromm-nitro-aniline andPhSO^Cl 
 Flat yellow needles (L.). 
 
 p-mtro-anilide Ph.S02.NH.C„H^(N02) 
 [1:4]. [139°]. From ^'-iiitro-aniline and 
 Ph.SOjCl. Yellow crystals. 
 
 o-Amido-anilide Pli.S02.NH.C„Hj(NH2) 
 [1:2]. [168°] . From the o-nitro-anihde by tin 
 and HCl (L.). Needles (from 60 p.c. alcohol). 
 V. sol. alcohol, si. sol. ligroin. — B'HCl. 
 
 p-Toluide Ph.SO^.NH.CsH^Me [1:4]. 
 [120°]. From the chloride and ^'-tolii^ine 
 (Wallach a. Huth, B. 9, 427). 
 
 m-Nitro-p-toluide 
 Ph.SO,.NH.C5HsMe(N02) [1:4:8]. [99°]. From 
 the preceding by nitration; or from Ph.SOjCl 
 and nitro-^-tolnidine (LeUmann, A. 221, 18). 
 Cubes (from alcohol). Not attacked by alco- 
 holic KOH. 
 
 Di-nitro-p-toluide 
 Ph.S02.NH.C„H,Me(N0,)2. [178°]. Formed by 
 nitration of the ^toluide. Yellow prisms, si. 
 sol. cold alcohol (LeUmann, B. 16, 595), Not 
 attacked by alcoholic KOH. 
 m-Amido-p-toluide 
 Ph.S02.NH.C,HsMe(NH3) [1:4:3]. [146-5°]. From 
 the nitro- compound by tin and HCl. Colourless 
 needles (from dilute alcohol) ; si. sol. water. 
 
 di-phenyl-amide Ph.SOjNPh^. [124°]. 
 From PhSO^Cl and NHPh^ at 200° (Wallach, 
 A. 214, 220). Silk-like needles (from alcohol). 
 Sol. alcohol, ether, or benzene, insol. water. 
 Cone. HjSOj forms a blue solution. Insol. 
 HClAq. 
 
 Phenyl-hydrazide CuHjjNjOjS i.e. 
 Ph.SOj.N^HjPh. Phenyl-bemene-sulphazide. 
 Di-phenyl sulphaside. [148°-150°]. Forina- 
 Uon'. — 1. By the action of SO^ upon diazo-beu- 
 zene (Kcenigs, B. 10, 1531 ; Wiesinger, B. 10, 
 1715). — 2. From benzene snlphonio chloride and 
 phenyl -hydrazine (Fischer, A. 190, 132).— 3. 
 From benzene-sulphinic acid (3. v.) and phenyl- 
 hydrazine hydrochloride (Escales, B. 18, 893). — 
 4. By reduction of CjHj.N2.SO2.C5H5 with zinc- 
 dust and acetic acid. Prepa/ration. — Aniline is 
 dissolved in alcohol saturated with SO, ; the 
 solution is cooled below 0° and a cone, solution 
 of about double the theoretical quantity of KNO^ 
 is slowly added ; after standing for 24-36 hours 
 it is precipitated by water ; the yield is 80 p.c. 
 Properties. — White felted needles (from alcohol). 
 With NaOEt it gives a very unstable crystalline 
 sodium compound CijHuNaNjSOj. Beaction. — 
 By boiling with aqueous alkalis (i.e. baryta- 
 water) it is decomposed into benzene sulphinio 
 acid, benzene, and N^; Ph.N^H^.SO^.Ph = PhH -F 
 PhSOjH + Nj (E., B. 18, 893; Limpricht, B. 20, 
 1238). 
 
 BENZENE-o-DISUIPHONIC ACID CsH^S^Oj 
 Le. CjH^(S0jH)2 [1:2]. From amido-benzene 
 m-sulphonic acid by sulphonation, diazotisa- 
 lion, and boiling with alcohol (Drebes, B. 9, 
 653). 
 
 Chloride C„Hj(S0201)2. [105°]. Foat. 
 sided plates. 
 
 Amide C,Hj(S02NH^)j. [233°]. 
 
 Benzene-m-disulphonic acid OgH4(S03H), 
 [1:3]. 
 
 Formation. — From amido-benzene p-sm- 
 phonic acid by sulphonation, diazotisation, and 
 heating with alcohol (Zander, A. 198, 8). 
 
 Preparation. — When benzene or benzene 
 snlphonio acid is treated with fuming H^SO, 
 both m and p disulphonic acids are formed. 
 The m acid is formed chiefly when the tempera- 
 ture is low or when the mixture is kept at a 
 high temperature for a short time only (Buckton 
 a. Hofmann, C. J. 9, 255: Barth a. Senhofer, 
 B. 8, 754, 1477 ; 9, 969 ; Limpricht, B. 9, 550; 
 Korner a. Monselise, B. 9, 583). Benzene (1 pt.) 
 is freed from thiophene by shaking with cone. 
 H2SO,, and is then dissolved in fuming (70 p.c.) 
 sulphuric acid (4 pts.) at 40°. The solution is 
 heated for 2 hours at 275° ; cooled ; poured into 
 water, and neutralised with lime ; CaSOj is re- 
 moved by filtration, and the lime salts of the 
 m and p acid may be separated by crystallisa- 
 tion, the former separating first (Binschedler a. 
 Busch, Monit. Scient. 1878, 1169 ; cf. Egli, B. 
 8, 817 ; Heinzelmann, A. 188, 159). 
 
 Properties. — Very deliquescent crystals (con- 
 taining 25aq). The alkaline salts are v. sol. 
 
 Salts.— Na2A"4aq.—K2A"aq. S. 66-6 at 
 100°. — BaA"2aq. S. 44-2 at 100°. Large 
 prisms.— CuA"6aq : v. sol. water. — CaA" Ijaq. — 
 ZnA"4aq.— PbA"2aq. S. (of PbA") 86-2 at 26°.— 
 Ag^A". 
 
 Beaction. — 1. By fusion with potash or soda 
 it is converted into resoroin. The acid is first 
 converted into ra-phenol sulphonio acid (at 180°). 
 The amount of resorcin formed by fusing this 
 body (1 mol.) with potash (24 mols.) at 270° for 
 10 minutes is 2-7 p.c, at 270° for 20 minutes it 
 is 21 p.c, and at 250° for 30 minutes it is 26 p.c. 
 When soda, or a mixture of potash and soda, is 
 used, the yield is rather less (Degeuer, /. pr. 
 128, 318). — 2. Bj fusion yfith potassiv/m cyanide 
 the potassium salt is converted into C5H4(CN)j, 
 which, when boiled with potash, gives isophthalio 
 acid (Wislicenus a. Brunner, B. 4, 984 ; Eoss- 
 Garrick, Z. 5, 549 ; Barth a. Senhofer, A. 174, 
 238 ; B. 8, 754 ; V. Meyer a. Michler, B. 8, 672). 
 
 Chloride 0,B.,{SOfil),. [63°]. From 
 sodium benzene disulphonate and PCI5 or 
 SjOjClj (Heumann a. Kochlin, B. 16, 483). Mono- 
 sytometrical crystals, a:6:c = l'1991 : 1 : 0-8688, 
 18 = 85° 44' (Otto, B. 19, 2424). 
 
 Amide C.HtiSO^TH'ki)!. [229°]. Needles. 
 
 Benzene-^-disulphonieacid C5Hj(S03H)2 [1:4], 
 Prepared as above. The potassium salt distilled 
 with KCN gives di-oyauo-benzene, which, on 
 saponification, gives terephthalio acid (Wislicenus 
 a. Brunner, B. 4, 984). 
 
 Salts. -K2A"aq: thin plates. S. (of E^A") 
 66-6 at 100°.— BaA"aq. S. (of BaA") 7-19 at 100°.— 
 CaA"aq.— CuA"4aq.— PbA"aq. S. (of PbA") 
 24-9 at 26°.— ZnA"4aq. 
 
 Chloride G,'H,(SO..Cl)^. [131°]. Needles. 
 
 Amide CjH4(S0jNHj)a- [288°]. Thin 
 scales (from water). 
 
 s-Benzene-tri-Bulphonic acid CaH3(S03H)3 
 [1:3:5]. Prepared by heating 5 pts. of the potassium 
 salt of the mono- or m- di-sulphonio acid with 6 
 
BENZENYL-AMIDO-NAPHTHYL MEROAPTAN. 
 
 469 
 
 pts. of ordinary H^SO, in an open diah till H^SO^ 
 volatilises ; this ready sulphonation is probably 
 due to the presence of KHSO, or of potassium 
 pyrosulphate. By heating the potassium salt 
 with KCN the nitrile of trimesio acid C,H,(C02H)j 
 is obtained. NaOH fusion yields phloroglucin. 
 The Ba salt is sparingly soluble in water. 
 
 Salts.— K,A"'3aq.—Ba3A"',.—Ba,A."'j6aq.— 
 Pb3A2"'4aq : slender needles, v. sol. water. — 
 Ag3A"'3aq (Senhofer, A. 174, 243). 
 
 Chloride: [184°]. Amide: [306°] (Jack- 
 son a. Wing, B. 19, 898). 
 
 Benzoyl-amide CbH3(S02NHBz)3. [285°]. 
 
 4;iiZi(ZeCsH3(S02NPhH)2[237°](J.^m.9,346) 
 
 Derivatives of the sulphonie acids of benz- 
 ene are described as — Diazobenzene sulphonio 
 
 ACn> (p. 405), SULPHO-BENZENE-AZOXY-BENZENE 
 
 soLPHONio ACID (p. 428), Amido-, Bbomo-, Bkomo- 
 AMIDO-, Beomo-nitko-, Ohlobo-, Iodo-, Methyl-, 
 NiTBO-, Propyl-, benzene sulphonio acids. 
 
 BENZENE DI-STTLPHOXIDB v. Phenyl 
 Benzene-thiosulphonatb. 
 
 BENZENE SULPHYDBATE v. Phenyl meh- 
 
 CAPTAN. 
 
 BENZENE THIOSITLPHONIC ACID 
 03H,.S0,.SH. 
 Preiparation. — 1. By the action of KHS on 
 benzene-sulphonio chloride. — 2. By heating a 
 solution of a salt of benzene-sulphinic acid with 
 sulphur. 
 
 Salts. — KA': y. sol. hot alcohol and water. 
 — NaA'liaq. 
 
 Ethyl ether CsHj.SOj.SEt. Ethyl- 
 phenyl-di-sulphoxide. From the potassium 
 salt and EtBr. Colourless heavy oil. Insol. 
 water, miscible with alcohol and ether. Slowly 
 volatilises with steam. On reduction with zinc 
 and HjSOi in alcoholic solution it gives phenyl 
 mercaptan and ethyl mercaptan. Boiling 
 KOHAq gives benzene sulphinic acid and di- 
 ethyl di-Bulphide (Otto, B. 15, 127). 
 
 Ethylene ether A'AH^: [85°]. Formed 
 by heating an alcoholic solution of the Na or 
 K salt (2 mols.) with ethylene bromide (1 mol.). 
 Small thin silky needles. Without taste or 
 smell. V. sol. benzene and hot alcohol, far less 
 in cold alcohol. By warming with aloohoKc 
 KOH it gives benzene sulphinic acid, ethane di- 
 Eulphinio acid CjHjCSOjH)^, and di-ethylene 
 tetra-sulphide (C^HJ^Si. By warming with 
 alcoholic KES it gives the potassium salt and 
 ethylene mercaptan C2H4(HS)2. If the alco- 
 holic solution is warmed with ethylene mer- 
 captan, benzene sulphinic acid and di-ethylene 
 tetra-sulphide are produced. On reduction it 
 gives primarily benzene sulphinic acid and 
 ethylene mercaptan. By warming with alco- 
 holic HjS it is converted into phenyl tetra- 
 Bulphide, ethylene sulphydrate, &e. (Otto a. 
 Bossing, B. 20, 2079, 2090). 
 
 Phenyl ether C5H5.SO2.SCSH5. Benzene 
 di-sulphoxide. Diphenyl di-sulphoxide. [45°]. 
 Formed by the decomposition of benzene sul- 
 phinic acid (2. «.) by boiling water, or even by 
 spontaneous decomposition (Pauly a. Otto, B. 
 9,1639; 10,2181; 11,2070). Monosymmetrical 
 prisms, a:6:c = l-446:l:l-4709 (Otto, B. 15, 131). 
 Beactions. — 1. By saponification with alkalis 
 it is decomposed into benzene sulphinic acid 
 and di-phenyl-di-sulphide : 
 
 3C,Hs.S0j.S0jHs -h 2H,0 =- 
 
 4C„H,.S02H-F(CeH3)2Sj. This probably takes 
 place in two stages : 
 
 (a) 2C,H5.SO.,.S08H5 h- 2H,0 = 
 
 30,Hs.SO,H-i-CsH3.SH. 
 (6) 0,Hj.S02.SC3H5-h C,Hj.SH = 
 C„H,.S0,H-H(C„H3),S,. 
 The benzene-thiosulphonio-phenyl-ether reacts 
 in the cold with sodium phenyl meroaptide 
 according to the last equation (6) (Otto a. 
 Eossing, B. 19, 1235).— 2. Zinc-dust added to 
 an alcoholic solution gives zino phenyl mer- 
 captide and zinc benzene sulphinate. — 3. H^S 
 forms benzene sulphinic acid, phenyl mercaptan, 
 phenyl tetra-sulphide, &c. — 4. Zino phenyl mer- 
 captide added to an alcoholic solution gives di- 
 phenyl di-sulphide and zino benzene sulphi- 
 nate. — 5. Phenyl mercaptan on heating forms 
 di-phenyl di-sulphide and benzene sulphinic 
 acid. — 6. Ethyl mercaptan at US'" gives di-ethyl 
 di-sulphide, phenyl-ethyl disulphide,- di-phenyl 
 di-sulphide, and other products (Otto a. Eossing, 
 B. 19, 3137). 
 
 BENZENYL ALCOHOIi t>. Ori^-BBNZoio 
 
 ACID. 
 
 BENZENYI-AMIDINE v. Benzamidinb. 
 BENZEN YI-TBI-AMIDO-BEH ZENE 
 
 0,3H„N3 Le. Ph.C<^^^>CeH3.NH,. [240°]. 
 
 Amido-phenylene-benzamidine. From benzenyl- 
 nitro-phenylene-diamine, tin, and HCl (Hiibner, 
 
 A. 208, 309). Needles, v. si. sol. water, v. sol. 
 alcohol.— B"2HC1.- B"2HNOs.— B"H2S04 2aq. 
 
 Benzoyl derivative 
 
 Ph.C<^^>C«H3NHBz. [125°-214°]. From 
 
 di-benzoyl-nitro-phenylene-diamine dissolved in 
 HOAc by boiling with tin and HCl (Euhemann, 
 
 B. 14, 2653). Plates (containing aq, from dilute 
 alcohol).— B'HCl : needles. 
 
 BENZENYL.(;8)-AMID0-a-NAPHTH0L 
 
 C„H„NO i.e. C,„H,<;l^^C.0eH5. [122°]. Prepared 
 
 by reduction of the benzoyl-derivative of 0- 
 nitroso-(o)-naphthol (Worms, B. 15, 1816). 
 Colourless needles. Sublimable. Sol. alcohol 
 and acetic acid, si. sol. water. 
 
 Benzenyl- (a)-aiaido- (fi) -uaphthol 
 
 0,A<^>C.C3H,. [136°]. 
 
 Formation. — 1. As a by-product in the re- 
 duction of (a)-nitro-(i3)-naphthy]-benzoate. — 
 2. By heating benzoyl-amido-(fl)-naphthol. — 
 (Bottcher, B. 16, 1936 ; C. C. 1884, 898). 
 
 Properties. — Long colourless needles. Sub- 
 limable. V. e. sol. alcohol, ether, and benzene, 
 si. Bol. petroleum-ether, insol. water. Dissolves 
 in strong acids. Its solutions have a beauti- 
 ful blue fluorescence. B'jHjGljPtClj : yellow 
 
 BENZENYL-(a)-AMIDO-NAPHTHYL MEB- 
 
 CAPTAN C,oHb<^|^C.C„H3. [103°]. Formed 
 
 by heating benzoyl-(a)-naphthylamine (2 pts.) 
 with sulphur (1 pt.) for two hours (yield 10 p.c.) 
 (Hofmann, B. 20, 1798). Obtained also by 
 oxidation of the thiobenzoyl derivative of (a)- 
 naphthylamine C,„H,.N:C(SH).C3H5 with potas- 
 sium ferricyanide (Jacobsen, B. ' 20, 1898). 
 Glistening colourless needles (from alcohol). 
 v. sol. ether, benzene, and hot alcohol. Verjf 
 weak base. 
 
460 
 
 BENZENYL-AMIDO-NAPHTHYL MERCAPTAN. 
 
 Pier ate B'C8Hj(N0 J,OH : [131°]; smaU 
 orange needles. 
 
 Benzenyl - (j3) - amido - napbthyl mercaptan 
 
 <3ioHa<g>C.OeH5. [107°]. Prepared by 
 
 heating benzoyl- (iS) - naphthylamine with sul- 
 phur. Felted needles.— B'jH^CljPtCli (Hof- 
 mann, B. 20, 1803). 
 
 BENZENYL- AMIDO -FEENANIHBOL v. 
 Phenahthrene. 
 
 BENZENYL-o-AMIDO-PHENOL C,.H,NO i.e. 
 
 Ph.C<g>C,H,. 
 
 815° 
 
 From 
 
 [103°]. (o. 
 
 lO-amido-phenol and BzCl or phthalic anhydride 
 (Ladenburg, B. 9, 1526). Plates (from dilute 
 alcohol). Insol. water, sol. dilute H2SO4. Split 
 up by HCl at 130° into benzoic acid and o-amido- 
 phenol. Its salts are decomposed by water. — 
 i'jHjPtCle. 
 
 BENZEHYL-DIAMIDO-DIPHENYL C.jHuNj 
 
 i.e. C,S,.C<^.^Gfi,.C^,. [198°]. From 
 
 T)enzoyl-nitro-^-amido-diphenyl, tin, and glacial 
 HOAc (Hubner, A. 209, 347). Plates (from 
 alcohol).-B'HCl.— B'jHjPtCl,.— B'^HjSO,. 
 
 BENZENYL ■ AMIDO - FHENYLENE 
 DIAMINE V. Benzenyl-tki-amido-benzbne. 
 
 BENZENYL-AMIDO-PHENYL MERCAPTAN 
 
 C.jHjNS i.e. [1:2] C8H,<;|^CPh. [115°]. (c. 360°). 
 
 Formation. — 1. By heating amido-phenyl 
 mercaptan with BzOl, with benzoic aldehyde 
 {probably benzyl alcohol is also formed), or with 
 henzonitrile (NHj being evolved). — 2. By heating 
 ■phenyl-aniUdo-acetonitrile with sulphur (H^S 
 «nd HON being evolved). — 3. In small quantity 
 by the action of benzoyl chloride on methenyl- 
 amido-phenyl mercaptan. — i. From thiobenzoic 
 anilide and alkahne KaFeOy, (Jacobsen, B. 19, 
 1068). 
 
 Preparation. — Benzanilide (2 pts.) is heated 
 ■with S. (1 pt.) for a few hours to boiling. The 
 jrield is 50 to 60 p.c. of the benzanilide used. 
 
 Properties. — Needles. Weak base. Sol. 
 alcohol, ether, CSj and HClAq. Has a pleasant 
 smeU of tea-roses and geraniums. It remains 
 almost unaltered on boiling with aqueous acids 
 or alkalis. On fusion with EOH it is decomposed 
 into benzoic acid and o-amido-phenyl mer- 
 ■captan. Salt. — B'HAuClj. 
 
 References.— UotmsiJin, B. 12, 2359 ; 13, 7, 
 1236; Tiemann a. Piebst, B. 15, 2033. 
 
 BENZENYL - AMIDO ■ THIO - CKESOL v. 
 Benzentl-amido-toltl mebcapian. 
 
 BENZENYL - AMIDO - THIO - PHENOL «. 
 Benzenyl-amido-phenyii mekoaptan. 
 
 BENZENYL - TBI - AMIDO - TOLUENE 
 
 €,.H,3N3 i.e. Ph.C^^^>C,H,Me.NH,. [|:i:3 J . 
 
 [183°]. From benzoyl-di-nitro-toluidiue, tin, 
 *nd HCl (Kelbe, B. 8, 877). Needles, insol. 
 water.— BHC1.—B'H2S04 aq 
 
 BENZENYL-TBI-AMIDO- TOLUENE 
 
 Ph.C<N^>C.H,Me.NH, [*:l «] (?). 
 
 Benzoyl derivative 02,H„N,0aq. 
 
 {195°-218°]. From di-benzoyl--4itro-»n-tolylene- 
 diamine, tin, and HCl (Buhemaun, B.U, 
 Needles (from alcohol). 
 
 BENZENYL-AMIDO-TOLYL MERCAPTAN 
 
 C„H„NS i.e. CsH3(CH3)<^>0-CA [1251. 
 
 Prepared by heating amido-tolyl mercaptan 
 CeH3Me(SH)NHj [1:3:4] with benzoyl chloride. 
 Slender needles.— B'HCl : tables, decomposed by 
 water.— (B'HCl)2PtCl4aq (Hess, B. 14, 493). 
 
 BENZENYL-AMIDOXIM v. Benz-amidoxim. 
 
 DI-BENZENYL TKI-AMINE 
 C„H,aN3i.e. {Ph.C(NH)}jNH. [109°]. Formed 
 by boiling benzamidine with kofi. Needles 
 (Pinner a. Klein, B. 11, 8). 
 
 BENZENYL - AMYL - PHENYLENE - DI- 
 AMINE V. Benzentl-phentlene-dumine. 
 
 BENZENYL - BROMO - PHENYLENE - DI- 
 AMINE 
 
 0,3H;BrN2 i.e. C^H^C^^jf >C,H3Br [|:4]. 
 
 [200°]. From benzoyl-bromo-nitro-aniline by 
 reduction (Hiibner, B. 8, 564 ; 10, 1710). Small 
 needles, insol. water. — B'HCl. — B'HNO..— 
 B'HoSOj. 
 
 BENZENYL-DICINNAMYLENE-DI-AMINE 
 PhCH:CH.CH— NHv 
 
 O33H2A i-e- I y^^ [207°]. 
 
 PhCH:CH.CH— N -^ 
 
 Phenyl - di - styryl - glyoxaUne di-hydride. 
 Formed by heating di-benzoyl-dicinnamylene-di- 
 amine with potash in a sealed tube (Japp a. 
 Wynne, O. J. 49, 470). Faint yellow crystals. 
 Boiled with HCl it forms a hydrochloride, 
 sol. EtHO, which yields a platinoohloride 
 (C^jH^^N^HClj^PtCl,. 
 
 BENZENYL-ETHOXIM-CHLORIDE 
 CsHjCOhNOEt (125°) at 45 mm. ; (230°) at 
 760 mm. V.D. (to H) =9-26 (obs.). Colourless 
 oil. V. sol. alcohol and ether, insol. water. It 
 Is very stable towards water, acids, and alkalis. 
 Formed by the action of NaNOj and HCl 
 upon the ethyl ether of benzenyl-amidoxim 
 C„H5C(NH2):NOBt. By heating with alcoholic 
 NHj the parent substance is reproduced. By 
 heating with sodium ethylate it yields benzenyl- 
 ethoxim - ethyl ether C,H5C(0Et):N0Et (Tie- 
 mann a. Kruger, B. 18, 727 ; 1087). 
 
 BENZENYL - ETHOXIM - ETHYL ETHER 
 CBH5.C(0Et) :NOEt. a ■ Ethyl-benz-hydroxamic- 
 ethyl ether. (128°) at 40 mm.; (238°) at 
 760 mm. V.D. (to H) = 96-75 (obs.). Colourless 
 oil. Insol. water. Formed by heating benzenyl- 
 ethoxim-chloride CaH5.C(N0Et)Cl with sodium 
 ethylate. By HCl it is decomposed into benzoic 
 ether and the ethyl-ether of hydroxylamine 
 H,N.OEt (Tiemann a. Kruger, B. 18, 742). 
 
 BENZENYL-ETHYL-AMIDINE CgH^Nj i.e. 
 PhC(NEt).NH2. From benzamidine and EtI 
 (Pinner a. Klein, B. 11, 7). Oil.— (B'HCl)2PtCl.. 
 
 DI-BENZENYL-IMIDO-AMIDE v. Di-benz- 
 
 ENYL-TEIAMINE. 
 
 BENZENYL - ETHYL - PHENYLENE - DI- 
 AMINE v. Benzenyl-phenylene-diamine. 
 
 BENZENYL-METHOXIM-CHLORIDE 
 CsH^-CChNOMe. (225° uncorr.). V.D. 74-95. 
 Formed by the action of HCl and NaNO^ 
 upon the methyl ether of benzenyl-amidoxim 
 C„H3.C(NH3):NOMe (Kriiger, B. 17, 1689 ; 18, 
 1057). Oily fluid. Very volatile with steam. 
 Sol. alcohol, ether, benzene, and ligroin, insol. 
 water. 
 
 BENZENYL - METHYL - PHENYLENE - DI • 
 AMINE V. Benzenyl-pbenylene-diauine. 
 
BENZENYL-XYLYLENE-DIAMINE. 
 
 BENZENYL - NAPHTHYI - AMIDINE v. 
 
 Naphthtl-benzamdjine. 
 
 BENZENTL-NAPHTHYLENE-DIAMINE 
 
 C„H„N, i.e. PhC<jj^>Ci.H„. [210°]. From 
 
 benzoyl-nitro-{;8).naphthylamine, tin, and HCl 
 in presence of alcohol (Ebell, A. 208, 328). 
 Yellowish crystals, si. sol. water, v. sol. alcohol. 
 Salts. — B'HCl. — B'HNOj. — B',H,SO,. — 
 B'CjH„I: small needles ; NaOHAq or hot water 
 removes the isoamyl iodide. 
 
 BENZENYI-OXAMIDINE is Benzentl-amid- 
 oxiM {q. v.). 
 
 BENZENYL. OXIMIDAMIDE is Benzentl- 
 
 AMIDOXIM {q. v.). 
 
 BENZENYL-PHENYL-AMIDINE v. Phenyl- 
 
 BENZAMIDINE. 
 
 BENZENYI-DI-PHENYL-DI-AMINE v. Di- 
 
 PHENTL-BENZ-AMIDINE. 
 
 BENZENYL-0-PHENYLENE-DI-AMINE 
 
 0„H.„N, i.e. G,H,.C<^^>C,H^. [280°]. 
 
 Anhydro-bemoyl-di-amido-benzene. From ben- 
 zoyl-o-nitro-aniline, tin, and HCl (Htibner, A. 
 208, 302; 210, 828). Plates (from glacial 
 HOAo). M. Bol. alcohol, si. sol. benzene and 
 water. 
 
 Salts .—B'HCl. — B'ja -PtCl.. — B'HI aq.— 
 B-HNO,.- B'jHjS04llaq. 
 
 Reactions. — 1. Benzoyl chloride at 200° 
 has no action. — 2. Heated with cyanogen 
 iodide and benzene, pale yeUow crystals of 
 
 Ph.O<^^(^^)>CeH< [106°] are formed (Howe, 
 
 Am. 5, 416). — 3. Methyl iodide forms 
 C.aHjMeNjMel, [141°], whence potash forms 
 C,3H,MeNjMeOH [152°], insol. hot water, si. 
 Bol. cold alcohol. It forms the follow- 
 ing crystalline salts: C^HaMeNaMeCl aq. — 
 (C„Hs,MeNjM:eCl)jPtCl,.— C,3H5,MeNjMeI,[280°]. 
 CijHjMeNjMeNOa. — C.aHsMeN^MeSO^H aq.— 
 4. Ethyl iodide forms at 180° CisHsEtNj, m. 
 sol. water. It forms soluble crystalline salts, 
 B'HCl and B'^H^SO^.- 5. Ethyl iodide at 210° 
 forms CijHgEtNjEtlj [155°] whence hot potash 
 liberates the crystalline ammonium base 
 C,3Hs;EtN2EtOH [132°], insol. water and alkaUs, 
 b1. sol. cold alcohol, v. e. sol. benzene and 
 ligroin. Its salts are crystalline and not de- 
 composed by NHj, NajCOs, or cold KOH, but 
 hot potash liberates the base. Salts. — 
 CiaHgEtNjEtCl 2aq. — (C,3HsEtN2EtCl)2PtCli. 
 — CiaHjEtNjEtl. — CisHjBtNjEtSO^Haq.— 
 6. Isoamyl iodide at 170° gives C,3Hg(C5H„)N.. 
 Salts. — B'HCl. — B'HI. — B'HNOa.- 
 B'H2S04 2aq.— 7. Isoamyl iodide at 165° for 24 
 hours gives 0i3H3(C5H„)Nj(C5H„)l3 [112°]. The 
 free ammonium base, C,3Hj|(C5H„)N2C5H,,OH 
 [81° and 92°] crystallises from alcohol, and is 
 insol. water. Salts. — B'CsHuClaq (and 3aq). — 
 B'2(C,H„),PtCl„. - B'C3H„N03.HN03. [90°].- 
 B'CsH,,!. — 8. Cone, nitric acid forms a nitro- 
 compound, C,3H„(NOj)N2, [196°].— 9. H^SO, 
 forms an unstable sulphonic acid. 
 
 BENZENYL • PHENYLENE ■ DIAMINE •^- 
 
 CAKBOXYLIC ACID C^,<™>C.CsH,.C02H. 
 
 Slender needles (containing l|aq). Almost 
 insol. in cold, v. sol. in hot, water. Prepared 
 by the oxidation of toluenyl-phenylene-diamine 
 
 4U1 
 
 C.H,<^^C.C„H, CH3 with K^CrA and 
 H,SO,. 
 
 Salts.— BaA'jCaq : small needles, si. sol. 
 water.— CaA'2 5aq : slender needles.— EA' 7aq: 
 long needles, v. e. sol. water. — AgA' : white 
 gelatinous pp. . 
 
 Reaction. — The silver salt on distillation 
 gives a ketone ' Anhydro-tolyl-ketamine' 
 C„H„N,0 or 
 
 C«H,<^jf>C.03H,.CO.C3H,0<NH-^C,H, 
 
 [277°] which forms salts B"2HC1 and B"H2PtCl„. 
 Ethyl ether EtA'.— [243°] ; colourless 
 needles (Stoddard, B. 11, 293 ; Bruckner, A. 205, 
 113 ; Hubner, A. 210, 337). 
 
 BENZENYL - PHENYL - THIUEAMIDOXIM 
 
 C,H,.C(NH.CS.NHC3H,):N0H. [163°]. Formed 
 by the combination of phenyl-thio-carbimide 
 with benz-amidoxim (Kriiger, B. 18, 1060). 
 Plates. V. e. sol. alcohol, ether, and benzene. 
 
 BENZENYL-PHENYL-UBAMIDOXIM 
 
 C8H,.C(NH.CO.NHCeH3):NOH. [115°]. Formed 
 by the combination of phenyl cyanate with 
 benz-amidoxim (Kriiger, B. 18, 1059). White 
 plates. V. B. sol. alcohol, ether and benzene, 
 insol. cold water. 
 
 BENZENYL-TOLYLENE-DIAMINE 
 
 C„H„N,i.e. C,H,.C<^^>C3H3.0H, [J:*]. 
 
 [240°]. From benzoyl-nitro-p-toluidine, tin, and 
 HCl (Hiibner, A. 208, 316). Also by heating 
 acetophenone with o-tolylene-diamine (Laden- 
 burg a. Eugheimer, B. 12, 951). Crystalline, 
 insol. water, v. sol. hot alcohol; mav be dis- 
 tilled. 
 
 Salts. — B'HCl : needles ; si. sol. cold water 
 and alcohol.— B'jHjSO, : needles; v. si. sol. cold 
 water. 
 
 Reactions. — 1. Methyl iodide at 240° gives 
 C„H„MeNjMel3 [106°] whence KOH forms 
 C„H„MeN2MeOH [144°], insol. water, of which 
 base the following salts are crystalline, viz. : 
 
 CHH„Me2NjC12aq.— (C.jH.iMe^NjjjPtCl,.- 
 CnHi.MejNjI.- CnHiiMe^N^SO^H. Nitrous acid 
 produoesanitro-compoundC„H,3(N02)MejN20H. 
 [165°] (Hubner, A. 210, 371) which forms a 
 platinochloride, (C,4H,„(N03)Me2N2Cl)2PtCl„ and 
 reduces to an amido-oompound. — 2. Ethyl iodide 
 at 300° gives C„H„Et2N3l3 [129°] whence 
 ChHuELNjOH [153°] and its salts 
 
 0„H„Et2N2ClHCl.-(C„H„Et2N2)2PtCl,.- 
 C^H.iEt^NjI.- C^Hi.EtjN^SO^H aq. 
 
 BENZENYL -p - TOLYL - TOLYLENE - DI - 
 
 AMINE ^'^«<^^C.03H3. [166°]. Needles or 
 
 prisms. Formed by reduction of benzoyl-nitro- 
 di-tolyl-amine with tin and HGl. 
 
 Salts.— B'HClaq.-B'^HjSO/ : prisms (LeU- 
 mann, B. 15, 832). 
 
 BENZENYL-XYLYLENE-DIAMINE 
 
 C,3H„N, i.e. C,H3.C<^2>C,H2Me, [«:l:s]. 
 
 [195°]. From benzoyl-nitro-xyUdine [185°], tin, 
 and glacial HOAc (Hiibner,^. 208, 320). Needles, 
 insol. water. Boiling fuming HNO3 forms a 
 compound, crystallising in yellow needles [202']. 
 S alts.— B'HCl.— B'HN0s.—B'2HjS04.— 
 B'HjCA. 
 
462 
 
 BENZENYL-XYLYLENE-DIAMINE. 
 
 Benzenyl-xylylene-diamine 
 
 C»H5C<^^g>CjHjMe2. [215°]. From benzoyl- 
 
 nitro-xylidine [178°]. Needles. — B'HClSaq 
 (Hubner, B. 10, 1711). 
 
 BENZ-EEYTHEENE Oj.H.s [307°-308°]. 
 Formed in leading benzene through a red-hot 
 tube (Berthelot, J. 1866, 541 ; 1867, 599, 605 ; 
 Schultz, B. 11, 95). Small leaflets. Almost 
 insoluble in alcohol, difficultly soluble in hot 
 acetic acid and in cold benzene. 
 
 BENZ-FUEIL C^^p, i.e. Ph.CO.CO.CHjO. 
 [41°]. From benz-furoin and Fehling's solution 
 at 50° (Fischer, A. 211, 229). Yellow needles. 
 Y. sol. alcohol or ether (unlike furil). Volatile. 
 
 Tetra-bromide CiaHsOsBr^. [127°-128°]. 
 Yellow needles. 
 
 BENZFTJEILIC ACID C,2H,„04 i.e. 
 C4HjO.CPh(OH).C02H. From benz-furil and 
 aqueous KOH at 60°. Prisms (from a mixture 
 of ether with light petroleum). Turns brown 
 at 108°. V. sol. ether, alcohol, or chloroform ; 
 si. sol. light petroleum. Its aqueous solution 
 gradually decomposes. The crystals in cone. 
 H2SO4 give a blood-red colour, turning brown. 
 The oily residue got on evaporating an ethereal 
 solution of benzfurilic acid gives with cone. 
 H2SO4 a reddish-violet colour, water then gives 
 a blackish-blue pp., which dissolves in cone. 
 HjSO, giving a blue colour (E. Fischer, A. 211, 
 231). 
 
 BENZ-FUEOiN C,2H,„0., i.e. Either 
 Ph.CH(OH).CO.C4H30 or C4H30.CH(OH).CO.Ph. 
 [137°-139°]. From furfurol (18 g.), benzoic 
 aldehyde (20 g.), alcohol (60 g.), water (80 g.), 
 and KCN (4g.) ; by boiling for 20 minutes (E. 
 Fischer, A. 211, 228, B. 13, 1339). Slender 
 prisms (from alcohol). May be distilled. V. 
 sol. hot alcohol, chloroform, or benzene, si. sol. 
 water or light petroleum. Alcoholic KOH forms 
 a dark-red solution vrith bluish-green reflex. 
 
 BENZGLYCOCYAMIlSrE CsHpNsOj. Formed 
 by boiling the dicyanide of m-amido-benzoic acid 
 {v. p. 157) with KOHAq (Griess, B. 1, 191 ; 3, 
 703 ; Z. 4, 725 ; 6, 728) or by the action of cyan- 
 amide on an alcoholic solution of ni-amido- 
 benzoio acid containing NH, (Griess, B. 7, 575), 
 Thin white four-sided plates (containing aq). 
 SI. Bol. hot water, v. si. sol. ether, insol. NHjAq, 
 Bol. aqueous mineral acids. Boiling baryta 
 converts it into )?i-amido-benzoic acid, urea, 
 NH3, and uramido-benzoic acid. 
 
 Salts .— B'HCl.— B'jHjPtCl^. 
 
 BENZGLYCOCYAMIDIHE CjHjNsO, i.e. 
 
 HN:C<^^2Zc(?'!>- ^""^med by the prolonged 
 heating of ' ethoxy-cyanamido-benzoyl ' (v. p. 
 155) with alcoholic NH, at 100°; or by the 
 action of cyanamide on o-amido-beuzoic acid 
 (Griess, B. 1, 191 ; 2, 415 ; Z. [2] 5, 574 ; B. 
 7, 574; 8, 322; 13, 977). Nacreous laminae, 
 V. si. sol. water, si. sol. boiling alcohol. Its 
 nitrate forms narrow laminse, v. si. sol. alcohol. 
 Platinoohloride: B'^H^PtCls. 
 
 m ■ Carbozy - phenyl - benz - glycocyamidine 
 HN.C,H4.C0 
 
 I I . Formed from a 
 
 C03H.CeH4.NH.C=N 
 mixture of ' dicyanamido-benzoyl-' 
 
 HN.CbHj.CO 
 
 I I and m-amido-benzoio acid by 
 
 NC -C-==-N 
 
 long boiling with water. Very small white 
 needles or plates. Insol. neutral solvents. 
 Tolerably strong acid. 
 
 Salts. — A"Ag2: white amorphous pp. — 
 A"2HjBa lOaq (Griess, B. 18, 2420). 
 
 ' Imido-pbenyl-benz-glycocyamidine ' so- 
 NH.CsH4.CO 
 called. HNiO^ | [1:3]. Formed bj 
 
 ^NH.CsH4.NH 
 heating cyancarbimidamidobenzoic acid with 
 o-phenylene diamine (Griess, B. 18, 2414). Six- 
 sided tables. Nearly insol. water, alcohol, and 
 ether. It has both acid and basic properties. 
 
 Salts: A'jBa.— A'HHCl : white six-sided 
 plates. 
 
 BEIfZHYDEAMIDE v. Benzoic aldehyde. 
 
 BENZHYDEAZOiN v. Tei-phenyl-hydrazoHN- 
 
 BENZHYDEOL v. Diphenyl cakbinol. 
 
 BENZHYDEOLENE C,3H,„. [210°]. Got by- 
 distilling succinate or benzoate of benzhydrol 
 (Linnemann, A. 133, 1), is identical with 
 tetra-phenyl-ethane (Zagumenny, J. B. 12, 
 431). 
 
 BENZHYDEOXAMIO ACID v. Hydkoxyl- 
 
 AMINE. 
 
 BENZHYDEYL ACETATE v. Acetyl-nwz- 
 
 HYDKOL. 
 
 BENZHYDEYLAMINE v. Di-fhenyl - Cab- 
 
 BINYLAMINE. 
 
 BENZHYDEYL-BENZOIC ACID v. Exo-OXY- 
 
 BENZYL-BENZOIC ACID. 
 
 BENZHYDEYL CAEBOXYLIC ACID v. Exo- 
 
 OXY-BENZYL-BENZOIO ACID. 
 
 BENZHYDEYL PHENOL 
 
 V. Dl-OXY-DI- 
 
 PHENYL-METHANE. 
 
 BENZHYDEYL-iso-PHTHALIO ACID v. OxY- 
 
 EENZYL-isO-PHTHALIO ACID. 
 
 BENZHYDEYL-PEOPIONIC ACID v. 7-0XT. 
 
 7-PHENYIi-BnTYIlIC ACID. 
 
 BEHZHYDEYL-PEOPIO-CAEBOXYLIC ACID 
 
 V. OXY-CAEBOXY-PHENYL-PBOPIONIO ACID. 
 
 BENZIDINE and derivatives v. Di-amido- 
 DiPHENYL arid derivatives. 
 
 BENZIL C,4H,„02 = C,H5.C0.C0.C„H5. Di- 
 henzoyl. [95°] (Limpricht a. Sohwanert) ; 
 (346°-348° corr.) (Wittenberg a. V. Meyer). 
 
 Formation. — 1. By passing chlorine into 
 melted benzoin: C„H5.CH(0H).C0.C„H5-i-CLj = 
 CsH5.C0.C0.CeH5 + 2HCl (Laurent, A. Ch. [2] 
 59, 402). — 2. By oxidising benzoin with nitric 
 acid (Zinin, A. 34, 188), and in small quantity 
 by the air-oxidation of benzoin dissolved in alco- 
 holic potash CnHijOj + = C,4H,„0j + B.fi (Lim- 
 pricht a. Schwanert, B. 4, 835). — 3. Together 
 with stilbene by heating stilbene dibromide with 
 water to 150° : SCsHj.CHBr.CHBr. C^H, + 2H,0 = 
 CsH5.CO.CO.CsH5 + 2CsH5.CH:GH.CsH5 -1- 6HBr 
 (L. a. S., A. 145, 338).— 4. Together with tolane 
 by heating tolane-dibromide with water to 200° ; 
 2CsH5.CBr:CBr.CsH5 -1- iUjO = 
 C„H„02 + CeH5.CiC.CsH5 + 4HBr 
 (L. a. S., B. 4, 380).— 5. From tolane-tetra- 
 chloride by heating it with glacial acetic acid 
 or with cone. H2SO4 to 165° : 
 
 CsH5.COlj.CClj.CsH5 -f 2HjS04 = 
 C,4H,A + 2S03-f4HC1 
 (Liebermann a. Homeyer, B. 12, 1975). — 6. By 
 heating benzoyl chloride with sodium amalgam: 
 2CsH5.COCl + Naj = C„H,.Oj + 2Na01 (KUnger, 
 B. 16, 996). 
 
 Preparation. — Benzoin is heated with twice 
 
BENZIL. 
 
 463 
 
 \U weight of nitric aoid (S.Cr. 1-4) until it is 
 converted into a clear oily liquid (Zinin). The 
 product is poured into water, and the benzil, 
 which at once solidifies, is purified by recrystal- 
 lisation from boiling alcohol. 
 
 Properties. — Crystallises from hot alcohol 
 in transparent yellow needles ; from ether, by 
 spontaneous evaporation, in large six-sided 
 prisms. Insol. water, v. sol. hot alcohol and 
 ether. The crystals are optically active, showing 
 sometimes dextro-rotation, sometimes Isevo -rota- 
 tion, but having no hemihedral faces. Inactive 
 in a fused state or in solution (Descloiseaux, G. C. 
 1870, 418). 
 
 Reactions. — 1. Benzil is readily attacked by 
 reducing agents. Iron filings and acetic acid, 
 or zinc and hydrochloric acid, acting upon the 
 alcoholic solution, convert it into benzoin (Zinin, 
 A. 119, 177). When heated with alcoholic potas- 
 sium hydrosulphide at 120° it yields a mixture 
 of deoxybenzoin (CBH5.CH2.CO.CJH5) and benzoin 
 (Jena, A. 155, 87). Sodium amalgam and water 
 convert it into hydrobenzoin (Zinoke a. Forst, B. 
 8, 797). When a solution of benzil in moist ether 
 is exposed in a sealed tube to sunlight the benzil 
 is reduced to bensil-benso'in CijH^jOb [134°-135°], 
 which separates in rosettes of white or pale yel- 
 low crystals on the sides of the tube, whilst the 
 ether is converted into aldehyde. On melting 
 benzil-benzoin, or on attempting to recrys- 
 talUse it from any of the usual solvents, it 
 breaks up into benzil and benzoin : CjoHj,©^ = 
 2CHH,„0,-^C„H,20, (Klinger, B. 19, 1864).- 2. 
 Benzil is very stable towards acids. It may be 
 boiled with fuming hydrochloric acid without 
 undergoing change ; cone, sulphuric acid dis- 
 solves it, and the addition of water precipitates 
 it unaltered ; ordinary strong nitric acid does 
 not attack it. On boiling it with fuming nitric 
 aoid, however, it yields a mixture of two 
 dinitrobenzils, Ci,B.s(^O^.fii, which may be 
 separated by crystallisation: octahedral crys- 
 tals [131°], si. sol. alcohol ; and lamina) [147°], 
 less soluble than the foregoing (Zagumenny, 
 J. B. 4, 278). An isodinitrobenzil [205°] has 
 been indirectly prepared by the oxidation of n- 
 or 7- dinitro-deoxybenzo'in ; v. si. sol. alcohol, 
 m. sol. boiling benzene or glacial acetic acid 
 (Golubeff, J. B. 13, 29). A mononitrobenzil, 
 OnHj(N02)02 [110°], has also been indirectly 
 obtained by boiling 1 part of deoxy-benzoin 
 with 8 parts of nitric acid (S.G. 1-2), or by 
 adding benzoin to nitric acid (S.G. 1-5) cooled 
 to 0°. Yellow laminse or flat needles ; m. sol. 
 alcohol, more readily in ether. Hot alcoholic 
 potash decomposes it into potassium m-azo- 
 benzoate and potassium ?ra-oxybenzoate : 
 2C„H,(NOJO,-i-4KHO = 
 N,(C.H4.CO,K), + 2C,H,K03 + 2H,0. 
 Tin and hydrochloric aoid convert it into amido- 
 deoxybenzoin, C„H„(NH2)0 (Zinin, A. Suppl. 3, 
 
 153). 3. When heated with soda-Ume, benzil 
 
 yields benzene and benzophenone, C0(CbHj)2 
 (Jena, A. 155. 87); distilled overheated litharge 
 it yields benzophenone (Wittenberg a. V. Meyer, 
 B. 16, 501). — 4. When benzil is heated with an 
 equal' weight of caustic potash or caustic soda 
 dissolved in 20 parts of water, the benzil slowly 
 dissolves, forming a benzilate {v. Benzixio acw) : 
 C.H,.C0.C0.CA-t-K0H = (0A)2C(0H).C00K. 
 A small quantity of diphenyl-oarbmol is formed 
 
 at the same time by the decomposition of the 
 benzilic acid (Klinger, B. 19, 1868). Alcoholic 
 potash dissolves benzil with a violet colour ; on 
 heating, the colour is discharged and tlie solution 
 contains potassium benzilate. According to 
 Klinger (loc.cit.) aqueous potash gives this colour- 
 ation only with benzoin, and then only when air 
 is admitted. When benzil is dissolved, without 
 heating, in very dilute alcoholic potash (4 grams 
 KOH to the litre) and allowed to stand, with 
 exclusion of air, for about a fortnight, it is con- 
 verted into a mixture of two compounds, CjjH^iOi 
 [200°-201°] (Limprioht a. Schwanert's so-called 
 ethyl-dibenzo'in) and OjoHjiO^ [232°]. The alco- 
 hol takes part in the formation of these com- 
 pounds : 2C„H„02 + JIjO = CaoHj^O, + B..fi, 
 and3C„H,„02 -1- 2023:^0 = CjsHj.Oj + 4HjO. These 
 two substances can be separated by recrystal- 
 lisation from alcohol, in which the compound 
 CjoHj^Oj is the more soluble. Thecom pound 
 CjjH^iO, is si. sol. boiling alcohol, si. sol. boiling 
 benzene, v. sol. boiling glacial acetic aoid ; de- 
 posited from alcohol in colourless granular 
 crystals with 1 mol. of alcohol of crystallisation 
 which is expelled at 120° but not at 100°; 
 crystallises also with 1 mol. of acetic acid and 
 with benzene of crystallisation. The com- 
 pound CjjHjjOj is finally purified by dissolving 
 in boiling phenol and precipitating with alcohol ; 
 yellow crystalline powder; v. si. sol. alcohol, m. 
 sol. boiling phenol (Japp a. Owens, G. J. 47, 
 90 ; cf. also Limpricht a. Sohwanert, B. 4 335). 
 Benzil also reacts with isopropyl alcohol : when 
 it is dissolved in a dilute solution of caustic 
 potash in isopropyl alcohol (2:100) and allowed 
 to stand for some months in a stoppered vessel 
 a compound G„U^O, [147°-148°] is formed; 
 2C,jH,„02-hC3H,0 = C3,H2,0^-^0, a reduction 
 taking place. CjiH^jOj forms very lustrous crys- 
 tals, of rhombohedral habit, v. si. sol. boiling 
 alcohol (Japp a. Easchen, G. J. 49, 832). — 5. 
 Benzil reacts with acetone in presence of caustic 
 potash, yielding the compounds a e t o n e-b e n zil, 
 CijHijOa; anhydracetone-benzil, C|,H,,02; 
 and anhydracetone-dibenzil, C„HjjOj {v. 
 AoBTONE-BENZiL, p. 32). With methyl ethyl 
 ketoneit yields methyl-anhydracetone ben- 
 zil, CisHiijO^: colourless thin prisms [179°]; 
 with diethyl ketone, dimethyl-anhydraoe- 
 tone-benzil, C|,H,s02 : rhomboidal plates 
 [150°]; with methyl propyl ketone, ethyl- 
 anhydraoetone-benzil, C,gH„02: needles 
 [156°]; mih methyl hexy I ketone, amyl-anhy 
 dracetone-benzil, C^^H^jO^: silky needles 
 [150-5°] ; all sol. alcohol' (Japp a. Burton., O. J, 
 51, 481). — 6. Benzil reacts with ammoniii, and 
 also with aldehydes and ammonia jointly, tc 
 form a number of well-characterised contlensa- 
 tion-compounds {v. Benzil, AMMONU-EEnrvATivEs 
 op). Heated with cutiZiree in a sealed tube at 200° 
 it yields benzil-anilide, CsH5.C(N.CbH5) .CO. C„H, 
 [105°]. Yellow prisms, sol. alcohol (Voigt, J. 
 pr. [2] 34,23).— 7. Warmed with (l,2,4)-tolylene» 
 diamine in alcoholic solution it forms diphe nyl- 
 toluquinoxaline : 
 
 C.H..CO H,N, 
 
 \C.H,.CH.: 
 
 C.H..C— N, 
 
 ■ ' I H- " >C.H,.CH.= II I \c.H,.CH,+2n.O 
 
 O.F,.CO H.N^ C,H,.0— N^ 
 
 (Hinsberg, B. 17, 322). Benzil also reacts with 
 ethylene-diamine to yield a crystalline compound 
 (Mason, B. 19, 113). ~ 8. Forms compoundi 
 
464 
 
 BENZTL. 
 
 with hydroxylamine and with phenylhydrazine. 
 BenzU with free hydroxylamine in aqueous- 
 alcoholic solution at the ordinary temperature 
 yields benzil-mono-oxim OsH5.C(N.OH).CO.C|iH5 
 [130°-131°], even when an excess of hydroxyl- 
 amine is employed. Small square white leaf- 
 lets, V. sol. alcohol and ether, si. sol. water 
 (Wittenberg a. V. Meyer, B. 16, 503). Boiled 
 with hydroxylamine hydrochloride in methyl 
 alcohol, with the addition of one drop of hydro- 
 chloric acid, a dioxim, {a)-diphenyl-glyoxim, 
 C,H5.C(N.0H).0(N.0H).0,H5 [237°] separates.. 
 Forms lustrous, white laminsB, si. sol. methyl 
 alcohol, alcohol, and ether. Dissolves in cono. 
 caustic soda and is reppd. by acids. Sol. with 
 difficulty in ammonia, the solution giving with 
 silver nitrate a yellow pp. (Goldschmidt a. V. 
 Meyer, B. 16, 1617). If benzil, hydroxylamine 
 hydrochloride, and alcohol, acidulated with hy- 
 drochloric acid, are heated in a sealed tube for 
 several hours at 170°, an isomeric (ff)-diph6nyl- 
 glyoxim [206°] is formed. White needles, v. 
 sol. boiling alcohol, si. sol. ether and boiling 
 water. Sol. caustic soda and ammonia. The 
 (o)-compound can be converted into the {;3)-com- 
 pound by heating it with alcohol in a sealed 
 tube at 180°. The nature of this isomerism is 
 not understood ; but analogous cases of iso- 
 merism have been observed in the benzil and 
 benzoin groups — thus benzil and isobenzil, hy- 
 drobenzoin and isohydrobenzoin (Goldschmidt, 
 B. 16, 2177). By heating benzU with phenyl- 
 hydrazine on the water-bath, benzil-di-phenyl- 
 hydrazide, C„H5.C(N2H.CA).C(N2H.C5H5).C,H5 
 [225°], separates. Faintly yellow needles; v. 
 sol. hot chloroform and benzene, si. sol. alcohol 
 and ether. Gives a dark-violet colouration with 
 cone, sulphuric acid. Does not regenerate 
 phenylhydrazine when heated with strong hy- 
 drochloric acid (Piokel, A. 232, 230).— 9. When 
 benzil in alcoholic solution is mixed with an 
 excess of nearly anhydrous hydrocyanic acid 
 and allowed to stand, large, colourless, tabu- 
 lar, rhombic crystals of bemil dihydrocyanide 
 C,lIyC{OB.).Gii 
 
 I are deposited (Ziniu, A. 34, 
 
 0aH5.C(0H).CN 
 
 189). The same compound is formed when an 
 ethereal solution of benzil is mixed with pow- 
 dered potassium cyanide and cone, hydrochloric 
 acid is added drop by drop, cooHng during the 
 operation. Melts at 132°, with decomposition 
 into benzil and hydrocyanic acid. Insol. water 
 and benzene, v. sol. ether and light petroleum. 
 When dissolved in alcohol it is decomposed, 
 even in the cold, into benzil and hydrocyanic 
 acid (Jacoby, B. 19, 1519). When finely pow- 
 dered benzil dihydrocyanide is mixed with a 
 large excess of a concentrated solution of HBr in 
 glacial acetic acid and left for some weeks, a solu- 
 tion is obtained which by spontaneous evapora- 
 tion deposits lustrous crystals of di-phenyl-tartra- 
 
 CeH5.C(0H).C0NHj,HBr 
 mide hydrobromide | 
 
 C,H5.C(OH).CONH2 
 [185°] and these, when decomposed by ammo- 
 nia, yield the free di-phcnyl-tariramide. V. sol. 
 alcohol, V. si. sol. ether (Burton, B. 16, 2232). 
 Pure benzil dihydrocyanide is not hydrolysed 
 by cone, hydrochloric acid, but when an alco- 
 holic solution of benzil, to which an excess of 
 
 anhydrous hydrocyanic acid has been added, is 
 saturated with gaseous HCl and allowed to stand 
 for some weeks, an acid, OigHuNO, (colourless 
 prisms, sol. boiling water, melting at 196°), and a 
 compound, C,jH,2N.p [196°-197°], are formed. 
 The compound OuHj^NjO forms lustrous pale 
 yellow laminse or ilat needles, si. sol. boiling 
 water and benzene, v. sol. boiling alcohol. It is 
 feebly basic and forms with hydrochloric acid a. 
 colourless salt which is stable only in presence 
 of excess of acid (Japp a. Miller, G. J. 61, 29). 
 When benzil is heated with absolute alcohol 
 and hydrocyanic acid aj; 200° for four hours, 
 it is decomposed into benzoic aldehyde and 
 ethylicbenzoate: CA.CO.CO.C^Hs + C.,H5.0H = 
 C„H5.CHO + C5H5.COj.C2H5, the hydrocyanic 
 acid apparently undergoing no change. Benzoio 
 acid is also formed (Michael a. Palmer, Am. 7, 
 191). Benzil and alcohol may also be made ta 
 react to form benzoio aldehyde and ethylic ben- 
 zoate by triturating benzil and potassium cyan- 
 ide with alcohol ; but in this case a portion of 
 the benzaldehyde is further changed into ben- 
 zoin by the action of the potassium cyanide. By 
 neutralising with sodium carbonate the small 
 quantity of benzoic acid which is also formed in 
 this reaction, and which would otherwise decom- 
 pose the potassium cyanide, 1 part of the cyan- 
 ide may be made to induce the foregoing change 
 in 50 parts of benzil (Jourdan, B. 16, 658). — 10. 
 Benzil unites with ni/triles in presence of cone, 
 sulphuric acid, taking up the elements of water. 
 Thus when powdered benzil (1 mol.) is sus- 
 pended in cone, sulphuric acid, and propionitrile 
 (2 mols.) is gradually added, cooling during the 
 process, a compound C2||H22N.,03 [197°] is formed : 
 C,4H,„03 -I- 2C3H5N -f H,0 = C'^oH^^NjOa. Lus- 
 trous, colourless needles; V. sol. hot alcohol. 
 Boiling with dilute sulphuric acid decomposes 
 it into benzil, propionic acid, and ammonia. — 
 With benzonitrile and sulphuric acid benzil 
 yields a mixture of two compounds which can 
 be readily separated by means of their very 
 different solubilities in hot alcohol : CjgHjjNjO, 
 [168°], analogous to the propionitrile derivative, 
 V. sol. boiling alcohol, crystallises from alcohol 
 in eiHorescent oblique prisms of the formula 
 (02sH2,N203)2BtOH ; and a compound CjjH^iNOa 
 [225°], almost insol. alcohol, v. sol. boiling 
 phenol, si. sol. boiling benzene, which crystal- 
 lises from benzene in microscopic, flat rect- 
 angular prisms : 2C,4H,„02 -I- OjHsN -H H^O = 
 OjbHjiNO, + CsHj.COjH (Japp a. Tresidder, B. 16, 
 2652). — 11. Heated with somewhat more than 
 the equivalent quantity of phosphorus penta- 
 chloride, benzil yields dichlorodeoxybensoin 
 (chlorobenzil) C^B.^.GG\.CO.C„Tl^ [71°]. Short, 
 thick rhombic prisms, insol. water, v. sol. ether, 
 not so readily in alcohol. When heated with 
 alcohol or water to 180" it yields benzil and hydro- 
 chloric acid. Zinc and hydrochloric acid, acting 
 on an alcoholic solution, convert the compound 
 into deoxybenzoin ; acetic acid and zinc-dust re- 
 duce it first to deoxybenzoin, and finally to stil- 
 bene. PCljat 200° replaces the remaining oxygen 
 atom by Clj, yielding tolane tetrachloride, 
 C,,H,„C1, (Zinin, A. 119, 177 ; J. 1880, 614; A. 
 149, 374). 
 
 Isobenzil. — 1. A substance having the same 
 composition as benzil is obtained by acting witli 
 sodium amalgam on a solution of benzoyl 
 
BENZIL, AMMONIA-DERIVATIVES OF. 
 
 465 
 
 chloride in anhydrous ether (Brigel, A. 135, 
 172). Ordinary benzil is formed at the same 
 time (Klinger, B. 16, 995). Isobenzil forms 
 colourless tabular monoclinio crystals, also lus- 
 trous laminaa or needles [145°-156°], sol. alcohol, 
 ether and CS2. It is probably a polymeride of 
 benzil, for when treated with bromine it yields 
 benzil (1 mol.) and benzoyl bromide (2 mols.) : 
 CosHjjO, + Br^ = C„H,„02 + 2CjH5.COBr. Heated 
 with alcoholic potash it gives the violet coloura- 
 tion of benzil and is converted into benzUio acid 
 together vrith a small quantity of benzoic acid 
 (Klinger, loc. cit.; alsoB. 19, 1862).— 2. By heat- 
 ing benzoic aldehyde with sodium amalgam in an 
 atmosphere of C02,Alex6ef (4. 129, 347) obtained 
 an oil (814° approx.) to which he assigned the 
 formula 0„H,„02. S.G. ia= 1-104 (approx.). 
 
 P. B. J. 
 BENZIL, AMMONIA-DERIVATIVES OF. 
 There are four general reactions known, accord- 
 ing to which compounds containing the dicar- 
 bonyl-group — CO.CO — ^form oondensation-com- 
 poimds with aldehydes and ammonia jointly. 
 As a knowledge of these reactions is necessary 
 to an understanding not only of the behaviour 
 of benzil with aldehydes and ammonia, but also 
 of that of benzil with anmionia alone, the gene- 
 ral equations for these reactions will be in- 
 troduced at this stage. In the following equa- 
 tions X' stands for the monad hydrocarbon-radi- 
 cle of the dicarbonyl-compound, and B' for the 
 monad hydrocarbon-radicle of the aldehyde : 
 
 X'.CO 
 
 I +B'.CHO + NH,= 
 
 X'.CO 
 X'.C-Ov 
 
 II >0.B' + 2H20. 
 
 X'.CO 
 
 I +B'.CH0 + 2NH,- 
 X'.CO 
 
 X'.C-NH. 
 
 II >C.E' + 3H20. 
 
 X'.C W^ 
 
 X'.CO 
 
 I +2B'.CHO + 2NH,= 
 X'.CO 
 
 E'.CH.NH.CO.X' 
 
 I +2HA 
 
 B'.CH.NH.CO.X' 
 
 Here the dicarbonyl-compound is broken up 
 into two halves, whilst the two aldehyde-groups 
 become directly united. Lastly : 
 
 X'.CO 
 IV. 2 • I +E'.0H0h-2NH,= 
 X'.CO 
 
 The constitution of the compounds of the 
 last-mentioned type is unknown (Japp a. Streat- 
 feild, 0. J. 49, 155; Japp a. Hooter, O. J. 
 45, 673 ; Japp a. Wynne, C. J. 49, 464). 
 
 It will be shown later on, that in the 
 reactions of benzil with ammonia a part of the 
 benzil is first broken up with formation of 
 benzoic acid and benzoic aldehyde, which latter 
 then takes part, together with benzU and 
 ammonia, in the final reaction. The benzil- 
 ammonia reactions are therefore in reality 
 
 I. 
 
 n. 
 
 m. 
 
 benzil-aldehyde-ammonia reactions, and will be 
 more readily understood if the reactions of the 
 latter class are described first. 
 
 Beaotions op Benzhi with Aiidehydes and 
 Ammonia: — 
 
 Equation I. (vide sii/pra). — ^Benzil gives no 
 reactions according to this equation so long as 
 free aldehydes are used, but with nascent ben- 
 zoic aldehyde, produced by the decomposition 
 of a portion of the benzil, it reacts according tc 
 this equation, yielding benzilam, CjiHisNO {vide 
 infra). In the case of some other dicarbonyl- 
 oompounds, however, such as phenanthraquinone 
 (g.v.), this reaction occurs vrith various free 
 aldehydes. 
 
 Equation II. — Benzil reacts according to 
 this equation with formic aldehyde, acetic alde- 
 hyde, isooaleric aldehyde, glyoxal, benzoic alde- 
 hyde (free), and p-oxybemoic aldehyde. The 
 compounds formed are derivatives of gly- 
 
 CH— NHv 
 oxaline || ^CH. 
 
 OH N-^ 
 
 Thus when benzil and formic aldehyde are 
 warmed with ammonia in alcoholic solution at 
 about 40° diphenylglyoxaline is formed : 
 0^.00 
 
 I +H.CH0 + 2NH3 = 
 
 CeHj.CO 
 
 OA.O-NH. 
 
 II "^CH + SH^O. [The excess of aloo- 
 
 0,H,.C N-^ 
 
 hoi and ammonia is expelled by heating ; the 
 base is extracted with dilute hydrochloric acid, 
 precipitated with ammonia, and crystallised 
 from hot alcohol. It separates from hot alcohol 
 on cooling in long oblique crystals (monosym- 
 metric), and from cold alcohol by evaporation 
 in short lustrous crystals (also monosymmetric, 
 but not referable to the same parameters). 
 [227°]. Monacid base. (0,5H,2Nj,H01)j,PtCl4 : 
 pale-yellow, amorphous precipitate, speedily 
 changing into microscopic flat needles (Japp, 
 C. J. 61, 558)]. — ^When acetic aldehyde is 
 substituted for formic aldehyde in the fore- 
 going reaction, methyldiphenylglyoxaline, 
 CA-O-NH. 
 
 II J^C.CH,, is formed. [Orthorhombio 
 
 C,H3.0 N-^ 
 
 crystals [235°], T. sol. ether and hot alcohol. 
 (C,BH,4N2,H01)2,PtCl4 2aq: yellow microscopic 
 needles (Japp a. Wynne)]. The base forms a 
 molecular compound vrith diphenylglyoxaline 
 (J.)]. Benzil, isovaleric aldehyde, and ammo- 
 nia yield isobutyldi/phen/ylglyoxalmB, 
 CeH5.C— NHv 
 
 II >C.CH2.CH(Cn,)2. [Needles 
 
 CHj.C ^N'^ 
 
 [223°], sol. hot benzene and alcohol. 
 (0,jH2oNj,HCl)2,PtOl4: amorphous yellowish- 
 brown precipitate, or small crystals (J . a. W.).] 
 Olyoxal, as a dialdehyde, reacts with twice the 
 proportion of benzil and ammonia, forming 
 
 C5H5.C— NH- 
 
 \f 
 
 ^NH-C.CA 
 
 C„H,.G W^ ^N — CC^Hs 
 
 [From hot 
 
 alcohol in tufts of silky needles of the formula 
 Ca„H22N„C2HjO. Melts above 300°. Feebly 
 basic (Japp a. Gleminshaw, 0. J. 51, 553)]. 
 Benzil, benzoie aldehyde, and ammonia yield 
 
466 
 
 BENZIL, AMMONIA-DEKIVATIVES OF. 
 
 (Badziszewski, 
 
 O5H5.C-NH. 
 hphine, || ^C.C„H. 
 
 OA-C N-^ 
 
 B. 15, 1493). In a similar manner p-oxy- 
 benzoic aldehyde gives p-oxylophime, 
 
 II >0.C5Hj(0H). [Tufts of oolour- 
 
 C.H,.C— N^ 
 
 less needles [254''-255°], v. sol. hot alcohol, sol. 
 caustic soda, forming a sodium compound. 
 Heated with acetic anhydride, it forms a mon- 
 acetyl - derwatme C2,H,5(C2H30)N20 [229°] ; 
 needles, with a faint satiny lustre, sol. hot alco- 
 hol. Distilled with zinc-dust, ^-oxylophine 
 is converted into lophine (Japp a. Bobinson, 
 
 C. J. 41, 326)]. 
 
 Equation III. — Illustrations of this equation 
 are to be found in the reactions of salicylic 
 aldehyde and furfuraldetvyde (pyromucio alde- 
 hyde) with benzil and ammonia. Cinnamic 
 aldehyde also reacts according to this equation ; 
 but in this case another reaction, according to 
 Equation IV., occurs simultaneously^ 
 
 Thus when equal weights of salicylic alde- 
 hyde and benzil are dissolved in warm alcohol 
 and the liquid is saturated with gaseous am- 
 monia, the condensation compound dibensoyl- 
 dioxystilbene-diamine separates as a crystal- 
 line powder : 
 
 CO.C.H5 
 208H^(OH).CHO-h I +2NH3 = 
 
 CO.CsHs 
 C„H,(OH).CH.NH.CO.C„H, 
 
 I + 2H,0. 
 
 C8H^(0H).CH.NH.C0.CjH5 
 [It is purified by dissolving it in boiling phenol 
 and precipitating with alcohol. Microscopic 
 plates, melting with decomposition above 300°, 
 insol. in the ordinary organic solvents, sol. boil- 
 ing phenol, sol. caustic soda, forming a sodium 
 compound. By fusion with caustic soda it yields 
 sodium benzoate and sodium salicylate. Heated 
 with dilute hydrochloric acid at 210° it is 
 hydrolysed into benzoic acid and dioxystilbene- 
 
 CjH4(0H).CH.NH2 
 diamine \ ; small lustrous 
 
 C„H,(OH).CH.NH, 
 laminea [180'5°], v. sol. hot benzene ; di-acid 
 base: the Pt salt, 0„H,jNA.2HCl,PtCl,4aq 
 forms thick, orange-coloured, rhomboidal plates 
 with bevelled edges, anhydrous at 100°. This 
 base is, however, more readily obtained from its 
 aoetyl-derivative {infra). When the condensa- 
 tion-compound is boiled with acetic anhydride 
 nntil it dissolves, dihenzoyl-dAacetoxystilbene- 
 C,H4(0.C,H30).0H.NH(C,H,0) 
 
 0eH,(0.C2H3O).CH.NH(C,H,O) 
 formed (rhomboidal laminae [225'-227°], sol. 
 acetic acid) ; and by boiling this compound for 
 eight hours with acetic anhydride the ben- 
 zoyl-groups are replaced by aoetyl-groups 
 yielding diacetyl - diacetoxystilbene-diamine 
 
 O.H,(0.02H30).OH.NH(OjH,0) 
 
 I (prisms 
 
 C,H,(0.02H30).CH.NH(CjH30) 
 [216°-219°] sol. glacial acetic acid and alcohol, 
 deposited from latter solvent with 1 mol. of 
 alcohol of crystallisation). This compound is 
 a tetra-acetyl derivative of the above-mentioned 
 base. By the action of caustic alkali or cone. 
 
 hydrochloric acid on this tetra-aoetyl-compound, 
 the four acetyl-groups may be removed in suc- 
 cessive pairs, yielding first diacetyl-dioxy 
 
 C„H,(OH).CH.NH(C,HaO) 
 stilbene-diamine \ (crya- 
 
 C3Hj(OH).OH.NH(0,H30) 
 taUine powder melting above 300°, sol. hot 
 phenol, sol. caustic alkalis), and finally dioxy- 
 stilbene diamine. The latter base is most con- 
 veniently prepared by heating the tetra-acetyl 
 compound with cone, hydroohlorio acid at 120°. 
 By heating the condensation-compound with 
 benzoic anhydride a dibenzoyl derivative, 
 corresponding with the diacetyl derivative _ is 
 obtained; it is a tetra-benzoyl derivative 
 
 C5Hi(0.C,H,0).CH.NH(C,H30) 
 of the base, thus: | 
 
 OeH,(O.C,H„0).CH.NH(C,H30) 
 Microscopic plates [246°-248°], sol. acetic acid ; 
 sol. dilute caustic potash on long boiling, re- 
 generating the condensation-compound. These 
 various acetyl and benzoyl derivatives may also 
 be synthesised from dioxystilbene-diamine by 
 treatment with acetic anhydride and benzoic 
 anhydride. The dibenzoyl derivative thus pre- 
 pared is identical with the original condensation- 
 compound (Japp a. Hooker)]. 
 
 Benzil, furfuraldehyde, and ammonia also 
 react according to Equation III. : 
 C„H,„0, + 203H,O, + 2NH3 = C,4H,,N,0« + 2H,0, 
 forming, however, two isomeric compounds of 
 the formula C^iHzoNjO,. One of these is an 
 analogue of the salicylic aldehyde compound ; 
 it is separated by means of its insolubility in 
 alcohol, and purified by dissolving in boiling 
 phenol and precipitating with alcohol. Crystal- 
 line powder, v. sol. hot phenol, si. sol. glacial 
 acetic acid. The isomeric compound crystallises 
 from alcohol in tufts of silky needles [246°] 
 (J. a. H.). 
 
 When cinnamic aldehyde, benzil, and am- 
 monia are allowed to react in alcoholic solution, 
 a mixture of two compounds is obtained. Boil- 
 ing alcohol extracts one of these, and the re- 
 maining compound, which is insoluble in 
 alcohol, is purified by dissolving in hot phenol 
 and precipitating with alcohol. The compound 
 soluble in alcohol is cinnimabemil, 03,H3„N20, 
 {infra). The compound insoluble in alcohol is 
 dibenzoyl-dicinnamyleiie-diamine and is formed 
 according to Equation III. : 
 
 C3H5.CO 
 2C,H,.CH:CH.CH0 + | +2NH,= 
 
 C,H,.CO 
 CA.CH:CH.CH.NH.C6.C,H5 
 
 I + 2H,0. 
 
 03H5.CH:CH.CH.NH.CO.C5H3 
 Crystalline powder, consisting of short micro- 
 scopic prisms [264°], insol. in the ordinary 
 organic menstrua, sol. hot phenol. When heated 
 with a solution of2)oios^ in methyl alcohol at 150°, 
 it parts with the elements of benzoic acid and is 
 converted into benzenyl-dicin/namylene-diamine 
 CsH5.CH:CH.CH— NHv 
 
 I \C.C3H5. Silky needles, 
 
 CsH,.CH:OH.CH N-^ 
 
 [223°], sol. benzene and alcohol. Monacid base : 
 Pt salt, (025H2jNj,HCl)2,PtCl,2aq, forms silky 
 needles. 
 
 Equation IV. — The above-mentioned soluble 
 product of the reaction of ^innamio aldehyde 
 
BENZIL, AMMONIA-DERIVATIVES OF. 
 
 467 
 
 with benzil and ammonia — cinnimabenzU, 
 CsjHggN.O, — is formed according to Equation IV.; 
 OA.CO 
 
 2 I +CsH5.0H:CH.CHO + 2NH3 = 
 
 C.H,.CO 03,H3,NA + 2H,0. 
 
 Crystallises from hot alcohol in two forms — 
 slender needles and minute short prisms [188'], 
 sol. benzene. A solution of potash in methyl 
 alcohol, when allowed to act upon it in the 
 cold, forms potassium benzoate and cinnidima- 
 benzil, C^^H^^O^: 
 CjjHsoNA + KOH = CjjHjjNA + CaHs.COOK. 
 Crystalline powder [283°], sol. hot phenol, pre- 
 cipitated by alcohol. By boiling cinnimabenzil 
 with dilute SMZp/Mtric oc«Z it is hydrolysed, yield- 
 ing benzilimide (in/ra), oinnamio aldehyde, ben- 
 zoic acid, and ammonia : C3,H3„N203 + 2H2O = 
 CjiHjjNOj-i-OsHsO + OiHjOj + NHa (Japp and 
 Beuzilimide 
 Wynne). 
 
 Keaoiions op Benzil with Ammonia alone. — 
 Laurent, Bevue Scient. 10, 122 ; 19, 440 ; Zinin, 
 A. 34, 190 ; Zinoke, B. 16, 890 ; Japp, B. 16, 
 2636 ; Henius, A. 228, 339 ; Japp a. Wynne, 
 G. J. 49, 473. 
 
 By heating benzil with alcoholic ammonia 
 the following compounds are obtained: ima- 
 benzil, C^^^.p,; benziUmide, G^JJ-nNO-^; 
 benzilam, O^iHisNO ; and lophine, C^iHuNj. At 
 the same time benzoic acid, ethyUo benzoate, 
 and benzamide are formed. This reaction was 
 first studied by Laurent, who prepared the first 
 three of the above-mentioned compounds, ascri- 
 bing to them, however, incorrect formulae. 
 
 Benzil is dissolved in alcohol so that the 
 solution is saturated at 40° ; gaseous ammonia 
 is passed into the warm liquid to saturation, 
 and the whole is allowed to stand for 24 hours. 
 Prismatic crystals of imabenzil are deposited, 
 whilst benzihmide, benzilam, and the other 
 compounds above enumerated remain in solution. 
 If slender acicular crystals of benzihmide should 
 separate they may be removed by warming with 
 alcohol, in which imabenzil is soluble only with 
 difficulty. The formation of imabenzil may be 
 expressed by the equation : 3C,4H,„02 + 2NH3 = 
 OasHjsNA + O5H5.COOH + HjO. Imabenzil 
 
 forms small lustrous orthorhombio prisms [194°], 
 si. sol. hot alcohol, decomposing on long boUing, 
 and yielding among other products benzilimide ; 
 the best solvent is hot methyl alcohol. Boiled 
 with dilute sulphuric acid (1 vol. acid : 2 vols, 
 water) it is converted into benzilimide, benzil, 
 and ammonia : 
 
 CjsHjsNA + H2O = CaH.jNO, + CnH.oOjH- NH, ; 
 whilst cold cone, sulphuric acid dissolves it, 
 converting it into benzilam, benzaldehyde, ben- 
 zoic acid, and ammonia : 
 
 C3,H2aNA + HjO = 
 CaH,sNO + C,H,0 + C,B.fi^ -H NH3 
 (Japp a. Wynne). The formation of benzilam 
 in this reaction was first observed by Laurent. 
 Boiling with alcoholic ^otosfe converts imabenzil 
 into benzilimide (Laurent). Acetic acid and 
 acetic anhydride act hke dilute sulphuric acid, 
 decomposing it on boiling with formation of 
 benzilimide and benzil (Henius). Heated for 
 some time to 140° it decomposes and melts, 
 forming benzilimide, benzilam, and lophine, 
 whilst an odour of benzoic aldehyde is peroepti- 
 We (H.). 
 
 The alcoholic ammoniacal mother-liquor 
 from the preparation of imabenzil yields, when 
 concentrated, a mixture of benzilimide and ben- 
 zilam. A similar mixture is obtained by heating 
 benzil with alcoholic ammonia for some hours 
 at 100°, the imabenzil which is first formed 
 being converted into benzilimide and benzilam ; 
 at 130° lophine is also formed (Henius). The 
 formation of lophine occurs according to the 
 equation 20,jH,„O2+ 2NH,= 
 
 C„H,„Nj + CsHj.COOH + 2Hp. 
 Benzilimide and benzilam are best separated by 
 boiling the mixture with light petroleum, which 
 extracts the whole of the benzilam, depositing 
 it on cooling, in rosettes of prisms, and hardly 
 dissolves the benzilimide, which may be puri- 
 fied by crystallisation from hot alcohol. Ben- 
 zilimide is formed from benzil and ammonia 
 according to the equation — 
 
 2C„H,.02 + NH3 = C2,H„N02 + C,H,.COOH. 
 Tufts of silky needles [137°-139°] (H.), sol. 
 hot alcohol. Concentrated sulphuric acid 
 dissolves it in the cold, abstracting the elements 
 of water, and converting it into benzilam (L.). 
 C^iH^NOj - HjO = CjiH.sNO. Heating with 
 acetic anhydride produces the same effect (H.). 
 Chromic wAxture oxidises it to benzoic acid 
 (H.). Benzihmide may also be prepared from 
 imabenzil by Laurent's method of boiling it with 
 alcohoUc potash. 
 
 Benzilam (G,^'B.^^O) may be obtained as 
 above, along with benzUimide, and separated 
 from it as already described, or it may be 
 obtained either from imabenzil or from benzili- 
 mide, by the action of cold cone, sulphuric acid. 
 The solution of imabenzil in the cold acid is 
 poured into water, when benzilam separates and 
 may be purified by recrystallisation from alcohol. 
 Most readily obtained by heating benzil with fused 
 ammonium acetate in a flask over a flame until 
 the anmionium salt is volatilised (Japp a. Wilson, 
 C. J. 49, 829, footnote) ; but as some lophine 
 is formed at the same time, the benzilam must 
 be extracted by means of hot light petroleum, 
 in which the lophine is practically insoluble. 
 The formation of benzilam from benzil and 
 ammonia may be expressed thus ; 
 20„H,„02 + NH3= Cj.H.sNO + CACOOH + H^O. 
 WeU-developed rhombic prisms (from a mixture 
 of ether and alcohol by spontaneous evapora- 
 tion (H.)), colourless when pure; thin lustrous 
 laminae, sometimes iridescent, (from hot alco- 
 hol); rosettes of prisms (from hot light petro- 
 leum). [113°-114°]. Distils at a high tempera- 
 ture without decomposition (L.). V.D. (air = l) 
 10-23 : calculated 10-28 (J.). With nitric acid 
 it yields a mono-nitro- derivative (needles 
 [178°-182°] from benzene) and a dinitro- deri- 
 vative (H.). Chromic mixture oxidises it to 
 benzoic acid (H.). 
 
 The above reactions of benzil with ammonia 
 may be explained as follows. In the first place 
 a portion of the benzil is broken up according 
 to the following equations : 
 
 (a) C,H„CO.CO.0eH,H-H.O = 
 CA.COOH-i-CsHs.CHO; 
 Benzoioacid Benzoic aldehyde 
 
 (b) C.H3.CO.C0.05H5H-EtOH=i 
 C,H3.C00Et + CeH,.CH0i 
 EthyUo benzoate 
 
468 
 
 BENZIL, AMMONIA-DERIVATIVES OF. 
 
 (e) CjH,.C0.C0.0eH5 + NH3=. 
 O.H5.CO.NH2+ C5H5.CHO. 
 
 Benzamide 
 These three compounds — benzoic acid, ethy- 
 lio benzoate, and benz amide— are always formed 
 in the reaction of benzil with alcoholic am- 
 monia. (The benzamide may also be regarded 
 as having been formed in a secondary reaction, 
 from ethyUo benzoate and ammonia.) The 
 benzoic aldehyde, which is the by-product in 
 every case, then reacts, in the nascent state, 
 with benzil and ammonia according to one or 
 other of the following equations : 
 
 OA.CO 
 (d) I -fCA.CH0 + NH3 = 
 
 C„H,.CO 
 
 OsHs.C- . 
 
 II 
 CA.O-NH- 
 
 Benzilimide 
 
 :C(OH).OsH5 + HjO. 
 
 This reaction of an aldehyde with a dicarbonyl- 
 compound and ammonia, in which benzilimide is 
 produced, is not known to occur in the case of 
 free aldehydes. 
 
 If the reaction occurs according to Equation 
 I. of the general reactions, henzilam is formed ; 
 
 OjH^.CO 
 (e) I -hOA.CHOHNH,= 
 
 II \0.CAh-2H,O. 
 O5H5.G— N'^ 
 Benzilam 
 
 These formulse for benzilimide and benzilam 
 account for the readiness with which the former 
 is converted into the latter by the action of de- 
 hydrating agents. 
 
 If the reaction occurs according to Equation 
 II., lophine is produced : 
 
 CA.CO 
 (/) I +OeH,.OHO + 2NH3 = 
 
 CA.CO 
 0^.0— NH. 
 
 II \C.C.H, + 3H30. 
 
 O5H5.C— N'^ 
 Lophine 
 
 Finally, if it occurs according to Equation IV., 
 the product is imahenzil : 
 
 CsHs.CO 
 (g) 2 I +CeH,.CH0 + 2NH3 = 
 
 0,H,.CO Oa^H^sNA + SH^O. 
 
 Imabeuzil. 
 
 But free benzoic aldehyde, with benzil and 
 ammonia, yields only lophine. 
 
 The foregoing equations express the forma- 
 tion of the various compounds obtained from 
 benzil with alcoholic ammonia. The reactions 
 in which the complex compounds discovered by 
 Laurent are formed thus really occur in two 
 stages, of which the first consists in the forma- 
 tion of benzoic aldehyde, the second in a benzil- 
 aldehyde-ammonia condensation (Japp, B. 16, 
 2636 ; Japp a. Wynne, 0. J. 49, 477). 
 
 F. E. J. 
 
 BENZILIC ACID G^;S.^fi,'= 
 (C„Hs).,C(OH).COOH. Diphenylglycollic acid. 
 [150°] (Jena). 
 
 Fcrrmation. — l. By warming benzil with 
 
 alcoholic potash: OjHs.CO.CO.OjHj + KOH - 
 {OeH5)2C(OH).COOK (Liebig, A. 25, 26 ; Zinin, 
 A. 31, 329). — 2. By boiling diphenyl-bromo-acetio 
 acid, (CsHs)2CBr.C00H (obtained by passing the 
 vapour of bromine over heated diphenyl-aoetio 
 acid), with baryta water (Symons a. Zinoke, A, 
 171, 131). 
 
 Preparation. — 1. Benzil is added to five times 
 its weight of melted potash to which a little 
 water has previously -been added. The whole 
 solidifies, owing to the formation of potassium 
 benzilate (B. Fischer, B. 14, 326 footnote). The 
 mass is dissolved in water, and the benzilic acid 
 is precipitated by hydrochloric acid and reorystal- 
 Used from boiling water. — 2. It can also be pre- 
 pared from benzoin. 15 g. benzoin, 20 g. KOH 
 and from 250 to 300 0.0. water are heated in a 
 current of air until everything has dissolved. 
 The solution is extracted vrith ether to remove a 
 small quantity of diphenyl-oarbinol which ia 
 formed by the decomposition of the benzilio 
 acid, and solid caustic potash is added. This 
 causes the separation of nacreous laminee of 
 potassium benzilate, which are removed by fil- 
 tration, washed with a solution of caustic potash, 
 and finally decomposed with sulphuric acid 
 (Klinger, B. 19, 1868). 
 
 Properties. — Small white monoclinic needles 
 with a satiny lustre. Heated above its melting- 
 point it turns red. Cone. H2SO4 colours it deep 
 red; the colour disappears on the addition of 
 water. V. sol. alcohol, ether, and boiling water ; 
 si. sol. cold water. Bitter taste. 
 
 Reactions. — 1. Heated for several hours to 
 180° it yields a deep-red liquid, and, on cooling, 
 solidifies to an amorphous mass, from which, 
 by treatment with alcohol, dibenzilic acid 
 CjaHjjOs [196°], benzophenone, and other pro- 
 ducts can be isolated (Jena). — 2. Chromic 
 mixture oxidises it to benzophenone: 
 (CsH,),C(OH).COOH-hO = 
 (C,H,)2C0 + C0, + H,0. 
 Benzophenone is also produced when silver 
 benzilate is heated, either alone or vrith water 
 (J.). — 3. Heated with hydriodic acid (127°) to 
 150° it is converted into diphenyl-acetic acid : 
 (C8H5)2C(OH).COOH -f 2HI = 
 (CeH5)2CH.C00H + Ij + H,0. 
 Zinc and hydrochloric acid, and sodium amal- 
 gam, are without action (J.). — 4. Barium benzi- 
 late, distilled with pth of its weight of soda- 
 Zime, yields diphenyl-carbinol : 
 
 (CsH5)jC(OH).0O0H = (C3H5)jCH.OH + CO^ 
 (J.).— 5. Treated with PCI5 it yields benzil 
 chloride, CnHnOjOl, a heavy, colourless liquid 
 (270°), which in contact with moist air is rapidly 
 decomposed into benzilic and hydrochloric acids 
 (Cahours, A. 70, 46). 
 
 Salts. — Benzilio acid is monobasic. 
 CnH,,0.,K: V. sol. crystalline salt (Zinin). — 
 (C|jH,|63)2Ba6aq: v. sol. crystalline crusts 
 with a fatty lustre (J.) ; separates from alcohol 
 in anhydrous needles (Symons a. Zincke). — 
 (C„H„03)2Pb : pulverulent precipitate, obtained 
 by adding lead acetate to an aqueous solution of 
 benzilic acid ; fuses on heating to a red liquid 
 (Zinin).— CuHiiOjAg: easily decomposable pre- 
 cipitate (J.). 
 
 Ethylia benzilate, CnHnOs.CjHj. Separates 
 as an oil when a solution of benzilic acid in 
 ethyl alcohol is saturated with gaseous HCl and 
 
BENZOIC ACID. 
 
 469 
 
 then diluted with water. Not volatile without 
 decomposition (J.). 
 
 Ethyl-bmziUc acid, CisHijOa, isomeric with 
 the foregoing, is a resinous substance obtained 
 by heating benzoin in alcoholic solution with 
 sodium ethoxide at 150°. Scarcely soluble in 
 potash and ammonia, save in presence of alcohol 
 (Jena a. Limpricht, A. 155, 96). 
 
 Dibmzilic acid, OjjHaOj [196°], obtained by 
 heating benzilio acid to 180° {v. supra), 
 crystallises from alcohol in minute needles. It 
 is an anhydride, and, by heating with water at 
 180°, is converted into benziUc acid (Jena, B. 
 2, 385). F. B. J. 
 
 SENZILIMIDE v. Bbnzil, ammonia-debi- 
 
 VATIVES OP. 
 
 BEIfZlUIDI! V. Benzoic aij)ehyde. 
 
 DI-BENZIMIDE OXIDE v. Benzonitkile. 
 
 BENZIMIDO-ACETATE v. Benzonitbile, 
 Combination 6. 
 
 BENZIUIDO-BENZOATE v. Benzoniibile, 
 Reaction 5. 
 
 BENZIMIDO- BUTYL -ETHEE v. Benzo- 
 NiiBiLE, Combination 5. 
 
 BEITZIUIDO- ETHYL. ETHEB v. Benzo- 
 nitkile, Combination 5. 
 
 BENZIMISO . NAPHTHYLAUIDE v. 
 NaphthiIi-benzamidine. 
 
 BENZO-ANILINE v. Auido-benzofhenone. 
 
 BENZO-TRI-CHLORIDE CjHsCla i.e. 
 OA.CCI3. M0I.W. 195-5. (214°). S.G.iil-38. 
 
 Formation. — 1. From benzoyl chloride and 
 PCI5 (Wohler a. Liebig, A. 3, 265 ; Sohischkoff 
 a. Eosmg, C.R. 46, 367 ; Limpricht, A. 134, 55 ; 
 135, 80 ; Bl. 1866, ii. 468).— 2. From benzyli- 
 dene chloride by chlorination (Cahours, C. B. 
 66, 703). — 3. By chlorination of toluene (Naquet, 
 O. B. 65, 407 ; 56, 482). . 
 
 Preparation. — ^By passing chlorine (3 mols.) 
 into cold toluene (1 mol.) exposed to direct 
 sunshine (Schranmi, B. 18, 608) or into boiling 
 toluene. 
 
 Properties. — ^Pungent liquid, insol. water, 
 which slowly converts it into benzoic acid (the 
 change is rapid at 140°). Alcohol at 130° forms 
 benzoic ether. 
 
 BeacUons. — 1. Sodium has no action. — 
 2. AgjO forms benzoic anhydride. — 3. Aqueous am- 
 monia at 140° gives benzoic acid, beuzamide, and 
 benzouitrUe, reacting thus: CjH5CCl3 + 4NHs = 
 3NH4CI + CbHsCN.— 4. Aniline forms di-phenyl- 
 benzamidine, Cjil5C(NCjH5).NH0sH5.— 5. Reacts 
 with arom^itic bases thus : CjHjCCl, + 2C5H5NXY 
 = 0,HjCCl(OjHjNXY)j + 2HC1= 
 
 CeH.C<^^|i0U2HCP ^'^^^'^^ ^OH 
 
 forms the oarbinol CeBfi{OB.){CeB.tNXY)p The 
 reaction requires presence of a metallic chloride 
 or other condensing agent ; it takes place most 
 easily with tertiary bases, least readily with 
 primary bases. The products are dyes, the 
 jjrimary bases giving violet, the. secondary 
 and tertiary green, colours. — 6. It acts simi- 
 larly on phenols: C.Hs.CCls + 2C„H50H = 
 2HC1 + 05H5CC1(C8H,0H)2. The products are 
 converted by treatment with water into carbinols 
 G5H4C(0H)(CeH^0H)2,the alkaline salts of which 
 are colouring matters (Doebner, A. 217, 226). — 
 7. Converted by heating with dry oxalic acid, 
 first into Ph.CO.Cl, then into (Ph.CO)jO) 
 
 (Ansohiitz, A. 226, 20).— 8. Copper produces, on 
 heating, C^HyCClj.CClj.C^Hs (Onufrowioz, B. 17, 
 833). 
 
 BENZO-CTJMIDE v. Phenyl amido-oumti, 
 
 KETONE. 
 
 BENZO-FXrEILIC ACID v. Benzeubilio arid. 
 
 ISO-BENZOGLYCOL Gfifii i.e. OJBiJOHUl), 
 [171°]. A crystalline substance formed by the 
 electrolysis of a mixture of benzene, alcohol, and 
 dilute HjSO, (Eenard, p. B. 91, 175). Sol. 
 water, alcohol, and ether. Eeduces Fehling's 
 solution and ammoniacal AgNOg. 
 
 Di-acetyl derivative C^^^Okc)^. [121°]. 
 (300°). Insol. water, sol. alcohol and ether. 
 
 DI-BENZO-HYDEOQUmONE v. Di-phenyl 
 
 DI-OXY-PHENYLENE DI-KETONE. 
 
 BENZOIC ACID C^H^O^ i.e. OeH^.CO^H. 
 Mol. w. 122. [121-4°] (Sohiff). (249-2 cor.) 
 (Kopp, A. 94, 303). S.G. 21 1-20 (Mendel^eff) ; 
 1-337 (Eudorff, B. 12, 250) ; 1-292 (SchrSder, B. 
 12, 562). S. -156 at 0° (Ost, J. jvr. [2] 17, 232) ; 
 -172 at 0°; -207 at 10°; -425 at 31°; 1-78 at 
 75° (Bourgoin, J. Ph. [4] 30, 488). S. (ether) 66 
 at 15°. S. (alcohol) 47 at 15° (Bourgoin, Bl. [2] 
 29, 245). H.F. 94,533 (Stohmann, J. pr. [2] 
 36, 2). S.V. 126 (Bamsay). S.V.S. 112-09 
 (S.). Boo 54-21 (in a 6 p.c. benzene solution, 
 Kanonnikofi). 
 
 Occurrence. — In various resins, e.g. gum ben- 
 zoin, dragon's blood, storax, and balsams of 
 Peru and Tolu (Blaise de Vigen^re, Traiti du 
 feu et du set, 1608 ; Liebig a. Wohler, A. 3, 249). 
 In castoreum (Wohler, A. 67, 360), in the 
 spindle-tree {Euonymus europceus). In putrid 
 urine (Liebig, A. 50, 168). In cranberries 
 (Loew, J.pr. [2] 19, 312). In the higher boiling 
 phenolic portion of coal-tar oils (Sohulze, B. 
 18, 615). 
 
 Formation. — 1. By oxidation of benzoic al- 
 dehyde, benzyl alcohol, toluene, cinnamic acid, 
 &c. — 2. In small quantity, by passing a current 
 of dry CO2 through a nearly boiling mixture of 
 aluminium chloride and benzene (Friedel a. 
 Crafts, O. B. 86, 1868).— 3. In small quantity, 
 by the action of H^SOj and MnOj on benzene, 
 especially when formic acid is added (Carius, A. 
 148, 51, 59). — 4. By distilling calcic phthalate with 
 lime (Depouilly, Bl. [2] 3, 163, 469).— 5. By the 
 action of HjSOj and MnOj on casein or gelatin 
 (Guckelberger, A. 64, 80). — 6. By fusing potas- 
 sium benzene sulphonate with sodium formate 
 (V. Meyer, B. 3, 112).— 7. From benzouitrile by 
 saponification. — 8. By passing COj into sodium 
 in bromo-benzene (Kekul6, A. 137, 129). 
 
 Preparation. — 1. From gum benzoin by 
 sublimation or by extracting with lime-water or 
 acetic acid (Mohr, A. 29, 178 ; Scheele, Opusc. 
 2, 23 ; Wohler, A. 49, 245 ; Loew, J. pr. 108. 
 257 ; Guichard, Bl. [2] 19, 357). Some varieties 
 of gum benzoin contain cinnamic acid, but this 
 acid is absent from the benzoin of Siam or 
 the Palembang benzoin from Sumatra ; the 
 latter yields 10 p.c. benzoic acid (Saalfeld, Ar. 
 Ph. [B] 16, 280). Benzoic acid that has been 
 sublimed from gum benzoin leaves a small 
 quantity of oily residue when treated with 
 aqueous Na2C03; this oil consists of guaiacol, 
 methyl benzoate, pyrocatechin, acetyl-guaiacol, 
 benzyl benzoate, benzophenone, and benzoyl- 
 guaiacol (Jacobsen, Ar. Ph. [3] 22, 366).— 
 2. From hippurio acid. Urine of horses or 
 
470 
 
 BENZOIC ACID. 
 
 oxen is left for some days to putrefy, when the 
 hippuric acid is split up into glyooooU and ben- 
 zoic acid ; milk of lime is added and the liquid 
 concentrated; excess of lime is ppd. by CO.,, 
 and the filtrate ppd. by Fe^Olj ; the ferric ben- 
 zoate is decomposed by HCl. Benzoic acid 
 prepared in this way crystallises in plates and 
 smells of urine, but by sublimation it may be freed 
 from the smell and then crystallises in needles 
 {Dymoni, Ph. [3] 14, 463).— 3. From benzo- 
 trichloride by decomposing it with water 
 under pressure, with lime or baryta-water, or 
 with ZnClj and glacial HOAc (2 mols.) at 100° 
 (Jacobsen, B. 13, 2018).— 4. From benzyl chlo- 
 ride by boiling with dilute HNOj (Lunge a. 
 Petri, B. 10, 1275; c/. v. Bad, D. P. J. 231, 
 538). 
 
 Properties. — Needles or pearly plates. When 
 pure it does not melt under water, but slight 
 impurities greatly affect its physical properties ; 
 the so-called salylic acid was impure benzoic 
 acid (Kolbe a. Lautemann, A. 115, 187 ; Kekul6, 
 A. 117, 159 ; Griess, A. Ill, 34 ; Eeiohenbach 
 a. Beilstein, A. 132, 309; Kolbe, J. pr. [2] 12, 
 151). Volatile with steam (1 g. passing over 
 with about 2,000 c.c. water). It dissolves in 
 cone. HjSOj, and is reppd. by water. It is not 
 attacked by boiling dilute HNO3 or CrOs (which 
 convert cinnamic acid into benzoic aldehyde) ; 
 its neutral salts give a buff-coloured pp. with 
 Fe,Cl„. 
 
 Reactions.— 1. Passage of the vapour through 
 a red-hot tube gives CO. and benzene. — 2. Dis- 
 tillation with lime produces benzene. — 3. Fusion 
 with NaOH produces benzene (75 p.c. of the 
 theoretical amount) and a little diphenyl (Earth 
 «,. Senhofer, B. 12, 1256).— 4. Fusion with KOH 
 produces chiefly jp-oxy-benzoic acid, but also 0- 
 and m- oxy-beuzoio acids, oxy-iso-phthalio acid, 
 diphenyl 0-, m-, and p- carboxylie acids, and a 
 brown amorphous substance (Earth a. Schreder, 
 M. 3, 799).— 5. MnOj and H^SO^ form CO^, 
 formic acid, and small quantities of phthalic 
 and terephthalio acids (Carius, A. 148, 50 ; 
 Oudemans, Z. [2] 5, 84). — 6. Hydrogen peroxide 
 and HjSOj produce salicylic acid (Hanriot, 0. B. 
 102, 1250). — 7. Vapours of benzoic acid passed 
 over heated zinc-dust form benzoic aldehyde 
 (Eaeyer, A. 140, 295). — 8. Sodium amalgam 
 reduces it to benzyl alcohol, and benzoleic acid 
 C,H,„02, and an oil O.^HnO^ (Kolbe, A. 118, 122 ; 
 Hermann, A. 132, 75). — 9. PCI5 forms benzoyl 
 chloride. — 10. Distillation with KSCN or 
 Pb(SCN)2 gives benzonitrile. — 11. Benzene and 
 P,^05 at 190° give benzophenone (Kollarits a. 
 Merz.B. 5,447). — 12. Dimethylanilinea,nS.F.fl^ 
 give C„H5.CO.C,H4.NMe, (0. Fischer, B. 10, 958). 
 
 13. Chlorine produces chloro-benzoic acids. — 
 
 14. Bromine forms brorao-benzoio acids. — 15. 
 Iodine in presence of HIO, forms iodobenzoio 
 acid.— 16. Cone. HNO3 forms m-nitro-benzoic 
 acid. — 17, Fuming H^SO, forms sulphobenzoio 
 acid. — 18. In the animal organism it is converted 
 into hippuric acid and excreted in the urine 
 (Wohler). — 19. CrjF, forms di-fluoro-benzoic 
 acid (Jackson a. Hartshorn, B, 18, 1993). 
 
 Salts. — Benzoic acid decomposes car- 
 bonates, but an alcoholic solution of potassium 
 benzoate is decomposed by COj. Calcium ben- 
 zoate gives on distillation benzophenone, and 
 Binallcr quantities of benzene, anthraquinone, 
 
 and tetra-phenyl-methane (Kekulfi a. Franohi- 
 mont, B. 5, 909). Calcium benzoate distilled 
 with calcium formate gives benzoic aldehyde. 
 Potassium benzoate distilled alone or with 
 sodium formate gives terephthalio and iso- 
 phthaMo acids (Eiohter, B. 6, 876 ; Conrad, B. 
 6, 1395). Cuprio benzoate gives on distillation 
 benzene, benzoic acid, di-phenyl oxide Ph^pO, 
 phenyl benzoate PhOEz, and phenol (List 
 a. Limpricht, A. 90, 190). Cyanogen bro- 
 mide acts upon potassium benzoate thus : 
 Ph.COjK -H CNBr = Ph.GN + COj -^ KEr (Cahours, 
 A. Ch. [3] 52, 201). Potassium benzoate when 
 electrolysed gives K and benzoic anhydride ; 
 in presence of excess of KOH acetylene is also 
 formed (Eourgoin, Z. [2] 4, 566). 
 
 Al2A's(OH)3aq : crystals (Sestini, Cioognani, 
 a. Zavatti, Bl. [2] 13,488).— NH^A': deliquescent; 
 on distillation it gives benzonitrile. — NHjHA'j. — 
 EaA'jSaq. — CdA'2 2aq. — CaA'^Saq: S. 3-6. — 
 CeA'2 3aq. — CoA'2 2aq. — CuA'^ 2aq : needles. — 
 CrA'2 Kaq.— CrA'3 a;aq.— Cr2A'4(OH)2 2aq (Schifl, 
 A. 124, 169).— Fe.,A'5(OH)3 6aq: buff -coloured pp. 
 — LaA'j 3aq. — PbA'j aq : plates.— PbA'2 2PbO.— 
 MgA'jSaq: S. 4-5 at 25°.— MnA'^ 4aq : large 
 flat prisms, S. 6-55 at 15° (Seubert, B. 20, 791). 
 — HgA'2 aq.— Hg^A'j. -- NiA'j 3aq. — KA' 3aq.— 
 AgA' : S. (alcohol) -5 at 20°. — NaA' aq.— 
 SnA'2 aq. — ZnA'2. 
 
 Methyl ether CeHsCC^Me. Mol. w. 136. 
 (199°) (Kopp) ; (195-5) at 768 mm. (Stohmann, 
 J.pr. [2] 36, 4). S.G. ^ 1-10 (Kopp); '£ 1-0862 
 (Eriihl). S.V. 149-8 (Eamsay). S.H. -363 H- -00075i. 
 H.F. 84,024 (S.). fi^ 1-5289. E „ 61-30 (B.). 
 Formed by distilling wood spirit (1 pt.), ben- 
 zoic acid (2 pts.), and H^SO, (2 pts.) (Dumas 
 a. Peligot, A. Ch. [2] 58, 50 ; Malaguti, A. Ch. 
 [2] 70, 387 ; Carius, A. 110, 210). 
 
 Ethyl ether Cfi^CO^i. Mol. w. 150. 
 V.D. 5-53 (calc. 5-2) (Troost, G. B. 89, 351). 
 (211-2° cor.) (Linnemaun, A. 160, 208); (211-4°) 
 (Stohmann, J. pr. [2] 36, 4). S.G. \° 1-0473 
 (Bruhl) ; IS 1-050 (L.). S.H. -374 + -00075« 
 (E. Schiff, A. 234, 300). H.F. 91,693 (St.). 
 IJi/s 1-517 (B.). E 00 68-82 (B.). Formed by 
 saturating a solution of benzoic acid (3 pts.) in 
 alcohol (2 pts.) with HCl and distilling the 
 liquid. Converted by Br at 270° into benzoic 
 acid and ethylene bromide (Naumann, A. 133, 
 199). Forms crystalline compounds with 
 titanic chloride : BzOEtTiClj.— BzOEt2TiCl4.— 
 TiCl4 2BzOEt(Demar(jay, 0.7?. 70, 1414), and 
 with aluminium chloride : BzOEtAlClj (Gus- 
 tavson, B. 13, 157 ; Scheele, Opuscula, 2, 141 ; 
 Dumas a. BouUay, A. Ch. [2] 87, 20 ; Wohler a. 
 Liebig, A. 3, 274 ; Deville, A. Ch. [3] 3, 188). 
 
 Propyl ether GJifiO.,Pi. (230°). S.Gt. a 
 1-032 (L.) ; ia 1-025 (S.). H.F. 98,990 (Stoh- 
 mann, /. pr. [2] 36, 4). S.H. -383 + •00075J 
 (Schiff, A. 234, 300). 
 
 Isopropyl ether CjHsCG^r. (218°). 
 S.G. 2 1-023 (Silva, Bl. 12, 225). According to 
 Linnemann (A. 161, 51) the ether splits up on 
 distillation into propylene and benzoic acid. 
 
 n-Butyl ether CbHs.COjCjHj. (247-3= cor.). 
 S.G. S2 1-00. 
 
 Isobutyl ether. (234°) at 755 mm. 
 S.G. is 1-002. H.F. 105,628 (St.). 
 
 Isoamyl ether CjHj.COjCsH,,. Mol. w. 
 192. (261°) (Kopp, A. 94, 311) ; (253°) (Stoh- 
 mann, J. pr. [2] 36, 4). V.D. 6-71 (calc. 6-65, 
 
BENZOIC ALDEHYDE. 
 
 471 
 
 Troost, C. B. 89, 351). S.G. a 1-004 (K.) ; 12 -993 
 (K.). H.C. 1,570,048 (St.). 
 
 Formed by heating ethyl benzoate with iso- 
 amyl alcohol at 230° for 60 hours (Friedel a. 
 Crafts, Bl. [2] 2, 100). 
 
 Octylether CjHs.CO.CsH,,. (306°) (Zinoke, 
 A. 152, 7). 
 
 Becyl ether 0„Hj.C0aC,„H2,. (over 280°) 
 (Borodin, /. 1864, 338). 
 
 C etyl ether G^,,.CO.J2i^s3- [30°] (Becker, 
 A. 102, 221). 
 
 Allyl ether C^H.-COAHs. (242°) (Zinin, 
 A. 96, 362) ; (230°) (Berthelot a. de Luca, A. 
 100, 860); (280°) (Cahours a. Hofmann, A. 
 102, 297). 
 
 Ethylene ether {C^S..^.CO.^).fi.,ll^. [67°]. 
 (360°). 
 
 Propylene ether lGJI..COXCJi.. [72°]. 
 (300°). 
 
 Isoamylene ether {C^^.G0^^G^i^.{XZ-6°'\ 
 tMayer, Bl. [2] 2, 451). 
 
 Other ethers of benzoic acid are described 
 as benzoyl derivatives of the hydroxylio com- 
 pounds from which they may be derived. 
 
 References. — V. also Aujehido-, Amido-, Beo- 
 M0-, Bbomo-ahido-, Bbomo-nitbo-, Bbomo-nitbo- 
 0XY-, Beomo-oxy-, Butyl-, Ohloeo-, Chlobo-iodo-, 
 Cklobo-oxy-, Cyano-, Fluoeo-, I0DO-, I0DO-OXY-, 
 
 NrrB0-,NlTE0-BUTYli-,NlTE0-0XY-,NlIE0-PE0PYL-, 
 OXY-, SOLPHO-, BENZOIC ACID. 
 
 Orthobenzoic acid CeH5.C(OH)3. Bemenyl 
 alcohol. 
 
 Ethyl ether C„H,.C(0Et)3. (220°-225°). 
 From benzotrichloride and NaOEt at 100' 
 (Limpricht, A. 135, 87). 
 
 Tri-acetyl derivative C5H5C(0Ac)3. 
 From CgHj.CCl, and AgOAc. Beadily splits up 
 into AcjO and OaHsOO.OAc. 
 
 Salphinide of benzoic acid v. Imjde or scl- 
 
 PHOBENZOIC ACID. 
 
 BENZOIC ALDEHYDE CjH^Oi.e. CsHj.CO.H. 
 Bemaldeh/yde. Oil of bitter ahnonds. Mol. w. 
 106. (179°). S.G. =5° 1-0455 (Briihl) ; « 1-0504 
 (MendelSeff, J. 1860, 7). S. -33 (Fluckiger, 
 J. 1875, 482). n^ 1-5624. E 00 51-65 (B.). 
 H.F. 23,254 (Stohmann, J.pr. [2] 86, 3). 
 
 Formation. — 1. From alinonds (3. v.). — 
 
 2. By oxidation of benzyl alcohol (Cannizzaro, 
 A. 88, 130), cinnamio acid (Dumas a. Peligot, A. 
 14, 50), and proteids (Guckelberger, A. 64, 60, 
 72, 86). — 2. By boiling benzyl chloride with 
 water and nitrate of lead (Lauth a. Grimaux, A. 
 143, 80), nitrate of copper, or sodium nitrate. — 
 
 3. By heating benzyUdene chloride with water 
 or alkaUs (Cahours, O. B. 56, 222).— 4. By mix- 
 ing benzyUdene chloride with cone. H2SO4, 
 diluting, and distilling (Oppenheim, Z. [2] 5, 441). 
 
 5. By passing vapour of benzoic or phthalic 
 acid overheated zinc-dust (Baeyer, A, 140, 295). 
 
 6. By reducing benzoic acid with SnOL, (Dusart, 
 J. 1862, 263), or sodium amalgam in slightly 
 acid solution (Kolbe, A. 118, 122).— 7. By dis- 
 tilling calcium benzoate with calcium formate 
 (Piria, A. 100, 104).— 8. From benzylidene chlo- 
 ride and silver oxalate (Golowkinsky, A. Ill, 252) 
 or potassium carbonate (Meunier, Bl. [2] 38, 159). 
 
 9. From toluene by successive treatment with 
 CrOjCl^ and water (Etard, O. B. 90, 534).— 
 
 10. From benzylidene chloride, acetic acid, and 
 ZnCl, : Ph.CHOlj + CH,.COjH = 
 
 Ph.CHO + CHjCOCl T HCl. 
 
 Preparation. — 1. Benzyl chloride (1 pt.) 
 is cohobated at 100° with water (10 pts.) and 
 lead nitrate (1| pts.), a current of COj being 
 passed through the apparatus. The product is 
 distilled and the light oil fractionated. It is 
 shaken with a saturated solution of NaHSOj, 
 and the resulting crystalline compound is washed 
 with alcohol, crystallised from water, and then 
 decomposed by boiling aqueous NajCO, (Lauth 
 a. Grimaux, A. 143, 80 ;Bertagnini, A. 85, 183).— 
 2. Crude benzylidene chloride is heated at 
 110°-1B0° with an equivalent quantity of dry 
 oxalic acid, the product is distilled in vacuo : 
 PhCHOlj + SjOfi, = Ph.CHO + 2HC1 + CO^ + CO 
 (Anschiitz, A. 226, 18). — 8. A mixture of benzyl 
 chloride (2 mols.) with benzylidene chloride 
 (1 mol.) obtained by chlorinating toluene tiU 
 the S.G. is 1-175 is boiled with water and MnOj 
 (2 mols.) (Schmidt). — 4. By heating benzylidene 
 chloride with aqueous KOH under pressure, or 
 by boiling it with milk of Ume.— 5. Bitter 
 almonds are freed from almond oil by pres* 
 sure. The press-cake (12 pts.) is made into a 
 paste with boiling water (110 pts.) ; after 15 
 minutes the paste is allowed to cool. The emul- 
 sin is destroyed by boiling, and therefore a second 
 quantity of the press-cake (1 pt.) is mixed with 
 cold water (6 pts.) and added to the first. After 
 12 hours' maceration the whole is distilled with 
 steam. The yield is 2 p.c. of the press-cake (Pet- 
 tenkofer, A. 122, 77 ; of. Liebig a. Wohler, A. 
 22, 1). In this operation amygdalin is split up 
 by the unorganised ferment emulsin, the pro- 
 ducts being benzoic aldehyde, prussic acid, and 
 glucose : 
 C2„H2,NO„ + 2B.fi = C,H„0 -h ONH -^ 2CeH,,03. 
 
 Benzoic aldehyde so prepared contains 
 prussic acid, which appears to be combined in 
 the form of the cyanhydrin CeH5.CH(0H).CN, 
 for a mixture of benzoic aldehyde and prussic 
 acid yields methylamine on reduction, while 
 crude oil of bitter almonds yields amido-phenyl- 
 ethane C5H5.CH2.GH2.NHi; again, a mixture of 
 benzoic aldehyde and prussic acid, on treatment 
 with chlorine, yields CjH^Cl.CO.Cl, while oil of 
 bitter almonds yields, by similar treatment, 
 CsH5.CH(OH).CO.N:CH.CsH5 (Pileti, G. 9, 446). 
 Prussic acid may be removed by shaking with 
 FeSO, and lime or potash, or by digesting with 
 HgO and water. The aldehyde is then purified 
 by means of NaHSOj as described under 1. 
 
 Properties. — Colourless oil. It is not poi- 
 sonous. It oxidises rapidly in the air, but the 
 addition of a little prussic acid hinders the oxida- 
 tion (Dusart, Bl. 8, 459). It does not reduce 
 Fehling's solution. 
 
 Reactions. — 1. Oxidised to benzoic acid by 
 air or other oxidising agents. Cone. HNO3, 
 however, forms m- (and a little 0-) nitro-benzal- 
 dehyde.— 2. Aqueous or alcolwlic potash gives 
 benzyl alcohol and potassium benzoate. — 3. Led 
 over red-hot pumice it is split up into CO and 
 benzene (Barreswil a. Boudault, A. 52, 360). — 
 4. PCI5 forms benzylidene chloride (Cahours, A, 
 70, 39). COCI2 acts similarly (Kempf, J.pr. [2] 
 1, 412). — 5. Chlorine forms benzoyl chloride 
 and a compound of that body with benzoic alde- 
 hyde, CbH5CHC1(0Bz) (Laurent a. Gerhardt, J. 
 1850, 489). Bromine acts similarly, forming 
 CA-CHBr(OBz) [70°] (Liebig a. Wohler, A. 3, 
 266 ; Claisen, B. 14, 2475).— 6. Succinyl chlo- 
 
472 
 
 BENZOIC ALDEHYDE. 
 
 ride produces sucoinio acid and benzylidene 
 chloride (Eembold, A. 138, 189).— 7. Sodium 
 amalgam reduces it, in presence of water, to 
 benzyl alcohol, hydrobenzoin, and isohydroben- 
 zoin. — 8. Potassium, cyanide produces benzoin. 
 9. Aqueous HI (S.G. 2-0) at 280° reduces it to 
 toluene (Berthelot, J. 1867, 346). — 10. H^S 
 forms tniobenzaldehyde. — 11. Aqueous NH, 
 forms hydrobenzamide (C5H5CH)3N2.— 12. 
 Ammonium sulphide forms thiobenzaldine 
 CjiHigNSj. — 13. NH, andsulphide of carbonform 
 NH2.CSS.N(CH.CjH,)i,.— 14. With acetia anhy. 
 dride and sodium acetate, on heating, it forms 
 sodium oinnamate {v. Pebkin's Stnthbsis, p. 
 108). The reaction probably takes place in Wo 
 stages : C5H5CHO + CHs-CO^Na = 
 
 05H5.CH(OH).CH2.C02Na = 
 H20 + CsH5.CH:CH.C0jNa.— 15. With Ac^Oand 
 sodium succinate it gives the lactone of 
 COjH.CH,.CH(CO2H).0H(OH).C,H5.— 16. With 
 sodium isobutyrate and isohutyrio anhydride it 
 forms CeH5.CH(OH).CMej.C02H, v. Oxy-phenyl- 
 VALEEio ACID (Pittig, A. 216, 119).— 17. With 
 AcjO and sodic butyrate at 100° it gives only 
 phenyl-angeJio acid, whereas at 180° the chief 
 product is cinnamio acid (Slocam, A. 227, 
 53). — 18. The reaction PhOHO + CH^XY = 
 HjO + Ph.CH:CXY takes place under influence 
 of dry HCl or aqueous or alcoholic EOH on 
 condition that X or T is of the form CO.Z, e.g. 
 benzoic aldehyde acting on acetone, mesityl 
 oxide, acetophenone, pyruvic acid, malonic ether, 
 and aceto-acetic ether. Ferkin's reaction is of 
 a similar nature. Occasionally intermediate 
 compounds of the form Ph.CH(OH).CHXY are 
 formed (Claisen, A. 218, 121). — 19. Sodium 
 malonate and Ac^O react in the cold, giving off 
 CO2 and forming cinnamic acid, as follows : 
 Ph.CHO + CB^CO^U),, = PhCH:C(C02H)2 + H^O 
 = PhCH:CH.OOjH + C02 + H20 (Stuart, 0. J'.43, 
 404). — 20. Sodmrni isostcccinate and Ao^O act 
 similarly, forming phenyl-iso-crotonio acid : 
 Ph.CHO + CHMe(C0jH)2 = 
 Ph.CH:CMe.C02H + CO^ + HjO. 
 21. Acetyl chloride and zinc-dust form diacetyl- 
 hydrobenzoiin ; while benzoyl chloride and zinc 
 dust form di-benzoyl-hydrobenzoin (Paal, B. 15, 
 1818 1 16, 636; 17, 909).— 22. Eeacts with 
 nitro-jaaraffins thus: Ph.CHO + H2C{N02).CH3 = 
 H2O + Ph0H:C(NO2)CH3 (Priebs, A. 225, 319).— 
 23. A solution of amiline in cone. HCl pps. 
 yellow crystals of a molecular compound. They 
 are only stable in presence of cone. HCl (Elbers, 
 
 A. 227, 357). If SnClj be also present a com- 
 pound (NPhH2HCl)2(C,H„0)3Sn0l4 is formed 
 (E.). — 24. Aniline forms benzylidene-aniline, 
 CjHs.CHiN.CjHj ; o-toluidine acts similarly. 
 When heated in presence of HCl or ZnClj 
 aniline forms di-amido-tri-phenyl-methane. 
 Dimethylaniline in presence of ZnOL gives 
 CeH5CH{C,H,NMe2)j (Fischer, B. 10, 1623) ; di- 
 methyl m- (but not o- or p-) toluidine behaves 
 similarly (Fischer, B. 13, 807).— 25. Ethylene- 
 diamine forms (05H5.CH:N)2C2H„ [54°] (Mason, 
 
 B. 20, 267).— 26. {$)-Naphthylamine forms ben- 
 Kylidene-(;8)-naphthylamine and then phenyl- 
 
 naphthacridiue dihydride PhCH<;^'°2°>NH 
 
 (Claisen, A. 237, 261). — 27. Besorcin in pre- 
 sence of HCl forms a resin C^uHjoOj (Baeyer, 
 B. 5, 25). Phenol, pyrocatechin, phloroglu- 
 
 cin, and orcin act similarly (Michael a. Eyder, 
 B. 19, 1388; Am. 9, 130). -28. (fi).Naphthol 
 left to stand for several days in the cold 
 with an acetic acid solution of benzalde- 
 hyde treated with a few drops of HCl forms 
 di-(;8)-naphthyl benzaldehydate (di-naph- 
 thyl-ortho-benzoic aldehyde) CsB.fi'H{OCj„'B,), 
 [205°]. It is a crystalline pp., si. sol. all ordinary 
 solvents ; insol. aqueous alkalis. By warming 
 with acetic acid and a few drops of HCl it is 
 converted into the isomeric di-oxy-di-naphthyl- 
 phenyl-methane C5H5.CH(Ci„Hj.OH)2 which at 
 the same time loses H2O, giving the compound 
 
 CsH5.CH<^'»^«>0 (Claisen, B. 19, 3317).— 
 
 29. Acetone in presence of aqueous NaOH pro- 
 duces C5H5.CH:CH.C0.CH3 and the compound 
 CjH5.CH:CH.C0.CH:CH.0eH:5. In general, com- 
 pounds containing the group CHj.CO react with 
 benzoic aldehyde, exchanging the Hj for CHPh 
 (Claisen, B. 14, 349, 2468; v. Benzylidenb- 
 aoetonb). — 30. Prussia acid forms mandelo- 
 nitrile or the oyanhydrin of benzoic aldehyde, 
 CsH5.CH(0H).CN (v. Mandelio acid). This is 
 converted by alcohol and HCl into mandelic 
 imido-ether, C„H5.CH(0H).C(NH).0Et (Volokel, 
 A. 52, 361 ; Tiemann, B. 14, 1967). Benzoic 
 aldehyde (4 vols.) mixed with nearly anhydrous 
 prussic acid (1 vol.) and shaken with alcoholic 
 KOH forms benzimide C^B^^fi^, [167°], a 
 flocculent substance, insol. water, alkalis, and 
 acids (Laurent, A. Oh. [2] 59, 397; 66, 193; 
 Zinin, A. 34, 188 ; B. 2, 552 ; Gregory, A. 54, 372). 
 31. Hydrogen iodide forms a pungent compound 
 C2,H,jl40 [28°] insol. water (Geuther a. Cartmell, 
 A. 112, 20). — 32. SOs forms a disulphonio acid 
 C„H3(SO,H)2.CHO (Engelhardt, J. 1864, 350).— 
 33. By treatment with a methyl-alcoholic 
 solution of sodium methylate a white solid 
 compound 0jH5.C(OMe)(OC,H,)(ONa) is 
 formed. The same body is formed by the 
 action of sodium methylate on benzyl-benzoate 
 or of sodium benzylate on methyl-benzoate. 
 By treatment with acetic acid it is split up into 
 a mixture of benzyl benzoate, methyl benzoate, 
 benzyl alcohol, and methyl alcohol. — 34. If 
 benzaldehyde is heated with a small quantity of 
 sodium benzylate for several days at 100°, it is 
 slowly polymerised to benzyl benzoate. Probably 
 the compound C5H5.C(OC,H,)20Na is first 
 formed, and then decomposes into benzyl 
 benzoate and sodium benzylate, which latter 
 again reacts upon a further quantity of benzal- 
 dehyde, producing more of the intermediate 
 compound, and so on (Claisen, B. 20, 646). — 
 35. By boiling with ammonium formate it yields 
 tri-, di-, and mono- benzyl-amine and their 
 formyl derivatives, together with other pro- 
 ducts (Leuchart, B. 19, 2128). — 36. Ammonium 
 sulphocyanide at 140° forms benzylidene-thio- 
 
 biuret C,H5CH<j^2;^|>NH [237°] (Brodsky, 
 
 M. 8, 27). — 37. Benzene-azo-benzene and ZnCl, 
 forms ' benzylidene-benzidine ' C,^^,^^fiJ(!) 
 [239°] (Barzilowsky, J. R. 1885, 366).— 38. Acts 
 upon an alcoholic solution of sodium aceto- 
 acetic ether, forming Cj^HjjO, [127°], sol. dilute 
 alkalis (Michael, /. pr. [2] 35, 450).— 39. Hy- 
 drazine-benzoic acid, NHj.NH.CjHj.COjH, forms 
 benzylidene-hydrazine-benzoic acid CuHuNjO, 
 [172° uncor.] (Koder, A. 236, 171). 
 
BENZOIC ALDEHYDE, AMMONIA-DERIVATIVES OF. 
 
 478 
 
 Combinations. — 1. With bisulphites. 
 C,HjCH(OH).SOsNaiaq. Small crystals, v. e. 
 sol. water, insol. cold alcohol. Decomposed by- 
 boiling -water, boiling dilute acids, or cold 
 alkalis or alkaline carbonates (Bertagnini, A. 
 85, 188). — C.H5CH(0H).S03K : laminse. — 
 C^s.CH(0H).S03NH,aq: formed by action ol 
 SOj on an alcohoHo solution of hydrobenzamide 
 (Otto, 4. 112,305).— {0,H,.CH(0H).S03f2Ba2aq: 
 from the Na salt and BaClj.— 2. With SOj and 
 aniline: (CeH.CHO)j(C,H3N)2S02 {Schifi, A. 
 140, 130). — p-Toluidine forms, similarly, 
 (C,H5O)2(0bH8N),SO2.— Am i do-acids shaken 
 with aqueous solutions of SOj and benzoic 
 aldehyde form crystalline compounds, e.g. (from 
 gl y o c o 1 1) , 03H5.0H(0H) .S03.NH,.CH,.C02H, 
 and OsH5.CH(OH).S03.NH3.C„H,.C02H (from 
 amido-benzoio acid) (Schiff, A. 210, 123). — 
 3. With inorganic salts. C,HsO l^CaC^?) 
 (Ekmann, A. 112, 175).— CiHjOBFa (Landolph, 
 /. 1878, 621). 
 
 Oximv. Benzaldoxim. 
 
 Phenyl-hydrazide O^'Bi^.CR^T'^^UGa'n.^. 
 [153°]. Formed by adding a solution of phenyl- 
 hydrazine hydrochloride and sodium acetate to 
 an aqueous solution of benzaldehyde ; the white 
 pp. is distinctly visible with a solution of 1 pt. 
 of benzaldehyde in 50,000 pts. of water (Fischer, 
 B. 17, 574). Can be crystallised from alcohol. 
 Insol. water. Acetyl derivative C,3H|,N2Ao 
 [120°], long needles (Schroeder, B. 17, 2096). 
 Benzoyl derivative C„H5.CH:N.NBzPh : 
 [122°]. Formed from benzaldehyde and M-benzyl- 
 phenyl-hydrazine. Very thin silky needles. 
 V. sol. alcohol (Michaehs a. Schmidt, B. 20, 1717). 
 
 Methyl-phenyl hydraside 
 PhMeN.N:CH.Ph. [102°-104-5°].— 1. Formed in 
 small quantity from the methyl-phenyl-hydra- 
 zide of phenyl-glyoxylie acid (q.v.) at 120°. 
 Benzoic aldehyde and methyl-aniline are also 
 formed. — 2. From benzoic aldehyde andmethyl- 
 phenyl-hydrazine in alcoholic solution. White 
 needles (WaUach, A. Ill, 352). 
 
 Derivatives of Benzoic ortho-aldehyde are 
 described as Benztlidene derivatives. 
 
 BENZOIC ALDEHYDE, AMMONIA-DERI- 
 VATIVES OF. The most important of these 
 are hydrobenzamide, a/marine, and lophine. 
 
 1. Hydrobenzamide CjiHijNji.e. (CjH5.CH)3N2. 
 Fribenzylidene-diamine. [110°]. 
 
 Formation. — ^By the action of ammonia 
 upon benzoic aldehyde (Laurent, A. Ch. [2] 
 62, 23; 66, 18), upon benzylidene acetate 
 CJB.yCKiO.C^Bifi), (Wicke, A. 102, 368), or 
 upon benzyfidene-dichloride (Engelhardt, A. 
 110, 78). 
 
 Preparation. — ^Benzoic aldehyde, which must 
 be free from hydrocyanic acid, is left for some 
 days in contact with strong aqueous ammonia. 
 The crystalline mass which separates is washed, 
 first with water and then with ether, and finally 
 recrystallised from alcohol. Heat accelerates the 
 action, but diminishes the yield. Equation: 
 30,H3.CHO + 2NH3 = (C„H,.CH)3N, + 3H,0. 
 
 Properties. — Crystallises from hot alcohol in 
 colourless rhombic ootahedra, which are gene- 
 rally wedge-shaped. Insol. water : sol. alcohol 
 and ether. Has a sweetish taste and is not 
 poisonous. 
 
 Beactions.—l. When heated for several 
 hours to 120°-130° it is converted into the iso- 
 
 meric amarine (Bertagnini, A. 88, 127). By 
 destructive distillation it yields lophine CjiHjjN, 
 (Laurent). — 2. Boiling with aqueous potash 
 converts it into amarine (Fownes, T. 1845, 263), 
 whilst alcoholic potash breaks it up into ben- 
 zoic aldehyde and ammonia. This last decom- 
 position is also effected by prolonged boiling 
 with alcohol alone. Fusion with potash pro- 
 duces very complex decomposition, yielding 
 among other products lophine. — 3. Dilute acids 
 hydrolyse it readily on boiling, slowly in the 
 cold, into benzoic aldehyde and ammonia. The 
 ease with which this hydrolysis occurs is best 
 accounted for on the assumption that hydro- 
 benzamide is tribenzylidene-diamine. — 4. Dry 
 hydrobenzamide absorbs gaseous hydrochloric 
 acid. During the process a non-nitrogenous 
 substance volatilises, and the residue, when 
 treated with water, yields benzoic aldehyde and 
 ammonium chloride. If instead of treating the 
 residue with water it is heated, benzonitrUe and 
 benzyl chloride distil over, whilst a complex mix- 
 ture of basic substances remains (Ekmann, A. 
 112, 151 ; Kuhn,4. 122, 308).— 5. It unites with 2 
 mols.of hydrocyanic acid to form hydrobenzandde- 
 dihydrocyanide, a yellow crystalline mass melt- 
 ing at 55°, which, when treated with hydrochloric 
 acid, is decomposed into benzoic aldehyde and 
 phenylamidoacetonitrile : 02,H,5N2,2HCN + HjO 
 = C,HsO-h2CsH5.CH(NH3).CN, the latter com- 
 pound being subsequently hydrolysed to the 
 corresponding acid (Plochl, B. 13, 2119). Under 
 other conditions the benzoic aldehyde and 
 phenylamidoacetonitrile thus formed may unite 
 -with elimination of water to form benzoyl-azo- 
 tide, C.sHijNj, thus: C,H30 + C,H,.CH(NH2).CN 
 = CisHijNj-i-HjO (Ploohl, B. 14, 1142). When 
 an ethereal solution of hydrobenzamide is mixed 
 -with 1 mol. of hydrocyanic acid, and gaseous 
 hydrochloric acid is passed into the liquid, a 
 hydrochloride of the monohydrocyanide of hydro- 
 benzamide, C2|H,gN2,HCN,HCl, separates. On 
 boiling this precipitate with concentrated hydro- 
 chloric acid, it is decomposed into benzoic 
 aldehyde, ammonia, and the hydrochloride 
 of an anhydride of the formula CisHjiN^O: 
 
 0„H„N„HCN +2_H,0= 0„H,.N-,0 -1- O.H,.OHO +NR,. 
 The free anhydride melts at 164° and sublimes 
 -without decomposition ; the acid CigHuNjOj 
 melts at 120° (Plochl, JB. 14, 1139).— 6. Dissolved 
 in absolute alcohol and treated in the cold with 
 3 p.c. sodium amalgam it yields benzylidene-di- 
 benzylimide C,H5.CH(NH.CH2.CsH5)2. Astronger 
 amalgam, aided by heat, converts it into 
 benzylamine and toluene (0. Fischer, B. 19, 748). 
 7. Hydrobenzamide is also acted upon by 
 chlorine, sulphurous anhydride, sulphuretted 
 hydrogen, and ethyl iodide, but the reactions 
 are not of importance. 
 
 2. Amarine : CjiHigN^. Isomeric -with hydro- 
 benzamide. Probable constitution : 
 CA.O.NHv 
 
 II >CH.C„H5 (E. Fischer, A. 211, 217; 
 
 C„H5.C.NH/ 
 
 Japp a. Eobinson, C. J. 41, 323) ; or 
 C„H„CH.NHv 
 
 I 
 
 >■ 
 
 C.CjHj (Olaus, B. 15, 2333). 
 
 C.Hj.CH-N'' 
 [100°]. 
 
 Formation. — 1. By the action of ammonih 
 upon an alcoholic solution of benzoic aldehyde 
 
474 
 
 BENZOIC ALDEHYDE, AMMONIA-DERIVATIVES OF. 
 
 (Laurent, C. Ji. 19, 353).— 2. By boUing hydro- 
 benzamide with aqueous potash (Pownes, T. 
 1845, 263). — 8. By heating hydrobenzamide to 
 120°-130° (Bertagnini, 4.88, 127).— 4. Together 
 with lophine by distilling the double compound 
 of benzoic aldehyde and ammonium hydrogen 
 sulphite with excess of slaked lime (Gossmann, 
 A. 93, 329). — 5. In small quantity when am- 
 monia acts upon a mixture of benzoin and 
 benzoic aldehyde :— ChHi^Oj + C,HjO + 2NH, = 
 CjiHigNj + SHjO (Eadziszewski, B. 15_, 1495). 
 
 Preparation. — Hydrobenzamide is heated 
 from 2 to 4 hours at 120°-130°. The vitreous 
 mass thus obtained is dissolved in boiling alco- 
 hol, and an excess of hydrochloric acid is added. 
 The amariue hydrochloride, which separates in 
 white crystals, is purified by recrystallising from 
 boiling alcohol and is then decomposed with 
 ammonia. 
 
 Properties. — Deposited from alcohol in lus- 
 trous prisms. Melts at 100° (Fovvnes), but by 
 boiling for some time with water, is converted 
 into a granular substance melting as high as 
 126°. This modification is reconverted into 
 prismatic amarine, melting at 100°, by recrystal- 
 lisation from alcohol (Glaus, B. 18, 1678). 
 Insol. water, v. sol. alcohol and ether ; the alco- 
 holic solution having an alkaline reaction. Has 
 a bitter taste, which is noticeable only after a 
 time. Very poisonous. Combines with acids 
 to form sparingly soluble salts which have 
 an intensely bitter taste. — Cj,H,5N2,HCl. 
 Needles, sparingly soluble in boiling water. 
 — (Cj,H,sN2,HCl)2,PtCl^. Yellow crystalline 
 salt (Gossmann). — C2,H,8N2,HI (Borodine, 
 A. 110, 79). — C2,H,bN2,HN03 (Pownes). 
 (CjiH.gNJ^HjSO, -I- 3IH2O (Groth, A. 152, 122).— 
 (Cj,H,5N2)2,H2Cr20,. Yellow precipitate, almost 
 insol. water. 
 
 BeacUons. — 1. By destructive distillation it 
 yields ammonia, toluene, and lophine, CjiHi^N^ 
 (Pownes; v. also Eadziszewski, B. 10, 70). — 2. By 
 limited oxidation, as when the chromate is boiled 
 with glacial acetic acid, it is converted into 
 lophine: CjiHuNj -h = CjiHibNj -F H^O (Piseher 
 a. Troschke, B. 13, 707). Excess of chromic acid 
 oxidises it to benzoic acid. — 3. When a hot alco- 
 holic solution of amarine is acidified with acetic 
 acid and a hot concentrated solution of an alkaline 
 nitrite is added, nitroso-amarine, C2iH„(NO)N2, 
 separates, and, by reorystallisation from alcohol, 
 may be obtained in rhombic tables, which, 
 when heated to 150°, decompose with formation 
 of lophine (Borodine, B. 8, 934).— 4. With 
 nitric acid in the cold, mononitro-amarine, 
 C2,H„(N02)N2, is formed ; hot nitric acid con- 
 verts it into dimtro-amarine, C2|H,„(N02)2N2. 
 The latter compound yields, with reducing 
 agents, diamido-amarine, C^tSisi'S'B.^)^'!^!.^. Salts 
 of these nitro- and amido- bases have been pre- 
 pared (Glaus a. Witt, B. 18, 1670).— 5. With 
 acetyl chloride an ethereal solution of amarine 
 yields a product which, when treated with 
 alcohol, is separated into amarine hydrochloride 
 and diacetyl amarine, C2,H,j(C2H30)2N2 [268°] 
 (Bahrmann, J. pr. [2] 27, 295).— 6. Amarine 
 reacts with the halogen compounds of the alkyls 
 to form substitution- and addition- compounds. 
 Thus when amarine, methyl iodide, and ether 
 are allowed to stand together in the cold, methyl- 
 amarine hydriodide, CjiHuMeNj.HI, is formed. 
 
 Ammonia is without action upon this salt, but 
 alcoholic potash liberates raethylamarine [184°]. 
 When amarine is heated with methyl iodide, a 
 dimethylamarine hydriodide, OjiHujMejNjiHI, is 
 formed. Like the monomethyl compound it is 
 not decomposed by ammonia ; by treatment 
 with alcoholic potash, dimethylamarine [146°] 
 is obtained, and this base unites vrith hydriodio 
 acid to form a hydriodide isomeric with the 
 foregoing and differing from it in being decom- 
 posed by ammonia even in the cold (Glaus a. 
 Elbs, B. 13, 1418). Dimethylamarine and the 
 other dialkyl-amarines do not combine with the 
 halogen compounds of the alkyls. 
 
 Further derivatives of amarine. — Ethyl- 
 amarine, C2,H„EtN2 [163°] (Glaus a. Scherbel, 
 B. 18, 3080) ; diethylamarine, C2,H,jEt2N2 
 [H0°-115°] (Borodine, A. 110, 62).—Bemyl- 
 amarine, G2,H„(0,H,)N2 [123°-124°] ; dihemyl- 
 amarine, G2,H,s(C,H,)2N2 [139°-140°] (Glaus a. 
 Elbs, B. 13, 1418; Glaus, B. 15, 2330; Glaus a. 
 Kohlstock, B. 18, 1849). — Ethylbeneylamarine, 
 C2,H,„Et(G,H,)N2 [135°] (G. a. K^.— Hydro- 
 mci%26ere22/Zamari»ie,G2,H,8Me(G,H,)NjO [208°] ; 
 hydrotrimethylamarine, 02,H„Me3N20 [158°] 
 (Glaus, B. 15, 2326). — Other derivatives : 
 02,H„N2(C,H,0).OEt; C2,H„N2(G02Et)2 ; and 
 C2,H,5N2(G02Et)(CONHEt) (Bahrmann, J. pr. 
 [2] 27, 295). — Ama/nme-silver, CjiHirAgNj (Glaus 
 a. Elbs, B. 16, 1272) ; diamarine silver nitrate, 
 (G2,H„Nj2,AgN03 aq [218°] (G. ». K.). 
 
 When amarine silver is mixed with one mo- 
 lecular proportion of an alkyl-halogen compound 
 (the latter diluted with benzene) and allowed to 
 stand in the cold, a double compound of amarine- 
 silver with the alkyl-halogen is obtained. At tho 
 same time a small quantity of monalkyl-amarine 
 is formed from the double compound by elimina- 
 tion of silver iodide. In this way the following 
 compounds have been prepared (Glaus a. Scher- 
 bel, B. 18, 3077) : amarine-silver methylo-iodidc, 
 G2,H„AgN2,GH3l [173°] ; amarine-silver ethylo- 
 iodide, 02,H„AgN2,G;H5l [115°]; amarine-silver 
 isopropylo-bromide, C2,H„AgN2,C3H,Br, [140°] ; 
 and finally amarine-silver benzylo-chloride, 
 C2,H„AgN2,G,H,Cl, [250°]. When amarine-sil- 
 ver is treated with benzoyl chloride it yields 
 bemoyl-amarine, C2,H,j(G,H50)N2, [180°], which 
 forms salts with acids and also unites with ben- 
 zoyl chloride to form benzoyl-amarine benzoyl 
 chloride, G2,H„(G,H50)N2,C,H50G1, [312°], and 
 with benzyl chloride to form benzoyl-amarine 
 benzylo-chloride, C2,H,;(C,H,0)N2,C,H,C1 [351°], 
 which latter is isomeric with benzyl-amarine 
 benzoyl chloride,G^,U,,{C,K,)T!i^,G,B.fiCl, [340°- 
 350°], obtained by the action of benzoyl chloride 
 upon benzyl-amarine. The bases corresponding 
 with these two chlorides are also isomeric. 
 Benzoyl-amarine also unites with methyl iodide 
 and with ethyl iodide to form additive compounds 
 melting at 318° and 354° respectively (0. a. S.). 
 CjHs.CNHv 
 
 3. Lophine G2,H,sN2= || ^C.G^H^. 
 
 CeH^.C-N-^ 
 Triphenylglyoxaline (Japp a. Eobinson, C. J. 
 41, 323). [275°]. 
 
 Formation.— 1. By the destructive distilla- 
 tion of hydrobenzamide (Laurent, A. Ch. 19, 
 369), of amarine (Pownes, T. 1845, 263), or of 
 tribenzylamine (Brunner, A. 151, 135). By 
 the limited oxidation of amarine with chromic 
 
BENZOIC ALDEHYDE, AMMONIA-DERIVATIVES OF. 
 
 478 
 
 acid (E. Fisoher a. Trosohke, B. 13, 708).— 
 3. By passing ammonia into a warm alcoholic solu- 
 tion of a mixture of benzil and benzoic aldehyde : 
 C,H,.CO 
 
 C.H,.CO 
 
 + aH,.0H0 + 2NH,= 
 
 (Eadziszewski, B. 15, 1493 ; cf. Japp, B. 15, 
 2410).— 4. By heating together p-oxybenzoio 
 aldehyde, benzil, and ammonia, ^-oxy-lophine, 
 C2,H,5(OH)N2, is formed (v. Benzil, ammonia- 
 DEBivATivES OF, p. 466) ; and this, by distillation 
 with zino-dust, is converted into lophine (Japp 
 a. Eobinson, C. J. 41, 323). — 5. By warming 
 cyanphenine, CjiHi^Nj, with acetic acid and zinc 
 dust, or by distilling it with potash and iron 
 filings, it is converted into lophine and ammonia : 
 CjiHi^N, + 2H2= C^iHijNj + NH, (Eadziszewski). 
 
 Preparation. — Hydrobenzamide is heated in 
 a retort until the more volatile products of its 
 decomposition — ^hydrogen, ammonia, and toluene 
 — have been given off. The residue, which can 
 only be distilled at a high temperature, is treated 
 with ether, and then dissolved in glacial acetic 
 acid. From this solution water precipitates 
 lophine, which is finally purified by recrystal- 
 lising it from boiling alcohol (Eadziszewski, B. 
 10, 70). 
 
 Properties. — Crystallises in very slender, 
 colourless silky needles [275°] (Eadziszewski). 
 Distils without decomposition at a high tem- 
 perature. The vapour-density agrees with the 
 formula CjiHuNj (Fischer a. Troschke). Insol. 
 water, si. sol. alcohol and ether. Its solution 
 in alcoholic potash phosphoresces when air is 
 admitted, owing to a process of oxidation, in 
 which the lophine is slowly converted into ben- 
 zoic acid and ammonia (Eadziszewski). Feebly 
 basic : the salts are partially decomposed by 
 water, in which they are for the most part inso- 
 luble ; but they may be crystallised from alcohol. 
 
 Salts. — (Laurent, A. Ch. 19, 369; Atkinson 
 a. Gossmann, A. 97, 283; Brunner, A. 151, 135). 
 02,H,jN2,HCl^aq : obtained by adding hydro- 
 chloric acid to an alcoholic solution of lophine. 
 According to Laurent and Brunner this salt is 
 anhydrous. — C2,H,jN2,2HCl:formedbytheaction 
 of gaseous hydrochloric acid upon lophine. — 
 (C2,H,jNj,HCl)2,PtCl4. : rhombic plates. Con- 
 tains 5HjO (Brunner). — Cj,H,eN2,HI. — 
 Cj,H,8N2,HN0j.— With silver nitrate it gives rise 
 to: C„H,eN2,AgN03; 2C„H,eN2,AgNOs ; and 
 2C„H,«N2,3AgN03 (A. a. G.). 
 
 BeacUons. — 1. Oxidation with chromic acid 
 in acetic acid solution converts lophine into 
 a mixture of benzamide and dibenzamide : 
 
 CsHj.CONHj + (CsHj.COjjNH 
 (Fischer a. Troschke). — 2. By the action of 
 bromine upon lophine hydrobromide, an 
 unstable perbromide of the formula, 
 C2,H,5N2Br„, HBr(?), is obtained (F. a. T.).— 
 3. Nitric acid yields, according to temperature 
 and concentration, either dinitrolophine, 
 C2,H„(NOj)2Nj, or trvmtrolopUne C2,H,3(N02)3N2 
 (Laurent; Ekmann, A. 112, 161).— 4. Heated 
 with concentrated sulphuric acid to 160°-170° 
 lophine is converted into lophine-disulpJwnic 
 aoid, C„H„Nj(S03H), (F. a. T.).-5. With 
 ethyl iodide at 100° it yields lophine hydriodide 
 
 and diethyllophimium iodide, CjiHijEtN^, Etl ,■ 
 and this latter compound, by treatment with 
 moist silver oxide yields the corresponding base 
 (Kflhn, A. 122, 326). 
 
 IsoMEEiDE OP LOPHINE. — Aocordiug to Kuhn 
 {A. 122, 813) an isomeride of lophine, 
 CjiHijNjJaq, is obtained, together with 
 ordinary lophine, by saturating hydrobenzamide 
 with gaseous HCl, and heating the mixture to 
 230°. Needles [170°], v. sol. boiling alcohol. 
 Forms salts. 
 
 AzoBENZOiLn)B,Cj2H33N5(?) (Laurent, .4. C/j.[3] 
 1, 306) and eibenzovlimide, CnHijNO (Eobson, 
 C. J. 4, 225), are also compounds which are 
 stated to have been obtained by the action of 
 ammonia upon benzoic aldehyde. They have 
 been very little studied. 
 
 Benzoic aldehyde, hydeooyanio acid, and 
 ammonia. — A number of compounds are obtained 
 when ammonia acts upon benzoic aldehyde 
 containing hydrocyanic acid. Some of these 
 are, however, more readily pirepared from the 
 hydrocyanides of hydrobenzamide {q. v.) and 
 have therefore been described under that 
 head. — 1. Benzoylazotide, C.sHijNj. Formed 
 along with other products when a mixture of 
 benzoic aldehyde, " hydrocyanic acid, and 
 ammonia is allowed to stand for some weeks 
 (Laurent, A. Ch. [2] 66, 180 ; vide supra, 
 ' Hydrobenzamide '). Crystalline powder, con- 
 sisting of minute rhombic prisms, si. sol. boiling 
 alcohol. By destructive distillation it yields 
 amarone, C,sHiiN, together with lophine and 
 other products. Amarone forms colourless 
 needles [233°], si. sol. boiling alcohol (Laurent, 
 Bevue Scient. 18, 207). — 2. Azohemoyl, CjjH^Nj, 
 is formed according to the equation : 
 
 SCjH^O + HCN + NH3 = CjjHijNj + SH^O 
 (Beilstein a. Eeineeke, A. 136, 175). White 
 crystalline powder, insol. water, v. sol. ether. 
 When warmed with alcohol and hydrochloric 
 acid it is decomposed into HCN, amarine, and 
 a base of the formula C^H^Nj, which latter 
 crystallises in laminse, melting at 122° (Miiller 
 a. Limpricht, A. Ill, 140). — 3. Bemhydramide, 
 C22H,bN20, is formed, along with the foregoing, 
 from the same generating substances according 
 to the equation: 3C,HsO + HCN + NH, = 
 Cj^HjjNjO + 2H2O, and differs from it by con- 
 taining the elements of a molecule of water 
 more. Microscopic crystals. SI. sol. alcohol, 
 V. sol. ether (Laurent, A. Ch. [2] 66, 180; 
 Laurent a. Gerhardt, A. 76, 302). 
 
 Benzoio aldehyde, ammonia, and sul- 
 PHUBETXED HYDKOGEN. — 1. Benzoic aldehyde and 
 ammonium sulphide, if mixed and allowed to 
 stand for some weeks, yield thio-benzaldin, 
 
 3C,H,0 + 2H2S + NH3 = CjiH.aNSj + 3HjO 
 (Laurent, A. Ch. [3] 1, 291 ; also [3] 36, 342). 
 Deposited from ether in monoclinic crystals 
 [125°]. When boiled with alcohol it gradually 
 evolves sulphuretted hydrogen. — 2. By the 
 action of ammonium sulphide upon crude oil of 
 bitter almonds Laurent obtained a compound 
 C,2H3»N,S3(?). 
 
 Benzoic aldehyde slowly reacts in the cold 
 with CSj and NH3 to form a compound, 
 C.sHnNjSj (Quadrat, A. 71, 13). The same 
 substance is formed when benzoio aldehyde 
 is mixed with ammonium thio - carbamate ; 
 2C,H.O + CSj + 2NH, = C,jH„NjSj + 2HjO (Mul 
 
BENZOIC ALDEHYDE, AMMONlA-DERlVATlVES OF. 
 
 der, A. 168, 238). Prismatic crystals, melting 
 with decomposition at 100°. Cannot be dis- 
 solved in alcohol or ether without decomposi- 
 tion. The compound may be regarded as M- 
 bemyUdene - ammonium dithio • carbamate, 
 NH,.CS.S.N(CH.C„H,)"j. F. E. J. 
 
 BENZOIC ALDEHYDE CABBOXYLIC ACID 
 
 V. AliDEHYDO-BENZOIC ACIB. 
 
 BENZOIC ALDEHYDE GEEEN v. Teira- 
 
 MBTHTL-DIAMIDO-TBrPHENYL-OAEBINOL. 
 
 BENZOIC ANHYDBIDE C„H,„03 i.e. 
 (CsHs.COjjO. Benzoyl oxide. Mol. w. 226. 
 [42°]. (360° i.V.). S.G. (Uquid) SI 1.227. 
 H.P. 104,815 (Stohmann, J.pr. [2] 36, 3). 
 
 Formation. — 1. FromBzCl and NaOBz, BaO, 
 HjCjO,, or £2020, ; or from NaOBz by the ac- 
 tion of PCI5, POCla, or SjClj (Gerhardt, A. Ch. 
 [3] 37, 299; Wunder, J. pr. 61, 498; Heintz, 
 P. 92, 458 ; Gal, A. 128, 127 ; Anschiitz, B. 10, 
 1882).— 2. From benzotriohloride (1 pt.) and 
 HjSO^ (3 pts. of 95-4 p.c.) (Jenssen, B. 12, 
 1495). — 3. By the action of the dry nitrates 
 (6 mols.) of Pb, Ag, Hg, Cu, or Zn upon ben- 
 zoyl chloride (1 mol.) {q. v.) (Lachowioz, B. 18, 
 2990). 
 
 Properties. — Trimetrio prisms, insol. water, 
 m. sol. alcohol and ether. Slowly converted 
 into benzoic acid by boiling water, more rapidly 
 by alkalis. Hot KH,Aq forms benzamide and 
 ammonium benzoate. Combines with bromine 
 (1 mol.). Gaseous HCl forms BzCl and HOBz. 
 
 Uized Anhydrides. — Mixed anhydrides of 
 the form BzOB are formed by the action of 
 benzoyl chloride on the alkaline salts of various 
 acids, or by the action of various alkoyl chlorides 
 on sodium benzoate. They are generally decom- 
 posed by heat into a mixture of two anhydrides ; 
 and by water, more rapidly by alkalis, into two 
 acids. 
 
 Benso-acetic anhydride Ac.O.Bz v. 
 
 ACETO-BENZOIO OXIDE, p. 17. 
 
 Benzo-isovaleric anhydride 
 Bz.O.CjHgO. OU (Chiozza, A. 84, 108). 
 
 Benzo-heptoic anhydride Bz.O.CjH^O. 
 Oil. S.G.lil'043(Chiozzaa.Malerba,4. 91, 102). 
 
 Benzo-pelargonic anhydride 
 BzO.CsH.jO. Oil (Chiozza, A. Ch. [3] 89, 209). 
 
 Benzo-myristic anhydride 
 BzO.CuHjjO. [38°]. 
 
 Benzo-stearic anhydride BzO.CjgHjjO. 
 [70°] (C. a. M.). 
 
 Benzo-angelic anhydride BzO.CsHjO. 
 (C). Oil. 
 
 Benzo-cinnamic anhydride 
 Bz.O.CsH,0. Oil. S.G. sa 1-184. 
 
 BenzO'CUminic anhydride 
 Bz.O.O,„H„0. Oil. S.G. ^1-115. 
 
 BENZOIC BROMIDE v. Benzoyl bbomibe. 
 
 BENZOIC CHLOKIDE v. Benzoyl chloride. 
 
 BENZOIC CYANIDE v. Benzoyl cyanide. 
 
 BENZOICIN V. Tri-benzoyl-GhrcEms. 
 
 BENZOIC OXIDE v. Benzoic anhydride. 
 
 BENZOIC PEROXIDE v. Benzoyl pekoxide. 
 
 BENZOIN C„H,202 = C6H,.CH(0H).C0.CsH5. 
 Phenyl-benzoyl-carbinol. [137°]. First prepared 
 by Stange (B. P. 16, 93), and almost simulta- 
 neously by Eobiquet {A. Ch. [2] 21, 254), by 
 acting with a solution of potassium hydroxide 
 or barium hydroxide upon crude oil of bitter 
 almonds containing HCN. 
 
 Formation. — 1. By partial oxidation of 
 
 hydro - benzoin, C,H5.CH(0H).CH(0H).C,H, 
 (Zinin, A. 123, 128).— 2. By treating benzil 
 CbHs.CO.CO.CjHs with zino and alcoholio 
 hydrochloric acid (Z., A. 119, 177), with acetic 
 acid and iron filings, or with K^S. 
 
 Preparation. — 200 g. of pure benzoic alde- 
 hyde are heated for a short time with a solution 
 of 20 g. of KCN in 800 g. of 50 p.c. alcohol, and 
 the liquid allowed to cool. Benzoin separates 
 and is removed by filtration. The filtrate, on 
 heating with more KCN, yields a fresh quantity 
 of benzoin (Zinoke, A. 198, 151). Two mols. of 
 benzoic aldehyde unite to form 1 mol. of 
 benzoin : 2CsH5.CHO = CsH5.0H(OH).CO.C„H5. 
 The action of the KCN is not understood. 
 
 Properties. — Colourless, lustrous, six-sided 
 prisms. SI. sol. boiling water. V. sol. hot al- 
 cohol ; si. sol. in cold. Cone. HjSO, dissolves 
 it with a violet colour. 
 
 Baactions. — 1. Partially decomposed by diS' 
 tillation. Bepeated distillation breaks it up for 
 the most part into 2 mols. of benzoic aldehyde ; 
 a smaller portion yields benzil and deoxy- 
 benzoin : 2C„H,202= CnHuOj + 0„H,20 + H^O 
 (Zinin, B. 6, 1207).— 2. Treated in alcoholio 
 solution with zinc and hydrochloric acid it is 
 converted into deoxybeuzoin (Zinin, A. 126, 218) ; 
 at the same time deoxybenzoin-pinacone, 
 C28H24(OH)2, and hydrobenzoin are formed (Gold- 
 enberg, A. 174, 332). Sodium amalgam reduces 
 it to hydrobenzoin. Heating with cone, hydriodic 
 acid for some hours to 130° converts it into di- 
 benzyl CijH,,, (Goldenberg). By distillation with 
 zinc-dust it yields stilbene, C,,H|2, together with 
 an oily hydrocarbon isomeric with stilbene (Jena 
 a. Limpricht, A. 155, 90). — 3. Nitric acid oxi- 
 dises it to benzil (Zinin) ; but chromic acid, or 
 potassium permanganate, converts it into benz- 
 aldehyde and benzoic acid (Zincke, B. 4, 839). 
 It reduces Fehling's solution in the cold, a pro- 
 perty common to all compounds containing the 
 group Cp.CH(OH) (B. Fischer, A. 211, 215).— 
 4. Fusion with caustic potash converts it into 
 benzoic acid with evolution of hydrogen (Liebig 
 a. Wohler, A. 3, 276). When distilled with soda- 
 lime, the benzoate which is first formed is decom- 
 posed by the excess of soda-lime, and benzene 
 is obtained (Jena a. Limpricht). The action of 
 alcoholic potash is complex : when benzoin and 
 alcoholic potash are heated with access of air, 
 benzoic acid, a small quantity of benzilic acid 
 (Cj^H.jOs), benzoin ether (C^sHj^Oj [157°]), and 
 a compound G^^'B.^fl^ (to which Limpricht a. 
 Schwanert gave the name ethyl-dibenzoin, assign- 
 ing to it the formula CjuHjsOj) are formed — this 
 last, however, is produced from benzil genejated 
 by the air-oxidation of the benzoin [v. Benzil). 
 If the benzoin is heated with alcoholio potash in 
 a sealed tube at 100° the products are benzoic 
 acid, hydrobenzoin, and ethylbenzilic acid 
 (CijHijO.,). With very concentrated alcoholic 
 potash at 160° benzoin yields benzoic acid, 
 stilbene, a compound C^gHasOj and a small quan- 
 tity of ethyl-benzilic acid. By heating benzoin 
 with a solution of sodium ethylate in alcohol, 
 ethyl-benzoin, CijH^Oj.CjHs [95°], is formed, 
 together with the various products already men- 
 tioned. Prisms, with a vitreous lustre, v. sol. 
 alcohol (Jena a. Limpricht, 4. 155, 89 ; Limpricht 
 a. Schwanert, B. 4, 336 ; Japp a. Owens, C. J. 
 47, 90). — 6. Chlorine acts like nitric acid, con- 
 
BENZO-DI-METHYL-DI-FURFURANE. 
 
 477 
 
 verting benzoin into benzil (Laurent, A. Ch. [2] 
 69, 401). — 6. When heated with fuming hydro- 
 chloric acid at 130° for 6 or 8 hours it yields 
 lepidene, CjbHjoO (q. v.), benzil, and a thick 
 yellow oil (Zinin, J. pr. 101, 160).— 7. When 
 boiled with dilute sulphuric acid it parts with 
 the elements of water, yielding oxylepidene : — 
 2C„H,202 = CasHjoOj + 2H2O (Limprioht a. 
 Sohwanert, B. 4, 335). Concentrated sulphuric 
 acid converts it into benzil (Zinin). — 8. Heated 
 with alcoholic ammonia for some hours at 100° 
 in sealed tubes it yields bemofinam, CjsHjjNjO 
 (silky needles, v. si. sol. alcohol, melting with 
 decomposition), henzoKnidam, CjsHjjNOj ? [199°] 
 (granular crystals, si. sol. alcohol), and Utra- 
 
 O^H^.C-N-COA 
 phenyl-azine, || | || [246°], to- 
 
 CsH3.C-N-0.C,H5 
 gether with some lophine, CjiHi^Nj. Tetra- 
 phenyl-azine is best prepared by heating benzoin 
 with ammonium acetate until the salt is volati- 
 lised, dissolving the product in the strongest 
 alcoholic hydrochloric acid, and ppg. with alco- 
 hol. V. si. sol. alcohol, v. sol. alcoholic hydro- 
 chloric acid, V. sol. boiling benzene, sol. with 
 blood-red colour in cold cone. H^SO^. Sublimes 
 without decomposition. Heating with soda- 
 lime converts it into tetraphenylene azine 
 CjaHisNj (Laurent, A. Ch. [2] 66, 181; Erd- 
 mann, A. 185, 181 ; Japp a. Wilson, O. J. 1886, 
 825; Japp a. Burton, O. J. 1886, 843; 1887, 
 98). — 9. Benzoin reacts with the primary 
 amines of the benzenoid series, when heated 
 with them to 200°, eliminating 1 mol. of water 
 and generating feebly basic compounds which 
 by boiling with acids are decomposed into 
 their generating substances. Anilbenzoln 
 CA.CH(0H).0(N.CA).C,H5 [99°], from ani- 
 line and benzoin, forms yellowish needles, 
 V. sol. most organic menstrua. Yields 
 with nitrous acid nitroso - anilbenzoln 
 C„H5.CH(OH).C(N.CeH,.NO).C„H5 [140°], with 
 acetic anhydride a moiMcetyl-derivative [153°], 
 and with bromine a monobromo - derivative 
 [168°]. Sodium amalgam reduces anilbenzoin 
 in alcoholic solution to hydrobenz&tn-anilide 
 C»H5.CH(OH).CH(NH.CeH5)CeH5 [119°], which 
 forms with sulphuric acid a salt not decomposed 
 by boiling with the dilute &cii.—p-Tolilbemo'in 
 C,H,.CH(OH).C(N.C„Hj.CH3).C,H5 [144°] re- 
 sembles in its properties and its behaviour 
 towards reagents the aniline compound. It 
 yields with nitric acid a mono-nitro- derivative 
 [125°] and a di-nitro- derivative [195°]. — 
 $ - Naphthilbenzcfim, [130°] also resembles 
 the aniline compound (Voigt, J. pr. 34, 
 1). — 10. Benzoin reacts with hyAroxylamine 
 and with phenyl -hydrazine. — Benzo'in-oxim, 
 C„H5.CH(0H).C(N.0H).C,H, [151°-152°]. An 
 alcoholic solution of benzoin is mixed with 
 an aqueous solution of hydroxylamine and 
 allowed to stand for a week. Microscopic 
 prisms, soluble in benzene (Wittenberg a. V. 
 Meyer, B. 16, 50i). —Benzo'in-phenylhydrazide, 
 OeH5.CH(OH).C(N.^.O.H,).C,H5 [155°]. Benzoin 
 and phenylhydrazine, together with a little 
 alcohol, are heated at 100°- Needles, sol. benz- 
 ene (Piokel, A. 232, 229).— 11. By heating with 
 aci-chlorides the hydroxylic hydrogen of benzoin 
 maybe replaced by acid radicles to form ethereal 
 gftlta. Penzoin acetate, Ci,H„(C2H,0)02 [75°]. 
 
 From benzoin and acetyl chloride. Monoclinio 
 prisms or tables, v. sol. ether and alcohol 
 (Zinin, A. 104, 120 ; Jena a. Limpricht, A. 155, 
 ^2).— Benzoin benzoate, 0,4H„(0,H50)02 [125°]. 
 By warming benzoin with benzoyl chloride. 
 Slender needles. Sol. hot alcohol. Yields a 
 mono-nitro- compound [137°] (Zinin). — Benzoin 
 succinate, {G^^li^fi^)fi^B.,0, [129°]. By heating 
 benzoin with succinyl chloride to 100°. Leaflets 
 from alcohol. Sol. also in ether and CS2 
 (Lukanin, B.5, 331). — 12. When benzoin is heated 
 with hydrocyanic acid and alcohol to 200° the 
 process of its formation is reversed and it is 
 broken up into benzoic aldehyde. A part of the 
 benzoic aldehyde undergoes a further change, 
 yielding amongst other products ethylic benzoate 
 (Michael a. Palmer, Am. 7, 192).— 13. Phenyl 
 cyanate forms Ph.CH(O.CONPhH).CO.Ph [163°] 
 (Gumpert, /. pr. r2] 32, 280). F. B. J. 
 
 BENZOIN, GVK. A resin which flows from 
 the bark of Styrax benzoin, a tree growing in 
 Sumatra, Borneo, Java, and Siam. Gum ben- 
 zoin contains, besides various resins, benzoic 
 acid and, frequently, cinnamio acid. Siamese 
 and Palembang benzoins are free from cinnamio 
 acid. Potash fusion produces benzoic, ^'-o^y- 
 benzoic, and protocatechuic acids, and pyro- 
 catechin. Distillation with zinc-dust gives 
 toluene and a little o-xylene, naphthalene, and 
 methyl-naphthalene. 
 
 References. — Unverdorben, P. 8, 397 ; Van 
 der Vliet, A. 34, 177 ; Kopp, C. B. 19, 1269 ; 
 Kolbe a. Lautemann, A. 115, 113 ; 119, 136 ; 
 Deville, A. Ch. [3] 3, 192 ; Ashoff, J. 1861, 400 ; 
 Wiesner, J. 1872, 1060; Theegarten, J. 1874, 
 922 ; Giamioian, B. 11, 274 ; Saalfeld, A. Ch. 
 [3] 16, 280. 
 
 BENZOIN DI-^-CAEB0X7LIC ACID 
 C„H,A*-«-C6Hj(C02H).CH(OH).CO.C«H,(C02H). 
 Formed by oxidation of di-2)-aldehydo-benzoin 
 with KMnOj. Short felted needles. Sublim- 
 able. Infusible. Ag^A". Di-methyl ether 
 Me^A": [126=] (Oppenheimer, B. 19, 1816). 
 
 BENZOLEIC ACID C,H,„02 Hydrobenzoic 
 acid. Formed, together with benzyl alcohol, by 
 the action of sodium amalgam on an aqueous 
 solution of benzoic acid kept acid by HCl (Her- 
 mann, A. 132, 75; Otto, A. 134, 303). Oil, 
 smelling of valeric acid, heavier than water, v. 
 sol. alcohol and ether.— EtA': oil. 
 
 BENZOLINE. A mixture of paraffins (hex- 
 ane, heptane, octane) boiling between 70° and 
 100° obtained by distilling petroleum or paraffin 
 oil. The mixture is also called petroleum 
 spirit or ligroin. 
 
 BENZOLON. Identical with lophine {v, 
 Benzil). 
 
 BENZODIMETHYLANILINE v. Dimethyl. 
 
 AMIDO-BENZOPHENONE. 
 
 m-BENZO-DI - METHYL - DI - FURFURANE. 
 
 C.,H,0.ie. ^^^ ^^^ 
 
 HC<C^«>C,H<CMe^OH. 
 
 (2) (6 or 4) 
 
 [c. 27°]. (270° at 720 mm.). Obtained by eva. 
 porating (^)-benzo-di - methyl - di - f urfurane - di - 
 
 carboxylic ether C8H2(<^Q*>C.C02Et)2 with 
 
 alcoholic KOH and lime, and dry distillation. 
 Prisms. Py warming with cone. HjSO, a pure 
 
478 
 
 BENZO-DI-METHYL-DI-FURFUKANE. 
 
 blue colouration 1b produced (Hantzach, B. 19, 
 2933; 20,1837). 
 
 ^-Benzo-di-methyl-di-furfurane 
 
 CeHj(<;^^^^CHV. [108°]. Obtained by 
 
 heating the potassium salt of the di-carboxylic 
 acid with lime. Large pearly tables with bluish 
 fluorescence. V. sol. alcohol, ether, etc. (Nuth, 
 B. 20, 1337). 
 
 Benzo-tri-methyl-tri-furfurane C,5H,203 i.e. 
 
 c/<^q®^ChV. [115°-120°]. Needles. 
 
 Very soluble in ordinary solvents. Formed by 
 evaporating the tri-carboxylic ether 
 
 C»r<^'^Q®^C.C02Et\ with alcoholic KOH and 
 
 lime, and dry distillation (Lang, B. 19, 2936). 
 
 o-BENZO - DI - METHYL - DI - FUBFXrEANE 
 DI-CABEOXTLIC ACID 
 
 CA {-^^^^^^CCO^n) J. Obtained by sapo- 
 nification of the ethyl-ether which is formed by 
 dissolving in cone. HjSO, the product of the 
 action of chloracetoacetic ether (2 mols.) upon 
 di-sodium pyrocatechin (1 mol.). Amorphous 
 solid.— BaA" 2aq. 
 
 Di-ethyl ether Et^A": [155°] ; short prisms 
 (from alcohol), or long white needles (from 
 ether) (Nuth, B. 20, 1337). 
 
 (a)-OT-Benzo-di -methyl - dl - f urfurane di-car- 
 bozylic acid CuHuOj i.e. 
 
 (1) (5) 
 
 HOjC.C.^ Q >CaHj< Q !>C.COjH. [Far 
 
 (2) (4 or 6) 
 
 above 810°]. Formed by saponification of the di- 
 ethyl-ether. This ether is obtained, together 
 with a much larger quantity of the (^)-isomeride 
 , by the action of ohloro-acetacetio ether upon di- 
 sodium resorcin 06H,(0Na)j in presence of 
 alcohol, extracting with benzene, dissolving the 
 undissolved portion in cone. H^SO,, pouring 
 into water, and extracting with ether ; when the 
 ethereal solution is mixed with hot alcohol and 
 allowed to cool the (o)-ether crystallises out, 
 whilst the (;8)-ether remains in solution. The 
 two ethers are also formed (the a in very small 
 quantity) by heating oxy-methyl-coumarilic ether 
 
 (4) *'^^ 
 CjH3(0H)<;'-'Q®^C.C0,Et with ohloro-aceto- 
 
 (2) 
 acetic ether and alcoholic NaOEt, and dissolving 
 the product in H^SO,. The acid is a white 
 microcrystaUine sohd. Scarcely soluble in 
 water, more readily in alcohol. The salts of 
 the heavy metals are all sparingly soluble. 
 Warm H^SO, produces a pure blue colouration. 
 
 Di-ethyl ether M'^^i^: [186°]; needles; 
 si. sol. alcohol (Hantzsch, B. 19, 2930). 
 
 (i3)-OT-Benzo-di - methyl-di -furfurane-di - car- 
 boxylic acid C„H,„Ob i.e. 
 
 (1) (6) 
 
 H0,C.C<^^^>CeH,<^^^C.C0,H. [Far 
 
 (2) (6 or 4) 
 
 above 310°]. Formed by saponification of its 
 di-ethyl ether. MicrocrystaUine sohd. Scarcely 
 soluble in water, more easily in alcohol. Gives 
 sparingly soluble pps. with the salts of the 
 heavy metals. The acid and its ether give a 
 pure blvie colouration with warm H^SO^. 
 
 acid OisHi-Og i.e. CA 
 
 Di-ethyl ether A"Et2: [141°] ; small white 
 needles; more soluble than the (3)-isomeride. 
 Formed, together with a small quantity of the 
 (i3)-ether, by the action of chloro-acetacetic ether 
 upon dry di-sodium resorcin, extraction with 
 benzene, dissolving the residue in cone. H^SO^, 
 pouring into water, and extracting with ether. 
 Also by heating oxy-methyl-ooumarilio ether 
 
 CbH3{0H) <^ q ^^C.COjEt with chloro-acetacetic 
 
 (2) 
 
 ether and alcohoUc NaOEt, and dissolving the 
 product in H^SO,. By evaporation with alco- 
 holic KOH and lime and dry distillation it 
 yields (j3) - benzo -di - methyl - di - furf urane 
 
 C,h/<^^^^Ch)2. (Hantzsch, B. 19, 2930). 
 
 ^-Benzo-di-methyl-di-furfuranedi-carboxylio 
 
 acid C5h/<'^q^^C.C02hV. Obtained by 
 
 saponification of its ethyl-ether which is 
 formed by dissolving in cone. H2SO4 the 
 product of the action of chloro-acetacetic ether 
 (2 mols.) upon di-sodium hydroquinone (1 mol.). 
 Amorphous solid (containing aq). 
 
 Salts AgjA": white pp. — BaA" 2aq : si. 
 
 sol. yellowish-white powder. 
 
 Ethyl ether Et^A": [150°]; glistening 
 greenish plates ; v. si. sol. aU solvents (Nuth, B. 
 20, 1334). 
 
 Benzo-trl-methyl-tri-furfurane-tri-carboxylio 
 
 (<'^^>c.co,h)3. 
 
 Formed by saponification of its ethyl ether which 
 is obtained by treating dry powdered tri-sodium- 
 phloroglucol (1 mol.) with chloro-acetacetic 
 ether (3 mols.), dissolving the product in HjSO, 
 and pouring into water. Gelatinous pp. (contain- 
 ing aq). Scarcely soluble in alcohol and ether. 
 Its salts are mostly insoluble and gelatinous. 
 Ba3A"'j 7aq : microcrystaUine. 
 
 Ethyl ether BtsA'" : [c. 298°] ; smaU white 
 glistening needles ; si. sol. all solvents, most 
 readily in chloroform (Lang, B. 19, 2935). 
 
 BENZOHAFHTHOITE v. Naphthoquinonb. 
 
 BENZONAPHTHYL-THIAMIDE v. Thioben- 
 
 Z02/Z-(o)-NAPHTHYLAMrNE. 
 
 BENZONITEILE CH^N i.e. CeH5.CN. Mol. 
 w. 103. [-17°] (Hofmann). (190-5°). S.G. 2 
 1-023; 12 1-008 (Kopp, A. 98, 373). S. 1 at 
 100°. S.V. 123-7 (Bamsay). 
 
 Formation. — 1. By the dry distillation of 
 ammonium benzoate (Fehling, A. 49, 91). — 2. 
 From benzamide by heating it alone or with 
 CaO (Ansohiitz a. Schultz, A. 196, 48), BaO 
 (Wohler, A. 192, 362), P,Os (Hofmann a. Buck- 
 ton, A. 100, 155), POI5 (Hencke, A. 106, 276), or 
 P2S5 (Henry, B. 2, 307).— 3. By heating hip- 
 purio acid alone (Limpricht a. XJslar, A. 88, 
 183), or with ZnClj (Gossmann, A. 100, 74). — 4. 
 By the action of BzCl or Bz^O on benzamide. — 
 5. By the action of BzCl on oxamide, on potas- 
 sium sulphocyanide (Limpricht, A. 99, 117), or 
 on potassium oyanate (Sohiff, A. 101, 93). — 6. By 
 heating Bz^O with potassium cyanate or sulpho- 
 cyanide. — 7. By the action of HgO on thiobenz- 
 amide.— 8. By heating benzoic acid with sul- 
 phocyanide of lead (Kriiss, B. 17, 1767), or of 
 potassium (Letts, B. 5, 678). — 9. From potas- 
 sium benzoate ^nd cyanogen broniide (Cfthoufs, 
 
BENZOPIIENONE. 
 
 479 
 
 A. Ch. [3] 52, 200).— 10. By distilling a mixture 
 of aniline and oxalio acid (Hofmann, C. B. 64, 
 388). — 11. Formed by distilling formanilide over 
 zino-dust ; the yield is nearly 20 p.e. of the 
 formanilide (Gasiorowski a. Merz, B. 17, 73 ; B. 
 18, 1001).— 12. Formed together with sodium 
 formate, by the action of dilute NaOH upon 
 aniline di-chloro-acetate (Gech a. Schwebel, C. C. 
 1877, 134).— 13. Formed by running an aqueous 
 solution of diazobenzene chloride into a hot so- 
 lution of Cuj(CN)j (Sandmeyer, B. 17, 2653).— 
 14. By heating tri-phenyl phosphate with potas- 
 sium oyanide or ferrooyanide ; the yield is 25 
 p.o. of the theoretical (Scrugham, A. 92, 318 ; 
 Heim, B. 16, 1771). — 15. By heating potassium 
 benzene sulphonate with KCN (Merz, Z. 1868, 
 33). — 16. From K^FeCyj and chloro- or bromo- 
 benzene at 400° (Merz a. Weith, B. 8, 918 ; 10, 
 749).— 17. From iodo-benzene and AgCy (Merz 
 a. Schehiberger, B. 8, 1630).— 18. Together with 
 terephthalonitrile, by passing a mixture of 
 benzene and cyanogen through a red-hot tube 
 (M. a. S.). — 19. By passing dimethylaniline 
 through a red-hot tube (Nietzki, B. 10, 474). — 
 20. By the action of OyCl on benzene in pre- 
 sence of aluminium chloride (Friedel a. Crafts, 
 Bi. [2] 29, 2).— 21. Frombromo-benzene,CysCl3, 
 and Na (Klason, J.pr. [2] 35, 83).— 22. By boiling 
 phenyl thiocarbimide with finely divided Cu. — 
 23. From phenyl carbamine by intramolecular 
 change at 240° (Weith, B. 6, 213).— 24. By the 
 action of acetic anhydride on benzaldoxim 
 (Laoh, B. 17, 1571). 
 
 Properties. — Colourless oil, smelling of al- 
 monds ; sinks in cold, but swims in hot water ; 
 miscible with alcohol and ether. 
 
 BeactUms. — 1. Cold aqmtms potash has no 
 action, but on boiling it forms NH, and KOBz ; 
 dilute acids act similarly. — 2. Heating with 
 ■potassmm gives KCy, cyaphenine, (08H5)3Cy3, 
 and other bodies (Bingley, Chem. Oaz. 1854, 
 329 ; Hofmann, B. 1, 198). When the boiling 
 alcoholic solution is treated with sodium, the 
 greater part is saponified whilst a smaller 
 portion undergoes reduction to benzylamine 
 and to benzene (Bamberger a. Lodter, B. 20, 
 1709). — 3. H^S or ammonium sulphide forms 
 thiobenzamide. — 4. Zn and HCl in alcoholic 
 solution form mono-, di-, and tri-benzylamiue 
 (Mendius, A. 121, 129 ; Spica, G. 10, 515).— 5. 
 Fuming HjSO< forms, on heating, benzene sul- 
 phonio acid ; at 20° it forms cyaphenine. Ben- 
 zonitrUe (lOg.) cooled with ice and treated with 
 fuming HjSO, (7 g.) added slowly, forms di- 
 benzamide NHBz, [148°], and 'benzimido-benz- 
 amide' NHBz.C(NH).CeH5 [106°], called by 
 Pinner a. Klein ' benzimido-benzoate ' and 
 ' dibenzimido-oxide,' respectively. Dilute HCl 
 converts the former into the latter (F. Gumpert, 
 J.pr. [2] 30, 87; Pinner, ibid., 125).— 6. Boiled 
 with zinc ethyl it gives ofi ethane (1 vol.) and 
 an define (1 vol.) and forms a product, whence, 
 by treatment first with alcohol, and then with 
 aqueous HCl, cyaphenine {c[.v.) and the hydro- 
 chloride of a base which erystaUises in six- 
 sided plates, OijH.ACl, is formed. This body 
 [257°] is readily soluble in alcohol, but sparingly 
 BO in water. Potash liberates the base as a 
 colourless oil (Frankland a. Evans, C. J. 37, 
 605).— 7. By exhaustive ohlorination with SbCl, 
 it yields penta-ohloro-cyano-benzene C,Cl5(CN) 
 
 (Merz a. Weith, B. 16, 2885).— 8. With methylal 
 and HjSO, it gives the benzoyl derivative of 
 methylene diamine (j. «.). — 9. With diphenyl- 
 amine hydrochloride at 180° it forms di-phenyl- 
 benzamidine ; but at 240° it forms a Base 
 C„H,3N, [183°], thus: C,H,C(NH)N(C.H,),- 
 NHj + CjjHijN. Properties. — Thick prisms (from 
 benzene), containing benzene of crystallisation ; 
 yellow tablets (occasionally from benzene) ; long 
 thin prisms (from alcohol). The tablets are 
 monoclinio, a:b:o = -5875:l"5014, L = 51°23' 
 (Bodewig). Soluble in benzene and ether, 
 slightly in alcohol. Its alcoholic solution is 
 neutral. Acetyl chloride does not act on it. 
 Salts: B'HCl. Narrow red prisms. [Above 
 220°.]— (B'HCl).,PtCl4. 
 
 Combinations. — 1. With metallic chlo- 
 rides. — (C,H5N)2AuCl3. — (C,H5N)jPt01,.— 
 (C,H5N)jSnCl,.— (C,H5N),TiCl, (Henke, A. 106, 
 284).— 2. With halogens. CsH5.CBr:NBr.— 
 (CjH5CN)jBr2: needles (Engler, A. 133,137).— 
 3. With hydrogen chloride: C,H5N2HC1 
 (Pinner a. Klein, B. 10, 1891; cf. Gerhardt, 
 Traiti, 4, 762). — 4. With hydrogen bro- 
 mide. 0,H5N2HBr. [70°] (Engler, A. 149, 
 307). — 5. With alcohols. — Benzimido- 
 ethyl ether, C5Hj.C(0Et):NH. The hydro- 
 chloride, B'HCl, is formed by passing dry HOI 
 gas into a mixture of ethyl alcohol and benzo- 
 nitrUe, diluted with ether. Large glistening 
 prisms ; decomposes on heating to about 120° 
 into ethyl chloride and benzamide (Pinner, B. 
 16, 1654). Benzimido - isobutyl ether 
 C,H5.C(0C,Hs):NH. The hydrochloride B'2HC1 
 is formed by passing HCl into a cooled mixture 
 of benzonitrile and isobutyl alcohol (Pinner a. 
 Klein, B. 10, 1890) ; it gradually loses HCl be- 
 coming B'HCl, [135°].— B'jHjPtCls.— B'HjSO^. 
 — 6. With acids. — Benzimido - acetate 
 C8H5.C(OAc):NH. [116°]. From benzimido- 
 isobutyl ether and Ac^O (Pinner a. Klein, B. 11, 
 9). — 7. With meroaptans. — Benzimido- 
 ethyl thio-ether C5H5.C(SEt):NH. From 
 benzonitrile, mercaptan, and HCl, or from thio- 
 benzamide and EtI (Bernthsen, A. 197, 348). 
 Oil; decomposes readily into mercaptan and 
 benzonitrile. — B'HCl. [188°]. — B'^H^PtCl,.— 
 B'HI. [142°]. Benzimido-isoamyl thio- 
 ether C5H,.C(S05H„):NH. The hydrochloride, 
 B'HCl, is formed by passing HCl into a mixture 
 of benzonitrile and isoamyl mercaptan (Pinner 
 a. Klein, B. 11, 1825). The free base is an 
 oil. Benzimido - benzyl - thio - ether 
 C„H5.C(S0,H,):NH. Prepared like the ethyl 
 ether.— B'HCl [181°]. 
 
 Derivatives of Benzonitrile are described as 
 Bromo-, Niteo- &c. benzonitkele. 
 
 BENZO-PHENOL v. Oxy-benzophenone. 
 BENZOPHEH ONE O.jH.oO i.e. CjHs.CO.C^Hs. 
 Di-phenyl-Utone. Mol.w.l82. [48°]. (305° i.V.). 
 FormaUon. — By the dry distillation of cal- 
 cium benzoate (Peligot,^.12, 41 ; Chancel, j1. 72, 
 279).— 2. From BzCl and HgPh^ (Otto, B. 3, 
 197). — 3. From BzCl and benzene in presence 
 of AljClj. — 4. From benzoic acid, benzene, and 
 PjOs at 190° (KoUarits a. Merz, B. 6, 446, 538). 
 5. From benzene, COClj, and Mfil, (Friedel, 
 Crafts, a. Ador, C. B. 85, 673).— 6. By oxidation 
 of di-phenyl-methane (Zincke, A. 169, 377). 
 Preparation.— FroBi B?C1, C,H,,aiid A1,C1,; 
 
480 
 
 BENZOPHENONE. 
 
 the yield is 70 p.e. of the calculated (Elbs, J. pr. 
 [2] 35, 465). 
 
 Properties. — Prisms ; insol. water, v. sol. 
 alcohol and ether. 
 
 BeacUons. — 1. Eedueed by HI to di-phenyl- 
 methane (Graebe, B. 7, 1624). — 2. Eedueed by 
 zinc-dust to di-phenyl-methane, tetra-phenyl- 
 ethylene, and tetra-phenyl-ethane (Staedel, A. 
 194, 307). — 3. Potash-fiision gives benzoic acid 
 and benzene. — 4. Eedueed to di-phenyl-carbinol 
 by sodium-amalgam or by heating with alcoholic 
 potash. — 5. Ammortia has no action. — 6. Zn 
 and alcoholic H^SO^ reduce it to beuzpinacone 
 and (o)- and (j3)- benzpinacolin (Zincke a. 
 Thorner, B. 11, 1396).— 7. AoCl in presence of 
 zinc-dust acts on an ethereal solution forming 
 crystalline (a)- and (;3)- benzpinacolin. — 8. PCI5 
 forms di-chloro-di-phenyl-methane. — 9. Passage 
 through a red-hot tube slightly decomposes it ; 
 the product contains benzene, di-phenyl, and 
 p-di-phenyl-benzene, while gaseous carbonic 
 oxide, hydrogen, and acetylene escape (Barbier 
 a. Eoux, C. B. 102, 1559).— 10. When heated 
 with ammonium formate at 200°-220° it yields 
 the formyl derivative of di-phenyl-oarbinyl- 
 amine (C5H5)2CH.NH.CHO (Leuchart a. Bach, B. 
 19, 2129). — 11. P2S5 at 100° forms CjsHjjS., 
 [158°], crystallising in lustrous flat monoclinic 
 needles. At 200° it turns deep blue (Japp a. 
 Easohen, O. J. 49, 481).— 12. PjS; at 140° forms 
 C^sHjjPjSs [227°], crystallising in minute plates, 
 insol. alcohol, si. sol. hot benzene. On melting 
 it turns deep blue. It is oxidised by CrOj in 
 HOAc to benzophenone (J. a. E.). 
 
 Oxim (CgB.^)fimOB.. Di-phenyl-Ttetoxim. 
 [140°]. Prepared by boiling an alcoholic solu- 
 tion of benzophenone (30g.) with hydroxylamine 
 hydrochloride (28g.) and a little HCl for a day 
 (Beekmann, B. 19, 988 ; Janny, B. 15, 2782). 
 Silky needles, v. sol. ether and acetone, m. sol. 
 benzene and ligroin, v. si. sol. cold water. Sol. 
 acids and alkahs. Eesolved by acids into its con- 
 stituents. By PCI5 or POCI3 it is converted into 
 <B-chloro-benzylidene-aniline, CuHj.N'.CCl.CjHs, 
 produced by intramolecular change from 
 (CjH5)jC:NCl (B.). By warming with cone. 
 HjSOi to 100° it is converted by similar isomeric 
 change into benzanilide (Beekmann, B. 20, 1507). 
 Salts. — C,3H,„N(0Na) : crystalline powder. — 
 0,sH,„N(OH),HCl : white powder. 
 
 Methyl- oxim C,3H,„N(0Me) : f92°] ; 
 yellow crystals. 
 
 Ethyl-oxim C,3H,„N{0Et) : (276°-279°); 
 fluid. 
 
 Benzyl-oxim C,3H,„N(00,H,) : [56°]; 
 white crystals. 
 
 Acetyl oxim C,3H,|,N(0Ac) : [55°]; white 
 crystals (Spiegler, B. 17, 810; M. 5, 203). 
 
 Phenyl Aj/drazicie PhjC:NjHPh. [137°]. 
 Got by boiling benzophenone with phenyl hydra- 
 zine and alcohol ; or by heating the oxim with 
 phenyl-hydrazine, Nj and NH, being evolved. 
 Needles (from alcohol). Insoluble in water, not 
 very soluble in alcohol. Heated for some time 
 with dilute (20 p.c.) HCl, it is resolved into 
 benzophenone and phenyl hydrazine (Pickel, A. 
 2i2, 228 ; Fischer, B. 17, 576 ; Just, B. 19, 1206). 
 
 Isomeride of Benzophenone. [26°]. (305°). 
 Sometimes formed in oxidising di-phenyl-me- 
 thi^ne or vp. distilling calcium acet%te with 
 
 calcium benzoate (Zincke, A. 159, 367). Eeadily 
 changes into ordinary benzophenone. 
 
 Derivatives of benzophenone are described as 
 Amido-, Bbomo-, Chloro-, Cyano-, Nitbo-, Oxy-, 
 &c., Benzophenone, and as Di-phenylene-keionb 
 oxmE. 
 
 BENZOPHENONE-CAEBOXYLIC ACID v. 
 Benzoyl-benzoic acid. 
 
 benzophenowe-di-^-cabboxtlic acid 
 
 [4:1] 0eH4(CO2H).CO.C5Hj(CO2H) [1:4]. Formed 
 by boiling di-^-cyano-benzophenone with aloo- 
 hohc KOH (Bromme, B. 20, 522). Also by the 
 oxidation of di-tolyl-methane, or di-methyl- 
 benzophenone, with chromic mixture (Weiler, 
 B. 7, 1185 ; Ador a. Crafts, B. 10, 2173). Mi- 
 croscopic needles. Sublimes at a high temper- 
 ature without melting. SI. sol. alcohol, benzene, 
 and ether. S. (hot water) =002. The NH, 
 salt gives pps. with salts of Fe, Co, Cu, Ba, and 
 Ca, but not with salts of Pb, Cr, Zn, Mg, and Ni. 
 
 Silver salt A"Ag2, Ag^O : insol. water. 
 
 Di-m ethyl ether A"Me2: [138°]; large 
 needles (B.).— Ag^A" (A. a. C). 
 
 Benzophenone dicarbozyllc acid 
 C,H,.C0.C„H3(C0,H),. 
 
 Benzoyl-isophthalic acid : [280°]. From 
 benzyl-isoxylene and chromic mixture (Zincke, 
 B. 9, 1762). SI. sol. hot water and CHCl,, v. 
 sol. alcohol. Converted by Zn and HCl into 
 the lactone of C8H5.C(OH)H.C5H3(COsH)j.— 
 Salts: CaA"act.— BaA"aq.— Ag.,A". 
 
 Methyl ether Meji.". [118°]. 
 
 Ethyl ether M^A.". [95°]. 
 
 Benzophenone dicarboxylic acid 
 CeH,,.CO.C„H,(CO,H),. [1:2:5]. 
 
 Benzoyl-terephthalic acid. [290°] (W.); 
 [285°] (E.). 
 
 Formation. — 1. By oxidising benzyl-cymena 
 with chromic mixture (Weber, /. 1878, 402). — 
 2. From benzoyl-p-xylene and HNO3 (S. G. 145) 
 at 170° (Elbs, J. pr. [2] 35, 479).— 3. From 
 phenyl ^-cymyl ketone and dilute HNO3. 
 
 Properties. — V. si. sol. water, v. sol. alcohol. 
 Eedueed by Zn and HCl to 
 
 C«H5.CH(OH).C8H3(COjH)j.— OaA"aq.— 
 BaA" 5aq.— A.gjA". 
 
 Methyl ether Ue^A.". [101°]: needles. 
 
 Ethyl ether :Ei^". [101°]: prisms. 
 
 Benzophenone tetra-carbozylic acid 
 CbH5.CO.CjH(C02H)j. From benzoyl-iso-durene 
 and KMnOj (Essner a. Gossin, Bl. [2] 42, 170). 
 
 BENZOPHENONE CHLOSIDE is exo-Bi- 
 
 OHLOBO-DI-PHENYL-METHANE (j. V.). 
 
 BENZOPHENONE OXIDE v. D^-phenyijdne- 
 
 KETONE OXIDE. 
 
 BENZOPHENONE STTLPHONE C„HaSO,i.e. 
 
 S02<^^«^<>C0. [187°]. From benzophenone 
 
 and fuming HjSO^ (Beekmann, B. 6, 1112 ; 8, 
 992). V. sol. ether, sol. alkalis; converted by 
 water at 190° into an isomeride (?) [175°]. 
 
 BENZOPHENONE DI-SULPHONIC ACID 
 C,3H5(S03H)20. From benzophenone and fum- 
 ing HjSOj by warming (Staedel, A. 194, 314). 
 Converted by potash fusion into phenol and p- 
 oxy -benzoic acid. — BaA". 
 
 Chloride CO(CaH4S02Cl)j. [122°] (Beek- 
 mann, B. 8, 992). 
 
 BENZOPHENYIi- v, BsKssoYit-f benyi,-. 
 
BENZOYL-ACETIO ACID. 
 
 431 
 
 BENZOPHOSPHINIC ACID is Carboxy- 
 
 BBNZENE PHOSPHONIO ACID {q. V.). 
 
 BENZOFINACOLIN is Benzpinaoolin (2. v.), 
 BBHZOPINACONE is Bekzpinaoone (g. «.). 
 BENZOftUINOL is Hydroquinonb (g. v.). 
 BENZOQUINONE is Quinone (3. «.). 
 BENZOSESOBCIN v. Dioxybenzophenone. 
 DI-BENZO-BESOKCIH v. Dioxyphenylene- 
 
 W-PHENYIi-M-KETONB. 
 
 BENZOSTILBINE is lophine (v. p. 474). 
 BENZO-STTCCINIC ACID v. Benzoyl-succinic 
 
 ACID. 
 
 BENZOTHIAHIDE v. Teio-benzamise. 
 BENZO-TOLUIDINE v. Phenyl amido-tolyl 
 
 KETONE. 
 
 BENZTEOPEINE v. Benzoyl-tkopeine. 
 
 BENZOXAMIDINE v. Benzamidoxiu. 
 
 BENZ-OXIMIDO-AMIDE v. Benzamidoxim. 
 
 BENZ-OXIMIDO-ETHYL-ETHER 
 C,H„NOj i.e. C5H5.C(OEt):NOH. Formed by 
 the action of hydroxylamine hydrochloride on 
 benz-imido-ether (v. Benzonitkile), (Pinner, B. 
 17, 184). Colourless fluid. Decomposes on 
 distillation. 
 
 BENZOXY- V. Bemoyl-OxTi: 
 
 BENZOXY-PEOPIO-CAEBOXYLIC ACID v 
 Cabboxy-benzoyl-pbopionio ACn). 
 
 BENZOYL. The radicle ObHj.CO. Benzoyl 
 derivatives obtained by displacement of H in 
 amidogen, imidogen, or hydroxyl, are described 
 under the compounds from which they are thus 
 derived. 
 
 Di-benzoyl is called Benzil {q. v.). 
 
 BENZOYL -ACET-CAKBOXYLIC ACID v. 
 
 AOETOPHENONE DI-CAEBOXYLIO ACID. 
 
 BENZOYL-ACETIC ACID CjHsOs i.e. 
 C5H5.CO.CH2.CO2H. Acetopheiione w-carboxylic 
 acid. [104°]. 
 
 Formation. — 1. From the ether by leaving 
 it 24 hours with cold dilute EOH (3 per cent.), 
 cooling to 0° and then adding dilute H2SO4. 
 The acid is then ppd. as white flakes (Baeyer a. 
 Vevkin,B. 15, 2705; 16, 2128; W. H. Perkin, 
 jun., C. J. 45, 176). — 2. From phenyl propiolio 
 acid and cone. H^SO,, the solution being poured 
 upon ice.— 3. From the ether by allowing it to 
 stand for 14 days with 20 vols, of cone. H^SO, 
 and then pouring upon ice (Perkin, C. J. 47, 240). 
 
 Properties. — Minute needles, which polarise 
 light (from benzene at 70° containing a little 
 light petroleum). At 104° 'it melts, and gives 
 off COj. SI. sol. light petroleum, v. sol. alco- 
 hol, ether, hot benzene, and hot water. FepGl,, 
 colours its alcoholic or aqueous solutions reddish- 
 violet. 
 
 Beaction. — 1. Seated alone or with dilute 
 HjSOj it gives acetophenone and COj. — 2. The 
 ammonium salt gives with AgNOj a pp. of AgA'; 
 with FcjClj a blackish-violet pp.; with FeSO^ 
 no pp. ; with OuSOj, a greenish-yellow pp. 
 
 Methyl ether MeA'. An oil prepared by 
 the action of cone. HjSOj on methyl phenyl- 
 propiolate (W. H. Perkin, jun., a. Caiman, 0. J. 
 49, 154). FejClj gives a violet colour in alco- 
 holic solution. Sodium ethylate gives a white 
 amorphous salt, OA.CO.CHNa.COjMe. This 
 salt is V. sol. water and hot alcohol. 
 
 Ethyl ether. A'Et. (2e5°-270°) at 760 
 mm. ; (230°-235°) at 200 mm. 
 
 Formation. — 1. From phenyl-propiolic ether 
 (100 g.) and H^SO, (3000 g.) at 0°. After three 
 
 Vol. I. 
 
 hours the product is poured upon powdered ice, 
 and the new body extracted with ether. — 2. By 
 heating diazo-aoetic ether with benzoic aide 
 hyde (Buohner a. Curtius, B. 18, 2371).— 3. By 
 heating EtONa (140 g.) with benzoic ether 
 (300 g.) at 100°, mixing the product with acetic 
 ether (350 g.) and heating for 15 hours at 100° 
 (Olaisen a. Lowman, B. 20, 651).— 4. By the 
 action of cold oono. HjSOj upon (a)-bromo- 
 cinnamio ether (Michael a. Browne, B. 19, 1392). 
 
 Properties.— Colourless oil. Partly decom- 
 posed when distilled. SI. sol. water, sol. alcohol 
 and ether. 
 
 Reactions. — 1. The alcoholic solution gives 
 with FCjCl,; a violet colour. — 2. Boiled with water, 
 or dilute HjSO,, it gives acetophenone, alcohol, 
 and COj. — 3. Boiling for 8 minutes produces 
 dehydro-benzoyl-acetio acid (g.v.). Boiling for 
 30 minutes forms two isomerides (C8Ha02)„. 
 One of these (n = 3 ?) crystallises in plates, 
 [275°], m. sol. hot alcohol, v. si. sol. benzene ; 
 sol. alcoholic NaOH but ppd. by OOj. The 
 second (n = 4 ?) is an acid, not being ppd. by 
 CO2 from its solution in alcoholic NaOH; cone. 
 H2SO4 forms a yellow solution, turning violet 
 when warmed (Perkin, jun.,.C/. J. 47, 262). — i, 
 NaNOj and H2S04 added to the sodium deriv( 
 tive produce an oxim of benzoyl-glyoxylio ether, 
 Ph.C0.C(N0H).C02Et [121°], whence alkalis 
 produce a substance CjHg04 [125°]. 
 
 Metallic derivatives.- BzCHNaCOjEt. 
 Got by adding NaOEt to alooholio solution of 
 the ether. Silky needles, turns brovm in air; 
 insol. ether. — (0„H,,O3)2Ba. — C,,H„Ag03. — 
 (C,,H,,03)2Cu: pale green; soluble in aqueous 
 NaOH. On boiling CU2O is ppd. 
 
 Nitrite V. Bbnzoyl-aoetonitbile. 
 
 Benzylidene-benzoyl-acetio ether 
 CsHj.0H:CBz.C02Et. [99°]. From benzoyl- 
 acetic ether and benzoic aldehyde, either by 
 passing HCl at 0° into the mixture, or by heat- 
 ing in a sealed tube (Perkin, jun., C.J. 47, 240). 
 Monoolinic prisms : a:6:c = l-2730:l: -7460 ; 
 j3 = 86°36'. Sol. hot methyl alcohol. Cone. 
 HjSOj forms a yellow solution, which becomes 
 colourless on heating. 
 
 Benzylidene-di-beuzoyl-di-acetic acid 
 (C02H.CHBz)2CHPh. [130°]. The ethers of 
 this acid are formed by dropping diazo-aoetio 
 ethers (2 mols.) into benzoic aldehyde (3 mols.) 
 at 170° (Buchner a. Curtius, B. 18,2374). They 
 dissolve in cone. H2SO4 forming rose-coloured 
 solutions, which turn brown on warming. The 
 acid and its ethers give off a smeU of hyacinths 
 when burnt. 
 
 Methyl ether [113°] : prisms. 
 
 Ethyl, ether [103°]: tables; NaOEt 
 added to its ethereal solution gives 
 (C0..Et.CNaBz)2CHPh. 
 
 Di-benzoyl-acetic acid CHBzj.COjH. [109°]. 
 Formed by the action of BzCl on sodium 
 benzoyl-acetie ether, and saponification of the 
 product with KOH (Baeyer a. Perkin, jun., B. 
 16, 2133 ; 0. ^.47, 240). Slender felted needles, 
 si. sol. cold alcohol and water, v. sol. ether ; sol. 
 aqueous alkalis. Fe2Clj gives a red coloura- 
 tion. Cone. HjSOj gives no colour on warming. 
 
 Reactions. — 1. Boiling water splits it up 
 into di - phenyl - methylene di - ketone, 
 (C5H5.C0)2CH2, and OOj. — 2. Boiling dilute 
 HjSOi gives acetophenone, benzoic acid, and CO.. 
 
 II 
 
483 
 
 BENZOYL-AOETIC ACID. 
 
 Salt.— AgA'. 
 
 Ethyl ether 'Etk'. Oil; not solid at - 10°. 
 
 Kethyl-lieiizoyl-acetio acid is (o)-BENzoyL- 
 
 rBOPIONlO ACID (g. v.). 
 
 Ethyl - benzoyl - acetic acid BzCHBt.COjH. 
 [111°-115°]. From NaOEt and EtI on alcohoUo 
 BzCHjCOjEt, and saponifying the oily product 
 by allowing it to stand for some days with alco- 
 holic KOH (Baeyer a. Perkin, jnn., B. 16, 2130 ; 
 C. J. 45, 180 ; 47, 240). SmaU needles, melts 
 about 115° with slight decomposition. Easily 
 soluble in alcohol, ether, and benzene. Boiled 
 with dilute alcoholic KOH, it gives phenyl- 
 propyl-ketone; benzoic and butyric acids are 
 also formed, especially if the potash be strong. 
 
 Ethyl ether EtA'. (232°) at 225 mm. 
 
 Fropyl-benzoyl-acetio ether BzCHPr.COjEt. 
 (239') at 225 mm. Prepared like the preceding. 
 Alkalis from phenyl-butyl-ketone. PCI5 forms 
 ;8-chloro-a-propyl-oinnamio ether. 
 
 Isopropyl-benzoyl-acetic ether 
 BzCHPr.COjEt. (237°) at 225 mm. From benz- 
 oyl-acetic ether, Na, and PrI. 
 
 Iso-butyl-benzoyl-aoetic ether 
 Bz.CH(CH2.CHMeJ.C02Et. (247°) at 225 mm. 
 Prepared like the preceding (Perkin a. Caiman, 
 O. J. 49, 165). 
 
 Di-ethyl-benzoyl-acetic acid BzCEtjCOjH. 
 [128°-130°]. From Bz.CHEt.CO^Et by NaOEt 
 and EtI. The diethyl-benzoyl-acetic ether is 
 saponified by standing for weeks with dilute 
 alcoholic KOH (Baeyer a. Perkin, jun., B. 16, 
 2131; C. J. 45, 183). Heated alone or with 
 dilute HjSO, it gives off COj. Boiling dilute 
 alcoholic KOH forms benzoic acid, diethylacetic 
 acid, and di-ethyl-acetophenone {v. amyl-phenyl- 
 ketone). 
 
 Tri-benzoyl-acetic ether. CBzj.COjEt. From 
 ethyl di-benzoyl-acetate, NaOEt, and BzCl (Per- 
 kin, jun., C. J. 47, 240). Thick yellow oil ; sol. 
 alcoholic KOH but reppd. by water. Boiling 
 dilute HjSOi forms aoetophenone. 
 
 BENZOYL-ACETIC-ALDEHYDS 
 CBH5.OO.CH2.CHO. Prepared by dissolving 
 sodium (1 atom) in 20 or 30 times its weight of 
 absolute alcohol, cooling to 0°, and adding aoeto- 
 phenone (1 mol.) and formic ether (1 mol.). On 
 long standing the sodium compound separates as 
 a granular pp. ; this is dissolved in water and the 
 aldehyde ppd. by acetic acid. Colourless un- 
 stable oil. Cuprio acetate gives a pp. of bright 
 green needles, which soon change to dark-green 
 prisms. It reacts with amines very readily. 
 
 Anilide CsHs.CO.CHj.CHrNCsHs : [141°]; 
 yellow prisms or plates ; sol. hot alcohol. 
 
 p-Toluide 0,H5.00.CHj.CH:NC,H, : [160°- 
 163°] ; small yellow crystals. 
 
 (0)-Naphthylamide 
 CsH5.C0.CH,.CH:NC,„H, : [182°]; small bronzy 
 crystals ; si. sol. almost all solvents (Olaisen a. 
 Fischer, B. 20, 2191). 
 
 BENZOYL - ACETIMIDO - ETHYLIC ETHER 
 CsH5.C0.CH2.C(NH).0Et. [89°-o oorr.]. 
 
 Benzoyl-acetonitrile CbHj.CO.CHj.CN treated 
 with alcoholic hydrochloric acid gives rise to 
 C,H5.C0.CH2.C(NHHCl)0Et and this loses HCl 
 when treated with ammonia giving the imido- 
 ether (Haller, Bl. [2] 48, 24 ; O. B. 104, 1448). 
 Properties. — Prisms or tables. V. sol. ether. 
 Reactions. — KNOj andH^SO^ give the nitroso- 
 derivative C»H4.C0.CH,.C(N.N0).0Et [117°], 
 
 which gives Liebermann's reaction. The hydro- 
 chloride of the base dissolved in aqueous alcohol 
 deposits MHjCl and benzoyl-acetio ether is left 
 in solution. 
 
 Hydrochloride B'.HCl. [140° oorr.]. 
 Entangled needles. Insol. aq and ether. Strongly 
 irritates the mucous membranes. 
 
 BESZOYL-ACETO-ACETIO ETHEE v. p. 21. 
 
 BENZOYL -ACETO-CABBOXYLIC ACID v. 
 
 ACETOPHENONB CAKBOXYIjIO ACID. 
 
 BENZOYL-ACETONE C,„H,„Oj i.e. 
 CsH5.CO.CH2.CO.CH3. Phenyl methyl me- 
 thylene di-ketone. Acetyl-acetOphenone. Acetyl- 
 bemoyl-methane. [61°]. (261°). 
 
 Formation. — ^By the action of dry NaOEt 
 upon a mixture of acetone and benzoic ether 
 (Claisen, B. 20, 655). 
 
 Preparation.— 1. Benzoyl -aceto-acetio ether, 
 formed by the action of benzoyl chloride upon 
 sodio-aceto-acetic ether, is boiled with water for 
 a few hours ; the yield is 25 p.c. — 2. Prepared 
 by adding aoetophenone (1 mol.) to a cooled 
 mixture of acetic ether (about 2 mols.) and 
 alcohol-free sodium ethylate ; yield : 80-90 p.c. 
 of the aoetophenone (Beyer a. Claisen, B. 20, 
 2078). 
 
 Copper compound (C,jHg02)2Cu : formed as a 
 pale green pp. by adding cuprio acetate to the 
 alcoholic solution. It is m. sol. alcohol and 
 benzene, from which it crystallises in bright 
 green needles. 
 
 Amide CeH5.CO.CH2.C(NH).CH3 : [143°]; 
 clear glistening trimetrio crystals, a:b:c 
 = •9927:1: -8820. 
 
 Anilide C„H5.CO.CH2.C(NPh).CH,: [110°]; 
 plates. By warming with HjSOj (10 pts.) it is 
 converted into {Py. l:3)-phenyl-methyl-quino- 
 line (Beyer, B. 20, 1770). 
 
 Properties. — Crystals ; distils undecom- 
 posed ; volatile with steam. Sol. hot water, 
 alcohol, and ether. Dissolves in alkalis with a 
 yellow colour. SI. sol. strong acids. Fefil, 
 gives a dark-red colouration. 
 
 Beactions. — By warming with alkalis or by 
 long boiling with acids it yields aoetophenone. 
 It has slightly acid characters, the H of the 
 central CHj group being replaceable as in 
 aceto-acetic ether, since it lies between two 
 CO groups. By heating with strong aqueous 
 NH3 at 120° it is converted into the imide 
 
 CsH5.C(NH) .CH2.CO.CH3 
 or CeH5.C0.CH2.C(NH).CH3. It condenses with 
 (1 mol.) of phenyl-hydrazine with elimination 
 of 2H2O, forming methyl-di-phenyl-pyrazol 
 (Fischer a. Bulow, B. 18, 2131). 
 
 Salts. — CijHjO^Na : small yellowish plates. 
 — CioHjO.^Ag : white pp. ; v. si. sol. water 
 (Fischer a. Kuzel, B. 16, 2239). 
 
 Oa;i77iC,„H„02Ni.e.CeH3.C(NOH)CH2.CO.CH3 
 or CeH5.CO.CH2.C(NOH).OH3. [66°]. Formed by 
 heating benzoyl-acetone with hydroxylamine 
 hydrochloride in alcoholic solution (Ceresole, B. 
 17, 812). White glistening scales. Volatile 
 with steam. V. sol. acetone, benzene, and CSj, 
 insol. water. 
 
 Di-benzoyl-acetone (CsH5.CO)2:CH.CO.CH3. 
 [102°]. Formed by the action of benzoyl 
 chloride upon sodio-benzoyl acetone (Fischer a. 
 Billow, B. 18, 2133). Small needles. Sol. 
 alcohol and ether, v. si. sol. water. Sodium 
 has no action upon it. 
 
BENZOYL-BENZOIC AOID. 
 
 483 
 
 BENZOYL -ACETONIMlBi; C,„H,,NO i.e. 
 OaH5.0(NH).CHj.CO.CH3 or 
 0A.-C0.CH,.C(NH).0H3. [143°]. Obtained by 
 heating benzoyl acetone with Btrong aqaeous 
 NHj at 120° (Fischer a. Bulow, B. 18, 2134). 
 Distils undecomposed. Small plates, or large 
 quadratic crystals. V. sol. dilute acids, by 
 heating mth which it is converted back into 
 benzoyl-acetone and NH,. 
 
 BESZOYL-AOETONITEILE 0,H,NO i.e. 
 CaH5.CO.CHj.CN. 
 
 Cyano-acetophenone. [81° cor.]. Formed by 
 the action of boiling water on benzoyl-cyanacetic 
 ether CsH5.00.CH(CN).C02Et (Haller, Bl. [2] 
 48, 23). White needles, sol. boiling water, alco- 
 hol, ether, and alkalis. Boiling cone. KOH 
 acts thus: CsH5.C0.CH,.CN + 2KH0 + H.,0 
 = NH3 + C„H5.C02K + CH3.C0,K. In alcoholic 
 solution gaseous HCl gives a body CiiHi^OjNCl 
 (probablyCaH5.CO.CH2.C(NHHCl)OEt[140corr.]; 
 whence ammonia in the cold gives the imido- 
 ether 0jH5.CO.CH2.C(NH).OEt). If the action of 
 the alcoholic HCl is prolonged, the products aie 
 the same as with KOH. 
 
 Silver salt CA.CO.CHAg.CN. White pp. 
 Insol. aq and alcohol ; sol. ammonia. 
 
 BENZOYLACETOPHENONE v. Di- phenyl 
 
 METHYLENE DI-KETONE. 
 
 BENZOYL - ACETYL-ETHANE v. AoBio - 
 
 PHENONE-AOETONB, p. 36. 
 
 Di-benzoyl-di-acetyl-ethane 
 C3H5.CO.CH.CO.CH3 
 CjdHjjOj i.e. I . Di-phenyl- 
 
 C,H5.C0.CH.C0.CH3 
 di-methyl-acetylene-tetra-ketone [175°]. Formed 
 by the action of an ethereal solution of iodine 
 upon 2 mols. of sodio-benzoyl-acetone (Fischer a. 
 Baow, B. 18, 2133). White needles. Sol. hot 
 alcohol, si. sol. ether, insol. water and dilute 
 alkalis. Decomposed by boiling with alkalis. 
 
 BENZOYL-ACBYLIG ACIB 
 C3H3.C0.CH:CH.C02H. White plates, [64°], 
 from water ; after fusion its melting-point is 
 altered to [97°]. Long needles, [99°] from 
 toluene. SI. sol. cold water and ligroin, v. sol. 
 other solvents. Prepared by the action of 
 Al^Clj on a mixture of benzene and maleio an- 
 hydride. By alkalis it is decomposed into 
 acetophenone and glyoxylic acid. On heating 
 by itself or with AOjO, it gives a red condensation 
 product (Pechmann, B. 15, 885). 
 
 Bromine addition product [135°]. Colour- 
 less crystals. 
 
 BENZOYL-ALLOPHANIC ACIB v. p. 127. 
 
 BENZOYL-ALLYL-ACETIC ACIB v. Allyl- 
 
 BBNZOYL-AOETIO ACID, p. 135. 
 
 BENZOYL-AMIDO- v. Amido-. 
 
 BENZOYL-AMIBO-ACETIC ACID v. Hip- 
 PCMO Acid. 
 
 BENZOYL - AMMELINE CiJEls^fi^ i.e. 
 CjHjBzNjO. From sodium cyanamide and BzCl 
 (Gerlich, /. jpr. [2] 13, 272). Brown resin, insol. 
 water and ether, sol. alcohol and aqueous 
 alkalis. Eesolved by distilling in a current of 
 hydrogen into benzonitrile, carbonic oxide, and 
 cyanamide. 
 
 BENZOYL-ANILIBE v. Aniline. 
 
 BENZOYL - ANILINE v. Amido - benzophb- 
 
 MONE. 
 
 BENZOYL-ANISIDINE v. Bemoyl-methyl- 
 
 AHIDO-PHENOL. 
 
 BENZOYL-AZOTIBE v. p. 475. 
 
 BENZOYL-BENZENE v. Benzophenonb. 
 
 Bi-benzoyl-benzene v. Phihalofhenone. 
 
 BENZOYL-BENZIDINE v. Di-Aumo - Di- 
 phenyl. 
 
 BENZOYL-BENZOIC-ACETIC ANHYDRIDE 
 C,H5.CO.C,H<.CO.O.CO.CH3. [112°]. Prepared 
 by heating o-benzoyl-benzoic acid with acetin 
 anhydride to 100° (Freiher a. Pechmann, B. 
 14, 1865). Large crystals. Insol. alkalis. At 
 200' it decomposes into acetic and benzoyl- 
 benzoic anhydrides. 
 
 o-BENZOYL-BENZOIC ACID ChHioOj i.e. 
 CsH5.OO.CsH4.CO2H [1:2]. Bemophenone car- 
 boxylic acid. Mol. w. 226. [87°] (Z.) ; [94°] 
 (Hemilian, B. 11, 838). 
 
 Formation. — 1. By oxidation of o- benzyl- 
 toluene (Zincke a. Plaskuda, B. 6, 907), phenyl- 
 o-tolyl-ketone (Behr a. Van Dorp, B. 7, 17), 
 or di-benzyl-benzene (Zincke, B. 9, 32) with 
 chromic mixture. 
 
 Preparation. — 150 grms. of AljCl, are slowly 
 added during 3 hours to a solution of 100 grms. 
 of phthalic anhydride in 1000 grms. of benzene 
 (pure), the benzene is then poured off and can 
 be used at once for a fresh operation, whilst the 
 solid residue is washed with dilute HCl and 
 with water, dissolved in NaiC03 and the acid 
 precipitated from the solution by HCl, and 
 finally recrystaUised from xylene (3 pts.) ; the 
 yield is 60 p.o. of the phthalic anhydride used 
 (Friedel a. Crafts, C. B. 86, 1368 ; 92, 833 ; 
 Freiherr a. Pechmann, B. 13, 1612). 
 
 Properties. — Triclinio needles (containing 
 aq). When dry it melts at 128°. 
 
 Beactions. — 1. PjOj at 190° forms anthra- 
 quinone. — 2. Hot fuming sulphuric acid forms 
 anthraquinone sulphonic acid (Liebermann, B. 
 7, 805). — 3. Sodium amalgam first reduces 
 it to C8H5.CH(OH).08H4.C02H and then to 
 CeH5.CH2.CiiHj.CO2H. — 4. Resorcin, pyrogallol 
 &c., on heating, form phthaleins. — 5. With 
 phenyl-hydrazine it gives a condensation-pro- 
 C— Ph 
 
 duct CjH^/^NjPh [182°] (Eoser, B. 18, 805). 
 
 CO 
 
 This forms small needles, si. sol. alcohol, insol, 
 water. 
 
 Salts . — CaA'j. — BaA'j. — ZnA'2 2aq. — 
 CuA'2 aq. 
 
 Methyl ether MeA'. [52°] : prisms. 
 
 Ethyl ether EtA'. [58°]. 
 
 Anhydride (Bz.C5H4.CO)20. [1201 (Pech- 
 mann, B. 14, 1866). 
 
 m-Benzoyl-benzoic acid Ph.CO.CjHj.COjH. 
 [1:3]. [161°]. 
 
 Formation. — 1. From phenyl - m-tolyl-me- 
 thane (10 g.), KjOrjO, (60 g.), H^SO, (90 g.) and 
 water (270 g.) by boiling for 3 days (Botering ; 
 Senff, A. 220, 237). It is purified by reduction 
 to Ph.CH(0H).C„H,.C02Na by sodium-amalgam, 
 crystallising this salt from water and oxidising 
 again with H2SO4 and KjCrjO,. — 2. A quantitative 
 yield is obtained by treating phenyl-m-tolyl- 
 methane at 130° with bromine-vapour sufBcient 
 to form Ph.CHj.CjHj.CHjBr and treating the 
 product with chromic mixture for 12 hours. — 
 3. From BZjO (1 mol.) and BzCl (2 mols.) in 
 presence of ZnClj (Doebner, A. 210, 277 ; B. 14, 
 648). — 4. Formed as a by-product in the pre- 
 
 ii2 
 
1S4 
 
 BENZOYL-BENZOIC ACID. 
 
 paration of isophthalophenone by the action of 
 AljClj on a mixture of benzene and iso-phthalyl 
 chloride (Ador, B. 13, 321). 
 
 Properties. — Long silky needles (from water 
 or glacial acetic acid), or small plates (from 
 alcohol). SI. sol. cold water, v. sol. benzene or 
 toluene, v. e. sol. alcohol or ether. May be sub- 
 limed as plates. Dissolves in cone. H2S04 giving 
 no colour. Potash-fusion gives benzoic acid. 
 Eeduced by sodium-amalgam to exo-oxy-benzyl- 
 benzoio acid {q. v.). 
 
 Salts. — BaA'2 3aq: white crystalline pow- 
 der. — BaA'2 4aq : small plates. — CaA'™ 2aii : 
 white crystalline powder. — AgA' : white leaflets. 
 
 Methyl ether MeA' [62°]. 
 
 ^-Benzoyl-benzoic acid CaH5.CO.C5H4.CO2H 
 [1:4]. [194°] . Formed by oxidation of phenyl- 
 ^-tolyl-methane,phenyl-^-tolyl-ketone,p-phenyl- 
 benzophenone or di-benzyl-benzene (Zincke, A. 
 161, 98 ; B. 6, 907 ; 9, 32 ; Goldschmiedt, M. 2, 
 438). Monoclinic plates (from water). V. si. 
 sol. cold water; b1. sol. hot water (difference 
 from the o- acid), v. sol. alcohol and ether, si. 
 sol. benzene. Sublimes in plates. 
 
 Salts. — CaA'2 2aq: needles. — BaA'^ 2aq. — 
 AgA': V. si. sol. water. 
 
 Methyl ether MeA'. [107°]. Satiny plates. 
 
 Ethyl ether EtA'. [62°]. Monoclinic. 
 
 DI-BENZOYL-BENZOIC ACID C^.H^G, i.e. 
 (CsH5.C0)2.CsH3.C02H. Two acids of this com- 
 position are formed, together with an acid 
 CisHiijOs, by oxidising the hydrocarbon C2,Hj„ 
 obtained as a by-product in the preparation of 
 benzyl-toluene (Weber a. Zincke, B. 7, 1153). 
 
 (a)-Acid. [82°]. Besinous, and forms resi- 
 nous salts. Potash-fusion forms benzoic acid 
 and a small quantity of an acid CisHuOj. 
 
 (;8)-Aoid. [212°]. Needles, insol. water, v. 
 sol. alcohol and ether. Its salts are si. sol. 
 water. Ethyl ether EtA'. [107°]. 
 
 DI-BENZOYL - BENZYLIDENE - DI - ACETIC 
 ACID V. Bemylidene-di-BEi<izoYi^-Di-MiBTio aoid. 
 
 BENZOYL-BENZOTRICHLOaiDE v. Phenyl 
 
 TRI-OHI.OSB-TOLTI. KETONE. 
 
 BENZOYL-BENZYL-ANILINE v. Benzyl- 
 
 ANILINS. 
 
 BENZOYL-BENZYL CHLORIDE v. Phenyl 
 
 OHLORO-TOLYL KETONE. 
 
 BENZOYL -BENZYLIDENE CHLOKIDE v. 
 
 Phenyl di-ohloeo-tolyl ketone. 
 
 BENZOYL-BEOMANILINEij.Bbomo-aniline. 
 
 BENZOYL BROMIDE CsH^.CO.Br. (219° i.V.). 
 [a little below 0°]. S.G. is 1-57. Colourless 
 fluid, which fumes in the air. 
 
 Preparation. — ^Benzoic acid (500 pts.) is 
 warmed with phosphorus tribromide (740 pts.) 
 and the product is separated from the phos- 
 phorous acid by distillation in vacuo ; the 
 yield is 400 pts. (Claisen, B. 14, 2473). The so- 
 called benzoyl bromide of Liebig and Wohler 
 {A. 3, 266) and of Paternd was probably benzyl- 
 idene -bromide -benzoate, CjH5CHBr(0Bz), a 
 compound of benzoic aldehyde with benzoyl 
 bromide. 
 
 BENZOYL - BEOMO - NITRANILIDE v. 
 Bbomo-nitro-aniline. 
 
 BENZOYL . BROMO - PHENOL v. Beomo- 
 phenol. 
 
 DI-BENZOYL-ISOBUTYRIC ACID 
 (C„H5.C0.CH,)jCH.C0„H. Di -phenacyl- acetic 
 acid. [133°j. Formed by loss of COj, by heat- 
 
 ing di - j8 - benzoyl - di - methyl - mabnic acid 
 (Bz.CH2)2C(COjH)j. Silky needles. V.sol.alco 
 hoi, ether, acetic acid, and hot benzene, msoJ, 
 ligroin. — A'Na : glistening needles (Kues a. 
 Paal, B. 19, 3147). 
 
 BENZOYL-CARBAMIC ACID. C,H,NO,. 
 
 Ethyl ether CA.CO.NH.CO.,Et. [110»i 
 Formed by boiling jbenzoyl-thiocarbamic ethe* 
 in alcoholic solution with PbO (Lossner, J. pr. 
 [2] 10, 254). Needles (from dilute alcohol), si. 
 sol. water. Decomposed by aqueous KOH into 
 KOBz, alcohol, NHs, and K^CO,. Alcoholic 
 KOH gives a pp. of OsHs.CO.NK.COjEt, v.e. sol. 
 water. 
 
 BENZOYL-CARBINOL Ph.CO.CH^OH [86°]. 
 Ph.C(OH)2.CH20H [74°]. Exo - oxy -phenyU 
 methyl ketone. Oxy-acetophenone. Aceto-phe- 
 none alcohol. Phenacyl alcolwl. 
 
 Formation. — 1. By the action of alkalis on 
 the acetate or chloride, CuHs.CO.CHjCl.— 2. 
 From phenyl-glycol (2 g.) and HNO3 (6 0.0. of 
 S.G. 1-36). The mixture is warmed and, as 
 soon as reaction sets in, it is cooled. The pro- 
 duct is diluted, neutralised with Na^COj, and the 
 crystalline carbinol filtered off. Ether extracts 
 a further quantity from the filtrate (Hunaeus 
 a. Zincke, B. 10, 1487). 
 
 Properties. — Prisms or plates (from benzol- 
 ine). Large crystals (from alcohol or ether). 
 V. sol. ether, alcohol, or CHClj. Large plates 
 containing HjO (from water or dilute alco- 
 hol). In drying these, decomposition readily 
 occurs, benzoic aldehyde being formed. The 
 carbinol combines with NaHSO,. Readily re- 
 duces ammoniacal silver nitrate or Fehling's 
 solution, the chief product of the oxidation being 
 mandelic acid C8H5.CH(OH).C02H (Breuer a. 
 Zincke, B. 13, 635). 
 
 Reactions. -^1. Heated alone it gives off 
 benzoic aldehyde and a pungent body. — 
 
 2. Heated with aqueous NaOH or baryta it 
 becomes yellow and forms benzoic aldehyde. — 
 
 3. Water at 140' acts similarly. — 4. With 
 HON it yields the nitrile of atroglycerio acid 
 CH2(OH).CPh(OH).C02H (Plochl a. Bliimlein, 
 B. 16, 1290). 
 
 Acetate Ph.CO.CH^OAc. [49°]. (270°). 
 From chloro-acetophenone and AgOAo (Graebe, 
 B. 4, 34) ; or from the carbinol and Ac^O 
 (Zincke). Trimetrio tables (from benzoline). 
 v. sol. alcohol, ether, or chloroform. M. sol. 
 benzoline. 
 
 Benzoate Ph.CO.CHjOBz. [117°] (Zincke). 
 From ohloro-aoeto-phenone and AgOBz or from 
 benzoyl - carbinol and BzjO. Small tables 
 (from dilute alcohol). V. sol. ether, benzene, 
 or CHCl,. 
 
 BENZOYL-CHLORANILIDE v. CHi.0H0-ANi- 
 line. 
 
 BENZOYL CHLORIDE C.H^.CO.Cl. [-1°] 
 (Lieben, A. 178, 43). (198°). (194°) (Brnhl, 
 A. 235, 11). S.G. ii! 1-21 ; \° 1-2122 (B.). V.D. 
 4-99 (oalc. 4-90). ^0 = 1-5537. S.V. 126-3 
 (Ramsay). 
 
 Formation. — 1. From chlorine and benzoic 
 aldehyde (Liebig a. W6hler,.4.3,262).— 2. From 
 benzoic acid and PCI3 (Cahours, A. Ch. [3] 23, 
 334).— 3. From benzoates and POClj (Gerhardt, 
 A. Ch. [3] 37, 291).— 4. In small quantities, by 
 the action of CI upon mandelic acid or on ben- 
 zoic ethers (Malaguti, A. Ch. [2] 70, 374).- -6, 
 
a-BENZOYL-ISO-HEXOIC ACID. 
 
 48S 
 
 By heating benzoic acid, NaCl, and K.S.jO, at 
 200° (Beketofl, A. 109, 256).— 6. By theaction o£ 
 COClj on benzene in presence of AljOlj (Friedel, 
 Crafts, a. Ador, B. 10, 1855). — 7. From benzoic 
 acid or benzoates and SjClj (Carius, A. 106, 
 300). — 8. By heating benzoic acid with ZnClj 
 and adding benzotrichloride (Z>. P. J. 239, 157). 
 C.H,CC1, + C,H,.CO,H = 2CbH,.C0C1 + HCl. 
 
 Properties. — Colourless pungent oil. Decom- 
 posed into HCl and benzoic acid slowly by cold, 
 quickly by hot, water. Alcohol reacts vigorously, 
 forming benzoic ether and HCl. Ether and CS2 
 dissolve it without decomposition. 
 
 BeacUons. — 1. Aqueous KOH gives KOBz 
 and KCl.— 2. Dry BaO at 150° forms Bz,0 (Gal, 
 A. 128, 127). — 3. Dry NH3 or ammonmm car- 
 bonate forms benzamide ; other bases act simi- 
 larly. — 4. Sodium has no action in the cold, but 
 in presence of ether at 100°, ' dibenzoyl ' [140°] 
 is slowly formed (Briegel, Bl. [2] 5, 278). -5. 
 Hydride of Copper forms CUoCl^ and benzoic 
 aldehyde (Ohiozza, A. 85, 232).— 6. KI forms 
 Bzl.— 7. HgCyj forms BzCy.— 8. KSCN forms 
 benzonitrile, CO,, and CS^ (Limpricht, A. 99, 
 117).— 9. Pb(SCN) forms BzSCN.— 10. KNCO 
 forms benzonitrile (Schiff, A. 101, 93) and cya- 
 phenine (Cloez, Bl. 1859, 100).— 11. NaOBz 
 gives BzjO (Gerhardt). — 12. Sodium formate 
 forms CO, NaCl, and benzoic acid. — 13. Potas- 
 sium oxalate forms BzjO, KCl, CO, and CO^. — 
 14. By the dry nitrates of Pb, Ag, Hg, or Cu, 
 it is converted into benzoic anhydride, with 
 formation of the chloride of the metal, N2O4, 
 and oxygen (Lachowicz, B. 18, 2990). — 15. 
 Cone. HjSOj forms, apparently, Bz.SOjH, which 
 on heating becomes beuzene-sulphonic acid 
 (Oppenheim, Z. [2] 7, 21).— 16. PCI5 at 200° 
 gives CSH5.CCI3, CeH^CLCCla, CaHsCl^.CCla and 
 at a higher temperature CCl, and chlorinated 
 benzenes (Sohisohkoff a. Bosing, /. 1858, 279 ; 
 Limpricht, A. 134, 55; Claus a. Hoch, B. 19, 
 1194).— 17. KHS forms BzSH.— 18. BaOj gives 
 BZ2O2. — 19. Sodium amalgam in acid solution 
 forms benzoic aldehyde and benzyl alcohol 
 (Lippmann, A. 137, 252).— 20. ENH^ forms 
 benzamide and dibenzamide (Baumert a. Lau- 
 dolt, A. Ill, 1).— 21. Succinic ether at 200° 
 gives succinic anhydride, EtOBz, and EtCl 
 (Kraut, A. 137, 254). 
 
 Com6ina«ow.— TiOljBzCl. [65°]. ' YeUow 
 crystals (Bertrand, Bl. [2] 34, 631). 
 
 BEBTZOYL-CHLOEO-TOLUIDE v. Chloho- 
 
 lOLtJIDINE. 
 
 BENZOYL-CHOLIC ACID v. Cholic acid. 
 
 BENZOYL-CBOTONIC ACID CnHiA i.e. 
 CjH5.C0.C(CH,):CH.C0jH. [113°]. Long pointed 
 crystals. Prepared by the action of ALClu on a 
 mixture of benzene and citraconic anhydride. 
 By alkalis it is resolved into phenyl ethyl ketone 
 and glyoxylio acid (Pechmann, B. 15, 891). 
 
 BENZOYL-CUMIDIC ACID v. Phenyl-xylyl- 
 
 KETONE DI-CARBOXYLIO ACID. 
 
 BENZOYL CTIMIDINE v. Cumidine. 
 BENZOYL-CYANACETIC ETHER v. Cyano- 
 
 BENZOYL-ACETIC ETHER. 
 
 BENZOYL CYANIDE CeH5.CO.CN. [33°]. 
 (208°). Formed by distilling BzCl with HgCy^ or 
 AgCy (Liebig a. Wohler, A. 3, 267 ; H. Strecker, 
 A. 90, 62 ; Hubner a. Buohka, B. 10, 480 ; Kolbe, 
 A. 90, 63 ; 98, 347), Formed also by mixing 
 iaonitroso-acetophenone C,H5.C0.CH:N0I1 with 
 
 AcCl in the cold, and then distilling the mixture. 
 The isonitroso-aoetophenone need not be sepa- 
 rately prepared, but amyl nitrite (1 mol.) can 
 be allowed to drop slowly into a warm mixture 
 of acetophenone (1 mol.) and acetyl chloride 
 (3 mols.), and the product distilled ; yield : 65- 
 70 p.c. of the theoretical (Claisen a. Manasse, 
 
 B. 20, 2196). Pungent crystalline mass. De- 
 composed slowly by water, more readily bv 
 KOHAq into HOBz and HON. Fuming HCl 
 forms CeH5.CO.CO.NH2 whence phenyl-glyoxylio 
 acid. Zinc and HCl reduce it to benzoic alde- 
 hyde. NH3 gives benzamide and NH^CN, 
 Aruiline gives benzanilide. PCI5 appears to 
 form CeH,.CCl2.CN (224°) (Claisen, B. 12, 626). 
 ZnEtj, diluted with ether forms 3 p.c. of 
 ' benzoyanidine ' C^jHigNOj, [124°], needles 
 (from alcohol) ; another product (200°-220°), 
 either contains phenyl ethyl ketone or yields 
 that body on oxidation (Frankland a. Louis, 
 
 C. J. 37, 742). 
 
 BENZOYL CYANIDINE v. Benzoyi. cyan- 
 ide. 
 
 BENZOYL CYANTJEATE v. Cyandbio acid. 
 
 BENZOYL - CYMENE - SULPHAHIDE v. 
 Cymene sulphonio acid. 
 
 BENZOYL-CYMENOL v. Cymenol. 
 
 BENZOYL CYMIDIDE v. Cymidine. 
 
 BENZOYL DESOXALIC ACID v. Desoxalio 
 acid. 
 
 BENZOYL-ISODUEENE v. Phenyl tetba- 
 
 METHYL-PHENYL KETONE. 
 
 0-TBI-BENZOYLENE-BENZENE C^H.jO, 
 
 i.e. Ce(CeHj.CO),. [above 360°]. Formed to- 
 gether with methylene - phthalyl by heating 
 phthalio .anhydride with malonic ether and 
 sodium acetate, or by the action of HjSO, on 
 phthalyl-aoetic acid (Gabriel a. Michael, B. 10, 
 1557 ; 11, 1007, 1679 ; 14, 925). Yellow crys- 
 tals. Soluble in nitrobenzene, nearly insoluble 
 in other solvents. Potash-fusion converts it 
 into phenenyl-tri-benzoio acid CeH3(CeHjC02H)j 
 [261°]. 
 
 DI - BENZOYL - ETHANE v. Di - phenyi,- 
 
 ETHYLENE-DI-KETONE. 
 
 BENZOYL -ETHYL- ACETIC ACID v. Ben- 
 
 ZOYL-AOETIO ACID. 
 
 BENZOYL - ETHYL - ANILINE v. Ethyl- 
 
 ANILINE. 
 
 BENZOYL -ETHYL -BENZENE v. Phenyl 
 
 ETHYL-PHENYL KETONE. 
 
 BENZOYL-ETHYL-0-CABBOXYLIC ACID v. 
 
 Phenyl ethyl ketone o-caeboxylio aoid. 
 
 BENZOYL-FOEMIC ACID v. Phenyl-oly- 
 
 OXYLIO ACID. 
 
 BENZOYL FLUOEIDE C,H,,.CO.F. (162°). 
 From HKF2 and BzCl (Borodin, A. 126, 60). 
 Pungent liquid ; attacks glass. Decomposed by 
 water into HF and HOBz. 
 
 DI-BENZOYL-FUMAEIC ETHER 
 C02Et.CBz:CBz.C02Et. Formed by the action 
 of iodine dissolved in ether upon the di- 
 sodium compound of di - benzoyl - succinate, 
 C02Et.CBzNa.CBzNa.C02Et (Perkin, 0. J. 47, 
 262). 
 
 BENZOYL-GALLIC ACID v. Gallic acid. 
 
 BENZOYL-GLYCOCOLL v. Hippubio acid. 
 
 BENZOYL-GLYCOLLIC ACID v. Glyoollio 
 Acn>. 
 
 a. BENZOYL- ISO. HEXOIC ACID v. lio- 
 
 &i(i^2-BENZ0YL-ACETI0 AOID. 
 
486 
 
 BENZOYL HYDRIDE. 
 
 BENZOYL HYDRIDE v. Benzoic aldehyde. 
 
 DI-BENZOYL-IMIDE v. p. 475. 
 
 DI-BENZOYL-INDIGO «. Indiqo. 
 
 BENZOYL lODANILINE v. Iodo-aniline. 
 
 BENZOYL IODIDE OeHs.CO.I. Easily-fusi- 
 ble crystalline mass obtained by heating BzCl 
 with KI (Liebig a. Wohler, A. 3, 266). 
 
 BENZOYL-ISATIN v. Isatin. 
 
 BENZOYL-ISETHIONIC ACID v. Isethionio 
 Lcca. 
 
 BENZOYL-LACTIC ACID v. Lactic acid. 
 
 BENZOYL-LEUCINE v. Leucine. 
 
 TRI-BENZOYL-MELAMINE v. Melamine. 
 
 BENZOYL - TEIMELLITIC ACID. Bemo- 
 phenone tricarboxylic acid C|sH|„0, i.e. 
 C„H,.CO.O,Hj(C02H)3 [5:1:2:4]. From phenyl 
 i((-cumyl ketone by oxidation with dilute HNOj 
 or KMnO. (Bibs, J. pr. [2] 35, 494). Salts.— 
 BaHA'". 
 
 BENZOYL-MESIDIDE v. Mesidine. 
 
 BENZOYL-MESITYLENE v. Phenyl tri- 
 methyl-phenyl ketone. 
 
 Dlbenzoyl-mesitylene v. Di- phenyl ini- 
 uethyl-phenylene diketone. 
 
 Tri-benzoyl-mssitylene OsjH^jOj i.e. 
 (CaH5.CO)sC||Me3. Tri-phenyl tri-methyl-phe- 
 nenyl tri-ketone. [216°]. Formed by heating 
 benzoyl-mesitylene or di -benzoyl -mesitylene 
 with BzCl and AljClj at 198°. Crystals (from 
 alcohol), V. si. sol. cold alcohol, v. sol. a mixture 
 of chloroform and acetone. When BzCl acts 
 on mesitylene in presence of AljClj below 118° 
 only benzoyl-mesitylene is formed ; at 150° di- 
 benzoyl-mesitylene is the chief product (Louise, 
 C. B. 98, 1440; A. Ch. [6] 6, 237). 
 
 o-BENZOYL-MESITYLENIC ACID C.^HnOj 
 i.e. CeHs.CO.CsHjMejOOOH. Phenyl xylyl ke- 
 tone carhoxylic acid. [185°]. Prepared in the 
 same way as the p- acid (v. infra) (Louise, Bl. 
 [2] 44, 418). Colourless crystals, insol. cold 
 water, si. sol. boiling water, sol. CHClj, acetone, 
 ether, and benzene. Its salts do not crystallise 
 well.— AgA'.— CuAV 
 
 p-Benzoyl-mesitylenic acid Ci^HuOa. [160°]. 
 Prepared by oxidising phenyl tri-methyl-phenyl 
 ketone (benzoyl-mesitylene) (Louise, Bl. [2] 44, 
 418 ; A. Ch. [6] 6, 218). Nacreous scales, very 
 sol. ether, CHCI3, acetone, &o., sol. boiling water. 
 
 Salts. — A'NHj: small brilliant crystals. — 
 A'Ag : white pp. sol. boiling water. — A'jBa 2aq : 
 long needles. — A'^Ca: long white filaments. — 
 A'jMg 6aq : crystals, sol. hot water. — SrA'j. 
 
 BENZOYL-METHANE v. Aoetophenone. 
 
 Di-beszoyl-methane v. Di-phenyl methylene 
 
 DIEEIONE. 
 
 Tri-benzoyl-methaiie (C„H5.C0)3CH. Me- 
 thenyl tri-phenyl tri-ketone [225°]. Formed by 
 the action of benzoyl-chloride on sodio-di-ben- 
 zoyl-methane (Baeyer a. Perkin, B. 16, 2135 ; 
 C. J. 47, 240). Small needles. Sublimable. 
 V. b1. sol. alcohol, v. sol. dilute alcoholic KOH. 
 Converted by NaOEt and BzCl into a substance 
 [260°-270°]. 
 
 BENZOYL - METHYLAMINE v. Methyl - 
 
 AMINE. 
 
 BENZOYL-METHVL-ANILINE v. Methyl- 
 aniline. 
 
 BENZOYL - DIMETHYLANILINE v. Di- 
 methyl-amido-bbnzophenone. 
 
 BENZOYL-TEIMETHYLENE v. Phenyl tki- 
 
 DI - (3 - BENZOYL - DI - METHYL • MALOKIC 
 ACID (C,H5.CO.CHj)sC(C02H),. Di^henaeyl- 
 malomc acid. [134°]. Formed by sapomfi- 
 cation of its ether, which is obtained by the action 
 of co-bromo-aceto-phenone upon sodio-malonio 
 ether. Large colourless prisms. V. sol. alcohol, 
 ether, and acetic acid, si. sol. water, insol. 
 benzene and ligroin. Reacts with phenyl-hydra- 
 zine. Evolves CO2 on heating, giving di-benzoyl- 
 isobutyric acid.— "A'^ : white needles or plates, 
 v. sol. water. — •'A"Ag2: nearly insol. white pp. 
 
 Di-ethyl ether A"Et2: [119°]; largewhite 
 glistening prisms or long flat needles ; V. sol. 
 water, benzene, acetic acid, and CSj, less in 
 alcohol, insol. ligroin. Beacts with phenyl- 
 hydrazine but not with hydroxylamine (Kues a. 
 Paal, B. 19, 3144). 
 
 BENZOYL-METHYL.:p-NITEANILINE v. p. 
 Niiko-phenyl-oj-amido-aoetophenone. 
 
 BENZOYL - METHYL - PHENYL - NITEOS - 
 AMINE V. Phenyl-amido-acetophenone. 
 
 BENZOYL- NAFHTHALIOE v. Naphthyl- 
 amine. 
 
 BENZOYL - NAFHTHYLAMINE - IMIDE . 
 CHLORIDE V. (u-Chlobo-benzylidine-naphthyl- 
 
 AMINE. 
 
 BENZOYL-NAPHTHYL-THIO-DEEAu.Naph- 
 
 ihyl-thio-ukea. 
 
 BENZOYL-NITEANILIDE v. Nitbo-aniline. 
 
 BENZOYL-NITEITE BzNO, (?). An oil 
 formed together with m-nitro-benzoio aldehyde 
 by the action of 20 vols, of a mixture of HNO, 
 (1 vol.) and H^SO^ (2 vols.) upon 1 vol. of ben- 
 zoic tjdehyde (Lippmann a. Hawliczek, B, 9, 
 1463). It is decomposed by distillation. 
 
 BENZOYL - NITEO - AMIDO - DIFHENYL v. 
 Nitko-amido-diphenyl. 
 
 BENZOYL . NITEO ■ AMIDO - PHENOL v. 
 
 NlTBO-AMIDO-PHENOL. 
 
 BENZOYL NITEO-ANISIDINE v. Nitbo- 
 
 AMIDO-PHENOL. 
 
 BENZOYL NITRO - CUMIDINE v. Niibo- 
 
 OUMIDINE. 
 
 BENZOYL ■ NITBO - NAFHTHALIDE v. 
 
 NlIRO-NAPHIHYLAMlNB. 
 
 BENZOYL - NITRO - DIFHENYLAMIDE v. 
 
 NiTBO-DIPHENYLAMINE. 
 
 BENZOYL-NITEO-TOLTTENE STTLFHAMIDE 
 
 V. Nitko-toluene sulphonio acid. 
 
 BENZOYL-NITEO-TOLUIDE v. Nitbo-tolu- 
 
 IDINE. 
 
 BENZOYL PEROXIDE C,4H,„04 i.e. BzA- 
 
 [104°]. BzCl is mixed with hydrated BaOj and 
 the resulting solid cake washed with water and 
 NajCOj, and crystallised from CSj (Brodie, Pr. 
 9, 361 ; 12, 655 ; Sperlich a. Lippmann, Sitz. 
 B. 62, 613). Trimetric crystals, insol. water, v. 
 sol. ether and benzene. Decomposed by heat, 
 giving off CO2 with slight explosion. Boiling 
 KOHAq forms and KOBz. Benzoyl peroxide 
 acts as an oxidising agent, splitting up into 
 Bzj,0 and : thus it oxidises jp-toluidine to 
 toluene-azo-toluene. 
 
 BENZOYL-PHENOL C5H5.OBZ v. Phenol; 
 CuHj.CO.CbH^OH v. Oxt-benzophenone. 
 
 BENZOYL-FHENOL SULFHONIC ACID v. 
 Phenol sulphonio acid. 
 
 BENZOYL-PHENYL-AMINE 
 0„H5.C0.C,H,NHj. Benzanilide (18 g.), BzCl 
 (14g.), and ZnOl^ give the ^-benzoyl derivative 
 [150°], together with a little of the o-benzoyl- 
 
BENZOYL-SUCCINIC ACID. 
 
 487 
 
 derivative CsHj.CO.OjH^NHBz [170°] (Higgin, 
 C.J. 41, 133). Dilute HCl at 120° Uberates the 
 fiee bases, which are described as Amu>o-benzo- 
 
 VHENONEB {q. v.). 
 
 jj-BENZOYL-PHENYL-CARBAMIC ETHER 
 CA-C0.0^4-NH.C0jEt [189°]. Prepared by 
 the action of chloroformio ether on p-amido- 
 benzophenone (Doebner a. Weiss, B. 14, 1839 ; 
 A. 210, 246). Plates. Sol. boiling alcohol, 
 boiling acetic acid, and chloroform, insol. cold 
 water. Decomposed by boiling EOH. 
 
 BENZOYL-FHENYL-CABBAMINE 
 C5H5.CO.C5H4.NC. Iso - cyano - bemophenone 
 [119°]. From ^-amido-benzophenone (10 g.), 
 chloroform (8 g.), and alcoholic KOH (Doebner, 
 A. 210, 246). Silky needles, volatile with steam. 
 SI. sol. hot water, v. sol. alcohol. Split up by 
 acids into formio acid and amido-acetophenone. 
 
 BENZOYL ■ FHENYIENE - DIAMINE v. 
 
 PHEinLBNE-DIAMINE. 
 
 BENZOYI-PHENYL-DI-ETHYL-AMINE v. 
 
 Dl-BTHYIi-AMIDO-BENZOPHENONE. 
 
 BENZOYL - PHENYL - DI - MEIHYL-AUINE 
 
 V. DlMBTHTL-AMIDO-BENZOPHENONE. 
 
 ^-DI-BENZGYL-DI-PHENYL-THIO-TIREA 
 
 SC(NH.CeH,.C0.CsH5)2. [166°]. Prepared by the 
 action of CS2 on an alcoholic solution of p- 
 amido-benzophenone in presence of a little 
 KOH (Doebner a. Weiss, B. 14, 1839). Colour- 
 less plates. Sol. chloroform, si. sol. hot alcohol, 
 ether, benzene and CSj ; insol. water. 
 
 BENZOYL-PHENYL-METHANE is Benzoyi,- 
 
 PHENYIi-OAEBAMIO ETHER {q. V.). 
 
 BENZOYL - PIPES - PROPYL ■ ALKE'lN v. 
 
 Benzoyl- Oxypkopyl-pipeeidine. 
 
 BENZOYL-PBOPANE-CARBOXYLIC ACID 
 V. Phenyl propyl ketone oaeboxtlio acid. 
 
 o-BENZOYL-PROPIONIC ACID C„H,„03 i.e. 
 CeH5.CO.CHMe.CO2H. Phenyl ethyl ketone 
 a-ca/rboxylic acid. From the ether and cone. 
 HjSO,, the mixture being left for 3 weeks. It 
 is an oil and gives a reddish-brown colour with 
 Fe^Clj. Alkalis produce phenyl ethyl ketone. 
 
 Ethyl ether CHj.CHBz.CO^Et. (227°) at 
 225 mm. Formed by the action of NaOEt and 
 Mel on benzoyl-aoetio ether (q. v.). Aromatic 
 smelling oil. Vefilg gives no colour in its alco- 
 holic solution. NaOEt forms the sodium de- 
 rivative CHj.CNaBz.CO^Et. Phosphorus penta- 
 chloride forms CaHj.CCliCMe.COjiEt (Perkin a. 
 Caiman, C. J. 49, 156). 
 
 iS-benzoyl-propionic acid 
 C5H5.CO.CH2.CHj.CO2H. Phenyl ethyl ketone 
 a-carboxylic acid. [116°] ; [114°] (Bisohoff, B. 
 19, 95). 
 
 Formation. — 1. By the reduction of benzoyl- 
 acrylic acid. — 2. By the action of AljClj (1| pts.) 
 on a mixture of succinic anhydride (1 pt.) and 
 benzene (10 pts.). The product is shaken with 
 water, when the acid remains dissolved in the 
 benzene, whence it is extracted by shaking with 
 KOH and ppg. with HCl (Burcker, Bl. [2] 35, 
 17 ; A. Ch. [5] 26, 433 ; Pechmann, B. 15, 889). 
 3. By oxidising its aldehyde. — 4. Its chloride 
 is formed by the action of AI2CI8 upon a 
 mixture of suocinyl chloride (1 mol.) and 
 benzene (1 mol.) (Claus, B. 20, 1375).— 5. By 
 heating benzoyl-isosuccinic acid above its melt- 
 ing-point, COj being evolved (Kues a. Paal, B. 
 18, 3325). 
 
 Properties.— \l\a.\i6 prisms, v. sol. hot water. 
 
 Converted by potash-fusion into benzoic and 
 propionic acids. Beduced by sodium amalgam 
 to 7-oxy-phenyl-butyric acid (or its lactone). 
 C5H5.CH(0H) .CH2.CH2.CO2H. 
 
 Salts. — ^BaA'2: needles. — AgA' : si. sol. 
 water. 
 
 Ethyl ether. EtA'. [32°] : white crys- 
 tals, turned red by heat. 
 
 Phenyl-hydrazide 
 C5H5.C(N2HPh).CH2.CH2.C02H. [65°]. White 
 silky needles, v. sol. alkalis, acids, alcohol, and 
 benzene, si. sol. ether. 
 
 BENZOYL-PROPIONIC ALDEHYDE 
 C5H5.CO.CH2.CH2.CHO. (245°). S.G.2 1-005; 
 — '998. Prepared by the action of water upon 
 the compound of phenyl propyl ketone with 
 Cr02Cl2. Oil, sol. ether and chloroform. It 
 readily reduces AgNOs, but does not combine 
 with NaHSOj. Sodium-amalgam reduces it to 
 syrupy C5H5.CH(OH).CH2.CH2.CH20H (0. 200°) 
 (Burcker, A. Ch. [5] 26, 469 ; C. B. 94, 220). 
 
 BENZOYL-PROPIONIC-CARBOXYLIC ACID 
 V. Phenyl ethyl ketone di-cakboxyiio acid. 
 
 BENZOYL-PYROCATECHIN v. Di-oxy-benz- 
 
 OPHENONE. 
 
 BENZOYL PYRROL v. Pykkol. 
 Psejt<io-benzoyl-pyrrol v. Pybeyl phenyl 
 
 KETONE. 
 
 BENZOYL PYRUVIC ACID CioHjOi i.e. 
 C5H5.CO.CH2.CO.CO2H. [156°]. Obtained by 
 saponification of the ethyl ether. Yellowish- 
 white prisms (from hot benzene). Strong acid. 
 Evolves CO2 at its melting-point. 
 
 Ethyl ether A'Et: [43°]. Prepared by 
 adding 48 pts. of acetophenone to a cooled solu- 
 tion of 9'2 pts. of sodium in 150 pts. alcohol, 
 and then 58'4 pts. of oxalic ether. The precipi- 
 tated sodium compound is washed with ether, 
 dried, dissolved in iced water, and decomposed 
 by CO2, when the benzoyl-pyruvic ether crystal- 
 lises out ; the yield is 78 p.c. of the theoretical. It 
 crystallises from petroleum-ether in long prisms. 
 V. sol. all ordinary solvents. Fefil, gives a 
 blood-red colouration. The aqueous alcoholic 
 solution gives with cupric acetate a light-green 
 pp. of (CjjHuOJjCu, this crystallises from hot 
 benzene or alcohol in long green needles. By 
 heating with dilute aqueous NaOH the ether is 
 split up into acetophenone, oxalio acid, and 
 alcohol. By boihng its acetic acid solution with 
 phenyl-hydrazine it is converted into di-phenyl- 
 pyrazol-carboxyUc ether C3HPhN(NPh).C02Et. 
 By cold alcoholic NHj it is converted into aceto- 
 phenone, oxamide, and alcohol (Beyer a. Claisen, 
 B. 20, 2181). 
 
 BENZOYL-QUINALDINE v. Methyl-quih- 
 
 OLYL PHENYL KETONE. 
 
 BENZOYL-EESORCIN v. Di-oxy-benzophe- 
 
 NONE. 
 
 Di-benzoyl-resorcin v. Dioxy-phenylene di- 
 phenyl DIKETONE. 
 
 BENZOYL-SUCCINIC ACID. Phenyl ethyl 
 ketone di-carboxylic acid. Ethyl ether 
 C02Et.CHBz.CH2.C02Et. (c. 265°) at 160 mm. 
 From sodium-benzoyl-acetio ether and chloro- 
 acetic ether (Perkin, jun., C. J. 47, 274). 
 
 Properties. — Thick colourless oil. Its alco- 
 holic solution gives a claret colour with FcjCl,. 
 Cono. HjSO, forms a yellow solution turned red 
 by beat. NaOEt forms a solid sodium com- 
 pound. Boiling baryta water decomposes it 
 
488 
 
 BENZOYL-SUCCINIC ACID. 
 
 into benzoic and succinic acids. Boiling dilute 
 HjSO, forms benzoyl-propionic acid. 
 
 Di-benzoyl-succinic acid 
 COjH.CHBz.CHBz.CO2H. Obtained by dissolving 
 the ether in alcoholic KOH and treating with 
 HjSO, (Perkin, jun., G. J. 47, 265). The acid 
 dissolved in alcohol gives a dark-green pp. with 
 PejOle. Cone. H^SO, forms a yellow solution, 
 turned crimson by heat. 
 
 Ethyl ether COjEt.CHBz.CHBz.CO^Et. 
 [130°]. Formed by adding iodine to a solution 
 of sodium benzoyl-acetic ether in dry ether 
 (Perkin, jun., 0. J. 47, 262). Crystals (from 
 alcohol) ; si. sol. cold alcohol, v. sol. ether. 
 Cone. HjSOj forms a colourless solution 
 turned red, olive-green, and finally bluish- 
 red by heat. Sodium ethylate forms 
 C02Et.CNaBz.CNaBz.C0jBt. In the alcoholic 
 solution Fe2Clj gives a red colour. Boiling dilute 
 sulphuric acid (1:2) forms an acid probably 
 diphenyl-furfurane dicarboxyho acid, CigHi^Os, 
 [238°], whence AOjO forms an anhydride 
 0,sH,„O„ [255°] (Baeyer a. Perkin, B. 17, 62). 
 
 jS-Benzoyl-iBosucoinio acid v. Phenyl ethyl 
 
 KETONE ai-m-OABBOXYLIO ACID. 
 
 BENZOYL SXILPHIDB (C,H5.CO)2S. [48°]. 
 From BzCl and potassium thiobenzoate (Engel- 
 hardt, Latschinoff, a. Malysoheff, Z. 1868, 357). 
 Waxy prisms, insol. water, v. sol. ether. Am- 
 monia forms benzamide and ammonium thio- 
 benzoate. Alcoholic KOH forms KOBz and 
 KSBz. AlcohoUo KSH forms KSBz. 
 
 Benzoyl disulphide (CaH5C0)2S2. Mol.w. 
 274. [128°]. Formed from CbH,.C0.SH by 
 atmospheric oxidation of its solution in CS^ 
 (Cloez, A. 115, 27), or by treatment with iodine, 
 Pe^Cla, or HNOj. Also, together with BzjS, by 
 warming BzCl with PbS and ether (Mosling, A. 
 118, 304). When heated above its melting- 
 point it turns violet. Prisms or tables (from 
 CSj), si. sol. boiling ether and alcohol. Insol. 
 water, NHjAq, and KOHAq. Alcoholic KOH 
 forms KOBz and KSBz. Alcoholic KHS forms 
 KSBz. 
 
 BENZOyi SULPHOCYAITIDE C^HjCOSCN. 
 S.a. is 1-20. From BzCl and Pb{SCN)2 in the 
 cold (Miguel, A. Ch. [5] 11, 300). Pungent 
 liquid. Decomposed by boiling water into 
 benzamide and COS. On long standing it de- 
 posits an isomeride [160°], which is decomposed 
 
 by water at 200° into NHj, benzoic acid, and 
 XT a 
 
 " BENZOYL. TARTAMC ACID v. Tabtabio 
 
 AOID. 
 
 BENZOYL-TESEPHTHALIC ACID v. Benzo- 
 
 PHENONB DIOABBOXYLIC ACID. 
 
 BENZOYL THIOAESENITE G^,B.,,kBSfi,i.e. 
 As(SBz)3. [179°]. From BzCl and As^Sj. An 
 ammoniaoal solution gives vrith HgClj a pp. of 
 Hg<SBz)2 (Eayman, Bl. [2] 47, 896). 
 
 BENZOYL-THIO-CARBAMIC ACID 
 CjHjNSOj. Methyl ether Bz.NH.CO.S.Me. 
 [97°]. From benzoyl sulphooyanide and methyl 
 alcohol (Miguel, A. Ch. [5] 11, 330). Slender 
 needles (from dilute alcohol). SI. sol. water, v. 
 sol. alcohol. Water in large excess at 100° 
 forms BzNHj, methyl alcohol, HjS, and COj. 
 Salt.— BzNNa.CO.SMe. From the ethereal 
 solution And MeONa. 
 
 Ethyl ether BzNH.CO.SEt. [74°], From 
 BzSCN and HOEt ; or from alcohol, BzCl, and 
 
 KSCN (Lossner, J. pr. [2] 10, 236). Long 
 needles ; v. si. sol. water, v. sol. alcohol. Boiling 
 KOHAq forms KOBz, KSCN, alcohol, OOj, NH„ 
 and HjS. Heated alone it gives benzonitrile, 
 CO, and mercaptan. Salt.— BzNK.CO.SEt: 
 
 BENZOYL THIOCYANATE v. Benzoyl 
 
 SULPHOOYANIDE. 
 
 BENZOYL-THIO-TTEEA v. Thio-ueba. 
 BENZOYL-THYMOL v. Thymol. 
 BENZOYL-TOLTJENE-SULFHAMILE v. ToL- 
 
 DENE SULPHONIO AOID. 
 
 BENZOYL-TOLXriDE v. Toluidine. 
 BENZOYL-TOLUIDINE - IMIDE - CHLORIDE 
 
 V. w-Chlobo-benzylidene-toluidene. 
 
 BENZOYL-TOLYLENE- DIAMINE v. ToL- 
 tlene-diamine. 
 
 BENZOYL-TROPEINE v. Teopin. 
 
 BENZOYL-UREA v. TJbba. 
 
 BENZOYL-TJEITIC ACID v. Phenyl tolyl 
 eetone di-oabboxylio acid. 
 
 o-BENZOYL-VALERIC ETHER v. Propyl- 
 Benzoyl-aoetio etheb. 
 
 BENZOYL-XYLENE v. Phenyl xylyl kb- 
 
 TONE. 
 
 BENZOYL-XYLIDE v. Xylidine. 
 
 (a)-BENZ-PINACOLINE C^^^J^) Le. 
 CjHj — C^CsHj 
 
 |>0 (?) [204°]. 
 C,H,-C/C,H, 
 
 Tetra-phenyl-ethylene oxide. 
 
 Formation. — 1. Together with the (j3)-modi- 
 fication by boiling a 5 p.o. alcoholic solution of 
 benzophenone with zinc and HCl (Thoruer a. 
 Zinoke, B. 11, 65).^2. Together with benz- 
 pinacone by heating an alcoholic solution of 
 benzophenone with zinc and H^SO, (Thomer a. 
 Zincke, B. 11, 1396).— 3. By the action of zinc- 
 dust on an ethereal solution of acetyl chloride 
 (1 mol.) and benzophenone (1 mol.). If the 
 acetyl chloride is used in excess the (a)-benz- 
 pinaooline first formed is converted into the 
 (5)-benz-pinacoline (Paal, B. 17, 911).— 4. By 
 the oxidation of tetra -phenyl -ethylene with 
 chromic mixture (Behr, B. 5, 277). 
 
 Properties. — Needles. Almost insoluble in 
 cold alcohol and in cold acetic acid. 
 
 Beactions. — 1. By acetyl chloride, HCl or 
 H2SO4, it is converted into the (/8) -modification. 
 2. By heating with soda lime it gives a hydro- 
 carbon [244°] which is possibly tetraphenyl- 
 ethylene. — 3. By CrOj and acetic acid it is 
 oxidised to benzophenone. 
 
 (3)-Benz-pinaooline (C,H5)3C.C0.0„H5 [179°] 
 (T. a. Z.) ; [182°] (Zagnmenny). 
 
 Formation. — By boiling a concentrated solu- 
 tion of benzophenone in alcohol with zinc and 
 HCl for 20 hours (Thomer a. Zinoke, B. 10, 
 1473 ; 11, 65). — 2. From benzpinacone and 
 AcCl or BzCl (Linnemann, A. 133, 28).— 3. 
 Prom benzpinacone and dilute H2SO4 or HCl at 
 200°. It is even slowly formed by repeatedly 
 reorystallising benzpinacone from hot alcohol 
 (Z.). — 4. From (a)-benzpinacoline by heating 
 with AcCl, HCl, or H^SO,. 
 
 Preparation. — HClAq is added to a saturated 
 solution of benzpinacone in HOAe until a tur- 
 bidity appears. The mixture is boiled 45 
 minutes, with gradual addition of HClAq (Zagn- 
 menny, Bl. [2] 34, 339 ; 35. 560). 
 
BENZYL ALCOHOL. 
 
 4S9 
 
 Prvperties.— Slender needles, v. al. sol. cold, 
 m. sol. hot, alcohol. 
 
 BeacHons. — 1. Gives on oxidation benzoic 
 acid and tri-phenyl-carbinol. — 2. Heating with 
 alcoholic EOH produces tri-phenyl-methane 
 and benzoic acid (Zagumenny, Bl. [2] 34, 330). 
 3. Reduced by HI to s-tetra-phenyl-ethane (?). 
 
 BENZPINACONE Oj^HgiOj i.e. 
 Ph2.C(On).C(OH).Ph2. Tetra-phmyl- ethylene 
 glycol. [168°]. S. (benzene) 8-8 at 80°; S. 
 (HOAc) 8-7 at 118°; S. (95 p.c. alcohol) 2-5 at 
 80°. 
 
 Formation. — From benzophenone by re- 
 ducing the alcoholic solution with Zn and 
 H2SO4 (Linnemann, A. 133, 26) or a solution in 
 acetic acid (10 pts.) diluted with water (2 pts.) 
 with zinc (Zagumenny, J. B. 12, 426). 
 
 Properties.— Minute prisms, si. sol. boiling 
 alcohol, V. sol. ether. On fusion it splits up into 
 benzhydrol and benzophenone (Thbrner a. 
 Zinoke, B. 10, 1473). 
 
 Beactions. — 1. Chromic acid oxidises it to 
 benzophenone. — 2. Sodium-amalgam reduces it 
 to di-phenyl-carbinol. — 3. Eeadily converted 
 into (a) or {$) benzpinacoline by dehydration ; 
 this is effected by BzCl, AcCl, dilute acids, or 
 even by reorystallisation from alcohol (Za.). — 4. 
 ACjO gives benzhydrol and benzophenone. — 5. 
 HI and P at 17fl° give tetra-phenyl- ethane 
 (Graebe, B. 8, 1054). 
 
 BENZ-URAMIDOXIM Cja.^'S, i.e. 
 CsH5.C(N0H)(NH.C0.NH,). [115°]. Formed by 
 the action of potassium cyanate upon benz- 
 amidoxim hydrochloride in cone, aqueous solu- 
 tion (Falok, B. 19, 1486). Long thin white 
 needles. V. sol. alcohol, ether, benzene, and 
 ligroin, si. sol. water. 
 
 BENZ - TJBANUIDDXIM CnH.jNjOj i.e. 
 C,H5.C(N0H).NPh.C0.NHj (?). Bern -phenyl- 
 uramidoxim,. [167°]. Formed by the action 
 of potassium cyanate upon benzaniUdoxim 
 hydrochloride in concentrated aqueous solution 
 (Miiller, B. 19, 1671). . YeUowish needles. Sol. 
 alcohol, ether, benzene, and chloroform, insol. 
 water. 
 
 BENZTL. The radicle phenyl-methyl, 
 CjHs.CHj. It is isomeric with methyl-phenyl 
 or tolyl CH3.CsH,. 
 
 BIBENZYIi V. S-Dl-PHBNSL-ETHANE. 
 
 BENZYL -ACETAMIDE v. Acetyl -Benttij^ 
 
 AMINE. 
 
 BENZYL ACETATE CeHs.CHj.O.CO.CHj. 
 (206°). S.G. !£? 1-057. From benzyl alcohol 
 (2 vols.), acetic acid (4 vols.) and H^SO, (1 vol.), 
 or by boiling benzyl chloride with alcoholic 
 KOAo (Cannizzaro, A. 88, 130). Formed also 
 by boiling a mixture of benzoic aldehyde and 
 glacial acetic acid with zinc-dust (Tiemann, B. 
 19, 855). Oil, smelling of pears. Sodium act- 
 ing upon benzyl acetate does not form benzyl 
 aoeto-acetate but the chief product is benzyl 
 /9- phenyl propionate: 4CH3.CO.^C,H, + Naj = 
 2CH3C02Na-h2C,H,.CH2.CO,C,H, + H„ and by 
 a secondary reaction, sodic phenyl-propionate, 
 Bodio phenyl-acrylate, and toluene : 
 
 2C,H,.OH2.COi,C,H, + Na^ - 
 C,H,CH..00,Na+0.H..0H:0H.C0,Na+20.H.0H. 
 (Conrad a. Hodgkinson, A. 193, 300). 
 
 BENZYL-ACETIC ACID v. /3-Peenyl-peopi- 
 
 Bi-benzyl-acetio acid C,jH,50j i.«. 
 (C^5.0Hj)2CH.002H. Di-phenyl-isobutyric acid 
 [85°]. Obtained by saponifying the ether, by 
 heating di-benzyl-malonic ether with alcoholia 
 KOH (Lellmann a. Sohleioh, B. 20, 439), or by 
 heating di-benzyl-malouio acid (Biachoff a. 
 Siebert, A. 239, 101). 
 
 Properties. — Prisms (from ligroin), si. sol. 
 cold water, v. sol. alcohol. Heated with soda- 
 lime it gives di-beuzyl-methane. 
 
 Salts. — AgA' : trimetric prisma, sol. boiling 
 water (Michael a. Palmer, Am. 7, 70).^ — BaAV^ 
 CaA'jaq. 
 
 Ethyl ether BtA.'. (above 800°). Formed, 
 together with j8-phenyl-propionio ether by 
 heating acetic ether with benzyl chloride and 
 sodium (Lydia Sesemann, B. 6, 1086 ; Merz a. 
 Weith, B. 10, 759). 
 
 BENZYL-ACETO-ACETIC ETHEE v. p. 24, 
 
 BENZYL-ACETONE C.oH.^O i.e. 
 C(iH5.CH2.CH2.CO.CH,. Methyl phenylethyl he- 
 tone. (23(5°). S.G. ffr^ -989. 
 
 Formation. — 1. By the dry-distillation of a 
 mixture of calcium hydrooinnamate and calcium 
 acetate ; the yield is 33 p.c. (Jackson, B. 14, 890). 
 2. From benzyl - aceto - acetic ether by boiling 
 with alcoholic KOH (Ehrlich, A. 187, 15). 
 
 Properties. — OU. Combines with NaHSOj 
 forming OioHijONaHSOjaq. Oxidised by CrOj 
 to acetic and benzoic acids. 
 
 BENZYL-ACETONE 7.CARBOXYLIC ACID 
 
 V. ACEITL-PHENYL-PKOPIONIO ACID. 
 
 Benzyl-acetone o-oarboxylic-acid C„H,,Oj 
 i.e. C02H.CsH^.CHj.CHj.CO.CH3. [114°]. Ob- 
 tained by boiling o-carboxy-benzyl-aceto-acetic 
 ether with baryta-water (Biilow, A. 236, 192). 
 Slender needles (from water). 
 
 BENZYL-ACETOXIM v. AoETOxm, p. 38. 
 
 BENZYL - ACETYL - SUCCINIC ETHEE v. 
 
 ACETYL-BENZYL-SUCCINIO ETHER, p. 39. 
 
 v-BENZYL-DI-ACETYL-PYEEOL v. Benzyl- 
 
 PYEKYLENE-m-METHYL-KETONE. 
 
 BENZYL ALCOHOL C^HjO i.e. CjHj.CHj.OH. 
 Mol. w. 108. (206-5°). S.G. f 1-0429 (Bruhl). 
 S. 4 at 17°. fig 1-5518. Ka, 53-16. H.F. 88,733 
 (Stohmann, /. jjr. [2] 36, 4). 
 
 Occurrence. — Balsam of Peru contains benzyl 
 benzoate, benzyl cinnamate and small quantities 
 of benzyl alcohol (Kraut, A. 152, 129). Liquid 
 storax contains benzyloinnamate{Laubenheimer, 
 
 A. 164, 289). Balsam of tolu contains benzyl 
 cinnamate and some benzyl benzoate (Busse, 
 
 B. 9, 880). In small quantity, together with 
 benzoic aldehyde, prussic acid, and a resin 
 in the volatile oil of cherry-laurel (Tilden, Ph. 
 [3] 5, 761). 
 
 Formation. — 1. Together with KOBz by the 
 action of alcoholic KOH on benzoic aldehyde 
 (Cannizzaro, A. 88, 129).— 2. From benzyl 
 chloride by converting it into benzyl acetate by 
 alcoholic KOAo, and boiling the product with 
 alcoholic KOH (Cannizzaro, A. 96, 246). — 
 8. From benzyl chloride by heating with an 
 aqueous solution of KjCOj (Meunier, Bl. [2] 
 38, 159) ; with water (10 pta.) and freshly ppd. 
 Pb(0H)2 (3 pts.) (Lauth a. Grimaux, A. 143, 81) ; 
 or merely with water (30 pts.) (Niederist, A. 
 196, 353). — 4. From balsam of Peru by boiling 
 with aqueous KOH (Kachler, J. pr. 107, 307).— 
 5. By the action of sodium-amalgam upon 
 
490 
 
 BENZYL ALCOHOL. 
 
 benzoic aldehyde (Priedel, J. 1862, 263), benzoic 
 acid, hippnric acid (Hermann, A. 132, 76 ; 
 133, 335), benzoyl chloride in presence of HCl 
 (Lippmann, Bl. [2] 4, 249), or benzamide 
 (Guareschi, G. 4, 465). 
 
 Preparatton. — 10 pts. of benzaldehyde are 
 shaken in a stoppered cylinder with a solution 
 of 9 pts. of KOH in 6 pts. of water, and left to 
 stand over-night. Sufficient water is then added 
 to dissolve the potassium benzoate which has 
 separated, and the solution is extracted with 
 ether; alter evaporating the ether the residue 
 is distilled ; the yield is 92 p.c. of the theoretical. 
 Benzyl alcohol cannot be dried with CaOlj as it 
 combines with it (Meyer, B. 14, 2394). 
 
 PropertAes. — Liquid with little odour, si. sol. 
 water, sol. alcohol and ether. 
 
 iJcoctioTCS.— 1. Oxidised by dilute HNO3 or 
 air and platinum black to benzoic aldehyde, and 
 by CrO, to benzoic acid.— 2. HI and P at 140° 
 reduce it to toluene (Graebe, B. 8, 1054). — 
 3. Alcoholic EOH forms toluene and benzoic 
 acid (Cannizzaro, A. 90, 253).— 4. Cone. H^SO^, 
 PjOj, and ZnCl, form a resin (Cannizzaro, A. 92, 
 113).— 5. BjOj at 110° forms di-benzyl oxide 
 (CjH5.CHj)20.— 6. Solid cyanogen chloride forms 
 benzylcarbamate and di-benzyl-urea (Cannizzaro, 
 G. 1, 33 ; B. 3, 517).— 7. Vrea nitrate at 120° 
 forms di-benzyl-urea and benzoic aldehyde ; at 
 140° it forms benzyl carbamate (Campisi a. 
 Amato, O. 1, 39). — 8. BCI3 forms s-di-phenyl- 
 ethane and benzyl chloride (Councler, B. 10, 
 1655). 
 
 Methyl ether CsH^.CHj.OMe. (168°). From 
 benzyl cMoride, EOH, and MeOH (Sintenis, A. 
 161, 334). Also from benzyl sulphide, methyl 
 alcohol, and Mel (Cahours, A. Ch. [5] 10, 23). 
 
 Ethyl ether CsHj.CHj.OEt. (185°). Gives 
 anthracene when heated with PjOj. Chlorine 
 in the cold forms HCl, ethyl chloride, and 
 CijHsCHO ; at a higher temperature it gives 
 EtCl and benzyl chloride. Chlorine in the cold 
 in presence of I forms chloro-benzoic aldehydes 
 and EtI (Sintenis, A. 161, 331). Br forms in 
 the cold HBr, EtBr, benzyl bromide, benzoic 
 aldehyde, and BzBr (Patern6, B. 5, 288). 
 
 Isobutyl ether CsHs.CH^.O.C.Hs. (0. 210°) 
 (Claus a. Trainer, B. 19, 3006). 
 
 Phenyl ether PhO.CH^Ph. [39°]. (287°). 
 From phenol-potassium, benzyl chloride and a 
 little alcohol at 100° with inverted condenser 
 for 3 hours (Staedel, A. 217, 44 ; Lauth a. 
 Grimaux, A. 143, 81; Sintenis, A. 161, 337). 
 GKttering white plates which feel greasy (from 
 alcohol). Cone. HCl at 100° splits it up into 
 phenol and benzyl chloride. Chlorine in pre- 
 sence of HgO forms the chloro-phenyl ether, 
 C„Hs.CH2.0,C„HjCl [71°] ; bromine forms simi- 
 larly C„H5.CH2.0.C„H4Br [60°]. 
 
 o-Tolyl ether C„H,.CH,.0.C„H4.CH, [1:2]. 
 Bemyl o-cresyl oxide. (285°-290°) (Staedel, B. 
 14, 899). 
 
 m-Tolyl ether CjH^.CHj.O.CsHj.CHa [1:3]. 
 [43°]. (300°-305°). Satiny tablets. 
 
 p-Tolyl ether CjHs.CHj.O.CbHj.CH, [1:4]. 
 1.41°]. From potassium ^-cresol, a little alcohol, 
 and benzyl chloride (Staedel, A. 217, 44). The 
 yield is 86 p.c. White silky scales or transparent 
 six-sided columns (from alcohol). Feels greasy. 
 
 (a)-Naphthyl ether. An oil, decomposed 
 by distillation. 
 
 {P)-Naphthyl ether CoHjO.OH^Ph. [99% 
 From (i8)-naphthol (70 g.), KOH (27 g.), a little 
 water and alcohol, and benzyl chloride (70 g.). 
 White plates (from alcohol). No smell. Not 
 volatile with steam (Staedel, A. 217, 47). 
 
 Other benzyl ethers are described under the 
 hydroxylated compounds from which they are 
 derived. 
 
 BENZYL-o-AMIDO-ACETOPHENONE 
 CsH,(NH0,H,).C0.CH3. [81°]. Formed by heat, 
 ing o-amido-acetophenone with benzyl chloride 
 (Baeyer, B. 17, 971). Large prisms. V. sol. 
 alcohol, ether, benzene, chloroform and CSj, si. 
 sol. ligroin. Weak base. 
 
 Nitrosamine C„H^(N(C,H,).N0)C0.CH3 
 [55°] ; long colourless needles. By heating with 
 H2SO, it gives a mixture of indigo and benzyl- 
 indigo. 
 
 B£NZYL-o-AKII)0-B£NZOIG ACID 
 C,H,NH.0,H,.C0^. [176° unoor.]. Formed to- 
 gether with its formyl derivative by oxidation of 
 benzyl-quinoline with alkaline KMnO^. Long 
 needles or thick prisms. 
 
 Salts C.jHisNOaHCl: [105° uncor.] ; large 
 tables.— (C„H,3N0j)2H2CljPtCli: [158° uncor.]; 
 orange yellow tables. 
 
 Formyl derivative C,H,N(CH0).0„Hj.C02H 
 [196°] ; large colourless tables (Claus a. 
 Glyokherr, B. 16, 1283). 
 
 BENZYL-AUIDO -IBI-FHENYL-nEIHAKE 
 PhjCNH.CHjPh. [110°]. The hydrochlo- 
 ride B'HCl [249°] is formed by the action of 
 benzyl chloride on oj-amido-tri-phenyl-methane 
 (Bibs, B. 17, 703). 
 
 Di-benzyl-amido-di-phenyl-methane 
 Ph.CH2.0sHiN(CH2Ph)2. From aniline hydro- 
 chloride and benzyl chloride at 120°- Also 
 from acetanilide and benzyl chloride at 120°. 
 White amorphous powder (Meldola, G. J. 
 41, 200). Soluble in benzene. Solutions have 
 a blue fluorescence. 
 
 BENZYLAMINE C,H,N i.e. CjHs.CHj.NH,. 
 M0I.W. 107. (184°). S.G. 11-99. 
 
 Formation. — 1. Together with di- and tri- 
 benzylamine by heating benzyl chloride with 
 alcoholic NH, (Cannizzaro, A. 134, 128; Lim- 
 pricht, A. 144, 304).— 2. Together with di- and 
 tri-benzylamine by the action of Zn and HCl 
 upon benzonitrile (Mendius, A. 121, 144 ; Spica, 
 G. 10, 515). — 3. By reducing thiobenzamide 
 CeH5.CSNHj with Zn and HCl (Hofmann, B. 
 1, 102). — 4. From benzyl cyanate and KOH 
 (Strakosch, B. 5, 692). — 5. By saponification of 
 its acetyl derivative, obtained by the action of 
 aoetamide on benzyl chloride (Eudolph, B. 12, 
 1297).— 6. By the action of bromine in alkaline 
 solution on phenyl-acet-amide CaHij.CH2.C0NHj: 
 the yield is 60 p.c. of the theoretical quan- 
 tity (Hofmann, B. 18, 2738; HoogewcrfE a. 
 Van Dorp, B. T. C. 5, 252).— 7. Together with 
 toluene, by energetic reduction of hydrobenz- 
 amide dissolved in absolute alcohol by means of 
 sodium or sodium-amalgam ; very good yield 
 (0. Fischer, B. 19, 748).— 8. By reduction of an 
 alcoholic solution of benzaldehyde-phenyl-hy- 
 drazide by means of sodium-amalgam and acetic 
 acid (Tafel, B. 19, 1928).— 9. By reduction of 
 benzaldoxim (6 pts.), dissolved in alcohol 
 (15 pts.), at 50°-60° with sodium-amalgam (160 
 pts. of 2 J p.c. Na), keeping acid by gradual 
 addition of acetic acid: good yield (Goldschmidt, 
 
BENZYL-BENZENE. 
 
 491 
 
 B. 19, 8232).— 10. In considerable quantity by 
 heating benzaldehyde witti glyooooll (Ourtius a. 
 Lederer.B. 19, 2462).— 11. Together with di- and 
 tri- benzyl-amine, as a by-produot, in the pre- 
 paration of di-benzyl-hydroxylamine from hy- 
 droxylamine hydrochloride, benzyl chloride and 
 NaOH (Walder, B. 19, 3293). 
 
 Properties. — Liquid, miscible with water, 
 alcohol, and ether. Separated from water by 
 EOH. Strongly alkaline, absorbs COj, forming a 
 crystalline carbonate, and fumes with HCl. With 
 cyanogen it forms a compound (C,H9N)2(CN)2 
 [140°] which crystallises from alcohol, and forms 
 a hydrochloride (C,H3N)j(CN)22HCl Strakoseh, 
 B. 5, 693). 
 
 Salts. — ^B'HCl: large leaflets or flat tables. 
 — B'HBr. — B'jHaPtClij : orange tables or ycJow 
 plates, si. sol. water.— B'^HjSOj. 
 
 Acetyl derivative CjHyCH^.NHAo [61°] : 
 (300°) ; crystalline solid, sol. water (Amsel a. 
 Hofmann, B. 19, 1285 ; Strakoseh, B. 5, 697 ; 
 Budolph, B. 12, 1297). 
 
 Di-benzylamine OnHi^N i.e. NH(0H2.C„HJ2. 
 S.G. 14 1-033. 
 
 Formation. — 1. By the action of NH3 on 
 CjHjCHjCl or by reduction of benzonitrile (v. 
 supra).— 2. By the action of bromine- water on 
 tribenzylamine (Limprioht, A. 144, 313). — 3. By 
 boiling benzoic aldehyde with ammonium for- 
 mate (Leuckart a. Bach, B. 19, 2128). — 
 
 4. Occurs together with mono- and tri-benzyl- 
 amine as a by-product in the preparation of 
 di-benzyl-hydroxylamine from hydroxylamine 
 hydrochloride, benzyl chloride, and NaOH.^ 
 
 5. Formed by the action of PCI3 upon di-benzyl- 
 hydroxylamine and treatment with water, the 
 reaction probably being : 
 
 (CjHJ^N.OH + PCI3 = (C,HJ,N.0.PCl2 + HCl and 
 
 (0,H,)2N.O.PClj + 3H20 = 
 (C,H,)jNHH-H3POj-f2HCl(Walder,B. 19, 3287). 
 Properties. — Liquid, insol. water, v. sol. 
 alcohol and ether. Does not absorb COj from 
 the air. On distillation it decomposes into 
 s-di-phenyl-ethaue,s-di-phenylethylene,lophine, 
 and various bases (Brunner, A. 151, 133). 
 
 Salts.— B'HNO,: [186°], very sparingly 
 soluble thin glistening needles.— B'HCl [256°]. 
 —B'HBr [276°].— B'HI [224°]. — B'^H^PtCl,: 
 golden-yellow needles. 
 
 Nitrosamine (C5H5.CH2)2N.N0 : [61°]; 
 white crystals : v. sol. alcohol and ether, insol. 
 water (W., cf. Eohde, A. 151, 366). 
 
 Picryl derivative (OgH.^.CB.2)2'S.OCs'B.,CSO^)3 " 
 [171°] ; orange plates. 
 
 Formyl derivative (C|jH5.CH2)2N.CH0 : 
 [52°] ; (above 360°) (Leuckart a. Bach, B. 19, 
 2128). 
 
 Di-sulphonia acid CnH,3N(S03H)2 (Lim- 
 pricht, A. 144, 317).-BaA". 
 
 Tri-benzylamine Oj,HaN i.e. (C5Hij.CH2)3N. 
 [91°]. 
 
 Formation. — 1. Prom benzyl chloride and 
 NH3 {v. supra). — 2. By heating di-benzylamine 
 with benzyl chloride at 100° (Walder, B. 19, 
 3287). — 3. Together with mono- and di- benzyl- 
 amine as a by-product in the preparation of 
 di-benzyl-hydroxylamine from hydroxylamine 
 hydrochloride, benzyl chloride, and NaOH (W.). 
 i. By heating benzaldehyde with rather more 
 than an equal weight of ammonium formate; 
 the yield is 40 p.o. of the benzaldehyde em- 
 
 ployed (Leuckart, B. 18, 2341). White plates 
 (from hot alcohol) ; v. si. sol. water. When 
 heated for a long time with Mel or EtI at 150°, 
 benzyl iodide and tetra-methyl- (or ethyl-) 
 ammonium iodide are formed (Marquardt, 
 B. 19, 1027). Fuming sulphuric acid forms 
 Cj,H,8(S03H)3N (Limprioht, A. 144, 311). 
 
 Salts.— B'HCl: [228°]; thick prisms or 
 iridescent plates, v. sol. hot alcohol, insol. 
 water. — B'jHjClaPtCl, : orange-yellow needles. — 
 B'HN03 : [125°] ; insol. water.— B'HBr : [208°]. 
 — B'HBrj.— B'HI : [178°].— B'HA1(S0J2 12aq: 
 [110°] ; sol. water. 
 
 Meihylo-iodide B'Mel: [184°]; needles 
 or plates ; sol. hot alcohol, si. sol. cold water. 
 
 Methylo -hydrate B'Me(OH): crystalline 
 solid ; alkaline reaction ; v. sol. water. On heat- 
 ing it evolves MeOH forming tri-benzylamine. 
 
 Methylo -chloride -platinum-salt 
 (B'Me01)2PtCl4 : [197°] ; orange pp. ; insol. cold 
 water and alcohol. 
 
 Ethylo-iodide B'Etl : [190°]; colourless 
 rhombic crystals ; sol. alcohol and hot water. 
 
 Isopropylo - iodide B'^rl : [170°] ; 
 needles ; si. sol. hot water. 
 
 BENZYIAMINE-aiy-DI-SULPHONIC ACID 
 CeH,.CH(S03H).NH(S03H). The di-sodium salt 
 A"Na2 3aq is formed by shaking benzaldoxim 
 with a 30 p.c. sodium bisulphite solution. It 
 crystallises in small white needles, v. e. sol. 
 water, insol. cold alcohol. By warming with 
 dilute acids it is split up into benzaldehyde, 
 sodium sulphate, and ammonium sulphite : 
 C8H5.CH(S03Na).NH(S03Na) + 2B.fi 
 = CsH^.CHO + NajSO, -I- (NH)^HS03. 
 Alkalis decompose it in the cold, and water on 
 boiling (Pechmann, B. 20, 2539). 
 
 BENZYL-ANILIHE CsH5.NH(C,H,). [33° un- 
 cor.]. (above 360''). Obtained by reducing thio- 
 benzoyl-aniline (Bernthsen a. Trompeter, B. 11, 
 1760). Formed also by boiling diazobenzene- 
 benzyl-anilide (50 g.) with HCl (200 o.c.) ; the 
 yield is 20 g. (Friswell a. Green, B. 19, 2036). 
 Yellowish crystals. 
 
 Salts.— B'HCl [203° uncor.] ; white plates; 
 decomposed by water.— B'^H^Cl^PtCl, [168° un- 
 cor.] ; slender yellow needles ; tolerably easily 
 soluble in water.— B'^C^H^O^.-E'CdOLi. 
 
 Benzoyl derivative [104°] (Fleischer, 
 A. 138, 229). 
 
 Di-benzyl-aniline CeH3.N(CH3.C„H5)j. [67°]. 
 (above 300°). Prepared by heating a mixture 
 of aniline (54 pts.), benzyl chloride (150 pts.) 
 and NaOH (30 pts.) on the water-bath for three 
 or four weeks. After cooling the solidified 
 cake is pressed, distilled with steam to remove 
 excess of benzyl chloride, washed with hot 
 water, and crystallised from alcohol. Colourless 
 needles. V. sol. ether, benzene, hot alcohol 
 and hot acetic acid, si. sol. cold alcohol and 
 cold acetic acid, nearly insol. water. Weak base. 
 
 Salts. — B'HClaq : glistening prisms. — 
 B'jHjCljPtCl^ : thin orange - yellow scales. 
 PicrateB'CsH2(NOj)sOH: [132], long yellow 
 needles (Matzudaira, B. 20, 1611). 
 
 TEI-BENZYL-AESINE v. p. 322. 
 
 BENZYL-BABBIIUBIC ACID v. Babbitubio 
 
 ACID. 
 
 BENZYL-BENZENE v. Di-PEENTL-MsiHAira:. 
 jj.Si-benzyl-benzeue C^oHis i.e. 
 {C;a.^.CB.,)fis^t. [86°]. Formed, together with 
 
403 
 
 BENZYL-BENZENE. 
 
 the o-isomeilde and di-phenyl methane, by the 
 action of zino on a mixture of benzyl chloride 
 and benzene, or by the action of H^SO, on a 
 mixture of benzene and methylal, OHj(OMe)., 
 (Zinote, B. 6, 119, 221 ; 9, 31). Transparenj 
 laminsB, b1. sol. ether, v. sol. benzene and hot 
 alcohol. CrOj forms (a)-dibenzoyl-benzene and 
 p-benzoyl-benzoio acid. 
 
 o-Di-benzyl-benzene {Gfi^.CB.^jfi^'Et. [78°]. 
 Silky needles (from alcohol) ; v. sol. ether and 
 alcohol. CrO, forms o-di-benzoyl-benzene and 
 o-benzoyl-benzoic acid. 
 
 BENZYL BENZOATE ChH.jOj i.e. 
 C„H,.CH2.0.C0.G,H,. (324° i.V.). [21°]. S.G. 
 (fluid, at 19°) 1-1224. From benzyl alcohol 
 and BzOl (Kraut, A. 152, 130). Formed also 
 by several days' heating of benzaldehyde at 
 100° with a small quantity of sodium benzylate ; 
 probably the compound CjH5.C(O0,H,)2ONa is 
 first formed and then decomposes into benzyl 
 benzoate and sodium benzylate, which latter 
 again reacts upon a further quantity of benzalde- 
 hyde, producing more of the intermediate pro- 
 duct, and so on. Large colourless crystals 
 (Claisen, B. 20, 646). 
 
 o-BENZYL-BEHZOIC ACID C„H,j02 i.e. 
 C„H5.CH2.C,H,.CO,H. Mol. w. 212. [114°]. 
 From o-benzoyl-benzoio acid and sodium-amal- 
 gam (Eotering, J. 1875, 598 ; B. 9, 683). Slender 
 needles; may be sublimed; si. sol. cold water, v. 
 sol. alcohol and ether. — CaA'22aq. — CaA'jS^ aq. 
 BaA'^S.^ aq.— AgA'.-MeA'. 
 
 fn-Benzyl-benzoic acid 
 Ph.CH;i.CeHj.C02H. [108°]. 
 
 Formation. — 1. From exo-oxy-benzyl-ben- 
 zoic acid, Ph.CH(0H).C6H<.C02H and cone. 
 HI at 170°. — 2. From exo-bromo- m-toluio acid, 
 CH.^r.CjHi.C02H, benzene and Al^Cl, (Senff, A. 
 220, 247). Yield 50 p.c. of theoretical from 
 toluic acid. — 3. A small quantity from benzoic 
 other, benzyl chloride, and ZnClj by boiling. 
 
 Properties, — Short slender needles (from hot 
 water), small plates (from hot dilute alcohol) ; 
 si. sol. cold water, m. sol. hot water, v. e. sol. 
 alcohol, ether or chloroform. Cone. H^SOj 
 forms a colourless solution. K2Cr20, and H^SO^ 
 give in - benzoyl - benzoic acid. — CaA'^ aq. — 
 BaA'24 aq. — AgA'. 
 
 ^-Beazyl-benzoic acid 
 Ph.CH,.C,H,.C02H [1:4]. [155°]. 
 
 Formation. — 1. By oxidising^-benzyl-toluene 
 with dilute ILjSOj (Zincke, A. 161, 106).— 2. By 
 reducing eaio-oxy-^-benzyl-benzoic acid with HI. 
 3. From ^-benzoyl-benzoic acid and sodium- 
 amalgam or HI and P (Graebe, B. 8, 1054). 
 
 ProperUes.—'M.inute needles (from water); 
 may be sublimed ; si. sol. cold water, v. sol. 
 alcohol and ether. Chromic mixture oxidises 
 it to p-benzoyl -benzoic acid.- CaA'jHA'. — 
 BaA'2 2aq. — AgA'. 
 
 BENZYL BBOMIDE C^-CH^Br. (199°). 
 S.G. « 1-4380. 
 
 Formation. — 1. From benzyl alcohol and 
 HBr (KekuU, A. 137, 190).— 2. From Br and 
 boiling toluene (Beilstein, A. 143, 369 ; Jackson 
 a. Field, Am. 2, 11). — 3. From benzyl chloride 
 and AsBr^ (Brix, A. 225, 163). 
 
 Preparation. — By the action of bromine (1 
 mol.) upon cold toluene (1 mol.) in direct sun- 
 shine ; the yield is quantitative (Schramm, B. 
 18, 603). 
 
 Properties. — Pungent liquid. The zinc-coppet 
 couple acts vigorously upon it, producing two 
 isomeric benzylenes. In presence of ether, the 
 zinc-copper couple produces dibenzyl, ZuBr^, 
 and C,H,ZnBr, whence water produces toluene : 
 2C,H,ZnBr + 20^0 = 2C,H3 -^ ZnBr^ -1- Zn(OH),. 
 In presence of alcohol, the couple produces 
 toluene and BtOZnBr. In presence of water, 
 the couple produces dibenzyl and a little toluene 
 (Gladstone a. Tribe, G. J. 47, 448). 
 
 BENZYL BUTYEATE 0„H„02 i.e. 
 C„H5.CHj.0.C0.Pr. (240°). S.G. ,fj 1-016 (Con- 
 rad a. Hodgkinson, A. 193, 320). 
 
 Benzyl isobutyrate Me^CH.COyCHjPh. 
 (228° i. v.). S.G. y 1-016. Prepared by boiling 
 an alcoholic solution of benzyl chloride and 
 potassio isobutyrate for five days with inverted 
 condenser. The product is mixed with water 
 and the oil distilled. 
 
 Properties. — Oil, with pleasant odour. 
 
 Beactions. — ^When benzyl isobutyrate (90 g.) 
 is heated with sodium (8g.) a violent action 
 occurs, the products being hydrogen, sodic iso- 
 butyrate, benzylic benzyl-isobutyrate {q.v.), sodio 
 benzoate, toluene, and an oil (C,,H,,0)„, (340°- 
 350°). The principal reaction is : 
 
 4Me2CH.C02.CIL,Ph + Na^ = 
 2Me2C(CH2Ph).00jC,H, + 2Me2CH.CO,Na + H^ 
 (W. E. Hodgkinson, C. J. 33, 496). 
 
 o-BENZYL-ISOBTTTYEIC ACID C„H,A i.e. 
 Me2C(CH2Ph)C02H. 
 
 Bemyl ether (0,H,)A'. (280°-285°). S.G. 
 1^ 1-0285. Prepared by the action of sodium on 
 benzyl-isobutyrate {q. v.). 
 
 Beactions. — 1. Heated with sodium a violent 
 action occurs, toluene, sodic benzoate, sodic 
 benzyl-isobutyrate and an oil, ChHjjO (350°- 
 355°) being formed. — 2. It is attacked by alkalis 
 with great difficulty, the saponification gives 
 isobutyrio not benzyl-isobutyrio acid (W. E. 
 Hodgkinson, C. J. 33, 503 ; A. 201, 171). 
 
 BENZYL CARBAMATE NH^.CO.O.CjH,. 
 [86°]. From benzyl alcohol and urea nitrate at 
 140° (Campisi a. Amato, B. 4, 412) or solid 
 cyanogen chloride (Cannizzaro, B. 3, 518). Large 
 plates (from water); si. sol. hot water, v. sol. 
 alcohol. Decomposes above 200° into benzyl 
 alcohol and cyanuric acid. 
 
 BENZYL-CABBAMIC ACID C,H,NH.CO.OH. 
 Benzyl-ammonium salt 
 C,H,NH.C0jNH30,H,. [99°]. From benzyl- 
 amine andCOj. Formed also by heating o-amido- 
 phenyl-acetic acid at 260° ; the yield being nearly 
 the theoretical (Tiemann a. Friedlander, B. 14, 
 1969). Plates, sol. water and alcohol, insol. 
 ether; volatile with steam. Decomposed by 
 acids or alkalis into CO^ and benzylamine. 
 
 BENZYL DI-CAEBOXY-GLUTACONIC ACID 
 
 V. Dl-OAKBOXY-QLUTACONIO ACID. 
 
 DIBENZYL-CABBOXYLIG ACID m Dl- 
 
 PHENYL-ETHANE-CAKBOXYLIO ACID. 
 
 DIBENZYL DI-CARBOXYLIC ACID v. Di- 
 
 PHENYL-SnCCINIC ACID and D1-PHENYI.-ETHANE 
 m-OABBOXYLIO ACID. 
 
 BENZYL CASBINOL v. Phenyl-eihyl al- 
 cohol. 
 
 BENZYL CHLORIDE C^,CH.e. OsHs.CH^CI. 
 Mol. w. 126-5. a-Chloro - toluene. (178°) at 
 754 mm. S.G. S 0-9453. S.V. 183-45 (Sohiff, 
 B. 19, 563; A. 220, 98); 133-13 piamsay). 
 
BENZYL-DI-ETHYL-AMINE. 
 
 493 
 
 Formation.— l.'Fiom benzyl alcohol and HOI 
 (Cannizzaro, A. 88, 129 ; 96, 246 ; Deville, A. 
 Ch. [3] 3, 178).— 2. By distilling toluene in a 
 current of chlorine (Lauth a. Grimaux, Bl. 
 1867, i. 105). 
 
 Preparation. — By passing chlorine (1 mol.) 
 into cold toluene (1 mol.) exposed to direct sun- 
 shine ; the yield is nearly theoretical (Schramm, 
 B. 18, 608). 
 
 Properties. — Oil, sol. alcohol and ether. 
 
 Reactions. — 1. Boiling alcoholic KOH forms 
 C,H,OEt.— 2. Alcohohc KOAc forms 0,H,OAo.— 
 3. Alcoholic KCN forms C,H,CN.— 4. Alcoholic 
 NHj forms, on heating, mono-, di-, and tri- 
 benzylamine. — 5. Hot dilute HNO3 (or a nitrate) 
 forms benzoic aldehyde. — 6. Boiling Pb(0H)2 
 forms benzyl alcohol. — 7. KOPh forms phenyl 
 benzyl oxide. — 8. Water at 180' gives a product 
 which, on distillation, yields benzyl-toluene and 
 anthracene. Before distillation the product is 
 perhaps CjH5.CH5,.CeH,.CH.,Cl (Van Dorp, B. 5, 
 1070; Zinoke, B. 7, 276').— 9. Long boiling 
 with water (30 vols.) produces benzyl alcohol. — 
 10. Sodium-amalgam produces a little s-di- 
 pheuyl-ethylene. — 11. Aromatic hydrocarbons in 
 presence of powdered zinc give ofi HCl and 
 form condensation products (Zincke, B. 6, 
 137). — 12. Ghloroformic ether and sodium 
 form di-phenyl-ethane exo-oarboxyUc ether, 
 PhCHj.CHPh.CO,Et (Wurtz, C. B. 70, 350).— 
 13. Heated with AljCl,, it gives off HCl, forming 
 toluene and anthracene (Perkin, jun. a. Hodg- 
 kinson, C. J. 37, 726). — 14. In carbon disulphide 
 solution yields, when chromyl chloride is added 
 gradually, a brown precipitate of composition 
 PhCHjCl, CrOjClj, slowly converted by moist 
 air into benzoic aldehyde ; 
 
 3Ph.CHC1.0.Cr(0H)CL + 3H,0 
 = 9HC1 + Cr A + CrOs + 3PhCH0. 
 
 The compound heated to 170° loses HCl, 
 forming a compound PhCHClCrOjCl, which also 
 yields benzoic aldehyde. 
 
 3PhCHC1.0.CrO.Cl + 3H2O 
 = GHOl -I- CrAs + CrOj + 3PhCH0 (Etard, A. Ch. 
 [5] 22, 235). — 15. HI reduces it to toluene.— 16. 
 Zinc dust gives toluene, phenyl-tolyl-methane, 
 and anthracene (Frost, Bl. [2] 46, 249). 
 
 BENZYL - CHIORO - MALONIC ACID v. 
 Chloko-benzyij-malonic acid. 
 
 BENZYL-CINCHOHINE v. CiNOHONnra. 
 
 a-BENZYL-CINNAMIC ACID CuH^O^ i.e. 
 C,H5.CH:C(CH:Ph).C0jH. [157°]. Formed 
 by the action of alkalis on the compound 
 Ph.S02.C(CH2Ph)2.C02Et (Michael a. Palmer, 
 Am. 7, 70). Large white needles, insol. water, 
 sol. alcohol. 
 
 p-BEHZYL - CEESOL CA.CHj.CeHaMe.OH. 
 (240°) at 40 mm. From benzyl chloride, 
 cvesol, and zinc (Mazzara, O. 8, 303 ; 11, 
 438; 12,264), 
 
 Reactions. — 1. Chloro - acetic acid and 
 KOHAq form CjHs.CHj.OsH^Me.O.CHj.COjH 
 [111°]. — 2. (a) - chloropropionic acid forms 
 0,H3.CH,.C<,H,Me.0CHMe.C0.,H. [115°].— 3. CO^ 
 and Na forms C,H,.CH,.C.H3(0H).00,Na. 
 
 Acetyl derivative CuHuAcO. (245°) at 
 40 mm. 
 
 BENZYL CBESYL OXIDE 
 CaH5.CH2.0.CsHj.CH„ V. Tolyl ether of Benzyl 
 
 ALCOHOL. 
 
 BENZYL CYANAMIDE O.HaNj i.e. 
 
 C.H5.CH,.NH.CN. [33°]. Formed by passing 
 CyCl into benzylamine in ether (Strakosoh, B. 
 5,694). Plates (from ether) ; insol. water, v. e. 
 sol. alcohol and ether. On keeping it chsnges 
 to isomeric tri -benzyl -melamine. Boiling HCl 
 forms benzyl-urea. 
 
 Di-benzyl-cyanamide (OsHsCHJjN.ON. [54°]. 
 From CyCl and dibenzylamine in alcohol (Lim- 
 pricht, A. 144, 317). Plates ; insol. water. 
 
 BENZYL CYANATE C„H,.CHj.N.CO. (175°- 
 200°). Formed, together with benzyl oyanurate, 
 by the action of silver oyanate on benzyl chloride 
 or bromide (Letts, O. J. 25, 446 ; Ladenburg a. 
 Struve, B. 10, 46). Pungent liquid. Changes 
 spontaneously into the cyauurate. Alcoholic 
 NH3 converts it into benzyl-urea. 
 
 BENZYL CYANIDE v. Phenyl-aoetonitkile. 
 
 BENZYL CYANTJHATE (C.HsCHJsN^CsO,. 
 [157°]. (above 320°). The chief product of the 
 action of silver cyanate on benzyl chloride (v. 
 supra) ; formed by isomeric change from benzyl 
 cyanate. Silky needles (from alcohol), insol. 
 water. Potash fusion gives KjCOj and benzyl- 
 amine. 
 
 BENZYL CYMENE C„H„„ i.e. 
 C„Hj.CH,,.C,H3MePr. [297°] (Mazzara, G. 8,508 ; 
 [308°] (Weber, /. 1878, 402). S.G. 1^ -97. 
 From benzyl chloride, cymene, and zinc. On 
 oxidation it gives benzoyl-terephthalio acid. 
 
 Benzyl-cymene disalphonic acid 
 C„H„(SO,H), (M.). 
 
 BKJSZYL-DTJEENE«.Benzyl-tetea-methyi,- 
 
 BENZENE. 
 
 BENZYLENE (O^Hj)^. Two hydrocarbons 
 of this composition are formed by the action of 
 the copper-zino couple upon benzyl bromide (or 
 chloride), (a)-benzylene, [42']; |iip -6091, is a 
 yellowish-red resin, si. sol. alcohol, v. sol. ether 
 and benzene. (;3)-benzylene is a brown resin, 
 insol. alcohol or ether (Gladstone a. Tribe, 0. J. 
 47, 448). 
 
 BENZYLENE- v. Benzylidene-. 
 
 BENZYLENE.DIAMINE v. Amido-benzyl- 
 
 AMINE. 
 
 BENZYLENE-IMINE C,H,N i.e. 
 CsHX I [1:2]. Formed by reduction of 
 
 \nh 
 
 o-nitro-benzyl-chloride with SnClj in cone. HCl. 
 Greyish yellow powder. Sol. chloroform and 
 acetic acid. Dissolves in HCl to a red fluores- 
 cent solution. The salts are amorphous. The 
 hydrochloride forms a reddish -yellow trans- 
 parent solid (B'HCl). The platinochloride 
 (B'jHjPtCy is an insoluble, amorphous, reddish- 
 brown powder (Lellmann a. Stickel, B. 19, 1611). 
 
 BENZYL ETHER C,,H„0 i.e. (C.H^.CHJ.O. 
 Di-bemyl ether, Di-benzyl oxide. (298° i. V.) 
 S. G. IS 1-036. ju 1-5525. Formed by heating 
 benzyl alcohol with BjO, at 120° (Cannizzaro, 
 A. 92, 115). Also by heating benzyl chloride 
 with water at 190° (Limpricht, A. 139, 313). 
 From benzyl chloride and sodium benzylate 
 (Lowe, 0. J. 61, 700). Decomposed by heat 
 into toluene and benzoic aldehyde. 
 
 BENZYL-DI-ETHYL-AMINE 0„H„N i.e. 
 C„H,.CH2NEtj. (212° cor.). From benzylamine 
 aiidEtl at 130° (Ladenburg a. Struve, B. 10,47, 
 561, 1152, 1634); or from di-ethyl-amine and 
 
494 
 
 BENZ YL-DI-ETII YL-A MINE. 
 
 benzyl chloride at 100° (V. Meyer, B. 10, 310, 
 964). 
 
 Ethylo-iodide OjHs.OHj.NBtjI. Large 
 crystals, v. sol. water. On diy-distillation it 
 gives triethylamine and benzyl iodide. — 
 OsH,.CHj.NEt3l3[87°]— (CsH5.CH2.NEt3Cl)jPtClj. 
 
 Si-benzyl-ethyl-amine CuHuN i.e. 
 {CsH5.CH2)2NEt. From di-benzyl-amine and 
 EtI p^impriobt, A. 144, 315).— B'HCl. 
 
 Ethylo-iodide (CaH5.CH2)2NEt2l. SI. sol. 
 cold water. 
 
 BENZYL-ETHTI-BENZEHE O.sH,, i.e. 
 C,H5.CHj.CsH,.Et [1:4]. Mol. w. 196. (295° 
 i.V.). S.G. iS -99. From benzyl chloride, ethyl- 
 benzene, and zinc (Walker, B. 5, 686) or from^- 
 ethyl-benzophenone, HI, and P (SoUsoher, B. 
 15, 1682). Oxidation gives ^-benzoyl-benzoic 
 acid. 
 
 BENZYL ETHYL OXIDE v. Benzyi. alcohol. 
 
 BENZYL ETHYL KETONE O^^.JO i.e. 
 OsH5.CH2.CO.CjH5. Mol. w. 148. (c. 226°). 
 S.G. 'IL* I'OO. From phenyl-aoetic chloride and 
 ZnEtj (Popoff, B. 5, 501). Does not combine 
 with NaHSOj. Oxidised by CrO, to benzoic and 
 propionic acids. 
 
 BENZYL - p - ETHYLFHENYL - CABBINOL 
 0^s.CH2.CH(OH).C8H,.C2H5 [1:4]. (350°). 
 Liquid. Formed by heating benzyl-ethylphenyl- 
 ketone with alcoholic KOH at 160°- Boiled with 
 dilute H2SO4 it gives phenyl-ethylphenyl-ethyl- 
 ene (SoUscher, B. 15, 1681). 
 
 BENZYL ETHYLFHENYL ^-KETONE 
 C5Hj.CH2.OO.CsH4.O2H5 [1:4]. Ethyl-desoxybm- 
 scyln. [64°]. Prepared by the action of Al^Clj on 
 a mixture of ethyl-benzene and phenyl-acetyl 
 chloride (Sollscher, B. 15, 1680). Boils uude- 
 compoaed. V.D. 8-03 (obs.). Small plates. 
 Sol. ether, benzene, and not alcohol, si. sol. cold 
 alcohol. On oxidation it gives terephthalic 
 acid. On reduction it gives phenyl-ethylphenyl- 
 ethane. 
 
 BENZYL - ETHYLPHENYL - METHANE v. 
 Phenyl-ethylphentl-ethane. 
 
 BENZYL-DI-ETHYL SULPHINE. Platino- 
 chloride (CsHjCHj.SEtjC^jPtCl,. From EtI 
 and di-benzyl sulphide, the product being treated 
 with AgOl and PtClj successively (SchoUer, B. 
 7, 1274). 
 
 DI-BENZYL-ETHYL-^jseJttfo-THIOTJEEA 
 C^HjoNjS i.e. C2H5S.C(NHj):NH. Formed by 
 heating di-benzyl-thiourea with ethyl iodide 
 at 300°. Oil. 
 
 Salts. — B'HI: [93°]; monoclinic prisms; 
 V. sol. alcohol, si. sol. water.— B'HjSO,: large 
 foursided rhombic soluble tables. — B'2HjPtOl5; 
 fine needles (Eeimarus, B. 19, 2349). 
 
 BENZYL-FLUOEENE Cj,H,5 i.e. 
 
 C5H5.CHj.C5H3<^-^>. [102°]. Formed by heat- 
 ing fluorene with benzyl chloride and zinc-dust 
 (Goldschmiedt, M. 2, 443). Plates (from alco- 
 hol). 
 
 BENZYL-FOBM-ALDEHYDE v. Phenyl- 
 
 ACETIC ALDEHYDE. 
 
 DI-BENZYL-GLYCOLLIC ACID Ci,B.,fi, i.e. 
 (03H50H2)2C(OH)COjH. Oxatolmc acid. a-Oxy- 
 di-phenyl-iso-butyrio acid. [157°]. 
 
 Formation. — 1. From the nitrile and cone. 
 HCl at 140°-160° (Spiegel, A. 219, 46 ; B. 18, 
 2219 ; 14, 1687).— 2. By boiling vulpic acid 
 (q.v.) with aqueous EOH : C,jH„0, + 3^0 
 
 = CH40 + 2CO, + 0,3H,aO, (Holler a. Streoker, 
 A. 113, 56). 
 
 Bhombio prisms (from alcohol): a:h:o = 
 •5113:1: -3058. Flufly mass of needles (from 
 benzene). Salt. — AgA'. 
 
 Reactions. — 1. HNO3 gives a viscid nitro- 
 aoid (MoUer a. Streoker).— 2. Cone, aqueous 
 KOH gives toluene and oxalic acid on boiling. — 
 3. Treated with PCI5 and HjO successively a 
 monophosphate, C,5H,503P0aHj, crystallising 
 in prisms, [160°] is formed. 
 
 Acetyl derivative. [106°]. Plates in 
 rosettes (from CHCI3 mixed with petroleum). 
 
 Methyl ether MeA.' : [71°]; needles. 
 
 Anhydride 0,5H,402._ [169°]. Got by 
 heating the acetyl derivative. Prisms (from 
 benzene). Y. sol. alcohol and ether. NajCO, Aq 
 converts it into sodium di-benzyl- glyoollate. 
 
 mtrile{Gjaifi'E,)fi(OS).CN. [11.3°]. From 
 di-benzyl ketone, KCN and HCl. Colourless 
 flat rhombs (from alcohol). At 113° it splits 
 up into HON and di-benzyl ketone. 
 
 Amide. [193°]. From the nitrile and cone. 
 HCl at 125°. Fluffy mass of long needles. 
 
 BENZYL - GLYOXALINE C3H3(C,H,)Nj. 
 [71°]. (310°). Formed by the action of benzyl 
 chloride on glyoxaUne (Wallach, B. 16, 539). 
 Colourless crystals. SI. sol. ether, insol. cold 
 water. — B'jHjOljPtClj : yeUow pp., insol. oold 
 water. 
 
 DI-BENZYL-GTJANIDINE O.sH.jNa i.e. 
 (C5H5.CH2NH)2C:NH. [100°]. Formed by boil- 
 ing benzylamine hydrochloride with benzyl- 
 cyanamide in alcohol (Strakosoh, B. 5, 695). — 
 Laminae (from alcohol). Sol. water, alcohol, 
 and ether.— B'HCl [176°]. 
 
 BENZYL-HyDBOXYLAMINE v. Hydboxyl- 
 
 AMINE. 
 
 BENZYLIDENE. The radicle C5H5.CH, also 
 called bemal or benzylene. The latter name 
 is more appropriate to the isomeric radicle 
 
 ' BENZYLIDENE-DI-ACETAUIDE 
 
 C„H,4N,02 i.e. CsH5CH(NH.C0.CH,)j. Formed 
 by boiling acetamide with benzoic aldehyde 
 (Both, A. 154, 72 ; Z. [2] 4, 650 ; 6, 680). 
 Silky crystals, si. sol. oold water and ether. 
 Not affected by boiling KOHAq but decomposed 
 by hot HCLA.q into benzoic aldehyde and NHjAc. 
 
 BENZYLIDENE DI-ACETATE CnHi^O, i.e. 
 CHPh(0Ac)2. Di-acetyl-benzoic ortho-aldehyde. 
 [45°]. From benzoic aldehyde and AojO or 
 from benzylidene chloride and AgOAc (Geuther, 
 A. 106, 251 ; Wicke, A. 102, 368 ; Hubner, Z. 
 1867, 277 ; Neuhof, A. 146, 323 ; Limpricht, 
 A. 139, 321 ; Perkin, Z. 1868, 172). 
 
 BENZYLIDENE-ACETIO ACID v. CnniAMic 
 
 AOID 
 
 Benzylidene-di-acetic acid v. Phenyl-olij- 
 
 TABIC ACID. 
 
 BENZYLIDENE -ACETO- ACETIC ACID v. 
 p. 24. 
 
 BENZYLIDENE-DI-ACETOACETIC-ETHES 
 
 C,.H„0.«.e.O,H..CH{CH.CH(00,Et).CO.OH.j,(?). 
 
 [153°]. Formed together with dehydro-benzyl- 
 idene - di - aoetoaoetic ether CuHj^Oj, by the 
 action of benzoic aldehyde (1 mol.) upon aceto- 
 acetic ether (2 mols.) in presence of a primary 
 amine. Long white needles. SI. sol. oold alco- 
 hol and ether (Hautzsch, B. 18, 2583), 
 
BENZYLIDENE-ANILINE. 
 
 405 
 
 Sehydro - benzylidene - di - acetoaoetic ■ ether 
 
 Ph 
 
 n w n „«==;w^ EtCOj— 0— CH— C— OOjEt. 
 OijHjjOs possibly ' .. 11 
 
 MeC— — CMe 
 [88°]. Formed as described above. Glistening 
 prisms. V. sol. cold or hot solvents (Hantzsoh, 
 B. 18, 2583). 
 
 SENZTLIBENE SI-AGETONAKINE v. p. 27. 
 BENZYLIDENE-ACETONE C,„H,„0 i.e. 
 Ph.CH:CH.C0.CH3. Aceto-cinnamone. Methyl- 
 styryl ketone. [42°] (152°) at 25 mm. (261° 
 i.V.) at 760 mm. 
 
 Formation. — 1. From benzoic aldehyde, 
 acetone and a little ZnClj at 260° (Glaisen a. 
 Clapar^de, B. 14, 2461).— 2. By heating a mix- 
 ture of calcium acetate with calcium oinnamate ; 
 also in small quantity by heating cinnamic alde- 
 hyde with Na and Mel at 130°, or by boiling 
 cinnamic aldehyde with MeOH and ZnCl^ 
 (Engler a. Leist, B. 6. 254). 
 
 Preparation. — From benzoic aldehyde (20 g.), 
 acetone (40 g.), water (1800 c.c.) and aqueous 
 (10 p.c.) NaOH (20 g.) in the cold. After four 
 days the oil that has separated is extracted with 
 ether, dried over CaClj and rectified in vaczio 
 (Claisen a. Ponder, A. 223, 188). 
 
 Properties. — Plates, apparently rectangular. 
 It has an odour of coumarin and rhubarb and 
 attacks the skin. Easily soluble in alcohol, 
 ether, benzene, and chloroform, less in petro- 
 leum-ether. In cone. HjSO, it forms an orange 
 solution. Forms a orystaUine compound with 
 NaHSO,, and a di-bromide 0,„H,„0Br2 [125°] 
 crystallising in needle^ from alcohol. 
 
 Phenyl hydrazide OmH,sNj : [156°]; 
 flat yellow needles ; sol. hot alcohol, si. sol. cold 
 alcohol and ether, insol. water (Fischer, B. 17, 
 576 ; Knorr, B. 20, 1099). 
 
 Oxim Ph.CH:CH.C(N0H).CH3. [116°]. 
 (220°) at 100 mm. Forms a bromide, [145°] ; 
 and an acetyl derivative [91°] (Zelinsky, B. 
 20, 922). 
 
 Si-benzylidine-acetone 
 PhCH:CH.CO.CH:CH.Ph. Cinnamone. Di- 
 siyryl ketone. [112°]. 
 
 Formati<m. — ^From benzoic aldehyde (20pts.), 
 acetone (6 pts.), and acetic acid (40 pts.), by 
 adding HjSO, (30 pts.) at 0° or passing in HCl. 
 
 Preparation. —From benzoic aldehyde (10 g.), 
 acetone (3 g.), water (100 g.) and dilute (10 per 
 cent.) NaOH (20 g.) left 4 days in the cold; or 
 from benzylidene-aoetone (7g.), benzoic aldehyde 
 (5 g.), water (200 g.), alcohol (150 g.) and dilute 
 NaOH (20 g.) (Claisen a. Ponder, .4. 223, 142; 
 cf. Claisen a. Olapar^de, B. 14, 850, 2460; 
 Schmidt, B. 14, 1459). 
 
 Properties. — Bright yellow monoclinio tablets 
 (from acetone or OHCy a:6:c = 4-886:l:l-378 
 j8 = 78° 43'. Eeadily soluble in chloroform or 
 acetone, less in ether or cold alcohol. Gives 
 an orange solution in HjSO^. 
 
 Tetrahromide C„HijOBr, : white needles 
 [208°-211°]. 
 
 BENZYLIDENE-DIACETONE-ALCAMINE 
 HjC— CH(OH)-CH, 
 
 C,3H„N0t.e. I I (?) 
 
 (CeHs)HC-NH - C(Ca,), 
 Ovy -phenyl - di-methyl-tetra-hydro- pyridine. 
 Thick colourless oil. Formed by reduction of 
 an acid solution of benzyUdene-di-acetonamine 
 
 (v. p. 27) with sodium-amalgam. — B'HCl : small 
 crystals, easily soluble in water and alcohol 
 (Fischer, B. 16, 2236). 
 
 BENZYLXDENE-DI-ACETONINE v. p. 34. 
 BENZYLIDENE - ACETOFHENONE 
 OjayCHiCH.CO.CsHs. Phenyl styryl ketone. 
 Phenyl cinnamenyl ketone. Benzylidene methyl 
 phenyl ketone. Benzal-acetophenone. [58°]. 
 (345°-348°). Formed by passing HCl gas into 
 a mixture of acetophenone and benzaldehyde ; 
 by adding H^SOj to the two latter bodies di- 
 luted with acetic acid ; by heating them with 
 acetic anhydride to 170° ; or by treating them 
 with dilute NaOH (Claisen a. ClaparAde, B. 14, 
 2463 ; Claisen a. Ponder, A. 223, 148). 
 
 Preparation. — 12 pts. of acetophenone are 
 mixed with 10°5 pts. of benzaldehyde and 8 pts. 
 of a 20 p.c. sodium methylate solution, and 
 allowed to remain in the cold for a few days 
 when the whole will have solidified to a crystal- 
 line mass ; the yield is 90 p.c. of the theoretical 
 (Claisen, B. 20, 657). Large trimetrio tables. 
 V. sol. chloroform, ether, benzene and CS^, m. 
 sol. alcohol, si. sol. petroleum ether. On oxida- 
 tion it gives benzoyl-formie and benzoic acids. 
 On boiling with dilute acids it is decomposed 
 into acetophenone and benzaldehyde. By re- 
 duction with HI and P it is converted into di- 
 benzyl-methaue. The HCl addition product 
 CBH5.CO.CHCI.CH2.C8H5. [120°] forms colourless 
 trimetric plates, sparingly soluble in cold alco- 
 hol and ether. It is prepared by the addition of 
 gaseous HCl to the ketone. The di-bromide 
 CsH5.CO.CHBr.CHBr.CsH5 [157°] forms short 
 colourless prisms sol. hot alcohol. Prepared 
 by the addition of bromine to the ketone. 
 
 BENZYLIDENE - $ - ACETYL - PEOPIONIC 
 ACID CijH.jOs i.e.CHPh:CH2.CO.Cnj.CH2.COaH. 
 BenzyKdene-lcevulic acid. Ginnamoyl-propionic 
 acid. [120°-125°]. Formed by heating Isevulic 
 acid with benzoic aldehyde and sodium acetate. 
 Small white crystals. The lead salt is insoluble. 
 Dissolves in cold cone. HjSOj with a red colour- 
 ation. Boiling cone. KOH splits off benzalde- 
 hyde. Eeduction in alkaline solution yields 
 benzyl-valero-lactone Ci^HijOj which forms large 
 prisms of melting-point [85°] (Erdmann, B. 18, 
 3441). 
 
 BENZYLIDENE-ISOAUYL-AMINE. An oil 
 formed from benzoic aldehyde and isoamyl- 
 amine (Schiff, A. 140, 93). 
 
 BENZYLIDENE DI-ISOAMYL DI- OXIDE 
 CsH5CH(0C5H„)j. (292° cor.). From benzyl- 
 idene chloride and NaOOsH,, (Wicke, A. 102, 
 363). 
 
 BENZYLIDENE - ANILINE C,3H„N i.e. 
 CjHj.CHrNPh. Anilide of benzoic aldehyde. 
 [49°] (Tiemann a. Piest, B. 15, 2028). 
 
 Formation. — 1. By warming aniline with 
 benzoic aldehyde (Laurent a. Gerhardt, Gompt. 
 chim. 1850, 117).— 2. By heating di-phenyl- 
 thio-urea with benzoic aldehyde (Schiff, A, 148, 
 836). 
 
 Properties. — LaminsB ; volatile with steam, 
 insol. water, v. e. sol. alcohol and ether. At 
 200° it changes to an isomeride which differs 
 from it in forming a salt B'jHjPtClj. 
 
 Hydrocyanide C^Hi^j. [82°]. Formed 
 by passing HCN into fused benzyUdene-aniline, 
 or by the action of KCN on a mixture of benzoic 
 aldehyde and aniline hydrochloride dissolved 
 
496 
 
 BENZ YLIDEN E-ANILINE. 
 
 in alcohol (Oeoh, B. 11, 246). It forms con- 
 oentrio needles, insol. alkalis and dilute aoids. 
 BENZ yLIDENE-DI-ANTIPYRINE v. Di-OXY- 
 
 lETBA-METHYL-DI-QUINIZYL-PHENYL-METHANE. 
 
 DI - BENZYLIDENE - BENZIDINE O^sHjoNj 
 i.e. C,jHe(N:CHPh)2. [232^ (0.) ; [239°] (B.). 
 Obtained by heating hydrazo-benzene or ben- 
 zene-azo-benzene with benzoic aldehyde and 
 ZnClj (Cl^ve, Bl. [2] 45, 188 ; Barzilovsky, J. B. 
 1885, 366). Yellow scales (from benzene and 
 chloroform). Eesolved by HCl into benzoic 
 aldehyde and benzidine. 
 
 BENZYLIDENE-DI-BENZAMIDE 
 C,,H„N202 i.e. C,H3.CH(NH.C0.C„HJj. [197°]. 
 Formed by heating benzoic aldehyde with benz- 
 amide (Both, A. 154, 76). Long silky needles 
 (from alcohol), insol. water. Eesolved by hot 
 HClAq into the parent substances. 
 
 BENZYLIDENE DI-BENZOATE 
 C,H5.CH(0Bz)2. From benzylidene chloride 
 and AgOBz (Bngelhardt, J. 1857, 471). Crys- 
 talline. 
 
 BENZYLIDENE-BENZYL-AMINE 
 C,H5.CH:N.CH2.C8H5. (c. 300°). Formed by the 
 action of PCI3 upon di-benzyl-hydroxylamine, 
 probably by intermediate formation of the chlo- 
 ride (CjH5.CH2),N.Cl. Oil. V. sol. alcohol and 
 ether, insol. water. 
 
 Salts.— B'HCl: [251°]; long plates or 
 tables ; v. sol. alcohol, sparingly in cold water, 
 more readily in hot. — B'jHjPtCl^" : small 
 golden-yellow crystals (Walder, B. 19, 1632). 
 
 BENZYIIDEHE BEOMIDE C.H.Br, i.e. 
 CjHj.CHBrj. Bemal bromide. a-Di-brmno- 
 toluene. (130°-140°) at 20 mm. From benzoic 
 aldehyde and PBrj. Can only be distilled in 
 vacuo. Sodium at 180' forms toluene and di- 
 benzyl (Michaelson a. Lippmann, Bl. [2] 4, 
 251). 
 
 BENZ ILIBENE-BKOMIDE BENZOATE 
 
 C,.H„BrO, i.e. CA.CH<q^^_(,^jj^. [70°]. 
 
 Colourless tables or prisms. Sol. alcohol, ether, 
 and acetic acid. Prepared by mixing benzalde- 
 hyde and benzoyl bromide. On distillation it 
 again decomposes into these bodies (Claisen, B. 
 14, 2475 ; cf. Liebig a. Wohler, A. 3, 266). 
 
 BENZYLIDENE-DI-BUTYKAMIDE 
 C,,H2,N,0, i.e. C,H5.CH(NH.CO.C3H,)2. Slender 
 crystals formed by heating butyramide with 
 benzoic aldehyde (Strecker, A. 154, 76). 
 
 BEN2YLIDENE-SI-CABBAMIG ACID 
 C,H5CH(NH.C02H)j. 
 
 Ethyl ether 'E%A"- [171°]. From carba- 
 mic ether, benzoic aldehyde, and HCl (Bischoff, 
 B. 7, 634). Crystals; maybe sublimed. 
 
 Propyl ether Pr^A". [143°] (Bischoff, B. 7, 
 1082). 
 
 BENZYLIDENE CHLOBAL-AMMONIA 
 C,,H,ClsNO i.e. CCl3.CH(OH)N:CH.C„H5. [130°]. 
 White leaflets. Decomposed by dilute acids 
 and by boiling water. Prepared by the action 
 of benzoic aldehyde on chloral-ammonia (Schiff , 
 B. 11, 2166). 
 
 BENZYLIDENE CHLOKIDE CjH.Clj i.e. 
 C^Hj.CHClj. Benzal chloride. Chlorobenzol. 
 Benzylene chloride. Mol. w. 161. (204°) at 
 756 mm. S.G. | 1-27. S.V. 154-25 (Sohifi, B. 
 19, 563). ^ 
 
 Formation.— 1. From benzoic aldehyde and 
 PCI, (Cahours, A. 70, 39 ; Suppl. 2, 253, 306). 
 
 2. By passing chlorine into boiling toluene 
 (Beilsteia, A. 116, 336; 146, 322; Lauth a. 
 Grimaux, Bl. 2, 347).— 3. From benzoic alde- 
 hyde and Buooinyl chloride (Bembold, A. 138, 
 189) or COCI2 (Kerapf, Z. 1871, 79). 
 
 Preparation. — 1. By passing 2 mols. 01 
 chlorine into cold toluene (1 mol.) exposed to 
 direct sunshine (Schramm, B. 18, 608).— 2. By 
 heating toluene (7 pts.) with PCI5 (30 pts.) at 
 190°; the yield being nearly that calculated 
 (Oolson a. Gantier, Bl. [2] 45, 87). 
 
 Properties. — Oil, with faint odour. 
 
 Beactions. — 1. Converted into benzoic alde- 
 hyde by water or aqueous K^COj at 130°, or by 
 warming with H2SO4 at 50° and treating the 
 product with water (Oppenheim, B. 2, 213). — 
 2. Alcoholic KHS forms benzyl disulphide and 
 di-thio-benzoio acid. — 3. Bed-hot soda lime 
 forms benzene (Limpricht, Bl. 1866, ii. 467).— 
 
 4. Chlorine forms ^-ohloro-benzylidene chloride. 
 
 5. Nitric acid forms ^-nitro-benzylidene chlo- 
 ride (Hiibner a. Bente, B. 6, 803 ; cf. Beilstein, 
 A. 146, 333).— 6. AgOAo forms CsHs.CHIOAo)^. 
 7. Silver oxalate forms benzoic aldehyde (Go- 
 lowkinsky, A. Ill, 252). — 8. Na forma di-phenyl- 
 ethylene. — 9. Mel and Na form oumene. — 
 10. NHj forms hydrobenzamide. — 11. ZnEij 
 diluted with benzene forms C„H,8 di-ethyl- 
 phenyl-methane and CjjHj, (Dafert, M. 4, 618). 
 12. Copper at 100° gives CPhCl^-CPhClj and 
 OPhHCLCPhHCl (Onufrowicz, B. 17, 833). 
 
 BENZYLIDENE ■ DI ■ GHLOBO ■ CHBOUIC 
 ACID V. Toluene. 
 
 DI-BENZYLIOENE- ETHYLENE ■ DIAKINE 
 C„H,5Nj i.e. CjH4(N:CH.C,H5)2. [54°]. Formed 
 by heating ethylene-diamine (1 mol.) with ben- 
 zoic aldehyde (2 mols.) to 120°. Large colour- 
 less tables. Y. sol. alcohol and benzene, insol. 
 water. Decomposed into its constituents by 
 acids (Mason, B. 20, 270). 
 
 BENZYLIDENE-EIHYLENE-DI-STJLFHIDE 
 
 .S.CH, 
 
 OeHj.CHC^ I . [29°]. Formed by passing 
 
 \S.CH, 
 
 HCl gas into a mixture of equal mols. of benz- 
 
 aldehyde and ethylene sulphydrate. Crystals. 
 
 Easily soluble in alcohol, ether, and benzene, 
 
 insoluble in water. Very stable body. By the 
 
 action of bromine upon the chloroform solution 
 
 a 
 
 di-ethylene-tetra-sulphide C2Hj<^g^^CjH, is 
 
 formed (Fasbender, B. 20, 460). 
 
 BENZYLIDENE-DI-ETHYL-DI-OXIDE 
 
 C,iH,.CH(0Et)2. (222° cor.) Diethyl derivative oj 
 benzoic ortho-aldehyde. From benzylidene chlo- 
 ride and NaOEt (Wicke, A. 102, 363). 
 
 BENZYLIDENE -DI-HEPTYLENE -TErRA- 
 
 TJKEA C.H^jNsO, i.e. 
 
 CH,.CH(NH.C0.NH.C;H„.NH.C0.NH2)j. 
 From' benzoic aldehyde and heptylene-diurea 
 (Schiff, A. 151, 195). Insoluble powder. 
 
 BENZYLIDENE-MALONIC ACID 
 
 Ph.CH:C(C0,H)2 [196°] (C.) ; [193°] (S.). 
 
 Formation. — 1. From the ether by aqueous 
 baryta. — 2. From benzoic aldehyde, malonic acid 
 and Ac,0 at 100° (Claisen a. Crismer, A. 218, 
 135). — 3. From benzoic aldehyde, sodic malon- 
 ate, and glacial acetic acid at the ordinary tem- 
 perature : Ph.CHO + CH .(COjNa), = 
 PhCH:C(CO;Na), + SJi. 
 The product is diluted with water, shaken out 
 
BENZYLIDENE-PHTIIAIJDE. 
 
 4G7 
 
 with ether, acidified, shaken again with ether 
 and the ether distilled oil (Stuart, G. J'.43,405 ; 
 V. alsoClaisen, A. 218, 129). 
 
 Properties. — Colourless glassy prisms. SI. 
 Bol. cold water, v. e. sol. hot water, v. sol. alcohol, 
 acetic ether or acetone, m. sol. ether or glacial 
 acetic acid. Insol. benzene, chloroform or 
 petroleum. Does not give in neutral solutions 
 a pp. with BaClj ; but on warming such a mix- 
 ture needles of the salt BaA" separate (charac- 
 teristic reaction). 
 
 Salt.— Ag^A". 
 
 BeaoUons. — 1. At 200° it splits up into CO^ 
 and cinnamio acid. — 2. Boiling water decom- 
 poses it into benzoic aldehyde and malonic acid, 
 some CO2 and cinnamio acid being also formed. 
 3. Eedueed by sodium amalgam to benzyl 
 malonic acid Ph.CH2.CH(C0.^H).,.— 4. Bromine 
 acts on its solution in chloroform forming 
 PhCHBr.CBr(C0.^H)2 [96°] whence water forms 
 a-bromo-cinnamio acid (Stuart, 0. J. 49, 360). — 
 5. Cold alcoholic potash forms crystals of 
 Ph.CH(0Et)0H(C0.,K)2, whence a silver salt, 
 PhCH(0Et)CH(C0jAg)2 may be got. The free 
 acid, if heated rapidly, melts at 120°-130°, split- 
 ting up into EtOH and benzylideue-malonio acid, 
 which then solidifies again, and melts a second 
 time at 190°. By crystallisation from water the 
 acid is partly split up into alcohol and benzyl- 
 idene-malonic acid. — 6. HBr forms /3-bromo- 
 phenyl - isosuccinic acid Ph.CHBr.CH(C02H)2, 
 which is decomposed by water into HBr, cin- 
 namio acid and COj (Stuart, C. J. 49, 360). 
 
 Ethyl ether Et^A". [82°]. (192°) at 17mm. 
 S.G. IS 1-111. Formed by passing HCl into a 
 mixture of malonic ether and benzoic aldehyde 
 or by treating the mixture with Ao^O at 160° 
 (Olaisen, B. 14, 348). Large transparent crys- 
 tals (Stuart, C.J. 49, 360). Boils at 308°-312° 
 with decomposition. 
 
 BENZYLIDEHE-MESITYI-OXIDE C,3H„0 
 i.e. (CH3)2C:CH.CO.CH:CH.CsH5. (179°) at 14 
 ram. Oil. PreparedbypassingHOlgasintoamix- 
 ture of mesityl oxide and benzaldehyde (Claisen, 
 B. 14, 351). Forms a tetrabromide [118°]. 
 
 BENZYLIDENE-METHYL-KETOLE C^.'ELJ!^ 
 [248°]. Colourless plates. Formed by reduction 
 of dimethyl-rosindole C^jHjjNj with zinc-dust 
 and NHj. It is oxidised in acetic acid solution 
 by PejCij back to di-methyl-rosindole (Fischer 
 a. Wagner, B. 20, 816). 
 
 BENZYLIDENE-DI-METHYI-DI-OXIDE 
 C|iH5CH(OMe)2. Di-methyl derivative of bemoic 
 orthoaldehyde. (208° cor.). From benzyhdene 
 chloride and NaOMe (Wicke, A. 102, 363). 
 
 BENZYLIDENE -DI - METHYL-p-PHENYL- 
 ENE-DIAMINE C8H5.CH:N.C5H4.NMe2. Benzyl- 
 idene - amido - di - methyl - aniline. Methyl- 
 phenylene-diamide of benzoic aldehyde [98°]. 
 Glistening plates or needles. Sol. hot alcohol 
 and benzene, si. sol. cold alcohol. Weak base. 
 Formed by mixing benzoic aldehyde and M-di- 
 methyl-^-phenylene-diamine, either directly or 
 in alcoholic solution. By HCl it is split up into 
 its generators. — B'SjClj : white solid (Calm, B. 
 17, 2940). 
 
 BENZYLIDENE - (Py. 3)-METHYL.(nJIN0L- 
 INE C„H,3N i.e. 
 ,CH:CH 
 
 \N : 0—1 
 Vol. I, 
 
 -CH = CH.0jH5(?). [100°]. formed 
 
 by heating quinaldine (methyl-quinoline) with 
 benzoic aldehyde or benzyhdene chloride and 
 ZuClj (Jaoobsen a. Reimer, B. 16, 2606). Glis- 
 tening colourless needles. Sublimable. Sol. hot 
 alcohol, insol. water. — B'HjOrjO, 2 Jaq : very 
 sparingly soluble reddish-yellow needles. 
 
 EENZKIIDENE - (/3) - NAPHTHYLAMINE 
 C,H5.CH:N.C,„H,. [108°]. From benzoic aldehyde 
 and ^Bj-naphthylamine (Claisen, A. 287, 261). 
 
 BENZYHDENE - (a) - NAPHTHYLAMINE-^- 
 SriPHONIC ACID C,„H„(N:CH.CsH5).S03H[l:41. 
 The sodium salt (A'Na) is obtained by shaking 
 a strong solution of sodium-(a)-naphthylamiue- 
 sulphonate with benzaldehyde. By long boiling 
 with water it is split up into its constituents 
 (Cahn a. Lange, B. 20, 2001). 
 
 BENZYLIDENE-DI-(/3)-NAPHTHYL-0XIDE 
 
 C„H.. 
 
 'C,„H„- 
 
 .CH<^q'»jt=^0. Anhydride of di-oxy-di- 
 
 naphthyl-phenyl-meihane, [190°]. Crystalline 
 solid. Insoluble in aqueous alkalis. 
 
 Formation. — 1. By heating a solution of 
 (3)-naphtholand benzoic aldehyde in acetic acid 
 to 200°, or with addition of H^SOj or HCl oa 
 the water-bath (Trzcinski, B. 17, 499).— 2. By 
 warming benzylidene di - naphthyl di - oxide 
 C5H5.CH{0.C,„H,)„ with acetic acid and a few 
 drops of HCl. In these reactions di-oxy-di- 
 naphthyl-phenyl-methane CjH5.CH(C„H5.0H)2 
 must first be formed and at once split oli HjO 
 (Claisen, B. 19, 3317). 
 
 Benzylidene-di-(i3)-naphthyl-di-ozide 
 C^HjjOj i.e. CsH5.CH(OC,„H,)2. Di-naphthyl 
 ortho - benzaldehyde. [205°]. From benzoic 
 aldehyde (5-3 pts.), (y3)-naphthol (7-2 pts.), 
 glacial HOAo (30 pts.), and fuming HCl (2 pts.) 
 at 0° (Claisen, A. 237, 269). Tables, si. sol- 
 CHCI3 and CSj, v. si. sol. alcohol and ether, 
 insol. alkalis. Cone. H^SO^ gives, on gentle 
 warming, a deep-red solution. HOAo and some? 
 HCl slowly convert it at 100° into benzylidene- 
 di-naphthyl oxide, a change which also occurs' 
 when it is heated at 210°. 
 
 BENZYLIDENE OXAMIDE OsHsNA' 
 Formed by warming oxamic ether with benzoic! 
 aldehyde (Medicus, A. 157, 50). Laminse. 
 
 BENZYLIDENE - PHENYL - DIAMINE », 
 Phenyl-benzamldine. 
 
 DI-BENZYLlDENE-^-PHENYLENE DI- 
 AMINE C^oH.sNj i.e. C,Hj(N:CHPh)2. [140°]. 
 From j)-phenylene-diamine and benzoic alde- 
 hyde at 120° (Ladenburg, B. 11, 590). Plates 
 (from alcohol). Eesolved by hot HOlAq into 
 the parent substances. 
 
 BENZYLIDENE-PHTHAL-ETHYL-IMIDINE 
 
 C„H,30Ni.e. CeH^<^( = ^^^«^'*)>NEt. Ethyl- 
 
 phthalimyl-henzyl. [c. 77°]. Formed by boiling 
 the ethyl-amide of deoxybenzoiu-o-carboxylic 
 acid C5Hj(CO.NHEt)CO.CH2.C5H5 with acetic 
 acid. Plates. V. sol. alcohol, benzene, benzoline, 
 and CS2 (Gabriel, B. 18, 2433). 
 
 BENZYLIDENE-PHTHALIDE CisH^Oj i.e. 
 
 C,Hj<;^=(^Q^^)>0. [99°]. Benzylidene. 
 
 phthalyl. Anhydride of deoxybenzo'in carboxylic 
 acid. 
 
 Fommtio7i.—l. By heating phthalic anhy- 
 dride (5 pts.) with phenyl-aoetic acid (5 pts.) and 
 NaOAc (1 pt.) (Gabriel a. Michael, B. 11, 1018). 
 
498 
 
 BENZYLIDENE-PHTHALIDE. 
 
 S. By heating phthalyl-phenyl-aoetia acid in 
 vacuo (Gabriel, B. 17, 2526). 
 
 PreparaUon. — A mixture of 100 g. phenyl- 
 ■aeetio acid, 110 g. phthalio anhydride and 2| g. 
 dry sodium acetate is heated for 2 hours, and the 
 product crystallised from alcohol ; the yield is 
 75-78 P.O. (Gabriel, B. 18, 3470). 
 
 Properties. — Long prisms (from alcohol) ; 
 insol. water, si. sol. cold alcohol. 
 
 Reactions. — 1. Hot aqueous KOH forms 
 potassium deoxybenzoin carboxylate. — 2. By 
 beating with alcoholic NHj at 100° it is con- 
 verted into deoxybenzoin carboxylamide 
 
 CjH4<^„q'j,j/ " ", which by solution in HiSO, 
 
 or by boiling with glacial acetic acid loses HjO 
 giving benzylidene-phthalimidine (phthalimidyl- 
 
 benzyl) C,H.<'^(='^^'^«^=)>NH. — 3. Simi- 
 larly ethyl-amine yields the ethyl-amide of de- 
 oxybeuzom-carboxyUe acid, and this on boiling 
 with acetic acid gives benzylidene-phthal-ethyl- 
 
 imidine CsH,^^^ = ^^<^«^*)>NEt (Gabriel, B. 
 
 18, 2433). — 4. By dissolving in benzene and 
 treatment with nitrous acid gas it yields 
 thecompoundC.H<C(NO,).(OH(NO,).C,HJs,0 
 
 <Gabriel, B. 18, 1251). 
 
 References. — V. Cyano- and Nitbo-benzyi.- 
 
 IDENE-PHTHALIDE. 
 
 Benzylideue-phtha1ide-di-bromide 
 
 C,H,<<^^'^(-^^^'-<^«^=)>0. [146"]. Formed 
 
 by the combination of benzylidene-phthalide with 
 bromine (Gabriel, B. 17, 2527). Thick glisten- 
 ing prisms. Sparingly soluble in alcohol. 
 
 {Iso) - Benzylidene - phthalide 0,5H,„02 i.e. 
 
 CjHjf 
 
 vCHiC.CgHg 
 
 [91°]. Formed by reduction 
 
 *\oo.o 
 
 •of nitro-benzylidene-phthalide 
 
 <C„H,<<'( = '^(^0^)-'^A)n^q^jjj^ jjj ^j^3p_ Pj.^ 
 
 pared by reduction of nitro-benzylidene- 
 phthalide ; yield, 47 p.o. of the phenyl-acetic 
 acid employed to prepare the benzylidene- 
 phthalide (Gabriel, B. 18, 3471). Flat colourless 
 needles. Easily soluble in alcohol and benzene, 
 sparingly in ligro'in. By further reduction with 
 HI and P at 200° it yields s-di-phenyl-ethane 
 o-carboxylio acid CsH5.CH2.CH2.CjHj.OO2H. 
 By boiling with aqueous NaOH it is converted 
 into deoxybenzoin - - carboxylio acid 
 C,H4(COjH).CH2CO.CsH5. Heated with alcoholic 
 NHj it gives isobenzyUdene phthalimidine 
 
 C.H,< 
 
 /' 
 
 CHiCCH, 
 
 (Gabriel, B. 18, 2445). 
 
 Phihal- 
 
 \00.NH 
 BENZYLIDENE-PHTHAI-IMIDINE 
 X C ^CH.05H5 
 .C.,H„ONi.e.O,H/^^\j^jj 
 
 'imidyl-hensyl. [183°]. Yellow plates. Formed 
 :from the amide of deoxybenzoin-o-oarboxylio 
 -acid C„H4(CO.NH2).CO.CH2.C„H, by solution in 
 ,H,S04 or by boiling with acetic acid (Gabriel, 
 :B. 18, 2433). V. also Bromo- and Nitko-benzyl- 
 
 StDENE-PHTHALIMIDINB. 
 
 Isobenzylidene-phthalimidineij. (Py. 4)-0xy- 
 
 (Py. 2)-rHENYL-ISO(3niNnLINB. 
 
 BENZYLIDENE-DI PIPEEIDINE 
 
 C8H5.CH(C5H,„N)2. [81°]. Formed by heating 
 piperidine with benzoic aldehyde. Colourless 
 prisms. Very unstable, being decomposed even by 
 boiling with water. Dilute acids resolve it into 
 benzoic aldehyde audpiperidine(Laun, B. 17, 678). 
 
 BENZYLIDENE-KHODANIC ACID 
 C,„H,NS20 i.e. C,Hj.CH:C(SH).CO.S.CN. [200°]. 
 Formed by the action of benzoic aldehyde upon 
 rhodanic acid in presence of dehydrating agents 
 (Nencki, B. 17, 2278). Yellow needles, sol. 
 water. By heating with baryta-water it is 
 split up into a-sulphydro-oinnamio acid 
 CjH5.CH:C(SH).C02H and hydrogen sulpho- 
 cyanide. Heated at 410° with cone. HjSO^ 
 (4pts.) it is converted into benzylidene-rhodanic- 
 oxy-sulphonic acid CuHyNSgOs (Ginsburg a. 
 Bondzynski, B. 19, 119). 
 
 BENZYLIDENE-RHODANIC-OXY-SUIPHO- 
 NIC ACID C,„H,NS205. Formed by heating 
 benzylidene-rhodanic acid with cone. HjSO^ (4 
 pts.) at 110°. Needles. V. sol. water and 
 alcohol. Very strong acid (Ginsburg a. Bond ■ 
 zynski, B. 19, 119). 
 
 BENZYLIDENE - EOSANILINE C2,H,3N3. 
 From rosaniline and benzoic aldehyde by heat 
 or by shaking with SOjAq (Schiff, A. 140,^111 j 
 Z. 1867, 176).— B'2H2PtCls. 
 
 BENZYLIDENE SELENIDE CeHjCHSe. 
 Seleno-bemoic aldehyde. [70°]. From benzyl- 
 idene chloride and alcohol KjSe (Cole, B. 8, 
 1165). Yellow needles (from alcohol), insol. 
 water. Not attacked by NHj. 
 
 BENZYLIDENE-DI-SKATOLE C25H22N2 i.e. 
 PhCH(C„HjN)2. [142°]. From skatole (2| pts.), 
 benzoic aldehyde (1 pt.) and a little ZnClj 
 (Wenzing, A. 239, 241). Insol. water; v. sol. 
 hot alcohol and ether. Boiling HCl does not 
 split ofi benzoic aldehyde. 
 
 BENZYLIDENE SULPHIDE v. Thio-benzoio 
 
 ALDEHYDE. 
 
 BENZYLIDENE THIO-BIITIIET Ci,H,N3S2 i.e. 
 C«H,.CH<N;C(SH)s^jjjj(jj ^23^o^_ ^^^^^^ 
 
 by heating benzoic aldehyde with ammonium 
 sulphocyanide at 137°-165° (Brodsky, M. 8, 27). 
 Minute prisms (from alcohol) ; insol. water, si. 
 sol. cold alcohol; sol. dilute KOH. Boiling 
 baryta-water forms benzoic aldehyde, barium 
 sulphocyanide, and di-phenyl-thio-urea. 
 
 Acetyl derivative CjHjAcjNsSj. [189°]. 
 
 BENZYLIDENE o-TOLUIDINE C^H^N i.e. 
 OeH,.CH:N.OjH,.CHs [1:2]. Benzaldehyde o- 
 toluide (314°). From o-toluidine and benzoi6 
 aldehyde (Etard, O. B. 95, 730). Eesolved by 
 boiling water into its generators. By passing 
 through a tube heated to dull redness it is con- 
 verted into phenyl-indole G8Hj<[]-|jS^0.0jH, 
 
 (Piotet, B. 19, 1063). 
 
 Benzylidene-2>-toliiidiue 
 CbHs.CHiN.CsH^.CHj [1:4]. From benzoic alde- 
 hyde and^J-toluidine at 100° (SchifE, A. 140, 96; 
 Eohler, A. 241, 359; Mazzara, O. 10, 370). 
 Melts below 100°, but changes at 160° into an 
 isomeride [120°-125°].— B'2H2PtCl3. 
 
 DI-BENZYLIDENE-TOLYLENE-DIAMINE 
 C2,H,3N2 i.e. 05H3Me(N:CHPh)2 [1:2:4] [122°- 
 128°]. From benzoic aldehyde and tolylene- 
 diamine at 100° (Schiff, A. 140, 98). Neutral 
 
BENZYL-METHYL- ACETO-ACETIO A CID. 
 
 499 
 
 crystalline mass ; at IIO^-ISO" it gives ama- 
 rine. 
 
 BENZTLIDENE-DI-UEEA C^H.jN.O., i.e. 
 CsH5.0H(NH.CO.NH2)2. Bemaldehyde di-ureUe 
 [195°]. Formed by adding benzoic aldehyde to 
 an alcoholic solution of urea (Sohiff, A. 151, 192). 
 Crystalline powder, insol. water and ether, sol. 
 alcohol. 
 
 Di-benzylidene-tri-urea C^jS^^TiJJO,. Powder, 
 formed by heating urea with benzoic aldehyde. 
 
 Tri-benzylidene-tetra-urea C25H28N8O4. 
 [0. 240°] . Powder, formed by heating benzyl- 
 idene-di-urea with benzoic aldehyde. 
 
 BENZYLIDENE-DI-UBETHANE v. Bbnztl- 
 
 IDENE-DI-OAKBAMIO ACID. 
 
 BENZYl-INDOLE 0,sH,5N i.e. 
 
 0^,<jjp^^OH. [44-5°]. Prom its oar- 
 
 boxylio acid (j. v.) by heat. Yellowish needles 
 (from alcohol). V. sol. benzene, light petroleum, 
 chloroform and ether. Turns pine wood mois- 
 tened with HCl yellow. Picrate forms red needles. 
 BENZYL-INDOLE CARBOXYLIG ACID 
 
 C,,H„NO, i.e. C,H4<j^^^ >0.C0;^. [195°, 
 
 with decomposition]. Pyruvic acid combines 
 at 16° with benzyl-phenyl-hydrazine, forming 
 •'CH3.C(C02H):N.NPhC,H, whence HOI at 100° 
 forms benzyl-indol-carboxylio acid (Antrick, A. 
 227, 362). 
 
 Properties. — Colourless needles (from glacial 
 acetic acid). SI. sol. water, chloroform, and 
 petroleum, sol. ether and alcohol, v. si. sol. 
 benzene. Converted by heat into CO^ and 
 benzyl indole. 
 
 BENZYL IODIDE C,H,I i.e. C„Hi.CH,I. 
 [24°]. S.a. 2= 1-73. 
 
 Formation. — 1. From benzyl alcohol in CSj 
 and iodide of phosphorus. — 2. Slowly formed 
 by the action of cold HI (S.G. 1'96) on benzyl 
 chloride (Lieben, Z. [2] 6, 736).— 3. From 
 benzyl chloride and KI (V. Meyer, B. 10, 
 311 ; Kumpf, A. 224, 126), Znlj, or Pbl^ (Brix, 
 A. 225, 154). 
 
 Properties.— Crystals : decomposed by dis- 
 tillation. Gives benzyl acetate with AgOAo, 
 and tribenzylamine with alcoholic NH3. Silver 
 nitrite gives benzoic aldehyde and acid (Van 
 Benesse, B. 9, 1454 ; Brunner, B. 9, 1744). 
 
 BENZYL. (psei((io)-ISATIN C,5H„N0j i.e. 
 
 C,H,<[j^Q^>CO. [131°]. From benzyl-indole 
 
 carboxylic acid and NaOCl in feebly alkaline 
 solution, the insoluble chloride then produced 
 being subsequently boiled with alcohoUo NaOH 
 (Antrick, A. 227, 365). 
 
 Properties. — Slender needles (from alcohol). 
 SI. sol. water, sol. ether. Shows the iudophenine 
 reaction with HjSOj and crude benzene con- 
 taining thiophene. 
 
 DI-BENZYL-KETONE C,sH„0 i.e. 
 COfCHjPh)^. Di-phenyl-acetone. Mol. w. 210. 
 [30°]. (320°). Formed by the dry distillation of 
 barium phenyl-aoetate. Prisms. CrOj oxidises 
 it to benzoic and acetic acids (Popoff, B. 6, 
 560). Eeduced by HI at 180° to di-benzyl- 
 methane (Graebe, S. 7, 1623). 
 
 BENZyL-MALONIC ACID C,„H,„04 i.e. 
 C H5.CH2.CH(C02H)j. Phenyl-isosuccinic acid. 
 [117°]. 
 
 Pormation. — 1. By saponification of its ether. 
 
 2. From benzylidene-malonic acid by sodium- 
 
 Properties. — Triolinio crystals, sol. water, 
 alcohol, and ether. Splits up at 180° into 00^ 
 and j3-phenyl-propionic acid. 
 
 Ethyl ether Et^A". (300°). S.G. \i 1-08 
 (Conrad, A. 204, 174; B. 12, 752). Sodium 
 benzyl-malonio ether is converted by iodine 
 dissolved in ether into ''G^B.fiE.„.Gl(CO^'E,t).^, 
 which is converted by alcoholic KOH into 
 ethoxy-benzyl-malonio ether (Bischoff a. Haus- 
 dorfer, A. 239, 110). Converted by alcoholic 
 NH3 into the amides CHjPh.CH(CONHj,)j 
 [225°] and CH,Ph.CH(CO,Et) (CONHj) [98°] 
 (Bischoff a. Siebert, A. 239, 96). 
 
 Di-benzyl-malonioacid(C.H..CHJ.,C(C02H)2. 
 [172°]. P. ; [163°] (B. a. H). Formed by saponify, 
 ing the ether (Perkin, C. J. 47, 821). Slender 
 needles (from water) or thick prisms (from 
 alcohol). V. e. sol. ether and alcohol, m. sol. 
 hot water, si. sol. hot ligroin. Gives di-benzyl- 
 aoetic acid on heating. 
 
 Ethyl ether (C,H5.CH2)2C(C02Et)2. (250°) 
 at 40 mm. S.G. f =1-093. Thick yellow 
 liquid. Formed by the action of benzyl 
 chloride upon sodio-malonic ether. By heat- 
 ing with alcoholic KOH it is converted into 
 di-benzyl-acetic acid (Lellmann a. Schleich, 
 B. 20, 439). Converted by treatment with aloo- 
 holic ammonia into COiEt.0H(C,H,).CO.NH2 
 and (C0.NHj),CH.CH2Ph, benzyl being split off 
 (Bischoff a. Si'ebert, A. 239, 97). 
 
 TRI-BENZYL-HELAMINE 
 (CuHj.CHj.NH.CN),. Formed spontaneously 
 from benzyl-cyanamide by isomeric change 
 (Strakosch, B. 5, 694).— B"'3HC1. 
 
 BENZYL.MEECAPTAN CH^S i.e. 
 C,H5.CH,.SH. Mol. w. 124. (195°). S.G. ^ 
 1058. From benzyl chloride and KHS in 
 alcohol (Miiroker,^. 136, 75; 140 86) Pungent 
 liquid with alliaceous odour. 
 
 Salts.— (C,H,S)jHg : needles.— 0,H,SHgCl. 
 -(C,H,S),Pb. 
 
 Benzoyl derivative CjHj.CHj.SBz. 
 [40°]. Colourless crystals (Otto a. Luders, JB. 
 13, 1285). 
 
 Ethyl derivative 0,H,SEt. (216°). 
 
 BENZYL-MESITYLENE C,sH,a i.e. 
 C5H5.CHj.05H2Me3. [36°]. (c. 302). V.D.7-35. 
 Prepared by boiling benzyl chloride with mesityl- 
 ene in presence of AljCl, (Louise, A. Ch. [6] 
 6, 176, C. B. 95, 1163). Prisms ; v. sol. alcohol, 
 ether, and benzene. 
 
 Reactions. — 1. HI at 180° gives toluene and 
 mesitylene. — 2. CrOs gives benzoyl-mesitylene. 
 3. HNO, forms a tri • nitro • derivative, 
 [185°] and an acid [236°]. — 4. Passage through 
 a red-hot tube forms two di-methyl-anthracenes, 
 anthracene, and phenanthrene. 
 
 Di-benzyl-mesitylene (CsHj.CH2)2CsHMe3. 
 [131°]. (355°) at 120 mm. From benzyl-mesityl- 
 ene, benzyl chloride, and Alfil^ (Louise, A. Oh. 
 [6] 6, 197). Minute prisms. 
 
 BENZYL.HETHANE v. EthyIi-benzene. 
 
 Di-benzyl-methane v. Di-phehyl-pbopane. 
 
 BENZYL HTJSTABD OIL v. Benzyl ibio- 
 
 OABBIMIDE. 
 
 BENZYL.METHYL.ACETIC ACID v. Phenyl- 
 
 ISO-BUTYBIO ACID. 
 
 BENZYL-METHYL-ACETO-ACETIC ACID v. 
 p. 25. 
 
 ek2 
 
500 
 
 BENZYL-DI-METHYL-AMINTl. 
 
 CsHs.CHjNMe^. Di-methyl-bemylamine. (184:°). 
 From benzyl chloride and aleoholio dimethyl- 
 aniine (Sohotten, B. 15, 424 ; Jackson a. Wing, 
 Am. 9, 78). Oil, misoible with alcohol and 
 
 Salts.— "B'HCl.—'B'HNOa.— B'^HjiPtCls.— 
 B'jH .FeCys.— B'jH^ZnClj. 
 
 Methylo-chlorideB'M.eGl: v/hiteorystaXs, 
 sol. water, v. si. sol. Na^COjAq.— (B'MeC^jPtClj. 
 
 BENZYL-TETKA-METHYL-BENZENE 
 C,H5.GH2.C„HMej [1:2:3:4:6]. [61°]. (c. 310°). 
 From benzoyl-iso-durene and fuming HI at 
 250° (Essner a. Gossin, Bl. [2] 42, 170 ; A. Ch. 
 [6] 1, 516). 
 
 BENZYI-METHYL-CARBINOL 
 C5H5.CH2.CH{OH).CH3. (215° i. V.). From 
 benzyl methyl ketone and sodium-amalgam 
 ;Errera, G. 16, 315). 
 
 BENZYL-METHYL-GLY0XIMC,„H,2NA^-«- 
 C,H,.CH2.C(NOH).C(NOH).CH3. [181°]. Formed 
 by the action of hydroxylamine hydrochloride 
 on isonitroso-benzyl-acetone (Schramm, B. 16, 
 180). Small white needles. Sol. alcohol and 
 ether. Sublimable. Weak acid. 
 
 Di-acety I -derivative CijH,„(N0Ac)2 — 
 [80°], small white crystals (Schramm, B. 16, 
 2188). 
 
 BENZYI- METHYI-KETONE CsH,„0 i.e. 
 CsH5.CHj.CO.CH3 Phenyl - acetone. (215°). 
 S.G. •- 1-010. Produced, together with acetone 
 and di-benzyl-ketone, by distilling calcium 
 acetate with calcium phenyl-acetate (Otto, J. 
 pr. [2] 1, 144). Unites with NaHSOj. By 
 heating with cone. H^SO^ on the \vater- 
 bath it is converted into the sulphonio acid 
 C5Hj(SOsH).OH2.CO.CH3; but by heating quickly 
 to a higher temperature it is split up into 
 »-toluene-sulphonic acid 0|,H,.CH2.S03H and 
 acetic acid (Krekeler, B. 19, 2625). 
 
 BENZYI-METHYL-KETONE STJLPHONIC 
 ACID CeHj(S03H).CHj.CH2.CO.CH3. Formed 
 by the action of fuming sulphuric acid upon 
 benzyl methyl ketone in the cold. — PbA'j 
 (Krekeler, B. 19, 2625). 
 
 BENZYL-METHYL-MALONIC ACID 
 C„H,,,0^ i.e. C„H5CH2.CMe(C02H)2. [135°]. 
 Colourless crystals. Prepared from the ether. 
 On heating it gives COj and phenyl-iso-butyric 
 acid. 
 
 Di-ethyl-ether A"Etr (300°). S.G. {|= 
 1'064. Prepared by the action of benzyl chlo- 
 ride on Bodio-methyl-malonic ether or of methyl- 
 iodide on sodio-beuzyl-malonio ether (Conrad a. 
 Bischoff, B. 13, 598 ; A. 204, 177). 
 
 BENZYL-METHYL OXIDE CSH5.CH2.O.CH3. 
 (170°). From benzvl chloride and KOMe 
 (Cahours, G. B. 80, 13'l7). 
 
 BENZYL-METHYL-PIPERIDINE 
 C3H3N(C,H,)(CH3). (245°). Colourless fluid. 
 Formed by dry distillation of the alkaline 
 hydrate produced by the action of moist 
 Ag^O on benzyl-piperidine-methylo-iodide. — 
 (BHC^jPtClj (Schotten, B. 15, 423). 
 
 DI - BENZYL - METHYL - (pseudo) - THIO - 
 
 UREA C,3H,3NjSi.e. CH3.S.C<^^'^Jj . Formed 
 
 by heating di-benzyl-thio-urea with methyliodide 
 at 100°. Oil. V. sol. alcohol and ether, insol. 
 water. 
 
 Salts.— B'HCl': [125°]; easily soluble 
 large rhombic four-sided tables. — BH^SOj: 
 [145°]; glistening needles; v. sol. water and 
 alcohol. — B'HI : [99°] ; octahedra ; v. sol. warm 
 alcohol, si. sol. hot water. — B'jHjCljPtClj : 
 sparingly soluble four-sided prisms (Eeimarus, 
 B. 19, 2348). 
 
 (a)-BENZYL- NAPHTHALENE 0„H„ i.e. 
 CsH,.CH2.C,„H,. [59°]. (0. 330°). S.G. i^ 1-166. 
 S. (alcohol) B-3 at 78°; S. (ether) 50 at 15°. 
 From naphthalene, benzyl chloride, and zinc- 
 dust (Frot6, C. B. 76, 639 ; Miquel, Bl. [2] 26, 
 2). Monoclinic prisms. Dilute HNO3 produces 
 phenyl (o)-naphthyl ketone [75°] . 
 
 Sulphonic acid C^jH^^SO^K. — EA' aq : 
 needles (from alcohol). 
 
 (j3).Beiizyl-naphthalene C,.Hn. [55°]- 
 (c. 345°). S.G. 2 1-176. S. (alcohol) 2-25 at 15°. 
 Formed, together with the preceding, by 
 heating naphthalene with benzyl chloride and 
 Al^Cls (Vincent a. Eoux, Bl. [2] 40, 163). Mono- 
 clinic prisms (from alcohol) ; v. e. sol. benzene 
 and chloroform. Nitric acid produces phenyl 
 (/3)-naphthyl ketone [82°]. 
 
 BENZYL-(a)-NAPHTHYLAMINE 
 0„H5.CH2.NH.Ci„H,. [67°]. From naphthyl- 
 amine and benzyl chloride (Frot6 a. Tommasi, 
 Bl. [2] 20, 67). 
 
 BENZYL-NAPHTHYL-KETONE 0„H„0 i.e. 
 C,„H,-CO— CH^.C^H^. [57°]. Tables. Prepared 
 by the action of AI2CI5 on a mixture of phenyl- 
 acetyl chloride and naphthalene. On reduction 
 with HI it gives phenyl - naphthyl - ethane 
 (Graebe a. Bungener, B. 12, 1078). 
 
 BENZYL - NAPHTHYL - METHANE v. 
 Phenyl-naphihyl-ethanb. 
 
 BENZYL-(/3)-NAPHTHYL OXIDE 
 CeH3.CH,.0.C,„H,. [99°]. White plates. Pre- 
 pared by the action of benzyl chloride on sodium- 
 (3)-naphthol (Staedel, B. 14, 899 ; A. 217, 47). 
 
 BENZYL-NAECEINE v. Naroeine. 
 
 BENZYL - NITKATE C,H5.0H2.NO3. la 
 perhaps formed by the action of benzyl chloride 
 on AgNOj (Brunner, B. 9, 1745). 
 
 BENZYL-NITEO-ARBUTIN v. p. 298. 
 
 BENZYL-NITEO-PHENYL-u.NiiKO-PHENTL- 
 
 BENZYL-. 
 
 BENZYL-ISO-NITEOSO-MALONIO ACID 
 
 CsH,.CH2.0N:C:(C02H)2. From its ether. The 
 potassium salt on dry-distiUation gives KCN, 
 potassium carbonate and benzyl alcohol. 
 
 Di- ethyl ether A'TBtj. Prepared by the 
 action of benzyl chloride and sodium ethylate 
 on iso-nitroEO-malonio ether (Conrad a. Bischoff, 
 B. 13, 599). 
 
 BENZYL -NITEOSO-MALONYL-TIEEA v. 
 Benzyl ether of Violceio acid. 
 
 BENZYL - OXALATE C„Hn0. i.e. 
 {G.'S.^.G'B^)^^:),. [81°]. From benzyl chloride 
 and silver oxalate (Beilstein a. Kuhlberg, A. 147, 
 341). Scales (from alcohol) ; may be distilled. 
 
 BENZYL OXAMATE CsHsNO, 
 i.e. NH,,.C0.C02.CH,Ph. [135°]. From 
 
 NH2.CCl2.C02.CH2Ph and benzyl alcohol (Wal- 
 lach a. Liebmann, B. 13, 507). 
 
 DI-BENZYL OXAMIDE Ci^H.^NjO, i.e. 
 C202(NH.CH2Ph)2. [216°]. From oxalic ether 
 and benzylamine; or by boiling benzylamine 
 cyanide with HCl (Strakosoh, B. 5, 694). Scales 
 (from alcohol). 
 
 BENZYL-OXANTHRANOL v. Oxamthbanoi. 
 
BENZYIi.PHOSPHINE. 
 
 501 
 
 TETRA-BENZTL-OXY-AMMONIUM IODIDE 
 
 V. HYDKOtYLAMINE. 
 
 BENZYL-OXY-BENZOIC ACID v. Oxy- 
 
 BENZtL-BKNZOIC ACID. 
 
 BENZYL-OXY-BTJTYIIIC ACID v. Oxy- 
 
 PUENYL-VAIiERIO ACID. 
 
 BENZYL-OXY-MALONIC ACID v. Benztl- 
 
 TABTBONIO ACID. 
 
 BENZYL-OXY-SULPHIDE v. Di-benzyl 
 
 BULPHOXIDE. 
 
 BENZYL - PHENANTHEENE C^.B.,^ i.e. 
 CHjPh.C„H5. [156°]. From benzyl chloride, 
 phenanthrene (q-v.) and zino-dust (Goldsohmiedt, 
 Mr2, 444). Needles (from benzene). CrOa gives 
 benzoic acid and phenanthraquinone. 
 
 p - BENZYL - PHENOL C^JS.fi i.e. 
 Ci^j.CBLj.GjHj.OH [1:4]. Oxy-di-phenyl-methane. 
 Mol. w. 184. [84°]. (325°- 330°). 
 
 Formation. — 1. From phenol, benzyl chlo- 
 ride and zino-dust (Paterno, 0.2,2; 3, 121). — 
 
 2. From benzoyl-anisol and HI (Paterno, B. 
 6, 288; 6, 1202).— 3. From PhOAo and 
 CjHj.CBLjCl alone or with Al^Cls, and saponifica- 
 tion of the product (Perkin, jun., a. Hodgkinson, 
 O. J. 37, 722 ; Eennie, O. J. 41, 228).— 4. By 
 heating phenol with benzyl alcohol and ZnClj 
 (Liebmann, B. 15, 152). — 5. By diazotising p- 
 amido-di-phenyl-methane and treating the pro- 
 duct with water (Basler, B. 16, 2719). 
 
 Properties. — ^Long needles or plates (from 
 alcohol). Sol. KOHAq but not NHjAq. 
 
 BeacUons. — 1. Distilling with P2O5 gives 
 benzene, phenol, and anthracene. — 2. By bro- 
 mination and nitration, or by nitration and 
 bromination it gives the same bromo-nitro- deri- 
 vative, when treated with HNO3 in CjH^Oj 
 forms CeH2(0H)(N0J^r [1:2:4:6]. Hence the 
 bromo-nitro- derivative CBH2(0H)(C,H,)(N0i,)Br 
 is either [1:2:4:6] or [1:4:2:6]. But the oxida- 
 tion of C,H,.CH,.CsHpMe to CsHsCO.CeH.OMe 
 [1:4] shows that the arrangement is [1:2:4:6]. — 
 
 3. Phosphorus pentachloride forms (CuHjJjPO, 
 [94°].— 4. Chloro-acetic acid and KOH convert 
 benzyl-phenol into CHjPh.CsHj.O.CHj.COjH, 
 [100°], while CH5.CHCI.CO2H and KOH give 
 rise to CHjPh.C„H,.O.CHMe.COjH [102°] (Maz- 
 zara, G. 11, 437 ; 12, 262). 
 
 Methyl derivative O^K^.CU^.G^KflMe. 
 Bemyl-armol. (305°). From anisol, benzyl 
 chloride, and zinc. Oxidised by alkaUne KMnOi 
 it gives the methyl derivative of ^-benzoyl- 
 phenol. 
 
 Acetyl derivative Ph.CH^.C^Hj.OAc. 
 (315°-320°). 
 
 Benzoyl derivative PhCH^.CijHj.OBz. 
 [86°]. 
 
 Sulphonic acid C,H,.CjH,(S03H)(0H). 
 
 Salts. — NHjA'aq: needles. — KA': feathery 
 crystals. — BaA'j. — C.jHijSOjBa aq: minute crys- 
 tals. — These salts are all sparingly soluble 
 (Eennie, C. J. 41, 34 ; 49, 406). They, as well 
 as the free acid, give a violet colour with Fefil,,. 
 
 ^-BENZYL-DIPHENYL C„H,j i.e. 
 CJi,.GB.^.Gja.^.C^B.^. [85°]. (286°) at 100mm. By 
 heating benzyl chloride and diphenyl with zinc 
 dust at 100° two benzyl-diphenyls are produced 
 together with traces of anthracene. The p- 
 hydrooarbon is less soluble and solidifies more 
 easily than its isomeride (Goldschmiedt, M. 
 2, 433). Leaflets or needles, m. sol. alcohol, v. 
 Bol. benzene and ether. CrOj oxidises it, to 
 
 phenyl-benzophenone and benzophenone p-car 
 boxylic acid. 
 
 o-Benzyl-diphenyl (?). [54°]. (c. 285°) at 
 110 mm. Prepared as above. Monoclinio 
 needles. CrOj oxidises it completely. 
 
 Bi-benzyl-diphenyl Ctja.g{CH..2Ph.)^. [113°]. 
 From di-benzoyl-diphenyl and HI at 170° (Wolf, 
 B. 14, 2032). LaminiB (from alcohol). 
 
 BENZYL-PHENYL- v. Phenyl-eenzyl-. 
 
 BENZYL-DIPHENYL-AMINE v. Di-phenyl- 
 
 BENZYL-AMINE. 
 
 M-DI-BENZ YL -p - PHEN YLENE - DIAMINE 
 C,H,(NH2).N(CH2.C,HJ2 [1:4]. Amido-di-benzyl- 
 aniline. [90°]. Obtained by reduction of p- 
 nitro-di-benzyl-anihne with tin andHOl. Glisten- 
 ing colourless needles. V. sol. ether and hot 
 alcohol, si. sol. cold alcohol. With Fe^Clj it 
 gives a deep-red colouration, with Fe^Clj and 
 HjS a blue insoluble pp. By cone. HCl at 170° 
 it is completely resolved into benzyl chloride 
 and p-phenylene-diamine. 
 
 Bemaldehyde compound 
 C„H5.CH(0H) .NH.C5H,.N (CH,.C„H5) j. [130°] 
 Microcrystalline yellow pp. V. sol. benzene, si. 
 sol. ether, insol. alcohol (Matzudaira.B. 20, 1614). 
 
 BENZYL-PHOSPHINE C,HgP i.e. 
 CJl^.CB.^.PH^. (180°). From benzyl chloride, 
 PHjI, and ZnO (Hofmann, B. 5, 100). Oil, 
 volatile with steam. — B'HI : decomposed by 
 water into its components. 
 
 Benzyl-triethyl-phosphonium chloride 
 PEt3(CH;Ph)Cl. From benzylidene chloride, 
 tri-ethyl-phosphine and alcohol (Hofmann, A. 
 Suppl. 1, 323). 
 
 Di-benzyl-phosphine (CH2Ph)2PH. [205°]. 
 Prepared together with the preceding, and sepa- 
 rated by steam-distillation, not being volatile. 
 Groups of needles (from alcohol) ; insol. acids. 
 
 Tri-benzyl-phosphine P(CH^Ph)s. Appears 
 to be formed as a by-product in the action of 
 benzyl chloride on PNaj (Letts a. Collie, Tr. E. 30, 
 181). Splits up on distillation into phosphorus, 
 s-di-phenyl-ethylene, dibenzyl, and toluene. 
 
 Tri-benzyl-phosphine oxide (CHj,Ph)jPO. 
 [213°]. Formed by heating PHjI with benzyhd- 
 ene chloride at 130° and boiling the product with 
 alcohol (Fleissner, B. 13, 1665). Formed also by 
 the action of couo. Ba(0H)2 on tetra-benzyl-phos- 
 phonium acid sulphate ; a weak solution of 
 baryta giving P(G,H,)jOH (Letts a. Collie, Tr. E. 
 80, 181). Needles; insol. water, sol. alcohol and 
 ether. - (C^H^POsHgCl,. — (C„H„PO)3Fe2Cl,. 
 — (02,H2,PO)3CoCl2. — (C2,H2,PO)3PdCl2. — 
 (C2,H„PO)3PtCl^. — (C„H2,PO)2Znl2. — 
 (C,,H,,PO),Br..-(0„H„PO),S. 
 
 Tri-benzyl-phosphine sulphide (CH2Ph)jPS. 
 [206°]. Obtained by distilling the acid sulphate 
 of tetra-benzyl-phosphonium (Letts a. Collie). 
 Long thin needles, m. sol. alcohol. 
 
 Tetra-benzyl-phosphonium hydroxide 
 P(C,H,)jOH. [over 200°]. Obtained by adding 
 BaG03 to the sulphate. Ehombohedral plates ; 
 V. sol. water and alcohol ; alkaline to litmus. 
 Decomposed by heat into P(C,H,)30 and toluene. 
 
 Tetra-benzyl-phosphonium salts. 
 
 Chloride P(CH,Ph)jCl. [224°]. From 
 benzyl chloride and PNaj (L. a. C). Crystallises 
 from water with 2aq, and from chloroform with 
 CHCI3. Split up by heat into tri-benzyl-phos- 
 phine, s-di-phenyl-ethylene, and HCl. 
 
 Platinochloride {P(CHjPh)4ClJ^tCl,. 
 
602 
 
 BENZYL-PHOSPHINE. 
 
 Sulphates.— {P(0,H,),}jSO, : [220^. — 
 P(C,H,),SO,H : [217°]. 
 
 Oxalate P(C,H,),C20jH : needles. 
 
 BENZYL-ISO-PHTHALIC ACID O.iH.jO, i.e. 
 O,H5.CHj.0jH3(C0jH)2. [243°]. From benzoyl- 
 iso-phthalio acid by reduction ■with sodium- 
 amalgam (Zincke, B. 9, 1765). Cryatalline 
 powder, v. si. sol. water. — BaA". — CaA"aq. 
 
 Benzyl-terephthalic acid 
 G^^.CB^C^^iCO^)^. Obtained by reduction 
 of benzoyl-terephthaUo acid (Weber, J. 1878, 
 403).— BaA". 
 
 BENZYL-PHTHAIIMIDINE C,jH,30N i.e. 
 ,OH^CH,.O.H. 
 O^H,^ N^H • [^^''°^- Colourless 
 
 plates or scales. Formed by reduction of benzyl- 
 idene-phthal-imidine by means of HI. 
 
 Nitrosamine C^SX >N(NO) 
 
 \co/ 
 
 [93°] ; yellow crystals, easily soluble in benzene, 
 ligroin, and chloroform (Gabriel, B. 18, 1262). 
 
 BENZYL-FHTHALIMISE 
 CsHjtCjOjtN.OHj.CjHs. Phthalyl-'bemylamine. 
 [116°]. Long needles. Obtained by heating 
 potassium phthalimide with benzyl chloride at 
 170°-180°. HCl at 200° splits it up into phthalio 
 acid and benzylamine (Gabriel, B. 20, 2227). 
 
 BENZYL-PIPERIDINE C,H,„N(0,H,). (245°). 
 Colourless liquid. Insol. water. Prepared by 
 the action of benzyl chloride on piperidine. — 
 (B'HCljjPtCli : sparingly soluble pp. 
 
 Methylo-iodide B'Mel. [145°]. Thick 
 prisms. By moist Ag^O it gives an alkaline 
 hydrate which on dry-distillation yields methyl- 
 benzyl-piperidine (Sohotten, B. 15, 423). 
 
 BENZYL PROPIONATE C,„B.,fi, i.e. 
 C,H,.CHj.0.C0.CHj.CH3. (220°). S.G.^f;^ 1-0860. 
 Decomposed by Ka into sodium propionate and 
 benzyl phenyl-butyrate (Conrad a. Hodgkinson, 
 A. 193, 320). 
 
 y - BENZYL - PYRROL C^H,:N.C,H,. (247° 
 uncorr.). Colourless crystalline solid. Melts 
 when touched with the hand. V. sol. alcohol 
 and ether, nearly insol. water (Ciamician a. 
 SUber, B. 20, 1869). 
 
 zz-BENZYL-PYRRYLENE-DI - METHYL- DI - 
 KETONE C,H2(CO.CH3)2NC,H,. v-Benzyl-di- 
 acetyl-pyrrol. [180°]. Formed by heating v- 
 benzyl-pyrrol with ACjO at 240°. Colourless 
 plates. Sol. ether and benzene, si. sol. water, 
 nearly insol. petroleum-ether (Ciamician a. Sil- 
 ber, B. 20, 1370). 
 
 BENZYL-QUINOLINmM SYSBOXISE v. 
 Bemylo-hydroxide of Quinoline. 
 
 BENZYL-EOSANILINES. From rosaniline 
 and benzyl chloride (Dahl, D. P. /. 263, 398) ; v. 
 
 KOSANILINE. 
 
 Methylo-iodide. From rosaniline, Mel and 
 MeOH (Hofmann, B. 6, 268). 
 
 BENZYL SELENIDE (CsHj.CHjjjSe. [46°]. 
 From benzyl chloride and P^Se^ (C. L. Jackson, 
 A. 179, 1). Long needles or prisms (from alco- 
 hol) ; faint odour, insol. water, v. sol. alcohol 
 and ether. HNO3 forms ' selenobenzyl nitrate ' 
 L88°].-{(C,H,)3Se}3PtCl^. 
 
 Benzyl diselenide (CH2Ph)3Se.^. [90°]. 
 Formed by boUing Na^Sej, benzyl chloride, and 
 alcohol for some hours (J.). Unctuous yellow 
 
 scales (from alcohol). With Mel it forms 
 (OHoPhisMejI, [65°] from which may be ob- 
 tained {(0H3Ph)SMe3ClKPtCl,. Cone. HNO, 
 forms toluene-exo-selinio acid, CjHj.OHj.SeO.^H. 
 
 BENZYL SELENO-CYANIDE CsH,NSe i.e. 
 C,H5.CH2.SeCy. [72°]. From benzyl chloride 
 and potassium selenocyanide (Jackson, B. 8, 321). 
 Prismatic needles with repulsive odour; insol. 
 water, v. sol. hot alcohol. HNO, forms 
 C»H,(NO,).CHj.SeCy [123°]. 
 
 BENZYL -SELEN- UREA CjH^NjSe i.e. 
 NH2.CSe.NH.CHjPh. [70°]. From benzylamine 
 hydrochloride and alcoholic potassium seleno- 
 cyanide (Spioa, O. 7, 90). Sol. water, alcohol, 
 and ether, gradually depositing Se. Cone. HCl 
 forms benzylamine, Se, and HON. 
 
 M-di-benzyl-seleuo-urea NH2.CSe.N(CHj,Ph)2. 
 [150°]. From dibenzylamine hydrochloride and 
 KSeCy. Thin prisms or needles ; v. sol. hot 
 water, alcohol, and ether. Cone. HCl forms Se, 
 CNH, and dibenzylamine. 
 
 TETRA-BENZYL-SILICANE C^jH^jSi i.e. 
 Si(CH2Ph)^. Silicon-tetra-bemyl. [128°]. (above 
 550°). S.G. ^ 1-078. Formed by the action of 
 sodium upon a mixture of benzyl chloride and 
 SiCl,, with addition of a little acetic ether 
 (Polis, B. 18, 1543; 19, 1023). Large mono- 
 symmetrical prisms, sol. ether, benzene, and 
 chloroform, si. sol. alcohol. May be distilled. 
 
 BENZYL SULPHIDE CnH„S i.e. (CH3Ph)3S. 
 [50°]. From benzyl chloride and alcoholic 
 KjS (Marcker, A. 136, 88). Thick trimetric 
 tablets (from ether), a:6:c = -813:1: -515 (Forst, 
 A. 178, 370 ; Bodewig). On distillation it gives 
 £-di-phenyl-ethylene and its sulphide (Barbier, 
 C. B. 78, 1772), toluene, benzyl meroaptan, 
 s-di-phenyl-acetylene sulphide SC^Phj, and 
 thionessal C2,H,sS. Mel forms SMe3l, benzyl 
 iodide and (CH2Ph)SMe2l; the latter gives rise 
 to the compound {(CH3Ph)SMe2Cll2Pt01j. 
 Ethyl iodide at 100° forms similarly (OjHJSEtjI 
 whence {(C,H,)SEt2Cl}jPtCl4 (Scholler, B. 7, 
 1274 ; cf. Cahours, A. Gh. [5] 10, 21). 
 
 DI- BENZYL DI- SULPHIDE {OJBi^.CB.j)A. 
 Sulphohensol. [70°]. 
 
 Formation. — 1. By the action of an alcoholic 
 solution of EH3 or K^S on benzyUdene di- 
 ohloride. — 2. By the action of aloohoUc KHS on 
 (o)-thiobenzoio aldehyde (Elinger, B. 15, 861). — 
 3. By the oxidation of benzyl mercaptan by air 
 or bromine (Marcker, A. 140, 86).— 4. By the 
 action of E^S, on benzyl chloride in alcohol (M.). 
 
 Properties. — White plates. Gives a crystal- 
 line pp. (C,4H2,S2AgNOj) with an alcoholic 
 solution of AgN03. 
 
 BENZYL-SULPHINIO ACID v. Toluene exo- 
 acLPHiKic Aom. 
 
 BENZYL SULPHOCYANIDE 
 C,H3.CH2.S.CN. [41°] (B.); [38°] (H.); (c.233°) 
 (B.); (256°) (H.). From benzyl chloride and 
 alcoholic potassium sulphooyanide (Henry, B. 
 2, 636 ; Barbaglia, B. 5, 689). Prisms (from 
 alcohol), insol. water; pungent smell. Com- 
 bines with HBr, forming a compound decom- 
 posed by water. Fuming nitric acid forma 
 0,H,(N02).CH2.S.Cy. 
 
 DI-BEHZYL-S0LPHONE C„H„SO, i.e. 
 (CH2Ph)2S02. [150°]. 
 
 FormaiAon.—!. Togetherwith0,H5.0Hj.S0,K 
 by the action of EjSO, on benzyl chloride 
 (Vogt a. Henninger, A. 165, 375).— 3. By oxida- 
 
BENZYL XYI.YL KETONE. 
 
 60a 
 
 Uon ol di-benzyl sulphoxide with KMnO^ and 
 HOAo (Otto a. Liiderg, B. 13, 1284).— 3. By tha 
 action of benzyl chloride on sadium benzene-sul- 
 phinate. — 4. By oxidation of di-benzyl sulphide. 
 
 Properties, — Small needles. Insol. water, sol. 
 alcohol, benzene, and acetic acid. By oxidising 
 agents it is readily oxidised to benzoic and sul- 
 phuric acids (Otto, B. 13, 1277). 
 
 BENZYL-SULPHONIC ACID v. Toluene- 
 
 eico-sniiPHoNio acid. 
 
 DIBENZYL-SUIPHONIC ACID v. 
 
 Di- 
 
 PHEHYL-BTHANE SULPHONIO ACID. 
 
 DI-BENZYL SULPHOXIDE C„H„SO i.e. 
 (CH2Ph)2SO. [133°]. From di-benzyl sulphide 
 and cold HNO3 (S.G. 1-3) (Maroker, A. 136, 89 ; 
 Otto a. Ludwig, B. 13, 1284). Laminss (from 
 water or alcohol). 
 
 BENZYL-SULPHTJROTJS ACID v. Toluene 
 
 SULPHONIC ACID. 
 
 BENZYL-TAETEONIC ACID C,„H,„05 i.e. 
 CbH,.CH2.C(0H):(C0,H).,. [143°]. Formedsimul- 
 taneously with oinnamic acid by the action 
 of EOH on benzyl-ohloro-malonio ether. On 
 heating it forms /S-phenyl-o-oxy-propionio acid 
 (phenyl-laotio acid [98°]) (Conrad, B. 13, 2160 ; 
 A. 209, 245). 
 
 BEirZYI-TEEEPHTHALIC ACID v. Benzyl- 
 
 PHTHALIC ACID. 
 
 BENZYL - THIO - CAEBAMIDINE CsHjoN^S 
 i.e. NH:C(NH2).S.CH;,Ph. Cyanamide-bemyl- 
 mercaptan. [72°]. From benzyl chloride and 
 thio-urea (Bernthsen a. Klinger, B. 12, 575). 
 Slender needles, m. sol. water ; decomposed by 
 heat into benzyl meroaptan and di-cyan-di- 
 amide.— B'HCl. [168°].— B'^H^PtCls. 
 
 BENZYL - THIO - CAEBIMIDE 
 C5H5.CH;j.N:CS. Benzyl mustard oil. (243°). 
 Benzylamine is dissolved in CS2 and the pro- 
 duct boiled with alcohol and HgClj (Hofmann, 
 Z. [2] 4, 690; B. 1, 201). Oil, smelhng like 
 water-cress. 
 
 BENZYL-THIO-GLYCOLLIC ACID v. Thio- 
 
 QLYOOLLIC ACID. 
 
 BENZYL-THIO-UEEA CgHioNjS i.e. 
 (CHjPh)NH.CS.NH2. [101°]. From potassium 
 sulphocyanide and benzylamine hydrochloride 
 (Paterno a. Splca, <?. 5, 388 ; B. 9, 81). Sol. 
 water and alcohol. 
 
 Benzoyl derivative 0,H,NH.CS.NHBz. 
 [145°]. From benzoyl sulphocyanide and benzyl- 
 amine (Miquel, A. Ch. [5] 11, 313). 
 
 s - Di - benzyl - tMo - urea (Ph.CHj.NH).,CS. 
 [114°]. From alcoholic benzylamine and CS^ 
 (Strakosch,-B. 5, 692). Four-sided plates, insol. 
 water, sol. alcohol and ether. Converted by 
 HgO into di-benzyl-urea. Alkyl iodides give the 
 following derivatives : 
 
 PhCH2.NH.CS.NMe.CHjPh.— 
 
 (C,H,.NH.CS.NMeC,H,),H2PtCl,.— 
 
 C,H,NH.CS.NMeC,H,HI [99°].— 
 
 PhCH2.NH.CS.NEt.CH,Ph.— 
 
 (C,H,NH.CS.NEtC,H,)2H2PtCl„.— 
 
 0,H,NH.CS.NEtC,H,HI [93°J.- 
 
 C,H,NH.CS.NEtC,H,H2S04.— 
 
 PhCH2.NH.CS.NPr.CH^h.— 
 
 PhCH2.NH.CS.N(C5H„).CH,Ph (Eeimarus, B. 
 
 19, 2348). 
 
 M-Di - benzyl -thio - urea (PhCHj)jN.CS.NHj. 
 [157°]. From potassium sulphocyanide and 
 di benzylamine hydrochloride (P.a.S.). Large 
 needles, m. sol. water. 
 
 BENZYL-THYMOL 0„H,„0 i.e. 
 C5H,MePr(CH„Ph)(0H). (255°) at 8 mm. 
 Formed, together with di-beuzyl-thymol by 
 heating benzyl chloride with thymol and zinc- 
 dust (Mazzara, O. 11, 346). Oil, insol. aqueous 
 alkalis, sol. alcohol and ether. Fe^Cla gives a 
 red colour on heating. 
 
 Acetyl derivative 0„H,bAc0. (245°) at 
 8 mm. 
 
 Di-benzyl-thymol C^t'E^fi i.e. 
 C,HMePr(CH2Ph)20H. [76°]. Prepared as above. 
 Silky laminse, sol. ether and HOAc, insol. water 
 and aqueous alkalis. FejCl^ gives a red colour 
 on heating. 
 
 Acetyl derivative CjjHjjAcO. [e.84°]. 
 
 Methyl derivative Osfi^^UeO. [90°]. 
 
 Benzoyl derivative 024H25BzO. [c. 78°]. 
 
 BENZYL - TOLUENE v. Phenyl - ioltl- 
 
 METHANE. 
 
 DI-BENZYL-TOLUENE C^,n^„ i.e. 
 CH3.GsH3(CH2Ph)j. (c.394°). A product of the 
 action of benzyl chloride on toluene in presence 
 of zino-dnst (Weber a. Zincke, B. 7, 1154). 
 
 BENZYL-p-TOLTJIDINEPhCHj.NH.CeHjMe. 
 (313°). From benzylidene-jj-toluidine (Kohler, 
 A. 241, 359). 
 
 Di-benzyl-p-toluidine Cj,H2,N i.e. 
 (Ph.CH2)2N.CBHjMe. [55°]. From benzyl chlo- 
 ride and^-toluidine (Cannizzaro, A. Swppl. 4, 80). 
 Slender needles, m. sol. cold alcohol. Weak base. 
 
 BENZYL-TOLYL- v. Tolyl-benzyi,-. 
 
 BENZYL - TOLYL - METHANE v. Phenyl- 
 
 TOLYL-ETHANB. 
 
 BENZYL-TOLYL OXIDE v. Benzyl alcohol. 
 
 BENZYL-UEEA C^^^^fi »■«• 
 NHj.CO.NH.CHjPh. [147°]. Formed, together 
 with di-benzyl-urea, by heating benzyl chloride 
 with potassium cyanate in alcoholic solution 
 (Cannizzaro, O. 2, 41). Also from benzyl cyanate 
 and alcoholic NH3 (Letts, C. J. 25, 448) or from 
 benzylamine chloride and potassium cyanate 
 (Paterno a. Spica, G. 5, 388 ; B. 9, 81). Long 
 needles (from alcohol) ; m. sol. water. At 200° 
 it splits up into NH3 and s-di-benzyl-urea. 
 
 s-Dl-benzyl-urea (CHjPh.NHj^CO. [167°]. 
 
 Formation. — 1. From benzyl chloride and 
 KNCO or urea. — 2. From benzyl-urea by heat- 
 ing. — 3. By heating benzyl alcohol with urea 
 nitrate (Campisi a. Amato, O. 1, 39 ; B. 4, 412). 
 4. From s-di-benzyl-thio-urea, HgO, and alco- 
 hol (Strakosch, B. 5, 692). 
 
 Properties. — Needles, insol. water, v. sol. 
 alcohol. Weak base. 
 
 M-Di-benzyl-urea (CHjPh)2N.C0.NHj. [125°]. 
 From di-benzyl-amine hydrochloride and KNCO 
 (Paterno a. Spica, Q. 5, 388 ; B. 9, 81). Thick 
 prisms ; si. sol. cold water. 
 
 BENZYL-UEETHANE v. Benzyl-oakbamio 
 
 ACID. 
 
 BENZYL-7»-XYLENE 0,^3.,, i.e. 
 CjHs.CHyCjHsMej. Phenyl - xylyl - methane 
 (296° i. v.). From m-xylene, benzyl chloride, 
 and zino-dust or Cu (Zincke, B. 5, 799 ; 9, 1761). 
 Oxidation gives benzoyl-iso-phthalio acid. Ap- 
 pears also to be formed by reducing phenyl xylyl 
 ketone with HI (SoUscher, B. 15, 1682). 
 
 Benzyl-p-xylene. (295°). From p-xylene» 
 benzyl chloride and zinc-dust (Z.). 
 
 BENZYL XYLYL KETONE 
 C„H,.CHj.C0.C„H.,(CH3)j. [1:2:4]. Dimethyl. 
 
504 
 
 BENZYL XYLYL KETONE. 
 
 deoxyhemdin (above 350°). Fluid. Formed 
 by the action of AljCIj on a mixture of m-xylene 
 and phenyl-acetyl-oMoride. On oxidation it gives 
 di-methyl-beuzoio acid (Sollsoher, B. 15, 1681). 
 
 BEBBAMINE C.bH^OjN. [156°]. Ooouvs 
 in the root of Berberis vulgaris, together with 
 berberine, oxy-aoanthiue, and at least one other 
 alkaloid. Small plates, containing 2a(i. Easily 
 Bol. ether. The hydrochloride forms small 
 plates, the nitrate needles. — ^B'^HjOl^PtClj 5 or 
 6 aq : yellow crystalline pp., si. Bol. cold water 
 (Hesse, B. 19, 3193). 
 
 BEEBEEIC ACID OgHsO^aq. An acid formed 
 by fusing berberine with KOH (Hlasiwetz a. 
 Gilm; J. 1864, 407). Needles; v. sol. alcohol 
 and ether, m. sol. water. Pe^Clj gives a green 
 colour turned red by ammonium tartrate. Ee- 
 dutes hot Fehling's solution and silver solution. 
 
 BEKBERINE C.,,H„N04 4laq. [120°]. 
 S. 22 at 21°. S. (alcohol) 1 at 15°- Occurs in 
 the root of the barberry, Berberis vulgaris, to- 
 gether with oxy-acanthine (g. v.), berbamine 
 and another alkaloid (Buohner, A. 24, 228; 
 Hesse, B. 19, 3190). Occurs also in Colombo- 
 root (Cocculus palmaius) (Fleitmann, A. 59, 
 160 ; Bodeker, A. 66, 384 ; 69, 40) ; in Meni- 
 spermum fenestratum (Perrins, C. J. 15, 339) ; 
 in Abeocouta bark from Coslor.Une polycarpa 
 (Stenhouse, Ph. 14, 455 ; C. J. 20, 187 ; Daniel, 
 A. 105, 360) ; in Lecmtice thalictro'ides (Mayer, 
 J. Ph. [3], 46, 496) ; in Xanthoxylon clava 
 Herculis (Chevallier a. Pelletan, Bere. J. 7, 266; 
 Perrins, A. Suppl. 2, 171) ; in bark of Geqffroyea 
 inermis (Gastell, J. 1866, 480) ; in Coptis trifolia 
 (Gross, J. 1874, 914) ; and in the root of Evodia 
 glauca (Martin, Ph. [3] 13, 337). 
 
 Preparation. — 1. The finely powdered root of 
 Hydrastis canadensis is extracted with alcohol ; 
 HjjSO, is added to the cooled extract, and the 
 pp. decomposed by NH3. The operation is 
 repeated a second time (Lloyd, Ph. [3] 10, 125 ; 
 cf. Meiiil, Am. J. Pharm. 35, 97; Procter, C.N. 
 9, 112). — 2. Barberry root is exhausted with 
 boiling water ; the extract evaporated, and 
 treated with 92 p.c. alcohol. The berberine is 
 purified by crystallisation from water or alcohol 
 (Buchner). 
 
 Properties. — Silky yeJow needles ; tastes 
 bitter ; si. sol. cold water and alcohol, insol. 
 ether. Turned brown by ammonia. On adding 
 iodine in potassium iodide to a solution of ber- 
 berine hydrochloride the periodide is ppd. It 
 crystallises from alcohol in red needles, but on 
 adding water, green plates separate. 
 
 Beactions. — 1. Zinc and dilute acids form 
 hydro-berberine. — 2. Potash-fusion produces two 
 acids, CsHjOj, and CgHjO^ (Hlasiwetz a. Gilm, 
 J. 1864, 406). — 3. Nitric acid oxidises it to 
 berberonic acid. — 4. KMnO, in presence of KHO 
 forms hemipio acid, [162^] (E. Schmidt a. Schil- 
 bach, Ar. Ph. [3] 25, 164). 
 
 Salts.— (Fleitmann, A. 59, 160 ; Henry, A. 
 115, 132; Perrins, O. /. 15, 339; Hlasiwetz, 
 A. Suppl. 2, 191). — B'HCl: slender yellow 
 needles. — B'H014aq. — B'HCl 2aq. S.G. ^p 
 1-397 (Clarke, Am. 2, 175). — B'^H^HgCl^. 
 — B'HHgCla (Hinterberger, A. 82, 314).— 
 B'jH^OljHgCyj (Kohl a. Swoboda, J. 1852, 550). 
 — B^2H,PtCl„: small needles. S.G. v 1-758 (C). 
 — B'HAuCl, : maroon coloured needles. — 
 
 B'HBr liaq. — B'HIj. — B'HI. — B'HCN. - 
 B'HSCNlAaq. — B'^H.PeCy,. — B'^HsFeCy, 
 — B'H,0,O^. — B'HCIO,. — B'CjHjO^iaq.— 
 B'C,n,0 laq.— B'C4H,(SbO)0, (Stenhouse, Pr. 
 12, 491). — B',H,Or,0,. — B'C,H,(N0,)30H.- 
 
 B'HjSO,.— B'HNO,.— B'^H^SjOaAg^SA- 
 
 Methylo-iodide B'Mel : needles (Bern- 
 heimer, O. 13, 345). 
 
 Ethylo-iodide B'Etl: needles. 
 
 Hydroberberine C2„H2,N04. Obtained by re- 
 ducing berberine in acid solution with zinc 
 (Hlasiwetz a. Gilm, A. Suppl. 2, 191). Granules 
 or needles (from alcohol). Beconverted into 
 berberine by HNO,. 
 
 Salts.— B'HCl. — B'2H,PfcCl,. — B'^H^SO.. 
 — B'H,SO,. — B'4(H,SOj34aq (?). — B'HI— 
 B'HNO,. 
 
 Methylo-iodide B'Mel: trimetrio crystals, 
 a:b:c = 1-033 : 1 : 1-789. -B'MeOH (Bernheimer, 
 O. 13, 342). 
 
 Ethylo-iodide B'Etl: prisms. 
 
 BERBEBONIC ACID v. Pykidine-tbi-cab- 
 
 BOXYLIO AOID. 
 
 BERGAMOT,OII OF. An aromatic essential 
 oil expressed from the rind of an orange. Citrus 
 bergamia. Its S.G. is -87. It contains a stear- 
 optene, a terpene, and a terpene hydrate (?). 
 By rectification a liquid (183°) may be got, 
 which absorbs HCl (Soubeiran a. Capitaine, 
 /. Ph. 26, 68, 509). The stearoptene {Berg- 
 aptene) is deposited after long keeping. It is 
 solid, [206°], but volatilises without decomposi- 
 tion. It may be (C3H„0Jx (Mulder, A. 31, 70 ; 
 Ohme, A. 31, 316). 
 
 BEEOENITE CHijO^aq. [130°]. S.G. 1-5 
 ['>Ju= —51° 30'. Obtained from Siberian saxi- 
 frage (Bergenia siberica) by extracting with hot 
 water, ppg. the tannins with lead acetate, andeva- 
 porating to crystallisation (Morelli, 0. B. 93, 
 646). Trimetric prisms. Tastes bitter. V. si. 
 sol. cold alcohol and water. 
 
 Acetyl derivativeCfS^kcO^ : amorphous, 
 v. sol. water, alcohol, and ether. 
 
 Tri-acetyl derivative CsB.,Aofi^. 
 
 Penta-acetyl derivative CjHjAc^Os. 
 
 BERLIN BLUE = Prussian Blue v. Perro- 
 cyanide of iron under Cyanides. 
 
 BERONIC ACID v. Pykidine di-oakboxylio 
 
 ACID. 
 
 BERYLLITIM. Be. (Glucinum.) At. w. 
 9-08. Mol. w. unknown. S.G. |»° (after com- 
 pression) 1-85 (Humpidge, Pr. 39, 1). S.H. 
 (100°) -4702; (200°) -540 ; (400°) -6172; (500=) 
 •6200 (Humpidge, Pr. 39, 1). S.H. (20°) -397 ; 
 (73°) -448; (157°) -519; (257°) -581 (Meyer's 
 calculation, B. 13, 1780, from data of Nilson and 
 Petterssou who worked with metal containing 
 about 95 p.c. Be; .B. 13, 1451). S.V.S. 4-92. 
 Crystallises in hexagonal, holohedral, forms ; 
 a:c = 1:1-5801 (Brogger a. Flink, B. 17, 849). 
 
 Occurrence. — Only in combination ; in beryl 
 (3BeO.Al203.6Si02) and some other silicates, 
 also in chrysoberyl Al^O^.BeO. Beryllium 
 oxide was recognised as a distinct body in 1797 
 by Vauquelin, the metal was obtained by Wohler 
 in 1827, but approximately pure beryllium was 
 not prepared until 1885, in which year Hum- 
 pidge obtained specimens containing 99-2 p.c. 
 Be, -1 Fe, and -7 BeO. 
 
 Preparation. — Wohler (P. 13, 577) obtained 
 an impure metal by the action of K on fused 
 
BERYLLIUM. 
 
 505 
 
 CeCUj; Debray (O. R. 38, 784) obtained purer 
 speoimens by using Na and a special form of 
 apparatus. Nilson a. Pettersson, by decompo- 
 Bing BeClj by Na in closed iron crucibles heated 
 in a wind -furnace {B. 11, 381), and sifting 
 the crystals through Pt gauze (B. 13, 1455), 
 obtained specimens containing 94-4 p.c. Be 
 (BeO = 4-89, Fe = -70) . Humpidge (Pr. 38, 188 ; 
 39, 1) purified BeO by solution in (NH,)2C03Aq 
 and decomposing the solution by steam ; be 
 mixed the BeO thus obtained with pure charcoal 
 and starch paste and heated in 01 in a glazed 
 porcelain tube ; the BeClj thus obtained was 
 placed in an iron boat, and this in an iron tube 
 surrounded by another tube of hard glass ; 
 another iron boat contained Na ; the Na was 
 heated in a stream of H, and the BeClj was 
 then vaporised (in H) over the molten Na. The 
 crystals of Be were washed in dilute NaOHAq, 
 to remove BeO, then in water, and dried. 
 
 Properties. — Steel-coloured, hard, hexagonal, 
 holohedral (Brogger a. Flink, B. 17, 849) crys- 
 tals. Unchanged in ordinary air; scarcely 
 changed by heating in air. Scarcely acted on 
 by or S at red heat, but burns in CI to BeClj 
 (Nilson a. Pettersson, B. 11, 384). Burns in 
 0-H flame (Humpidge, T. 174, 601). Dissolves 
 slowly in acids, also in aqueous alkalis, with 
 evolution of H. Many of the properties ascribed 
 to Be by Wohler (P. 13, 577), and Debray (A. 
 Ch. [3] 44, 5), were the results of experiments 
 with very impure material. Emission-spectrum 
 characterised by the lines 3320-5, 2649-4, 2493-2, 
 and 2477-7, of which 3320-5 is the most promi- 
 nent (Hartley, C. J. 43, 316). The atomic 
 weight of Be has been determined (i) by 
 analyses, and determinations of V.D., of BeClj 
 and BeBrj; (ii) by determinations of S.H. of 
 Be; (iii) by analyses of various compounds, 
 especially recently of the pure crystallised sul- 
 phate by Nilson a. Pettersson [B. 13, 1451) 
 [for older analyses v. Berzelius, P. 8, 187; 
 Awdejew, P. 56, 101 ; Klatzo, J.pr. 106, 227] ; 
 (iv) by the application of the periodic law. 
 There has been much investigation and dis- 
 cussion concerning the value to be given to the 
 atomic weight of Be ; some chemists insisted 
 that 13-65 is the true value, and that the oxide 
 is Be.flj. The determinations of the V.D. of 
 Bed, and BeBr^, the careful measurement of 
 the S.H. of almost pure Be, and the considera- 
 tion of the physical and chemical relations of 
 Be and its compounds to other elements carried 
 out on the lines suggested by the periodic law, 
 have finally established the value 9-08-9-1 for 
 the atomic weight of Be. The S.H. of Be in- 
 creases rather rapidly as the temperature 
 increases, and approaches a constant value, equal 
 to about -62, between 400° and 500' (Hum- 
 pidge, Pr. 39, 1). The relation between S.H. 
 and temperature is expressed by the empirical 
 formula Kj = -3756 + -001064 - -00000114«'^ (Hum- 
 pidge, Pr. 38, 188). The product of S.H. into 
 At. w. (-62 X 9-1 = 5-64) is lower than the mean 
 value of this quantity for the solid elements, 
 but is nearly the same as that obtained for B, 
 C, and Si. The atom of Be is divalent in the 
 gaseous molecules BeClj and BeBi^; these are 
 the only compounds of Be at present known in 
 the gaseous state. A comparison of the spec- 
 trum of Be with those of In and Al on the one 
 
 hand, and of Mg, Ca, Ba, Sr, on the other, shows 
 that Be is rather to be classed with the lattei 
 than with the former elements; the value 9-1 
 for the atomic weight of Be is thus confirmed 
 {v. Hartley, C. N. 48, 195). Beryllium is a 
 markedly positive, or metallic, element ; it does 
 not exhibit allotropy. It is chemically related tc 
 Mg, Ca, Sr, and Ba, in much the same way that Li 
 is related to Na, K, Cs, and Eb. BeO resembles 
 MgO, but is distinctly less basic ; e.g. it dis- 
 solves in KOHAq, and does not combine directly 
 with B..fl; compare also [BeO'H'', H2S0'Aq] = 
 16,096, with [MgO'HS H-SO*Aq] = 31,216. 
 Analogies also exist between Be and Al ; e.g. 
 the existence of many basic salts ; Be, however, 
 does not form an alum; BeClj does not com- 
 bine with NaCl and KGl as klfil, does. In 
 dilute acid solutions Be is electronegative to Mg 
 but positive to Al ; in caustic alkali solutions 
 the electrochemical order is -l-Al, Mg, Be — 
 (Humpidge, Tr. 174, 601). Be forms only one 
 series of compounds, BeCl2, BeSO^, Be2N03, &c.; 
 it exhibits a marked tendency to form basic 
 salts, e.g., BeSO,.Be0.3H20, BeCOj.3Be0.5H,0, 
 &o. Brauner (JB. 14, 58) sums up the chemical 
 relations of Be in the three statements 
 (1) Li:Be = Be:B. (2) Li:Na = Be:Mg = B:Al. 
 (3) Li:Mg = Be:Al=B:Si. The chemical rela- 
 tions of Be will be more fully discussed in the 
 art. Maonesium mexais; v. also the remarks on 
 Group II. in art. Classifioation. The following 
 are the principal papers bearing on the At. w. 
 of Be : Beynolds, P. M. [5] 3, 38 ; ibid. Pr. 35, 
 248 ; Humpidge, Pr. 35, 358 ; 38, 188 ; 39, 1 ; 
 Hartley, G. J. 43, 316 ; ibid. Pr. 36, 462 ; Car- 
 nelley, Pr. 29, 190 ; ibid. B. 17, 1357 ; Brauner, 
 B. 11, 872; 14, 53; Meyer, B. 11, 577; 13, 1780; 
 Nilson a. Pettersson, B. 11, 381, 906; 13, 1451, 
 2035 ; 17, 987. 
 
 Reactions. — As most of the reactions said to 
 characterise Be have been obtained by experi- 
 menting with material far from pure, the 
 following statements must be accepted as pro- 
 visional only. — 1. Hydrochloric acid, whether 
 gaseous or aqueous, reacts readily to produce 
 BeClj. — 2. Sulphuric acid dissolves Be, forming 
 BeSOjAq. — 3. Nitric acid acts very slowly even 
 when hot and concentrated. — 4. Be dissolves in 
 warm KOHAq or NaOHAq. 
 
 Combinations. — 1. Be combines readily with 
 01, Br, and I to form BeCL, BeBr^, and Bel^ 
 respectively. — 2. It also combines very readily 
 with Si ; and, according to the observations 
 of Wohler, made, however, with very impure 
 material, with P, Se, and S ; later experiments 
 seem to show that Be and S do not combine 
 when heated together (Nilson a. Pettersson, B. 
 11, 381).— 3. An alloy of Be and Fe was de- 
 scribed by Stromeyer as a white solid, less 
 malleable than iron, obtained by strongly heat- 
 ing BeO with Fe and charcoal. 
 
 Detection. — 1. Caustic potash or soda pps. 
 EeOHjO soluble in excess, but reppd. on dilu- 
 ting and boUing. — 2. Amvwnium carbonate pps. 
 the carbonate easily soluble in excess ; this 
 reaction distinguishes salts of Be from salts of 
 Al. — 3. Be salts give no colour when heated with 
 C0.2NO3. 
 
 Estimation. — As oxide, by ppg. by excess of 
 NHjAq, washing, drying, and strongly heating. 
 BeO is separated from Al^Oj by the action of 
 
606 
 
 BERYLLIUM. 
 
 (NHJ,C03 («. Hofmeister, J.pr. 76, 1); or by 
 converting the alumina into potash alum (v. 
 Soheffer, A. 109, 144). 
 
 Beryllium, Alloys of. Little or nothing is 
 known ; v. Bbhyllium, Combinations, No. 3. 
 
 Beryllium, Bromide of. BeBrj. Mol. w. 
 168-6. [abt. 600°] (Carnelley, B. 17, 1357) ; sub- 
 limes readily at 450°. V. D. 90 (Humpidge, Fr. 
 38, 188). 
 
 Preparation. — 1. By heating Be in Br vapour 
 (Wohler, P. 13, 577).— 2. By heating BeO 
 mixed with charcoal and made into a paste 
 with starch, in dry Br (Humpidge, T. 174, 601). 
 Crystals of hydrated BeBr, are obtained by 
 dissolving freshly ppd. BeO.HjO in HBrAq, and 
 evaporating (Berthemot, A. Ch. [2] 44, 394). 
 
 Properties. — Long white needles ; very deli- 
 quescent. Heated in air, partly sublimes, and 
 is partly decomposed into BeO and Br. 
 
 Beryllium, Chloride ofi BeCl^. Mol. w. 80, 
 at low temps. = 160 =Be2Cl<. [about 600°] but 
 sublimes considerably lower (Carnelley, C. J. 
 87, 26; V. also ibid. B. 17, 1857). V. D. (685° 
 to 1500°) 40-96 (mean of 4) ; V. D. (520°) 60-4 
 (Nilson a. Pettersson, B. 17, 987 ; J. pr. [2] 
 33, 1). 
 
 Preparation. — 1. By heating Be in CI. — 2. 
 By heating BeO and in CI, and subliming in 
 HCl.— 8. By heating Be in perfectly dry HCl, 
 and subliming in the same (Nilson a. Pettersson, 
 B. 17, 987). 
 
 Properties. — Snow-white crystalline mass ; 
 easily fused and volatilised ; melts to a colour- 
 less refractive liquid; may be sublimed un- 
 changed in pure dry N or CO^; but is easily 
 decomposed into BeO and CI if a little air is 
 present (Nilson a. Pettersson, B. 17, 987). Is 
 practically a non-conductor of electricity 
 (Nilson a. Pettersson, B. 11, 382 ; Humpidge, T. 
 174,601). 
 
 Reactions. — Dissolves in water with produc- 
 tion of much heat ; on evaporation, an oxychloride 
 Be2.0Clj.H20(=BeCl2.BeO.H20) is obtained; if 
 the solution is placed over H2^S04 under a bell- 
 jar, crystals of BeCl2.4H20 separate out (Awde- 
 jew, P. 56, 101 ; Atterberg, Bl. [2] 24, 358). 
 
 Combinations.— 1. With chlorides of various 
 heavy metals, to form double compounds ; espe- 
 cially BeCl,.8HgCl2.6H20, and BeCl.,.SnClj.8HjO 
 (Atterberg, B. 7, 473) ; BeClj.PtClj.9H,0 
 (Thomsen, B. 3, 827; 7, 75). The salt 
 BeCl2.PtCl4.9H2O is analogous in composition to 
 the Ca double salt CaClj.PtCl4.9H2O ; dried from 
 120° to '',00° the Be salt retains 4H2O, and corre- 
 sponds with double Ba-Pt salt, BaCl2.PtCl4.4H2O. 
 2. "With ether to formBeCl2.2(C2H5)20 (Atterberg, 
 Bl. [2] 24, 358). 
 
 Beryllium, Fluoride of. Hydrated BeO dis- 
 solves easily in HFAq ; on evaporation, a trans- 
 parent, gum-like, mass is obtained which becomes 
 opaque at 100°, but remains soluble in water ; 
 this is probably BePj (Berzelius). The double 
 compounds BeF2.2KP, and BeFj.KF, are de- 
 scribed by Marignac {A. Ch. [4] 30, 45), the 
 former obtained by adding much KFAq, the 
 latter by adding little KFAq, to a solution of 
 BeO.HjO in HFAq, and evaporating. The com- 
 pounds 2NaF.BeP2, NaP.BeF2, and 2NH4F.BeF2 
 are also described by Berzelius. 
 
 Beryllium, Hydrated oxide of, v. Bebylliuu, 
 
 BYDItOXIDEB OF. 
 
 Beryllium, Hydroxides of. A compound of 
 Be, H, and 0, agreeing in composition with the 
 formula Be02H2( = BeO.HjO) is obtained as a 
 white powder by ppg. a hot solution of a Be 
 salt by NHjAq, or KOHAq, boiling, collecting, 
 washing, and drying at 100° (Atterberg, Bl. [2] 
 24, 358 ; Weeren, P. 92, 91) ; on heating more 
 highly, BeO remains. Van Bemmelen {J. pr. 
 [2] 26, 227) says that the pp. by KOHAq has 
 the composition BeO.HjO only when heated to 
 150°-180° : he describes a gelatinous hydrate, 
 BeO.H20, obtained by the action of NHjAq on 
 BeSOjAq, washing with cold water and drying 
 in dry air at 15°-20° ; the composition of this 
 hydrate is constant up to 200°. The compound 
 BeOjHj is not re-formed by the action of water 
 on BeO (for more details of this action v. Van 
 Bemmelen, I.e.) ; it seems better to regard it as 
 a hydrated oxide, BeO.H^O, than as a hydroxide 
 Be(0H)2. Other hydrates of BeO are said to 
 be obtained by drying the pp. by NH^Aq over 
 HjSO,, or merely in air, but the composition of 
 these bodies is variable (v. Schaftgotsch, P. 50, 
 183 ; Atterberg, B. 7, 473 ; Van Bemmelen, 
 J. pr. [2] 26, 227). The gelatinous BeO.H^O is 
 easily soluble in acids, also in NaOHAq and 
 KOHAq, and in (NH4)2C03Aq. By boiling the 
 solution in KOHAq a ppt. of 3Be0.4H20 (Atter- 
 berg, B. 7, 473) is obtained (but v. Van Bem- 
 melen, /. pr. [2] 26, 227). BeOjH^ acts as a 
 basic hydroxide towards acids ; Thomsen gives 
 the following values for its heats of neutralisa- 
 tion, solid BeOjHj being used in each case 
 {Th. 1, 363); [BeO'H^H^SO^Aq] = 16,096 ; 
 [BeO''H^2HClAq] = 13,644. These values are 
 much less than those for the alkaline earth 
 hydroxides (about 31,000 for H2S04Aq). 
 
 Beryllium, Iodide of. Belj. Mol. w. un- 
 known, as V.D. has not been determined. 
 Described as colourless needles obtained by 
 heating together Be and I (Wohler, P. 13, 577 ; 
 Debray, A. Ch. [3] 44, 5). Easily decomposed 
 by action of hot air into BeO and I (De- 
 bray, I.C.). 
 
 Beryllium, Oxide of. BeO. Mol. w. un- 
 known. S.G. 8-016. S.H. (0° to 100°) -2471 
 (Nilson a. Pettersson, B. 13, 1454). S.V.S. 8-8. 
 
 Preparation. — Beryl is fused with NaKCO, 
 in graphite crucibles in a wind-furnace; the 
 fused mass is heated for some time with excess 
 of H2S04Aq, water is added and Si02 removed 
 by filtration, the liquid is evaporated until a 
 crust begins to form and is then allowed to 
 stand for 24 hours or more ; potash alum and 
 K2SO4 separate out ; the mother liquor is again 
 evaporated and a second crop of alum crystals 
 is obtained and removed ; the mother liquor 
 is now poured into a warm cone, aqueous solu- 
 tion of ammonium carbonate, the pp. (of 
 AI2O3 &o.) is digested in contact with the liquid 
 for four or five days and then filtered, the in- 
 soluble portion is again heated with (NH4)2C0aAq 
 and the liquid is filtered off. The solution in 
 (NH4)2C03Aq contains BeO, free, or almost free, 
 from AI2O3, CaO, Fefi, &a. ; the BeO may be 
 obtained by boiling the solution (Nilson a. 
 Pettersson, B. 11, 883), or by acidulating, boiUng 
 off CO2, and ppg. by NHjAq (Hofmeister, J. pr. 
 76, 3) ; in either case, the ppd. BeO.icHaO 
 should be again treated with (NH4)2C03Aq and 
 then reppd. There are various other ways ol 
 
BETH-A-BARRA COLOUR. 
 
 507 
 
 preparing BeO.asH-^O from beryl Iv. espeoially 
 Joy, J. pr. 92, 232; Soheffer, A. 109, 146; 
 Berzelius, P. 8, 187 ; Debray, A. Gh. [3] 44, 15). 
 
 Properties. — A white, loose, infusible powder ; 
 insoluble in, and unacted on by, water ; soluble 
 in acids and in molten KOH. According to 
 Ebelmen (j4. 80, 213) BeO is obtained in hexa- 
 gonal crystals (a:<! = l:l-587) by cooling a 
 solution of the oxide in molten boric acid ; 
 Debray obtained similar crystals of BeO by 
 strongly heating ammonium-beryllium carbonate 
 {A. Gh. [3] 44, 15). H. Bose desoribed crystals 
 of BeO obtained by heating the ordinary oxide 
 in a porcelain oven (Ph. G. 1848. 486) ; S.G. of 
 these crystals == 3'02. 
 
 Reactions and Gombinations. — 1. With most 
 acids to form salts, e.g. BeSOj, Be.2N0j, &o. ; the 
 oxide becomes less easily soluble in acids by 
 heating. — 2. Decomposes molten potassium car- 
 bonate with evolution of COj; on addition of 
 water BeO remains dissolved in the KOHAq. — 
 3. Does not combine directly with water, but 
 various hydrates, of which BeO.HjO is the most 
 important, are obtained by the action of 
 NHjAq on solutions of Be salts {v, BsKZhLivu, 
 
 HYDROXIDES of). 
 
 Beryllium, Ozychlorlde of. 
 Bej0C]^=Be0l2.Be0. Said to be formed by 
 evaporating an aqueous solution of BeCl^. 
 
 Beryllium, Phosphide of. Desoribed by 
 Wohler as a greyish powder obtained by heating 
 Be in vapour of F ; existence very doubtful as 
 Wohler's Be was very impure. 
 
 Beryllium, Salts of. Salts obtained by re- 
 placing H of acids by Be : they are generally 
 obtained by the action of aqueous acids on 
 BeO.HjO. Most of the commoner salts — sul- 
 phate, nitrate, oxalate, chloride — are soluble in 
 water and have a sweetish taste ; the carbonate 
 and phosphate are insoluble in water. When 
 heated, the salts of Be are completely decom- 
 posed, except the acid be non-volatile. The 
 chief salts of Be are the following (they are 
 described under the headings Carbonates, Ni- 
 XBATEs, &c.) carbonates, chromates, molyhdates, 
 nitrates, perchlorate, periodates, phosphates, 
 selenate, selerdtes, silicates, sulphates. The 
 following salts probably exist, but few if any 
 definite facts concerning them are known : — 
 bromate, chlorate, hypophosphite, iodate, phos- 
 phite, tungstate, vanadates. 
 
 Beryllium, Selenide of. Existence very 
 doubtful. 
 
 Beryllium, Silicide of. Be readily combines 
 with Si ; when Be is prepared in porcelain vessels 
 a portion of the SiOj is reduced and as much as 
 20 p.c. Si may combine with the Be to form a 
 hard, brittle mass. It is doubtful whether any 
 definite compound of Be and Si has been 
 obtained. 
 
 Beryllium, Sulphide of. Described by 
 Wohler (P. 13, 577) as a greyish fused mass, 
 which evolves H^S by action of acids ; obtained 
 by heating Be in S vapour. But existence is 
 extremely doubtful ; according to Fremy {A. Ch. 
 [8] 88, 326) no sulphide of Be is produced by 
 heating BeO in S, or CSj, vapour. According 
 to Nilson a. Pettersson (B. 11, 384), Be and S 
 do not combine when heated together. 
 
 M. M. P. M. 
 
 BERTLLITIM, ORGAWIC DERIVATIVES OF. 
 
 Beryllium ethide BeEt^. (185°_188°). From 
 HgEt^ and Be at 130°. Takes fire in air 
 (Cahours, J. 1873, 520). 
 
 Beryllium propide BePr^. Does not take 
 fire in air. 
 
 BETA — Compounds beginning with beta- or 
 bet- are desoribed as /3 compounds under the 
 word to which this prefix has been added. 
 
 BETAlNE CsHi.NOj i.e. MesN<^'^Q 2>C0. 
 
 Internal anhydride of the methylo-hydroxida 
 of di-methyl-amido-acetic acid. S. 16 at 25°. In 
 thehydrated condition CsHuNOj aq, it may be re- 
 presented by the formula Me3N(OH).CH,.C02H. 
 
 Occurrence.— 1. In the juice of beet -root 
 (Beta vulgaris), and in beet-root molasses 
 (Soheibler, Z. 6, 505 ; B. 8, 155 ; Liebreich, Z. 
 6, 506 ; B. 3, 161). The unripe root contains 
 •25 p.c. ; the ripe root only -1 p,o. The betaine 
 is not present in the root as such, but is liberated 
 by treatment with HCl or baryta. — 2. In man- 
 gold wurzel (Soheibler, Z. [2J 5, 539).— 8. In 
 cotton seed (Eitthausen, J. pr. [2] 30, 32).— 4. 
 In the leaves and branches of Lycium barbarum 
 (HarmS a. Husemann, A. Suppl. 2, 383 ; 3, 245 ; 
 Ar. Ph. [3] 6, 216).— 5. In putrefying flesh 
 (Gautier, Bl. [2] 48, 13). 
 
 Formation. — 1. From tri-methyl-amine and 
 chloro-acetio acid (Liebreich, B. 2, 13). — 2. By 
 oxidation of neurine Me3N(0H).CH2.CH20H. 
 
 3. GlycocoU (1 mol.) is dissolved in KOHAq and 
 mixed with Mel (3 mols.) and MeOH ; the 
 liquid being kept alkaline (Griess, B. 8, 1406). 
 
 4. Silver glycocoU and Mel gives the iodide, 
 Me3NI.CHj.CO2H. 
 
 Preparation. — 1. Diluted molasses are boiled 
 for twelve hours with baryta ; excess of baryta 
 is removed from the filtrate by COj ; the liquid 
 is evaporated to a treacle and exhausted with 
 alcohol ; the alcoholic solution is treated with 
 alcoholic ZnCl2 ; the pp. is recrystallised from 
 water, and decomposed by baryta ; the barium 
 is exactly removed from the filtrate by H^SOj, 
 and betaine hydrochloride crystallises on eva- 
 poration (Liebreich, B. 3, 161 ; cf. Soheibler, 
 B. 2, 292 ; Fruhling a. Schulz, B. 10, 1070). 
 
 Properties. — Large crystals (containing aq) 
 (from alcohol). Ppd. as plates by adding ether 
 to an alcoholic solution. Deliquescent. Over 
 H^SOj the crystals become CsHuNOj. Sweet 
 taste ; neutral to litmus ; inactive. Decom- 
 posed by heat, giving off odours of NMe3 and of 
 burnt sugar. Not affected by CrOj or HI. 
 Fusion with potash gives oS NMe,. Iodine in 
 EI pps. brown needles of a periodide. 
 
 Salt s.— B'HCl or Me3NCl.CH,.C0,H : mono- 
 clinic tables, v. sol. water. — B'HAuCli: platea 
 or thin needles. — B'^H^PtOls 2aq (B.).— 
 B'jH,PtCl8 4aq (L.).— (B'H01)2HgClj.— B'ZnCl^. 
 — B'KI2aq [139°] (Korner a. Menozzi, &. 13„ 
 351).— B'KI i2iQ°].—B't-B.J.JlBiI,)^ (Kraut, A, 
 210, 318).— B'jHjSO,. 
 
 Methyl ether.— lo^ie INMCa.CHj.COjMe. 
 From silver glycocoU and Mel (Kraut, A. 182, 
 180). 
 
 BETH-A-BARBA COLOUR CaHj^Oj. [135°] . 
 A dye extracted from a West African woocE 
 (Sadler a. Bowland, Am. 3, 22). When dried at 
 100° it contains 3aq in the molecule. 
 
608 
 
 BETORCIN. 
 
 BETOBCIN C,H,„Oj i.e. C,H,Me,(OH),. 
 {1:4:3:5]. [163°]. (o. 279°). e-Orcin. Di-oxy- 
 ^-xylene. Di-7nethyl-resorcin. 
 
 Formation 1. By boiling (5)-picroerythriii 
 
 ^sith baryta (Stenhouse, A. 68, 104 ; Lamparter, 
 A. 134,248; Meu3chutkin,BZ.2,428).— 2. From 
 ^mido-xylenol, OsHjMe2(NH2) (OH) [1:4:3:5] by 
 the diazo- reaction (ICostanecki, B. 19, 2321). 
 
 Preparation. — The lichen Usnea harhata is 
 ithoroughly extracted with cold water (10 pts.) 
 ;and CaO (1 pt.), the extract is mixed with HCl. 
 A pp. of usnic and barbatio acids is formed. 
 This mixture (Ipt.) is boiled with water (40 pts.) 
 .and CaO (1 pt.) for four hours. An insoluble 
 basic calcic usnate is formed while the barbatio 
 acid splits up into CO2 and betorcin. Air must 
 be excluded, for betorcin oxidises very readily. 
 The filtrate is at once neutralised with HOI, 
 acidified strongly with acetic acid, evaporated 
 (to 5 pts.) filtered from some tarry matter, and 
 ■evaporated further to crystallisation. Eeorystal- 
 lised first from benzene, then from water. 
 Yield jg per cent. (Stenhouse a. Groves, 0. J". 
 57, 396). 
 
 Properties. — Less soluble in water than orcin. 
 ■Gives a more crimson colour with hypochlorites 
 than orcin does. FcjClj gives a green colour. 
 Ammoniacal solutions turn red in air. Boiled 
 with NaOH and chloroform it forms a red, 
 non-fluorescent solution. 
 
 BETITLIC ACID CasHjA- [195°]. From 
 tetulin and CrOj in HOAo (Hausmann, A. 
 182, 378). Wbite powder, v. si. sol. water, v. 
 sol. alcohol. — Pb3(C35H5,OJ2. 
 
 BETULIN CjAoOs. [251°]; [258° cor.] 
 <Hausmann, A. 182, 369). S. (alcohol) -7 at 15° ; 
 4-2 at 78°. Occurs in the bark of the birch 
 (Lowitz, Crell. Ghem. Ann. 1788, i. 302 ; Hiine- 
 teld, J.pr. 7, 53; Hess, J.pr. 16, 161; Stahelin 
 a. Hofstetter, A. 51, 79; Paterno a. Spica, O. 
 •7, 508). 
 
 Preparation. — The bark ia extracted with 
 •96 p.o. alcohol, the alcohol evaporated and the 
 residue after washing with water and with soda- 
 •Bolution is crystallised from benzene or naphtha, 
 the crystals are finally decolourised with animal 
 <;harcoal and recrystallised from alcohol (Fran- 
 <!himont, B. 12, 7). 
 
 Needles ; may be sublimed. Insol. water, v. 
 el. sol. CS2, b1. sol. alcohol and ether. At 130° 
 it gives an Anhydride G^^'&^fip On distilla- 
 i;ion alone with powdered zinc, PjOj, or P^Sj, 
 hydrocarbons are produced of doubtful con- 
 ■fititution. 
 
 Acetyl derivative C35H5jO(OAc)2 [216°]. 
 
 BETULIN-AMABIC ACID C,„H,.,0„. From 
 ibetulin and fuming HNO5 (Hausmann, A. 
 182, 374). Crystals, v. si. sol. water, v. e. sol. 
 ;alcohol and ether. At 110° it gives the anhy- 
 dride 03eH,eO„ [181°]. 
 
 Salts. — KAbHjoO,^. — CaBaCs,H,,0,2. — 
 
 Ethyl ether EtiOjeHjBO,^. [117°]. 
 
 BETUIOBETIC ACID C^Ji^fi,. [94°]. A 
 white resin found on young birch-shoots and 
 leaves (Kosmanu, J. Ph. [3] 26, 197). Insol. 
 water, v. sol. alcohol and ether. Oxidised by 
 HNO3 to picric acid. — XgOggS^fl^ : flocculent pp. 
 
 BEZOAB. — A concretion found in the stomach 
 sa intestines of a variety of goat, Capra (zgragus, 
 
 or of the gazelle, Antilope Dorcas. They contain 
 ellagic and lithopellic acids. 
 
 BICHBOMATES, same as Dichbouates, q. v. 
 under Chromium, acids op. 
 
 BICUHYBA FAT.— The fat of Myristica 
 bicuhyba consists chiefly of the glyceridea of 
 myristio and oleic acids ; it also contains small 
 quantities of resins and free fatty acid (myristio 
 acid), and a very small amount of an ethereal 
 oil (Noerdlinger, B. 18, 2617). 
 
 BIEBBICH SCABLET v. p. 368. 
 
 BILE. — A liquid secreted by the liver. It is 
 viscid, of green or brown colour, and has a bitter 
 taste. S.G. about 1'02. Faintly alkaline. Pos- 
 sesses an emulsifying power like soap. Its 
 composition varies. Ox-bUe contains sodium 
 glycocholate and taurocholate, cholesterin, urea, 
 fats, salts of acetic and propionic acids, glyceryl 
 tri-acetate, glyceryl tri-propionate, pigments, 
 mucus, KCl, phosphates of Na, Ca, and Mg, 
 and traces of iron, manganese, and silica. 
 Human bile is of a similar composition. 
 
 Latschinoff {B. 18, 3039) has shown that 
 saponified ox -gall contains, in addition to choUc 
 acid (which is derived from the glyoo- and 
 tauro- oholic acids), a new acid to which he gives 
 the name choleic acid. The latter acid, accord- 
 ing to this investigator, occurs in two forms=^ 
 anhydrous CjjH^oOjjand hydrated C^sH^O^ljaq. 
 Mylius (B. 19, 369) has found that oholic acid 
 by putrefactive fermentation is reduced to a 
 body (the ' desoxycholic acid ' of M.) which L. 
 considers as identical with his so-called ' hydra- 
 ted crwleic acid.' As however L. (B. 20, 1043) 
 was unable to convert his ' anhydrous choleic 
 acid ' into the ' hydrated choleic acid ' by any 
 other method than by boiling with acetic acid 
 and M. (B. 20, 1968) was unable to efiect the 
 conversion even in this way, there appears to 
 be little doubt that these so-called ' anhydrous ' 
 and ' hydrated choleic acids ' are quite distinct 
 acids (the conversion by AcOH is probably er- 
 roneous), the latter being identical with the 
 ' desoxycholic acid ' of M. Hence the ' anhy- 
 drous ' acid will be described as choleic acid, the 
 ' hydrated ' as deoxycholic acid. Both these 
 acids according to L. give dehydrocholeic acid 
 on gentle oxidation, and cholanic acid on more 
 vigorous oxidation. 
 
 To choUc acid L. assigns the formula CjsHjjOs, 
 but M. (B. 19, 369, 2000 ; 20, 1968) has shown 
 by a long series of careful analyses that, almost 
 beyond a doubt, it is represented by the formula 
 CjjH^Oj originally proposed for it by Strecker. 
 On oxidation it first gives dehydrocholic acid 
 C^i^ifls and then bilianic acid C^jHjjOs (but 
 no cholauio acid, which when obtained from 
 cholio acid by earlier investigators, was due to 
 the presence of choleic acid). 
 
 Pig's bile contains sodium hyoglycocholate 
 and hyotaurocholate instead of glycocholate and 
 taurocholate ; it also contains glyoero-phosphoric 
 acid and neurine derived from the decomposi- 
 tion of lecithin. In other respects it resembles 
 ox-bile. The various constituents of bile are 
 separately described. 
 
 Pettenkofer's test. Bile, or an aqueous solu- 
 tion of a salt of bile, is mixed with two-thirds 
 of its volume of HjSO, and a drop of a 10 p.o. 
 solution of sugar is added. On warming to 75° 
 a crimson colour is produced. The reaction in 
 
BTSIMUTH. 
 
 ao'.y 
 
 given by glycooholio, taurooholio, hyoglycocholio, 
 hyotaurooholic, and by oholio acid (Pettenkofer, 
 4. 52, 92 ; cf. Neukomm, A. 116, 30 ; Strass- 
 burg, PflUger's Arch., 4, 461). The test may be 
 modified by using phosphoric acid. The sub- 
 stance to be tested, together with very Uttle 
 cane sugar, is dissolved in 3 drops of a mixture 
 of syrupy phosphoric acid (5 vols.) and water 
 (1 vol.) and the tube is then dipped into boiling 
 water. A crimson colour soon appears (Kolbe, 
 J. pr. [2] 27, 424). A red colour is produced by 
 many other substances than those mentioned, 
 hence it is necessary to confirm it by observing 
 the absorption spectrum which contains three 
 bands: one extending from midway between o 
 and D to D, the second midway between d and E, 
 and the third between B and r (Heynsius a. 
 Campbell, PflUger's Arch., 4, 497 ; cf. Schenk, 
 Fr. 12, 119). 
 
 BILE COLOTTEINO MATTERS v. Piombnts, 
 
 ANIMAIi. 
 
 BILIANIC ACID 
 C,,H3,0a probably 02oH33(CO),(CO,H)3. 
 Formed by further oxidation of dehydrooholic 
 acid C2„H3,(CO)(CHO),COjH. 
 
 Preparation.— Choiio acid (20 pts.) in fine 
 powder is added to a mixture of K.fii,0, 
 (40 pts.) and 11.804 (60 pts.) in water (160 pts.), 
 finally warming on the water-bath till the re- 
 action is complete. It is isolated by conversion 
 into the acid potassium salt, which is sparingly 
 soluble in alcohol, and then into the di-ethyl- 
 ether (Mylius, B.20, 1981; cf. ClSve, Bl. [2] 85, 
 378 ; LatschinoH, B. 19, 480 ; Bl. [2] 46, 818). 
 
 Properties. — Flat needles (containing Jaq.). 
 Tri-basic ketonic acid. 
 
 Salts. — A"2Ba3 6aqor8aq: tables or prisms. 
 — A"'HBa 2aq : hexagonal tables, si. Bol. water 
 and alcohol. — Ajg^K'". 
 
 Di-ethyl ether A"'HEt2: [198°]; long 
 flat needles ; sol. alcohol, less sol. ether. — 
 A"'2Et,Ba.— A"'jEt4Pb. 
 
 Tri-ethyl ether A^Etji [127°]; satiny 
 tablets, or thick pillars. 
 
 Di-oxim 0,3H„(C:NOH),(CO,H)3. Formed 
 by warming a slightly alkaline solution of bili- 
 anio acid with hydroxylamine. Glistening tables. 
 Sol. dilute alcohol, nearly insol. water and abso- 
 lute alcohol. Dissolves in alkalis, forming acid 
 or neutral salts. 
 
 Di-phenylhydrazide 
 C,3H3,(C:N2HPh)2(C02H)3 : colourless needles. 
 Nearly insol. acetic acid and hot alcohol, insol. 
 water. Dissolves in alkalis. 
 
 iso-Bilianic Acid C„H„08 (?). [234°--237°]. 
 Flat needles. Formed in small quantity, to- 
 gether with bilianic acid, by oxidation of cholic 
 acid with KjCr^O, and H^SO,. 
 
 Salts.— A"'H2K: silky rhombic plates, si. 
 sol. water and alcohol.— A"'Ag3 : amorphous pp. 
 — A"'2Ba6aq: amorphous, si. sol. water, insol. 
 alcohol. 
 
 Methyl ether M"me^: [98°]; needlea 
 (LatschinofE, B. 19, 1530). 
 
 BILIC ACID OisH^^O,. [about 190°]. Pre- 
 pared by careful oxidation of cholic acid with 
 chromic acid mixture (Bgger, B. 12, 1068). 
 White needles. Sol. hot water and alcohol, si. 
 sol. ether. Dibasic acid. It gives Pettenkofer's 
 reaction with sugar and H2SO4. By oxidation it 
 is converted into cholesterio acid (CijHieO,). 
 
 BINARY THEORY OF SALTS. The name 
 salt was given in ancient times to the solid 
 residue obtained by boiling sea-water; it was 
 then extended to include all solid substances 
 easily soluble in water and obtainable by evapo- 
 rating watery liquids. At a later time the 
 possession of a taste more or less resembling 
 that of sea-salt was regarded as a characteristic 
 property of all salts. When the composition of 
 the bodies called salts began to be studied, a three- 
 fold division was made into acid salts, alkaline 
 salts, and neutral salts (v. Acid, Ahum, Salt). 
 Lavoisier's discovery of the nature of oxygen led 
 to the definition of acids as highly oxygenated 
 compounds ; and Davy's decomposition of soda, 
 potash, lime, and baryta, showed that these 
 alkaline salts were also compounds of oxygen. 
 But as neutral salts were formed by the mutual 
 action of an acid and an alkali, it followed that 
 they too were oxygenated compounds. A 
 neutral salt, or we may say simply a salt, for 
 the qualifying word neutral had been dropped 
 by this time, was then regarded as constituted 
 of two parts, an acid or electro-negative part, 
 and a basic or electro-positive part. From this 
 time dualistic views prevailed ; every compound, 
 said Berzelius, must be constituted of two parts, 
 which may themselves be simple or complex, 
 and of these parts one is positively and the 
 other negatively electrified. Such a salt as 
 sulphate of soda, for instance, was regarded as 
 constructed of positive soda and negative sul- 
 phuric acid, rather than as formed by the mutual 
 interaction of the elements sodium, oxygen, and 
 sulphur. When, chiefly as a result of the 
 work of Davy and Dulong, acids had come to 
 be regarded as composed of the positive element 
 hydrogen united with a negative element or 
 group of elements, and salts were said to be 
 formed by putting metals in the place of the 
 hydrogen of acids, the conception of a salt as a 
 binary structure stiU remained. One part of 
 every salt was a positive element, a metal; the 
 other part was a negative radicle, either a non- 
 metal or a group of non-metallic elements. 
 
 In some such way as this arose the binary 
 theory of salts, a theory which is based on the 
 notion of every salt being a definite structure, 
 and which conceives it possible to place all salts 
 in one class, regard being had for classificatory 
 purposes rather to the composition than to the 
 properties of salt (1). CiiAbsifioation and 
 Salts). M. M. P. M. 
 
 BIRCH BARE. Contains betulin (g;. v.) and a 
 kind of tannin which is turned green by FCjCls 
 (Stahelin a. Hofstetter, A. 51, 79). 
 
 BISMUTH. Bi. At. w. 208. Mol. w. probably 
 208 (v. Biltz a. Meyer, Z. P. C. 4, 249). [268°-3] 
 (Eudberg, P. 71, 462 ; Eiemsdyk, C. N. 20, 82). 
 (1090°-1450°) (Carnelley a. Williams, C. J. 35, 
 565). S.G. f 9-759 (Schroder, P. 106, 226). S.G. 
 liquid 10-055 (Boberts a. Wrightson, A. Oh. [5] 
 30, 274). S.G. is lowered by great pressure. 
 S.H. (20°-48°) -0305 (Kopp, T. 155, 71) ; 
 (9°-102°) -02979 (B^de, Mim. B. 1855-56. 28) ; 
 (Uquid 280°-380°) -0363 (Person, A. Oh. [3] 
 24, 129). C.B. (12°-41°) -001333 (Kopp, A. 
 81, 1) ; (0°-100°) -001316 (Matthiessen, Pr. 
 15, 220 ; V. also Fizeau, P. 135, 872 ; 138, 267). 
 Ht. of fusion at 266°-8 = 12,640 (Person, A. Oh. 
 [3] 24, 129). T. 0. (Ag = 100) 1-8 (Wiedemann 
 
610 
 
 BISMUTH. 
 
 a. Franz, P. 89, 497). B. C. atO" (Hg at 0° = 1) 
 •8676 (Lorenz, W. 13, 422, 582). Cryst. form, 
 Iiexagoual. a:c = 1:1-3035; isomorphous with 
 Te, As, Sb. S.V.S. abt. 21-3. H.C. [Bi', O'] 
 abt. 95,500 (Wooda, P. M. [4] 4, 370). 
 Emission-spectrum characterised by very many 
 lines ; in arc-spectrum the predominant lines 
 are 4722-1, 4119, 3595-3, 3510-4, 3396-2, 2593, 
 2524, 2400-8, 2277 (Liveing a,. Dewar, T. 174, 
 187, V. also, regarding spectrum of Bi, Hartley 
 a. Adeney, T. 1884. 63). 
 
 Occurrence. — Uncombined with other ele- 
 ments, in Saxony and other parts of Germany, 
 in Norway, Spain, California, and in Cornwall 
 and Cumberland, &c. Also as Bi^O, (Bismuth 
 ochre), Bi^Sj (Bismuth glance), Bi^Teg, Bi^Cu^Sj, 
 BijPb^Sa, *o-) &o. Bismuth has been known 
 for many centuries ; Basil Valentine (15th cen- 
 tury) seems to have been the first to recognise 
 it as a definite metallic body. Bergmann gave 
 the earliest fairly accurate account of its 
 reactions. 
 
 Formation. — Native bismuth is melted in 
 iron tubes, and the metal is run off from 
 gangue &o. into pots. By remelting with J5 of 
 its weight of KNO3, at as low a temperature 
 as possible, until the nitre forms a solid slag on 
 the surface, approximately pure Bi is obtained. 
 
 P?-epara<io;i.— Approximately pure metal is 
 dissolved in the minimum quantity of HNOjAq, 
 much water is added, the pp. of basic nitrate is 
 washed, boiled twice with pure KOHAq, or 
 NaOHAq (Herapath.D. P. J. 169, 40), dissolved 
 in as little HNOjAq as possible, and water is 
 again added. The pp. is washed, dried, mixed 
 with hlacTc flux (obtained by heating cream of 
 tartar in a closed vessel) and heated at about 
 270°-280° in a closed crucible. The reduced 
 metal is washed in dilute HClAq, and in water, 
 and dried. Traces of As, Sb, or Fe, which yet 
 remain in the metal are removed by partially 
 oxidising and melting under the small quantity 
 of BijOj formed : this may be effected (1) by 
 adding a little pure KNO3, melting in an open 
 porcelain crucible, keeping molten for some 
 time, allowing to cool until a small quantity of 
 the metal solidifies, and pouring ofi the still 
 molten metal from the more solid oxides on 
 the surface ; (2) by melting under NajCOs con- 
 taining 2-0 p.c. KCIO3 and proceeding as in (1) 
 (Turaoh, J. pr. [2] 14, 309) ; (3) by strongly 
 heating with Ipart cream of tartar, then running 
 the molten metal (which contains K) into a 
 crucible containing charcoal, heating for a little, 
 running into an open porcelain vessel, strongly 
 heating in air for some time, and finally pour- 
 ing off the molten metal from the slag on the 
 surface (Mehu, jD. P. J. 211, 187). Lowe 
 {Fr. 22, 498) recommends ppn. of Bi3N03 in 
 HNOjAq by KOH, solution of pp. in excess of 
 KOH in presence of glycerine, addition of 
 grape sugar, filtration from Ag and Cu, and 
 boiling ; pure Bi is ppd. Bi is obtained in 
 well-formed crystals by melting the commercial 
 metal with a little KNO3 in a crucible until a 
 small quantity taken ouS appears yellow on the 
 surface (indicative that foreign metals are 
 oxidised), removing the scum of oxides from the 
 surface, covering tho molten mass with pieces 
 of charcoal (to prevent oxidation), allowing to 
 cool until a firm crust has formed, piercing two 
 
 holes in the crust, and pouring off the still 
 molten metal ; the crucible is found to be lined 
 with crystals of Bi. 
 
 Properties. — Very lustrous; white with a 
 slightly reddish tinge ; very easily crystallises ; 
 brittle ; diamagnetic, but not so when molten 
 (Faraday, P. Suppl. 3, 1 ; Weber, P. 73, 241 ; 
 87, 145 ; Eeioh, P. 97, 283 ; Pliicker, P. 72, 339 ; 
 76, 576 ; 81, 133). For thermo-electric behaviour 
 V. Svanberg, O. B. 31, 250 ; Franz, P. 83, 374 ; 
 Matteucci, G. B. 40, 541. Bi expands as it 
 solidifies (for method of demonstrating this v. 
 Bottger, D. P. J. 212, 441). May be distilled at 
 a high temperature (over 1100°) in an atmo- 
 sphere of H. The atom of Bi is trivalent in the 
 gaseous molecule BiClj. Bi forms numerous 
 alloys most of which melt at low temperatures, 
 and expand on solidification {v. Bismuth, alloys 
 of). The atomic weight of Bi has been deter- 
 mined (1) by finding V.D. of, and determining 
 CI in, BiCl, (Dumas, A. Ch. [8] 55, 129 a. 176) ; 
 
 (2) by oxidising Bi to Bi203 by means of HNO, 
 (Schneider, P. 82, 303 ; J. pr. [2] 30, 237 ; Lowe, 
 Fr. 22, 498; Marignac, A. Gh. [6j 1, 289); 
 
 (3) by converting BijOj into sulphate (Marignac, 
 I. c). The exact value to be given to the at. w. 
 of Bi is still doubtful ; it is certainly not greater 
 than 208. Bi is metallic in its chemical func- 
 tions; it shows a marked tendency to form 
 basic rather than normal salts ; many of these 
 basic salts may be represented as containing 
 the group BiO e.g. BiO.NOj, (BiO)i,SOj, &c.; 
 several oxychlorides and oxybromides are known ; 
 no hydride of Bi has yet been obtained; the 
 oxides of Bi are salt-forming in their reactions 
 with acids, none of them is an anhydride, but 
 moist BijOj dissolves in very cone, boiling 
 KOHAq probably with formation of compounds 
 in which Bi acts as part of the negative radicle 
 (v. BiSMUTHio OXIDE Under Bismdih, oxides of). 
 Bi shows distinct analogies to As and Sb, also 
 to the other members of Group V., in its chemical 
 relations; for fuller discussion v. Bismuth, 
 OHEMiOAii BELATioNs OF. Bi salts are used in 
 medicine: the alloys are used in printing, 
 soldering, &c. 
 
 Beactions. — 1. Very superficially oxidised in 
 ordinary air : heated in air or oxygen burns to 
 BijOj.— 2. Decomposes steam at a red heat. — 
 3. Combines directly with several elements, 
 especially 0, 01, Br, I, S, Se, and Te: [Bi,01'] 
 = 90,630 (Th. 2, 410); [Bi^.O'] = abt. 95,000 
 (Woods, P. M. [4] 4, 370).— 3. Scarcely acted on 
 by hydrochloric acid dilute or cone— 4. With 
 hot cone, sulphwric acid a basic sulphate is 
 formed. — 5. Quickly dissolved by nitric acid 
 with formation of Bi.3N03. — 6. Oxidised, but 
 slowly and partially, by fusion with potassium 
 nitrate or chlorate. 
 
 Estimation. — Generally as Bi^Oj, after ppn. 
 from a solution free from HCl and chlorides by 
 excess of ammonium carbonate, and warming for 
 some time ; the pp. is washed, dried, and heated 
 whereby Bi203 is produced. Also by adding 
 much water to a solution in as little HCl as 
 possible, warming, collecting BiOCl, and drying 
 at 100°-110° (traces of Bi remain unppd.) ; 
 the BiOCl may be reduced by heating with 
 ECN, and the Bi weighed. Ppn. as BijSj and 
 weighing is not to be recommended, as Bi^S, 
 is easily oxidised in moist air. Volumetric 
 
BISMUTH. 
 
 methods of estimating Bi, none of which how- 
 ever is altogether satisfactory, have been based 
 on (1) ppn. of Bi(I03)j from acetic acid solu- 
 tions by a measured mass (excess) of HIOjAq, 
 and determination of residual HIOj (Buisson a. 
 Ferray, M. S. [3] 3, 900) ; (2) ppn. of Bi chro- 
 mate from nearly neutral solutions by K^CrO^Aq 
 or KjCrjOjAq ; (3) pptn. of Bi phosphate by 
 standardised Na^HPOjAq ; (4) ppn. of Bi 
 oxalate, conversion into basic oxalate by boiling 
 water, and titration with K^Mn^OjAq ; (5) ppn. 
 of double oxalate of Bi and K by standardised 
 KjCjO^Aq and determination of residual Kfifit 
 by KjMnjOjAq (Pattison Muir, C. J. 29, 483 ; 
 32, 674; 33, 70; (with Bobbs) O. J. 41, 1). 
 
 Chemical Relations of Bismuth. — ^Bi is the 
 highest known member of Group V. ; this group 
 contains the following elements : — 
 
 Ecmseriet 2 4 6 8 10 12 
 
 N=14 V=61 Nb=94 Di=U2 Ta=182 — 
 
 OddKTia 3 6 7 9 II 13 
 
 P=31 Aa=7S Sb=120 Br=166 Bi=208 — 
 
 Taken as a whole these elements are negative 
 and their compounds with H and react as acids. 
 As the group is ascended the negative charac- 
 ters become less marked until Bi is reached; 
 omitting N, the oxides MjOj of the even series 
 members, so far as known, are salt-forming in 
 their reactions with acids ; but in the odd series 
 members these oxides, on the whole, are salt- 
 forming only in their reactions with bases, until 
 Series 9 is reached, when the character of the 
 oxides M2O3 becomes decidedly basic. The 
 oxides MjOj, on the whole, are aoid-forming, but 
 the acidic functions of Bi^Oj are very feeble. 
 Salts formed from acids by replacement of H are 
 obtained in the oases of V, Di, Er, and Bi ; but 
 most of the salts of vanadium, and many of those 
 of Bi, seem to contain groups of the form M^Oj,, 
 acting as the more positive part of the salt ; 
 several salts of the normal type, e.g. Bi.SNOj, are 
 however known and several normal Er and Di 
 salts have been prepared. Vanadium is charac- 
 terised by the great number of complex com- 
 pounds into which it enters, sometimes as part 
 of the positive, sometimes as part of the nega- 
 tive, group of the salt. Considering the composi- 
 tions of the haloid, and oxyhaloid compounds, we 
 find that, so far as investigation has gone, com- 
 pounds of the form MXj and MOX3, where X = 
 a halogen element, exist when M is any member 
 of the group except Bi or As (N is omitted as 
 there is much doubt concerning the composition 
 of its haloid compounds), and in the case of As 
 compounds of AsFj with KF, &a., seem to exist ; 
 the compounds BiBrj(CeH5)3 and BiCl2(C5H5)3 
 are known as solids (Miohaelis, B. 20, 52). 
 The haloid compounds BiX3 are less easily oxi- 
 dised than the corresponding compounds of P, 
 As, or Sb. The basic character of the oxides of 
 bismuth, the existence of many salts in which 
 Bi acts as the metallic element, the stability of 
 the haloid compounds BiX, and the non-exis- 
 tence of BiXj, the non-existence of any com- 
 pound in which 61283 acts as the negative 
 radicle ; these, among other properties, show 
 that Bi must be classed as the distinctly 
 metalho element of Group V. But the feebly 
 acidic functions of Blfis towards strong alkalis, 
 the readiness with which so-called basic salts of 
 bismuth are formed, the fact that Bi^O, nnd 
 
 611 
 
 Bi^O, form no corresponding salts, the existence 
 of several complex oxyhaloid compounds : these, 
 among other properties, show that the genera] 
 non-metalho character of Group V. to some 
 extent belongs to Bi. 
 
 Bismuth, Alloys of. Bismuth alloys with 
 many metals when melted with them; these 
 alloys are characterised by low melting points, 
 and, many of them, by the expansion which 
 they undergo as they cool after being melted. 
 The most technically important alloys are : — 
 Newton's metal ; 8 parts Bi, 5 Pb, and 3 Zn, 
 M.P. = 94°-S: Base's metal ; 5 Bi. 3 Pb, 2 Sn, 
 M.P. = 91°-6 : Wood's metal ; 15 Bi, 8 Pb, 4 Sn, 
 3 Cd, M.P. = 68°: Fusible metal; 2 parts Bi, 
 1 Pb, 1 Sn, M.P. = 93°-7; this alloy expands 
 from 32° to 95°, contracts gradually to 131° 
 when its volume is less than at 32°, then 
 expands to 174°, after which its expansion is 
 uniform. 
 
 Amalgams of Bi are easily formed at or- 
 dinary temperatures. Alloys with copper are 
 formed below the melting point of Ou ; an alloy 
 of 2 parts Bi with 1 part Cu begins to expand 
 after solidification (Marx, S. 58, 470). An alloy 
 of 3 parts Bi with 1 part iron is magnetic. 
 Alloys of Bi and palladium are hard as steel ; 
 with ^ part spongy platinum Bi forms an easily 
 fusible alloy which separates into Pt and Bi 
 when fused at a low red heat. Bi does not alloy 
 with zinc; on mixing melted Zn and Bi two 
 layers are formed, one containing a little Bi and 
 much Zn, the other much Bi and little Zn. 
 
 Bismuth, Bromides of. Only one bromide, 
 BiBrj, has been obtained with certainty; but 
 many facts point to the existence of a lower 
 bromide, probably BiBrj. 
 
 Tbibromide. BiBr,. (Bismutlwus bromide.) 
 Mol. w. unknown, but probably as represented 
 by formula. [210='-215°] (Pattison Muir, C. J. 
 29, 144). (Between 454° a. 498°) (CarneUey a. 
 WiUiams, O. J. 33, 283). 
 
 Formation. — 1. By heating powdered Bi in 
 CO2 charged with Br vapour. — 2. By adding 
 powdered Bi to a solution of Br in dry ether, 
 and evaporating in vacuo. 
 
 Preparation.— 1^ parts Br are allowed to 
 flow, in small successive quantities, into 1 
 part powdered Bi in a small retort with the 
 beak tilted upwards ; when the mass is cool, 
 the retort is very gently warmed for some days, 
 and from time to time a few drops of Br are poured 
 into the retort ; the bromide forms in yellow 
 crystals a little distance above the heated 
 mass. 
 
 Properties and Beactions.—Golien yellow 
 crystals; S.G. j^5-4; very deliquescent ; soluble 
 in dry ether ; decomposed by water to BiOBr 
 and EIBrAq ; partially reduced to Bi by heating 
 in hydrogen ; heated with Bi203 forms BiOBr ; 
 by action of nitrogen oxides obtained by heating 
 starch with HNOjAq the oxybromide BijOisErj 
 is produced ; unchanged when heated in COj or 
 SO2 ; reacts with ammonia, when heated in that 
 gas, to form (1) BiBrj.SNH, which is a straw- 
 yellow powder, soluble in HClAq and yielding 
 BiBr3.3KH^Cl.H20 by evaporation over H^SO^ ; 
 
 (2) probably BiBr3.2NH3, an olive-green solid; 
 
 (3) an ash-grey, crystalline, infusible, solid, pro- 
 bably BiNjBr. The compound 2BiBrj.5NH, ia 
 
612 
 
 BISMUTH. 
 
 obtained (along with Bi), as a greyish -green pow- 
 der, by heating Bi^O.sBrj to dull redness in dry 
 NH, (Pattison Muir, C. J. 29, 144; 16, 27). 
 A. solution of BiBr3 in saturated KClAq deposits 
 crystals of BiCljBr.K^.liH^O (Atkinson, O. J. 
 43, 292). Does not combine with CI. 
 
 DxBKOMiDE.— Probably BiBr2 or Bi^Brj. In 
 preparing BiBrs dark grey crystals are formed 
 if there is a deficit of Br; these contain Br 
 nearly agreeing with the formula BiBr, ; on 
 heating they give Bi and BiBrj. Weber (P. 
 107, 599) obtained a brown mass — probably a 
 lower bromide than BiBrj— by heating BiBr^ 
 with Bi; Macivor (0. N. 30, 190) obtained a 
 dark grey solid, melting at 198°-200°, by heating 
 Bi and Br. 
 
 Bismuth, Chlorides of. Two chlorides are 
 known, BiClj and Bi2Clj : all attempts to form 
 a chloride with more CI than BiClj have failed. 
 Both may be obtained by the direct combination 
 of Bi and CI ; Bi^Cl^ is separated into BiClj, Bi, 
 and CI, by heating ; BiCl, is reduced to BijCl, 
 by heating with Bi, or with Hg^Clj. 
 
 Tkiohlobide. — BiClj (Bismuthous chloride), 
 Mol. w. 314. [227°] (Pattison Muir, C. J. 29, 
 144). (427°-439°) (Carnelley a. Williams, G. J. 
 33, 281). 
 
 Formation. — 1. By heating 1 part powdered 
 Bi with 2 parts HgClj in a retort. — 2. By dis- 
 solving BijOj in HClAq, evaporating to dryness, 
 heating in air and then in a retort. — 3. By 
 heating BijO, in dry CI. 
 
 Preparation. — Powdered Bi is heated in a 
 current of dry CI, in a retort with the beak 
 tilted upwards and furnished with an exit tube 
 passing into cone. HjSO,; when a light yellow 
 liquid has been formed, the stream of 01 is 
 slackened and the retort is very gently heated 
 for some time ; crystals of BiClj sublime on to 
 the upper parts of the vessel. The crystals 
 may be distilled into small tubes in a current 
 of dry N ; the tubes are at once sealed. 
 
 Properties and Beactions. — White, very deli- 
 quescent, crystals, melting in CI to a pale 
 yellow liquid; S.G. ii° 4-56; soluble in dry 
 alcohol. Heated in air between two watch 
 glasses part sublimes and an oxychloride — 
 BigOjClj or BijOjClj — remains. The same oxy- 
 chloride is obtained by the action of nitrogen 
 oxides (from starch and HNOjAq) on BiClj. 
 Heated in hydrogen BijClj and Bi are formed, 
 at a higher temperature all the CI is removed. 
 Decomposed by water to BiOCl and HClAq ; the 
 amount of change depends on the relative 
 masses of BiClj, HCl, and H^O, and on the 
 time ; when the reacting bodies are mixed in 
 the ratio BiClj: 26HC1 : 10,000 H^O a little 
 BiClj remains unchanged even after 14 days 
 action {v. Pattison Muir, C. J. 35, 311 ; Ostwald, 
 J. pr. [2] 12, 264). Heated with sulphur 
 BiSCl is formed {v. Bismuth sulphochlokide). 
 Not acted on by^CrOzCl^ ; scarcely acted on by 
 SO2 ; does not combine with Br (P. M., O. J. 
 39, 33). 
 
 Combinations. — With ammonia to form 
 (1) 2BiCl3.NH3, a red, fusible, crystalline, 
 solid; (2) BiCl3.2NHs, a greenish solid; (3) 
 BiCla.SNHj, a white, volatile solid (D6h&ain, 
 C B. 54, 724). These ammonio-chlorides by 
 treatment with HClAq yield compounds of the 
 form KBiClj.^NH^Cl, where x varies from 1 to 2, 
 
 and y from 1 to 6. With potassium chloride 
 forms BiCl3.2KC1.2^H20; also with sodium 
 chloride forms corresponding salt with 3H2O;. 
 a solution of BiCl, in hydrochloric acid 
 when evaporated gives needles of BiCl3.2HCl 
 (Jacquelain, A. Ch. [2] 62, 363). 
 
 DiCHLOBiDE.— Probably Bi^Clj. Mol. w. un- 
 known. 
 
 Formation. — 1. By gently heating BiCl. in 
 H ; but the product is mixed with Bi and BiClj. 
 2. By heating BiClj with Bi (Weber, P. 107, 
 596),— 3. By heating BiGls.xNE.fil in H to 300' 
 (Schneider, P. 96, 130). 
 
 Preparation. — A very intimate mixture of 
 2 parts HgCl with 1 part extremely finely 
 powdered Bi is heated to 230°-250° in a closed 
 tube for some time ; the mixture melts to a. 
 dark brownish black liquid, and Hg (with a. 
 little Bi) collects at the bottom of the tube ; the- 
 sides of the tube are tapped from time to time- 
 to make the Hg settle ; after cooling the Bi^Clj, 
 solidifies over the Hg, it is removed as quickly 
 as possible to another tube — which is at once 
 closed — and again melted ; this process ia 
 repeated several times ; nearly pure Bi^Clj,. 
 containing a very little Hg and Bi, is finally 
 obtained (Schneider, P. 96, 130). 
 
 Properties and_ Beactions. — Black, or nearly 
 black, extremely deliquescent, solid ; -with water 
 forms BiOCl ; with potash gives Bi^Oj which is- 
 quickly oxidised to BijOj.xHjO; with dilute- 
 mineral acids gives Bi salts and Bi ; heated ta 
 about 300° gives BiCla and Bi. 
 
 Bismuth, Cyanides and Ferrocyanidea of, 
 V. Cyanides. 
 
 Bismuth, Fluoride of. Only one fluoride of 
 Bi has as yet been prepared (Pattison Muir, 
 Hoffmeister and Eobbs, G. J. 39, 33), BiFj. 
 Mol. w. unknown. 
 
 Prepa/ration. — 1. Bifl, is added in small 
 successive quantities to HPAq heated in a Pt 
 dish until the oxide ceases to be dissolved ; the 
 liquid is decanted and evaporated at 100° ; the 
 residue, BLP3.3HP, is warmed at about 110°- 
 120° in a closed Pt crucible until dry, and ia then 
 heated (in the closed crucible) so long as HP is 
 evolved.— 2. Excess of saturated KFAq is added 
 to a solution of Bi(K03)3 in the minimum quan- 
 tity of diiute HNOjAq, the pp. is thoroughly 
 washed with boiling water, diied at 100°, and 
 heated to dull redness in a closed Pt crucible. 
 
 Properties. — Grey, heavy, crystalline, solid. 
 S.G. f g 5-33. Unacted on by water ; insoluble 
 in alcohol; scarcely changed or volatilised by 
 heating to redness in open Pt dish ; not oxi- 
 dised by heating in nitrous oxides (from starch 
 and HNOjAq) ; dissolved, with decomposition, 
 by hot HGl, HNO3, or H^SOiAq. Combines with 
 HP to form BiP3.3HP {v. supra) which is a 
 crystalline, greyish-white, deliquescent solid, 
 decomposed by boiling water to BiOP (v. Bis- 
 muth oxyeluokide). 
 
 Bismuth, Haloid Compounds of. BiP, ; 
 BiCl,, BijCli ; BiBr3 (? Bi^BrJ ; Bil,. The V. D. 
 of BiCl3 only has been determined; the other 
 formulffi are probably molecular. BijCl, and 
 BijBrj are decomposed by heat to Bi and BiX3 ; 
 the others are unchanged when heated out of 
 air ; heated in air aU except BiP3 are more or 
 less oxidised, BiCl3 to the greatest, and Bil, to 
 the least, extent. Bilj is a very stable com- 
 
BISMUTH. 
 
 SI 3 
 
 pound (v. Bismuth, fluobidb of ; oHLORtDEs op ; 
 BBomDES OF ; and iodidb of). 
 
 Bismuth, Hydrated oxides, or hydroxides of, 
 
 0. BiSMDTH, OXIDES OF. 
 
 Bismuth, Iodide of. Bil,. Mol. w. unknown ; 
 probably as represented by formula. 
 
 Formation. — 1. By heating an intimate 
 mixture of 1 part BijSj with li parts I, in a 
 large, loosely covered flask, and then heating 
 the sublimed Biljat 100° to remove I (Schneider, 
 P. 99, 470).— 2. By dropping BiSNOj in dilute 
 HNOjAq into cone. KIAq, dissolving the brown 
 pp. in fairly cono. HIAq, and ppg. Bil, by as 
 little water as possible (Eammelsberg, P. 48, 166), 
 drying pp. at 100°, and removing free I by one 
 or two washings with absolute alcohol. — 3. By 
 the action of HIAq on Bi^Oj. 
 
 Preparation. — An intimate mixture of 1 part 
 Biwith 2 parts I is gently heated in a flask with 
 a long neck passing into another flask ; the 
 sublimate is finely powdered and again heated ' 
 in the same way as before ; this is repeated once 
 or twice ; and finally the mass is distilled in a 
 fairly rapid current of dry CO^ (Weber, P. 14, 
 113 [slightly modified]). 
 
 Properties and Reactions. — (Pattison Muir, 
 Hoffmeister a. Eobbs, G. J. 39, 33.) Dark grey, 
 metal-Uke, lustrous, crystals (probably hexagonal, 
 NickUs, C. B. 50, 872) ; S.G. 5-65. S. (alcohol 
 at 20°) c. B'5. Unchanged in air ; heated in 
 air a very little BijOjis formed. Unchanged by 
 heating in hydrogen, or with sulphur, or in 
 sulphv/r dioxide. Slowly changed to BiOI by 
 a large quantity of cold water, more quickly 
 by boiling water. Very partially converted into 
 BiOI by heating in N oxides (from starch and 
 HNOjAq). Bilj is much more stable than either 
 Bids or BiBrj. 
 
 Combinations. -^iih. HI toformBiI3.HI.4H2O 
 (Arppe, P. 44, 248). With MI (M = Na, K, NHJ, 
 and MI2 (M = Ca, Ba, Mg, Zn), to form double 
 compounds isomorphous with the corresponding 
 compounds of Sbl, : obtained by direct com- 
 bination of the iodides, or by acting on Bi with 
 I in presence of the iodide MI or MI^ ; they are 
 all deliquescent, and are easily resolved by water 
 into their component iodides (NickUs, G. R. 51, 
 1097 ; Linan, P. Ill, 240). 
 
 Bismuth, Oxides and hydrated oxides of. 
 Four oxides are known, Bi^Oz, Bi^Oj, BijO,, 
 BLjOj; as none has been gasified, the V.D. 
 and hence the molecular weight of none is 
 known. These oxides all react with acids to 
 form the same series of salts, BiXj, where 
 
 X =N03, ^'~'' &o. ; if much water is present, 
 
 basic salts, usually of the form BiOX, are 
 produced ; in the reactions of BijOj with acids 
 Bi is separated as metal ; in the reactions of 
 BijO, and Bi^Oj oxygen is evolved. Bi205.a;HjO 
 is slightly soluble in very cono. boiling KOHAq, 
 but no salts have been certainly obtained in 
 which the acid radicle is composed of Bi and 0. 
 BijOj is easily oxidised to BijOj ; BijOjand BijOj 
 are deoxidised to Bi203 by heating in air or 
 oxygen to about 320' and 250° respectively; 
 BijOj is unchanged when heated in air or 
 oxygen. BijOj is not hydrated by contact with 
 water ; BijO, and BijOj are hydrated in moist 
 air, in contact with water they are partially and 
 slowly deoxidised to hydrates of BijOj. 
 Vol,. I. 
 
 The more important papers on the oxides and 
 hydrated oxides of Biareas follows :— 1. Ouoxides 
 containing less than BijO, :— Thomson (Proa. 
 Glasgow Phil. Soa. 1841-42, 4) ; Heintz (P 
 63, 55, 559) ; Schneider (P. 88, 49 ; 97, 480) ; 
 Arppe (P. 64, 237) ; Vogel {Kastner's Archiv, 
 23, 86) ; Berzelius {Lehrbuch, 2, 574 [5th ed.l) ; 
 Sohiff (A. 119, 331); Pattison Muir (O. J. 
 32, 128).— 2. On oxides containing more than 
 Bi203 :— Jacquelain [1838] {J.pr. U,l); Heintz 
 [1844] (P. 63, 559) ; Arppe [1845] (P. 64, 237) ; 
 Bottger [1858] (/. pr. 73, 494) ; Schroder [1862] 
 (A. 121, 204) ; Boedeker [1862] {A. 123, 61) ; 
 Wernicke [1870] (P. 141, 109) ; 0. Hoffmann, 
 [1884] (A. 223, 110); Pattison Muir [1876 to 
 1886] (O. /. 29, 144; 31, 24; 32, 128; ibid. 
 39, 21 [withHofemeistera. Eobbs]; 61, 77 [with 
 Carnegie]) ; Hasebrook [1887] (B. 20, 213).— 3. 
 On Bi^O, : — Bonsdorff (P. 41, 305) ; Fuohs (S. 
 67, 429) ; Stromeyer (P. 26, 553) ; Liebig {Mag. 
 Pharm. 35, 114) ; Pattison Muir {l.c.). 
 
 Hypoeismuthous oxide. BijOj {Bismuth 
 suboxide. Bismuth dioxide. Black oxide of 
 bismuth). 
 
 Preparation. — A mixture of 1 part SnClj 
 and 2-5 parts Bi203 is dissolved in as little 
 fairly cone. HClAq as possible, the solution is 
 poured into an excess of KOHAq (about 1 KOH 
 in lOAq) in a stoppered flask so that the flask ia 
 nearly filled with the liquid; the stopper ia 
 placed in the flask, and the black pp. ia allowed 
 to settle ; the pp. is washed with cold KOHAq 
 (in air-free water) less concentrated than that 
 used in the ppn. the flask being each time 
 nearly filled with the liquid, and then with air- 
 free water ; it is then quickly dried by pressing 
 between filter paper, and placed over H2SO4 mi 
 vacuo (Schneider, P. 88, 45). 
 
 Properties and Reactions. — ^Blaok, crystal- 
 line, powder ; begins to oxidise in air at about 
 180° ; at red heat quickly oxidised to BijO, ; 
 oxidised to Bi204.!BH20 and BijO^.^HjO by boiling 
 with KOHAq and Br; oxidised to Bi204.a;H20 
 by K2Mn20aAq ; when moist, BijOj is rapidly 
 oxidised in air to Bi203.2H20 ; oxidised by con- 
 tact with a very little HNOjAq, decomposed to 
 Bi2.6N03 and Bi by more HNOjAq, dissolvea 
 entirely by a considerable quantity of the same 
 acid; decomposed by HClAq or HjSOjAq to 
 BiCl3, or Bi sulphate, and Bi; deoxidised, to 
 Bi, by heating in H or CO ; decomposed by 
 boiling KOHAq with formation of Bi (Schneider, 
 l.c. ; Pattison Muir, l.o.). No hydrate of Bi^Oj 
 has been definitely obtained. Solution of Bi,Oj 
 in tartaric acid is said to give BijSj by reaction 
 with HjS (Schneider), v. Bismuth disulphide. 
 
 BiSMUTHOus OXIDE. BijOj {Bismuth trioxide). 
 S.H. (12°-97°) -0609 (Eegnault, A. Gh. [3] 1,129). 
 S.G. =8-21 (Herapath, P.M. 64, 321); 8-08 
 (Playfair a. Joule, G. J. Mem. 3, 57). Occurs 
 native generally associated with oxide of iron. 
 
 Formation. — 1. By heating Bi in air or 0. 
 
 2. By ppg. Bi nitrate or chloride solution by 
 excess of alkali and boiUng; thus prepared 
 always contains some oxynitrate or oxychloride. 
 
 Preparation. — 1. Basic Bi nitrate, obtained 
 by ppg. solution of Bi in HNOjAq by large 
 excess of water, ia heated in a Pt dish with 
 constant agitation untH oxides of N are no 
 longer evolved. If this oxide is fused with 
 KOH it orystallisea on cooling in rhombic 
 
514 
 
 BISMUTH. 
 
 prisma, a;6:<!=-8165:l:l-064 (NordenskjOld, P. 
 114, 512).— 2. BiOCl (q.v.) is shaken for some 
 time with very cone. KOHAq, until the change 
 to BijOj and KCl is complete ; the Bi^Oj is 
 washed with cold water until quite free from 
 KOH and KCl and dried : the oxide may be 
 thus obtained in distinct crystals. 
 
 Properties and BeacUons. — Heavy, yellowish- 
 white, solid ; unchanged by heating in air or 
 oxygen. Dissolves in acids to form Bi salts 
 (v. Bismuth, salts of). HFAq heated with 
 BijOs dissolves part of it as BiFj.SHF and 
 converts the rest into BiOF.2HF; HXAq (X = CI 
 or Br) added to Bi^Os little by little converts the 
 whole of the Bi into BiOX, on addition of more 
 HXAq the BiOX dissolves as BiXj ; with a little 
 HIAq Bils is alone formed, if very dilute HIAq 
 is added and the temperature is raised BiOI only 
 is produced, with considerable excess of fairly 
 cone. HIAqBiljis formed and dissolved. Heated 
 in c/iZorme.BiCljis formed; with bromine BiBr, 
 and Bi,,0,,Br, are produced. Heated in carbon 
 monoxide reduction begins at about 200°, and 
 in hydrogen at about 240°. BijO, is not hydrated 
 in moist air; nor is it altered by contact with 
 water. Unchanged by heating in nitrogen. 
 Oxidised to Bi^O, and "Bifi^hj action of chlorine 
 in presence of much hot KOHAq ; scarcely oxi- 
 dised by KjMn208Aq («. further Hypoeismuihio, 
 and BisMCTHic, oxide), 
 
 Hydeated bismuthous oxide. BijOj.ajHjO ; 
 x = l, 2, and 3. The hydrate with 2H2O is 
 obtained by dissolving Bifi^xUfi in cone. 
 HClAq, ppg. by KOHAq, and drying over 
 HjSOj in vac-uo: the hydrate with ILfi is 
 obtained by dissolving Bi205.a;H20 in cone. 
 H2SO4, reducing by SO2, ppg. by KOHAq, and 
 drying as before (P. M., C. J. 32, 131). 
 BijOs-SHjO is very difSoult to obtain quite free 
 from oxy- salts and BijO, ; pps. formed by adding 
 KOHAq to BijO, in HCl, HNO,, or HjSO,, and 
 washing with cold water, always contain basic 
 chloride, &o. ; if washed with hot water they 
 contain Bi^O,. Nearly pure Bi20s.3H20 is ob- 
 tained by dissolving BijO, in the minimum of 
 HNOjAq, pouring into excess of cone. NHjAq, 
 washing with cold water until the washings 
 contain no nitrates, then repeatedly agitating 
 with very dilute NajCOjAq (to decompose traces 
 of basic nitrates), again washing repeatedly 
 with cold water, and drying m vacuo over HjSO,. 
 The hydrates of Bi^Oj are white solids, easily 
 dehydrated by heat, partially even by contact 
 with hot water; Bifi^ does not directly com- 
 bine with water. The hydrates behave towards 
 acids and oxidisers similarly to Bifi,. None 
 of these hydrates shows the slightest in- 
 dications of acidic functions. Thomsen gives 
 the thermal values [BiS 0^ SH^O] = 137,740 ; 
 [BiO'H',HClAq] = 14,180, with formation of 
 BiOCl + 2H20Aq (Th. 2, 244). 
 
 Hyfobismuthio oxide, and Hydbates, Bi^Oj; 
 Bifit-Hfi; Bi204.2H20 (Arppe, SchrSder, 
 Bottger, Wernicke, Pattison Muir). Preparation 
 of Bi^Of — BijOj is suspended in KOBLAq, S.G. 
 abt. 1"35, the liquid is kept nearly boiling, and 
 CI is passed in until the solid is dark chocolate- 
 red and quite homogeneous to the eye ; the solid 
 is washed with hot water until the washings are 
 neutral to Htmus, kept in contact with dilute 
 HNO^q (1 couo. acid to abt. 20 water) until the 
 
 colour of the solid has become brownish-yellow 
 (12-16 hours) (to dissolve any BijO, and reduce 
 any Bi^Os), washed free from acid, and boiled 
 with cone. NaClOAq (to reoxidise any traces of 
 BijOa) until a heavy, yellow-brown, powder is 
 formed which settles quickly; this powder is 
 washed with hot water until quite free from 
 alkali and CI, and dried at 180°. 
 
 Hydrates.— It the drying is conducted over 
 HjSO^ the hydrate BijOi.HjO is obtained. If 
 BIjOs.eH^O {v. infra) is treated with warm 
 HNOjAq until the colour is orange-yellow, 
 washed, and dried over H^SOj, the hydrate 
 Bi204.2H20 is obtained. These hydrates are 
 also formed, the first by the action of ordinary 
 air on Bi^O,, and the second (with 2H2O) by the 
 action of moist air on Bi204 : they part with 
 their water of hydration at about 150°. 
 
 Properties and Beactions.—Bifit is a brown- 
 ish-yeUow solid; S.G. |^ 5-6; deoxidised (to 
 BijOa) and dissolved by fairly cone. HNOjAq, 
 or HCLAq, more slowly by cone. H2S04 ;_ slightly 
 deoxidised by contact with water in direct 
 sunlight, oxidised to BijOj.ajHjO by CI inpresenoe 
 of hot cone. KOHAq ; is not oxidised by ozonised 
 at 100°-140°; heated in CI gives BiCl, and a 
 little BijOjCls ; heated in Br gives BiBr, and con- 
 siderable quantity of Bi„0,3Br,. Heated in CO 
 reduction begins at abt. 105° and the change to 
 BijOa is complete at about 245°-250° ; with H 
 the corresponding temperatures are abt. 200° 
 and 265°, respectively ; heated in air or in the 
 temperatures are abt. 240° and 320°, respectively. 
 Neither of the hydrates exhibits any decided 
 acidic functions. 
 
 BlSMUIHIO OXIDE, and HyDKATE, BijOj 
 
 {Bismuth peroxide). Bi205.H20 (Bismuthio 
 acid). S.G. BijOs 5-917 (Brauner a. Watts, P.M. 
 1881. 62). S.V.S. 42. S.G. Bi205.H20 5-76. 
 
 Preparation. — BijOj, or BiOjH,, or BiOCl, is 
 suspended in about 10 parts of cone. KOHAq, 
 S.G. about 1-38, the liquid is kept nearly 
 boiling and CI is passed in until a dark-red 
 homogeneous solid is formed ; this solid is washed 
 with hot water until the washings do not change 
 the colour of red litmus paper and every trace of 
 chloride is removed, it is then warmed for a 
 very short time with a little cone. HNOjAq 
 until its colour is scarlet, washed repeatedly and 
 quickly with dilute HNOjAq, each quantity of 
 acid being more dilute than the preceding, and 
 then with cold water until every trace of acid is 
 removed. If the solid is now dried over 
 H2S04, Bi205.H20 is obtained; if this is dried 
 at 120° BijOj remains (Pattison Muir, 0. J. 
 39,22). 
 
 Properties and Reactions. — A red, heavy 
 powder ; combines with water to form Bi205.HjO ; 
 in contact with much water is slowly deoxidised 
 with production of hydrates of Bi204 and BijO,; 
 also deoxidised by hot dilute HNOjAq, giving 
 first Bi204.2H20, and then hydrates of BijO,. 
 Deoxidised to 81^04 by heating in current of air 
 or oxygen at about 250°, and to Bi20j by heating 
 in the same gases to about 305° ; reduction in 
 CO begins at about 70°, in H at about 100° ; 
 reduction to BijOi is complete in H current at 
 about 215°, and to Bi203 at about 255°. Beacta 
 with CI, and Br, to give BiClj and a little 
 BijOjCla, and BiBr, and a little Bi,iO,^r„ 
 
BISMUTH. 
 
 616 
 
 reapeotively. Does not exhibit any decided 
 aoidio functions ; BijOj-HjO, however, dissolves 
 in about 100 parts of boiling KOHAq so con- 
 centrated that solidification begins the moment 
 the lamp is removed ; on cooling, dissolving in 
 as little water as possible, and nearly neutralising 
 by HOlAq (or by exposure to air) yellowish- 
 white solids are obtained from which all potash 
 is removed only by very long-continued washing 
 with boiling water. The solids dried at 100° 
 contain a little water, Bi, and generally rather 
 more than is required by Bi^Os. Solutions of 
 BijOj.HjO in very cone, boiling KOHAq, there- 
 fore, probably contain compounds of the form 
 JcBijOs.yKjO. In the preparation of BijOs the 
 very cone. KOHAq dissolves a little of the BijOj 
 as this is formed ; on nearly neutralising with 
 HClAq a white pp. is obtained, which, after long- 
 continued washing with boUing water, consists 
 of BijOj.SHjO (Pattison Muir a. Carnegie, G. J. 
 51, 77). In the preparation of Bi^Oj a por- 
 tion of the potash is very obstinately retained ; 
 the whole of the potash can scarcely be removed 
 by washing with boiling water : compounds of 
 the form xBip^.yK.jd are probably formed, but 
 every attempt to isolate these bodies has failed. 
 
 Bismuth, Ozyhaloid compounds of. Oxy- 
 bromides, oxychlorides, oxyiodides, and an oxy- 
 fluoride, of bismuth have been prepared. All 
 the haloid compounds BiXj, where X = CI, Br, 
 or I, are oxidised by heating in air ; only a 
 very little BiOI is produced by long-continued 
 heating Bil, ; BiBr, gives BisOisBrj, as BiClj 
 gives BijOjCl,. The same oxyhaloid compounds 
 are formed by the reaction between N oxides, 
 (from starch and hot HNOjAq) and hot BiXj : 
 the oxidation is carried furthest in the case of 
 BiBr,, in this case the whole or nearly the 
 whole of the haloid compound may be oxidised. 
 The most stable haloid compounds towards 
 oxidisers are BiPj and Bil.. 
 
 OxYBBOMTDES. Three oxybromides are known : 
 BiOBr, Bi„0,3Br„ and BisO.sBrs. 
 
 Bismuthyl bromide, BiOBr, is produced by 
 the action of water on BiBr, ; or by heating 
 together BijOj and BiBrj ; or by dissolving 
 BijOj in HBrAq (BiBr, is formed in solution) 
 and adding Bi^Oj little by little. It is a white 
 amorphous powder ; S.G. |^ 67 ; insoluble in 
 water ; unchanged when heated to redness ; 
 mixed with charcoal and heated in dry CI, 
 BiClj is formed; reacts with cold HClAq to 
 form BiCla and BiBrj, with cold HIAq to form 
 Bil, and HBrAq, and with hot HFAq to form 
 BiBr,, BiOF and BiPa.SHP. BiOBr heated 
 in NH3 is reduced to Bi, and a little 
 ajBLBra-T/NHj is formed, x probably = 2 and y 
 probably = 5 (Pattison Muir, 0. J. 29, 144). 
 
 The oxybromide Bii.OisBr, is produced by 
 heating dry Bi^O, with excess of Br for some 
 hours and removing unoombined Br by warming 
 in free contact with air. It is a cream-coloured, 
 non-deliquescent, amorphous powder : un- 
 changed by heating in air ; unacted on by 
 water ; dissolved by warm HClAq and HNOjAq 
 (P.M., O.J. .HI, 24). 
 
 The oxybromide Bifiy^^c^ ia produced (1) by 
 slowly subliming BiBrj in contact with a little 
 air; (2) by passing N oxides (obtained by 
 heating stwch and HNO,A(j|) into melted BiBr, j 
 
 in the first reaction only a little of the BiBrj is 
 oxidised, in the second reaction most of the 
 BiBr, is oxidised. In either case the product is 
 washed with water and dried at 100°. This 
 oxybromide is a . grey, lustrous, crystalline, 
 powder ; unchanged by water, or by heating to 
 redness ; soluble in HClAq and cone. HNOjAq ; 
 slowly reduced by H, finally giving Bi ; heated 
 in dry NH3, Bi remains, and a greyish-green 
 sublimate of 2BiBr3.5NH, is formed (P. M., 0. J. 
 30, 12 ; 31, 24 ; 32, 40). 
 
 OxvoHLOEiDES. Three oxychlorides, BiOCl, 
 BijOjClj, Bi^OjCl, (or Bi^OsOlJ, are known. 
 
 Bismipthyl chloride, BiOCl, is formed by 
 adding water to BiClj in a little HClAq ; or by 
 pouring Bi.SNOj in HNOjAq into dilute NaClAq ; 
 or by reacting on excess of Bi^O, with very 
 dilute HClAq ; or by digesting a solution of 
 BiCl, in HClAq with excess of Bi^O,. The pp. 
 is washed with cold water and dried at 100°.' 
 This compound is a white, lustrous, crystalline, 
 powder (known commercially as ' pearl white ') 
 S.G. ^ 7-2. Eeaots with cold HBrAq to give 
 BiCl, and BiBrj ; with cold HIAq to give BiCl, 
 and Bil, ; with hot HFAq to form BiClg, BiOF, 
 and BiFj.SHP. Eeduced to BiClj by heating 
 with charcoal in dry CI (Jaoquelain, J.pr. 14, 1 ; 
 Arppe, P. 64, 237 : Oesten, P. 110, 428 ; Heintz, 
 P. 68, 55 ; Pattison Muir, C. J. 39, 37). 
 
 The oxychloride BijOjClj is said to be pro- 
 duced by heating BiOCl to redness (Arppe). 
 
 The oxychloride Bi30.^Cl3 is formed in small 
 quantities by slowly subliming Bid, in contact 
 with a little air, and in large quantities by 
 passing N oxides (by heating starch with 
 HNOjAq) into melted BiCl3. The analytical 
 numbers agree fairly with BisOjClj and also 
 with Bi^OjClj. The compound is a yellowish- 
 white, hard, crystalline, solid; unchanged in air, 
 or by water, or by heating to redness ; soluble in 
 hot HClAq or HNOjAq ; boiled with NaOHAq, 
 BijOj and NaClAq are formed (P. M., 0. J. 32,40). 
 
 OxTFLUoKiDE. Only one is known. Bismuthyl 
 fliwride, BiOF, is obtained by heating BijO, with 
 large excess of HFAq so long as any reaction 
 occurs, boiling the residue with water until every 
 trace of acid is removed, and drying at 100° ; if 
 the washing is conducted with cold water until 
 nearly neutral, BiOF.2HF remains ; when this ' 
 is strongly heated in a closed Pt crucible, BiOP 
 is obtained in crystalline form. The liquid ob- 
 tained by boiling Bi^Oj with HFAq evaporated 
 at 100° gives BiFj.SHF ; when this salt is boiled 
 with water it is slowly decomposed to BiOF. 
 BiOF is a heavy, white, crystalline, powder; 
 S.G. 13 7-55. With HF it forms the double 
 compound BiOF.2HF. Eeacts with cold HClAq 
 to form BiClj and HFAq; with HBrAq to form 
 BiBrj and HFAq ; with HIAq to form Bil, and 
 HFAq (P. M., HofEmeister a. Bobbs, O. J. 39, 21). 
 
 Oxyiodides. Bismuthyl iodide, BiOI, is pro- 
 duced by boiling Bilj with HjO in small quan- 
 tities ; by subliming Bil, in air ; or, also in small 
 quantities only, by reacting with N oxides (from 
 starch and hot HNO,Aq) on hot Bil,. BiOI is 
 a heavy, red, crystalline powder, unchanged 
 by water, or by heating in air ; by long-continued 
 heating to bright redness in air a very little 
 BijO, is formed; reacts with HClAq, HBrAq, 
 and HFAq, similarly to bismuthyl chlorida 
 
616 
 
 BISMUTH. 
 
 and bromide (Schneider, J. pr. 74, 42i ; P. M., 
 H. a. B., I.C.). 
 
 Another oxyiodide, probably 3BiOI.4Bi20a, 
 is obtained as a yellow powder by pouring a 
 dilute solution of BiSNOj into KIAq mixed with 
 Na02H30,Aq {Fletcher a. Cooper, Ph. 1882). 
 
 Bismuth, Oxysulphide of. According to 
 Hermann {J. pr. 75, 452) the compound 
 BijOjS, is formed by heating 1 part S with 3-55 
 parts BijOj to low redness in a retort ; S.G. 6'3. 
 A compound of Bi, S, and 0, occurs as Earelinite 
 (said to be Bi^OjS). 
 
 Bismuth, Fhosphide of. No definite com- 
 pound has been isolated. Berzelius (Lelwbuch, 
 2, 582 [5th ed.]) says the two elements do not 
 unite directly, but that a phosphide is formed 
 by leading PH, into Bi.SNOj solution. 
 
 Bismuth, Salts of. These compounds are 
 obtained in a few cases by the reaction between 
 Bi and an acid, e.g. Bi.3NOs, but more generally 
 by using Bifi^.xH.fi in place of Bi, or by double 
 decomposition from Bi.3N03 in HNOaAq or 
 BiClj in HGlAq. Bismuth salts are insoluble in 
 water ; they are decomposed by water with 
 production of so-called basic salts : the salts of 
 Bi may indeed be arranged in two classes, 
 normal and basic, as types of which may be 
 taken the nitrates Bi.BNO, and BiO.NOj, re- 
 spectively. Many of these basic salts are most 
 simply regarded as derived from acids by re- 
 placement of H by BiO ; they are often called 
 bismuthyl salts : other basic salts, however, 
 at present at any rate, are best represented 
 as compounds of acid-forming oxides with 
 BijOj. All the basic nitrates for instance, and 
 many of these salts are known, belong to the 
 general form a;Bi203.i/N205.H20. The salts ob- 
 tained by reactions between acids and the oxides 
 BijO, and Bi^Os are the same as those which 
 are formed when BijOj is used. The more 
 important salts of Bi are the nitrates and sul- 
 phates, also bromate, chlorate, oxalates, phos- 
 phates, tartrates, &o. (v. Nitkates, Sulphates, 
 &o. &o.). 
 
 Bismuth, Selenide of. Bi^Sej. Black, lus- 
 trous, metal-like, powder; S.G. 6-82. Obtained 
 by passing HjSe into Bi.SNOj in as little HNOsAq 
 as possible, or by heating together 1 part Se and 
 1'8 parts Bi, and repeatedly melting the pro- 
 duct in contact with Se. Insoluble in solutions 
 of alkalis or alkali-sulphides ; decomposed by 
 HNOjAq ; gives up Se when heated. Combines 
 with BiCl, {v. infra) (Berzelius ; Schneider, P. 
 94,628). 
 
 Bismuth, Seleuochloride of, BiSeCl. 
 ( = Bi2Se3.BiCl3). Formed by adding powdered 
 BijSej to molten 2NHiCl.BiCla. Steel-grey, 
 needle-shaped, crystals. Heated in CO^ is 
 separated into BijSe., and BiClj (Schneider, l.c.). 
 
 Bismuth, Sulphides of. One well-marked 
 sulphide of Bi, Bi^Sj, is known ; another, 
 BijSj, corresponding to the oxide Bi^Oj, probably 
 exists. Attempts to prepare a sulphide with 
 more S than BijSj have failed (Pattison Muir, 
 C. J. 33, 192). Sulphide of bismuth does not 
 react with more positive sulphides as a salt- 
 forming compound (comp. Schneider, Z. [2] 5, 
 630 with P. M., O. J. 33, 192). 
 
 EisJiDTH TBisuLPHtDE. BijSj. Ocours native 
 as bismuth glance. S.G. 6"6. Bhombio forms, 
 a:6 = X;-9884; isomorphous with AsjS, and 
 
 Sb^Sj. Obtained by heating a mixture of 1 part 
 S with 4i parts Bi till a grey crystalline mass 
 is formed, and then repeatedly heating this 
 with a little S : also by passing HjS into an 
 acid solution of a Bi salt. If the pp. thus 
 obtained is heated with an alkali-sulphide 
 solution to 200° the Bi^Sj is said to become 
 crystalline. Steel-grey, crystaUine, lustrous, 
 solid: strongly heated it is separated into Bi 
 and S ; unacted on by alkali or alkali-sulphide 
 solutions. 
 
 Bismuth Disulphide. 2Bi2S.2.H20. Said to 
 be ppd. by HjS from alkaline solutions of Bi^Oj 
 Sciineider (P. 97, 480) dissolved 8 grams Bi tar- 
 trate in the necessary quantity of KOHAq, added 
 air-free water to make up to 1500 c.o., then 
 2 grams SnClj in KOHAq, and passed in air-free 
 H.jS until the liquid became colourless. He 
 washed the black pp. with KOHAq and then 
 with HjO (air-free), and dried at 100°. A black 
 powder ; becomes lustrous by compression ; 
 decomposed by heating into Bi and BijSj, by 
 HClAq into Bi, BiCls, and H^S. 
 
 Bismuth, Sulphochloride of, v. Bisuuth, 
 
 ThIO-HAIjOID COMPOtTNIlS OF. 
 
 Bismuth, Sulphoiodide of, v. Bismuth, Thio- 
 
 HAIOID COMPOUNDS OF. 
 
 Bismuth, Sulphocyanide of, Bi(SCN)3, v. 
 Cyanides. 
 
 Bismuth, Tellaride of. No deiinite com- 
 pound has been isolated; telluric bismuth, 
 approximately BijS3.2Bi2Te3, occurs native. 
 According to Berzelius (Lehrbuch, 2, 583 
 [5th ed.]) the two elements may be melted 
 together in all proportions. 
 
 Bismuth, Thiohaloid compounds of. Only 
 two are known : BiSCl, and BiSI. The former is 
 obtained by the direct reaction between BiCl, 
 and S, but Bil^ and S do not react together ; 
 when BiBrj and S are heated together there are 
 indications of the formation of a thio- compound, 
 but none has yet been isolated {v. P.M.,H. a.E., 
 C. J. 39, 21). The thio- compounds are much 
 less stable than the corresponding oxy- com- 
 pounds ; V. Bismuth, oxthaloid compounds of. 
 
 Bismuth Thioghloeide (sulphochloride) BiSCl. 
 Obtained by heating S with BiCl,, or by adding 
 powdered Bi^Sj to molten 2NH,Cl.BiCl3, and 
 washing the product with very dilute HClAq. 
 Small, metal-like, greyish, needles ; easily de- 
 composed into its constituents, e.g. by heating 
 in CO2, by H, by HClAq or HNOjAq, and by 
 alkalis (Schneider, P. 93, 464). 
 
 Bismuth Thio-iodide {sulpho-iodide),'BiSl,ii 
 said to be formed, as long needles, by strongly 
 heating I, S, and Bi.^Sj, placed in alternate 
 layers in a large crucible (P. 110, 147). 
 
 Bismuthic Acid and Bismuthates (so called). 
 BijOj.HjO is sometimes called bismuthic acid ; 
 bodies obtained by dissolving BijOj in much 
 molten KOH, or by saturating with CI cone. 
 KOHAq holding Bi^O, in suspension, have been 
 described as bismuthates. But later experi- 
 ments have shown that these bodies cannot be 
 isolated although they probably exist in presence 
 of much potash. The acidic functions of 
 Bi.jOi.H^O are extremely feeble, 0. Bismuihm 
 oxide under Bismuth, oxides or, p. 515. 
 
 M. M. P. M. 
 
BIURET. 
 
 517 
 
 BISMUTH, ORGANIC DERIVATIVES. 
 
 Bismuth, mono'inethyl compounds. 
 
 Di-chloride BiMeClj. [242°]. Obtained by 
 adding BiMe, to an acetic acid solution of BiCla. 
 White plates. M. sol. alcohol and acetic acid, 
 insol. ether (Marquardt, B. 20, 1520). 
 
 Di-bromide BiMeBiv [214°]. Formed 
 by mixing ethereal solutions of BiMej and BiBrj. 
 Yellow powder. SI. sol. alcohol, benzene, and 
 acetic acid, insol. ether (M.). 
 
 Di-iodide BiMeL. [225°]. Formed by 
 heating BiMoj with methyl iodide at 200° (M.). 
 Glistening red crystals. Sol. alcohol, si. sol. 
 acetic acid, insol. ether. 
 
 Oxide BiMeO. Formed by adding NH, to 
 an alcoholic solution of the double compound of 
 BiMeBrj and BiBr,, which is obtained as a yellow 
 crystalline pp. on mixing ethereal solutions of 
 BiMCj (1 mol.) and BiBr, (2 mols.) (Marquardt, 
 B. 20, 1522). White powder. Insol. water. Dis- 
 solves in KaOH and in dilute HKO,. Ignites in 
 the air if gently warmed. 
 
 Bismuth di-methyl compounds. 
 
 Chloride BiMc^Cl. [116°]. Formed by 
 passing chlorine into a solution of BiMcj in 
 petroleum-ether, cooled in a freezing-mixture. 
 White micro-crystalline powder. V. sol. alcohol, 
 insol. ether (Marquardt, B. 20, 1519). 
 
 Hydroxide BiMe2(0H). Formed by the 
 action of water upon the double compound of 
 BiBrj and BiMejBr, which is ppd. as an oily 
 liquid by mixing ethereal solutions of equal 
 mols. of BiBrj and BiMej. Crystalline solid. 
 Ignites in the air spontaneously. Dissolves in 
 aqueous NaOH. Decomposed by aqueous HCl 
 with evolution of CH, (Marquardt, B. 20, 1523). 
 
 Bismuth tri-methide BiMe,. Tri-methyl- 
 bismuthine. (110°). S.G. 2-3 at 18°. Obtained 
 by slowly adding an ethereal solution of bismuth 
 bromide (2 mols.) to an ethereal solution of zinc 
 methide (rather more than 3 mols.). Mobile 
 refractive liquid, of unpleasant pungent odour. 
 In the air it fumes and rapidly oxidises, when 
 heated in the air it explodes violently. Volatile 
 with steam, but decomposes on long boiling 
 with water. Dilute H^SO, or HNO3 have little 
 action upon it, but cone. HOI decomposes it 
 with evolution of CHj and production of BiClj. 
 It does not combine with alkyl haloids or with 
 halogens. The latter replace Me forming 
 BiMe.,Cl, &c. (Marquardt, B. 20, 1517). 
 
 Bismuth mono-ethyl compounds. 
 
 Chloride BiEtClj. Prepared by adding 
 alcoholic HgCL^ to alcoholic BiEtj (q. v.). 
 
 Iodide BiEtlj. From the chloride and KI. 
 Golden, six-sided plates. 
 
 Oxide BiEtO. From the iodide and potash. 
 Yellow amorphous powder, takes fire in air. 
 
 Nitrate BiEt(N03)2. From the oxide and 
 HNO,. Crystalline tufts. 
 
 Bismuth di-ethyl bromide BiEtjBr. Formed 
 (jy dropping bromine into a cooled solution of 
 BiEtjinpetroleimi-ether. White powder. Y. sol. 
 alcohol, insol. ether. Ignites in the air on warm- 
 ing (Marquardt, B. 20, 1520). 
 
 Bismuth tri - ethide BiEt3. Tri - ethyl- 
 bismuthine. (107°) at 79 mm. S.G. 1-82. 
 
 Preparation. — 1. An alloy of Bi and K is 
 made by strongly heating bismuth (5 pts.) with 
 cream of tartar (4 pts.). This alloy is treated with 
 EtI (Breed, A. 82, 108).— 2. Obtained by slowly 
 
 adding an ethereal solution of bismuth bromide 
 (2 mols.) to an ethereal solution of ZnEtj (rather 
 more than 3 mols.) (Marquardt, B. 20, 1519). 
 
 Properties. — Stinking oil. It cannot be dis- 
 tilled at ordinary atmospheric pressure, for on 
 heating to 150° it detonates violently ; volatile 
 with steam. Fumes and takes fire in air. V. sol. 
 alcohol, ether, and acetic acid. Its ethereal 
 solution exposed to air deposits BijOsH^O. 
 Forms unstable compounds with non-metals. 
 BiEt3S.Bi2S3 is a yellow solid, insoluble in water, 
 soluble in yellow ammonium sulphide. BiEtj 
 throws down calomel from alcoholic HgCl^, but 
 when alcoholic HgClj is added to alcoholic 
 BiEt3, crystals of BiEtClj may be got : 
 BiEt3 -I- 2HgOl2 = 2HgEtCl + BiEtCl^ (Dunhaupt, 
 
 A. 92, 371). 
 
 Bismuth-tri-phenyl Bi(0jH5)3. Tri-phenyl- 
 bismuthine. [82°]. S.G. 1-5851 at 20°. Formed 
 by heating bromo-benzene containing some acetic 
 ether with an alloy of sodium and bismuth 
 (10 p.c. Na). Colourless needles or tablets. Sol. 
 hot alcohol, sparingly in cold, v. sol. ether and 
 petroleum ether. By boiling with cone. HCl it 
 is completely decomposed into benzene and bis- 
 muth chloride. It combines with Cl^ forming 
 the chloride (CjH5)3BiClj which crystallises in 
 thick prisms, [140°], sol. hot alcohol, si. sol. 
 ether and cold alcohol, v. sol. benzene, not 
 decomposed by cone. HCl. The bromide 
 (CuH5)3BiBr2 forms long prisms, [119°], v. sol. 
 benzene, si. sol. alcohol and ether (Michaelis a. 
 Weitz, B. 20, 54). 
 
 BITTER AI.M0ND OIL v. Aljionds and 
 Bekzoic aldehyde. 
 
 BIURET C^H^NjO, i.e. NH„.C0.NH.C0.NH3. 
 AUophajmmide. Moi. w. 108. [190°]. S. 1-25 
 at 0° ; 1-54 at 15° ; 45 at 100°- 
 
 Formation. — 1. Urea is heated at 150°-170° 
 untU the melted mass becomes pasty and ceases 
 to give off NH3. The product is extracted with 
 hot water (Wiedemann, P. 74, 67 ; Hofmann, 
 
 B. 4, 262). — 2. By passing the vapour of cyanic 
 acid into melted urea (Finck, A. 124, 331). — 
 3. Urea is treated with chlorine till the mass 
 becomes pasty (Hoppert a. Dogiel, Z. [2] 3, 691 ; 
 B. 4, 475).— 4. By the action of NHj on allophanio 
 ether (H. a. D.). — 5. By heating ' amido-di- 
 cyanic acid ' (p. 1G3) with H SOj (1 pt.) and water 
 (2 pts.) at 60°-70° (Baumann, B. 8, 708).— 
 6. By the action of NH3 upon tri-bromo-acetyl- 
 urea (Baeyer, A. 130, 154). — 7. By heating urea 
 with PCI3 at 100° (Weith, B. 10, 1743).— 8. By 
 mixing dilute solutions of urea and potassio 
 cyanate, acidifying with acetic acid, evaporating, 
 adding a little HjSOj and extracting with alcohol 
 (Drechsel, J. pr. 123, 472).— 9. By electrolysis 
 of a solution of NHj, using carbon electrodes 
 (MiUot, Bl. [2] 46, 244). 
 
 Properties. — Long needles (containing aq) ; 
 or long anhydrous laminaj (from alcohol). Split 
 up by heat into NH, and oyanurio acid. Dis- 
 solves unchanged in cold cone. HjSO,. Its 
 solution is not ppd. by salts of lead or silver or 
 by tannin. A little CuSO, followed by KOH 
 gives a deep violet solution. 
 
 Reactions.— 1. At 120° it absorbs HCl form- 
 ing B'jHCl which at 160°-170° in a current of 
 HGl gives H^O, CO, guanidine, cyanurio acid, 
 and urea. — 2. Boiling cone. HClAq forms NHj, 
 urea, and guanidine. — 3. Boiling baryta-water 
 
618 
 
 BIURET. 
 
 forms CO2, NH,, and urea.— 4. With NaClO it 
 evolves ^ of its nitrogen, with NaBrO it evolves f 
 (Fentou, 0. J. 35, 14).— 5. HNO3 gives CO^ and 
 NjO in equal volumes (Franchimont, B. T. G. 
 6, 216).— 6. COCl,at 60° forms carbonyl-di- 
 biuret (C2H,Ns02)2CO (E. Schmidt, J. ^ir. [2] 6, 
 47) ; a crystalline powder, v. si. sol. cold water, 
 insol. alcohol and ether. This body is converted 
 by boiling baryta- water into urea and cyanurio 
 acid ; and by COCI2 at 140° into cyanurio acid ; 
 Hg(N0j)2 gives, in hot dilute solution, a pp. of 
 C,H,N,0,3HgO. 
 
 Salts. — B'jHCl; decomposed by water. — 
 AgjC^HjNaOj : ppd. by adding AgNOj (2 mols.) 
 and NHjAq to a saturated aqueous solution 
 of biuret (1 mol.) ; sol. HNO3 and NHjAq 
 (Bonn6 a. Goldenberg, JB. 7, 287). — Cyanurate 
 B'CsNsHjOj : needles ; formed on crystallising 
 biuret from water. It has probably been mis- 
 taken for urea cyanurate from which it differs 
 in yielding with baryta water, barium cyanurate 
 and biuret, in giving off 3 atoms of nitrogen as 
 ammonia when heated with barium hydrate 
 (urea cyanurate yields 2 atoms), in giving off 
 14'8 p.c. nitrogen with sodium hypobromite, 
 (while urea cyanurate gives 11-5 p.c, both re- 
 sults corresponding to 2 atoms nitrogen) 
 (Herzig, M. 2, 411). 
 
 Biuret dieyanamide C^^fi^ i.e. 
 NH(C0.NH.C(NH).NHj)2. From acetyl -urea 
 (2 pts.) and guanidine carbonate (5 pts.) at 
 110°-150° (Easinski, J. pr. [2] 27, 157). Amor- 
 phous substance, v. sol. acids and fixed alkalis, 
 insol. NHjAq. Does not give the biuret reaction 
 with CUSO4. 
 
 BIXIN CjgHj^Os. [176°]. A colouring mat- 
 ter contained in annatto seeds {Bixa orellana) 
 (Preisser, A. 52, 382 ; Girardin, J. Ph. [3] 21, 174 ; 
 BoUey a. Mylius, Bl. [2] 3, 230 ; Stein, J. pr. 
 102, 175). 
 
 Preparation.—Annatio (1,500 g.) is digested 
 at 80° with alcohol (2,500 g. of 80 p.c.) with 
 addition of NajCOj (150 g.) ; after filtration, the 
 residue is again digested with alcohol (1,500 g. 
 of 60 p.c). The mixed filtrates are ppd. by 
 adding half their bulk of water and cone 
 NajCOaAq; the ppd. sodium-bixin is dissolved 
 in alcohol (60 p.c.) and re-ppd. with NajCOgAq. 
 The sodium-bixin is then decomposed by HCl 
 (Eti, B. 11, 864 ; 7, 446). 
 
 Properties. — Minute red leaflets ; insol. water, 
 b1. sol. alcohol, benzene, CSj, and acetic acid, 
 v. e. sol. ether. Cone. HjSOj forms a bright 
 blue solution, whence water gives a dark green 
 pp. It reduces cold Fehling's solution. 
 
 Reactions. — 1. Distillation with zinc dust 
 gives m-xylene, ethyl-toluene, and an oil C^H,, 
 (270°-280°). Eeduoed by sodium-amalgam to 
 
 Salts. — C29H3sNa052aq : lustrous red crys- 
 tals, V. sol. water, insol. alcohol, and ether. 
 — CnHjjNaaOs 2aq : dull red powder. — 
 CjsHj^kOs 2aq.— CnHjjKjOs 2aq. 
 
 BLEACHING-POWDER v. hypochloeites, 
 under Chlokine, oxtaoids op. 
 
 BLOOD. In vertebrates, the blood is a some- 
 what viscous, and to the naked eye homo- 
 geneous, red liquid. The blood which leaves 
 the lunga 01 gills is of a bright scarlet- colour, 
 and that in the systemic veins of a purplish 
 hue, which on exposure to the air, or on shak- 
 
 ing with oxygen, becomes of the bright arterial 
 scarlet colour. This differfence in tint is due to 
 the amount of oxygen present in combination 
 with the red pigment hsemoglobin ; in the lungs 
 a loose combination called oxy-hsemoglobin ia 
 formed which is scarlet ; in the tissues this oxy- 
 gen is given up, and the blood returning to the 
 heartis of the purplish colour due to hemoglobin. 
 
 Specific Gravity. Eoy {Proc. Physiol. Soc. 
 1884) has introduced a method for ascertaining 
 the specific gravity of living blood. A drop of 
 blood is introduced into a mixture of glycerin 
 and water of known specific gravity ; if the drop 
 tends to rise or sink, it is assumed that it is of 
 lower or higher specific gravity than the liquid 
 in which it is placed. The average specific 
 gravity of human blood thus found was 1-060. 
 Defibrinated human blood has an average 
 specific gravity of 1-055. Pfliiger {Pflilger's 
 Archiv, i. 75) found the specific gravity of dog'a 
 blood to be 1-060 ; and Gsohleidlen that of 
 rabbit's blood 1-048. 
 
 Characters. — Blood is always feebly alkaline 
 in reaction (Kuhne, Virchow's Archiv, 33, 65 ; 
 Liebreich, B. 1, 48 ; Sohafer, Journal of Physio- 
 logy, 3, 292). Under the microscope the blood 
 is seen not to be a homogeneous red liquid, but to 
 consist of a nearly colourless liquid, the plasma 
 or liquor sanguinis, holding in suspension large 
 numbers of solid bodies, the corpuscles. These 
 corpuscles are of two kinds, the coloured and 
 the colourless. 
 
 Bed corpuscles. These owe their colour to 
 hemoglobin, and are much, more numerous 
 than the white corpuscles. They vary in size 
 and structure in different groups of the vertebrate 
 sub -kingdom. In Mammalia, with the exception 
 of the Camelide, they are biconcave, circular 
 discs ; they have no nucleus except during em- 
 bryonic life ; and they have a tendency to run 
 into rouleaux when the blood is at rest, but if it 
 is disturbed they readily become separated. In 
 the Camel tribe they have an elliptical outline. 
 Their average diameter in mammals is •007--008 
 millimetre and about one-fourth of that in 
 thickness; there are very slight variations 
 in different classes of mammals. In birds, 
 reptiles, amphibians, and fishes, the red cor- 
 puscles are biconvex, oval discs, with a nucleus ; 
 they are largest in the amphibia. C Schmidt 
 gives the specific gravity of red blood corpuscles 
 as 1-089, Weloker as 1-105. 
 
 According to C. Schmidt, 1,000 parts of 
 moist red corpuscles contain — 
 
 Water 
 
 s°"^^ { E^ : 
 
 Organic 
 
 688 parts. 
 303-88 „ 
 8-12 „ 
 
 According to Hoppe Seyler and Jiidell {Med. 
 Chem. TJntersuchungen, Heft iii. p. 386) 100 
 parts of dried corpuscles contain — 
 
 Human blood Dog'a Goose's 
 
 I. II. blood blood 
 
 Proteids 12-24 5-10 12-55 36-41 
 
 Hffimoglobin 86-79 94-30 86-50 62-65 
 
 Lecithin 0-72 0-35 0-59 0-46 
 
 Cholesterin 0-25 0-25 0-36 0-48 
 
 The nuclei of the red corpuscles consist 
 mainly, according to Lauder Brunton, of nuclein, 
 a substance very akin in its properties to mucin 
 (Journal of Anat. and Physiology, 2nd series, 
 
BLOOD. 
 
 519 
 
 rol. 3, p. 91). The mineral constituents ol the red 
 corpuscles have been investigated by 0. Schmidt, 
 and the following tables contrast those of the 
 red corpuscles with those of the plasma in man. 
 
 1000 parts of moist corpuscles yield — 
 Mineral matter (exclusive of iron, which 
 
 is contained in the heemoglobin 
 Chlorine 
 
 Sulphuric anhydride 
 Phosphorus pentoxide 
 Potassium 
 Sodium . 
 Calcium phosphate 
 Magnesium phosphate 
 
 1000 parts of plasma 
 Mineral matter 
 Chlorine 
 
 Sulphuric anhydride 
 Phosphorus pentoxide 
 Potassium 
 Sodium . 
 Calcium phosphate 
 Magnesium phosphate 
 
 8-120 
 1-686 
 0-066 
 1-134 
 3-328 
 1-052 
 0-114 
 0073 
 
 8-550 
 3-640 
 0-115 
 0-191 
 0-B23 
 8-341 
 0-311 
 0-222 
 
 The remarkable difference in the distribution 
 of potassium and sodium seen in the above does 
 not, however, hold for most animals as the 
 following table shows (Gamgee, Physiological 
 Chemistry, p. 122). 
 
 Blood Cells. 
 
 K. Na. CI. 
 
 Man 40-89 9-71 21-00 
 
 Dog 6-07 86-17 24-88 
 
 Cat 7-85 35-02 27-59 
 
 Sheep 14-57 88-07 27-21 
 
 Goat 37-41 14-98 31-73 
 
 
 Liquor Sanguinis. 
 
 
 
 K. 
 
 Na. 
 
 01. 
 
 Man 
 
 5-19 
 
 87-74 
 
 40-68 
 
 Dog 
 
 3-25 
 
 39-68 
 
 37-81 
 
 Cat 
 
 5-17 
 
 37-64 
 
 41-70 
 
 Sheep 
 
 6-56 
 
 38-56 
 
 40-89 
 
 Goat 
 
 3-55 
 
 37-89 
 
 40-41 
 
 Probably the only gaseous constituent of the 
 red blood corpuscles not in a state of chemical 
 combination is carbonic acid. 
 
 Blood tablets. Besides the red corpuscles, 
 a number of colourless discs of -002--003 milli- 
 metre diameter are also seen: they are also 
 called heematoblasts {Blutplattchen ofBizzozero). 
 By some they are supposed to be stages in the 
 development of red corpuscles ; by others to 
 take part in the formation of fibrin. Wooldridge 
 considers them to be identical with the proteid 
 he calls fibrinogen a, which can be precipitated 
 from liquor sanguinis by exposure to cold. 
 
 Colourless corpuscles or leucocytes. These 
 are animal cells, and consist of nucleated 
 masses of protoplasm, more or less granular, 
 and exhibiting during life contractility, the 
 movements so produced being called amoeboid. 
 They are not constant in size, but in man they 
 average about O'Ol millimetre ; they are some- 
 what larger in the lower vertebrate groups. In 
 mammals there is on the average one white or 
 colourless corpuscle to 330 or 350 red ones. 
 
 Our knowledge of the chemical constituents 
 of the white corpuscles is meagre ; they are 
 lighter than the red ones ; the great mass of 
 the protoplasm is undoubtedly proteid in nature ; 
 and the nucleus consists mainly of nuclein 
 
 (Miesoher, Med. Ohem. Untersuch., Heft iv., 
 p. 441). By micro-chemical investigation, the 
 presence of glycogen can often be demonstrated 
 by iodine, and of fat granules by osmic acid. 
 
 Coagulation of blood. Within a few minutes 
 after having been shed, blood passes first into 
 the state of a soft red jelly, which gradually 
 acquires greater consistence; and by the con- 
 traction of one of its constituents expresses a 
 fluid, the serum, in which the clot or crassa- 
 mentum ultimately floats. 
 
 Coagulation is due to the separation from 
 the blood plasma of a solid proteid substance 
 called fibrin. The clot consists of fibrin 
 entangling the corpuscles. By stirring blood, 
 or whipping it with twigs immediately after 
 it is shed, fibrin free from corpuscles adheres 
 to the twigs as a yellowish stringy mass. 
 Under the microscope, coagulation is seen 
 to consist of the separation of fijie filaments 
 from the plasma, which start from or entangle 
 the blood plates, and corpuscles. 
 
 Coagulation of the blood is hastened by ex- 
 posure to a temperature rather above that of the 
 body ; by contact with foreign matter, or by agita- 
 tion ; and by dilution with not more than twice 
 its volume of water. Coagulation is hindered or 
 prevented by exposure to a low temperature ; 
 by contact with living tissues, or by the addi- 
 tion of large quantities of neutral salts such as 
 sodium chloride, sodium sulphate, or magnasium 
 sulphate. When these precautions are taken, 
 the corpuscles sink, and the plasma can be 
 drawn off : in the last case mixed however 
 with salt solution, the inhibitory influence of 
 which on coagulation can be removed by diluting 
 the mixture with water ; fibrin is then formed. 
 
 Many theories have been held with regard 
 to the cause of the coagulation of the blood. 
 Nearly up to the end of the last century, the 
 clot was believed to be simply a mass of 
 adherent corpuscles. Hewson, 1772 {v. Hewson'g 
 works, edited by Gulliver, Sydenham Soc), was 
 the first to show that it was really due to the 
 separation of some substance from the plasma. 
 Buchanan (London Medical Oaeette, vol. 18) 
 showed that squeezed blood-clot had the power 
 of hastening the coagulation of the liquor peri- 
 cardii ; and as this power was espeoiaUy shown 
 by the buffy coat, he supposed that it was due 
 to the white corpuscles ; he compared the action 
 of these corpuscles to that of rennet on milk. 
 Denis (Mimoire sur le sang, 1859, p. 32), by 
 saturating the liquor sanguinis with sodium 
 chloride, obtained a proteid pp., which after 
 being redissolved in water underwent coagula- 
 tion. To this precursor of fibrin he gave the 
 name plasmine. A. Schmidt (Archiv f. Anat. 
 u. Physiol. 1861, 545) separated plasmine into 
 its two constituents, both proteids of the globulin 
 class, to which he gave the names fibrinogen 
 and fibrinoplastin or paraglobulin (now called 
 serum-globulin). He thought both of these sub- 
 stances were necessary for coagulation, and that 
 they united to form fibrin under the influence 
 of a ferment. This fibrin-ferment he prepared 
 from serum, by ppg. it with the serum proteids 
 by means of absolute alcohol ; after leaving the 
 pp. some months under alcohol, the proteids 
 were by this means rendered insoluble, while 
 the ferment could be extracted with water. 
 
590 
 
 BLOOD. 
 
 Gamgee {Journal of Physiology, 1879) obtained 
 (ibrin-feiment by extracting blood-clot with 
 8 p.c. sodium chloride solution. The extract 
 contained a small quantity of a globulin-like 
 proteid, and had very marked power in inducing 
 coagulation. Hammarsten (PflUger's Archiv, 
 14, 211; 17, 413; 18, 38; 19, 563) modified 
 Schmidt's theory by showing that paraglobulin 
 is not necessary for the formation of fibrin, but 
 that fibrinogen is the only true fibrin precursor 
 which under the influence of the fibrin ferment 
 is converted into fibrin. The presence of para- 
 globulin, however, hastens coagulation perhaps 
 by its combining with alkaline carbonates which 
 otherwise would impede the action of the fer- 
 ment: other proteids such as casein, or even 
 salts such as calcium chloride, will, however, take 
 its place. 
 
 The source of the fibrin-ferment seemii to be 
 the white corpuscles. Eauschenbaoh has pointed 
 out ( Ueber die Wechselwirhungen zwischen Pro- 
 toplasma und Blutplasma, Inaug. Diss. Dorpat, 
 1883) that leucocytes are of two kinds : o leuco- 
 cytes which are acted upon and disintegrated 
 by the plasma when the blood is shed, two of 
 the products of such action being paraglobulin 
 and fibrin ferment ; and jS leucocytes which re- 
 main unaltered. 
 
 The latest theory of the coagulation of the 
 blood is that of L. C. Wooldridge (Beitrage zur 
 Physiologie, Leipzig, 1887, 221). He injects 
 peptone into the circulation of an animal, and 
 kills it by bleeding ; the blood remains uncoagu- 
 lated for many hours, and the corpuscles are 
 removed by oentrifugalising ; if a substance con- 
 taining lecithin be then added to the peptone 
 plasma, coagulation occurs. By cooling peptone 
 plasma, a pp. is produced ; this consists of little 
 rounded discs similar to blood tablets ; this is 
 called fibrinogen A ; after its removal from the 
 plasma coagulation does not occur : the forma- 
 tion of fibrin is supposed to be due to the 
 lecithin contained in fibrinogen A combining 
 with fibrinogen B (Hammarsten and Schmidt's 
 fibrinogen). 
 
 Human blood yields from 2-2 to 2-8 parts of 
 fibrin per 1,000. 
 
 Serum. This is the plasma, minus the ele- 
 ments of fibrin. It contains three classes of 
 constituents; proteids, extractives, and salts. 
 The proteids consist of globulin and albumin. 
 Owing to the disintegration of the white corpus- 
 cles the globulin is rather more abundant than 
 in the plasma. The following table of Ham- 
 marsten's (PflUger's Arclivv, 1878) represents 
 the percentage of these substances in the serum 
 of some of the commoner mammals : 
 
 Seimm from Horse 
 « » Or 
 ., „ Maa 
 „ „ Babbit 
 
 Total Total Serum Serum 
 
 Solids Proteids Globulin Albumin 
 8-S97 7-257 4-566 2-r,77 
 8-965 7-499 4-109 3-329 
 9-207 7-019 3103 4-610 
 
 7-625 6-226 1-783 4-436 
 
 The globulin appears to be a single substance ; 
 it is coagulated by heat at 75° C. : by fractional 
 heat-coagulation, however, the serum albumin 
 can be differentiated in some animals into two, 
 in some into three proteids (Halliburton, Journal 
 of Physiology, 5, 152 ; Kauder, Arch.f. exp. Path, 
 u. Pharmac., 20, 411) ; in the cold-blooded 
 animals the total quantity of proteids in the 
 
 serum is much lower, the serum globulin iff 
 always greatly in excess of the serum albumin, 
 and the latter substance is not differentiabla 
 into several proteids by fractional heat-coagu- 
 lation (Halliburton, Journal of Physiology, 8, 
 319). 
 
 The extractives of serum are organic sub- 
 stances present in small quantities, which are 
 extracted by various liquids, especially by alco- 
 hol or ether. There is about 0-2 p.c. of fats 
 and oholesterin ; about -08 to 0-12 p.o. of glucose 
 (Pavy, Croonian Lectv/res on Diabetes, London, 
 1878) ; urea 0-02 to 0-04 p.o. ; and creatine, 
 creatinine, xanthine, hypoxanthine, uric acid, 
 and hippuric acid in still smaller quantities. A 
 yellow pigment is found dissolved in varying 
 quantities in the serum of most animals ; Ham- 
 marsten (Maly's Jahrbericht, 1878, 129), Mao- 
 Munn (Pr. 31, 231) and others have described 
 this as a bUiary pigment; Kxukenherg (Sitzungsb, 
 der Jenaischen Oesellsch. f. Med., 1885), and 
 Halliburton (Joum. of Physiology, 8, 324) have 
 described it as a lipochrome. 
 
 The salts of serum amount to 0-7 to 0-9 p.c. 
 
 Oases of the blood. From the blood as a 
 whole, or from the plasma, coloured corpuscles, 
 or serum, a mixture of carbonic acid, oxygen 
 and nitrogen can be separated. Oxygen is 
 present in much larger quantities than could be 
 held in simple solution in the blood, and is, in 
 fact, held in feeble combination with haemo- 
 globin; only a small part being in solution in 
 the liquor sanguinis. Carbon dioxide is partly 
 in a state of chemical combination, but chiefly 
 in a state of simple solution. It is contained 
 in great part in the liquor sanguinis, but in 
 part also in the corpuscles. The nitrogen is 
 held in simple solution in the liquor sanguinis. 
 Arterial blood of the dog yields for every 100 
 volumes 58-3 vols, of mixed gases composed of 
 22-2 vols, of oxygen, 34-3 vols, of carbonic anhy- 
 dride, and 1-8 vols, of nitrogen. The maximum 
 amount of oxygen observed has been 25-4 vols. 
 (Pfluger, Centralbl.f. d. med. Wissensch. 1868). 
 In venous blood, the nitrogen is the same as in 
 arterial, the oxygen is less in amount (from 8 
 to 12 vols, per 100 of blood), and the CO2 greater 
 (from 40-50 vols, per 100 of blood). 
 
 Lymph. This is the name applied to that 
 portion of the blood that transudes through the 
 walls of the blood-vessels, and after supplying 
 the tissues with nutritive materials and receiving 
 the products of their combustion returns to 
 the large veins by means of the lymphatic 
 vessels. 
 
 Lymph is a transparent liquid, which during 
 digestion is more or less milky, owing to the sus- 
 pension in it of fatty matters absorbed from the 
 alimentary canal. Its specific gravity varies 
 between 1-012 and 1-022, and its reaction is 
 alkaline. 
 
 Under the microscope, the lymph is seen to 
 contain colourless corpuscles. In a time varying 
 from 3 to 20 minutes after it has left the vessels, 
 lymph undergoes coagulation,fibrin being formed. 
 The amount of fibrin which separates is between 
 0-4 and 0-8 per 1000, being less than that which 
 separates from blood. Lymph is, in fact, simply 
 dilute blood plasma; urea and carbonic acid, 
 however, are rather more abundant in lymph 
 than in blood. 
 
BLOOD, 
 
 521 
 
 The Blood in Disease. 
 
 Antsmia. The chief change is a reduction 
 Sn the number of red corpuscles, and the diminu- 
 tion of the amount of hasmoglobin they contain. 
 In severe cases there is also a reduction in the 
 solid constituents of the plasma. 
 
 Leitcocyfhcemia. This is associated with 
 great increase in the number of white corpuscles, 
 which may become nearly as numerous as the 
 red. The blood is poor in haemoglobin, and 
 rich in hypoxanthine and lactic acid (Scherer). 
 Charcot found in the blood, spleen, and liver of 
 patients suffering from leucocythsemia colourless 
 elongated crystals, which he and Vulpian were 
 inclined to consider as proteid in nature ; while 
 they were regarded by Salkowski as consisting 
 of a mucin-like substance. Schreiner states 
 that they consist of the phosphate of a base, to 
 the hydrochloride of which he gives the formula 
 C2H3N.HCI (A. 194, 68). 
 
 Qout. In this disease uric acid accumulates 
 in the blood, probably owing to non-elimina- 
 tion by the urine ; there is also a large quantity 
 of oxalic acid (Garrod, Medicc-Ghwurg. Trans., 
 31, 83 ; 37, 54). 
 
 Bheumatism. The fibrin is much increased 
 in amount : the same is, however, true for other 
 inflammatory conditions. There is no excess of 
 uric acid in the blood. Lactic acid is said to be 
 the materies morbi by some, but this has never 
 been satisfactorily demonstrated. 
 
 Fevers. — In various zymotic fevers, and sep- 
 tic diseases, the presence of different forms of 
 bacteria has been described, or in some cases 
 only presumed to exist in the blood. The best 
 known of these are the spirillum of relapsing 
 fever, the bacillus anthraois of splenic fever, 
 and the bacillus malarise of Klebs and Crudeli 
 of intermittent fever. Pigment granules of a 
 dark colour are also said to occur in the blood 
 of ague patients. It is probably a derivative of 
 haemoglobin (Marchiafava). 
 
 Diseases of the liver. In jaundice, bilirubin 
 and in some cases the bile salts also accumulate 
 in the blood ; in acute yellow atrophy the blood 
 contains leucine and tyrosine. 
 
 Diabetes mellitus. In this disease the most 
 marked feature is an increase in the amount of 
 glucose in the blood. The peculiar odour of 
 the breath in diabetics is stated to be due to 
 acetone, and death is often said to result from 
 aeetonaemia. It is probable that acetone does 
 not exist free in the blood, but is derived from 
 the splitting up of aceto-acetic ether. 
 
 In some cases of diabetes a lipamic (fat in 
 the blood) condition has been described. But 
 there is no doubt that this may occur without 
 evidence of disease, and also in other diseases 
 than diabetes. 
 
 Bright's disease. In addition to an anamic 
 condition, there is an increase in the amount of 
 urea in the blood. The convulsions and coma 
 that are apt to supervene when the elimination 
 of urea is defective have been designated evi- 
 dences of uroimic poisoning. It is probable, 
 however, that in these oases it is not urea 
 itself which is the poison, but probably some 
 substance or substances antecedent to urea. 
 Frorichs' theory that the poison is ammonium 
 carbonate is now given up as untenable. 
 
 The Blood of Invertebrate Animals. 
 Our knowledge conoernmg the blood of inver- 
 tebrate animals is much less complete than that 
 of the vertebrates. In certain marine animals 
 the circulating fluid is chiefly sea water in 
 which a number of corpuscles are suspended 
 (e.g. echinoderms) : in other invertebrates such as 
 Crustacea the blood is a highly organised fluids 
 and rich in proteid constituents, but even in 
 these the amount of saline matters varies with 
 the habitat, being much more abundant in 
 marine than in fresh-water animals. There is 
 never any distinction into blood proper and lymph 
 in invertebrate animals ; hence the name hcemo- 
 lymph is sometimes given to their circulating 
 fluid ; the term hydrolymph is applied in those 
 cases in which the blood is chiefly water, and 
 contains but few organic constituents. 
 
 Hsemoglobin is contained in the blood of 
 many invertebrates (Laukester, PflUger's Archiv, 
 4, 315), chiefly worms, but also in a few crusta- 
 ceans, insects, molluscs, leeches, and echino- 
 derms. With the exception of four worms and 
 two molluscs, however, it does not occur in 
 special corpuscles as in the blood of vertebrates, 
 but dissolved in the liquor sanguinis, colourless 
 corpuscles only being found in the blood. In 
 other invertebrates this red pigment is replaced 
 by others, which apparently have a similar 
 respiratory function ; the most important of 
 these other respiratory proteids are (1) htemo- 
 cyanin, a blue pigment occurring in various 
 crustaceans, arachnids, and molluscs (Fredericq, 
 G. R. 87, 996). This contains copper as one of 
 its constituent elements ; when oxidised it is 
 blue, when reduced it is colourless. (2) Chloro- 
 cruorin, a green pigment, closely related to 
 haemoglobin, found in the blood of certain 
 worms (Lankester, Joum. of Anat. and Physiol., 
 2, 144). (3) Hcemerythrin, a, purplish red pig- 
 ment found in a few gephyrean worms (Krqkeu- 
 berg, Vergl. phys. Studien, Iste Beihe, 3te Abth. 
 p. 82). In all these cases, the pigment is dis- 
 solved in the blood plasma, which has thus a 
 respiratory in addition to a nutritive function. 
 In addition to these pigments, others occur 
 which have apparently no respiratory function; 
 thus chlorophyll appears in the blood plasma of 
 many moths and butterflies (Poulton, Pr. 38, 
 269; tetronerythrin, a red lipoohrome in the 
 blood plasma of certain Crustacea (HaUiburtou, 
 Journ. of Physiol., 6, 300). Various coloured 
 granules are described in the corpuscles of holo- 
 thurians and sea urchins (Geddes, v. Gamgee's 
 Physiol. Ghem., 134), and the blood of the 
 limpet is described by Krukenberg as being of 
 an orange colour. 
 
 The blood of most invertebrates is alkaline 
 in reaction, the only known exception being 
 that of moths and butterflies which is acid 
 (Poulton). 
 
 With regard to the coagulation in the blood 
 of invertebrates Halliburton {Joum. of Physiol., 
 6, 300) was able, in the case of the Crustacea, 
 to separate crustacean fibrin, and to show that 
 as in vertebrate blood it was formed from a 
 previously soluble fibrinogen under the influence 
 of a ferment. Crustacean fibrinogen and fibrin 
 differ but little from that of vertebrate blood 
 and the fibrin ferment is identical with that 
 
B92 
 
 BLOOD, 
 
 obtained by Schmidt from vertebrate blood. The 
 coagulation of crustacean blood is also hindered 
 by cold, or admixture with neutral salts. The 
 coagulum formed when the blood of cephalopods 
 is shed is stated by Fredericq to be only a Plas- 
 modium of cells. 
 
 [The foregoing article has only discussed 
 blood from a general point of view. The various 
 constituents will be described under their proper 
 headings ; the proteids including hemoglobin 
 and the other blood pigments will be described 
 under the heading Proteids.} W. D. H. 
 
 BLOWPIPE V. Analysis. 
 
 BOHEIO ACID C,H,„08. [100°]. Occurs 
 (to the extent of "2 p.c), together with querci- 
 tannic acid, in black tea {Thea bohea) (Eoch- 
 leder, A. 63, 202). Yellow amorphous resin, v. 
 sol. water and alcohol ; ppd. by alcoholic or 
 ammoniaeal lead acetate. — ^BaA"aq.— PbA"aq. — 
 PbA"PbO. 
 
 BOIIING-POINTS V. Physical methods; 
 
 sec. THERMAL. 
 
 BOLSIK CjjHs^Og. A glucoside which may 
 be extracted by boiling alcohol from the leaves 
 of Boldoa fragrans, in which it occurs to the 
 extent of '3 p.c. It is a syrup, volatile with 
 steam, and decomposed by hot dilute HCl into 
 glucose, MeCl, and an oil CisH^jO, (?) sol. alco- 
 hol, insol. water (Chapoteaut, G. B. 98, 1052). 
 According to Bourgoin a. Verne [Bl. [2] 18, 481) 
 the leaves of Boldea contain an alkaloid, 
 boldine. 
 
 BOLETUS V. AoAEicns. 
 
 BONE-OIL (Anderson, Tr. E. 16, 4 ; 20, ii. 
 247 ; 21, i. 219 ; 21, iv. 571 ; A. 70, 32 ; 80, 44 ; 
 94, 358 ; 105, 335). The following substances 
 have been isolated from the tar obtained in the 
 dry-distillation of bones : 
 
 By-products. 
 
 Methylamine 
 
 Aniline 
 
 Pyridine 
 
 Methyl-pyridine 
 
 Di-methyl-pyridine 
 
 Quinoline 
 
 Phenol 
 
 Propionitrile 
 
 Valeramide 
 
 Toluene 
 
 Ethyl-benzene 
 
 Naphthalene 
 
 Chief Constituents. 
 
 Butyronitrile 
 
 Valeronitrile 
 
 Hexonitrile 
 
 Isohexonitrile 
 
 Deconitrile 
 
 Palmitonitrile 
 
 Stearonitrile 
 
 Pyrrol 
 
 Methylpyrrol 
 
 Dimethylpyrrol 
 
 Hydrocarbons : 
 
 CjH,, (Dihydro-m- 
 ethyl-toluene ?) 
 
 C,||H,j (Dihydro-m- 
 methyl-cumene ?) 
 
 CiiH,8 
 
 Weidel a. Ciamician {B. 13, 65) consider that 
 the nitriles are formed by the action of NH, at 
 the high temperature on the fatty acids con- 
 tained in the bones ; the pyridine bases they 
 believe to be formed by the combination of the 
 acrolein (from the glycerin in the fats) with 
 ammonia, methylamine, &a., whilst pyrrol and 
 itshomologues are products of the decomposition 
 of gelatin. 
 
 BOBATES. Salts of boric acid v. Bobon, 
 OXYAOIDS or, p. 528. 
 
 BORAX V. Borate of sodium : under Boeon, 
 OXYAOIDS OP, p. 529. 
 
 SOBIC ACIO V. BoBOjj, oxyaoids of, p. 528. 
 
 BOBIC ANHTDBIDE v. Bobon, oxidi or, 
 p. 527. 
 
 BOBIDES. Compounds of boron with one 
 other more positive element. — Very few of these 
 compounds exist; manganese forms a crystal- 
 line boride probably MnaB^; platinum easily 
 combines with boron to form PtB (?) ; and 
 aluminium and boron appear to form a kind of 
 alloy, the proportion of the elements in which 
 varies within very wide limits: two definite 
 borides of Al are also known (v. Iridium, Ikon, 
 Manoanbbe, Palladium, Platinum, Aluminium, 
 borides of). 
 
 BOENEENE. A mixture of terpenes (q. v.), 
 exuding from Dryobakmops camphora, holding 
 borneol in solution (Gerhardt, Traits, 3, 628, 641). 
 
 BOKNEOL CjjHisO i.e. C,„H„ OH. Borneo 
 camphor, Tetra-hydride of (1, 4, 6)-methyl- 
 propyl-phenol(1). Mol.w.l54. [198°] (P.); [207°] 
 (W.) (212°). B 00 75-30 in a 22-5 p.o. alcohoUo 
 solution (Eanonnikoff). 
 
 Occurrence. — In Dryohalanopa camphora, 
 being extracted from hollow cavities in the trunk 
 of old trees (Pelouze, A. 40, 326). In the essen- 
 tial oil of valerian (Gerhardt, A. 45, 34 ; Bruy- 
 lants, B. 11, 451). To the extent of 4 or 5 p.c. in 
 oil of rosemary (Bruylants, J. 1879,944; Weber, 
 A. 238, 89). 
 
 Formation. — 1. By heating camphor with 
 alcoholic KOH (Berthelot, A. Ch. [3] 56, 78). — 
 2. By the action of sodium on camphor (Bau- 
 bigny, Z. [2] 3,71 ; Haller, O. R. 105, 227). 
 
 Preparation from camphor. — (Jackson a. 
 Menke, Am. 5, 270 ; 6, 404 ; Kachler a. Spitzer, 
 M. 5, 50 ; B. 15, 16, 2730 ; Immeudorff, B. 17, 
 1036). Camphor (50g.) is dissolved in alcohol 
 (500 o.c. of 96 p.c), and sodium (60g.) added 
 slowly. Towards the end of the operation water 
 (50 O.C.) is added (0. Wallach, A. 230, 225). 
 
 Properties. — Eegular crystals ; very readily 
 sublimes in plates. SmeUs like camphor, but 
 more peppery. Has a burning taste. The 
 alcoholic solution is dextrorotatory; artificial 
 borneol has a somewhat higher rotatory power 
 (c. 43°) than the natural borneol ([a]D = 33°, 
 (Biot; Kachler). V. si. sol. water, sol. alcohol 
 and ether. Lighter than water. The rate of 
 etherification of borneol resembles that of pri- 
 mary alcohols (Menschutkin, J. B. 13, 162). 
 
 Beactions. — 1. P^Oj converts it into one or 
 more terpenes (borneene). — 2, Boiling HNO, 
 (S.G. 1'42) gives camphor and its oxidation 
 products.— 3. Behaves as an alcohol with regard 
 to PCI5. — 4. HCIO converts it into camphor. 
 
 Sodium borneol C,„H|,ONa: six-sided 
 plates (from benzene). Combines with COj, 
 forming C,jH„0(C02Na) (Kachler a. Spitzer, 
 M. 2, 235). 
 
 Bromide. — Bromine added to an ethereal 
 solution of borneol forms crystals of a mixture 
 of bromides (? C,„H,sOBra and (C,„H,jO)jBrj). 
 
 Hydrobromide. (C,„H,gO)2HBr. Crystal- 
 line pp. got by passing HBr into a solution of 
 borneol in light petroleum. The compound is 
 unstable and is decomposed both by water and 
 by alcohol. 
 
 Hydriodide. (0i„Hj80)2HI. Prepared 
 similarly. 
 
 Methyl derivative C,„H,jOMe. (194°cor.), 
 From sodium-borneol and Mel (Baubigny, 2, 
 1868, 299). 
 
BORNYL PHENYL-OARBAMATE. 
 
 523 
 
 Ethyl derivative 0,„H„OEt (202°) (B.). 
 
 Formyl derivative 0,„H„O.CHO. (225°- 
 230°). In oil of valerian (Bruylauts). 
 
 Acetyl derivative Oi„H„OAo. (221°) 
 {K. a. S.) ; (227°) (M.). Occurs in oil of valerian 
 (Bruylants, B. 11, 456) ; and may be formed by 
 the action of AojO upon borneol (Montgolfier, 
 A. Oh. [5] 14, 50), or of AgOAo upon bornyl 
 chloride (Kaohler a. Spitzer, A. 200, 352). On 
 standing it becomes crystalline [24°]. Fusion 
 with NaOH gives NaOAo and borneol. 
 
 Isovaleryl derivative 0,„H„0(C5H|,0). 
 (255°-260°). 
 
 Stearyl derivative C,„H„0(0,8Hj50). 
 From borneol and stearic acid at 200° (Berthelot, 
 A. 112, 366). Oil. 
 
 Benzoyl derivative C,„H„OBz. Oil. 
 
 IsBTorotatory borneol 0,„H„OH. [35°]. (210°). 
 (Perrot, A. 105, 67). [a]D = - 33°- Occurs in the 
 alcohol produced by fermentation of the sugar 
 of madder-root (Jeanjean, A. 101, 95). SmaU 
 regular crystals ; si. sol. water, rotating upon it. 
 HNOj forma Isevorotatory camphor. 
 
 Laevorotatory borneol C,„H„OH. [204°]. 
 S.G. 1-02. From Ngai camphor (Hanbury, /. 
 1874, 537). 
 
 laevorotatory borneol 0,„H„OH. [201°]. 
 [a]D=-37°21' in alcohol of 82 p.c. at 22°. 
 From thymene picrate and boiling NaOHAq 
 (Lextreit, /. Ph. [5] 13, 265). HNO3 converts 
 it into a Isevorotatory camphor [176°] (204°). 
 
 Laevorotatory borneol 0,oH„OH. Formed, 
 together with ordinary borneol, by the action of 
 Na on dextro- or Isevorotatory camphor (Mont- 
 golfier, A. Oh. [5] 14, 21 ; O. B. 89, 101). 
 
 Inactive borneol 0,„H,80. [199°]. (210°). 
 Among the products of the distillation of colo- 
 phene (g. v.). Also from its acetyl derivative. 
 Properties. — Differs from dextrorotatory 
 borneol only in being inactive. The crystals 
 float on water, but when pressed into a solid 
 cake they sink (unlike camphor). Oxidised by 
 HNO3 to inactive camphor (Armstrong a. Tilden, 
 O. J. 35, 752). Heated with a large quantity 
 of HCl it forms 0,„H,5HC1. 
 
 Acetyl derivative 0,„H„OAc. (215°). 
 From terebene and HOAo at 100° (Bouchardat 
 a. Lafont, Bl. [2] 45, 164 ; O. B. 102, 171). 
 
 According to Haller there are two true bor- 
 neols [o]j = + or — 37°, and the others are mo- 
 lecular compounds of these (v. Oamphob and 
 
 ClNEOIi). 
 
 BOENYIAMINE 0,„H,sN probably 
 
 KCHj 
 I [160°]. (200°). V.D. 5-5 (for 
 
 OH.NHj, 
 5-3). OD= -18° 35' 41". 
 
 Formation. — 1. By reduction of camphor- 
 oxim in alcoholic solution by means of sodium. 
 2. By saponification of its formyl derivative 
 obtained by heating camphor with ammonium 
 formate at 220°-240°. 
 
 Properties. — Crystalline solid, having an 
 odour resembling both camphor and piperidine. 
 In its physical properties it greatly resembles 
 camphor. VeryvolatUe with steam. Subhmable 
 even at the ordinary temperature. Y. sol. alco- 
 hol, ether, &c., nearly insol. water. Alkaline 
 reaction to litmus. Takes up 00^ from the air. 
 Primary base. Gives the carbamine reaction. 
 LiBVorotatory, Isomeric with oamphylamine. 
 
 Salts. — B'HCl : easily soluble white needles 
 [0.280°].— B'jClAPtCli: golden-yellow plates, 
 T. sol. hot water or alcohol. — B'H^SO^; easily 
 soluble rhombio tables.— B'jHjCljHgClj. 
 
 Formyl derivative C,gH,.NH0HO ; 
 [61°] ; colourless glistening plates. 
 
 Acetyl derivative CioH,.NHAo : [141°] 
 colourless plates. 
 
 Benzoyl derivativeCt„'S,.'NEBz: [131°]; 
 colourless plates ; insol. water and cold hgroin 
 (Leuohart a. Bach, B. 20, 104). 
 
 BOBNYL BBOMIDE 0,„H„Br. [75°]. From 
 borneol and HBr (Kaohler, A. 197, 98). 
 
 BOBNYL CABBAMATE C„H,„NOj i.e. 
 C,(,H,O.CONHj. [115°] . From sodium-borneol 
 in toluene by the action of cyanogen (Haller, 
 G. B. 93, 1511 ; 94, 869). Monoclinic needles 
 (containing aq.). SI. sol. hot water ; sublimes 
 partially at 100°. Dextrorotatory. Benzoic 
 aldehyde and HCl form CHPh(NH.C0.0.0,c,H„)2 
 
 [187°]. Of. OiNEOL. 
 
 BORNYL CAEBONATE (0,„H„)jC03. [215°]. 
 Extracted by boiling alcohol from the residue 
 left in the preparation of cyano-borneol from 
 sodium borneol and cyanogen (Haller, G. B. 94, 
 86). White plates or hexagonal tables, insol. 
 water and alkalis, si. sol. cold alcohol, sol. ether. 
 May be sublimed. The rotatory power varies 
 with that of the borneol from which it is pre- 
 pared. Boiling alcoholic KOH gives KjOOj and 
 borneol. 
 
 BDRNYL-CABBONIC ACID C,„H„O.COjH. 
 Bcymeol-carboxylic acid. From sodium-borneol 
 and CO2 (Baubigny, Z. 1868, 299 ; Kachler a. 
 Spitzer, M. 2, 236 ; G. 0. 1881, 859).— NaA' : 
 crystalline, v. sol. water; slowly decomposed 
 by water with separation of borneol. 
 
 BOBNYL CHLOEIDE C,„H„C1. [157°]. 
 Formation. — ^From borneol (1 pt.) and HCl 
 (9 pts.) at 100° (Berthelot, A. 112, 366). 
 
 Preparation. — From PCI5 (60g.), light petro- 
 leum, and borneol (45g. added in portions of 
 6g.). The product is shaken with water and the 
 petroleum allowed to evaporate in the cold, 
 when bornyl chloride separates (Wallaoh, A. 
 230, 231 ; Kachler, A. 197, 93 ; JS. 11, 460). 
 
 Properties. — Crystals. V. sol. light petro- 
 leum, m. sol. alcohol. Laevorotatory. 
 
 Beactions. — 1. Converted into HCl and oam- 
 phene C,„H,s [52°1 (c. 160°), by heating with 
 water (40 pts.) at 95° (Kaohler, A. 197, 96) ; 
 better by warming with aniline (W.). A little 
 borneol is also formed by the action of water on 
 bornyl chloride (Kachler, A. 200, 342 ; Eiban, 
 A. Gh. [5] 6, 382). — 2. Sodium acting on a solution 
 in benzene forms camphene CjgH,, and hydro- 
 camphene C,„H,j. 
 
 BOBNYL-METHYL-UBEA 
 C,„H„.NH.CO.NHMe. [200°]. Formed by the 
 action of methyl oyanate upon bornylamine in 
 ethereal solution. Plates. V. sol. ether and 
 hot water (Leuchart a. Bach, B. 20, 108). 
 
 BOBNYL OXIDE C,„H„0 i.e. (C,„H„),0 (?). 
 (285°-290°). Occurs in the essential oil of 
 valerian (Bruylants, B. 11, 456). Not attacked 
 by melted KOH. 
 
 BOBNYL PHENYL-CAEBAMATE 
 
 OC<^Q„ H '■ ■SoJ'wz/Z - phenyl • urethane. 
 
 [133°]. Formed by the action of phenyl cyanate 
 upon borneol. Needles. Sparingly sol. cold 
 
634 
 
 BORNYL PHENYL-CARBAMATE. 
 
 Ugroin and alcoliol, v. sol. other solvents 
 (Leuchart, B. 20, 115). 
 
 BOEHXL-PHENYL-THIO OKEA 
 C,„H„.NH.CS.NHCjH5. [170=]. Formed by 
 the action of phenyl mustard-oil upon bornyl- 
 amine in ethereal solution. Colourless needles. 
 Nearly insol. Ugroin (Leuchart a. Bach, B. 20, 
 109). 
 
 BOKNYL-PEENYL-TTEEA 
 C,„H„.NH.C0.NHC,H5. [248°]. Formed by the 
 action of phenyl oyanate upon bornylamine in 
 ethereal solution. Silvery plates or fine needles. 
 Sparingly soluble in ether and cold alcohol, 
 easily in hot alcohol, insoluble in water (Leu- 
 chart a. Bach, B. 20, 108). 
 
 BOENYL-UEEi C,„H„.NH.CO.NH.„ [164°]. 
 Formed by boiling bornylamine hydrochloride 
 with potassimn cyanate. Colourless needles. 
 Easily soluble in hot water and alcohol (Leu- 
 chart a. Bach, B. 20, 108). 
 
 BOENESITE C,H„0„. [175°]. [o]d = 32°. 
 Methyl-dambose. A volatile substance occurring 
 in the caoutchouc of Borneo. SubUmes at 205°. 
 Sweet taste ; does not ferment. After boiling 
 with dilute acids it reduces Fehling's solution. 
 At 120° it is split up by fuming HI into Mel 
 and da-nbose (Girard, 0. B. 73, 420). 
 
 BjEOFLUOBISES, v. under Boron, fluokide 
 OF, p. 526. 
 
 BOEON. B. At. w. 10-97. Mol. w. unknown, 
 as V.D. has not been determined. S.G. — 
 amorphous not determined, but greater than 
 1-84— oryst. 2-53-2-68 (Wohler, A. 141, 268 ; 
 Hampe, A. 183, 75). S.H. about -37 at 250°, 
 probably about -5 at 1000° {v. post ; p. 525). 
 Crystallises in dimetric forms, a:c = 1: -5762 
 (Sella, P. 100, 646) ; but crystals probably con- 
 tained C and Al {v. post). S.V.S. about 4-4. 
 Combines directly with and CI with produc- 
 tion of much heat : [B^O'] = 317,200 ; [B,CP] = 
 104,000 (Troost a. Hautefeuille, A. Ch. [5] 
 9, 70). Chief lines in emission-spectrum are 
 2496-2, 2497, 3450-1 (Hartley, T. 175, 49). 
 
 Occurrence. — Not as boron ; chiefly as borax 
 and boric acid in volcanic districts, also as 
 borate of Mg with MgCl^ (Boracite), as borate 
 of Ca with Ca silicate (Datolile), &o. Borax, or 
 tincal, has been known in commerce for many 
 centuries ; boric acid was prepared from borax 
 in 1702 by Homberg ; the element was obtained 
 by Gay-Lussac and Th^nard in 1808 by de- 
 oxidising boric acid by potassium, which metal 
 had been obtained by Davy the year before. 
 
 Formation.— X. By reduction of B^Oj by E 
 (Gay-Lussao a. Th^nard, O. A. 80, 363).— 2. Bv 
 reduction of BPj.KPby K (BerzeUus,P. 2, 113).— 
 8. By electrolysis of fused B.Oj (Davy, O. A. 
 35, 440).— 4. By reduction of BCla by H at a red 
 heat (Dumas, A. Ch. 81, 376).— 5. By fusing 
 dry borax with amorphous P (Dragendorff, CO. 
 1861. 865).- 6. By heating BP3.ICP or BP...NaF 
 with Mg (Wohler a. Deville, A. Ch. [3] 52, 62; 
 Geuther, J. Z. 2, 209).— 7. By heating 8,0^ 
 with Mg and treating the product with HClAq 
 (Jones, C. J. 35, 42). 
 
 Preparation. — Amokphous. 10 parts fused 
 B2O3 in coarse powder are mixed with 6 parts 
 Na in small pieces, the mixture is placed in an 
 iron crucible heated to full redness, 4 to 5 parts 
 of fused NaCl are added, and the crucible is 
 covered. When all action has ceased the 
 
 molten mass is stirred with an iron rod, and 
 
 the contents of the crucible, while still hot, are 
 poured into water containing a Uttle HCl. The 
 NaCl, borax, and BjOj, dissolve, and the boron 
 remains. The boron is washed with very dilute 
 HOlAq, then with alcohol, and then with 
 ether; it is then dried at a very gentle heat 
 (Wohler a. DeviUe,4. 101,113 a. 347; 105, 67). 
 
 CnvsTALLiKE. Amorphous B is pressed as 
 tightly as possible into a small Hessian crucible, 
 a hole is then made in the mass and a rod of 
 Al (4-6 grams) is placed in the hole: the 
 crucible is covered and placed in another, 
 larger, covered, crucible ; the space between is 
 filled with powdered charcoal, and the crucibles 
 are heated to 1500° or 1600° for 1^ to 2 hours ; 
 after cooling the mass is treated with dilute 
 HCLAq which dissolves Al, and BN formed in 
 the process (Wohler a. Deville, A. 105, 67). 
 According to Hampe (A. 183, 75) the crystals 
 obtained by this process, or by any process said 
 to yield crystalline B, contain Al, and some of 
 them also ; Hampe gives the formula AlB,j 
 to the black crystals, and C^AljBjg to the 
 reddish-yellow crystals, obtained by the fore- 
 going method (v. Aluminium, bobides of ; and 
 Aluminium, borocakbide of). 
 
 Properties. — Amorphous boron is a greenish- 
 brown, opaque powder ; tasteless ; odourless j 
 non-conductor of electricity ; very infusible, but 
 melts when placed between the poles of a 
 battery of 600 Bunsen-cells. Said to be slightly 
 soluble in water ; Eeinitzer (Sitz. W. 82, 736) 
 supposes that the body which dissolves is a 
 hydride of B (v. Boron, hi'dbide of). Insoluble 
 in alcohol or ether. Heated in vacuo or in an 
 inactive gas, e.g. H, B becomes darker in colour, 
 heavier, and more compact. Heated in 0, burns 
 to B^Os, [B=,0»] = 817,200 : heated in air, B,^0, 
 and BN are produced. Oxidised by heating with 
 KNO3, K2CO3, KOH, cone. HNOaAq, or aqua 
 regia. Combines directly with many elements 
 e.g. S, CI, Br, N. The properties assigned by 
 Wohler a. Deville and others to crystalline B, 
 are, according to Hampe's experiments, the 
 properties of ALB^, AlB,,, and CjAljBj, (v. 
 Aluminium, eoeide op, and bohocarbibb of). 
 The atom of B is trivalent in gaseous molecules 
 (data BClj, BBrj, BP,). The atomic weight of 
 B has been determined (i) by finding the V.D. 
 of BCI3 and BBrj and estimating the CI and Br 
 respectively in these compounds (Deville a. 
 Dumas, A. Ch. [3] 55, 180) ; (ii) by dehydrating 
 borax (Berzelius, P. 2, 129 ; 8, 19) ; (iii) by 
 converting dehydrated borax into Na^SO^ by 
 action of HFAq and H2S0jAq (Berzelius, P. 2, 
 128 ; also Arfvedson, P. 2, 127) ; fiv) by deter- 
 mining the S. H. of boron {v. infrcL). Boron is a 
 non-metallic element in its chemical reactions ; 
 its oxide, B^Oj, is an anhydride; boric acid, 
 HJB^Oj, corresponds in composition to nitrous 
 acid , but thermal data show that boric acid is di- 
 basic ; the acids H3BO3 and H.JSjO, (and several 
 salts derived from the latter) are also known (v. 
 BoKON, oxYAciDs of). B^O, scems to form com- 
 pounds with PjOi, SOj, and WOj. In some respects 
 B shows analogies with C and Si : — physical 
 properties ; existence of acid containing P 
 (HBFj) ; direct combination with N ; existence 
 of many borotungstates ; probable existence of a 
 gaseous hydride, &o. In many points B resem- 
 
BORON. 
 
 626 
 
 bles N and P :— trivalenoy of B atom; oom- 
 position of compounds (BjOj. HjEjOj, BCl,, 
 BOCI3, &o.) ; BjSj not a salt-forming sulphide 
 in reactions with sulphides of very positive 
 metals; existence of a B analogue of tartar 
 emetic, &o. Boron is the first member of Group 
 III (periodic law) ; the succeeding members of 
 this group are all decidedly metallic; but 
 Al^Oj-SHjO dissolves in KOHAq, and forms 
 aluminates (g. v.) ; Al^Sj is also somewhat 
 analogous to BjS, : the compositions of several 
 B compounds are similar to those of the corre- 
 sponding compounds of members of Group 
 III., e.g. MA. MXj [X = C1, Br]. AlCl, 
 and BOI3 combine directly with POCI3. The 
 differences between the chemical functions 
 of B and the other elements of the group to 
 which B belongs seem to be wider than is usual 
 between the first and the following elements of 
 the same group. The boron group comprises 
 the following : 
 
 Geoup III. 
 
 Even Series 2. i. 6. 8. 10. 12. 
 
 B(n) So(40 T(89) La(139) Yb(ir3) — 
 Odd Series 3. 6. 7. 9. 11. 
 
 A!(27) Ga(69) Iu(n4) — Tl(204). 
 
 These elements are all metallic with the ex- 
 ception of B ; in the reactions of B^Oj towards 
 certain acids (p. 527) B shows that it may act 
 as a feebly metal-like element. Boric acid is 
 an extremely weak acid ; its affinity is very 
 small. The borates are very unstable salts, 
 easily decomposed; even by water, to boric acid 
 and basic oxides. The last member of the group, 
 Tl, shows distinct analogies with the 11th series 
 member of the next group, viz. Pb ; B shows dis- 
 tinct analogies with the 2nd series member of the 
 next group, viz. 0. B occurs in Series 2, all the 
 succeeding members of this series — C, N, 0, 1? — • 
 are very negative and non-metalUc ; the general 
 character of the series to which it belongs is 
 stamped upon B, and the group-character is but 
 feebly marked. It must, however, be remembered 
 that very few compounds of B, except the 
 borates and their derivatives, have been fully 
 studied. 
 
 Specific heat. The S.H. of B as determined 
 by Kopp, Eegnault, and Mixter a. Dana {A. 126, 
 362 ; Suppl. 3, 1, 289 ; J. 1861. 29 ; A. 169, 388) 
 varied from -225 to -262 for the temperature- 
 interval B0°-70°. In 1873-4 Weber carefully 
 determined the S.H. of crystallised boron {v. 
 P. M. [4] 49, 161, 276) ; the foUowing table 
 summarises his results : 
 
 5f.JBr. of crystallised boron. 
 
 t. 
 
 S.H. 
 
 B.H. X At. w. 
 
 -40° 
 
 •1915 
 
 2-11 
 
 + 77 
 
 •2737 
 
 3-01 
 
 177 
 
 •3378 
 
 3^72 
 
 233 
 
 •3663 
 
 4-03 
 
 The S.H. increases as temperature rises, but 
 the rate of increase per 1° is much smaller at 
 high than at low temperatures. The variations 
 in the rate of increase are almost identical with 
 those observed in the case of carbon (2. v.) ; 
 assuming that this identity remains at tem- 
 peratures above 233°, the value which the 
 S.H. of crystallised boron will attain at about 
 1600° is approximately •S. Weber did not 
 analyse the crystals of boron used ; they were 
 prepared by beating borig aoid with 4I. Accord- 
 
 ing to Hampe's investigation crystals thus 
 prepared are a definite compound of B and Al 
 (ante, p. 524). 
 
 Beactions.—l. Heated in air, BjO, and BN 
 are formed.— 2. Heated in oxygen, B burns to 
 BjOs- — 3. Heated to redness in N, BN is formed. 
 
 4. B combines directly with many elements, 
 e.g. CI, Br, S, and some metals (v. Bobides). — 
 
 5. Water is not decomposed by B at 100' but 
 at a red heat. Steam reacts with B to form 
 boric acid and H.— 6. B is oxidised by heating 
 with nitric acid, cone, sulphuric acid, or ajua 
 regia ; or by the action of molten nitre, or 
 various oxides of heavy metals. — 7. B is also 
 oxidised by heating with potash (H is evolved), 
 or with alkaline carbonates (G is separated, 
 Berzelius, P. 8, 19), or with 'phosphoric acid 
 (P is separated, Wohler a. Deville, A. Oh. [3] 52, 
 63). — 8. B burns when heated in nitric oxide 
 forming BjOj and BN ; N^O is without action on 
 B. — 9. At a red heat B decomposes sulphuretted 
 hydrogen, hydrogen chloride, and ammonia, 
 forming respectively B.^S3 and H, BCI3 and H, 
 BN and H. — 10. Many metallic chlorides and 
 sulphides, e.g. PbCl,, AgCl, PbS, are reduced to 
 metal when heated with B.— 11. From aqueous 
 solutions of gold chloride B pps. Au. — 12. 
 Aqueous solutions of caustic alkalis do not 
 react with B. — 13. So-called crystalline boron 
 reacts similarly to amorphous boron, but the 
 reactions occur only at high temperatures ; it is 
 oxidised with much difficulty. 
 
 Eefereiues. — Gay-Lussac a. Th^nard, O. A. 
 30, 368 ; Davy, G. A. 35, 440 ; Berzelius, P. 2, 
 113 ; Wohler a. Deville, A. 101, 113 ; 103, 347 ; 
 105, 67. 
 
 Boron, Bromide of. BBr,. Mol. w. 250-22. 
 (90-5°) (Wohler a. Deville, A. Ch. [3] 52, 89). 
 S.G. 2-69 (W. a. D. I.e.). V. D. 127. 
 
 Formation.-— 1. By action of Br on Bfi, and 
 at red heat (Poggiale, O. B. 22, 127).— 2. By 
 heating Bfi, with PBr, (Gustavson, B. 2, 
 661). 
 
 Preparation. — Amorphous B is loosely 
 packed into a glass tube, the tube is gently 
 warmed and H is passed through it until every 
 trace of moisture is removed ; the H stream is 
 stopped, the corks of the tube are removed for 
 a moment or two, and then the B is gently 
 heated in a, stream of dry Br vapour, and the 
 liquid BBr, is led into a dry flask surrounded 
 by ice-cold water. The BBrj is freed from Br 
 by digestion with Hg, and distillation. 
 
 Properties and Beactions. — Colourless, 
 strongly fuming, liquid. Beaots with H^O to 
 form HBrAq and HjBOaAq. Forms a compound 
 with dry NH3 {v. also Nickl^s, C. B. 60, 800 ; 
 Gautier, 0. R. 63, 920). 
 
 Boron, Chloride of. BClj. Mol. w. 11708. 
 (18°-23) at 760 mm. (Eegnault, Acad. 26, 658). 
 S.G. ii 1-35 (Wohler a. Deville, A. Ch. [8] 52, 
 63). V. D. 58-2. H.F. [B, Cl»] = 104,000 (Troost 
 a. Hautefeuille, C. B. 70, 185). 
 
 Foniiation. — 1. By direct combination of 
 B and CI (Berzelius, P. 2, 147).— 2. By the 
 reaction of CI with BjO, and C at a red heat 
 (Dumas, A. Ch. [2] 31, 436 ; 38, 376).— 3 By the 
 reaction of B with dry HCl. — 4. By reaction 
 between HgCl^, PbCl^, or AgCl, and amorphous 
 B.— 5. By heating BjO, with PCI, to 150" for 
 some days (Gustftvson, S. 3, 426 ; 4, 975). 
 
626 
 
 BORON. 
 
 Pnparation. — Amorphous B is heated in H 
 until quite dry, then in dry 01 (details v. Bobon, 
 BBOMiDB or) ; the exit-end of the tuhe is con- 
 nected with a T tube, the upper part of which 
 is surrounded with a mixture of snow and salt, 
 and the lower limb passes into a dry tube 
 also surrounded by snow and salt. 
 
 Properties. — Colourless, highly refractive, 
 liquid. Very expansible by heat. Fumes in 
 air with decomposition. 
 
 Reactions. — 1. With water forms H3B03Aq 
 and HClAq; [BCl', Aq] = 79,200 (Troost a. 
 HautefeuiUe, A. Ch. [5] 9, 70).— 2. Not decom- 
 posed by heating with sine-dust to 200° ; or 
 with sodium below 150°, at 150° B is separated. 
 3. Heated for some time with superficially 
 oxidised sodium-amalgam at 150° B is separated 
 (Gustavson, B. 3, 426).— 4. Heated with PjOj, 
 the compound BClj.POCls is formed {v. infra) 
 (Gustavson, B. 4, 975). — 5. Heated with sulphur 
 irioxide,Bfi, and SO^Olj are formed (Gustavson, 
 l.c.).—6. With alcohol forms B(0Et)3 and HCl.— 
 7. With NOj reacts to produce BCI3.NOCI, Bfi,, 
 and (Geuther, J.pr. [2] 8, 854). 
 
 Combinations. — 1. BClj vapour passed into 
 POCI3 forms crystals of BCI3.POCI3 (Gustavson, 
 B. 4, 975). This compound melts at 73° in a 
 closed tube ; by sublimation it separates into BCl, 
 and POCI3 ; it is decomposed by water, or moist 
 air, into H3P04Aq, HjBOsAq, and HOlAq. The 
 same compound is produced by the reaction of 
 BClsWithP^Oj, and of B^OsWith POCI3 (G.l.c.).~ 
 
 2. With ammonia gas gives 2BCI3.3NH3, with 
 production of much heat (Berzelius, P. 2, 147). 
 
 3. The compounds BCI3.ONCI, and BCI3.CNH, 
 are known (Martins, A. 109, 80 ; Gautier, 0. B. 
 63, 920). 
 
 Boron, riuoride of. BF3. Mol. w. 68-27. 
 V. D. 33-7. S. (0°) 1043. 
 
 Formation. — 1. By reaction, at white heat, of 
 an intimate mixture of 1 part B^Oj with 2 parts 
 CaPj free from silica ; Gay-Lussac a. Th^nard 
 (A. Ch. 69, 204) prepared BP3 by this method, 
 in 1810, using vessels of flint, and collecting the 
 gas over Hg. — 2. By heating 1 part B.fi^ with 
 2 parts CaFj and 12 parts cone. HjSOjAq in 
 glass vessels (J. Davy, T. 1812. 365) ; or 1 part 
 BjOa, 1 part CaP^, and 20 parts HjSO, (Perrari, 
 J. Ph. 19, 48). Prepared thus, the gas always 
 contains SiP, (Berzelius, P. 2, 116). 
 
 Prepdration. — 100 parts KBP^ are mixed with 
 15-20 parts fused and finely powdered B^Oj, 
 and the mixture is heated with cone. HjSO, ; 
 the gas is collected over Hg (Schiff, A. Suppl. 
 5, 172). 
 
 P}-qpe?-<ies.— Colourless gas, with suffocating 
 odour, condensed to a limpid liquid at— 110° and 
 strong pressure (Faraday, A. 56, 152). Acts on 
 organic matter like cone. H^SOj ; incombustible ; 
 not decomposed by electric sparks ; does not 
 act on glass; is very stable, not decomposed 
 by Fe at red heat. 
 
 Beactions.—l. with water forms borofluor- 
 hydric acid HBF^Aq {v. infra), or fluoborio 
 acid HB0j.3HP {v. p. 530), according as the 
 BF3 is passed into water until the reaction is 
 acid, or until the water is saturated {v. infra). 
 [BP', Aq] = 24,510 (Hammerl, 0. B. 90, 312).— 
 2. Cone, sulphuric acid absorbs BF3 (about 50 
 vols.), on adding water boric acid is ppd. 
 (J. Pavy, T. 1812, 365).— 8. Alkali, aaialkali-r.e 
 
 earth, metals react at red heat, forming boro- 
 fluorides and B (Berzelius, P. 2, 138).— 4. With 
 alcohol borio acid and ether are formed. 
 
 Combinations. — With ammonia to form 
 BPj.NHj, a solid body not decomposed by subli- 
 mation ; also BF3.2NH3 and BP3.3NHS, liquids, 
 decomposed by heat, by exposure to air, or by 
 dry COj, giving NH, and BF3.NH3 (J. Davy, T. 
 1812. 368). According to Kuhlmann (A. 39, 320) 
 BF3 also combines with the oxides of N. 
 
 BoBOrLUOKHTDBIC AoiD, AND BoEOFLUOBrDES. 
 
 HBP,, MBF,. (Hydrofluoboric acid.) When 
 BF3 is led into water until the liquid shows a 
 strongly acid reaction, and the liquid is cooled, 
 i of the B of the BF, separates as H^BjO, and 
 the rest remains in solution in combination with 
 H and P. By neutralising the liquid with 
 KOHAq, and evaporating, a salt having the 
 composition KBP, is obtained. If the acid 
 liquid is evaporated HP is evolved, and 
 H2B.^04.6HF remains in solution («. fIiUOBoeic 
 ACID under Boeon, oxtaoids or). According to 
 Landolph (C. B. 86, 603) the acid HBF4 may be 
 obtained as a colourless liquid, boiling at 130° 
 with partial decomposition, by the reaction be- 
 tween BF3 and anethol (CjH,.OCH3.03H5) : the 
 acid reacts with a little water to produce HFAq 
 and HBOjAq. A solution of HBFj is also ob- 
 tained by dissolving crystallised boric acid in 
 dilute, cooled, HFAq. 
 
 BoEOFiiUOBiDES. Thesc salts have been 
 chiefly studied by Berzelius (P. 2, 113). They 
 are obtained by the reactions between (1) me- 
 tallic oxides or carbonates and HBF^Aq, (2) BP3 
 or HB02.3HPAq and metallic fluorides, (3) 
 HFAq and metallic fluorides mixed with HBOj ; 
 in the last case half the metal of the fluoride 
 usually forms an oxide. Most borofluorides are 
 crystalline, soluble in water, decomposed by 
 heat to BP3 and metallic fluoride ; heated with 
 cone. HjSOj, BF3, HBP,Aq, and metallic sul- 
 phate, are produced ; fused with alkali carbo- 
 nates they form a mixture of alkali metal fluo- 
 ride and alkali borate, this reaction affords the 
 basis of a method for analysing the borofluo- 
 rides (v. Marignac, Fr. 1, 405). Many boro- 
 fluorides are partially decomposed by water 
 forming so-called basic salts, e.g. Ba(BF J2.2H2O, 
 Ca(BF4)2, Pb(BFJj; some— e.gr. the Ba or Pb 
 salt — are partially decomposed by alcohol ; the 
 aqueous solutions of several — e.g. NH4.BF,, 
 Ca{BPj2 — redden blue litmus. 
 
 Potassium, borofluoride KBP4. Obtained as 
 a gelatinous pp. by adding HBP^Aq to a soluble 
 K salt. Prepared by Stolba (C. O. 1872. 395) 
 by heating to boiling 1 part crystaUised boric 
 acid, 2 J parts powdered CaPj, and 51 parts 
 cone. HjSO,, cooling, filtering, ppg. KBFj by 
 addition of a soluble K salt, crystallising from 
 hot water — S. (cold) 70. — The salt forms white 
 lustrous six-sided tables ; may be crystallised 
 from alcohol or alkali carbonate solutions ; 
 melts when heated, and at a high temperature 
 decomposes to BPj and KP. 
 
 The other borofluorides are Al2(BP,)^, 
 NH^BF,, Ba(BP,)2.2H20, Ca(BP,)2, Ou(BF,)3, 
 Pb(BPj2, LiBP„ Mg(BFj2, NaBP„ Y^(BF^,, 
 Zn(BF,)2. 
 
 Boron hydride. No hydride of B has been 
 obtained free from H ; but the experiments of 
 Jones (C. J. 35, 41), and pf Jones a. Taylor 
 
BORON. 
 
 697 
 
 (O. J. 39, 213), leave little doubt that a gaseous 
 hydride exists and show that its composition is 
 probably BHj. 
 
 Pre^ratAon, — An intimate mixture o! 1 part 
 recently heated BjO, and 2 parts Mg dust is 
 placed in a Hessian or iron crucible, the lid is 
 firmly wired down, and the crucible is heated in 
 an ordinary fire ; a violent reaction occurs, the 
 crucible is at once removed from the fire ; the 
 fused mass — a mixture of B, Mg, MgjBj, MgjNj, 
 and MgO — is placed in a small flask along with 
 a little HjO, and cone. HClAq is allowed to drop 
 into the flask from a stoppered funnel tube ; the 
 gas is collected over water, or is dried by CaCl^ 
 and collected over Hg. MgjB, may also be 
 prepared by direct combination of B and Mg, 
 or by heating Mg in BCI3 vapour (J. a. T., C. J. 39, 
 214). The gas consists of H mixed with a very 
 small quantity of B hydride. 
 
 ATialysis. — A known volume of pure H was 
 burnt, by hot CuO, to HjO, and the H^O was 
 weighed ; an equal volume of the gas prepared 
 as above was burnt in the same apparatus, and 
 the H2O was weighed ; the excess of HjO in the 
 second experiment over that in the first gave a 
 measure of the H combined with B as B hy- 
 dride. The results showed the composition of 
 the hydride to be BH^ where x>2 and is ap- 
 proximately = 3. 
 
 Properties and Reactions. — Colourless, very 
 disagreeable odour, sparingly soluble in water, 
 solution seems to be unchanged on keeping. 
 Gas burns with bright green flame producing 
 H2O and B2O3. Decomposed by passing through 
 a hot tube to B and H. Beacts with AgKOjAq 
 producing small quantity of a black pp. con- 
 taining B andAg, and decomposed by HjO giving 
 B hydride. Beacts with K.^Mn^OgAq giving 
 MnOj and HjBOjAq. Combines with NH, 
 (cone. NHjAq) to form a crystalline compound, 
 of unknown composition, decomposed by acids. 
 
 References. — Older attempts to prepare hy- 
 dride of boron : Wohler a. Deville (A. Ch. [3] 
 52, 88); Geuther {J. 1865. 125); Gustavson (Z. 
 1870. 521) {v. also Eeinitzer, Sits. W. 82, 736). 
 Compounds of B with paraffin-radicles are 
 known, e-ff. BEt, («. Bobon, Okoanio dekiva- 
 TrvES or). 
 
 Boron, Hydroxides of, v. Bobok, ox^acids 
 
 OP. 
 
 Boron, Iodide of. Not known. Wohler a. De- 
 ville (A. Ch. [3] 52, 90), by the action of I on B at 
 a high temperature, obtained a body which they 
 regarded as an oxyiodide. Agl does not react 
 with B even at the melting point of Ag. 
 
 Boron, Nitride of. BN. Mol. w. unknown, 
 as compound has not been gasified. Obtained 
 in 1842 by Balmain by melting B2O3 with KCN 
 (P.M. [3] 21, 170; 22, 467 ; 23, 71; 24, 191). 
 Composition determined by Wohler in 1850 (A. 
 74, 70). 
 
 Formation. — 1. By heating B in N, or in 
 NH3.— 2. By heating to whiteness a mixture of 
 4 parts B^Os and 1 part charcoal powder in N. 
 3. By heating borax (WShler, l.c.), or boric acid 
 (H. Eose, P. 80, 265), with NH.Cl, or K^FeCy^ 
 (W. I.C.), or KCN, or Hg(CN)2, or urea 
 (Darmstadt, A. 151, 255).— 4. By heating 
 2BCI3.3NH3 and passing the vapour, along with 
 NH,, through a hot tube (Martins, A. 109, 80). 
 
 5. By heating the compound of BCL with NH,Et 
 to 200° (Gustavson, Z. [2] 6, 521). 
 
 Preparation.— k mixture of 1 part dehy- 
 drated borax and 2 parts NHjCl— or 7 parts 
 B^a with 9 parts urea (Darmstadt, l.c.) — is 
 strongly heated in a covered Pt crucible, the 
 finely powdered mass is boiled with much water 
 containing a little HCl, washed with hot water, 
 BjO, is removed by careful treatment with 
 HFAq (Wohler, I.e., could not remove all BjO, 
 thus), and the BN is washed and dried. 
 
 Properties. — White, light, amorphous, po^*- 
 der ; insoluble in water ; infusible ; soft (like 
 tale) to the touch ; heated in the edge of a flame 
 exhibits greenish-white phosphorescence; very 
 stable and very slightly acted on by most 
 reagents, e.g. by heating in air, 0, 1, H, COj, or 
 CS2, or with cone. HClAq or HNOjAq or KOHAq. 
 
 Reactions. — 1. At a very high temperature 
 reacts with chlorine, to give BClj (Darmstadt, 
 A. 151, 255). — 2. Heated to redness in steam, or 
 to 200° in a closed tube with water, NHj and 
 
 H3BO3 are formed 3. With molten potash, 
 
 NH3 and K borate are produced. — 4. With 
 molten potassium carbonate KCNO and KBO2 
 are formed, if much BN is used KCN is also pro- 
 duced. — 5. Oxides of Pb, Cu, or Hg are reduced 
 by heating with BN, with formation of NO or N^O, 
 (Wohler, A. 74, 70).— 6. Heated with cone. 
 sulphuric acid, or with cone, hydrochloric acid 
 to 200° in closed tubes, NH, and HjBOa are 
 formed. — 7. With oono. hydrofluoric acid 
 NH4.BP4 is formed. — 8. Heated in an alcohol- 
 flame fed with oxygen, BN burns to B2O3. 
 
 Boron, Oxide of. B2O3. (Boric anhydride.) 
 Mol. w. unknown, as compound has not been 
 gasified. [577-^] (Carnelley, C. J. 33, 278). S.G. 
 1-75-1-83 (Playfair a. Joule, C. S. Mem. 3, 57 ; 
 V. also Ditte, A. Ch. [5] 13, 67). S.H. (16°-98°) 
 •2374 (Eegnault, A. Ch. [3] 1, 129). H. F. 
 [B',0'] = 317,200 (Troost a. Hautefeuille, A. Ch. 
 [6] 9, 70). 
 
 Preparation. — By heating B in 0, or by 
 strongly beating boric acid {q. v.). 
 
 Properties. — Semi-transparent, colourless, 
 brittle, inodorous, glass-like, solid ; volatilised at 
 a very high temperature (Ebelmen, A. Ch. [3] 
 22, 211) ; volatilised in steam or alcohol- vapour ; 
 non-conductor of electricity (Lapschin a. 
 Tichanowitsch, P. M. [4] 22, 308 ; Bowgoin, 
 
 0. R. 67, 798). 
 
 Reactions. — IBfi, is a very stable compound ; 
 it is not decomposed by heating with powdered 
 charcoal or with P vapour. It is an anhydride, 
 but appears to show a feebly basic character in 
 its reactions with certain acids (infra 6-8). 
 
 1. Heated with potassium, sodium, or aluminium, 
 metallic oxide and B are formed. — 2. Mixed 
 with charcoal and heated in nitrogen, chlorine, 
 bromine, or carbon disulphide, BN, BCI3, BBrj, 
 or B.jSs, is formed. — 3. Salts of most acids, e.g. 
 sulphates, nitrates, carbonates, are decomposed 
 by heating with Bfi, to a high temperature, 
 with production of borates and volatilisation of 
 the acid (v. Tate, O. J. 12, 160).— 4. Beacts with 
 most metallic oxides at high temperatures 
 to form borates. — 5. With water forms boric 
 acid (2. v.). — 6. BjO, is said to react with 
 fuming sulphuric acid to form a compound 
 xB.fl3.ySO3.zB.fi ; the values given tox,y, and a by 
 different chemists varjr ; thus Merz gives the for- 
 
628 
 
 BORON. 
 
 mula5BjOs.2SO,.2H20(X^.99,181),anaSohnltz- 
 Sellaok gives theformulaB.^Os.3S03.H20(B.4,15)- 
 This compound is easily decomposed by heat to 
 BjOj and SO3. — 7. B2O; is said to form a com- 
 pound with phosphoric anhydride, B2O3.P2O5: 
 this body is produced by heating together 
 HjBOs and cone. H^POjAq (Vogel, Z. 1870. 125), 
 and removing excess of the latter by hot water ; 
 it is also formed, according to Gustavson (B. 3, 
 426 ; 4, 975), by heating Bfi, with PCI5 to 140° 
 for 3-4 days, and also by heating B^Og with 
 POCI3 to 150°-170° for 8 to 10 hours, distiUing 
 ofE the POCI3.BCI3 formed {v. Boeon, ohlokide 
 OF ; Combinations, No. 1) and strongly heating 
 the residual solid. Bfi^.V-fi^ is said to be in- 
 soluble in hot water, to be unacted on by acids, 
 dissolved by boiling KOHAq, and to be decom- 
 posed by heating with Na, giving Na phosphide, 
 and probably phosphide of B. — 8. A com- 
 pound of BjO, with tungstic anhydride 
 (B203.9W03.a!H20) is described by Klein (Bl. [2] 
 36, 205), V. TuNOSTOBORATES, under Tungsten. — 
 9. B2O3 dissolves in hydrofluoric acid, forming 
 B2Os.6HF.HjO ( = HjB204.6HF) (v. Fluobokio 
 Acid, under Bokon, oxyacids of, p. 530). — 10. 
 When a solution of 1 part BjOj and 2 parts 
 KH.CjH,©, in 24 parts H^O is evaporated to 
 dryness at 100°, and the residue is treated with 
 alcohol, a white, amorphous solid remains, in- 
 soluble in alcohol but very soluble in water. 
 This solid has the composition C^H^KBO,; its 
 reactions are similar to those of tartar emetic ; 
 probably it is the K salt of an acid E.G^HjOj-OH 
 analogous to the acid Sb.O^HjOj.OH obtained 
 by Clarke a. Stallo (B. 13, 1787) {v. Meyrac, 
 J. Ph. 3, 8 ; Soubeiran, J. Ph. 3, 399 ; 11, 560 ; 
 25, 741; 35, 241; Duflos, S. 44, 333; Vogel, 
 J. Ph. 3, 1; Eobiquet, J. Ph. [3] 21, 197; 
 Wackenroder, Ar. Ph. [2] 58, 4; Wittstein, 
 B. P. [3] 6, 1, 177 ; Duve, /. 1869. 540 ; Biot, 
 A. Ch. [3] 11, 82 ; V. also under Tartkates). 
 
 Boron, Oxyacids of, and their Salts. Three 
 definite hydrates of 320, appear to be known ; 
 orthohoric acid B2O3.3H2O ( = H.|B03), metahoric 
 acid B2O3.H2O ( = 'H.^.f>^, and pyroboric (or 
 tetraboric) acid 2B2O3.H2O { = H^B ,0,). Another 
 hydrate 2B2O3.3H2O was described by Berzelius 
 (S. 23, 161) as obtained by heating H3BO3 
 ' considerably over 100°.' Most metallic borates 
 may be regarded as derived from H.^BjOj ; some 
 — e.g. borax — from HjBjO, ; a few are perhaps 
 derived from HuB^Oj, e.g. Ca^BjOg ; and in 
 addition to these several borates exist which 
 at present must be regarded simply as com- 
 pounds of B2O3 with metallic oxides {v. infra). 
 All the boric acids are ' weak ' acids, their salts 
 are easily decomposed by reactions with other 
 acids ; the affinity of boric acid is extremely 
 small, NajBjOj in solution is entirely decomposed 
 by an equivalent of H^SOj (Th. 1, 209). Borates 
 of the less positive metals are usually formed 
 only by fusing together B2O3 and the metallic 
 oxides. Many of these borates are decomposed 
 by water ; some of them are partially converted 
 into carbonates when exposed to the action of 
 moist air ; borates even of the very positive 
 metals readily combine with boric acid to form 
 acid salts, but these salts, although containing 
 excess of boric acid, usually turn red litmus 
 blue; even alkali borates are partially decom- 
 posed by water. Thonisen's thermal inves- 
 
 tigation of boric acid proves that the aciil 
 obtained by dissolving B2O3 in water is dibasio { 
 thus : — 
 
 m[mNaOHAq,B^O'Aq] 
 
 1 11,101 
 
 2 20,010 
 
 3 20,460 
 6 20,640 
 
 The normal Na borate is therefore NajB^O^. 
 When boric acid is added to a solution of this 
 salt heat is produced; thus : — 
 
 TO[Na2B^0'Aq,mB'0'Aq] 
 1 2,192 
 
 4 4,944 
 
 Acid salts are therefore probably formed, but 
 the reaction of the solution towards litmus is 
 still alkaline (Th. 1, 206). 
 
 Orthobokio Acid. H3BO3 (Boracic Acid ; 
 Boric Acid). [184°- 186°] (CarneUey, C. J. 33, 
 275). 
 
 Occurrence. — In the waters of many volcanic 
 districts, e.g. in Tuscany ; in many mineral 
 springs ; in combination with Na^-as borax — 
 in the waters of certain lakes in S. America, 
 Thibet, Ceylon, &a. ; in several minerals, e.g. 
 boracite (borate of Mg), boronatrocalcite (borate 
 of Ca and Na). 
 
 Formation. — 1. By oxidising B with agtia 
 regia, evaporating, dissolving in water, and 
 recrystallising. — 2. By dissolving Bfi, in 
 water. 
 
 Preparation. — 3 parts crystallised borax are 
 dissolved in 12 parts boiling water, and (after 
 filtering if necessary) 1 part cone. H^SOj is 
 added ; boric acid separates on cooling. The 
 crystals are gently heated, reorystallised from 
 water, dried, fused in a Pt crucible (to remove 
 all HjSOJ, again reorystallised from water, and 
 dried by pressure between filter paper. 
 
 Properties.— White, semi-transparent lam- 
 inae ; triclinic (Miller, P. 23, 558), monoclinio 
 (Kengott, Sits. W. 12, 26). S.G. i^ 1-434 
 (Stolba, /. pr. 90, 457). S. (19°) 3-9, (25°) 6-72, 
 (37-5°) 7-9, (50°) 9'84, (62-5°) 16-34, (75°) 21-15, 
 (87-5°) 28-17, (100°) 33-67 (Brandos a. Pirnhaber, 
 Ar. Ph. 7, 50 ; v. also Ditto, C. B. 85, 1969). 
 S.G. of HsBOaAq saturated at 15° = 1-0248 
 (Stolba, /. pr. 90, 457). Heat of solution, 
 [H=BO',Aq]=-5395 {Th. 3, 196). Soluble in 
 alcohol and several oils (Eose, P. 80, 262); 
 soluble in warm cone. HjSO,, HOI, or HN03,Aq, 
 but most of the boric acid separates on cooling. 
 Aqueous solution turns blue litmus wine-red, 
 and turmeric paper cherry red; alcoholic solu- 
 tion burns with green-edged flame. 
 
 Beactions. — 1. Heated to 100° HjBjOj ia 
 produced (Schaffgotsch, P. 107, 427 ; Bloxam, 
 C. J. 12, 177 ; Merz, J.pr. 99, 179) ; heated to 
 140° for a long time, or to 160° in a current of 
 dry air, H2B^0, is formed (Merz, I.e. ; Ebelmen 
 a. Bouquet, A. Ch. [3] 17, 63) ; heated to about 
 300° the oxide B^O, remains. Berzelius (S. 23, 
 161) said that Bififi^ ( = 2B2O3.3H2O) is 
 formed by heating H3BO3 to a temperature 
 ' considerably above 100° ' ; Merz (Z.c.) afBrmed 
 the production of 8B2O3.H2O at 270°.— 2. Boil- 
 ing cone. HgBOjAq dissolves a few metallic 
 sidphides and oxides (Tissier, 0. B. 39, 192 ; 45, 
 411) ; decomposes alkali and alkaline earth 
 carbonates (Popp, A. Suppl. 8, 10). — 8. With 
 alkalis ani alkali-carbonates salts of the form 
 
BORON. 
 
 530 
 
 M^BjO, or M.p3.,0j.a;H..3a0, are generally pro- 
 duced ; few metallic salts of the form M3BO3 
 are certainly known ; hence HjBOjAq reacts as 
 HjBjOjAq (■!;. also Borates). Ethereal salts of 
 H3BOJ— e.sr. EtjBOa, MejBOs-are known, but 
 none of them is directly formed from HoBO. 
 (p. 530). 
 
 Metaeoeio acid, HjBjO^ ; and Pyroboeio or 
 Tetkabobic acid.HjBjO,. Formed by heating 
 H3BO3 (ti. siipra) ; glass-like, amorphous solids. 
 Some salts of H^BjO^ are obtained by the reaction 
 between HjBjOjAq and alkalis ; salts of HjBjOj 
 are obtained indirectly (v. infra). 
 
 Borates. No borate is quite insoluble in 
 water ; the alkali borates are very soluble. The 
 less soluble borates are easily decomposed by 
 water, the easily soluble salts are also decom- 
 posed, but less quickly; an alkali borate, for 
 instance, in oonc. aqueous solution slightly 
 reddens litmus, but when much water is added 
 the litmus becomes blue. Solutions of alkali 
 borates absorb COj and H^S ; they decompose 
 NH^ salts when boiled with them ; dilute solu- 
 tions react with Hg and Ag salts similarly to 
 alkali solutions. A few borates can be obtained 
 as definite, fairly stable, salts by precipitation 
 from solutions ; KE3fi^.21Ifi separates from a 
 solution of KjCOj in excess of B^OjAq to which 
 much KOHAq has been added ; MgB20i.4H20 
 is said to be formed by the reaction between 
 borax solution and Mg2N03Aq. The more 
 definite borates are generally obtained by melt- 
 ing together B^O, and basic oxides. As a class 
 the borates very readily undergo change ; the 
 composition of very many is therefore extremely 
 doubtful. H. Eose, who investigated many 
 borates, did not attempt to wash his prepara- 
 tions, but pressed them between filter paper till 
 dry, and then determined the quantities of the 
 admixed foreign salts. Most borates seem to 
 belong to the two forms M^B^O, and MjB^O, ; 
 many may be represented as M^fi^-xH^Bfi, 
 and U^Bfi,.xB.fiJO), ; a tew— e.g. SMgO-BPa— 
 may be regarded as derivatives of H3BO3. The 
 best-marked borates are the salts of K and Na. 
 
 Potassium borates. — (1) Normal meta- 
 borate, K2B.^0i. Monoclinic crystals (a:6:c = 
 2-744:l:2-676) ; by melting, at white heat, 1 part 
 BjOj with 1-95 parts KjCO,, dissolving in water, 
 evaporating to a syrup out of contact with air, 
 and crystallising (Schabus, Bestimmung der 
 KrystallgeslaUen &c. [Wien, 1855], 31).— (2) 
 Acid metaborate, K2B2O4.H2B2O4.4H2O. Eegular 
 six-sided prisms ; by saturating boiling K2C03Aq 
 with BjOjAq, adding KOHAq to strongly alka- 
 line reaction, evaporating, and crystallising 
 (Laurent, A. Ch. [2] 67, 215). Said to sometimes 
 crystallise with 5HjO in rhombic prisms ; and 
 to lose HljO when heated in a closed vessel. — • 
 (3) Other acid salts. Kfi.fi i.2E.2Bfi^.6H.fl, 
 obtained like (2), but using less KOHAq. 
 2Kfifii.4,B.fifit.5B.fi{oy: 4:E.fi), by adding 
 BjOjAq to boiling KjCOjAq until solution has a 
 slightly acid reaction (Eammelsberg, P. 95, 199; 
 Eeissig, A. 127, 33). 
 
 Sodium borates. — (1) Normal meta- 
 borate, l!iafi.pi.iB.fi. Large monoclinic 
 prisms ; by fusing 1 part dry NafiO, with 1-17 
 parts BjOa (or with 3-6 parts crystallised 
 borax), dissolving in water, and crystallising 
 Vol,. I. 
 
 out of contact with air. Melts at 57° ; salt 
 with SHfi separates on cooling. Mixed with 
 NaJP, in solution, and crystallised, the salt 
 Na2B2O4.6NaF.H2O separates {v. Fldoboeio acid) 
 (Hahn, /. 1859. 128).— (2) Acid metaborates. 
 Na2B2O4.3H2B2O4.7H2O, lustrous, hard, crystal- 
 line crust, obtained by boiling solution of 2 
 equivB. borax with 1 equiv. NH4OI so long 
 as NH3 is evolved, and crystallising (BoUey, A. 
 68, 122). Na2B2O4.4H.2B2O4.7H2O, small crystals, 
 obtained by dissolving in water 1 equiv. borax 
 with 3 equivs. H3BO3, and crystallising (Laurent, 
 C. B. 29, 5).— (3) Orthoborate. NajBOj. Said 
 to be formed by fusing B2O3 with excess of 
 NaOH (Bloxam, O. J. 14, 143).— (4) Tetra, or 
 jayro, borates, (a) Borax. NaJBjOj.lOHjO, 
 ordinary or prismatic borax ; Na2B40,.5H20, 
 octahedral borax. The former occurs native ; 
 it is obtained by purifying crude borax, or by 
 fusing 1 part dry Na2C03 with 2-34 parts H3BO3, 
 dissolving in warm water, and slowly crystallis- 
 ing from a solution of S.G. 1-14-1-15 (B.P. 104°), 
 stopping when the temperature has fallen to 25°- 
 30°. The salt with 5H2O separates from aqueous 
 solutions of ordinary borax of S.G. 1-246 at tem- 
 peratures between 56° and 79°, or from super- 
 saturated solutions of the same salt protected 
 from dust, or from aqueous solutions of any 
 strength evaporated at 10° to 12° (Gernez, 
 C.R. 78, 68). Ordinary borax crystallises in 
 large, transparent, colourless, doubly refractive, 
 monoclinic prisms (a:6:c = l-0995:l:-5629. = 
 73° 25'). S.G. 1-69 (Filhol, A. Ch. [3] 21, 415). 
 S. (0=) 2-8, (20°) 7-9, (40°) 17-9, (60°) 40-4, (80°) 
 7d-2, (90°) 119-7, (100°) 201-4 (Poggiale, A. Ch. 
 [3] 8, 468). S.G. of solution saturated at 15° = 
 1-0199 (contains 38-494 borax) (Michel a. Kraft, 
 A. Ch. [3] 41, 471). Insol. 'in alcohol. Heat 
 disappears during solution ; [Na^B'O'.10H^O,Aq] 
 = -25,860 (Thomsen). S.H. (19°-50°) -385 
 (Kopp, T. US, 71). Eefractive indices (23°, 
 Na light) for a = 1-4463, for ;8 = 1-4682, for 
 7 = 1-4712 (Kohlrausch, W. 4, 1). The crystals 
 effloresce in air (according to Sims only when 
 they contain sodium carbonate) ; when heated 
 they melt and give off IOH2O, leaving burnt 
 borax (NajBjO,), which melts at a red heat to a 
 glass-like mass {vitrified borax) of S.G. 2-36 ; 
 exposed to moist air this takes up IOH2O. Solu- 
 tion of borax in water is alkaline to Htmus ; it 
 dissolves many organic compounds more readily 
 than water, e.g. benzoic acid and gallic acid ; some 
 compounds insoluble in water dissolve in borax 
 solution, e.g. stearic acid, various gums, resins, 
 and oils ; ASjOj dissolves easily ; silicic acid 
 only very slightly. Molten borax dissolves 
 many metallic oxides and salts forming fusibla 
 double salts ; hence its use as a flux, and also 
 in analysis. Crystals of corundum were ob- 
 tained by Ebelmen {A. 80, 205) by dissolving 
 AI2O3 in molten borax, and crystals of rutile and 
 tridymite by dissolving TiOj and Si02, respec- 
 tively, in the same solvent (G. Eose, J. pr. 101, 
 228 ; 108, 208). Octahedral borax crystallises 
 in hard, transparent, regular octahedra. S.G. 
 1-8. Unchanged in dry air, but in moist air 
 changed to prismatic borax. Melts to a glass- 
 like mass. 
 
 (b) Amorphous tetraborate. 
 Na2B40,.4H20. Obtained according to Sohweizer 
 {A. 76, 267) by evaporating aqueous borax 
 
 MM 
 
530 
 
 BOEON. 
 
 solution at 100° and drying the residue at the 
 same temperature for a long time. 
 
 (c) NajBjC.BHjO was found by Bechi 
 (Am. S. [2] 17, 129 ; 19, 120) in an old lagoon ; 
 it has not been prepared artificially. 
 
 The remaining borates have been chiefly 
 investigated byBerzelius (S. 23, 160 ; P. 2, 113 ; 
 9, 433 ; 33, 98 ; 34, 561) ; Arfvedson (Gm.-K. 
 6th ed.) ; Gmelin (v. Gm.) ; H. Kose (P. 9, 176 ; 
 19, 153 ; 86, 561 ; 87, 1, 470, 587 ; 88, 299, 482 ; 
 S9, 473; 91, 452); Wohler (P. 28, 525); 
 Eammelsberg (P. 49, 445) ; Ebelmen {A. Ch. [3] 
 16, 129 ; 17, 54; 33, 34) ; Bouquet {A. Ch. [3] 
 17, 54) ; BoUey {A. 68, 122) ; Herapath (P. M. 
 [3] 34, 375) ; Laurent (A. Ch. [2] 67, 215) ; 
 Tissier (C. B. 39, 192 ; 45, 411) ; Bloxam (C. J. 
 12, 177 ; 14, 143). For an account of various 
 supposed compounds of MO with B.Os v. Ditte 
 (A. Ch. [5] 80, 248). The following are the 
 salts which have been chiefly examined ; but the 
 composition of many is not settled. 
 
 Aluminium. — 2AI2O3.B2O3.3H2O ; 
 3AI2O3.2B2O3.7H2O (H. Eose). — 3Al203.Bj03 
 (Ebelmen). 
 
 Ammonium. — (NHJ2B2O1.H2B.Pj.2H2O (also 
 SHjO) (Arfvedson).— (NHJ.B20<-5H2B20^.4H20 
 (Bechi, Am. S. [2] 17, 129 ; 19, 120). 
 
 (NHJ2B204.3H. B20,,.3H20 (Gmelin).— 
 (NHJ2B2O1.4H2B2O4.2H2O (Bammelsberg). 
 Barium. — BaB2O4.10H2O (Berzelius) . — 
 BaB204.H20 (Eose). — BaB2Oj.H2B2O4.4H2O ; 
 BaB204.2H2B204.12H20 ; 2BaB204.H2B204,14H20 
 (Laurent).— 683(803)2; 2Ba0.B203; 5Ba0.2B203 
 (Bloxam).— 2Ba0.3B203 ; BaBjO, (Ditte, O. B. 
 77, 788). . 
 
 Cadmium.—CiBfit ; 2CdB2O4.CdO2H2.2H2O 
 (Bose). 
 
 Calcium.. — 
 CaB20i.2H20 ; 2CaB2O4.H2B2O4.4H2O (Bose).— 
 CaB204.H2B204 (Tiinnermann). — 
 CaB2O4.3H2B2O4.6H2O (Laurent).— 
 CaB20,; 3Ca0.2B203; 2CaO,3B20s; 
 3Ca0.3Mg0.4B203 (Ditte). 
 Co6aZ«.— 2CoB20j.Co0.^2-3H20 (Rose). 
 Copper. — Composition very uncertain (v. 
 Tiinnermann, Eose, Laurent, BoUey ; also 
 leEoux, C. B. 64, 126; Pasternaclj, A. 151, 227 ; 
 Poussier, B. 6, 1138). 
 
 Didymium.—T)iB03 (Cl^ve, Bl. [2] 43, 364). 
 Iron. — Fe(B204)3.3H20 ; found in a lagoon- 
 crater (Bechi, Am. S. [2] 17, 129 ; 19, 120). 
 Basic salts of uncertain composition are formed 
 by the reactions between alkali borates and 
 solutions of ferric salts ; borates of Fe and Na 
 seem to be produced by ppg. iron alum with 
 alkali borates (Eose). 
 
 Lead.— PhBfit.B.fi ; 2PbB2O4.H2B2O4.3H2O ; 
 PbB20j Ji2B204.3H20 (Herapath ; v. also Eose). 
 Double salts : PbB204.Pb(N03)2.H20 ; 
 PbB2O4.PbCl2.H2O (Herapath). 
 Magnesium. — MgB204.4H20 ; 
 MgB2O4.2H2B2O4.6H2O ; MgB2O4.3H2B2O4.8H2O; 
 MgB204.5H2B204.13H20 (Laurent ; Eammelsberg). 
 —MgB204.8H20 (Wohler).— Mg3(B03)2(Ebekaen). 
 Double salts: 6Mg0.3X20s.2B263 (X = Cr or 
 Fe) (Ebelmen). Ditte describes various com- 
 pounds of the form aMgO.j/CaO.xBjOj. 
 
 Nickel. — ^NiB204.2H20 (Eose) : also various 
 vague basic salts. 
 
 Bubidium.—RhJBfir^^aO (Eeissig, A. 127, 
 S3). 
 
 SiZwr.- Ag.32O4.H2O ; 3Ag2O.4B.2O3 (Eose). 
 
 Strontium.— SiBfl,; SrB40,; 3Sr0.2B20, ; 
 2Sr0.3B203 (Ditte). — 3SrB204.2H2B20,.5H20 
 (Eose).— SrB204.H.,B204.3H20 ; 
 
 SrB20..3H2B204.3H20 (Laurent). 
 
 Zinc. — Very vague (v. Bose). Bflscher {A. 
 151, 234) describes the double salt 
 ZnO.4NH3.2B2O3.6H2O. 
 
 [? Samarium borate. — SmB03 (ClJve, Bl. [2] 
 43, 170.] 
 
 Fluoboeic Acid, and Fluoboeates. BjOj ap- 
 pears to react as a feebly basic oxide towards the 
 anhydrides of a few acids, e.g. SO3 and P2O5 (v. 
 BoKON, OXIDE OP, Beactions, Nos. 6, 7). H3BO3 
 dissolves in cone. HFAq ; by concentration, and 
 cooling over H2S0,|, a thick syrup-like liquid is 
 obtained (S.G. 1-684) containing H2B204and HF 
 in the ratio H2B204:6HF. This liquid is gene- 
 rally regarded as a definite acid, called fiuo- 
 boric acid. This liquid chars organic matter 
 like H2SO4. The same liquid is obtained by 
 saturating water with BF, and distilling (Gay- 
 Lussae a. ThSnard, Becherches physico-cM- 
 miques, 2, 38 ; Berzelius, P. 58, 503 ; 69, 644). 
 The liquid is decomposed by water into HBF4Aq 
 and H2B2O4 {v. BoKOFLUOKHYDKio Acn>, under 
 BoKON, FLuoEiDE OF). If this liquid is neutral- 
 ised by NaOHAq or KOHAq, and the solution is 
 evaporated, the salts M2B2O4.6MF.H2O (M = Na 
 or K) are obtained (Berzelius). The same salts 
 are also formed, when M = K by fusing KF with 
 H3BO3, and when M = Na by crystallising mixed 
 solutions of NajBjOj and NaF. It is very doubt- 
 ful whether the so-called fluoboric acid is a 
 definite compound or not. According toBasarow 
 (0. B. 78, 1698) the liquid prepared as de- 
 scribed is decomposed by distillation ; at 140° 
 BF3 is given off, at 160° to 170° a thick, 
 heavy, fuming liquid (S. G. 1-77) comes over, 
 at 175°-185° a less fuming liquid is produced, 
 and as the temperature rises the distillate 
 becomes lighter and fumes less in air. The 
 heavy distillates are decomposed by water 
 with separation of H3BO3. The salts obtained 
 by Berzehus are separated by crystallisation 
 into MF, which crystallises out first, and a 
 mixture of MF with M2B2O4 (Basarow). Solu- 
 tion of the so-called acid reacts with AgN03Aq 
 to give Ag2B204 and Ag20. Basarow regards 
 fluoboric acid as a mixture of HjBjOj with HBP4 
 and HF. Landolph (B. 12, 1583) describes the 
 bodies H4B20,.3HF and H4B20g.2HF; the first 
 is obtained in small quantities by the reaction 
 between BF3 and CsHu, the second is one of 
 the products of the action of BF3 on hot anethol. 
 Both bodies are fuming, acid, liquids; they 
 seem to be fairly stable ; the first is unchanged 
 by distillation. 
 
 BoEOTONGSTATES. Many compounds of the 
 forma;B2O3.yWO3.0MO (MO = metallic oxide) have 
 been obtained: the acid B2O3.9WO3.2H2O.l8aq 
 has been prepared. The principal borotung- 
 states will be described under Tungsten as 
 
 TUNGSIOBOKATES. 
 
 Detection and Estimation of Boric Acid. 
 Free boric acid is detected by its action on 
 turmeric paper, or by the green colour which it 
 imparts to the flame of burning alcohol ; borates 
 do not give these reactions, therefore they must 
 be decomposed by HjSOjAq before applying the 
 alcohol test, or by HClAq before applying the 
 
BRASSIO ACID. 
 
 631 
 
 turmeric paper test. There is no very satis- 
 factory method for estimating boric acid. The 
 most insoluble salt is KBF^ ; it is obtained from 
 borio acid or borates by adding excess of 
 KOHAq, then evaporating with excess of HFAq, 
 dissolving out sulphate, nitrate, &o. of K, by 
 KC.HjOjAq, washing with alcohol, and drying 
 at iOO'. Marignac (Fr. 1, 405) evaporates the 
 Bolution of the borate with excess of NH^ClAq and 
 MgCljAq, with various precautions, and finally 
 obtains a mixture of MgO and Mg borate in 
 which he then estimates the amount of MgO 
 and so gets the amount of borio acid (v. also 
 Ditte, C. iJ. 80, 490 a. 561). As borio acid 
 interferes with estimation of some other bodies, 
 e.g. phosphoric acid, it is sometimes necessary 
 to remove it ; this may be done either by boiling 
 with alcohol and H.,SOjAq (EtjEOj goes off), or 
 with HF and H^SOjAq (BF3 goes off). Bosen- 
 bladt (Fr. 26, 18) describes a method based on 
 the volatilisation of boric acid by distillation 
 with methylio alcohol ; the method gives good 
 results (v. also Goooh, C.N. 55, 7). 
 
 Boron, oxychlorides of. Two are known, 
 BOCl and BOCl, ; neither exists as a gas ; both 
 are decomposed by heat. BOCl is a white 
 gelatinous solid, obtained by heating Ti.fi^ with 
 BOlj, in the ratio B20j:2BCl3, to 150^ ; at a high 
 temperature it is decomposed to BCI3 and B^Oj 
 (Gustavson, Z. 1870. 521). BOCI3 is described 
 as a yellowish-green liquid ; it was obtained, 
 along with BCI3, by passing CI over a heated 
 mixture of BjO, and C, removing CI from the 
 gaseous products by Cu turnings, condensing, 
 and removing BCI3 by evaporation (Counoler, 
 J.pr. [2] 18, 399). The conditions under which 
 BOCI3 is formed are not definitely known ; 
 Counoler obtained the best result when relatively 
 little carbon was used, and a fairly rapid stream 
 of CI was passed through the tube. BOCI3 is 
 decomposed by heat into BCI3, B.^Oj, and CI; 
 and by water to H3BO3, HCl, and CI. No oxy- 
 chloride of B is formed by the action of ozone 
 on BCI3, or by passing electric sparks through a 
 mixture of BCI3 and (Miohaelis a. Becker, B. 
 14, 914). 
 
 Boron, sulphide of. B^Sj. Mol. w. unknown, 
 as compound has not been gasified. 
 
 Formation. — 1. By heating B in S vapour to 
 white heat (Berzelius, P. 2, 146).— 2. By gently 
 heating B in dry H^S (Wohler a. Deville, A. 105, 
 72). 
 
 Preparation. — Small pellets are made by 
 mixing powdered BjOj with soot and oil and 
 heating out of contact with air; these are 
 heated to full redness in a porcelain tube, in a 
 stream of dry CSj ; the tube is connected with 
 two small flasks surrounded by snow and salt. 
 The BjSs collects on the surface of the condensed 
 CS, ; it is separated from CS2 and dried in an 
 atmosphere of H (Fremy, A. Ch. [3] 38, 812). 
 B.,S3 is a white solid (with a yellowish tinge, 
 Promy), consisting of groups of small crystals ; 
 it smells strongly, and its vapour acts on the 
 eyes ; it is rapidly decomposed by moisture to 
 B2O3 and HjS ; it may be melted in an atmo- 
 sphere of H, and volatilised in a current of H^S. 
 
 M. M. P. M. 
 
 BOSON, ORGANIC DEBIVATIVES OF. 
 
 Boron tri-msthide C3H9B i,e. BMej. V.D. 1-91 
 (oalc. 1-93). Prom ethyl borate and ZnUe^, thus : 
 
 2B(0Et)3 + SZuMe^ = 2BMe3 + 3Zn(OEt)2 (Frank- 
 land, C. /. 15, 373). Pungent gas. V. si. sol. 
 water, v. sol. alcohol and ether. Takes fire in 
 air, burning with a green flame. Not affected 
 by cone. H.^SOj or by HI. Combines with 
 potash forming BMcjEOH. Combines with 
 ammonia forming BMeaNH, [56°] (110°). Com- 
 bines also with NaOH, CaO, and BaO. 
 
 Boron tri-ethide BEtj. Mol. w. 98. (95°). 
 S.G. 22; -696. V.D. 3-40 (oalc. 3-40). From 
 BCI3 or B(0Et)3 and ZnEt^ (Frankland, Tr. 
 1862, 167 ; Pr. 25, 165). Pungent oil. Takes 
 fire in air. Slowly decomposed by HCl, evolving 
 CjHij. Violently attacked by chlorine. 
 
 Combinations. — 1. With ammonia it forms 
 a liquid BEtjNHj. — 2. By careful oxidation, 
 first in air, then in oxygen, it forms an oxide 
 BEtjOj, (125°). Water decomposes this oxide, 
 forming ethyl-boric acid, BEt(0H)2. Ethyl- 
 boric acid is crystalline, and may be sub- 
 limed ; its solutions are acid, but it does 
 not form salts. A compound BEt(OEt)2B(OEt)3 
 (c. 112°) appears to be formed by the action 
 of ZnEtj (1 mol.) on boric ether; it is decom- 
 posed by water into alcohol, BBt(0H)2 and 
 B(0H)3 ; and by ZnEtj it is converted into 
 BEt2(0Et) (103°), which absorbs oxygen, becom- 
 ing BEt(OEt)j. Di-ethyl-boric ether, BEt2(0Et) 
 is saponified by water, and the acid absorbs 
 oxygen, becoming crystalline BEt(0Et)(0H), 
 which is converted by water into ethyl-boric acid 
 BEt(0H)3. 
 
 Boron-phenyl-di-chloride CbH^BCIj. [about 
 0°]. (175°). Prepared by heating boron tri- 
 chloride with mercury di-phenyl at 200° 
 (Michaelis a. Becker, B. 15, 180). Colourless 
 fuming fluid. By the action of water it gives 
 phenyl-boric acid, and by the action of alcohol, 
 phenyl-boric ether. 
 
 Boron -p- tolyl - dichloride CbH^(CH3).BC1j. 
 [27°]. Colourless crystals. Prepared by heat- 
 ing boron tri-ohloride with mercury di-^-tolyl 
 (Michaelis a. Becker, B. 15, 185). 
 
 BORO-TARTAR-EMETIC v. Bobon, oxide 
 OF ; Reactions, No. 10 ; also under Tabtbates. 
 
 BOROTUNGSTATES. Compounds of the 
 form xB203.j/W03.zMO(M = metal), v. Tungsio- 
 BOBATES, under Tdnosten. 
 
 BRASILEIN V. Bbazilein. 
 
 BRASS V. CoFPEB, Alloys of. 
 
 BRASSIC ACID C^jH^O^. [60°]. Prepared 
 by just melting its isomeride, erucic acid, with 
 dilute HNO3, and adding . sodium nitrite. 
 LaminEB (from alcohol) . Combines with bromine. 
 Potash-fusion gives arachic acid. 
 
 Salts. — NaA' : laminse (from alcohol). 
 
 Ethyl ether EtA': [30°j ; (above 360°); 
 glistening plates ; obtained by etherifying the 
 acid or by the action of nitrous acid upon ethyl 
 erucate. 
 
 Olycerin-di-brassic ether C3H5(0H)A'2: 
 (dibrassidin) [65°] ; crystals, si. sol. ether. 
 Formed from glycerin-di-erucio ether by nitrous 
 acid. 
 
 Olycerin-tri-brassic ether CjH^A', : 
 Tribrassidin. [47°], after heating [36°]; colourless 
 crystalline powder ; v. sol. ether, nearly insol. 
 alcohol. Obtained by the action of nitrous 
 acid upon rape-seed oil, and crystallisation 
 of the solid product from ether. 
 
 Amide C^iHji.CONHj: [90°]; colourless 
 
 u II 2 
 
532 
 
 BRASSIC ACID. 
 
 needles ; formed by the action of NH, gas upon 
 tbe anhydride. 
 
 Anilide CjiH^.CONHPh: [78°]. 
 
 Anhydride (Oj,H„.CO)20: [29°]; glisten- 
 ing tables; v. sol. ether and benzene, insol. 
 alcohol and water; formed by the action of 
 PCI3 upon brassio acid and subsequent addition 
 of alcohol (Eeimer a. Will, B. 19, 3320; cf. 
 Wesky, J. pr. 58, 449 ; Hausskneoht, A. 143, 40 ; 
 Fitz, B. 4, 444 ; Goldschmiedt, SiU. B. 74, 394). 
 
 BRASSYLIC ACID 0„Hj„0<. Mol. w. 216. 
 [109°]. Formed, together with its aldehyde and 
 dioxybehenolic acid, by the action of fuming 
 HNO3 on behenolic acid (Haussknecht, A. 143, 
 45). Crystalline, v. si. sol. cold water, v. sol. 
 alcohol and ether. 
 
 Salt s.— CaA" 3aq.— Ag^A". 
 
 BEASSTIIC ALDEHYDE C^^B^fi,. The 
 chief product of the action of fuming HNO3 on 
 behenolic acid {v. supra). Oil, lighter than 
 water, volatile with steam. Sol. NaOHAq and 
 reppd. by HCl. Oxidised by bromine to brassylic 
 acid. 
 
 BRAZILEiN CisHi^OsHjO. 
 
 Formation. — By the oxidation of brazilin by 
 air in presence of alkalis, or in ethereal solution 
 by HNO3 (Eeim, B. 4, 334 ; E. Kopp, B. 6, 446 ; 
 Liebermann a. Burg, B. 9, 1883; Buchka a. 
 Brck, B. 18, 1142). 
 
 Preparation. — Extract of Brazil-wood is dis- 
 solved in hot water and, after cooling, NH3 in slight 
 excess is added. The solution is exposed to air, 
 when a pp. is formed which is crystallised from 
 hot dilute acetic acid (Hummel a. A. G. Perkin, 
 0.^41,373). 
 
 Properties. — Minute crystals with grey lustre. 
 Eeddish-brown when powdered. Very slightly 
 soluble in cold water, more so in hot water. The 
 solution is yellowish-pink with greenish-orange 
 fluorescence. Alkaline solutions are carmine 
 red, but slowly turn brown in air. 
 
 Reactions.— 1. If hot glacial acetic acid be 
 slowly added to a solution in cold cone. H2SO4, 
 minute orange needles of iso-braziWin sulphate, 
 OijHiiOiSOiH, are got. Its alkaline solutions 
 are carmine red quickly turning brown in air. 
 Alcohol turns iso-brazilein sulphate scarlet, 
 forming the basic salt C,sH,2O52(0,„H|,O4SO4H). 
 
 2. Cone. HCl at 100° forms C,sH„0.,Cl. Minute 
 red prisms with violet lustre, called iso-brazilein 
 chlorhydriu. Its aqueous solution is orange. — 
 
 3. HBr at 100° forms, similarly, O.jHiiOjBr. 
 Brazilein resembles hsematein (g. v.) in these 
 reactions. 
 
 BEAZILIN CijHijOs. Occurs in Brazil-wood 
 (the wood of GcesaVpima crispa) and in Sapan- 
 wood (from CcBsalpinia Sapan) (Chevreul, A. Gh. 
 66, 226 ; E. Kopp, B. 6, 447 ; Bolley, J. pr. 93, 
 451). 
 
 Preparation. — The dark brownish-red crusts 
 deposited during the preparation and storage of 
 commercial extract of Brazil-wood consist of 
 brazilin and its lime compound. The crusts 
 are washed with dilute (5 p.o.) HCl and then 
 extracted with very dUute (12 p.c.) alcohol. 
 
 Properties. — Colourless crystals (containing 
 aq). Sol. water, alcohol, and ether. Turns 
 orange in air. Forms a carmine solution in 
 aqueous NaOH in air ; this solution is bleached 
 by zinc-dust, but re-oxidised to brazilein by air. 
 
 Aqueous solutions are also turned red by NH, 
 or baryta when exposed to air. 
 
 Beactions. — 1. Besorcin is among the pro- 
 ducts of its dry distillation. — 2. KCIO, and 
 HCl give iso-tri-ohloro-glycerio acid (Benedikt, 
 
 A. 178, 100). 
 
 Salt. — PbA"aq : small colourless needles. 
 
 Tri-acetyl-derivative C,„H„(OAc)302 ; 
 [106°] ; slender colourless needles. 
 
 Tetr a -acetyl -derivative C,uH,j(0Ac)40: 
 [151°] ; glistening needles (Buchka a. Erck, B. 
 18, 1138). 
 
 BREIDIIT V. Abbol-a-bbea. 
 
 BRIMSTONE v. Shlphue. 
 
 BRITANNIA METAL v. Tm, alloys of. 
 
 BRITISH GUM v. Dextkin. 
 
 BROMAL V. BrOMO-AOETIO ALDEHYDE. 
 
 BROMALIDE C^H^BrA i.e. 
 
 CBr3.CH<^'^Q°>CH.CBr3. Tri-lromo-ethyl- 
 
 idene tri-bromo -lactate. [158°]. Formed by 
 heating bromal hydrate with HjSOj ; or by warm- 
 ing a mixture of bromal and tri-bromo-laotio 
 acid (Wallach, A, 193, 1 ; Wallach a. Eeiuecke, 
 
 B. 10, 2128). Monocliuic crystals, insol. water, 
 sol. ether. Decomposed by alcohol. 
 
 BROMANIL is Tetea-bbomo-quinone (g. v.). 
 BROMATES AND PERBROMATES.— Salts 
 of bromlc and perbromic acids ; v. Bbouhie, 
 
 OXYACIDS OP. 
 
 BROMHYDRIC ACID. HBr. {Sydrobromic 
 acid. Hydrogen bromide.) Mol. w. 80'75. [—73°]. 
 (-69°) (Faraday, r. 1823. 189). V. D. 39-1. 
 S. (-25° to 0° at 760 mm.) about 690 ; S. (-25° 
 to 0°at -2 mm.) about 345 (Eoozeboom, B. T. G. 
 4, 102). H. F. [H,Br] = 8,440; [H,Br,Aq] = 
 28,376 ; [H,BrAq] = 27,837 {,Th. 2, 29). 
 
 -^xAt. wt. = 20-6 (Gladstone, 2*. 1870. 9). 
 
 H and Br do not combine at ordinary tempera- 
 tures even in direct sunlight. 
 
 Formation. — 1. By burning H charged with 
 Br vapour. — 2. By passing a mixture of H and 
 Br over hot Pt ; for details of method v. Harding, 
 B. 14, 2085. — 3. By the action of electric sparks 
 on H and Br. — 4. By the action of Br on HjO, 
 more quickly in presence of oxidisable bodies 
 such as P, S, As, or lower oxides of these 
 elements. — 5. By passing HjO and Br through 
 a hot tube (Bourson, G. B. 13, 1154).— 6. 
 By passing H^S into Br and HjG (Naumann, 
 B. 9, 1577).— 7. By passing HI into Br (Haute- 
 feuille, C. B. 64, 705).— 8. By the mutual action 
 of Na^SOj (Mtoe, C. B. 28, 478), or Na^SA 
 (Gladstone, P. M. [3] 35, 345), Br, and H^O; 
 (NajSOjAq + Ufi -f Br^ = Na^SO^Aq + 
 2HBrAq:Na2S203Aq + H^O + Br^ = 
 Na^SOiAq 4- S + 2HBrAq). 
 9. By leading Br into melted paraffin at 185° 
 (Champion a. Pellet, 0. B. 70, 620). 
 
 Preparation. — 1. When smaU quantities are 
 required, BBr may be prepared by the action of P 
 and Br on H^O (4:B.fi -h P -1- 5Br = HsPO^ + 5HBr). 
 A glass tube is bent 3 times at about a right 
 angle ; a little Br is placed in one bend and a 
 few pieces of P in the other; pieces of glass 
 moistened with a very little water are placed in 
 the limb of the tube above the P ; a cork with 
 delivery tube is fitted into the open end of the 
 tube above the glass, and the other end of the 
 
BROMHYDRIC ACID. 
 
 633 
 
 tube is closed by a ooik. The Br is then very 
 gently warmed ; the reaction occurs when the Br 
 vapour reaches the moist P, and the HBr passes 
 off through the delivery tube. — 2. When larger 
 quantities of HBr are required it is advisable to 
 use amorphous P. In a flask fitted with a cork 
 carrying an exit tube and a small stoppered 
 separating funnel, is placed 1 part amorphous 
 P mixed with some dry sand, the P is moistened 
 and then covered with a layer of dry sand 
 (Liunemann, A. 161, 198 note) ; the exit tube is 
 connected with a IJ tube nearly filled with glass 
 beads moistened with cone. HBrAq and pieces 
 of ordinary P (any Br which may come over is 
 converted into HBr in this tube) ; this is 
 followed by a drying tube containing CaCIj or 
 PjOj, and from this a delivery tube passes into a 
 dry cylinder filled with dry Hg standing in a 
 Hg trough. Ten parts of Br are placed in the 
 separating funnel and allowed to drop slowly 
 into the flask; HBr is evolved. Towards the 
 close of the operation the flask is gently warmed. 
 If it is desired to prepare an aqueous solution 
 of HBr, the (J tube is fitted with an exit tube 
 passing into the tubulus of a retort placed 
 vertically and arranged so that the beak dips a 
 little way under the surface of water in a bottle ; 
 should the flow of HBr slacken, the water rises 
 into the body of the retort but cannot flow back 
 into the generating vessel. — 3. By the action of 
 con. HjPOjAq on KBr ; 1 part KBr, 1 part 
 HjPO,, and 3 parts KJO being used (Bertrand, 
 C. jB. 82, 96).— 4. By decomposing the bromide 
 of an alkaline earth metal by HjSOjAq; Ber- 
 trand (I.e.) employs two parts CaBr.^, 2 parts 
 cone. HjSOj and 1 part HjO. If an alkali 
 bromide is used, the HBr contains much Br and 
 some SOj. — 5. An aqueous solution of HBr maybe 
 obtained by slowly adding P in small pieces to 
 Br mixed with a considerable quantity of water 
 in a vessel surrounded by ice, then adding a, 
 little more Br and then a few pieces of P (re- 
 peating if a strong solution is required), and 
 distilling from HaPO^Aq {v. Topsoe, B. 3, 400). 
 
 Properties.— BBi is a colourless gas, with 
 pungent, acid, very irritating, odour ; excites 
 inflammation when applied to the skin ; fumes 
 in moist air ; dissolves very largely in water ; 
 (v. infra) is absorbed by, and melts, ice ; at - 73° 
 liquefies, and then crystallises. Melsens (0. B. 
 77, 781) obtained liquid HBr by saturating wood 
 charcoal with the gas (15,500 gram-units of 
 heat are produced for every 81 grams HBr 
 absorbed, Favre, A. Ch. [5] 1, 209), placing the 
 charcoal in one end of a closed glass tube bent 
 to an obtuse angle, the other end of which was 
 well cooled, and heating the charcoal in a water 
 bath. An aqueous solution of HBr forms a 
 colourless, strongly acid liquid ; the affinity is a 
 very little less than that of HClAq v. Affinity. 
 The cone, solution fumes in, but is not de- 
 composed by exposure to, air. S.G. of solution 
 saturated at 0° = l-78; 1 c.c. contains 1-46 
 grams HBr ( = 82-02 p.c. HBr by weight) which 
 almost agrees with the composition calculated 
 from the formula HBr.H^O (Bineau, A. 44, 237). 
 Boozeboom {B. T. C. 5, 363) has obtained 
 the hydrate HBr.H^O as a solid at low 
 temperatures and under a pressure of 3 atmos. 
 If cone. HBrAq is distilled at 760 mm. pressure 
 HBr is evolved, it HBrAq containing less 
 
 than 47 p.c. HBr is distilled at 760 mm. 
 HjO is evolved, in each case the B. P. 
 becomes constant at 126° and the solutioii 
 contains 47*38 — 47"86 p.c. HBr ; the composition 
 of this liquid is almost exactly that expressed 
 by the formula HBr.SHjO (V. D. = 14-1 agreeing 
 with V. D. calculated for HBr + 5B..fl) ; but it 
 is not probable that the liquid consists of a true 
 hydrate, as the composition varies with the 
 pressure ; thus if the pressure is 1,952 mm. the 
 constant B. P. is 153° and the liquid contains 
 46-3 p.c. HBr {v. Eoscoe, A. 116, 203). If dry 
 air is passed through HBrAq at a constant 
 temperature, either HBr or H^O is removed, and 
 the composition becomes constant; at 16° the 
 liquid finally contains 51"65, and at 100° 49"36, 
 p.c. HBr (Eoscoe, I.e.). The S.G. and p.c. 
 composition of HBrAq are given in the following 
 tables (Topsoe, B. 3, 404 ; Wright, 0. N. 23, 
 242). 
 
 Temp. S.G. P.O. HBr. Temp. S.O. P.O. HBr. 
 14° 1-055 7-67 13° 1-302 33-84 
 
 14 1-075 10-19 13 1-335 36-67 
 
 14 1-089 11-94 13 1-349 3786 
 
 14 1-097 12-96 13 1-368 39-13 
 
 14 1-118 15-37 13 1-419 43-12 
 
 14 1-131 16-92 13 1-431 43-99 
 
 14 1-164 20-65 13 1-438 44-62 
 
 IB 1-200 24-35 14 1-451 45-45 
 
 13 1-232 27-62 13 1-460 46-09 
 
 13 1-253 29-68 14 1-485 47-87 
 
 14 1-490 48-17 
 
 s.o. 
 
 Temp. 16° (Wright) P.O. HBr. 
 
 1-080 
 
 10-4 
 
 1-190 
 
 23-5 
 
 1-248 
 
 30-0 
 
 1-385 
 
 40-8 
 
 1-475 
 
 48-5 
 
 1-515 
 
 49-8 
 
 Beactions. — 1. Not decomposed by heat alone, 
 even at 700° (Hautefeuille, O. B. 64, 705).— 
 2. Decomposed by heating with many metals, 
 e.g. K,Na, Na amalgam, Sn, &c. with formation 
 of metallic bromide and H. — 3. Chlorine forms 
 HOI and Br. — 4. Cone, nitric or sulphuric acid 
 forms Br, H^O, and NO^ or SOj. — 5. Lead or 
 silver oxide forms metallic bromide and HjO 
 at ordinary temperatures ; most of the other 
 metallic oxides decompose HBr in a similar 
 way on warming. — 6. Metallic peroxides, and 
 acids containing metals {e.g. HSbO,), form 
 metallic bromides and Br. — 7. Aqueous solution 
 of HBr is decomposed by most metals with 
 formation of metallic bromide and H; most 
 metallic oxides dissolve in HBrAq forming 
 bromides. The heat of neutralisation of HBrAq 
 by MOHAq or M(0H)2Aq, when M = an alkali 
 or alkaline earth metal, is the same as the heat 
 of neutralisation of HClAq, viz. 13,750 ; but the 
 quantity of heat produced by the action of HBrAq 
 on the hydrated oxides of Pt and Au, and on 
 HgO, is much greater than the quantity of 
 heat produced by the action of HClAq on the 
 same compounds ; the diSerences are 
 for AUO3H3 13,810 
 
 „ PtoA 11,890 
 
 „ PtO^Hi 16,300 
 
 „ HgO 12,290. 
 
 The action of HBrAq on these hydrated oxides 
 is very different from the action of the sama 
 
5a4 
 
 BROMHYDEIC ACID. 
 
 aoid on the hydrated oxides of E, Ca, Mg, &o. ; 
 in the former cases there is little doubt that 
 Boids of the form H^HgEr^, H^PtBrj, H^PtBrj, 
 and HAuBr, are formed in the solutions {v. 
 Xhomsen, Th. 3, 538). Many double bromides 
 of Au, Hg, andPt— e.j.PtBr4.2KBr— are rather 
 to be regarded as alkali salts of these acids 
 than as double salts {v. Th. 3, 417 ; also 
 Gold, Meeouey, PiLLADinM, Platinum). — 8. 
 HBrAq is decomposed by bromic acid solution ; 
 EBiO^Aq + 5HBrAq = SH^OAq + 6BrAq.— 
 
 9. Cone, sulphuric acid heated with HBrAq 
 forms H2O, SO2, and Br; dilute H2S04Aq does 
 not decompose HBrAq at ordinary temperatures. 
 
 10. Chlorine sets free Br from HBrAq. — 11. 
 HBrAq is partly decomposed by potassium 
 permanganate solution in the cold, quickly and 
 completely on heating. — 12. By electrolysis of 
 HBrAq, HBrOgAq is produced (Eiche, C. B. 46, 
 S48). — 13. Sromme dissolves in HBrAq forming 
 a dark-coloured liquid. 
 
 Combinations. — 1. With ammonia and phos- 
 phime ; Ogier (0. B. 89, 705) gives the thermal 
 data, [NH=,HBr] = 45,600; [PH=,HBr] = 23,000 ; 
 using gaseous constituents and forming solid 
 MHjBr. — 2. With water probably to form the hy- 
 drate HBr.HjO {v. Properties). The heats of solu- 
 tion and dilution of HBr have been measured by 
 Thomsen {Th. 3, 13 and 72) ; the results indi- 
 cate the existence in the solution of the hydrate 
 HBr.HjO, but do not suggest the formation of 
 any other definite hydrate on dilution. The 
 heat of dilution appears to be a continuous 
 hyperbolic function of the quantity of water 
 added, provided the composition of the acid to 
 start with is HBr.HjO ; the results cannot, 
 however, be expressed by quite so simple a 
 formula, involving a single constant, as is 
 applicable in the case of chlorhydric acid (q. v.). 
 It is quite possible that the reactions of HBrAq 
 are the reactions of the acid HBr.HjO (? = 
 HjBr.OH), and that HBr itself is not an acid 
 {v. Presidential Address to Section B. by Prof. 
 Armstrong, B. A. Meeting, 1885). Berthelot 
 (Bl. [2] 19, 385 ; O. B. 64, 414 ; 66, 742) thinks 
 that HBrAq contains a number of hydrates, 
 some partially dissociated, and also the com- 
 pound HBr {v. Chloehtdeio acid). Eoozeboom 
 {B. T. C. 4, 108, 331 ; 5, 351, 363 ; also Van't 
 Hoff, ibid. 4, 414) has determined the relations 
 between vapour-pressure and temperature of 
 solutions of hydrated HBr. M. M. P. M. 
 
 BEOmiC ACID HBrOa v. Beomine, oxy- 
 
 AOIDS OF. 
 
 SHOMIDES. Binary compounds of Br with 
 more positive elements i.e. with any element 
 except F, CI, or 0. Br forms binary compounds 
 with most of the elements. The greater number 
 may be produced by direct combination. The 
 formation of metallic bromides is usually 
 accompanied with production of much heat; 
 thus, [K^ Br^] = 190,620 ; [Ca, Br^ = 140,850 ; 
 [Zn, Br-] = 75,930; [Hg, Br^ = 50,550; 
 [Au, Br'] = 8,850. (Liquid Br was used.) Some 
 metallic bromides are formed by the action of 
 Br on the oxides; e.g. AgBr by Br on Agfi. 
 Alkalis and alkaline earths in aqueous solutions 
 are decomposed by Br, giving bromides and 
 bromates ; certain metallic salts, in aqueous 
 solutions, form bromides and peroxides ; e.g. 
 jBalts of Mn, Ki, Co, and Pb. Metallic iodides 
 
 are decomposed wholly or in part by Br, giving 
 metallic bromides and free I. Many metallio 
 chlorides are partly decomposed when heated in 
 closed tubes to about 300° with equivalent 
 quantities of Br; after a time equilibrium is 
 established in the system consisting of chloride, 
 bromide, CI, and Br ; this equilibrium is not 
 overthrown by increasing the mass of Br, the 
 temperature, or the time (Potilitzin, B. 14, 1044 ; 
 15, 918; 16, 3051). Metallio bromides are 
 usually formed by the action of HBrAq on the 
 oxides (comp. Beomhydeio Acid ; Beactions, 
 No. 7). Most metallic bromides are white ; thty 
 aregenerally isomorphous with the corresponding 
 chlorides ; most of them are not decomposed by 
 heat alone, but some, e.g. those of Au and Pt, 
 give up all their Br when heated. Some metallio 
 bromides are decomposed by Jlfi, e.g. those of 
 Bi and Sb ; others are decomposed when their 
 aqueous solutions are evaporated, e.g. MBi\; 
 most are decomposed by heating in air in 
 presence of steam. Metallio bromides are decom- 
 posed by certain peroxides and oxidising agents, 
 e.g. MnOj, K^Mn^O^Aq, KjCr^OjAq, HNO^Aq, 
 with separation of Br ; cono. H^SOjAq sets free 
 a little HBr, but decomposes most of the 
 bromides to sulphate and Br with simultaneous 
 formation of SO2 ; HCl and HOLAq form HBr 
 and metallic chloride. When a metallio bromide 
 is heated with solid Xfiv^O, and cono. H^SO,, 
 free Br is obtained (distinction from chlorides). 
 Aqueous solutions of alkali bromides dissolve 
 large quantities of Br, probably with formation 
 of perbromides in solution; Berthelot (C. B. 
 91, 195 and 706) gives the numbers (using 
 gaseous Br) [KBrAq, Br'^ = 11,500. Aqueous 
 solutions of alkali, alkaline earth, and magnesian 
 bromides partly decompose AgCl when the salts 
 are shaken together for a few minutes at the 
 ordinary temperature; the percentage of AgBr 
 formed varies from 95 when LiBrAq is used, to 
 84-8 when CdBrjAq is employed (Potilitzin, B. 
 18, 1522). The binary compounds of Br with 
 the non-metals are fairly stable bodies ; they are 
 usually produced by direct combination. 
 Bromides of B, P, C, and Si are stable a,s gases. 
 Br forms definite, stable, compounds only with 
 the more metallic and positive members of the 
 oxygen group of elements ; bromides of Te are 
 gasifiable, Se^Brj is fairly stable, but is decom- 
 posed by heat, SjBrj is a feebly-marked body, 
 and no oxide of Br is known. Bromide of 
 iodine is a fairly well marked compound, 
 [I, Br] = 2,500 (Berthelot, G. B. 90, 841 ; using 
 liquid Br and solid I). Bromine chloride is very 
 easily decomposed, and no compound of Br and 
 F is definitely known. If N bromide exists it is 
 extremely unstable (». also Halogen ELEMENrs, 
 BiNABY compounds OF I for the individual 
 bromides v. the articles on the various elements.) 
 
 M. M. P. M. 
 BEOHIDES, ORGAITIC v. Beomine, oeoanio 
 
 COMPOUNDS OF. 
 
 BEOMINE. Br. At. w. 79'75. Mol. w. 
 159-50. [-24-5°] (Baumhauer, B.i, 927), [-7-2°] 
 (Philipp, B. 12, 1424 ; according to Philipp, the 
 lower M.P. was due to presence of CI). 
 [-7-05°] (Eamsay a. Young, C. J. 49, 453); 
 (63°) (Pierre, A. Ch. [3] 20, 5); (59'27°) (Thorpe, 
 0. /. 37, 172) ; (58-7°) (Eamsay a. Young, Z.c). 
 S.G. 2 3-1872 (Pierre, l.c.) ; 2 3-18828 (Thorpe, 
 
BROMINE. 
 
 636 
 
 (30°) 3-126, 
 
 of fusion = 
 
 26, 268). 
 
 I.C.). S.G. at B.P. 2-9822 (Thorpe, l.c.). V.D. 
 80 {v. p. 536, Properties). S.H. (solid -78° to 
 -20°) ■08'432 (Eegnault, A. Ch. [3] 26, 286). 
 S.H. (liquid 13° to 45°) -1071 (Andrews, C. J. 1, 
 18). S.H.p. (equal mass of H,0 = 1) (83°-228°) 
 •05552 (Begnault, Acad. 26, 1) : S.H.y. (equal 
 mass of H20 = l) -0429; (equal volume of air 
 = 1) 1-395 (Clausius, Mechan. Wdrmetheurie, 1, 
 
 62 [1876]). ^^: (20°-388°) 1-293 (Strecker, 
 b.xi.v. 
 
 W. 13, 20 ; experimentally determined). Ex- 
 pansion (0° to B.P.) V = 
 
 1 + -00106218( + ■00000187714(''--0000000030853(' 
 (Thorpe, i.e.). S. (5°) 3-68, (10°) 3-327, (15°) 
 
 3-226, (20°) 3-208, (25°) 3-167, 
 
 (Dancer, O. J. 15, 477). Heat 
 16,185, Eegnault {A. Ch. [3] 
 
 ^^xAt. wt. = 16-23 (Gladstone, T. 1870.9). 
 
 Emission-spectrum ; marked lines are 3980, 
 6356, and lines beginning with 6999 (Salet, 
 A. Ch. [4] 28,26). Absorption-spectrum charac- 
 terised by many bands between 6801-5 in the red 
 and 5244-1 in the green (Eoscoe a. Thorpe, T. 
 1877. 207). 
 
 Bromine was discovered by Balard in 1826 
 (B. J. 7, 102) ; it waa previously obtained by 
 Liebig, but supposed by him to be iodine chloride 
 {v. Hofman's Life Work of Liebig) ; and by 
 joss, but regarded by him as selenion (J", pr. 
 1, 129). 
 
 Occurrence. — Never free ; widely distributed, 
 but not in large quantities, chiefly in combina- 
 tion with K, Na, and Mg. In sea water (for 
 quantities, v. Berglund, B. 18, 2888), sea-weed, 
 saline springs, and many marine plants and 
 animals (Kindt a. Wohler, P. 10, 509 ; Stroh- 
 meyer, S. 49, 249 ; Hembstadt, B. J. 7, 110). 
 According to Marchand (C. B. 31, 495) all 
 waters, including rain and snow, contain traces 
 of bromides. In various minerals, chiefly as 
 AgBr in Mexico and Chili (Berthier, A. Ch. 77, 
 417 ; 79, 164) ; in minute quantities in Silesian 
 zino ores (Hollunder, B. J. 8, 82) ; in Chili salt- 
 petre (Griineberg, /. pr. 60, 172) ; &a., &c. 
 
 Preparation. — The starting-point is the con- 
 centrated liquor of certain saline springs, the 
 residual liquor obtained in working the salt 
 deposits at Stassfurt, or the solution of the ash 
 of sea plants. The liquid is freed from the less 
 soluble salts, chiefly chlorides and sulphates, 
 by concentration and crystallisation, mixed with 
 MnOj and HClAq, and distilled. The quantities 
 of the reacting materials are arranged so that 
 there is always an excess of bromide, in order 
 to prevent formation of bromine chloride 
 {v. Mohr, A. 22, 66). In some cases the con- 
 centrated liquor is heated with H^SOjAq, sul- 
 phates are then removed by crystallisation, and 
 the mother liquor is distilled with MnO^ and 
 H,SOjAq (v. Herrmann, P. 13, 175 ; 14, 613). 
 The Br is condensed in water and converted 
 into NaBr and NaBrO, by treatment with 
 NaOHAq, the liquid is evaporated to dryness, 
 the residue heated to decompose NaBrOj, and 
 the NaBr is decomposed by pure MnOj and 
 HjSOjAq. Iodine may be removed from the 
 original liquor, before decomposing by MnO.;and 
 acid, by the action of CI, or by ppg. as Cu^Ij 
 (Bussy, B. J. 18, 117; Balard, B. J. 7, 102). 
 Chlorine may be removed by decomposing the 
 
 distillate from the first action of MnO.^ and acid 
 by BaOAq, evaporating to dryness and heating, 
 dissolving out BaBrj in alcohol, filtering from 
 insoluble BaClj, evaporating to dryness, and de- 
 composing by MnOj and H^SO^Aq (Piria, B. J. 
 19, 277). Adrian (/. 1870. 248) removes 01 by 
 washing the distillate with water and small 
 successive quantities of ether ; he then digests 
 with starch paste to remove I, and again distils. 
 Stas {Fr. 25, 213) frees from I and CI by dis- 
 solving in KBrAq, adding ZnO and distilling. 
 Cyanogen is occasionally found in samples of 
 Br; it may be detected by conversion into 
 K3]?e(CN)j, by digesting with iron fihngs, and 
 rapidly filtering (Phipson, 0. N. 28, 51). Bromo- 
 f orm is another impurity ; it is detected by its 
 odour, after addition of EIAq sufficient to con- 
 vert all the Br into KBr, and removal of the I 
 by the action of NajSjOjAq (Eeymann, B. 8, 
 790). Bromine is prepared from laboratory 
 residues containing Br compounds by making 
 alkaline with KOHAq, and distillation vrith solid 
 K^CrjO, and excess of H^SO^Aq (2 parts strong 
 acid to 1 part water by weight) added gradually 
 through a funnel tube (Bolas a. Groves, C. J. 
 [2] 9, 784). To prepare pure Br for atomic 
 weight determination, Stas removed I from com- 
 mercial KBr by dissolving in water, adding 
 BrAq to J of the liquid till the I which at first 
 separated redissolved forming a clear orange- 
 yellow coloured liquid, adding the other J of 
 the liquid and shaking repeatedly with pure 
 CS.^. The liquid was then warmed to remove 
 all CSj ; the KBr was oxidised to KBrOj by the 
 action of CI in presence of pure KOHAq (for 
 details v. Stas, Nouv. B. 159 ; or pp. 159-160 of 
 Aronstein's German trarfslation Untersuchungen 
 iiber die Gesetze der chein. Proportionen, &a.) ; 
 the KBrOj was purified by repeated crystallisa- 
 tion, and a part of it was converted back to 
 KBr by heating in a porcelain vessel in small 
 successive quantities. By decomposing a mix- 
 ture of KBr and KBrO, (in the ratio 5KBr:KBr03) 
 with pure H^SOjAq, Br was obtained. A por- 
 tion of this Br was then digested with mili of 
 lime and NHjAq, wherebyCaBr^Aq was obtained ; 
 this liquid was saturated with another portion 
 of the purified Br ; water was added to pp. Br ; 
 the ppd. Br was separated, and digested several 
 times with pure dry CaBrj (prepared by the 
 action of part of the purified Br on CaO) ; the 
 Br was then shaken in contact with pure P2O5, 
 then allowed to remain in contact for 12 hours 
 with pure BaO which had been strongly heated, 
 and finally poured off and distilled. All opera- 
 tions were conducted in apparatus made wholly 
 of glass. 
 
 Properties. — At ordinary temperatures a 
 dark brown-red volatile liquid with most irri- 
 tating odour (Ppaiios = a stench) ; in thick layers 
 almost black ; vapour is yellowish red, and 
 becomes less transparent as temperature is 
 increased {v. Andrews, B. A. 1871. (Sec.) 66) ; 
 solidifies to a grey-brown crystalline mass with 
 semi-metallic lustre. Very poisonous. Vapour 
 acts on mucous membrane and causes violent 
 irritation. Non-conductor of electricity ; but 
 an aqueous solution of Br is a better conductor 
 than pure water (such a solution contains some 
 HBr) (Balard, A. Ch. [2] 32, 371; De la Eive, 
 B. J. 8, S3; Solly, A. 20, 124). Dissolves 
 
636 
 
 BROMINE. 
 
 aparingly in water (v. supra) ; solutions of x 
 parts Br by weight .in 1,000 parts HjO have 
 following S.G. (Slessor, J. ia58. 100) :— 
 
 X. S.G. T. S.G. X. S.Gt. 
 
 10-7 1-009 12-3 1-0122 20-9 1-018 
 
 11-7 1-0093 18-7 1-0149 31-31-7 10236 
 12-0 1-0099 19-5 10158 
 Solution in water is attended with production of 
 heat [Br'.Aq] = 1080 {Th.2, 25) ; solution is pale 
 orange-yellow. Dissolves more readily in alco- 
 hol, and in all proportions in ether, CSj, and 
 CHClj ; solution is accompanied by chemical 
 change ; soluble also in cone, aqueous solutions 
 of KBr and many other metallic bromides, fre- 
 quently with formation of perbromides ; also in 
 cone. HClAq and HBrAq, and in liquid SOj 
 (Sestini, Z. 1868. 718). Br is absorbed by wood 
 charcoal with considerable rise of temperature 
 (Melsens, O. B. 77, 781). In presence of H^O, 
 acts as a bleacher and disinfectant. 
 
 The atomic weight of Br has been determined 
 (1) by analyses, and determinations of V. D., of 
 many gaseous compounds, e.g. BrH, Br^Cd, BrjB, 
 BrjSn, &o. ; (2) by determination of S. H. of 
 solid Br ; (3) by comparison of bromides &c. 
 with isomorphous chlorides and iodides &c. ; 
 (4) by syntheses of AgBr by Marignac (B. J. 
 24, 198) ; by syntheses of AgBr by Stas (Nouv. 
 B. 158, 171) ; by reduction of AgBrOj by Stas 
 (Nouv. B. 199); byconversion of KBr to AgBr 
 by Stas {I.e. 308) ; by conversion of AgBr to 
 AgCl by Dumas {A. Ch. [3] 55, 162). In gaseous 
 molecules containing Br the atom of Br is 
 monovalent. Br acts as a strongly negative 
 non-metallic element ; it combines directly with 
 ntost metals forming salts ; its compounds with 
 non-metals one of which is H are acids. The 
 lubstitution of H by Br in carbon acids seems to 
 increase the relative affinity of the acids 
 (v. Affinity, p. 83) ; generally speaking, the 
 introduction of Br in place of H in carbon 
 compounds is accompanied by the production of 
 more or less acidic properties. 
 
 In its chemical relations Br stands between 
 CI and I ; the heat of formation, in solution, of 
 a metallic bromide is usually about n 11,000 
 gram-units less than that of the chloride, and 
 about n 26,000 gram-units more than that of 
 the iodide, of the same metal, where n is a 
 whole number, usually 1, 2, 8, or 4 ; metallic 
 bromides are wholly or partly decomposed by 
 CI, and metallic iodides by Br; metallic chlorides 
 are partially decomposed by Br (v. Reactions, 
 No. 12). The relative affinities of the acids 
 HCl, HBr, and HI in aqueous solution are, 
 however, nearly the same (v. Affinity, p. 77). 
 In its compounds, Br appears to be positive to 
 CI, F, and 0. No oxide of Br is at present 
 known ; the oxyacids of Br exist only in pre- 
 sence of water ; they are much less stable than 
 the oxyacids of iodine : one of the oxyacids of 
 CI (HCIO4) liiis been obtained in separate and 
 definite forms, although it is an extremely un- 
 stable compound ; oxides of CI are known as 
 gases, and an oxide of I (IjOJ exists as a solid 
 body. No oxide or oxyacid of F is known (v. 
 Bromides, Haiogen Elements, and Halogen 
 Elements, einaby compodnds of). 
 
 The S.G. of Br gas at 99° was found by 
 MitscherHch to be 6-54 (air = l) and by Meyer 
 it. Ziiblin to be 5-38 at 100°: the S.G., calcu- 
 
 lated on the assumption that 2 x 79-75 - 159-50 
 parts by weight of Br occupy 2 volumes, is 5-51. 
 At very high temperatures (approximately 
 1570°) the S.G. is less than the calculated; 
 Meyer a. Zublin (B. 13, 405) obtained values lying 
 between those calculated from the formuloe Br, 
 and f Brj ; when the Br was obtained by decom- 
 posing PtBr^ at high temperatures the S.G. at 
 1570° nearly agreed with that calculated for 
 f BTj (3-66). The S.G. of Br vapour diluted 
 with 10 volumes air, at 50° under the B.P. of Br, 
 was determined by Langer a. Meyer to be 5-52 
 (B. 15, 2769). Jahn's determinations (B. 15, 
 1288) show that bromine does not attain the 
 S.G. calculated for Brj until it is heated about 
 160° above its B.P. ; the deviations are small ; 
 the S.G. at any temperature up to about 220° 
 may be approximately found by the formula 
 B.(i. = a + bt, where a=5-8691 and 6= --00163. 
 (For S.G. of CI and I gases v. these elements ; 
 v. also Halogen Elements.) 
 
 Beactions. — 1. Br dissolves in water with 
 production of heat [Br^ Aq] = 1080 {Th. [2] 25) ; 
 the water is slowly decomposed, more quickly 
 in direct sunlight, with formation of HBr and 0. 
 Bromine water, therefore, acts as an oxidiser ; 
 e.g. HNO^Aq is oxidised to HNOjAq (Schonbein, 
 /. pr. 37, 144), Mn(C,H302)2Aq to MnO^ 
 (Kiimmerer, B. 4, 218) ; sugar, mannite, 
 benzene, &o., &a., to various oxidised derivatives 
 (Blomstrand, A. 123, 248). If NO is led into Br 
 cooled below 0° the gas is absorbed, and on 
 adding water HBr and higher oxides of N are 
 formed (Landolt, A. 116, 177). — 2. Steam mixed 
 with Br and passed through a red-hot tube 
 yields HBr and 0. — 3. Hydrogen peroxide 
 evolves 0, and HBr is formed (Schonbein, A. 
 108, 169). — 4. Aqueous solutions of potash or 
 soda are decomposed by Br forming KBi-Aq (or 
 NaBrAq) and KBrO^Aq (orNaBrO^Aq) : CaO and 
 BaO form bromides and 0. — 5. Aqueous ammonia 
 yields NHjBrAq and N.— 6. Urea is decomposed 
 by BrAq with evolution of N. — 7. Hydriodic 
 acid and iodides in solutions are decomposed by 
 Br with formation of HBrAq, or MBrAq, and 
 I. — 8. Sulphuretted hydrogen yields HBr, and S 
 which partly combines to form SjBrj; this 
 decomposition proceeds either in presence or 
 absence of water (Naumann, B. 9, 1574). — 9. In 
 contact with excess of silver nitrate solution, 
 AgBr and HBrOAq are produced (Spiller, /. 
 1859. 67). — 10. With carion disulphide, crystal- 
 line CjSjBre is formed (Hell a. Drech, B. 15, 987). 
 
 11. Carbon compounds are usually acted on by 
 Br ; sometimes H is withdrawn, sometimes this 
 is accompanied by substitution of Br, and some- 
 times more complete decomposition results. — 
 
 12. Br partly decomposes metallic chlorides when 
 heated in equivalent quantities to 270°-300° ; if 
 the mass of Br is increased, the amount of 
 decomposition increases up to a limit which is 
 not passed by increasing the mass of Br, the 
 temperature, or the time of action (Potilitzin, B. 
 14, 1044; 15, 918; 16, 3051). According to 
 Humpidge (B. 17, 1838) AgCl is partly decom- 
 posed by contact with water and an equivalent 
 quantity of Br ; thus 5-2 p. c. CI was removed 
 from AgCl after 24 hours' action at 11°, and 
 14-53 p. c. after 12 hours' action at 44°. 
 
 Combinations. — 1. With water at 4° forming 
 red octahedral crystals of Er.lOHjO which are 
 
BROMINE. 
 
 637 
 
 asoomposed to Br and H^O at 15° (Lowig, P, 
 14, 114; 16, 375). For dissociation-pressures 
 V. Eoozeboom (B. T. G. 4, 65).— 2. Combines 
 directly with most ot the elements, especially 
 the metals, often with production of much heat 
 and sometimes light (v. Bromides). Does not 
 combine directly with or 0. According to 
 Merz a. Weith (B. 6, 1518) dry Br and Na 
 do not combine even at 200^. Combines with 
 liquid CI at -90° (Donny a. Mareska, O. B. 20, 
 817). No oxide of Br is at present known. 
 
 Detection. — The physical properties of Br 
 enable this body to be easily detected when 
 uncombined. Bromides are decomposed by 
 ClAq, giving Br and chloride of the metal. 
 Solution of NjOj in cone. H^SO^Aq does not 
 decompose bromides, but does decompose iodides 
 with production of I ; on this reaction is based 
 a method for detecting bromides in presence of 
 iodides. Solid bromides are decomposed by 
 heating with K.fii.fl, and cone. H^SOjAq, with 
 formation of Br ; chlorides yield CrO^Cl^. 
 
 Estimation. — Free Br may be estimated 
 volumetrioally by measuring the I set free by 
 it from KIAq, or by finding the mass of Asfi^ 
 which it oxidises to As^Oj in an alkaline so- 
 lution ; Br may also be combined with H to 
 form HBrAq, by treatment with HjS, or SO2, in 
 aqueous solutions ; the HBr may then be esti- 
 mated by ppg. with AgNO^Aq. Br in bromides 
 is usually estimated as AgBr, ppn. being ac- 
 complished by addition of AgNOjAq ; insoluble 
 bromides may be fused with Na^COs, dissolved, 
 and acidulated with HNO^Aq. In presence of 
 chlorides, or iodides, Br in bromides must be 
 determined by indirect methods (v. Manuals of 
 Analysis). 
 
 Bromine, Chloride of. BrCl. Mol. w. un- 
 known. Chlorine is absorbed by Br with 
 formation of a red-yellow, mobile, very volatile, 
 liquid, which gives oS a dark yellow, very 
 irritating, vapour with strong bleaching pro- 
 perties ; many metals burn in this vapour to 
 chloride and bromide (Balard, A. Ch. [2] 
 32, 371). If the Br is cooled to 0° the Uquid 
 finally contains Br and CI in the proportion 
 BrCl ; at ordinary temperatures less CI than is 
 required by the composition BrCl is absorbed 
 (Bornemann, A. 189, 183). At temperatures 
 above -1- 10° the compound BrCl decomposes 
 with evolution of CI. By adding a little H2O 
 to BrCl, and cooling to 0°, yellow-brown crystals 
 of BrCl.lOHp separate (Bornemann, l.o.) ; these 
 melt at 7°, and are decomposed by NH3 to N, 
 NHjBr, and N chloride (Lowig, Das Brom und 
 seine chemischen Verhaltmsse; Heidelberg, 
 1829, p. 64). An aqueous solution of BrCl, 
 obtained by dissolving Br in ClAq, is decom- 
 posed by alkalis giving alkali bromate and 
 chloride ; in sunlight HBrOjAq and HClAq are 
 formed ; reducing agents, e.g. SO^Aq, Zn 
 powder, Fe filings, P, NO, &o., withdraw CI, and 
 Bet Br free (Sohonbein, /. pr. 88, 483). 
 
 Bromine, Cyanide of : better called Cyanogen 
 Bromide. Obtained by action of Br on Hg(CN)j, 
 KON, or HCN ; v. Cyanic acids, vol. ii. p. 313. 
 
 Bromine, Hydrate of. Bi.10B.jO. Obtained 
 by cooling a saturated solution of Br in H^O ; 
 V. Bkomine ; Combinations, No. 1. 
 
 Bromine, Iodide of : better called Bromide of 
 Iodine ; v. Iodine. 
 
 Bromine, Oxyaoids of. No oxide of Br is 
 known. The acids HBrO and HBrOj exist in 
 aqueous solutions only ; both solutions are 
 decomposed on heating, HBrOAq even at 30°. 
 Perbromic acid, HBrO,,, was said by Kammerer 
 to be produced by the action of Br gas on 
 HClOjAq (J.pr. 90, 190) ; but later experiments 
 have shown that this acid has not yet been 
 obtained (v. Pattison Muir, C. J. 30, 469; 
 Maclvor, G. N. 33, 35; Wolfram, A. 198, 95), 
 BrAq is not oxidised by such reagents as 
 KjMn.OgAq, E^Cr^OjAq, HNO^Aq, or HClOAq; 
 but the action of HClOaAq or HCIOjAq pro- 
 duces HBrOjAq. Dilute solutions of HBrO and 
 HBrOj are also formed by electrolysing HBrAq, 
 MBrAq, or BrAq ; also by the action of metallic 
 oxides on BrAq. No salts of HBrO are known 
 except in aqueous solutions ; salts of HBrOj 
 exist as solids, they are all easily decomposed 
 by heat with evolution of 0, and frequently 
 also of Br. The addition of to KBrAq would be 
 attended by disappearance of much heat ; Thom- 
 son gives these numbers [KBrAq, 0'] = — 15,930 ; 
 also [Br2,0,Aq] = - 16,200. The following data 
 show that the heat of formation of the oxy- 
 acids of Br is less than that of HBr, and ia 
 also less the more the acid contains : — 
 [H,Br,Aq] = 28,380 ; [H,Br,0,Aq] = 26,080 ; 
 
 [H,Br,0',Aq] = 12,420 {Th. 2, 400). These data 
 are analogous with those for the corresponding 
 compounds of CI, but differ from the data for 
 the similar compounds of I {v. Halogen Ele- 
 ments). 
 
 I. HTPOEBOMons Acid, and Hypobeomites. 
 HBrOAq and MBrOAq. Gay-Lussac obtained a 
 gas by the action of Br on dry HgO and supposed 
 it to be an oxide of Br ; Pelouze, and more 
 recently Dancer (C J. 15, 477), proved that 
 only is thus produced. An aqueous solution 
 of HBrO is obtained by the action of BrAq on 
 the oxide, or nitrate, of Hg, or Ag ; Hg^O and 
 PbO do not oxidise BrAq (Spiller, 0. N. 6, 249). 
 
 Formation. — ^By the action of BrAq on HgO 
 — repeating several times —Hg^OBrj, HBrOAq, 
 and HgBrOAq, are formed ; by distilling in 
 vaoiio, a liquid containing 6-2 p.c. Br as HBrO 
 is obtained, but it cannot be quite freed from 
 HgBrO (Balard, A. Ch. 32, 337). 
 
 Preparation. — Pure BrAq is shaken with 
 excess of AgNOjAq until the colour and odour 
 of Br have gone ; the straw-coloured liquid is 
 then at once distilled m vaciio ; at 50 mm. 
 pressure it boils at 40°. The distillate gets 
 richer in HBrO until -736 p.c. Br is present 
 as HBrO (then it gets poorer in the acid) ; about 
 465 p.c. of the Br used is changed to HBrO. 
 
 Properties and iJraciiows. — Solution with 
 6-2 p.o. Br as HBrO decomposes at 30° giving 
 Br and HBrOjAq; solution with -736 Br as 
 HBrO decomposes, into same products, at 60°. 
 HBrOAq is a strongly bleaching liquid ; it is 
 decomposed by Ag^O (and slowly by contact 
 with AgNOjAq) with formation of and AgBr, 
 by HjOjAq with evolution of ; and by HCLAq, 
 HBrAq, and HIAq, with formation of Br 
 (Schonbein, /. pr. 88, 475). 
 
 No hypobromites have been obtained except 
 in dilute aqueous solutions. By the action 
 of alkalis, alkali carbonates, or phosphates 
 (Fritzsohe, A. 40, 251), on BrAq, yellow, 
 strongly bleaching, liquids are produced ; these 
 
533 
 
 BROMINE. 
 
 liquids are very unstable, decomposing in 
 air, quickly at 30°. They decompose urea 
 with evolution of N ;— CON^H^ + SHBrOAq = 
 COj + Nj+SHBrAq + aH^OAq (B. Kuop, C.C. 
 1870. 132). Balard (A. Ch. 32, 337 ; J. pr. i, 
 165) described bodies resembling bleaching 
 powder, obtained by the action of BrAq on 
 CaOjHj and BaO^Hj ; by the addition of water 
 and filtration, bleaching solutions were pro- 
 duced, very unstable, and easily decomposed, 
 even by CO^. 
 
 II. Bkomio Acid aud Bbomates. HBrOjAq 
 and MBrOj. Bromio acid, HBrOj, is known only 
 in aqueous solution. 
 
 Formation. — 1. By electrolysis of HBrAq 
 (Eiche, 0. R. 46, 348).— 2. By action of heat 
 on hypobromites in solution. 
 
 Preparation. — BaBrOj is prepared by adding 
 Br little by little to cone. BaOjHjAq until the 
 liquid is slightly red, when BaBrO, pps. and 
 BaBrj remains in solution. The BaBrOj is crys- 
 tallised from hot water, dried, and ground to 
 fine powder; 100 parts are digested for some 
 time in the cold or at a very gentle heat, with 
 24 parts cone. H^SOj mixed with 240 parts 
 H^O ; excess of HjSOj is removed from the 
 liquid by gradual addition of BaO^HjAq ; the 
 acid liquid is evaporated in vacuo (Eammels- 
 berg, A. 40, 147). Kammerer passes Cl^O 
 into Br under H^O until the colour of 
 the Br has disappeared; SCl^O + Br^Aq -H Hp 
 = 2HBr03Aq + lOClAq (J.pr. 85, 452). 
 
 Properties and fleaciions. —HBrOjAq may be 
 concentrated in vaciw until the liquid contains 
 50-59 p.c. HBrOj ; the composition then nearly 
 agrees with the formula HBr03.7H.p. When 
 concentrated by heating in an open vessel de- 
 composition begins when the liquid contains 
 4-27 p.c. HBrOa, with production of Br, 0, and 
 HjO. HBrOjAq is a colourless, acid liquid, 
 with a bromine-like smell. Oxidisable bodies 
 decompose HBrOjAq with separation of Br ; e.g. 
 5S02-H2HBr03Aq + 4H.,0 = 5H.,SO,Aq-l-Br2Aq; 
 5H2S + 2HBr03Aq = 6H,0Aq + 5S + Br^Aq. Iod- 
 ine quickly decomposes HBrOjAq, forming 
 HIO3 (Kiimmerer, J. pr. 85, 452) ; CI, dilute 
 H2S04Aq, and dilute HNOjAq, are without 
 action. HBrAq decomposes HBrOsAq, forming 
 H2O and Br; HClAq and HIAq form H^O and 
 BrCl or IBr. The heat of neutralisation of 
 HBrO^Aq is the same as the mean value for the 
 stronger monobasic acids ; [HBrO'Aq, NaOHAq] 
 = 13,780 {Th. 1,240). Bromic acid is monobasic 
 and forms one series of salts, the bromates, 
 MiBrOj and M"2BrO, ; these salts are formed 
 by the action of HBrOjAq on the oxides, 
 hydroxides, or carbonates, of the metals ; the 
 alkali and alkaline earth salts are also formed, 
 always with bromides, by the action of Br on 
 aqueous solutions of the alkali or alkaline earth 
 hydroxides. (For special methods v. individual 
 salts ; also Kammerer, /. pr. 85, 452.) The 
 bromates crystallise well ; .they are all soluble 
 in water ; the least soluble are AgBrOj and 
 HgBrOj. They are decomposed by heat ; 
 sometimes is evolved and metallic bromide 
 remains, e.g. bromates of alk&lis, Hg, and Ag ; 
 sometimes Br and O are evolved, and oxide 
 remains, e.g. bromates of Mg, Al, Zn ; or a mixture 
 of oxide and bromide remains, e.g. bromates of 
 Pb, Cu, &e. Dilute HNO^q, H^SO^Aq, or 
 
 HjPOjAq, decomposes bromates giving HBrOjAi} 
 most of which decomposes to Br, 0, and H.,0. 
 Solutions of bromates react similarly to solution 
 of HBrOj towards SOj, H^S, HClAq, HBrAq, 
 and HIAq. The bromates have been chiefly 
 investigated by Kammelsberg (A. 40, 147; P. 
 90, 16) ; Lowig (B. J. 12, 120) ; and Marignao 
 (G. B. 45, 650; /. 1857. 127). The following 
 are the better-studied salts. 
 
 Barium bromate Ba,(BTO^).,.B..fl. Pris- 
 matic, monoclinic, crystals; isomorphous with 
 Ba(C103)2 (Marignac a. Eammelsberg) ; S. (100°) 
 4-2 ; (15°-18°) -77. Prepared by decomposing 
 KBrOjAq by BaiCjHsOjjAq. 
 
 Cadmium bromate Cd(Br03)2.H20. Co- 
 lumnar trimetric crystals; prepared by 
 CdSOjAq-t-BaBrOjAq. S. (15°-18°) 125. On 
 heating, leaves CdO and CdBr^ (Eammelsberg). 
 
 Calcium bromate Ca(Br03)2.H20. Mono- 
 clinic plates (Marignac) ; prepared by 
 CaO^HjAq + HBrOsAq. S. (15°-18°) 99. 
 
 Heated to 180° loses B..fl, at higher tempera- 
 ture gives and CaClj (Eammelsberg). 
 
 Cobalt bromate Co(Br03)2.6H20. Trans- 
 parent, hyacinth-coloured, monometrio octa- 
 hedra; prepared by HBrOaAq -1- C0CO3, or 
 Ba(Br03).^q + CoSOjAq. S. (15°-18°) 45-5. 
 Heated, gives CoO (Eammelsberg). 
 
 Copper bromate Cu(Br03)2.5H20. Blue- 
 green crystals, eifiorescing over HjSOj in vacuo ; 
 very soluble; lose H^O completely, and a 
 little Br also at 200°- Prepared similarly to 
 Co(Br03)2. 
 
 Lead bromate Pb(BrOs)2.H;0. Buiall, 
 lustrous, monoclinic prisms ; isomoiphous with 
 Sr(Br03)j.H20 (Eammelsberg). S. (15°-18°) 1-33. 
 Prepared by HBrOjAq + PbCOj, or cone. 
 Pb(C2H302)2Aq-hKBrO,Aq. Heated over 180° 
 gives Br, PbOj, and PhBr^, at higher tempera- 
 tures gives PbjO,, Br, and PbBr^. 
 
 Magnesium bromate Mg(Br03)2.6H20. 
 Large, efflorescent, monometrio octahedra; S. 
 (15°-18°) 71-5 ; loses all H^O above 200°. Pre- 
 pared by MgO + HBrOjAq, or 
 
 MgSiPsAq-HKBrOjAq. 
 
 Mercury bromates Hg2(Br03)2, and 
 Hg(BrOa)2.2H20. Mercurous bromate is pre- 
 pared by Hg2(N03)2Aq -h KBr03Aq or 
 HBrOjAq -t- Hg^O ; mercuric bromate by 
 HBrOaAq + freshly ppd. HgO. Both form 
 small white crystals ; the mercurous salt forms 
 yellow basic Hg2(Br03)2.Hg20 by the action 
 of H.P; when heated it decomposes with de- 
 tonation (Eammelsberg). The mercuric salt 
 decomposes at 130°-140°, with slight explosion, 
 to HgO, HgBr^, and Hg^Br^. S. (15°-18°) -17, 
 (100°) 1-6. 
 
 Nickel bromate Ni (Br03)j.6H20. Prepared 
 as, is isomorphous with, and generally re- 
 sembles, the Co salt (?. v.). S.(15°-18°) 28, 
 (Eammelsberg; v. also Marbach, P. 94, 412). 
 
 Potassium bromate KBr03. Prepared by 
 adding Br, or BrCl, to cone. KOHAq ; or by 
 adding Br to K^COsAq which has been previously 
 saturated with CI. Ehombohedra (Eammels- 
 berg ; Marignac, J. 1859. 139 ; v. also for crys- 
 talline forms, Lowig, B. 3. 12, 120 ; Fritzsche, A. 
 40, 251 ; Marbach, P. 94, 412). S.G. J-pf 8-271 
 (Kremers, P. 99, 443). S. (0°) 3-1, (20°) 6-9, 
 (40°) 13 2, (100°) 60 (Kremers, P. 97, 1). Insol. 
 
BROMO-AOETIO ACID. 
 
 539 
 
 in alcohol. B. P. of saturated EBiOsAq = 104°. 
 EBrOa, when heated, molts at 350", then begins 
 to decompose, at first slowly, then rapidly and 
 explosively, with evolution of and a little 
 Br. According to Pritzsohe {A. 40, 251), crystals 
 of KBrOj prepared from exactly neutral solu- 
 tions, or from solutions containing a httle 
 acetic acid, decrepitate before decomposing, and 
 lose 1-3 p.c. of their mass (chiefly water) ; if 
 the resulting powder'is placed in warm water, 
 O is evolved at the surfaces of the undissolved 
 particles, but most of the is again absorbed by 
 the liquid j on evaporation, pure KBrOj crys- 
 tallises out. Fritzsche supposes that KBrOj is 
 partly decomposed by heat to hypobromite and 
 perbromate, that the latter acts on water, 
 evolving and forming KBrOjAq, and that the 
 O is absorbed by the KBrOAq with formation 
 of KBrOaAq. KBrOj is decomposed by cone. 
 HjSOjAq, with evolution of and Br (Lowig) ; 
 by HNOjAq, with production of KNOjAq, Br, 
 and (Penny, A. 37, 206). KBrOjAq decomposes 
 HjS, separating S, and forming HBrAq, and 
 H2S04Aq. Heated with combustible bodies, 
 KBrOj evolves rapidly and explosively. 
 
 Silver bromate AgBrOj. Dimetric prisms 
 (Marignao). Prepared by AgNOaAq + HBrOjAq 
 or KBrOjAq, and crystallising from hot water. 
 Stable in air free from organic matter. Decom- 
 poses on heating. 
 
 Sodium bromate NaBrOj. Prepared as 
 KBrOj. At 4° crystallises with a;H.^O forming 
 efflorescent needles (Lowig) ; above 4° the 
 anhydrous salt separates, isomorphous with 
 KBrO, according to Lowig {B. J. 12, 120). 
 S.G. 1^ 3-339. S. (0°) 28, (20°) 38-5, (60°) 62-5, 
 (100°)' 99 (Kremers, P. 97, 1). B. P. oi saturated 
 NaBrO3Aq = 109°. Decomposes when heated as 
 EBrO,(q.v.). 
 
 Strontium bromate Sr(Br05)2.H20. Mono- 
 clinic prisms. Is amorphous with the Ba salt 
 (Eammelsberg). S. (15°-18°) 33. Loses H^O 
 at 120°- Prepared by SrCOj + HBrOaAq. 
 
 Zinc bromate Zn(BrOs)2.6H20. Mono- 
 metric octahedra, isomorphous with the Mg 
 salt ; prepared as Co(Br03)2.6H20. Melts at 
 100° ; loses eH^O at 200° with partial decom- 
 position to ZnO, Br, and 0. S. (15°-18°) 100. 
 Soluble in NHjAq (Eammelsberg). 
 
 Besides the foregoing, bromateg of Ce, La, 
 and Di of the form M(Br03);.6H20 have been 
 prepared (Eammelsberg, Marignac, Herrmann 
 J. pr. 82, 385). Bromates of Al, Or, Fe, and 
 V ; of Pd, and Pt ; of Bi ; and of Sn, seem to 
 exist. They have, however, either not been 
 obtained in definite form, or have been very 
 slightly examined. 
 
 Bromine, Sulphide of: better called Sul- 
 phnr Bromide {v. Sulphdk). M. M. P. M. 
 
 BEOMINE, ACTION ON OBGANIC BODIES 
 V. Bkomo-oompodnds. 
 
 BE.0MO-. Use of this prefix applied to inor- 
 ganic compounds : for bromo-ccmpounds and 
 hrcmio -salts v. the element the bromo-oom- 
 pound of which is sought for, or the salts to the 
 names of which bromo- is prefixed. Thus 
 bromochloride of carbon will be found under 
 Cabbon; bromo-chromate of potassium under 
 Cbbomates. 
 
 BBOMO-ACENAPHTHENEv. AcENACEiBi:itE. 
 
 BEOMO-ACENAPHTHYLENE v. Aoenaph- 
 
 IHTLENE. 
 
 BBOMO-ACETAL v. Bkomo-aceiio aldehxde. 
 
 BROMO-ACETAMIDE v. Beomo-acetio acid. 
 
 v-Bromo-acetamide v. Aceto-bromo-amide, p. 5. 
 
 BEOMO-ACETAMIDO- v. Beomo-amido-. 
 
 BBOMO-ACETANILISE v. Beomo- aniline. 
 
 BEOMO-ACETIC ACID OjHjBrOj i.e. 
 CH,Br.CO,H. [51°]. (208°). 
 
 Formation. — 1. By bromination of acetic 
 acid (Perkin a. Duppa, A. 108, 106; Hell a. 
 Mflhlhauser, B. 11, 241; 12, 735).- 2. By heat- 
 ing ethyl acetate with bromine at 150° (Crafts, 
 
 A. 129, 50).— 3. From glyooUic acid and HBr 
 (Kekul6, A. 130, 11). — 4.- By atmospheric oxida- 
 tion of an alcoholic solution of bromo-ethylene 
 (Gloclmer, A. Suppl. 7, 107). — 5. By the action 
 of bromine on dry glycerin (Barth, A. 124, 341). 
 6. From chloro-acetio acid and HBr (Demole, 
 
 B. 9, 561). — 7. From ethylene bromide and 
 fuming HNO3 (Kaohler, M. 2, 259). 
 
 Preparation. — Br, glacial acetic acid, and 
 some CS2 are boiled with inverted condenser ; the 
 yield is nearly theoretical (Michael, Am. 5, 202). 
 
 Properties. — Deliquescent rhombohedra; v. 
 sol. water. Blisters the skin. 
 
 Reactions. — 1. Heated with zinc it yields 
 Zn(0Ac)2 and ZnBrj. — 2. NH3 forms glyoocoU. 
 3. Silver benzoaie forma glycoUide, benzoic 
 acid and AgBr. — 4. Silver powder at 130° forms 
 succinic acid. — 5. Benzyl sulphide (G.,^.).,^ 
 forms benzyl bromide and S(CH2.CO.^H)2 (Letts, 
 Tr. E. 28, 612). Allyl sulphide acts similarly.— 
 6. Bromo-acetio acid and its ethyl salt unito 
 directly with Me.^S and its homologues, forming 
 hydrobromides of 'thetines' (Crum Brown a. 
 Letts, B. 7, 695). 
 
 Salts. — The NHj, K, Ba, and Ca salts are 
 V. sol. water.— PbA',: lamina, si. sol. cold 
 water. — AgA' : crystalline ; explodes at 90°. — 
 UrjOjNaA'j (Clarke a. Owens, B. 14, 35). 
 
 Methyl ether MeA'. (144°) (P. a. D.). 
 
 Ethyl ether EtA'. (159°). Converted by 
 Na into aceconitic ether (u. p. 2). 
 
 Chloro-ethyl ether CH^CLCH^.A'. (214°). 
 S.G. LLf 1'65. From chloro-ethyl chloro-acetate 
 and Br (Henry, C. B. 97, 1308). Decomposed 
 by heating with water into glycol chlorhydria 
 and bromo-acetic acid. 
 
 Bro-ino-ethyl ether 
 CH3.CHBr.0.C0.CH.,Br. (135°) at 370 mm. S.G. 
 12 1-962. From CH3.CHCl.OAc (v. p. 105) and 
 Br at 100° (Kessel, B. 10, 1999 ; 11, 1916). Oil. 
 Boiling alcoholic EOH forms bromo-acetic ether, 
 EtBr, acetal, and crotonic aldehyde. 
 
 Di-bromo-ethyl ether 
 C2HsBr2.0.C0.CH2Br. A non-volatile oil, ob- 
 tained by heating the preceding (I mol.) with 
 Br (1 mol.) at 120°. 
 
 Tri-bromo-ethyl ether 
 CjHjBrj.O.CO.CH^Br. An oil formed by heating- 
 bromo-ethyl bromo-acetale (1 mol.) with Bi 
 (2 mols.) at 160°. 
 
 Tetr a -bromo -ethyl -ether 
 CjHBrj.O.CO.CH^Br. (177°). From the preceding; 
 (1 mol.) and Br (1 mol.) at 170°. Decomposed 
 by alcohol into EtBr and bromo- and di-bromo- 
 acetic ethers. 
 
 Penta-bromo-eihyl ether 
 CjBrs.O.CO.CH^Br. (c. 197°). Formed by br<v 
 minating the preceding. 
 
640 
 
 BROMO-ACETIC ACID. 
 
 Isoamyl ether C^^^M. (207°). 
 
 Chloride v. Bkomo-acetyl ohloeidb. 
 
 Bromide v. Beomo-aoettl bbomide. 
 
 Anhydride (CHjBr.CO),0. (245°). Ob- 
 tained by distilling Ao.O.CO.CHjBr which is 
 (oimed by the action of AcONa on Br.CO.CH^Br 
 <Naumann, A. 129, 273 ; Gal, C. B. 71, 273). 
 
 Amide CH,Br.C0.NH2. [165°]. From 
 bromo-acetic ether and 20 p.o. NH3 at 0° (Kessel, 
 
 B. 11, 2116). V. sol. water, si. sol. alcohol, 
 insol. ether. 
 
 Nitrile CR^r.C^. (149°). S.G. i21-771. 
 V.D. 4 06. Bromo-acetonitrile is formed by the 
 action of bromine-water on iodo-acetonitrile 
 <Henry, O. E. 103, 413). The dibromide of 
 acetonitrile (p. 35) may be looked upon as a 
 hydrobromide of bromo-acetonitrile ; when water 
 ds added to its alcoholic solution needles of the 
 imide (CH2Br.CO)2NH [98°] gradually separate 
 <Engler, A. 133, 137 ; 142, 69). 
 
 Di-bromo-acetie acid CHBr.,.C02H. [45°-50°]. 
 (233°). Formed, together with CH^Br.COjH, 
 when a mixture of bromine and acetic acid is 
 exposed to sunlight (Perkin a. Duppa, 0. J. 11, 
 22 ; Schaffer, B. 4, 368). Formed also by the 
 .action of Br on acetic ether at 130° (Carius, B. 
 
 3, 336), and as a. by-product in the preparation 
 of tri-bromo-acetic aldehyde by passing bromine- 
 Tapour into alcohol. Crystalline mass, v. sol. 
 alcohol and ether ; its vapour is very pungent. 
 
 Salts. — Excepting Ag and merourous salts, 
 ithe dibromo-acetates dissolve readily in water. — 
 1^H,A'.— KA' aq.— BaA'2 4aq.— BaA'2 6aq (Bene- 
 ■dikt, A. 189, 160).— PbA'^: stellate groups of 
 needles. — AgA': needles ; decomposed by boil- 
 ing water into AgBr, glyoxylic acid, and dibromo- 
 acetic acid ; decomposed by ether at 100° into 
 AgBr and an oil, CjHjBr^O,, whence water forms 
 ■di-bromo-acetic and glyoxylic acids (Perkin, 
 
 C. J. 32, 91). 
 
 Ethyl etherGHBx2.C02^\,. (193°). Formed 
 'by heating the acid with alcohol or by adding 
 Iromal-hydrate (4 pts.) to an alcoholic solution 
 of KCy (1 pt.) (Remi, J. B. 7, 263). 
 
 Amide CHBrj.CO.NH^. [156°]. Formation. 
 — 1. From di-bromo-acetic ether and NHj 
 <Sohaffer, B. 4, 369; Kessel, B. 11, 2116). 
 — 2. From penta-bromo-aceto- acetic amide 
 •CBrs.CO.CBr2.CO.NH2 and boiling water (Stokes 
 a. V. Pechmann, Am. 8, 375). — 3. From penta- 
 bromo-acetone and NH3 (Cloez, A. 122, 121). — 
 
 4. From asparagine and bromine (Guaresohi, B. 
 t), 1435) . Properties. — Needles ; may be sublimed ; 
 m. sol. cold, V. sol. hot, water, alcohol, and ether. 
 
 Nitrile CHBrj.CN. [142°]. Formed, together 
 -with bromoform and COj by the action of Br 
 on aqueous cyano-acetic acid (Hoff, B. 7, 1571). 
 
 Tri-bromo-acetic acid CBrj.COjH. [130°] 
 (S.) ; [135°] (Gal, C. B. 77, 786). (250°). 
 
 Formation. —1. By the action of water on 
 iri-bromo-aeetyl bromide. — 2. By heating aqueous 
 •malonic acid with bromine (Petrieff, B. 8, 730).— 
 3. By heating tri-bromo-aoetic aldehyde with 
 HNO, (Schaffer,B. 4, 370). 
 
 Properties. — Monoclinic tables, v. sol. water ; 
 its vapour is pungent. Decomposed by boiling, 
 giving off Br and HBr. The salts, excepting 
 the silver and mercurous salts, are v. sol. water 
 and alcohol, but decomposed by heat, both when 
 dry and when in solution, into bromoform and 
 a metallic carbonate. 
 
 Salts. — NaA'2^aq: lustrous laminte. - 
 BaA'2 3aq: tables. — PbA'^: stellate groups of 
 needles. — AgA' : very unstable laminsB. 
 
 Ethyl ether'E.iK'. (225°). 
 
 Amide CBrs.CO.NH^. [121°]. Formed, 
 together with the preceding by the action ot 
 bromine on asparagine suspended in water 
 (Guareschi, O. 6, 375). Formed also by treat- 
 ing hexa-bromo-aeetone with ammonia (Weidel 
 a. Gruber, B. 10, 1148). Monoclinic laminje ; 
 may be sublimed ; si. sol. alcohol, ether, and 
 cold water. Split up by boiling alkalis into 
 bromo-form, CO2, and NHj. 
 
 BKOKO-ACETIC ALDEHTDES. 
 
 Bromo-acetic ortho-aldehyde. 
 
 Ethyl ether CH2Br.CH(OEt)2. Bronio- 
 acetal. (171°). From aoetal and bromine 
 (Pinner, B. 5, 149) or by treating vinyl ethyl 
 oxide with Br and decomposing the product 
 CHjBr.CHBr.OEt with NaOEt (Wislicenus, A. 
 192', 112). AlcoholicKOH at 170° converts it into 
 CH20H.CH(0Et)„ while NaOEt forms at 100° 
 CH2(0Et).CH(0E"fc)2. 
 
 Di-bromo-acetic aldehyde CHBrj.CHO. (142°). 
 Formed by dropping Br (2 mols.) into a solution 
 of paraldehyde (1 mol.) in acetic ether (Hage- 
 mann, B. 3, 758 ; Pinner, A. 179, 67). Liquid, 
 V. sol. water and alcohol. Blisters the akin. 
 Slowly changes to an isomeric modification, 
 insol. water. Combines with water, forming 
 the solid hydrate CHBr2.CH(0H)j. 
 
 Tri-bromo-acetic aldehyde CBrj.CHO. 
 Bromal. Mol. w. 281. (174°). S.G. 3-34. 
 
 Formation. — 1. By the action of Br on alco- 
 hol (Lowig, A. 3, 280; Sohiifter, B. 4, 366).— 
 
 2. Together with the preceding, by the bromina- 
 tion of paraldehyde. 
 
 Properties. —Pungent liquid ; decomposed by 
 aqueous alkalis into bromoform and formic acid. 
 
 Reactions. — 1. Fuming HNOjforms tri-bromo- 
 acetic acid. — 2. Alcoholic KCy forms di-bromo- 
 acetic ether and HCy (Eemi, B. 8, 695). — 
 
 3. Cone. HjSOj forms bromalide C5H2Br50, 
 or tri - bromo - ethylidene tri - bromo - lactate 
 
 [158°]. This body is 
 
 [97°] (Klimenko, 
 
 .0.00 
 CBr3.CH< I 
 
 \0.CH.CBr3 
 
 also formed by the action of tri-bromo-lactic 
 acid on bromal (Wallaoh, A. 193, 52). It 
 is insol. water, and decomposed by alcohol. — 
 4. Tri-chloro-lactic acid forms the corresponding 
 
 >o.co 
 
 CBr3.CH< I [150°].— 5. Lactic acid 
 
 \0.CH.CC1, 
 .O.CO 
 forms CBr3.CH<f | 
 
 \0.CH.CH5 
 B. 9, 968). 
 
 Combmations. — l.With water: Tri-bromo- 
 acetic orthoaldehydeoi Bromal-hydrate 
 CBrs.CH(0H)j. [54°]. Crystallises on evapo- 
 rating an aqueous solution of bromal. Decom- 
 posed by distillation into HjO and bromal. — 
 2. With alcohol: CBr3.CH(0H)(0Bt). Bromal 
 alcoholate [44°]. Thick needles ; si. sol. water ; 
 resolved by distillation into its components. — 3. 
 WithsodiumbisulphiteCBrs.CH(OH).S03Na: 
 lamina.— 4. With ammonia CBr,.CH(0H).NH.2: 
 crystals, insol. water; decomposed at 35° (Schiff a. 
 Tassinari, B. 10, 1786).— 5. With acetamide : 
 CBrj.CH(OH).NHAo, [160°] (S.a. T.).-6. With 
 
BROMO-ACETONE. 
 
 541 
 
 ethyl carbamate: CBivCH(OH).NH.CO^Et. 
 BromaUmthane [132°] (Bisohoff, B. 7, 632). 
 BEOMO-ACETIC BEOMIDE v. Bkomo-aoettl 
 
 BROMIDE. 
 
 BEOMO-ACETIC CHLOEIDE ij.Beomo-aoetyl 
 
 CHLORIDE. 
 
 BEOMO-ACETIC OXIDE v. Anhydride of 
 Bkomo-acetio acid. 
 
 BEOMO-ACETO-ACETIC ACID Ethyl - 
 ether C„H„Br03 i.e. CH3.C0.CHBr.C0,Et. 
 S.G. w 1-511. 
 
 Formation. — By addition of Br (1 mol.) to 
 an ethereal solution of aceto-aoetio ether (Duis- 
 berg, B. 15, 1379 ; A. 218, 138). 
 
 Properties. — Pungent brown liquid ; si. sol. 
 water, v. sol. ether and alcohol. Gradually de- 
 composes on standing, giving off HBr. Fe^Cl,, 
 turns its aqueous solution deep red. It is dis- 
 solved by baryta- water, and on adding Cu(0Ac)2 
 the solution gives a sap-green crystalline pp. 
 Cu(05H5Br03)j which on reerystalhsation from 
 alcohol or CSj separates as dark -green needles. 
 
 Reactions. — 1. Alcoholic NH3 forms suc- 
 oinyl-succinio ether. — 2. Na added to its ethe- 
 real solution also produces succinyl-suooinio 
 ether (dihydride of di-oxy-terephthalio ether). — 
 3. NaOEt produces succinyl-sucoinic acid 
 fWedel, A. 219, 92). These reactions may be 
 represented thus : 2CH3.CO.CHBr.COaEt 
 CHjCO.CH.COjEt 
 -2HBr+ I I 
 
 COjEt.CH.CO.CH2 
 
 CH:C(0H).CH.C02Et 
 = 2HBr+ I I 
 
 C02Et.CH.C(0H):CH 
 
 Anilide CH3.CO.CHBr.CO.NHPh. [138°]. 
 Bromine added to the anilide of aceto-acetio 
 ether in chloroform forms an additive product 
 which on warming yields bromo-aceto-acetic 
 anilide (Knorr, A. 236, 79). Pearly plates (from 
 alcohol) ; si. sol. water. Cone. H2SO4 produces 
 bromo-oxy-methyl-quinoline. 
 
 Methyl-bromo-aceto-aoetlc ether 
 CH3.CO.CMeBr.C02Et. Obtained by bromination 
 of methyl-aceto-acetid ether. Liquid. Converted 
 by heat into EtBr and C5H5O3 (Pawlow, 0. B. 
 97, 99). 
 
 Ethyl-bromo-aceto-aoetic ether 
 CH3.C0.CEtBr.C02Et. S.G. 1'35. Obtained by 
 adding Br to ethyl-aceto-acetic ether in ethereal 
 solution (Wedel, A. 219, 102). Pungent liquid. 
 Fe^Clj turns its alcoholic solution violet. At 
 100° it gives EtBr and C.^Hj^Oj or CjHsOs, 
 probably CH3.CO.C(CO,H):CH.CH3 (cf. Demar- 
 9ay, A. Oh. [5] 20, 465). 
 
 Iso-bntyl-bromo-aceto-acetic ether 
 CHa.CO.CiC^HjjBr.COjEt. From iso- butyl- 
 aceto-acetic ether and Br at —5° (Demarpay, 
 Bl. [2] 31, 513 ; 33, 516 ; A. Oh. [5] 20, 433 ; 
 C. B. 86, 1085, 1135). Alcoholic KOH converts 
 it, according to Demarpay, into hexoic, methyl- 
 isobutyl-glyceric, heptoic, oxyheptoic, and gly- 
 collio acids; according to Pawlow (0. B. 97, 
 99) alcoholic KOH forms an acid OgK^fi, or 
 CH3.CO.C(C02H):CH.gr with evolution of EtBr. 
 
 Di-bromo-aceto-aoetic ether 
 CH3.C0.CBrj.C02Et(?).S.G. ^ 1-884. From aceto- 
 aoetio ether (10 g.) in ether (10 g.) treated with 
 Br (24-6 g.) (Duisberg, 4. 213, 143). Pungent oil. 
 
 BeacUans.—l. Aqueous Fe^Clj gives a deep 
 
 red colour. — 2. Baryta-water gives a claret 
 colour, but Cu(OAo)2 gives no pp. in this solu- 
 tion. A sap-green pp. Cu(C„H,Br203)2 is, how- 
 ever, formed when cone. Cu(OAo)2Aq is added t(v 
 an alcoholic solution of the ether ; it crystallises 
 in needles (from alcohol). — 3. Diluted with 
 ether and treated with Na, di-bromo-aceto-aoetio 
 ether (80 g.) gives di-oxy-terephthalic ether (2 g.). 
 NaOEt may be used instead of Na (Wedel, A. 
 219, 74). 
 
 Ethyl-di-bromo-aceto-aeetio ether 
 C„H,Br2Et03 i.e. CHjBr.CO.CBrEt.CO.,Et (?). 
 S.G. 1-64. A yellowish oil, got by bromination 
 of ethyl-aceto-acetic ether. Fe^Clj colours its 
 alcoholic solution wine-red (Wedel, A. 219, 102). 
 
 Tri-bromo-aoeto-acetic ether 
 CH3Br.CO.CBr2.C03Et. S.G. ^ 2-144. From 
 aceto-acetic ether (10 g.) in chloroform (20 g.) 
 by addition of bromine (38 g.) (Duisberg, A. 
 213, 145). Yellow liquid, slightly pungent. V. 
 si. sol. water. When heated, it gives off HBr. 
 
 Beactions. — 1. Aqueous Fe^Clj gives after 
 some time a shght red pp. — 2. Gives in alco- 
 holic solution with cupric acetate a green pp. 
 Cu(C„H^r303)2 (Wedel, A. 219, 95). 
 
 Ethyl-tri-bromo-aceto-acetic ether 
 C,H,3r3Et03 i.e. CHBr^.CO.CBrEt.COjEt (?). 
 S.G. 1-86. Its alcoholic solution is turned wine- 
 red by Fe^Cla. 
 
 Tetra- and Penta-bromo-aceto-acetic ethers, 
 so called, are mixtures of tri- with per- bromo- 
 aceto-acetic ether. 
 
 Pen ta-bromo-aceto-acet amide 
 CBr3.CO.CBr2.CO.NH3. [0. 148°]. From di-oxy- 
 amido-pyridine and bromine-water (Stokes a. 
 V. Pechmann, Am. 8, 375). Needles or prisms; 
 converted by boiling water into di-bromo-aoet- 
 amideand OHBr,. Alcoholic NH3 gives di-bromo- 
 malonamide and CHBr3. 
 
 Per-bromo-aceto-acetio ether CjBruOj i.e. 
 CBr3.C0.CBr2.C0.C,3r5. [69°-70°]. From tri- 
 bromo-aoeto-acetic ether and bromine at 80° 
 for 2 days. Colourless crystalline mass. Not 
 affected by air. Gives no colour with FOjClj and 
 no copper pp. (Wedel, A. 219, 97). 
 
 BEOMO-ACETO-AMIDO- v. Bromo-amido-. 
 
 TEI-BEOMO-ACETO-GUANAMIDINE 
 C4HjBr3N303. From bromine and aqueous 
 acetoguanamide (Nenoki, B. 9, 236). Minute 
 needles, insol. water, alcohol, and ether. Split 
 up by boiling with water into bromoform and 
 cyanuric acid. 
 
 BROMO-ACETOL v. Di-bromo-pkopane. 
 
 BEOMO-ACETONE CHa.CO.CHjBr. S.G. 1-99. 
 
 Formation. — 1. By adding 1 mol. bromine to 
 acetone, either pure or mixed with water or with 
 CS2 (Linnemann, A. 125, 307 ; Emmerling, B. 
 6, 22). — 2. By the action of a weak electric cur- 
 rent on a mixture of acetone and HBr (Eiohe, 
 0. B. 49, 276). 
 
 Preparation. — 1. A stream of dry air satu- 
 rated with bromine (138 g.) is passed through 
 100 g. cooled acetone (Emmerling a. Wagner, A. 
 204, 27). — 2. Bromine (Imol.) is passed through 
 a solution of 1 mol. acetone in 10 vol. water 
 (Sokolowsky, B. 9, 1687). 
 
 Properties.— YeHo'w, very pungent-smelling 
 oil, quickly turning violet when dry, more per- 
 manent when mixed with a little water. AgjO 
 oxidises it to formic and acetic acids (Linne- 
 mann, Site. B. 68, 437). Aqueous KjCOj forms 
 
C4C 
 
 BliOMO-ACETONE. 
 
 a syrupy acid CijHijO, (?) Bromo-acetone com- 
 bines with NaHSOj. 
 
 «-Di-bromo-acetone CHs.CO.CHBr^. S.G. 2-5. 
 Prepared by adding bromine (2 mols.) to acetone 
 {1 mol.) mixed with a large quantity of water. 
 Liquid, volatile with steam. Not very pungent. 
 Combines with NaHSOj. 
 
 s-Di-bromo-acetone CH^r.CO.CHJBr. [24°]. 
 From di-iodo-aoetone and AgBr at 150° ; or 
 from di-chloro-acetone and aqueous KBr. Long 
 needles with pungent smell (Volker, A. 192, 96). 
 Eeduoed by Zn and H^SO., to acetone. 
 
 Tri-bromo-acetone CBrj.CO.CHj. Formed by 
 the action of alkalis upon hexa-bromo-methyl 
 methenyl di-ketone. NH, gives bromoform 
 (Combes, A. Ch. [6] 12, 241). 
 
 Tetra-bromo-acetone hydrate CaHjBr^Oaaq. 
 [43°]. From Ba (10 pts.) and acetone (1 pt.) in 
 the cold ; when the resulting solid mass is re- 
 crystallised from dilute alcohol a mixture of 
 tetra- and penta-bromo-acetone is first deposited, 
 and afterwards prisms of tetra-bromo-acetone 
 hydrate CsHjBr^O 2aq. The hydrate is insol. 
 water, sol. alcohol (Mulder, /. 1864, 330). 
 Perhaps this body is- (C3H2Br,0)HOEt. 
 
 Penta-bromo-acetone CaHBrsO. [76°]. 
 
 Formation. — 1. From Br (12 pts.) and acet- 
 one (1 pt.) (Mulder, /. 1864, 330 ; cf. Steiner, 
 B. 7, 505, 1284). — 2. Separates on adding water 
 to an alcoholic solution of 'phlorobromin,' 
 that has stood some time (Benedikt, C. G. 
 1878, 101 ; A. 189, 168).— 3. From potassic 
 citraconate and Br (Cahours, A, 64, 351 ; 
 Grimaux, J. 1874, 522).— 4. From chelidonio 
 acid and Br (Wilde, A. 127, 167).- 5. From 
 aqueous pyruvic acid and Br at 100° (Wichel- 
 haus, A. 152, 260). 
 
 Properties. — Trimetric needles (from dilute 
 alcohol); a:6:c = -698 : 1 : -086 (Ditscheiner a. 
 Friedlander, Z. Kryst. 3, 103). Converted by 
 aqueous or alcoholic NHj into di-bromo-acet- 
 amide. Aqueous KOH forms bromoform, HBr, 
 CO2, and formic acid. 
 
 Hexa-bromo-acetone CBr3.CO.CBr3. [112°]. 
 
 Formation. — 1. By the action of Br on an 
 aqueous solution of tri-amido-phenol hydro- 
 chloride or hydrobromide, or on 'bromo-di- 
 chromazin ' the first product of the action of 
 bromine on these salts. — 2. From bromanilic 
 acid and Br (Hantzsch a. Echniter, B. 20, 2040). 
 3. From di-amido-guaiaool hydrochloride and Br 
 (Herzig, M. 3, 825). 
 
 Properties. — Monoolinio prisms (from chloro- 
 form), insol. water. Decomposed by alcohol. 
 
 Reactions. — 1. Boiling NaOHAq or water at 
 180° form bromoform and COj. — 2. Boiling cone. 
 HNO3 has no action, but at 150° it produces 
 bromo-picrin CBr3N02.— .3. Dry NH3 gives rise 
 to tri-bromo-aoetamide and CBr3H. — 4. Sodium 
 amalgam reduces it to iso-propyl alcohol. 
 
 BKOMO - ACETONITRILE v. NiiRiLB op 
 Beomo-acetic acid. 
 
 oj-BRGMO-ACETOPHENONE CsHjBrO i.e. 
 CsHj.CO.CHjJSr. Phenyl bromo-methyl ketone. 
 Phenacyl bromide. [50°]. 
 
 Formation. — 1. From acetophenone and Br 
 (Emmerling a. Engler, B. 4, 148 ; Hunnius, B. 
 10, 2006; Staedel, B. 13, 837;).— 2. Formed, 
 together with CO^ and HBr, by boiling a-phenyl- 
 o-oxy-/3.dibromo-propionic acid with water 
 (Bottinger, JS. 14, 1238). 
 
 Preparation. — 1385 pts. of bromine are slowly 
 run into a mixture of 100 pts. of acetophenone 
 and 500 pts. of glacial acetic acid. After stand- 
 ing an hour it is gently heated on a water bath 
 till colourless, when it is at once poured into a 
 large quantity of cold water ; theyield is 133 pts. or 
 80 p.o. of the theoretical (Mohlau, B. 15, 2464). 
 
 Properties. — Trimetric prisms (from dilute 
 alcohol) ; pungent ; v. sol. alcohol and ether, 
 insol , water. 
 
 Reactions. — 1. KMnO, forms benzoic acid. — 
 2 Alcoholic NH3 forms iao-indole CsH,N. — 
 3. With sodio-malonic ether it forms 
 C„H5.CO.CH,.CH(C02H)2.— 4. With sodio-aceto- 
 acetic ether it forms acetophenone-aceto-acetio 
 ether (v. p. 36). — 5. AnUine forms phenyl- 
 amido-acetophenone (Mohlau, B. 14, 172).— 6. 
 Reacts with hydroxylamine hydrochloride with 
 production of iso - nitroso - acetophenone - oxim, 
 C„H5.C(NOH).CH2.NH.OH [163°] (Schramm, B. 
 16, 2183). — 7. An alcoholic solution of phenyl 
 hydrazine reacts thus : Ph.CO.CHjBr -i- NjHjPh 
 = HBr + HjO + Ph.C,H2N2Ph. The product 
 forms yellow needles (from alcohol) [137°]. It 
 is very soluble in ether, chloroform, and CSj, 
 less in alcohol or light petroleum. It is de- 
 composed by acids (0. Hess, A. 232, 234). 
 
 w-Di-bromo-acetophenone G^JI^.GO.CKBz^. 
 [37°]. Prepared by adding bromine (2 mols.) to 
 a cold solution of acetophenone (1 mol.) in acetio 
 acid, warming to 65°-70°, and pouring into 
 water ; the yield is c. 80 p.o. of the theoretical 
 (Engler a. Hassenkamp, B. 18,2240; c/. Hunnius, 
 B. 10, 2010 ; Fittig a. Wurster, A. 195, 161). 
 
 Properties. — Trimetric tables (from CSj) ; 
 insol. water. Oxidised by KMnOj to benzoic acid. 
 
 Reactions. — 1. Alcoholic KOAc forms 
 Ph.C0.CH(0Ac)2. — 2. Alcoholic hydroxylamine 
 ■forms phenyl-glyoxim Ph.C(N0H).CH(N0H) 
 [152°]. — 3. By treatment with NH3 a portion 
 breaks up into benzamide and CH2Br2 whilst 
 another part yields isoindileucine CisHuN^O. 
 
 a-TEI - BROMO-ACETOPHENONE-o-CAS- 
 BOXYLIC ACID CBrj.CO.CeHi.CO^H. [100°]. 
 From phthalyl-aoetio acid and Br. Eesolved by 
 alkalis into CHBr3 and phthalio acid (Gabriel 
 a. Michael, B. 10, 1551, 2199 ; 11, 1007). 
 
 BROMO-ACETOTHIENONE v. Thienyi 
 
 BEOMO-METHIL KETONE Bud BbOMO-IHIENYIi 
 METHYL KETONE. 
 
 HEXA-BROMO-ACETYL-ACETONE v. Hexa- 
 
 BK0M0-m-METHYL-METH1LENB DI-KETONE. 
 
 BROMO-ACETYL-BENZENE is Bkomo-aceto- 
 
 PHENONE (g. V.) . 
 
 BEOMO-ACETYL BROMIDE CH2Br.CO.Br. 
 (150°). S.G. £i 2-317. 
 
 Formation. — 1. From AcBr and Br at 100° 
 (Gal, A. 129, 54).— 2. From AcBr and PBr^ at 
 150° (Samosadsky, Z. [9] 6, 105).— 3. From 
 AcCl (64 pts.) and Br (120 pts.) at 100° (Hiibner, 
 A. 124, 315 ; Naumann, A. 129, 257 ; Gal, A. 
 132, 179). — 4. By direct combination of M-di- 
 bromo-ethylene CBr2:CH2 with oxygen (Demole, 
 O. B. 86, 542). 
 
 Properties. — Pungent liquid : blisters the skin. 
 
 Reactions. — 1. Aqueous Na^COaforms sodium 
 bromo-acetate and sodium glyooUate. — 2. Dis- 
 tillation with NaOAc produces Ao^O, bromo- 
 acetio anhydride and glyooUide. — 3. ZnMe, 
 gives a compound whence water liberates 
 
J5itUMU-ACRYLIC ACID. 
 
 643 
 
 methyl -isopropyl-carbinol, acetone, and methyl 
 ethyl ketone (Winogradow, A. 191, 127). 
 
 J)i-bromo-acetyl bromide CHBrj.CO.Br. 
 (194°). From the preceding and Br at 150° (G.). 
 Formed also by the action of oxygen on tri- 
 bromo-ethylene (D.). Fuming liquid ; con- 
 verted by alcohol into di-bromo-aoetic ether. 
 
 Tri-bromo-acetyl bromide CBr3.CO.Br. 
 (220°-225°). From the preceding and Br at 
 200° (G.). Slowly converted by water into tri- 
 bromo-acetic acid. 
 
 BKOMO-ACETYL CHLORIDE CH,Br.COCl. 
 S.G. 2 1*91. Pungent liquid, produced by the 
 action of PCI3 on bromo-aoetio acid (Wilde, A. 
 132, 171). 
 
 BEOMO-ACETYL CYANIDE CH.,Br.CO.CN. 
 [79°]. Formed, together with CH,CN.CO.Br by 
 the action of AgCy on bromo-acetyl bromide 
 (Hiibner, A. 131, 68). Monoelinic tables, decom- 
 posed by water into HCy and CHjBr.COjH. 
 
 BROHO-ACETYLENE CBr-CH. Formed by 
 the action of alcoholic KOH on CH,Br.CBr5 
 (Eeboul, A. 125, 81), on CH.Br.CHBr/ (Alexe- 
 jeff, Z. 6, 644), or on CHBr:CHBr (Sawitsch, A. 
 119, 183 ; Fontaine, G. R. 70, 1361 ; Saban^eff, 
 Bl [2] 45, 245). 
 
 Preparation. — Acetylene dibromide is heated 
 with NaOH and dilute alcohol in an apparatus 
 filled with nitrogen. The gas is condensed by a 
 freezing-mixture (S.). 
 
 Properties. — Gas at ordinary temperatures; 
 m. sol. water. In the liquid form it is decom- 
 posed by light into s-tri-bromo-benzene and 
 other products. It takes fire in air ; when 
 slowly mixed with air bromo-acetic acid is 
 formed. Ammoniacal cuprous chloride gives 
 a red pp. of cuprous aoetyHde. Br forms 
 CHBr2.CBr,. 
 
 ;8-BEOMO-;3-ACETYL-PROPIONIC ACID 
 C.H^BrOj i.e. CH3.C0.CHBr.CHi,.C0,H. Bromo- 
 levulic acid. [59°]. Crystallised from CS,. 
 
 Formation. — 1. By bromination of a solution 
 of /8-acetyl-propionio acid in cone. HCl below 0°. 
 2. By the action of water upon (a)-angelico- 
 lactone dibromide (Wolff, A. 229, 266 ; v. V)i- 
 
 BROMO-OXY-VALERIO ACIb). 
 
 Properties. — Widie needles (from CSJ. Sol. 
 alcohol, ether, and water. 
 
 Reactions. — By the action of aqueous NajCOj 
 it yields oxy-acetyl-propionic acid and aoet- 
 acrylic acid. By heating with cone, aqueous NH3 
 at 110°-120° di-methyl ketine (tetra-methyl- 
 pyrazine) CjMejN^ is formed, with evolution of 
 CO2. With aniline it gives di-phenyl-tetra- 
 methyl-di-hydro-pyrazine CiMejNjPhj (Wolff, 
 B. 20, 425). 
 
 Ethyl ether -EtA.'. (240°). S.G. is 1.439. 
 From Br and ethyl iS-aoetyl-propionate (Conrad 
 a. Guthzeit, B. 17, 2285). Malonic ether and 
 NaOEt convert it into methyl propyl ketone tri- 
 carboxylic ether (C0,Et),CH.CHAc.CH2.C02 Et 
 (0. 283°) S.G. ia 1-097. 
 
 Di-bromo-;8-acetyl-propionic acid CfigBi-fls. 
 [115°]. SoUdifies about 94°. From y3-acetyl- 
 propionic acid, chloroform and Br. From 
 bromo-)3- acetyl -propionic acid and bromine. 
 Long thin needles (Wolff, A. 229, 266 ; Hell a. 
 Kehrer, B. 17, 1981). 
 
 Tri-bromo-j3-acetyl-propiouic acid CjHjBrjOj. 
 [82°]. From ;8-acetyl-propionio acid, Br and 
 chloroform (Wolff, A. 229, 267). 
 
 BR0M0-psc2tc?o-ACETYI-PYRR0I v. Bbouo- 
 
 PTBRTL-METHYL KETONE. 
 
 BROMO-ACETYL-UREA v. Ukea. 
 
 BROMO- ACIDS v. Bromo- compounds. 
 
 BR0M0-MET-ACS0LElN(C3H,BrO)3(?).[78°]. 
 Acrolein takes up Br forming di-bromo-propionio 
 aldehyde, a liquid which polymerises, becoming a 
 gummy mass, which may also be obtained by 
 the action of Br on metacrolein. NaOEt con- 
 verts this gummy metacrolein dibromide into 
 bromo-met-acrolein (Grimaux a. Adam, Bl. [2] 
 36,136). Needles (from alcohol). Has no smell; 
 does not reduce Fehling's solution. When dis- 
 tilled with H^SOj (1 vol.) diluted with water (1 
 vol.) it gives off extremely pungent vapours 
 which may be condensed to a liquid, sol. water, 
 which is probably bromo-aorolein. By heating 
 with NaOEt it is converted into CuH-BrOa [140°]. 
 
 a-BROMO-ACRYLIC ACID CjHjBrO, i.e. 
 CH,:CBr.C02H. [70°]. From an. or a^S-di-bromo- 
 propionio acid and alcoholic KOH (Philippi a. 
 Tollens, A. 171, 333 ; Wagner a. ToUens, A. 
 171, 340 ; Erlenmeyer, B. 14, 1867). 
 
 Properties. — Rectangular monoolinic plates, 
 V. sol. water and alcohol. Decomposed by dis- 
 tillation or exposure to light. Combines with 
 HBr forming a;8;di-bromo-propionic acid. 
 
 Salts. — AgA'. — BaA'j 4aq. — CaA'^ 4aq. — 
 KA'.— NaA' aq.— NH^A'.— Zn A V 
 
 Ethyl ether 'E.ik'. (c. 157°). (77°) at 30 
 mm. With sodium malonic ether it gives 
 C0,Et.C(CH,).CH(C02Et), identical with the 
 compound from a0-di- bromo -propionic ether 
 and di-sodium-malonic ether (Michael, J. pr. [2] 
 35, 134). 
 
 /8-Bromo-acrylic acid CHBr:CH.C02H. [116°]. 
 From bromalide or from tri-chloro-ethylidene 
 tri-bromo-lactate by reduction with Zn and HCl 
 (Wallaoh, A. 193, 55). Formed also by the 
 addition of HBr to propiolic- acid (Bandrowski, 
 B. 15, 2702; Stolz, B. 19, 540). Plates or 
 needles, sol. water and chloroform ; explodes 
 on heating. 
 
 Acryl-coUoids. This name is applied by 
 Wagner a. Tollens to three bodies having the 
 composition (GJifl3)x. 
 
 a-Acryl-colloid. Is formed in the pre- 
 paration of - a-bromo-acrylic acid from a^S-di- 
 bromo-propionic acid, especially when the action 
 becomes violent. Insol. water, alcohol, and 
 ether, sol. NH3Aq and not reppd. by HCl. 
 
 P-Acryl-colloid is formed when o-bromo- 
 acryliu acid is left over H.^SOj. It is a porous 
 mass, sol. NHjAq and reppd. by HCl. 
 
 ■y-Acryl-colloid is formed with separation 
 of EtBr, by heating ethyl a-bromo-acrylate. 
 Amorphous ; insol. NHjAq, but becoming 
 gummy therein. 
 
 a3-Di-bromo-acrylio acid CHBriCBr.COjH. 
 [86°]. S. 5-19 at 18°. 
 
 Formation.— 1. From mnco-bromic acid and 
 cold baryta-water (Jackson a. Hill, B. 11, 1673 ; 
 Am. 3, 111 ; 4, 169, 273 ; Hill a. Andrews, P. 
 Am. A. 16, 192; 17, 133).— 2. From alco- 
 holic KOH and aa;8.tri- bromo -propionic acid 
 (Michael a. Norton, Am. 2, 18; Mauthner a. 
 Suida, Sitz. B. 83_, 273 ; M. 1, 104).— 3. From 
 a;8;8-tri-bromo-propiomc acid and alcoholic KOH. 
 
 Properties. — Pearly plates (from alcohol). 
 Sol. ether and chloroform, si. sol. benzene and 
 CS,. Boiling baryta-waterforms bromo acetylene, 
 
M4 
 
 BROMO-ACRYLIO ACID. 
 
 CO2, formio, malonio, and bromo-propiolio acids. 
 Heated with Br in a sealed tube it forms tetra- 
 bromo-propionio acid. 
 
 Salts. — AgA' : slender needles. — PbA'^ aq : 
 pearly plates, si. sol. cold water. — BaA'j aq. S. 
 6-28 at 18°.— CaA'i, 3aq : long needles.— KA'. 
 
 )3j8-Di-bromo- acrylic acid CBr2:CH.C02H. 
 [86°]. S. 3-06 at 20°. From tri-bromo-suocinio 
 acid by heating with water (Pittig a. Petri, A. 
 195, 70). Formed also by the union o£ HBr 
 with bromo-propiolio acid (Hill, B. 12, 660 ; 
 Hill a. Mabery, P. Am. A. 16, 211). 
 
 Prqperiies.— Large plates ; boils with partial 
 decomposition at 243°-250°. V. e. sol. alcohol, 
 and ether ; m. sol. cold water. Does not com- 
 bine with HBr in the cold. Does not combine 
 with Br in the cold, but at 100° it forms tetra- 
 bromo-propionic acid (Mabery a. Eobinson, Am. 
 5, 251). 
 
 Salts.- BaA'j 2aq : S. 12-64.— CaA'^ SJaq. 
 
 Ethyl ether EtA'. (213°). 
 
 Tri-bromo-aorylic acid CBr2:CBr.C02H. 
 [118°]. S. 1-37 at 20°. From a;8;8;3-tetra-bromo- 
 propionic acid and alcoholic KOH at 60° 
 (Mauthner a. Suida, M. 2, 109). Formed also 
 by treating bromo-propiolic acid with bromine- 
 water (HiU, Am,. 3, 178) ; and from di-bromo- 
 iodo-acrylio acid and Br at 100° (Mabery a. 
 Lloyd, Am. 4, 92). Monoclinic prisms, a:6:c 
 = -502:l:-559 (Melville, P. Am. A. 17, 154). 
 Tricliuic pyramids, a:b:c = 1-128 : 1 : 1-150 ; a = 
 89° 13', )3 - 62° 26', 7 = 91° 14' (Beoke, If. 2, 111). 
 V. sol. alcohol and ether. Does not combine 
 with bromine, even at 200°. The Ba salt yields 
 tri-bromo-ethylene when boiled with water. 
 
 Salts.— BaA'2 5aq.-BaA'2 3aq. S. (of BaA'j) 
 SO-6.— CaA'j 3aq.— AgA. 
 
 BKOMO-ADIPIC ACID CsH^BrO^. From 
 adipic acid and Br (1 mol.) at 160° (Gal a. Gay- 
 Lussao, C. B. 70, 1175). Dark-brown mass, 
 smelling like camphor; converted by boiling 
 alkalis into adipomalic (or oxyadipio ?) acid 
 (v. p. 64). 
 
 (o)-di-bromo-adipic acid C^^tfit. From 
 adipic acid Br (2 mols.) at 160° (G. a. G.). 
 Powder ; decomposed by water. Water at 150° 
 forms adipotartario (or di-oxy-adipio ?) acid 
 (v. p. 64). 
 
 (/3) - di - bromo - adipic acid CjHgBrjO^ 
 [115°-122°]. Formed together with bromo- 
 hydromuoonio acid, by the action of Br on a 
 solution of hydromuconic acid (Limprioht, A. 
 165, 265). Needles. Converted by moist AgjO 
 or baryta into di-oxy-adipic acid. 
 
 (7) - di - bromo - adipic acid CjHsBrjO^. 
 [175°-190°]. Formed by adding Br to a warm 
 solution of hydromuconic acid in glacial HOAo 
 (L.) Small needles. Converted by moist AgjO 
 into muconic acid, and by sodium-amalgam to 
 hydromuconic acid. 
 
 Tri-bromo -adipic acid CjH^BrjOj. [177°-180°]. 
 Formed by treating a hot solution of hydro- 
 muconic acid with excess of Br (L.). Small 
 needles. Converted by boiling baryta- water into 
 tri-oxy-adipic acid. 
 
 Tetra-bromo-adipic acid CjHsBr^O,. [211°]. 
 Formed by heating hydromuconic acid with Br 
 and water at 100°. CrystaUine. V. si. sol. 
 water, v. sol. alcohol. H. W. 
 
 BBUMO-.a;SGnL£TIN V. .SsouLEiiN, p. 65. 
 
 BBOaiO-ALDEHYDE v. Bbomo-acbiio usi-a- 
 
 HYDE. 
 
 BBOUO-ALIZABIN' v. Bbomo-di-oxy-anthra 
 
 QUINONE. 
 
 DI-BKOMO-DIAIIYL v. 
 
 Di-BaoMo-HExiN- 
 
 BROMO-AILYt ACETATE OsH^BrOAc i.e. 
 CHBr:CH.CH2.0.Ac (?). (164°). S.G". i^ 1-57. 
 From bromo-allyl bromide (;3-epidibromhydrin; 
 and alcoholic KOAc (Henry, B. 5, 453). Fra- 
 grant liquid ; not attacked by PCI.,. H. W. 
 
 a-BEOMO-ALLYL ALCOHOL CaHsBrO i.e. 
 CHi,:CBr.CH20H. (152°). From a-bromo-allyl 
 bromide (o-epidibrorahydrin) and water at 130° 
 (Henry, B. 14, 403). Liquid; converted by 
 aqueous KOH into propargyl alcohol. 
 
 j8-Bromo-aUyl alcohol CHBr:CH.CH20H(?). 
 (155°). S.G. 151-6. From ;3-bromo-allyl acetate 
 (v. sup.) by distillation with solid NaOH (Henry, 
 B. 5, 453). Is perhaps identical with the pre- 
 ceding. 
 
 DI-BEOMO-DI-ALLYL-AMINE C^H^r^N i.e. 
 (CaHjBrjjNH. From s-tri-bromo-propane (tri- 
 bromhydrin) and alcoholic NH3 at 100' (Max- 
 well Simpson, P. M. [4] 16, 257). Also from 
 bromo-allyl bromide and alcoholic NH3 (Eeboul, 
 A. Suppl. 1, 232). Alkaline liquid, v. si. sol. 
 water. Converted by alcoholic NH3 at 250° into 
 methyl-pyridine.— B'jHjPtCls.- B'HgClj. 
 
 BBOMO-ALLYL BBOKIDE v. Di-bbomo- 
 
 PBOPYLENE. 
 
 BBOMO-ALLYLEH'E v. PEOPABoyL bkomide. 
 
 Bromo-diallylene v. Hexonyl eeomide. 
 
 BBOMO-ALLYL ETHYL OXIDE v. Eihyi. 
 bromo-allyl oxide. 
 
 BROMO-ALLYL NITEATE 
 CHBr:CH.CH2.0.N0j (?). (140°-150°). S.G. l» 
 1-5. From j3-bromo-allyl bromide and AgNO, 
 (Henry, B. 5, 452). 
 
 BROMO - ALLYL OXIDE C^HsBr^O i.e. 
 (0HBr:CH.CH2)2O (?). Bromo-allyl ether, (c. 
 214°). S.G. i^ 1-7. Formed together with prop- 
 argyl alcohol from i8-bromo-allyl alcohol and 
 solid KOH (Henry, B. 6, 729). 
 
 BROMO-ALLYL THIO-CARBIMIDE 
 C3H4BrN.CS. (c. 200°). From bromo-allyl 
 bromide and alcoholic potassium sulpho- 
 cyanide (Henry, B. 5, 188). 
 
 BR0M0-ALLYL-THI0-1TREA 
 (03HjBr)NH.CS.NH2. [111°]. From the pre- 
 ceding and ammonia (H.). 
 
 TRI-BROMO-ALOIN v. Aloin, p. 141. 
 
 BBOMO-AMIDO-ACETOFHENOIfE 
 [5:2:1] C,H3Br(NH,).C0.CH3. 
 
 Acetyl derivative 
 OeH3Br(NHAo).CO.CH3. [160°]. Obtainod by 
 bromination of acetyl-o-amido-acetophenone in 
 acetic acid solution (Baeyer a. Bloem, B. 17, 
 965). Slender felted colourless needles, sol. hot, 
 si. sol. cold, alcohol ; v. si. sol. cold water. By 
 KMuO, it is oxidised to bromo-isatin [255°]. 
 By boiling with KOH it yields bromo-indigo. 
 
 Mum-Tri-bromo-o-amido-acetophenone [5:2:1] 
 C„H3Br(NH,).CO.CHBr2. [c. 145°]. Fine felted 
 orange yeUow needles. V. sol. alcohol and ether, 
 si. sol. water. Obtained by saponification of the 
 acetyl derivative by boiling it with a mixture oi 
 alcohol and aqueous HBr. 
 
 Acetyl derivative 
 C,H3Br(NHAo).CO.CHBrj: [185°], yellowish 
 granular crystals, v. sol. chloroform, al soL 
 
BROMO-AMIDO-BENZENE SULPHONIC ACID. 
 
 645 
 
 aleohol. Formed by the action of bromine 
 vapour on dry aoetyl-o-amido-aoetophenone 
 mixed with a little iodine. By boiling with HOI 
 it yields oi-di-chloro-m-bromo-o-amido-aoetophe- 
 none. By KMnOj it is oxidised to bromo-isatin. 
 By boiling with dilute NaOH and exposure to 
 the air it gives bromo-indigo (Baeyer a. Bloem, B. 
 17, 966). 
 
 DI-BEOMO-AMIDO-ANTHEAQTJINONE 
 C„H5Br2(NH2)Oj. [170° uncorr.]. Prepared by 
 reduction of dibromo-nitro-anthraquinone with 
 stannous chloride (Glaus a. Diernfellner, B. 14, 
 1334). Slender red needles. SI. sol. all solvents. 
 Has no basic properties. 
 
 BBOMO-AMIBO-BENZENE v. Bbomo-ani- 
 
 hlKE. 
 
 (1, 2, 4)-BR0M0-AMID0-B£irZ£N£ SUL- 
 PHONIC ACIB CsHeBrNSOa i.e. 
 05H3Br(NHj)S03H [1:2:4]. Bromo-aniline sul- 
 phmic cuM. S. 1-49 at 11° (S.) ; 2-61 at 20° 
 (A.) ; 1-31 at 4° (La.). 
 
 Formation. — 1. By reduction of (1, 2, 4)-bro- 
 mo-nitro-benzene sulphonio acid (Goslioh, A. 
 180, 100). — 2. By sulphonation of o-bromo-ani- 
 line (Andrews, B. 13, 2126).— 3. From bromo- 
 benzene p-sulphonio acid by nitration and re- 
 duction. — 4. From very dilute aqueous amido- 
 benzene m-sulphonio acid and bromine-water 
 (Langfurth, A. 191, 176). -5. From (1, 3, 4, 6)-di. 
 bromo-m-amido-benzene sulphonio acid, fuming 
 HCl,and red P at 150° (Limprioht, B. 10, 1542). 
 6. By heating the same acid with water at 250° 
 (L.). 
 
 ProperUes. — Anhydrous needles (from cone, 
 aqueous solution) or four- and six-sided columns 
 containing aq (from dilute solution). SI. sol. 
 alcohol. Eeduced by HI and P, or by water at 
 120°, to amido-benzene TO-sulphonic acid. 
 
 Salts. — KA'IJ aq (La.). — KA' aq (Spiegelberg, 
 A. 197,257).— BaA'^aq.—BaA'jSaq. S.(ofBaAy 
 6-22 at 17°.— PbAV— CaA'j2aq.— AgA'l^aq. 
 
 (1, 4, 3)-Bromo-amido-benzene sulphonic acid 
 OeH,Br(NHj)S03H [1:4:3]. S. -47 at 15°. 
 
 FormaiSm. — 1. By heating ^'-bromo-aniline 
 ethyl-sulphate (Nolting, B. 8, 1095).— 2. By 
 adding bromine to a cold aqueous solution of 
 barium aniline o-sulphonate (Limprioht, A. 181, 
 196). — 3. By nitration and reduction of bromo- 
 benzene TO-sulphonic acid (Thomas, A. 186, 126). 
 4. From acetyl-^-bromo-aniline and fuming 
 HjSO, (Boms, A. 187, 368). 
 
 Properties. — Slender silky needles (contain- 
 ing aq) or large efflorescent prisms (with 2aq). 
 SI. sol. cold water, v. si. sol. alcohol. Converted 
 by Br into tri-bromo-aniline. HI and P form 
 aniline o-sulphonio acid. 
 
 Salt a.— NHjA'.— KA'.— BaA'j aq.— CaA'j aq. 
 — PbA',2aq. 
 
 (l,4,2)-Broino-amido-benzene snlphonic acid 
 C,H,Br(NH2)S03H [1:4:2]. S. 1-14 at 18°. From 
 bromo-benzene o-sulphonio acid by nitration 
 and reduction (Bahlmann, A. 181, 203 ; 186, 
 318). Needles (from cone, aqueous solutions) 
 or rhombohedra (?) containing 2aq (from dilute 
 aqueous solution) ; v. sol. hot water, insol. alco- 
 hol and ether. Beduced by HI and P to aniline 
 »i-Bulphonio aoid. Salts. — BaA'22aq: needles, 
 Y. e. sol. water.— PbA'j.—AgA'. 
 
 Bromo-amido-benzene sulphonio acid 
 0^aBr(NHj)(SOsH) [l:a!:2]. S. -74 at 8°. 
 Formed in smaller quantity in the preparation 
 
 Vol. I. 
 
 of the preceding (B.). Prisma; fll. sol. cold 
 water. — BaA'^saq: laminaa, v. sol. water. 
 
 Bromo-amido-benzene sulphonio acid 
 CsHjBr(NH2)(S0sH) [l:3:a;]. From acetyl m. 
 bromo-aniline and fuming H^SO, (Boms, B. 8, 
 1072). Needles.— BaA'j 2aq. 
 
 (l,2,8,5)-Broma- amido-benzene disnlphome 
 acid OjH2Br(NHJ(S03H)2 [1:2:3:5]. Formed 
 by bromination of (l,2,4)-amido-benzene disul- 
 plionio acid (Zander, A. 198, 1). Needles (con- 
 taining aq) ; V. sol. water, si. sol. alcohol. 
 
 Salts. — The acid salts are less soluble than 
 the normal ones. — (NH4)2A"2aq. — BaA"3aq. — 
 BaH^A''^ 5aq.— PbH^A" 6aq.- K^A" 2aq. 
 
 Bromo-amido-benzene disulphonic acid 
 CsH,Br(NHj){SOsH)j [1:4:3:5] or [:4:1:3:6] 
 or [2:1:3:5]. Formed by adding bromine to an 
 aqueous solution of (1 or 4, 3, 5) -amido-benzene 
 disulphonic acid (Heinzehnann, A. 188, 179). 
 Prisms (containing 2^aq) ; v. e. sol. water. — 
 BaA"8aq.— PbA"3aq. 
 
 Bromo-di-amido-benzene sulphonic acid 
 C5H2Br(NH2),S03H [1:2:6:4]. Bromo-m-phmyU 
 ene-diamine sulphonic acid. S. '51 at 17°- 
 Got by reducing 05Brs(N02)2S03H with SuClj 
 (Bassmann, A. 191, 244). Long white needles 
 (containing aq), turns yellow in air. When 
 pure it is si. sol. water, when impure it is very 
 soluble. Insol. alcohol. Paper moistened with 
 its solution turns red in air. The aqueous 
 solutions of its salts turn blue or red when 
 evaporated. Converted by diazo- reaction into 
 ^-bromo-benzene sulphonio acid. — BaA'j aq. 
 
 (1,3,2,5) -Di-bromo-amido-benzene sulphonio 
 acid CeH2Br,(NH,)(S03H) [1:3:2:5]. Formed 
 by adding bromine to an aqueous solution of 
 aniline p-sulphonio acid (Sclunitt, A. 120, 138 ; 
 Lenz, B. 8, 1066 ; A. 181, 24). Formed also by 
 brominating (l,2,4,)-amido-benzene disulphonio 
 acid (Zander, A. 198, 16). Needles or prisms 
 (containing 2aq) ; v. sol. water and hot alcohol ; 
 ppd. by cone. H^SO, from its aqueous solution. 
 Br forms tri-bromoaniline. — BaA'^ 2aq. — 
 BaA'j B|aq. S. (of BaA'j) -16 at 11°.— PbA', 2aq. 
 
 BeacUons. — POI5 forms a product (probably 
 CjHjBrj(NH.POCySO,Cl) from which alcohol 
 produces CeH2Br,(S02Cl)NH.PO(OEt)2. [170°] 
 (Laar, J. pr. 128, 256). V. also di-methyi.- 
 
 AMIDO-BENZBNE SULPHONIO ACID. 
 
 (l,3,4,6)-Di-bromo-amido-benzene sulphonio 
 acid C,H2Br2(NH2)S03H [1:3:4:6]. S. -252 at 
 10°; -249 at 7°; -194 at 4° (Berndsen, A. 177, 
 84; Beckurts, A. 181, 213; Eeinke, A. 186,286; 
 Knuth, A. 186, 301 ; Langfurth, A. 191, 180 ; 
 Bassmann, A. 191, 229, 238; Spiegelberg, A. 
 197, 266). 
 
 Formation. — 1. From amido-benzene m-sul- 
 phonio acid and bromine. — 2. From (1, 2, 4)- 
 bromo-amido-benzene sulphonio acid and Br. — 
 
 3. From the corresponding OsHjBr2(N02)S03H. — 
 
 4. From (l,3,5,2,6)-tribromo-nitro-benzene sul- 
 phonic acid, Sn, and HCl. — 5. From tribromo- 
 amido-benzene sulphonio acid by treating with 
 water at 150°, or by treating with Sn and HCl. 
 
 Properties. — Needles (from hot water) ; si. 
 Bol. water, insol. alcohol. 
 
 Reactions. — 1. Water sX 250° forms o-bromo- 
 aniline sulphonio acid and aniline m-sulphonio 
 acid. — 2. Diazo- reaction gives (l,3,4)-di-bromo- 
 benzene sulphonic acid. — 3. Warmed with 
 
 NN 
 
646 
 
 BROMO-AMIDO-BENZENE SULPHONIO AOID. 
 
 strong alcohol and KNO, a yellow crystalline 
 body, possibly 0,tt,Brj(SO,H).N,H.OeH2BrjS03K, 
 is formed. Heated in sealed tubes with alcohol, 
 it splits up into dibromo-benzene sulphonic acid 
 and amido -dibromo-benzene sulphonic acid 
 (Bassmann). 
 
 Salts.-BaA'26aq. S. (of BaAy 2-99 at 7° ; 
 3-12 at 9°; 3-9 at 28°. — KA'aq. — NH^A'.- 
 CaA'j 2aq.— CaA'^ 5aq.— PbA'j. S. 2-9 at 22-5°. 
 
 (l,2,4>S)-Di-bromo-amido-benzene sulphonic 
 acid CBH^r2(NH,)(S03H) [1:2:4:5]. S. -109 at 
 10° ; '153 at 24°. From (l,2,4)-di-bromo-ben. 
 zene sulphonic acid by nitration and reduction 
 (Spiegelberg, A. 197, 279). Trimetrio tables ; 
 V. si. sol. alcohol.— NH^A' aq. — KA' 2aq. — 
 BaA'j aq: S.(ofBaAy •67at 11°.— PbA'^aq: S. 
 (of PbA'j) -11 at 11°.— OaA'^Saq.— CaA'2 4aq.— 
 AgA'. S. -053 at 11°- 
 
 (l,3,4,S)-Si-bromo-amido-benzene sulphonic 
 acid CjHjBrj(NHJ(S03H) [1:3:4:5]. S. 3-13 at 
 10"5°. From amido-benzene o-sulphonic acid 
 by bromination (Limpricht, A. 181, 198 ; B. 8, 
 1429), or from (l,3,5)-di-bromo-benzene sul- 
 phonic acid by nitration and reduction (Lenz, 
 A. 181, 36). Trimetric tables (anhydrous) or 
 4-Bided prisms (with aq). Converted by Br into 
 tri-bromo-aniUne. 
 
 Salts.— KA'aq.—NaA'aq. S. (of NaA') 3-7 
 at 12°.— BaA'j 4aq. S. (of BaA'j) -20 at 11°.— 
 PbA'^aq. 
 
 Si-bromo-amido-benzene sulphonic acid 
 C,H2Brj(NIL()(S03H) [1:4:2 ?:6]. S. -62 at 10-5°. 
 From (l,4,2)-di-bromo-benzene sulphonic acid 
 by nitration and reduction (Boms, A, 187, 862). 
 Needles or prisms. — KA'. — ^BaA'j aq. 
 
 Dl-bromo-amido-benzene disniphonic acid 
 C5HBrj(NH2) (SOjH)^ [1:4:3 ? :2:6 ?]. From ^-di- 
 bromo-benzene disulphonic acid by nitration and 
 reduction (Boms, A. 187, 867). Crystals; v. 
 Bol. water.— KjA".—BaA". 
 
 Di-bromo-amido-benzeue di-snlphonic acid 
 CeHBr,(NH,){S03H)2. [1: 4or6 :2:3:5]. From 
 (l,2,4)-amido-benzene disulphonic acid and Br 
 (Heinzehnann, A. 188, 182). Prisms (contain- 
 ing 4aq) ; v. sol. water.— (NHJ^A". — EaA".— 
 BaA"8aq.— PbA"8aq. 
 
 Si-bromo-di-amido-benzene sulphonic acid 
 CjHBr2(NH2)2SOsH [1:3:2:6:4]. One of the pro- 
 ducts of the reduction of C^rs(NH2)2S0,H 
 (Bassmann, A. 191, 244, 248). Tablets (contain- 
 ing aq), V. si. sol. water. 
 
 Tri-bromo-amido-beuzeue sulphonic acid 
 CeHBr3(NHJS03H, [1:3:5:4:6]. S. 13-7 at 14°. 
 16-6 at 7° (B.). 
 
 formation. — 1. From amido-benzene ot-su1- 
 phonic acid and Br (Berndsen, A. 177, 86).— 2. 
 From the corresponding nitro- acid, by Sn and 
 HCl, some di-bromo-amido-benzene sulphonic 
 acid being also formed (Eeneke, A. 186, 282; 
 Knuth, A. 186, 298 ; Langfurth, A. 191, 198).— 
 3. From(l,2,4)-bromo-amido-benzene sulphonic 
 acid by bromination (Spiegelberg, A. 197, 276). 
 
 ProperUes. — Thin needles (containing aq). 
 Sol. cold water and alcohol. Heated with water 
 at 145° it becomes CeH2Br2(NH2)S03H. 
 
 Salts.— BaA'^gaq. S.(dry). -43 at 7° (L.), 
 ■34 at 3° (Bassmann, A. 191, 221).— KA' aq. -935 
 at 4° (B.).- PbA'^eaq. S. (of PbA'j,) -73 at 14°. 
 
 Tri-bromo-amido-benzene sulphonic acid 
 C„HBr3(NH2)(S03H) [1:2:3:4:5]. From (1, 2, 8, 5)- 
 tri-bromo-benzene sulphonic acid by nitration 
 
 and reduction (Lenz, A. 181, 43). Tufta of slon 
 der needles (containing aq), v. sol. water and 96 
 p.o. alcohol. — BaA'j IJaq. 
 
 Tri-bromo-amido-benzene sulphonic acid 
 CeHBr3(NHi,)(S03H) [1:2:5:6:4]. From the cor- 
 responding nitro- acid (Spiegelberg, A. 197, 288). 
 Long prisms (containing l^aq) or slender 
 needles (with aq). V. sol. water and alcohol. — 
 KA'aq. S. (of KA') 209 at 1°.— NH^A'.— 
 CaA',3iaq.— BaA'j. S. -096 at 1°.— PbA'^ 2aq. 
 S. -40 at 3-5°.- AgA' Jaq. S. (of AgA') -46 at 10°. 
 
 Tri-bromo-di-amido-benzene sulphonic acid 
 CsBr3(NHj)2S03H [1:8:5:2:4:6]. A product of 
 reduction of C6Br3(N02)2S03H (Bassmann, A. 
 191, 249).— BaA'2 IJaq. 
 
 Tetra-bromo-amido-benzene sulphonic acid 
 CeBr4(NH2)S03H. [1:2:3:5:4:6]. B. 2-25 at 11° 
 (Beckurts, A. 181, 223). Got by reducing 
 CBBr4(N02)S03H with Sn and HCl, not allowing 
 the temperature to rise to 100°, or Br^ will be 
 displaced by Hj. Needles (containing 2aq). V. 
 sol. alcohol and water. 
 
 Salts.— (Langfurth, A. 191, 204) BaA'^aq. 
 S. (of BaA'J -4 at 10°.— CaA'., 7aq, KA' IJaq. 
 S. (of KA') 1-71 at 15°. 
 
 Tetra-bromo-amido-benzene sulphonic acid 
 C„Br,(NH,)(S03H) [1:2:3:4:5:6]. S. -03 at 11°. 
 From the nitro acid (Spiegelberg, A. 197, 302). 
 Needles (containing 2aq). V. sol. alcohol.— 
 KA'aq. S. (of KA') -106 at 11°.— CaA'^ 2aq. S. 
 (of CaA'J -107 at 11-5°.— BaA'^aq. S. (of BaA'3) 
 •0155 at 11-5°. 
 
 (a) - BROMO - - AHIBO ■ BENZOIC ACID 
 0BH3Br(NH2)C02H [1:2:3]. Bromo-cmthraniUa 
 add. [170°]. From the corresponding nitro- 
 compound by Sn and HCl (Hubner, A. 222, 104; 
 of. A. 148, 244; 149, 134). Needles; m. Sol. 
 water. Sodium amalgam reduces it to o-amido- 
 benzoic acid [144°]. Nitrous acidforms the diazo- 
 derivative CeHjBrCOjH.Nj.NH.CBHaBrCOjH.— 
 Salts . — AgA'. — BaA'2 aq. — OuA'j. 
 
 Acetyl derivative 
 C,H3Br(NHAc)(C02H) [1?:2:3]? [215°]. Obtained 
 by brominating acetyl-o-amido-benzoio acid 
 (Jackson, B. 14, 879). 
 
 (;3)-Bromo-o-amido-benzoic acid. Bromo-OM- 
 thramlioacid. CsH3Br(NH2)C0.,H [1:4:3]. [208°]. 
 
 Formation. — 1. By reducing (1, 4, 3)-bromo- 
 nitro-benzoic acid (Hiibner, Ohly a. Philipp, A. 
 143, 242 ; Meeker, Hiibner a. Petermann, A, 
 149, 133). — 2. By boiling bromo-isatoic acid 
 with cone. HCl (Dorsch, /. pr. [2] 33, 85). 
 
 Properties. — V. sol. acetone, sol. alcohol, 
 ether, chloroform, benzene, and glacial acetic 
 acid, si. sol. boiling water. Sodium-amalgam 
 reduces it to o-amido-benzoic acid [144°]. 
 
 Salts. — BaA'24aq: needles, v. sol. water. 
 
 Amide. CeH3Br(NH,)C0.NH,. [177°] . From 
 bromo-isatoic acid and NHjAq. Flat needles. V. 
 sol. alcohol, acetone and glacial acetic acid, m. 
 sol. water and benzene. Insol. ether. 
 
 (l,2,4)-Bromo-m-amido-benzoic acid 
 CjHjBrJNHJCOjH [1:2:4]. [225°]. By re- 
 ducing the nitro- acid by Sn and HCl. Small 
 colourless needles (from water), becomes reddish 
 in air (Hiibner, A. 222, 179; Burghard, B. 8, 
 558 ; Eaveill, B. 10, 1707). Beduced by sodium- 
 amalgam to m-amido-benzoio acid. — HA'HOl.— 
 CuA'j.— PbA'2. 
 
 (l,3,5)-Bromo-m-amido-beuzoic acid 
 OaH,Br(NHj)CO,H [1:3:5]. [215°]. From the 
 
BEOMO-AMIDO-(a)-NAPHTHOQUINONE-IMIDB. 
 
 547 
 
 corresponding nitro- aoid by Sn and HCl (Hese- 
 mann a. Kohler, A.222, 169). Needles (from aloo- 
 hol). Turns red in light. Salts.— HA'HCl.— 
 (HAOjHjSO,.— BaA'j4aq.— CaA', 5Jaq. 
 
 (l,4,2)-Bromo-m-a]uido-1>enzoic acid 
 0,H,Br(NH2)C0jH [1:4:2]. [180°]. From 
 (l,4>2)-bromo-mtro-benzoio aoid, Sn, and glacial 
 HOAo (Burghard, B. 8, 560). Flat needles (Smith, 
 B. 10, 1706). 
 
 (l,2,4,5)-I)i-bromo-o-amldo-benzoic acid 
 CeH,Brj(NHj).COjH [1: 2or6 :5:4]. Di-bromo- 
 anthraniUc acid. [226°-228°]. 
 
 Formation. — 1. From di-bromo-nitro-benzoio 
 aoid (Smith, B. 10, 1706). — 2. From o-nitro- 
 toluene and bromine at 170° (Waohendorff, A. 
 185, 281 ; Grieff, B. 13, 288).— 3. From isatoio 
 acid (2. V.) and bromine (Dorsch, J. pr. [2] 33, 37). 
 
 PreygerUes. — Clumps of needles (from alco- 
 hol). Long needles (when sublimed). Sol. alcohol, 
 acetone and glacial acetic aoid, si. sol. ohloro- 
 iform, benzene, ether, and water. 
 
 Amide G^^xJ^B^)CO.T^Ii^. [197°]. 
 Pearly tablets (from alcohol-acetone). Formed 
 from di-bromo-isatoic acid and NHjjAq at 100°. 
 
 Bi-bromo-o-amido-benzoic acid 
 C„H2Br2(NH2)C02H [l:2or6 :5:4]? Di-hromo- 
 anthranilio acid. [225°]. S. 1 ; S. (alcohol) 
 2. From the nitro- acid by reduction (Hubner, 
 A. 222, 189). Colourless needles. Eeduoed by 
 sodium amalgam to o-amido-benzoio acid. — 
 BaA'j4aq. — CaA'j4iaq. — SrA'2 2aq. — CuA',. 
 This acid is probably identical with the pre- 
 ceding. 
 
 (l,3,4,5)-Si-bromo-o-amido-benzoic acid 
 CsHJBr5,(NHj)C02H [1:3:4:5}. Di-bromo-an- 
 thravAlic add. [225°]. S. 1 ; S. (HOAc) 3. 
 By reduction of the nitro- acid by Sn and HCl 
 (Hesemann a. Kohler, A. 222, 175). Beduced 
 by sodium amalgam to o-amido-benzoic acid. 
 Needles (from alcohol). — BaA'2 4aq.— CaA'j4aq. 
 — CuA'j. 
 
 (l,3,5,4)-I)i-bromo-o-ainido-benzoic acid 
 CjH2Brj(NH2) (COjH) . Di - bromo - anih/ranilic 
 acid. [196°]. From benzoic acid by bromina- 
 tion, nitration, and reduction (Angerstein, A. 
 158, 16). Needles (from dilute alcohol). Beduced 
 by sodium-amalgam to o-amido-benzoio acid. 
 
 Sl-bromo-ji-amido-benzoic acid 
 C„HjBrj(NHj)C02H [1:3:2:5]. Obtained by 
 adding bromine-water to an acidified solution of 
 ^-amido-benzoic acid (Beilstein a. Geitner, Z. 
 [2] 1, 505 ; A. 139, 1). Needles (from alcohol).— 
 NH,A' 2aq. — NaA' 5aq. — CaA'^ 6aq.— BaA'j 4aq. 
 
 Tri-bromo-o-amldo-benzoic acid 
 C,HBr3(NH2)C02H [l:2:x:4:5].. Tri-hromo- 
 anthraniUc acid. [o.ll9°]. From isatoic acid 
 and bromine (Dorsob, J.pr. [2] 33, 37). 
 
 Properties. — Slender needles. May be sub- 
 limed. Very soluble in glacial acetic acid, 
 alcohol and acetone, sol. ether and chloroform, 
 less soluble in benzene, si. sol. hot water. 
 
 Trl-bromo-m-amido-beuzoic acid 
 C„HBr3(NH2)COj,H [1:3. 5:4:6]. [170°]. From 
 7re-amido-benzoic aoid and bromine-water (Beil- 
 stein a. Geitner, Z. [2] 1, 505 ; A. 139, 6 ; VoU- 
 brecht, B. 10, 1708). Needles; m. sol. hot 
 water. On dry distillation it gives tri-bromo- 
 aniline. — NaA'4aq. — BaA'j 6aq. 
 
 Tri-bromo-dl-amido-beuzoic acid 
 CeBr,(NH2)j(C0jH) [1:3:6:2:4:6]. From s-di- 
 amido-benzoic acid and bromine-water (Griess, 
 
 A. 154, 332). Long needles (from dilute alco- 
 hol). SI. sol. cold water. — AgA'. 
 
 Tetra-bromo-o-amido-benzoic acid 
 CjBr,(NH2)C02H [1:2:3:4:5:6]. [115°]. Prom 
 isatoic acid and excess of Br (in glacial acetic 
 aoid) (Dorsch, J. pr. [2] 33, 38). White needles. 
 At 100° it sublimes in long slender needles. 
 
 BEOMO-AMIDO-HYDEOCARBOSTYKIL v. 
 p. 164. 
 
 BEOMO-AMIDO-HYDEOCINNAMIC ACID 
 V. Bromo-amido-3-phenyl-peopionio aoid. 
 
 BROMO-AMIDO-NAPHTHALENE v. Bkomo- 
 
 NAPHIHYLAMINE. 
 
 BEOMO-AMIDO-NAPHTHOIC ANHYDEIDE 
 
 NH CO 
 
 CiiHjONBr i.e. 
 
 Bromo-rmph- 
 
 Br 
 
 thosfyril. [257°]. By reduction of bromo-nitro- 
 (a) -naphthoic acid with FeSOj and aqueous NH, 
 and ppn. with acetic acid the amido- acid is 
 obtained, and by boiling with alcohol it is con- 
 verted into the anhydride, which crystallises out 
 on cooling in brown needles (Bkstrand, B. 19, 
 1136). 
 
 Si-bromo-amido-naphthoic anhydride 
 .CO 
 CijHjBrj^ I . Di-bromo-naphthfOstyril. [270°]. 
 
 \nh 
 
 Prepared by heating amido-naphthoio anhydride 
 
 .CO 
 CioH(i\ I suspended in water with a large 
 
 \nh 
 
 excess of bromine. Yellow needles (from alcohol). 
 M. sol. hot acetic acid. 
 
 Acetyl derivative CnHiGNBrjAc [185°]; 
 small yellow needles (Ekstrand, B. 19, 1136). 
 
 BEOMO-AMIDO-(a)-NAPHTHOQUINONE 
 
 ^«^*<CacS^'^- 1^^°^°^- Formed by boiling 
 bromo-amido-(o)-naphthoquinone-imide 
 .CO C(NHj) 
 
 C,H,^ 
 
 
 with dilute acids. Orange 
 
 C(NH).CBr 
 
 silky needles. Subhmable. By boUing with 
 dilute alkalis it is converted into bromo-oxy-(o)- 
 naphthoquinone. 
 
 Acetyl derivative: [137°]; sulphur- 
 yellow needles (Zincke a. Gerland, B. 20, 1514). 
 BEOMO - AMIDO - (a) - NAPHTHOQUINONE - 
 .CO-C(NHj) 
 / II 
 
 IMIDE OsHji 
 
 \f 
 
 [200°]. Obtained 
 
 C(NH).CBr 
 
 by adding bromine (5 o.o.) to di-amido-(o)-naph- 
 thol or its stanno-chloride (10 g.) suspended in 
 acetic aoid. Orange-yellow needles (from alco- 
 hol). V. sol. hot alcohol and hot benzene. By 
 SnClj it is reduced to bromo-di-amido-(o)-naph- 
 thol. By boiling with dilute acids it is con- 
 verted into bromo- amido- (o) -naphthoquinone 
 ,C0.C(NH2) 
 
 0,H,< 
 
 /" 
 
 By boiling with dilute NaOH 
 
 \CO.CBr 
 
 it is converted into bromo-oxy-naphthoquinone- 
 
 imide 0,H(' 
 
 .CO — C(OH) 
 / II 
 
 \, 
 
 C(NH).CBr 
 
 The latter body 
 nk2 
 
648 
 
 BROMO-AMIDO-(a)-NAPHTHOQUINONE-IMIDE. 
 
 when treated with cono. HCl or alcoholic NaOH 
 IS converted into bromo-oxy-naphthoquinone 
 
 OsH^^^qq'q^j ' which is also formed by boil- 
 ing the bromo-amido-naphthoquinone with dilute 
 alkalis (Zinoke a. Gerlaud, B. 20, 1510). 
 
 BEOMO-o-AMISO-FHENOL 
 CeH3Br{NHJ(0H) [1:3:4]. [128°]. Formed by 
 reducing bromo-nitro-phenol with Sn and HCl 
 (P. Schiitt, J. pr. [2] 32, 61). Thin plates (from 
 CS2). Needles (from alcohol). Sol. ether, benz- 
 ene, hot water, and hot chloroform. FejCl, 
 turns the aqueous solution cherry-red. 
 
 Salts. — B'HCl". Very soluble plates.— 
 B'HBrx. CrystaUises very easily. — B'^H^SO,. 
 
 Acetyl derivative C„H3(OH)(NHAo)Br. 
 [178=]. Plates or needles (from water). 
 
 Methyl ether C„H3Br(NH2)(OMe). [98°]. 
 From the nitro- compound, Sa and HCl (Staedel, 
 A. 217, 59). Plates (from benzene). V. sol. 
 benzene, ether or hot alcohol, insol. water. 
 Salts .— B'HCl.— B'jHjSO,.— B'^H^CjO^. 
 
 Ethyl ether [57°]. Broad needles (from 
 alcohol). V. sol. benzene, alcohol or ether. 
 Salts .— B'HCl.— B'jHjSO,.— B'ACjO.. 
 
 Bronio-m-amido-phenol CjH3Br(NH2)OH 
 [a!:l:3]. Ethyl ether C5H3Br(NHJOBt. Liquid; 
 V. sol. alcohol and ether, v. si. sol. water. The 
 hydrochloride, sulphate, and oxalate crystallise 
 in white plates CsH3Br(0Et)NHj, HCl, SnOl^ 
 (Lindner, B. 18, 612). 
 
 Bromo-p-amido-pheuol 
 C3HsBr(NH2) (OH) [1:3:6]. [158°]. Prepared 
 by reducing bromo-nitro-phenol, or its benzyl 
 derivative, by Sn and HCl (0. Holz, /. pr. [2] 
 32, 65). Short needles (from dilute alcohol). 
 Sol. ether, benzene, and chloroform, si. sol. cold 
 water. 
 
 Salts. — B'HCl: silvery plates.— 
 (B',HCl)2SnCl2.— B'HBr. 
 
 Acetyl derivative CjH3(0H)(NHAc)Br. 
 [167°]. Thick needles (from hot water). Solu- 
 ble in alkalis. 
 
 Methyl ether. 
 From the nitro- compound, Sn and HCl (Staedel, 
 A. 217, 68). Oil. Insol. water, v. sol. benzene, 
 alcohol, or ether. B'HCI.— B'jHjSOj.— B'^HjOjO,. 
 
 Ethyl ether 
 From the nitro- compound, Sn and HOI. Oil. 
 B'HCl.— B'2HjSO,.—B'2HiCj04. 
 
 Si-bromo-o-amido-phenol 
 05HiBr,(NHj,)(0H) [1:3:5:6]. [92°]. Formed 
 by reducing di-bromo-o-nitrophenol (Holz, J.pr. 
 [2] 32, 69). Slender yellow needles (from dilute 
 alcohol). Sparingly soluble in water, v. sol. 
 alcohol, ether, benzene, and chloroform. 
 
 Salts. — B'HCl: plates. — (B'HC^^SnClj : 
 needles.— B'HBr : needles. 
 
 Acetyl derivative 05H2(0H)(NHAc)Br2. 
 [186°]. Yellowish needles (from hot water). 
 Sol. alkalis. 
 
 Methyl ether CsH2Br2(NHj)(OMe). From 
 the nitro- compound by Sn and HCl (Staedel, 
 A. 217, 63). Oil. Sol. alcohol, ether, or dilute 
 acids, insol. cold water, si. sol. hot water. 
 B'HCl.- B'jH^SO,. [177°].— B'jHjOjO,. 
 
 Ethyl ether C<,H2Brj(NHJ(0Et). [92°]. 
 Quadratic crystals (from alcohol). V. sol. alco- 
 hol or ether.— B'HCl.— B'2HsS04.—B'jH3CjO J. 
 
 IK-bromo-o-amido-phenoI. 
 
 Ethyl ether C,HjBrj(NHj)OEt [1:8:4:5]? 
 
 [53°]. o-Amido-phenetol,03Hi{NHi)OEt (10g.),is 
 boiled with glacial acetic acid (100 g.) andbromina 
 (11'7 g.). The product is poured into water and 
 the oil that separates is distilled with steam and 
 recrystallised from alcohol. Glittering prisms, 
 grouped in tufts. Besembles di-bromo-o-toluJ- 
 dine in being but feebly basic (Mijhlau a. Oehmi- 
 chen, J. pr. 132, 479). 
 
 Di-bromo-m-amido-phenol. 
 
 Ethyl ether G,IL,Bt2('SK;iOE1i. Prom 
 the nitro- compound. Oil. The hydrochloride, 
 sulphate, and oxalate crystallise in needles. — 
 C5HjBr2(OEt)NH2,HCl,SnCl2: glistening plates 
 (Lindner, B. 18, 613). 
 
 Bi-bromo-p-amido -phenol. 
 C,'BJBr:^{-Sn^)On [1:3:5:2]. [180°] (M. a. B.) ; 
 [190°] (L. a. G.). Formed by reducing the 
 nitro- compound (Mohlau, B. 16, 2845 ; Holz, 
 /. pr. [2] 32, 67 ; Mohlau a. Bohmer, J. pr. [2] 
 24, 470 ; Lellmann a. Grothmann, B. 17, 2731), 
 Formed also by reducing di-brominated^-diazo- 
 phenol (2. V.) with tin and HOI (Bohmer, J. pr, 
 132,469): 
 
 C,H,Br,<^ + 2H, = C,H,Br,(0H).NH2 + NH,. 
 
 Properties. — Ppd. by NaHCO, from solution 
 of its hydrochloride as microscopically small 
 needles grouped in tufts. Turns blue in air. 
 SI. sol. ether, v. sol. alcohol, m. sol. hot water. 
 
 Salts. — B'HCl : glittering plates.— 
 (B'HCljjSnClj.— B'HBr. 
 
 Beactions. — ^When NjO, is passed into an 
 alcoholic solution of its hydrochloride, yellow 
 crystals of diazo-dibromo-phenol (q. v.) are ob' 
 tained, but this body is isomeric with that by the 
 reduction of which the dibromo-amido-phenol 
 was prepared. An ' intra-molecular change ' 
 must therefore have occurred somewhere. 
 
 Acetyl derivative C3H2Brj(NHAc)(0H). 
 [174°]. Glittering plates (from dilute alcohol). 
 Methyl ether From the nitro- compound 
 [127°], Sn, and HCl. White porcelain-like mass. 
 Extremely sol. ether, benzene, or alcohol (Stae- 
 del, A. 217, 70 ; Staedel a. Damm, B. 11, 1749). 
 Salts.— B'HCl. -B'jH^SO^.-B'jHjC^O, [195°]. 
 
 Ethyl ether [67°]. Needles (from alco- 
 hol). V. sol. alcohol, ether, or benzene. Salts. — 
 B'HCl.— B'^H^SO^.—B'^HjOjO,. 
 
 Iri-bromo-o-amido-phenol. 
 
 Ethyl ether CeHBr3(NHj)0Et [1:3:4:5:6]? 
 [77°]. From amido-phenetol (5 g.), glacial acetic 
 acid (50 g.) and bromine (17'5 g.). The product 
 is poured into water, and the pp. crystallised 
 from alcohol. Long silky needles. Nearly 
 insol. boiling cono. HCl. It is totally decom- 
 posed when heated to a temperature a little 
 above its melting-point. 
 
 Tri-bromo-m-amido-phenol 
 C,HBr3(NH3).OH [1:3:5:2:6]. [115°]. Formed 
 by reduction of tri-bromo-m-nitro-phenol (Dac- 
 eomo, B. 18, 1168). Colourless silky needles. 
 Sol. alcohol, ether, benzene, and hot, si. sol. 
 cold, water. FcjCl, gives a green colouration. 
 
 Ethyl ether CBHBra(NHj)OEt. Solid, v. 
 sol. alcohol and ether, si. sol. water.— B'HCl : 
 
 white needles, sol. alcohol B'^H^SO^ : white 
 
 needles, sol. alcohol. — B'HOlSnCL : white 
 needles (Lindner, B. 18, 614). 
 BKOMO-AMIDO-DIPHEWYL. 
 Acetyl derivative CuHgBrNHAc. [247^. 
 From Br and ;j-amido-diphenyl in glacial 
 
BEOMO-AMIDO-THYMOL. 
 
 649 
 
 HOAo (HtLbner, A. 309, 846). Needles (from 
 Rlcohol), 
 
 Di-bromo-di-amido-diplienyl 0,jH:8Brj(NHj)j. 
 [89°]. Prom di-bromo-di-nitro-diphenyl by Sn 
 and HCl (Fittig, A. 132, 207). Inaol. water.— 
 B"2HC1. 
 
 Di-bromo-di-amido-diphenyl 
 [2:4:1] CeH^r{NHJ.C„HjBr(NH2) [1:2:4]. Di- 
 broino-bemidine. [152°]. Obtained from [3:1] 
 C.H<Br.NH.NH.08H^Br [1:3] and HCl (Gabriel, 
 B. 9, 1407). Trimetrio crystals, m. sol. cold 
 alcohol.— B" 2HC1.— B"BLjPtCl8. 
 
 Di-bromo-di-amido-diphenyl 0,jH5Br2(NH2)j 
 [1:5:2].,. [108°corr.]. SmaU plates. Formedbythe 
 action of an alcoholic solution of SnCl^ and 
 H2SO4 on jj-bromo-benzene-^-azo-bromo-benz- 
 ene. Treated with nitrous acid in alcoholic 
 solution it gives an azimido- body OuHjNjBrj 
 which forms glistening violet needles, [206°], 
 si. sol. alcohol (Sohultz, B. 17, 465). 
 
 Tetra-bromo-di-amldo-dlplieuyl CijEgBr^Nj. 
 Tetra-bromo-betizidine. [286°]. Prepared by 
 bromination of benzidine (Claus a. Bisler, B. 
 14, 86). Slender colourless needles. Sol. alco- 
 hol, ether, CS^, C^He; insol. water and acids. 
 
 BBOUO-AUIDO-PHENYL-ACETIC ACID 
 C6H3(Br)(NIL,)(CHj.COjH)[l:2:5].[136°].Formed 
 by saponification of the acetyl derivative of its 
 nitrile, or by bromination and saponification of 
 the acetyl derivative of p-amido-phenyl-acetic 
 acid (Gabriel, B. 15, 840). Colourless plates. 
 Sol. alcohol and ether, insol. CSj. 
 
 Acetyl derivative [165°]. 
 
 Nitrile C,H3(Br)(NH,)(CH20N). Acetyl de- 
 rivative C5H3Br(NHAo)(OH2CN) [129°]. Long 
 colourless needles. Sol. alcohol, si. sol. cold 
 water. Formed by bromination of the acetyl 
 derivative of jp-amido-phenyl-acetonitrile (Ga- 
 briel, B. 15, 840). 
 
 Bromo-amido-phenyl-acetio acid 
 C,H3Br(NH2)CHj.C02H [l:2or6:4]. [134°]. 
 From the nitro- compound [114°] by Sn and 
 HCl (P.P. Bedson, 0. J. 37, 98). Silky needles 
 (from water). Sol. alcohol and CHCI3. SI. sol. 
 ether. — ^B'HCl aq : turns red in air. 
 
 (a)-Bromo-amido-p]ienyl-acetic acid 
 C,H3Br(NH2)CHj.C02H. [167°]. From the 
 nitro- acid [169°] by Sn and HOI (Bedson). 
 White needles (from water), reddens in air. 
 Sol. alcohol and chloroform, si. sol. ether. 
 
 Salt . — ^B'HClaq : white needles (from water). 
 
 (;3) -Bromo-amido-phenyl-acetic acid 
 C3H3Br(NH3)CHj.C02H. [186°]. From the nitro- 
 aoid [162°] by Sn and HCl (Bedson). The hydro- 
 chloride is less soluble in water than those of 
 the two preceding bodies. 
 
 (1, 3, 2, 5)-Bromo-di-amido-plienyI-acetic acid 
 03H2(Br)(NHj),.CH2.C02H [1:3:2:5]. [0. 200°]. 
 Long colourless needles. Formed by reduction 
 of (1, 3, 2, 5)-bromo-nitio-amido-phenyl-acetic 
 acid (Gabriel, B. 15, 1995). 
 
 BROMO-AMIDO-PHENYI-ETHANE 
 C,H,„ErN i.e. 03H,Br.CHj.CH2.NH2. Bromo- 
 phenyl-ethyl-amine (253°). From phenyl-pro- 
 pionamide, KOHAq, and bromine (Hofmann, B. 
 18, 2740). Pearly plates (from water).— B'HCl. 
 
 (1,2,5) BEOMO .AMID0-;8 - PHENYL - PEG - 
 PIONIO ACID GjH3(Br)(NH2).CjH,.C02H [1:2:5]. 
 Brono -amido-hydrodnnamic acid TlO_5°]. 
 Formed by bromination of the acetyl deriva- 
 tive of j7-amido-phenyl- propionic acid, and 
 
 saponification of the product (Gabriel, B. 15, 
 2292). Long glistening crystals. Sol. most 
 ordinary solvents and in acids and alkalis. 
 
 Acetyl derivative: [160°]. Longoolour- 
 less needles, soluble in alcohol, ether, and 
 benzene. 
 
 Bromo-m-amido-plieiiyl-propionio acid 
 C.H3(Br)(NHJ.C2H,.CO,H [2:1:5]. [117°-H9°]. 
 Long prisms. Sol. water, alcohol, ether, and 
 CsHj. Prepared by reduction of p-bromo-m- 
 nitro-hydrocinnamic acid with tin and HCl. — 
 A'HCl : glistening soluble needles (Gabriel a. 
 Zimmermann, B. 13, 1684). 
 
 (eso) -DI-BKOMO-o-AMIDO - PHENYI-VALE- 
 EIC ACID 
 
 C,H2Brj(NH2).CHj.CH2.0H,.CHj.C02H. [96°, 
 with aq]. Long colourless needles (containing 
 aq). Formed by reduction of an alcoholic solu- 
 tion of di-bromo-amido-pheuyl-di-bromo-valerio 
 acid C5HjBr2(NH2).CHBr.CHBr.CHj.CH2.C02H 
 with zinc and HCl. V. sol. ordinary solvents, 
 insol. cold water. It could not be converted into 
 an inner anhydride, even by dehydrating agents. 
 
 Ethyl ether G,.H,„Br.,(NH2)C0^t; thick 
 oil; its hydrochloride forms whiteneedles [136°]. 
 
 Acetyl derivative 0,i,H,„Br2(NHAc)C02H 
 [206°] ; aggregates of thin white needles ; v. sol. 
 alcohol, ether, &a. 
 
 Acetyl- ethyl-ether 
 C„Hi„Brj,(NHAc)C02Et [139°]; colourless crys- 
 tals ; V. sol. alcohol, ether, and acetic acid, more 
 sparingly in benzene, insol. water and ligroiin ; 
 in small quantities it can be distilled undecom- 
 posed (Diebl a. Einhorn, B. 20, 380). 
 
 S^-eso-Tetra-bromo-o-amido-phenyl -valeric 
 acid, C,H,Br„(NH2) .CHBr.CHBr.CHj.CH3.CO3H. 
 [167°]. Formed by bromination of o-amido- 
 styryl-propionio acid dissolved in chloroform. 
 Small microscopic needles. V. sol. alcohol, 
 ether, and acetic acid, insol. water and CSj 
 (Diehl a. Einhorn, B. 20, 379). 
 
 BEOMO-AMIDO-QriNOLINE 
 C,H5N(Br)(NH3). [164°]. Large monoolinic 
 prisms, or long colourless needles (containing 
 aq). Sol. alcohol and ether. 
 
 Salts . — B'HNOg : glistening yellow needles. 
 —B'HCl: soluble red prisms. -B'^H^ClaPtCl,: 
 microscopic orange needles. 
 
 Acetyl derivative C3H5N(Br)(NHAo). 
 [105°]. Thin colourless plates (La Coste, B. 15, 
 1920). 
 
 DI-BEOMO-AMIDO-RESOECIN 
 CBHBr2(NHJ(0H)j [1:2:4]. Di-ethyl ether 
 0sHBr2(NHJ(0Et)j [112°]; glistening needles 
 or plates (Will a. Pukall, B. 20, 1126). 
 
 BROUO-AMIDO-STYEENE 
 CeH3Br(NH2).C,H3. 
 
 Acetyl derivative [183°]; felted needles, 
 sol. alcohol, ether, and acetic acid ; formed by 
 bromination of ^-amido-cinnamio acid dis- 
 solved in AoOH (Gabriel a. Herzberg, B. 16, 2043). 
 
 BEOMO-AMIDO-SUCCINIC ACID 
 C3H2Br(NH2)(C03H)j. [140°]. From di-brcmo- 
 succinio acid and alcoholic NH3 (Claus, B. 15, 
 1850). Eadiating needles ; v. sol. water and 
 alcohol. — AgA'. 
 
 BEDMO-AMIDO-THYHOL 
 CeHBr.MePr(NH2)(0H). Prepared by adding 
 Na^CO, to dilute solution of its hydrobromide {v. 
 infra). Long colourless prisms, rapidly turning 
 deep violet. 
 
660 
 
 BROMO-AMIDO-THYMOL. 
 
 Eydrobromide. — B'HBr. By adding 
 moderately strong HBr to thymoquinone-ohloro- 
 imide (j. v.) a, yellow floooulent pp. is formed. 
 Ether extracts bromo-thymoquinones from this, 
 leaving the above salt, which is soluble in water 
 and alcohol, but is thrown down as needles when 
 HBr is added to its concentrated aqueous solu- 
 tion (Andresen, J. pr. 131, 182). 
 
 Bromo-amido-tliymol [c. 90°]. Prom bromo- 
 nitro-thymol, zinc-dust, and HCl (Mazzara a. 
 Disoalzo, G. 16, 196). Scales. Converted by 
 nitrous acid gas into bromo-tbymoquinone [48°]. 
 
 BROMO-AMIDO-TOLUENE v. Bkomo-iolu- 
 iniNE. 
 
 Bromo-di 'amido-tolueue v. BBOMo-ToiiTLENH 
 
 CUMIiqE. 
 
 BROMO - AMIDO - TOITJENE STJLPHONIC 
 ACID CjH2(CH3)(NHj)BrSO,,H [1:2:3:5]. Bromo- 
 toluidine sulphcmic acid. From o-toluidine sul- 
 phonio acid and bromine-water (Nevile a. 
 Winther, G. J. 37, 627). Prisms. 
 
 Reactions. — 1. Converted by diazo- reaction 
 into a bromo-toluene sulphouio acid whose sul- 
 phochloride melts at [56°] and whose amide at 
 ¥147°].— 2. Heated with HClatl60°it gives dibro- 
 po-o-toluidine [44°] and two mono-bromo-tolu- 
 fdines, an oil and a crystalline body, [54°-57°]. 
 One of these bromo-toluidines must be ob- 
 tained from the acid by displacement of SOjH 
 by H, and must subsequently give rise to the other 
 mono- and the di-bromo toluidine. Inasmuch 
 as oilybromo-toluidine, C6H3Me(NH2)Br [1:2:3], 
 heated with HCl at 160° gives a substance 
 [40°-47°] and crystals [53°-55°], while the crys- 
 talline bromo-toluidine [54°-57°] is not affected 
 by this treatment,, we must suppose the snlphonio 
 acid to be CjH,(CH3)(NH2)BrS03H [1:2:3:5] 
 rather than [1:2:5:8]. When it is heated with 
 HCl the oily bromo-toluidine is first formed, but 
 this being unstable changes into its crystalline 
 isomeride and the crystalline dibromo-toluidine. 
 
 Bromo-amido toluene sulphonic acid 
 C,HjMe(NH2)Br(S03H) [1:4:2:3 or 5]. S. -532 at 
 21°. From o-bromo-toluene by sulphonation, 
 nitration, and reduction (Schafer, A. 174, 360). 
 Trimetric laminsB (from hot water) or nodules 
 (from alcohol). Converted by bromine- water into 
 tri-bromo-toluidine [82°]. 
 
 Salt s.— BaA'j aq. — PbA'^ aq. 
 
 Bromo-amido-tolnene sulphonic acid 
 C,HjMe(NH2)Br(S03H). [1:5?:4:3]. From (1,4,2)- 
 bromo-toluene sulphonic acid by nitration, and 
 reduction (S.). Needles (from water). V. si. 
 sol. water. — BaA'2 4aq. 
 
 Bromo-amido-toluene sulphonic acid 
 C„H2Me(NH2)Br(S03H) [1:2?:4:6]. _ S. 3-2. From 
 (l,4,3)-bromo-toluene sulphonic acid by nitration 
 and reduction (Schafer, A. 174, 360). Prisms 
 (from water). Bromine-water gives tri-bromo- 
 toluidine [72=].— BaA'2 2aq.— NaA'2 2aq. 
 
 Bromo-amido-toluene sulphonic acid 
 C,HjMe(NH2)Br(S03H) [l:4:a;:2]. S. -23 at 20'. 
 From boiling aqueous ^-toluidine o-sulphonic 
 acid and bromine (Jenssen, A. 172, 230; B. 
 7,55). Needles (from water). V. si. sol. boiling 
 water.— KA' aq. — BaA'j 7aq. 
 
 Bromo-amido-toluene sulphonic acid 
 C,H2Me(NH3)Br(S03H). S. -19 at 20°. From 
 o-toluidine sulphonic acid by conversion into 0- 
 bromo toluene sulphonic acid, nitration, and re- 
 
 duction (Pagel, A. 176, 800). MInuts thin 
 prisma. —BaA'j aq. 
 
 Bromo-amido-toluene sulphonic acid 
 C«H2Me(NH2)Br(S03H) [1:4:5? :3]. Formed, to- 
 gether with di-bromotoluidine, by passmg bro- 
 mine-vapour into cold aqueous jp-toluidine ra- 
 sulphonio acid (v.Pechmann, A. 173, 210; Lim- 
 prioht, B. 7, 452). Clumps of needles. V. e. sol. 
 water. Converted by diazo- reaction into (3 or 
 5, 1, 2) bromo-toluene sulphonic acid. — KA'. — 
 BaA'2 2aq.— PbA'j.— AgA'. 
 
 Di-bromo-o-amido-toluene sulphonic acid 
 C„HMe(NH2)Br2S0sH [1:2:?:?:4]. S. -64 at 
 13'5°. From o-toluidine jj-sulphonio acid 
 C„H3Me(NH2)(SOsH) [1:2:4] and bromine (Hay- 
 duct, B. 7, 1358; A. 172, 211). Capillary 
 needles containing aq (from water).— BaA'^ 9aq. 
 
 Bi-bromo-amido-toluene sulphonic acid 
 C,HMe(NH2)Br2(S03H) [1:2:3?:?:5?]. From 0- 
 toluidine by sulphonation and bromination. 
 Needles (containing aq). V. sol. hot water and 
 hot alcohol. Gives tri-bromo-toluidine [112°] 
 when distilled with KOH.— BaA'j 4aq.— 
 PbA'j 3aq (Gerver, A. 169, 880). 
 
 Bromo-dl-amido-toluene sulphonic acid 
 C„HMe(NH2)2BrS03H [1:2?:6?:3?:4]. From 
 toluene ^-sulphonic acid by nitration and re- 
 duction (Sohwanert, A. 186, 360). Tables ; si. 
 sol. water. — KA'2iaq. 
 
 DI-BEOMO-AMYL ALCOHOL CjHioBr^O i.e. 
 CH2Br.CHBr.CHEt.OH. Di-hromo-di-ethyl-car- 
 hinol. From vinyl-di-ethyl-carbinol and bromine 
 (Wagner, J. B. 16, 320). Non-volatile liquid. 
 
 BBOMO-o-AMYL-ANTHBAOENE 
 >C(C3Hj|)v 
 C„H,„Br ie. C,H ,< | >C,H,. [76°]. Yel- 
 
 ^CBr ^ 
 low needles. Fluorescent. Prepared by bromi- 
 nation of amyl-anthracene in CSj. 
 
 Picric acid compound. [110°]. Orange- 
 yellow needles (Liebermann a. Tobias, B. 14, 797). 
 
 BROMO-sec-AMYL-BENZENE C^H.^Br i.e. 
 C,H5.CHEt.CHBr.CH3(?). (0. 79°) at 40 mm. 
 S.G. ^ 1-28. Oil. Obtained by brominating 
 seo-amyl-benzene (Dafert, M. 4, 620). Decom- 
 posed slowly by boiling water into HBr and 
 pentenyl-benzene. 
 
 7-5-di-bromo-amyl-benzene [53°-54°] 
 Ph.CHBr.CHBr.CH2.CH2.CH3. From phenyl- 
 amylene {q. v.) and bromine. Needles or plates. 
 
 V-S-di-bromo-isoamyl-benzene 
 Ph.CHBr.CHBr.CH(CH3)2. [128°-129°]. From 
 phenyl-iso-amylene and Br (Schramm, A. 218, 
 394). Needles (from alcohol). 
 
 Tri-bromo-isoamyl-benzene C„H,sBra. [140°]. 
 Obtained by brominating iso-amyl-benzene at 
 100' Bigot a. Fittig, A. 141, 161). Needles. 
 
 BEOMO-ISOAMYLENE CjHjBr. Fmtewyl- 
 bromide. (100°-110°). From ' isoamylene ' by 
 successive treatment with bromine and alcoholic 
 KOH (Bauer, A. 120, 167). Successive treat- 
 ment with conc.HjSOj and water forms amylene 
 dibromide and a ketone CjHuO (Bouchardat, 
 C. B. 93, 316). 
 
 m-Bromo-iso-amylene (111°) Pr.CH:CHBr. 
 From isovaleric aldehyde by successive treat- 
 ment withPCljBrj and alcohoUo KOH (Bruylants, 
 S. 8, 406). 
 
 T-Bromo-w-amylene CH;,:CBr.CHj.CH2.CH,. 
 (123°). S.Q.£1-10. From methyl propyl ketone 
 
BUOMO-ANILINE. 
 
 661 
 
 by suooessive treatment with PClaBrj and alco- 
 holic EOH (B.). 
 
 Bromo-amylene OjHjBr. (111°). From di- 
 bromo-hexoio acid CH3.CHBr.CBrBt.COjH and 
 cold aqueous Na^COj (Fittig, A. 200, 36). 
 
 Bromo-amylene CjHjBr. (115°). From iso- 
 valerylene and HBr (Beboul, Z. 1867, 173). 
 
 Bromo-amylene OjHgBr. (0. 106°). S.G. is 
 1*173. From isoprene OjHg and HBr (Bouohar- 
 dat, J. 1879, 577). 
 
 Di-bromo-amylene OjHjBrj. (0. 170°). From 
 isovalerylene and bromine (Beboul, A. 135, 372). 
 
 Di-bromo-amylene C^HaBrj i.e. &.CBr:CHBr. 
 (175°). From isopropyl-acetylene and Br (Bruy- 
 lanta, B. 8, 407). 
 
 Di-bromo-amylene OsHgBrj i.e. Pr.CBr:CHBr. 
 (190°). From ra-propyl-acetylene and Br (B.). 
 
 BROMO-AMYLENE GLYCOL 05H„Br(0H)j. 
 From amylene dibromide by successive treatment 
 with AgOAc and solid KOH (Bauer, J. 1861, 664). 
 
 TEI-BROMO.j)-ISOAMYL-TOLTJENE 
 CijHijBrj i.e. OuHMeBrj-CsH,,. From ^-isoamyl- 
 toluene and bromine at 100°. Sticky Uquid 
 (Bigot a. Fittig, A. 141, 165). 
 
 TEI-BROMO-ANETHOL C,„HjBr30. From 
 anethol and Br. Crystals (Cahours, A. 41, 60). 
 
 BBOMO-ANUIC ACID v. Di-BBOuto-ni-oxT- 
 
 QUINONE. 
 
 0-BEOMO-ANILINE CsH^BrN i.e. 
 CjH,Br(NH2) [1:2]. Mol. w. 172. [81°]. (229° 
 i. v.). From o-bromo-nitro-benzene by reduc- 
 tion with tin and HCl (Fittig a. Mager, B. 7, 
 1175). 
 
 Acetyl derivative C^H^BrNHAo. o-Bro- 
 mo-acetaniUde. [99°]. Long needles (Korner, 
 a. 4, 330). 
 
 m-Bromo-aniline CsH<Br(NH2) [1:3]. [18°], 
 (251°). Formation. — 1. From m-bromo-nitro- 
 zene (Fittig a. Mager, B. 8, 364). — 2. m-nitro- 
 diazo-benzeue sulphate (from TO-nitraniline) is 
 treated with a hot solution of cuprous bromide 
 and the crude »»-bromo-nitro-benzene reduced 
 with tin and HCl (Sandmeyer, B. 18, 1495). 
 
 Acetyl derivative CsH^BrNHAc. [88°]. 
 Needles (from dilute alcohol) (Soheufelen, A. 
 231, 175). 
 
 j).Bromo-aniline C8H,Br(NHj) [1:4]. [62°]. 
 (MUls, P. M. [5] 14, 27). [66°] (Korner, J. 1875, 
 342). 
 
 Formation. — 1. By reducing jp-bromo-nitro- 
 benzene with tin and HCl (Eiche a. B^rard, A. 
 133, 52; Fittig a. Mager, JB. 7, 1175; 8, 364).— 
 2. By bromination of acetanUide and distilla- 
 tion of the product with KOH (Mills, P. .\f. [4] 
 49, 21 ; Pr. 10, 689).— 3. By distilling bromo- 
 isatin with KOH (Hofmann, A. 53, 42).— 4. In 
 small quantity by brominating aniline with Br 
 vapour or in benzene solution (KekuM, Z. 1866, 
 687). , , 
 
 Properties. — Trimetric crystals; insol. cold 
 water, v. sol. alcohol and ether. Decomposed 
 on boiling, giving aniline, and di- and tri-bromo- 
 aniline. 
 
 Reactions.— I. HCl at 160° gives aniline and 
 di-bromo-aniline (Fittig a. Buohner, .4. 188, 23). 
 2. Sodium acts on it in ethereal solution form- 
 ing benzene-azo-benzene, aniline, and NaBr 
 (Anschiitz a. Schultz, B. 9, 1398; Claus a. 
 Boques, B. 16, 909).— 3. By dissolving in cooled 
 fuming HNO3 it is converted into tri-nitro-anilin» 
 (picramide) (Hager, B. 18, 2578).— 4. By nitra- 
 
 tion of p-faromaniline dissolved In 10 pts. of 
 H^SO, bromo-nitro-aniline CaH3Br(N0j)(NHj) 
 [4:3:1] is produced (Nolting a. GoUin, B. 
 17, 266). — 5. Cyanogen forms a compound 
 C,H,Br.NH.C(^NH).C(NH).NHC„H4Br [245°] ; 
 white plates (from alcohol) (Senf, J. pr. [2] 35, 
 530). 
 
 S alt s.— B'HCl : monoclinic— B'jHjPtCl,.— 
 B'HBr Jaq : monoolinic prisms (Staedel, B. 16, 
 28).— B'jHjSOi : lamina.— B'^HjOjOi. 
 
 Formyl derivative CsH,Br.NH(CO.H). 
 [119°]. Long white needles. Insol. cold water, 
 si. sol. hot water, v. sol. alcohol and ether. 
 Prepared by heating ^i-bromaniline with formic 
 ether, or by brominating f ormanilide (Dennstedt, 
 B. 13, 234). 
 
 Thioformyl derivative 
 0„H,Br.NH(CS.H) [190°]. Needles. V. sol. 
 hot ether and alcohol. Prepared by the action 
 of P2S5 on the preceding body (Dennstedt, B. 13, 
 236). 
 
 Acetyl derivative [166°]. From acetanilide 
 in glacial HOAo and Br (Eemmers, B. 7, 346 ; 
 Gurke, B. 8, 1114). Also from p-bromo-aniline 
 and AoCl (Korner, (?. 4, 329), or aeetamide 
 (Kelbe, B. 16, 1200). Monoclinic prisms : a:b:c = 
 l-538:l:l-435 (Panebianoo, Q. 9, 357). M. sol. 
 alcohol, V. si. sol. water. 
 
 Isobutyryl derivative 
 CeHjBr.NH.C,H,0. [128°]. From isobutyryl- 
 aniline and Br vapour (Norton, Am. 7, 117). 
 Needles (from alcohol). 
 
 Benzoyl derivative 0|jH4Br(NHBz). 
 [202°]. From benzanihde and Br (Meineoke, B. 
 8, 564). 
 
 Oxalyl derivative 020j(NH.C5H4Br)2. 
 [above 200°]. From Br and oxanihde in HOi" 
 (Dyer a. Mixter, Am. 8, 351). 
 
 Di-bromo-aniline CsH3Br2(NH2) [1:3:4]. [79°]. 
 
 F(yrmation.—l. By saponifying dibrominated 
 acetanUide (Griess, A. 121, 266), or brominated 
 0- or p-bromo-aoetanilide (Korner, O. 4, 329). — 
 2. Together with mono- andtri-bromo-aniline by 
 brominating aniline (KekulS, K. 2, 635). — 3. By 
 distilling di-bromo-isatin with KOH (Hofmann, 
 A. 53, 47). — 4. Together with mono- and tri- 
 bromo-aniline by heating nitrobenzene with 
 cone. HBrAq at 190° (Baumhauer, B. 2, 122 ; 
 Z. [2] 5, 198).— 5. By reducing di-bromo-nitro- 
 benzene (Wurster, B. 6, 1491). 
 
 Properties. — Needles or long plates. 
 
 Salt s.— B'HCl.— B'jH3PtCls.—B'jH2S04. 
 
 Acetyl derivative CsHaBrjNHAc. [146°]. 
 
 Benzoyl derivative CjHjBrjNBz^ [1:3:4]? 
 [134°]. From benzaniUde and Br (Hubner, B. 
 10, 1710). 
 
 s-di-bromo- aniline C3H3Brj(NH2) [1:3:6]. 
 [67°]. From ^-nitro-acetanilide, by suocessiva 
 conversion into nitro-aniline, di-bromo-nitro- 
 aniline, and di-bromo-nitro-beuzene, and reduc- 
 tion of the product (Korner, O. 4, 368 ; Langer, 
 A. 215, 116). Needles. 
 
 Di-bromo-aniline C^H3Br2(NH„) [1:2:4]. 
 [80°]. From the corresponding di-bromo-nitro- 
 benzene [58°] (Korner, G. 4, 370). 
 
 Di-bromo-aniline CeH3Brj(NHj) [1:4:3]. 
 [52°]. From the corresponding nitro- compound 
 [85°] (Eiche a. Berard, 0. B. 69, 141 ; Meyer a. 
 Stuber, A. 165, 180). 
 
 Iri-bromo-anilin* OJS^tt^^'B^ [l:3;e:6]. 
 [119°]. (300°). 
 
663 
 
 BROMO- ANILINE. 
 
 Formation, — 1. By the action of bromine on 
 aniline or on an aqueous solution of a salt of 
 aniline (Fritzsohe, A. 44, 291 ; J. pr. 28, 204 ; 
 Hofmann, A. 63, 60). — 2. By the action of Br 
 on 0- or p-bromo-aniline (Korner, O. 4, 305). — 
 
 3. By reduction of tri-bromo-nitro-benzene (K.). 
 
 4. Together with aniline and di-bromo-aniline 
 by the dry distillation of ^J-bromo-aniline or by 
 heating it with HClAq at 160° (Buohner, B. 8, 
 361). 
 
 Preparation. — Bromine (500 g.) is gradually 
 added to aniline (100 g.) ; as soon as a solid mass 
 is formed glacial acetic acid is added and the 
 addition of bromine continued until the mass 
 has a red colour. The product is washed 
 with dilute alcohol and water and crystallised 
 from alcohol (H. Silberstein, J.pr. [2] 27, 101). 
 Yield 80 per cent. 
 
 Properties. — Long colourless needles. 
 
 Reactions. — 1. N^Oj passed into tri-bromo- 
 aniline half dissolved, half suspended in alcohol, 
 gives a yellow pp. of tribromo-diazo-benzene 
 nitrate. — 2. Converted by diazo- reactions into 
 s-tri-bromo-benzene and into M-tetrabromo-ben- 
 zene. — 3. Cone. HNO3 gives di-bromo-di-nitro- 
 methane, tetra-bromo-quinone, M-tetra-bromo- 
 benzene, picric acid, and oxalic acid (Losanitsch, 
 B. 16, 472). 
 
 Salts. — The salts are very unstable, and 
 cannot be formed in aqueous solution. B'HBr : 
 small white needles [190°J, insol. ether and 
 benzene ; decomposed by water.— B'HCl : small 
 white needles (Gattermann, B. 16, 635). 
 
 Acetyl derivative OsHjBrjNHAo. [2B2°] 
 (Eemmers,B. 7, 349). 
 
 DiacetylderivativeC^SJ&v^ko^.[i23:°'\. 
 
 Tri-bromo- aniline CsH^BralNHj) [1:2:8:5]. 
 [above 130°]. From tri-bromo-nitro-benzene 
 [112°] (KSrner, G. 4, 328). Its salts are not 
 decomposed by water. 
 
 Xetra-bromo-aniline CsHBrj(NH2) [1:2:3:5:6]. 
 [115°]. Formed by brominating m-bromo- 
 aniline, or (1, 4, 3)-di-bromo-aniline (Korner, O. 
 4, 328; Wurster a. Nolting, B. 7, 1564). Is a 
 by-product in the action of bromine on nitro- 
 benzene in presence of Fe^Brj (Scheufelen, A. 
 281, 161). Needles. Converted by the diazo- 
 reaotion into M-tetra-bromo-benzene. 
 
 Penta-bromo-aniline CjBrjNH^. [222°]. Ob- 
 tained by brominating (1, 3, 5)-di-bromo-aniline 
 (Korner, O. 4, 368). Large needles (from 
 alcohol mixed with toluene). 
 
 BBOMO-ANILIXi: SULFHONIC ACID v. 
 Bromo-amido-benzenb sulphonio acid. 
 
 BROMO-ANISIC ACID v. Methyl derivative 
 of Bbomo-oxt-eenzoio aoid. 
 
 BKOMO-ANISIDIHE v. Methyl-Bsom- 
 
 AMIDO-PHENOL. 
 
 BBOMO-ANTHKACENE C.iHaBr. [100°]. 
 Obtained by warming anthracene dibromide. 
 Needles. Forms a red picric acid compound. 
 
 {A. l,2)-Di-bromo-anthra!!ene CjiHsBr,. [221°]. 
 From Br and anthracene in OS2 (Graebe a. Lie- 
 bermann, A. Suppl. 7, 275). From triphenyl- 
 methane in CSj and bromine in sunlight (tri- 
 phenyl-methyl bromide being also formed) (Allen 
 a. KoUiker, A. Tin, 109; 228, 254). Golden 
 needles (from toluene) ; may be sublimed. V. si. 
 sol. alcohol and ether. Alcoholic KOH at 100° 
 forms anthracene. Dilute HNO, gives anthra- 
 
 quinone. The compound with picric acil is ted. 
 Combines with Br forming C.^HsBr, [170°- 180°], 
 decomposed at 180^ into tri-bromo-anthracene, 
 HBr, and Br. 
 
 Di-bromo-anthraoene C,4HaBrj[B. 1:2]? [192°]. 
 From di-bromo-anthraquinone, HI, and P at 
 150° (MiUer, A. 182, 367). Golden tables (from 
 alcohol). Oxidises to di-bromo-anthraquinone. 
 
 Iri-bromo-anthracene CijHjBr,. (A. 1, 2. B.) 
 [169°]. Formed by heating {A. 1, 2)-di-bromo- 
 anthracene tetrabromide (G. a. L.). Yellow 
 needles (from benzene). Oxidised by HNO, to 
 bromo-anthraquinone (Claus a. Hertel, B. 14, 
 979).— Bromide: OnH,Br,. 
 
 Tetra-bromo-anthracene 
 CnHjBr, (A. 1, 2, B. 1,2)? [264°]. Fromdi-bromo- 
 anthracene tetrabromide and alcoholic KOH 
 fAnderson, A. 122, 304 ; G. a. L.). Yellow needles 
 (from xylene). Gives di-bromo-anthraquinone 
 on oxidation. — Bromide: CuEgBr, [212°] 
 (Hammersohlag, B. 10, 1212). 
 
 Penta-bromo-anthracene CiiH^Brj. [212°], 
 Formed by heating tetra-bromo-anthracene 
 tetrabromide at 230° (H.). Yellow powder. 
 Oxidises to tetra-bromo-anthraquinone. 
 
 Hexa-bromo-anthracene CuHjBrj. [310°- 
 320°]. Prepared by the action of Br in presence 
 of I on di-bromo-anthracene (Diehl, B. 11, 178). 
 Oxidised by KjCrjO, and H;,S04 to tetra-bromo- 
 anthraquinone [0. 300°]. 
 
 Hexa-bromo-anthracene CijHjBrg. [above 
 370°]. From C^H^Brs and alcoholic NaOH (H.). 
 Silky yellow needles (from kerosene). Oxidation 
 gives tetra-bromo-anthraquinone [above 370°]. 
 
 Hepta-bromo-anthracene C^HjBr,. [above 
 850°]. Prepared by the prolonged action of Br 
 at 200° in presence of I on di-bromo-anthraoene 
 (D.). Yellow needles. Insol. alcohol and ether. 
 
 Octo-bromo-anthracene CuH^Brj. Formed by 
 very prolonged action of iodine bromide at 360° 
 onhepta-bromo-anthlacene(D.). Needles. Insol. 
 most ordinary solvents, si. sol. nitro-benzene 
 and aniline. 
 
 {A. 1) - BROMO - ANTHRACENE-(^. 2)-CAR. 
 
 BOXYLIC ACID 0,H4<;^(^°|^)>CjH4. [266°]. 
 
 Formed by the action of bromine upon anthra- 
 cene-(4.)-carboxylic acid in acetic acid. Long 
 glistening yellow needles. Sublimable. SoL 
 alcohol, ether, and acetic aoid, v. si. sol. benzene 
 and water. Its solutions have a blue fluor- 
 escence. Evolves CO2 at its melting - point 
 leaving bromo-anthracene. 
 
 Salts. — ^AgA': yellow microscopic prisms. 
 — KA': long very slender yellow needles. — 
 BaA'j: yellowish needles (Behla, B. 20, 704). 
 
 DI-BROMO-ANTHRACENE DISVLPHONIO 
 ACID C„H|iBr2(S0sH)j. From di-bromo-anthra- 
 cene and fuming HjSO, (Perkin, C. 3. 24, 19). 
 Oxidises to anthraquinone disulphonic acid. 
 
 Salts .— Na^A".— BaA". 
 
 BROMO-ANTHRANOL C,,H,OBr i.e. 
 
 OA 
 
 /C(OH). po ^ 
 
 ■j\ I 
 \CBr 
 
 [148°-151°]. Formed by the action of (1 mol. of) 
 bromine upon anthranol (1 mol.) dissolved in CSj. 
 Yellowish crystals. Insol. boiling aqueous, but 
 converted by cold alcoholic KOH iuto an wang« 
 K salt (Goldmann, B. 20, 2437). 
 
BROMO-BARBITURIC ACID. 
 
 65S 
 
 W-bromo-aathrftnol 0„H,OBrj i.e. 
 
 C„H4<^Qgj. ^OjHj. Anthr-ac^uinone - bromide. 
 
 [157°]. Formed by the action of (rather more than 
 2 mol. of) bromine upon anthranol (1 mol.) dis- 
 solved in OS,. Large rhombic crystals. Insol. 
 aqueous alkalis. By boiling with acetic acid it is 
 readily converted into anthraquinone. 
 
 (B. l)-BSOMO-ANTHfiA.auINON£ 
 C„H^rO,. [188°]. Yellow needles. Sub- 
 limable. Prepared by heating o-bromo-benzoyl- 
 benzoic acid CBHjBr.CO.CsHj.COjH with H^SO, 
 to 180°. On fusion with KOH it gives erythro- 
 oxy-anthraqoinoue (Fechmann, B. 12, 2127). 
 
 (B. 2) - Bromo - anthraquinone CuHiBrOj. 
 [187°]. Formed by oxidation of tri-bromo- 
 anthracene with CrO, and HOAc (Graebe a. 
 Liebermann, A. Suppl. 7, 290). Yellow needles; 
 iuay be sublimed ; si. sol. alcohol, m. sol. hot 
 benzene. Converted by potash-fusion into ali- 
 zarin. 
 
 Di-bromo-anthraquinone C^^fli^^i- [265°]. 
 
 Formation. — 1. By brominating anthra- 
 quinone (Graebe a. Liebermann, A. Suppl. 7, 
 289 ; Diehl, JB. 11, 181).— 2. By oxidation of 
 tetra-bromo-anthracene or di-chloro-di-bromo- 
 anthracene with CrOj (G. a. L. j Hammersohlag, 
 B. 19, 1107). 
 
 Properties. — ^Boils with slight decomposition, 
 b1. sol. boiling alcohol, m. sol. glacial HOAc. 
 Potash-fusion at 250° gives alizarin. Accord- 
 ing to Perkin (0. J. 37, 554; priv. com.) the 
 di-bromo-anthraquinone formed by the first 
 method melts at 245° (or 250° cor.) and differs 
 from that formed by the second method, which 
 melts at 275° (or 281-5° cor.) by giving, on 
 potash-fusion, not only alizarin but also flavo- 
 purpurin and anthrapurpurin (tri-oxy-anthra- 
 quinone). 
 
 Iri-bromo-anthraquinone OnHsBrjOj. [186°]. 
 Prepared by the action of Br in presence of I 
 upon anthraquinone or di-bromo-anthraquinone 
 at 260° (Diehl, B. 11, 182). Yellow needles; 
 insol. alcohol. 
 
 Tri - Ijromo - anthraquinone CnH^BrjO^. 
 [365°]. From penta-bromo-anthracene, CrOj, 
 and HOAc (Hammerschlag, B. 10, 1213). Flat 
 needles (by sublimation). 
 
 Tetra - bromo - anthraquinone CnH^Br^Oj 
 [295°-300°]. Formed by oxidising hexa-bromo.. 
 anthracene [320°] or by brominating tri-bromo- 
 anthraquinone [186°] in presence of I (D.). 
 Yellow needles. 
 
 Tetra - bromo - anthraquinone OnH^Br^Oj. 
 [above 370°]. Formed by oxidising hexa-bromo- 
 anthracene [above 370°] (H.). Yellow needles. 
 
 Penta - bromo - anthraquinone C,4H3Br502. 
 Formed by oxidation of hepta-bromo-anthra- 
 cene (D.). Sublimes with difficulty without 
 melting; si. sol. boiling toluene. 
 
 DI-BSOMO-DIANTHRYL C^gHj^rj. [far 
 above 300°]. Yellow prisms (from toluene). 
 Formed by bromination of dianthryl dissolved 
 in OS, (Liebermann a. Gimbel, B. 20, 1855). 
 
 DI- BROMO -APOPHYLLENIC ACID 
 C^H^BrNO, i.e. C5NHjBr(C0,H)(C0jMe) or 
 
 CjNH2MeBr(C02H)<;Q°>. Methyl -ether oj 
 
 bromo -pyridine dicarboxylic acid ? From bromo- 
 tarconine (a derivative of narcotine) and Br 
 (v. Qerichten, A. 210, 91). Hard prisms (con- 
 
 taining 2aq) ; sol. hot water. Its solutions 
 give no pps. with salts of Pb, Ag, or Cu. Heated 
 with cone. HOI it forms COj, MeCl, and a 
 bromo-pyridine carboxylio acid (?) [199°]. 
 
 Salt.— BaA'jSaq. 
 
 DI . BROMO - APOPHYLLIN C„H,„Br,NjO,. 
 [229°]. From bromo-taroonine or bromo-apo- 
 phyllenio acid and bromine-water (v. Gerichten, 
 A. 210, 94). Six-sided tables (containing 4aq) ; 
 sol. water, insol. ether. Alkalis form a deep- 
 red solution. HCl at 150° gives CO.^, MeCl, 
 di-bromo-pyridine, and di-bromo-pyridine me- 
 thylo-chloride. 
 
 S alt s.-B"HCl.— B"2HC1.— B"2H2ptCl„aq.— 
 B"HBr.— B"2HBr. 
 
 Dl - BROMO - ATROIAOTIC ACID v. ;8;8-Di- 
 
 BKOMO-n-OXT-ci-PHENTL-PKOPIONIO ACID. 
 
 BROMO - ATROPIC ACID C„H,BrOj i.e. 
 Ph.CjHBr.COjH. Exo-bromo-a-phenyl-acrylic 
 acid. [130']. From the compound of atropic 
 acid (1 mol.) with HBr (2 mols.) by boiling with 
 water (Pittig a. Wurster, A. 195, 162). Slender 
 needles (from water). 
 
 TETRft. BROMO - AURIN C^H.oBr^Oj. 
 Formed by brominating aurin dissolved in 
 HOAc (Dale a. Schorlemmer, C. J. 35, 152; 
 cf. Zulkowsky, M. 8, 465). Bronzed crystals. 
 Alkalis form violet solutions. 
 
 Salt. — A"Ag2 : dark violet insoluble pp. 
 
 Ethyl ether A"Et, : [110°-115°] ; micro- 
 scopic reddish crystals ; sol. alcohol, ether, and 
 benzene (Ackermann, B. 17, 1626). 
 
 BROMO-AZO-BENZENE v. pp. 874, 379. 
 
 TETRA-BROMO-AZOPHENINECsHjsBr.N,. 
 [243°]. Formed by heating 2)-nitroso-di-phenyl- 
 amine withp-bromo-anihne and^-bromo-aniline 
 hydrochloride at 100°. Greatly resembles azo- 
 phenine (0. Fischer a. Hepp, B. 20, 2481). 
 
 BROMO-AZO-TOLTJENE v. p. 394. 
 
 DI-BROMO-AZOXY-BENZENE v. p. 427. 
 
 BROMO-AZOXY-TOLUENE v. p. 428. 
 
 BROMO - BARBITURIC ACID C^HaBrNA- 
 
 i.e. CHBr<[^QQ'jTTi^CO. Bromo-malonyl-urea. 
 
 TJreide of bromo-malonic acid. From di-bromo- 
 barbiturio acid by reduction with Na or Zn, or 
 by evaporating with aqueous HON (Baeyer, 
 A. 130, 134). Small needles; si. sol. cold 
 'wflitsr 
 
 Salt s .— NHjA'. — ZnA'j8aq. — ZnA'^ 6aq 
 (Mulder, B. 12, 2309). 
 
 Di-bromo-barbituric acid C4H2Br2N203. Di- 
 bromo-malonyl-urea. Formed by the action of 
 Br on barbituric, nitro-barbituric, nitroso-bar- 
 bituric, and hydurilic acids (Baeyer, A. 127, 199 ; 
 ISO, 130). 
 
 Preparation. — From di-bromo-oxy -methyl- 
 uracil and fuming HNO3 (Behrend, A. 236, 
 62). 
 
 Properties. — Trimetric crystals. Sol. water, 
 V. sol. hot alcohol and ether. 
 
 Reactions. — 1. Boiling water forms alloxan 
 and HBr. — 2. HI reduces it to hydurilic and 
 barbituric acids. — 3. H^S forms dialuric acid. — 
 4. Bromine water forms COj and tri-bromo- 
 acetyl urea. — 5. Alkalis form COj, tri-bromo- 
 acetyl urea, and bromo -barbituric acid. — 6. 
 Thio-urea forms so-called thio-pseudo-uric acid 
 CsN^HjO^S (Trzoinski, B. 16, 1057).— 7. Potas- 
 iium sulphocyanide forms gulphooyano-barbi- 
 turio aoid OjNjHjSO, (T.). 
 
S64 
 
 BROMO-BARBITURIO AOID. 
 
 Dibromo-di-harbituric acid CJifiii'Sfifit aq. 
 Prisms (Baeyer, A. 130, 145 ; cf. p. 440). — 
 C.H<Br.,N,0,HBr. Prisms, v. si. sol. water. 
 
 DI-BEOMO-EEHENIC ACID Oj^H^jBr^Oj. 
 [43°]. From eruoie acid OujHjjOa and bromine 
 (Hausskneoht, A. 143, 40 ; Otto, A. 135, 226). 
 Nodules. Converted by alooholio KOH to bromo- 
 erucio acid, 02,Hj,BrOj and behenolio acid 
 C^oHjdOj. Moist AgjO forms oxy-erucio acid and 
 di-oxy-behenio acid. Sodium amalgam forms 
 eruoioaoid. Salts. — BaA^— PbA'^. 
 
 Di-bromo-behenio acid O^jH^Br^Oj. [54°]. 
 From brassio acid and bromine (H.), Eeduoed 
 by sodium-amalgam to brassio acid. Alooholio 
 KOH at 220° gives behenolio aoid. 
 
 Tri-bromo-behenic acid CajH^iBrjOz. [32°]. 
 From bromo-eruoic acid and bromine (H.). 
 
 Tetra-bromo-belienieaeid O^JinBijO^. [78°]. 
 From behenolio acid and bromine (H.). 
 Laminae (from alcohol). 
 
 BBOMO-BENZALDEHYDE v. Bbomo-benzoio 
 
 AIDEHTDE. 
 
 BEOMO-BEWZAMIDE v. Armde of Bromo- 
 
 BENZOIO AOID. 
 
 BBOMO-BENZANILIDE v. Anilide o/Bbomo- 
 
 BENZOIO AOID. 
 
 BKOMO-BENZENE C^^t. Phenyl bromide. 
 Mol. w. 157. (156°). S.G. f 1-4914. m« 1-5736. 
 E 00 55-81 (Bruhl). S.V. 119-9 (Schiff, B. 19, 
 664). Vapour vressure : Eamsay a. Young, 
 0.^.47,646. 
 
 Formation. — 1. From bromine and benzene, 
 either boiling or in sunlight (Couper, A. Ch. [3] 
 52, 809 J Schramm, B. 18, 606). The reaction 
 is promoted by the presence of I (Ador a. Billiet, 
 B. 8, 1287) or Al^Clj (Greene, C. B. 90, 40 ; 
 Leroy, Bl. [2] 48, 210).— 2. Formed by running a 
 solution of NaNOj into a hot solution of CUjjBrj 
 and aniline in dilute H2SO4 (Sandmeyer, B. 17, 
 2652). — 3. By heating diazobenzene with a large 
 excess of strong HBr ; the yield is 32 p.o. of the 
 theoretical (Gasiorowski a. Wayss, B. 18, 1938). 
 4. From phenol and bromide of phosphorus 
 (Eiche, A. 121, 357). 
 
 Properties. — Oil; not attacked by KOH, KCy, 
 or AgOAo. 
 
 Beactions. — 1. Boiling with AI2CI8 produces 
 benzene and di-bromo-benzenes (Dumreicher, 
 B. 15, 1867).— 2. Converted in the animal sys- 
 tem into ^-bromo- phenyl -mercapturio acid 
 C„H,„BrNSOs, jp-bromo-phenol, bromo-pyrooate- 
 chin, and bromo-hydroquinone (Baumann a. 
 Preusse, H. 3, 156 ; Jafffi, B. 12, 1092).— 3. 
 Converted by cone. HjSO, into di-bromo-benzene 
 Bulphonio aoid and bromo-benzene di-sulphonic 
 aoid (Herzig, M. 2, 192).— 4. CISO3H forms 
 C,H,Br(S03H) [1:4] and CaH^Br-SO^.O^H^Br 
 (Beokurts a. Otto,B. 11, 2061). — 6. Heating with 
 MeONa gives CjHsOMe and phenol (Blau, M. 7, 
 621). According to Fittica {B. 17, 2634) there 
 is a second bromo-benzene [c. 62°]. 
 
 o-Di-bromo-benzene C^HjEra [1:2]. [—1°]. 
 (224°). S.G.2 2-003. Formed in small quan- 
 tity in preparing p-di-bromo-benzene from ben- 
 zene and Br (Eiese, B. 2, 61; A. 164, 176). 
 Formed also from o-nitraniline vid o-bromo- 
 nitro-benzene (Korner, G.4, 333). HNO3 forms 
 chiefly di-bromo-nitro-benzene [58°]. 
 
 wi-Di-bromo-benzenB OjH.Brj [1:31. (219°). 
 S.G. '-^^ 1-955. 
 
 Formation.— t.- From (l,8,4)-dl-bromo-am'> 
 line (Meyer a. Stuber, A. 165, 169).— 2. From 
 s-di-bromo-aniline. — 3. Fromm-di-nitro-benzene 
 vid m-nitro-aniline, m-bromo-nitro- benzene, 
 and m-bromo-aniline (K.). — 4. Together with the 
 p- isomeride by the action of Br on benzene in 
 presence of AljClj (Leroy, Bl. [2] 48, 211). 
 
 Properties. — Has not been solidified. Yields 
 with HNOs two nitro- derivatives [62°] and [83°]. 
 Sodium acting on an ethereal solution forma 
 diphenyl, C^Hj^Brj [220°] and C^BHi^Br.^ [250°], 
 (Goldschmiedt, M. 7, 45). 
 
 p-Di-bromo-benzene CsHiBr^ [1:4]. [89°]. 
 (219°). S.V.S. 127-8 (Sohifi). 
 
 Formation. — 1. By bromination of benzene 
 or bromo-benzene (Couper, A. Oh. [3] 52, 309 ; 
 Eiche a. B6rard, A. 133, 51 ; Biese, A. 164, 162 ; 
 Jannasoh,B. 10, 1355). — 2. Fromjp-diazo-bromo- 
 benzene perbromide by heating with alcohol 
 (Griess, G. J. 20, 66). — 3. From^-bromo-phenol 
 and PBr^ (A. Mayer, A. 137, 219).— 4. From ben- 
 zene, Br, and Fe^Olj (Scheufelen, A. 231, 188). 
 
 Preparation. — 1. By treating benzene with 
 Br and a little I.— 2. Bromine (960 g.) is added 
 slowly to benzene (240 g.) and k\C\ (30 g.). 
 On adding water in excess, the product de- 
 posited consists of crystals of the para- com- 
 pound, with an oil, consisting chiefly of the 
 meta- compound. This oil, however, contains 
 some para-di-bromo-benzene in solution. To 
 separate this, the oil is treated with fuming 
 H2SO4. The meta- derivative is easily sulpho- 
 nated in this way, but the para- is not affected. 
 On adding a large excess of water, the solid 
 CgHjBrj [1:4] is ppd., and the clear solution of 
 the meta-sulphonate distilled with steam gives 
 C,H,Br2 [1:3] (Leroy, Bl. [2] 48, 211). 
 
 Properties. — ^Prisms or plates, isomorphous 
 with p-di-ohloro-benzene (Friedel, Bl. [2] 11, 
 38). Sublimable. SI. sol. alcohol. 
 
 BeaoUons. — 1. Heated for 30 minutes with 
 Al-zOlc (j part) gives CjH.Br, CsH^Br^ [1:3], and 
 twotribromobenzenes,CjH3Br3 [1:2:4] and [1:3:5] 
 
 (L.) 2. HNO3 forms a nitro- derivative [85°].— 
 
 3. In ethereal solution sodium forms diphenyl, 
 di-phenyl-benzene, and CjsHjjBr^ [265°] and 
 CjjHsjBrj [300°] (Eiese, A. 164, 164; Gold- 
 schmiedt, M. 7, 42). — 4. Mel and Na form p- 
 xylene.— 5. NaOEt at 190° gives CjH^BrOBt, 
 bromo-benzene, and benzene (Balbiano, O. 11, 
 401).— 6. NaOMe forms C^H^BrOMe, C3H4(OMe)j 
 and C,H4(0Me)(0H) (Blau, M. 7, 621).— 7. Con- 
 verted by cone. H^SOj into tetra- and hexa- 
 bromo-benzene (Herzig, M. 2, 192). 
 
 c-Tri - bromo ■ benzene CgHsBr, [1:2:3]. 
 Mol. w. 315. [;87°]. From (l,3,5,2)-di-bromo- 
 nitro-aniline vi& tri-bromo-nitro-benzeue, and 
 tri-bromo-aniline (Korner, O. 4, 401). Tables 
 (from alcohol) ; may be sublimed. 
 
 s-Tri-bromo-benzene CsH3Br3 [1:3:5]. [119°]. 
 (278°). Formation. — 1. From ordinary tri- 
 bromo-aniline (Stuber, B. 4, 956 ; A. 165, 173 ; 
 Eeinke, A. 186, 271 ; Biissmanu, A. 191, 206 ; 
 Silberstein, J.pr. [2] 27, 104).— 2. From (1,3,5)- 
 di-bromo-aniline (K.). — 3. In small quantity by 
 the action of light on bromo-acetylene (Sa- 
 banejeff, J. B. 17, 176). 
 
 Properties. — Needles (from alcohol) ; si. sol. 
 alcohol. Boiling oono. H^SO, forma hexa- 
 bromo-benzene (Herzig, M. 2, 197). NaOMe 
 
BROMO-BENZENE SULPIIONIC ACID. 
 
 556 
 
 forms CaHjBrj(OH) and O^n^Br^OUe [11°] (Blau, 
 K. 7, 621). 
 
 u-Tri-bromo-beuzene CsHaBrj [1:2:4]. [44°]. 
 (275°). Formation. — 1. From hexa-bromo- 
 benzene and alooholio KOH (Mitsoherlioh, P. 
 35, 374; Lassaigne, Bev. Scient. 5, 360). — 
 2. Prom (1,3,4)- di-bromo-phenol and PBrj 
 (Mayer, 4. 137, 224).— 3. From (1,3,4) -di-bromo- 
 aniline (Griess, 2V. 154, 667). — 4. From o-, m-, 
 and p-, di-bromo-benzene by nitration, reduction, 
 and diazotisation (K.). — 5. Got from each of 
 the dibromobenzenes by heating with water and 
 bromine at 250° (Wroblewsky, A. 192, 220).— 
 6. From benzene, bromine, and Fe^Clj (Scheu- 
 felen, A. 231, 188).— 7. As a by-product, in 
 the preparation of CjHjBr^ by the action of Brj 
 upon C„H|j in presence of AljClj (Leroy, Bl. [2] 
 48, 213). Properties. — Needles ; si. sol. alcohol. 
 s-Tetra-bromo-benzene OjIIjBr^ [1:2:4:5]. 
 Mol. w. 394. [175°]. Formation. — 1. From p- 
 di-bromo-benzene and Br at 150° (Riche a. 
 B^rard, A. 133, 51).^2. From M-tri-bromo-ben- 
 zene and Br. — 3. From nitro-benzene and Br 
 at 250° (Meyer, B. 15, 46).— 4. From benzene 
 (80 g.), PsjOls (5 g.), and bromine (240 g.) ; the 
 mixture must be cooled (Scheuf elen, A. 231, 187). 
 Properties. — Long needles (from alcohol). 
 
 M-Tetra-bromo-benzene OsH^Br^ [1:2:3:5]. 
 [98-5°]. (329°). Formation.—!. From (1,3,5,2)- 
 tri-bromo-phenol and PBrj (Korner, 4. 137,218; 
 Mayer, A. 137, 227). — 2. From (1,3,5,2) -tri- 
 bromo-aniline (Wurster a. Nolting, B. 7, 1564 ; 
 V. V. Biohter, B. 8, 1428 ; Silberstein, /. pr. [2] 
 27, 118). — 3. From C.HBr^SOjH by heating 
 with HCl (Biissmann, A. 191, 224).— 4. One of 
 the products obtained by heating tri-bromo- 
 diazo-benzene nitrate with benzene (Silberstein, 
 J. pr. [2] 27, 110). Properties. — Long needles, 
 V. si. sol. alcohol. HNOj (S.G. 1-50) gives a 
 nitro- derivative [96°] ; fuming HNOj (S.G. 1-54) 
 gives a di-nitro- derivative [228°]. 
 
 Tetra - bromo - benzene CsHlfBrj. [160°]. 
 From p-nitro-benzoio acid and Br at 280° (Hal- 
 berstadt, B. 14, 911). Needles (from alcohol). 
 
 Tetra - bromo - benzene CjHjBr,. [138°]. 
 From ^J-di- bromo -benzene and boiling cone. 
 KjSOi (Herzig, M. 2, 195). One, if not both, 
 of the two last-mentioned bodies is, doubtless, a 
 mixture. 
 
 Fenta-bromo-benzene CjHBrj. Mol. w. 473. 
 [260°]. Formation. — 1. From Br and nitro- 
 benzene or di-nitro-benzene at 250° (Kekul6, A. 
 137, 172).— 2. From s-tri-bromo-benzene and 
 fuming HjSOj at 100° (Biissmann, A. 191, 208).— 
 3. From alizarin and BrI at 260° (Diehl, B. 11, 
 191). Properties. — Silky needles ; v. si. sol. 
 alcohol, sol. benzene. 
 
 Heza - bromo - benzene CsBrj. Per-bromo- 
 henzene. [above 315°]. Formation.— 1. By the 
 action of Br containing I upon benzene, toluene, 
 or benzene-azo-benzene at 250°-400° (Gessner, 
 B. 9, 1505). —2. From tetra-bromo-quinone and 
 PBrj at 280° (Buoff, B. 10, 403).— 3. From p-di- 
 bromo-benzene (or tri-brbmo-benzene) and cone. 
 H,S04 (Herzig, M. 2, 192).— 4. By heating at 
 360° per-bromo-methane, per-bromo-ethane, per- 
 bromo-butane, per-bromo-pentane, or per-bromo- 
 hexane (Merz a. Weith, B. 11, 2235).— 5. By 
 beating benzene with bromine and AljBrj. — 6. 
 By heating pentabromo-phenol with PBij at 260° 
 (Merz a. Weith, B. 16, 2890).— 7. From bromine 
 
 (300 g.), FojOl, and benzene (17 g.) in the cold. 
 Good yield (110 g. instead of 119 g.) (Soheufelen, 
 
 A. 231, 189). Properties. — ^Long needles (from 
 toluene). V. si. sol. alcohol and toluene. 
 
 BEOMO-BEITZENE o-SITLPHOlIIC ACID 
 OsHiBr.SOjH [1:2]. From o-amido-benzene sul- 
 phonio acid (Berndsen a. Limpricht, A. Ill, 101 ; 
 Bahlmann, A. 181, 203 ; 186, 315). Long deli- 
 quescent needles ; v. e. sol. alcohol. — NHjA'. — 
 KA'aq. — BaA'^ aq. — BaA'j 2aq. — CaA'^ 2aq. — 
 PbA'^ 3aq.— AgA'. 
 
 Chloride CeH^Br.SO^Cl [51°]. 
 
 Amide 08H,Br.S0.,NHj [186°]. 
 
 Bromo-benzene m-sulphonic acid 
 OjH^Br.SOsH [1:3]. From amido-benzene m- 
 sulphonic acid (Berndsen, A. VII, 92). Formed 
 also by brominating benzene sulphonic acid or 
 its silver salt (Boss Garriok, Z. [2] 5, 549 ; Genz, 
 
 B. 2, 405 ; Nolting, B. 8, 819 ; Thomas, A. 186, 
 133). Very deliquescent.— KA' aq. S. (of KA') 
 4-4 at 0°.— PbA'j2aq.— PbA'jSaq.- S. (of PbA'j) 
 5-78 at 7°.— BaA'j 2aq. S. (of BaAg 3-5 at 14°. 
 CuA',.-AgA'. 
 
 Chloride CsH^Br.SOjOl. Oil. 
 
 ^TOitZeCeH^Br.SO^NH^. [154°]. 
 
 Bromo-benzene- p-sulphonic acid 
 CjHjBr.SOsH [1:4] [88°]. Deliquescent needles. 
 
 Formation. — 1. By snlphonating bromo- 
 benzene with HjSO,, CISO3H, or SO3 (Couper, 
 
 C. R. 45, 230; Boss Garrick, Z. [2] 5, 549; 
 Armstrong, Z. [2] 7, 321; Nolting, B, 8, 594).— 
 2. Fromjp-amido-benzene sulphonic acid (Meyer, 
 A. 156, 291 ; Berndsen, A. Ill, 92). 
 
 Reactions. — The K salt distilled with KjFeCy, 
 gives terephthalonitrile. 
 
 Salts.— (Goslioh, B. 8, 352; A. 180, 93).— 
 NH,A'.— KA'.— CaA'22aq.— BaA'j.— PbA'i,2aq.— 
 PbA'j.- ZnA'2 6aq.— CuA'2 6aq.— AgA'. 
 
 Chloride 0,H,Br.S02Cl. [75°]. 
 
 Amide [164°] (Bassmann, A. 191, 247). 
 
 Acetyl-amide CsHjBr.SO^NHAc [199°]. 
 
 Anilide CsH^Br.SO^NHPh [119°]. 
 
 Bromo-benzene di-snlphonic acid 
 0eHsBr(S03H)2 [1:3:4?]. From the correspond- 
 ing amido-benzene disulphonio acid (Zander, A. 
 198, 28). Deliquescent needles. — BaA" 3aq. — 
 PbA"aq. 
 
 Chloride CBH3Br(S02Cl)2 [104°]. 
 
 Amide G^TaL^BxiBO^T^B.^)., [210°]. 
 
 Bromo-benzene di-snlphonic acid 
 0,H,Br(S03H), [1:2:4]. 
 
 Formaticm. — 1. From the corresponding 
 amido-benzene disulphonio acid (Zander, A. 
 198, 10). — 2. From bromo-benzene p-sulphonio 
 acid and SO3 at 210° (Nolting, B. 7, 1311). 
 
 Properties. — Slender deliquescent needles. 
 EjA"aq.— BaA"4aq. S. (of BaA") 6 at 22°.— 
 Ab A" 
 
 ^Chloride C„H3Br(S0,Cl)j [103°]. 
 
 Amide C,B.^Bi(SO^^^)i [239°]. 
 
 Bromo-benzene di-snlphonic acid 
 05H3Br(SO3H)2 [1 or 4:5:3]. From the corre- 
 sponding amido - benzene disulphonio acid 
 (Heinzelman, A. 188, 177). Deliquescent needles. 
 
 Salts.- (NH J,A".— BaA"2iaq.— PbA" 2iaq. 
 
 Chloride C„H3Br(S02Cl)2 [99°]. 
 
 Amide C3H3Br(S02NH2), [245°]. 
 
 o-Di-bromo-benzene sulphonic acid 
 0sH3Br2(S0aH) [1:2:3]. From the corresponding 
 di-amido'benzene sulpbonio acid (Sachsa, A, 
 188, 153). Deliquescent priems. 
 
S56 
 
 BBOMO-BENZENE SUf^PHONIC ACID. 
 
 Salts.— KA'. — BaA'jSaq. S. (of BbA',) 
 '143 at 10''.-CaA'j2aq.— PbA'jSaq. 
 
 Chloride CJB,,-Bi^.SOJDl [127°]. 
 
 Amide OsR^ii-SO^SH^ [215°]. 
 
 o-Si-bromo-benzene snlphonic acid 
 CeH3Br2(S03H) [1:2:4]. [67°]. From sUver 
 bromo-benzene m- or p- sulphonate and bromine 
 (Limpricht a. Goslich, ^1. 186, 145). From 
 CjH3Br(NHj)S03H by diazo- reaction (Langfurth, 
 A. 191, 179 ; Spiegelberg, A. 197, 263). The free 
 acid crystallises with 3aq [68°]. 
 
 Salts.— KA'. — NH,A'. — BaA'22aq. — 
 EaA'jBaq. S. (of BaAy -3 at 11°.— CaA'j.- 
 PbA', 2aq. S. (of PbA'J -26 at 7°.-AgA'. 
 
 Chloride OsHaBrjSO.Cl. OU. 
 
 Amide CsH3Br2S02NH2-[175°]. 
 
 m-Di-bromo-beuzene sulpbonic acid 
 CsHjBrjjSOaH) [1:3:5]. Prom dibrominated o- 
 orp- amido-benzene sulphonio acid by the diazo- 
 reaotion (Limpricht, B. 8, 1066 ; A. 181, 201 ; 
 Sohmitt, A. 120, 158 ; Lenz, A. 181, 23). It is 
 also a product of the action of cone. HjSO, on 
 bromo-benzene (Herzig, M. 2, 192). Crystalline. 
 
 Halts.— NH^A'.—KA'.—BaA'23iaq. S. (of 
 BaA'J -28 at 18°. — CaA'j3iaq.— PbA'j l^aq. 
 S. (of PbA'j) -21 at 18°. 
 
 Chloride OsHjBrj.SOjCl. [57-5°]. 
 
 Amide C5H3Brj,.S02NH2. [203°]. 
 
 m-Di-bromo-benzene sulphonic acid 
 CsHaBrjSOjH [1:3:4]. [80° when hydrated] ; 
 [110° anhydrous]. From C„HiBr2.(NH2)S03H 
 [1:3:4:6] by diazo- reaction (Langfurth, A, 191, 
 184; Bassmann, A. 191, 232). Slender deli- 
 quescent needles (containing aq). Sol. alcohol, 
 insol. ether. With HBr at 180" gives HjSOiand 
 m-di-bromo-beuzene. 
 
 S alt s .— NH,A'.— KA'. — BaA'22iaq (L.).— 
 BaA'2 2aq (B.). S. (anhydrous) 2 at 10° (L.); 
 1 at 20° (B.).— CaA'^Saq. S. (anhydrous) 
 3-34 at 10°.— PbA'^Saq. S. (anhydrous) 1-43 
 at 8°.— AgA'. 
 
 Chloride CjHjBr^SOjOl. [79°]. 
 
 Amide CjHgBr^SOjNH^. [190°] (anhydrous). 
 
 p-Bi-bromo-benzene snlphonic acid 
 C„H,Brj(S03H) [1:4:2]. [128°]. 
 
 Formation. — 1. By bromination of silver o- 
 or m-bromo-benzene sulphonate (Bahlmann, A. 
 181, 206; Limpricht, A. 186, 139).— 2. By sul- 
 phonation of p-di-bromo-benzene (Douglas Wil- 
 liams, Z. [2] 7, 302 ; Hubner a. Williams, A. 
 167, 117 ; Wolz, A. 168, 81).— 3. From nitrated 
 bromo-benzene o- or m-sulphonic acid (Thomas, 
 
 A. 186, 129 ; B.). — 4. From brominated amido- 
 benzene o-sulphqnio acid (B.). Prisms (con- 
 taining 3aq), [98°]. Cone. HBr at 250° gives 
 HjSOj and ^-di-bromo-benzene. 
 
 Salts.-icf. Boms, A. 187, 350).— NH,A'.— 
 NaA'liaq.-KA'aq. S. (of EA') 5-79 at 21°.— 
 AgA'l|aq.-AgA'3aq. S. (of AgA') 1-69 at 
 10°.— BaA'j. S. 1-01 at 16°.— BaA'., aq.— 
 BaA'j 2aq.— BaA'j 5aq.— CaA'^ 4aq. S. (of CaA'J 
 6-90 at 22°.— CaA'jSaq.- CaA'jlOaq.— PbA'jSaq. 
 
 B. (of PbA'j) 2-56 at 21°.-PbA'24aq.— CuA'2l4aq. 
 
 Chloride C„HjBr,(S0,01) : [72°]. 
 
 Amide C„H3Br2(S03NH2). [193°]. 
 
 Anhydride (aji^'Bi^SO^)^. Obtained by 
 the action of fuming sulphuric acid upon p-di- 
 bromo-benzene. Amorphous powder. Nearly 
 insol. alcohol, ether, and benzene. By boiling 
 alkalis it is converted into salts of the acid; 
 very slowly attacked by boiling water. POlj con- 
 
 verts it into the chlorid« (Bosenberg, B. 19, 
 653). 
 
 m-Si-broma-benzene di-sulphonic acid 
 C3HjBrj(S03H)2. Fiom.Osn,(SO:,)i{SO,B.)i (Lim- 
 pricht, B. 8, 290). Deliquescent. 
 
 ^-Di-bromo-benzene disulphonic acid 
 C|iH2Br2(SOsH)j. Formed by aulphonating ^j-di- 
 bromo-benzene (Boms, A. 187, 366). Small 
 columns. — KjA".— BaA" 4|aq. 
 
 Chloride 0sB.^T^{S0fil)2. [161°]. 
 
 Amide C,B.^t^{B02^n^)^. [240°]. 
 
 l!ri-bramo-beuzene sulphonic acid 
 O^H^BrsSOsH [1:3:5:6]. [145°] (anhydrous). 
 Formed by sulphonating s-tri-bromo-benzene 
 (Eeinke, A. 186, 271; Bassmann, A. 191, 206). 
 Also from C8H(NH2)Br3S03H [1:2:4:6:8] by diazo- 
 reaction (Langfurth, A. 191, 191). Six-sided 
 tables (containing aq) [95°]. Water at 180° 
 forms H2SO4 and s-tri-bromo-benzene. 
 
 Salts.— NH4A'aq.—KA'3aq.-KA'aq. S. 
 (of EA') -81 at 5-5 (B.).— BaA'2 9aq.— BaA'j6aq. 
 — BaA'2 2aq. S. (of BaA'j) -41 at 5-5° (L.) ; -22 
 at 7-5° (B.).— CaA'2 8aq. S. (of CaA'^) 1-95 at 7° 
 (L.) ; 3-5 at 2-5° (B.).— CaA'2 4aq.— CaA'j7aq.— 
 PbA'2 aq.— Pb A'j 9aq.— PbA'2 2aq. S. (of PbA'^) 
 •36 at 7° (B.).— AgA' aq. 
 
 Chloride. OsH^BrsSO^Cl. [65°]. 
 
 Amide. CsHjBrjSOjNHj. Deoomposea 
 above 220°. 
 
 Tri-bromo-benzene snlphonic acid 
 CeH^Bra-SOsH [1:2:4:5]. [140° anhydrous]. 
 From (1, 2, 4, 5)- or (2, 4, 1, 5)-di-bromo-amido- 
 benzene sulphonic acid by diazo-reaction (Lang- 
 furth, A. 191, 188 ; Eeinke, A. 186, 288 ; Knuth, 
 A. 186, 303 ; Spiegelberg, A. 197, 282). Needles 
 (containing 3aq) [80°]. With HBr at 200° gives 
 HjSO, and 0«H3Br3 [1:2:4]. 
 
 Salts.— NH,A'aq.—KA'aq. S.(of KA') 1-03 
 at 20° (B.) ; -77 at 22° (S.).— BaA'^ 3aq. S. -122 
 at 12°.— BaA'2 2aq.— BaA'2 6aq.— CaA'^ 6aq.— 
 PbA'j4aq.— AgA'. 
 
 Chloride.— C^B^i^SOfil [86-5°]. 
 
 ilmiie.- CjBLjBrsSOjNHi, [c. 225°]. 
 
 Anhydride (CaHjBrs.SOj)^^ Obtained 
 by the action of fuming sulphuric acid upon 
 tri-bromo-benzene (1:2:4). Amorphous powder. 
 Almost insol. alcohol, ether, and benzene. By 
 boiling aqueous alkalis it is converted into salts 
 of the acid ; only very slowly attacked by boiling 
 water. PCI5 converts it into the chloride (v. 
 supra) (Bosenberg, B. 19, 654). 
 
 Tri-bromo-benzene sulphonic acid 
 CBH2BrsS03H [1:2:3:5]. From di-brominated 
 amido-benzene ^-sulphonic acid (Lenz, B. 
 8, 1067; A. 181, 29). — NH,A'. — KA'.— 
 CaA'2 2iaq. S. -39 at 20°.— BaA'j, 3aq. S. (ol 
 BaA'j) -021 at 18°.— PbA'j SJaq. S. -056 at 21°. 
 
 Chloride O^H^BrsSOjOl. [127°]. 
 
 Amide OABrsSO^NHj [210°]. 
 
 Tri-bromo-benzene sulphonic acid 
 CjHaBrsSOaH [1?:2:3:5]. From silver (1, 2, 4)- 
 di-bromo-benzene sulphonate and Br (Goslich, 
 A. 186, 154). Is perhaps identical with the 
 preceding. — BaA'^ 3|aq. 
 
 Chloride [121^]. Amide [152°]. 
 
 Tri-bromo-benzene sulphonic acid 
 CsajBr3S0sH [1:3:4:5]. From nitrated (1, 3, 5)- 
 di-bromo-benzene sulphonio acid (Lenz, A, 
 181, 39).— KA'aq.— BaA'jaq. 
 
 Chloride OsHjBrjSOjOl. [86°]. 
 
 Amide OjHjBrsSOjNHj. Blackens at 225°. 
 
BROMO-BENZOIO ACID. 
 
 C57 
 
 Tri-bromo-benzene sulphonic acid 
 OjHjBrjSOaH. Possibly identical with the pre- 
 ceding. From nitrated (1, 4, 2)-di-bromo-benz- 
 ene sulphonic acid (Boms, A. 187, 364). — 
 KA' 3iaq.— BaA'j2aq. 
 Amide [above 220°], 
 Tri-bromo-benzene sulphonic acid 
 OgHjBrjSOjH. From silver bromo-benzene o- 
 Bulphonate and Br (Bahlmann, A. 181, 207). 
 Chloride CsH^BrsSO^Cl. [56°]. 
 Amide CjH^^rsSOjNHj. [202°]. 
 Tri-bromo-benzene sulphonic acid 
 CsHjBrjSOjH. Formed at the same time as the 
 preceding (B.). 
 
 Chloride CeHfBrjSOjCl. [72°]. 
 Amide OsHjBrjSdjNHj. [187°]. 
 Nine tri-bromo-benzene sulphonic acids are 
 here described, but only six are indicated by 
 theory. 
 
 Tri-bromo-benzene di-sulphonic acid 
 CjHBr3(S03H)j. From benzene m-di-sulphonio 
 acid by nitration, reduction, bromination to 
 C5HBrj(NH2)(S03H)2and diazotisation (Heinzel- 
 mann, A. 188, 183).— S alt : K^A". 
 
 Tetra-bromo-benzene-sulphonic acid 
 CjHBr^SOjHSaq [1:2:3:5:6]. 
 
 Formation. — 1. From CsHBr3(NIl,)S0,H 
 [1:3:5:4:6] by diazo- reaction (Beokurts, A. 181, 
 216; Langfurth, A. 191, 199; Knuth, A. 186, 
 229 ; Reinoke, A. 186, 282).— 2. From CjHjBr, 
 and HjSO« (Bassmann, A. 191, 223). Needles. 
 Not hygrosoopie but v. sol. alcohol and water. 
 
 BeacHon. — ^With cone. HBr at 150° gives 
 H,S04 and {l,2,3,5)-tetra-bromo-benzene [98-5°]. 
 ' Salts.— KA'. S. -63 at 6°.— BaA'^. S. -37 
 at 12° (L.); -16 at 15° (Ba.).— BaA'jliaq.— 
 CaA'jSaq.-S. (of CaA',) -54 at 3°; -66 at 19° 
 (Ba.). — NH,A'. — PbA',.PbO 3aq.— PbA'^ IJaq. 
 S. (of PbAg -89 at 11° (Ba.).— PbA'^ 4aq. 
 Chloride C^HBr^SO^Cl. [96°]. 
 Amide CjHBrjSOjNHj. Minute needles. 
 Not melted at 300°. 
 
 Tetra-bromo-benzene sulphonic acid 
 0,HBrj(S03H) [1:2:3:4:5]. [169°]. From 
 (l,2,3,5)-tri-bromo-benzene sulphonic acid by 
 nitration, reduction, and diazotisation (Lenz, A. 
 181, 23). Also in the same way from (1,2,4,5)- 
 tri-bromo-benzene sulphonic acid (Spiegelberg, 
 A. 197, 292). Lamin» (containing 2aq). 
 
 Salts.— KA'aq. S. (of KA') -194 at 11°.— 
 
 NH,A'. S. -95 at 11°.— BaA'^aq. S. (of BaA'^) 
 
 ■0204 at 10-5°.— CaA'2 3aq. S. (of CaA'j) -159 
 
 at ll°.-PbA'23aq. S. (of PbA'^) -0484 at 11°. 
 
 — AgA'iaq. S. (of AgA') -146 at 11°.— AgA'aq. 
 
 Chloride C^HBr^SO^Cl. [120°]. 
 
 Amide CsHBr^SOiNH,,. Turns brown at 240°. 
 
 Penta-bromo-benzene sulphonic acid 
 
 CjBrsSOsH. S. -548 at 10°. From either 
 
 tetra-bromo-amido-benzene sulphonic acid by 
 
 diazo- reaction (Beckurts, A. 181, 226 ; Hein- 
 
 zehnann a. Spiegelberg, A. 197, 306; Langfurth, 
 
 A 191, 205). Needles or plates (containing aaq). 
 
 Salts.— NH,A'.- KA'aq. S. (of KA') -116 at 
 
 10-5°.- CaA'24aq. S. (of CaA,) -78 at 14°.— 
 
 BaA'„ aq. S. (of BaA'^) -0088 at 13°.— BaA'jlJaq. 
 
 AgA'lAaq. 
 
 Chloride Cfiv,SOfi\. [154°]. 
 
 Amide C^BrsSCNH^. Decomposes at 250°. 
 
 BKOMO -BENZIDINE v. Bbomo-di-amido- 
 
 9IFHENYL. 
 
 0-BKOMO-BENZOIC ACID CjHjBrOj i.e. 
 CsHjBr.CO^H [1:2]. Mol. w. 201. [148°]. 
 (Z. ; J. a. W.) ; [150°] (E.). 
 
 Formation. — 1 From o-amido-benzoio acid 
 (Eiohter, B. 4, 465).— 2. By heating OsH,Br(NO.,) 
 [1:3] with KCy at 180° (E.).— 3. By oxidation 
 of o-bromo-toluene (Zincke, B. 7, 1502 ; Eahlis, 
 A. 198, 99), o-bromo-diphenyl (Schultz, A. 207, 
 353), or o-bromo- benzyl alcohol (Jackson a. 
 White, Am. 2, 316). 
 
 Properties. — Long needles (from water) ; m. 
 sol. water, v. sol. alcohol, and ether ; slightly 
 volatile with steam. 
 
 Salts. — BaA'j.- BaA'2 2H0Et.— CaA'jSaq. 
 — KA'2aq. — ZnA', — PbA'^HOEt. — OuA',aq. 
 [257°].— HOCuA'. 
 
 Methyl ether MeA'. (247°). 
 
 Ethyl ether EtA'. (255°). 
 
 Anilide C.H,Br.CONPhH. [142°]. 
 
 m-Bromo-benzoic acid CsHjBrCOjH [1:3]. 
 [155°]. (280°). 
 
 Formation. — 1. From AgOBz and Br 
 (Peligot, A. 28, 246 ; Angerstein, A. 158, 2).— 
 2. From benzoic acid and Br in the sunshine 
 (Herzog, N. Br. Arch. 23, 16) or by heating 
 them with water at 100° or 160° (Eeinecke, Z. 
 1865, 116 ; 1869, 100 ; Hubner, A. 143, 233 ; 
 149, 131). — 3. By heating benzamide with Br 
 and water (Eeinecke, Z. 1866, 367 ; Friedburg, 
 
 A. 158, 26). — 4. From m-amido-benzoic acid by 
 diazo- reaction (Griess, A. 117, 25 ; Hubner, A. 
 222, 100).— 5. From C8H,Br(N02) [1:4], KCy, 
 and alcohol at 200° (Eichter, B. 4, 464).— 
 6. By oxidation of m - bromo - toluene (Wro- 
 blewsky, Z. [2] 5, 332 ; A. 168, 156) or m-bromo- 
 benzyl alcohol (Jackson, Am. 1, 93). — 7. By 
 the action of a hot solution of cuprous cyanide 
 in potassium cyanide upon to - bromo - diazo - 
 benzene - chloride (from TO-bromaniline), and 
 saponification of the crude nitrile (Sandmeyer, 
 
 B. 18, 1496). — 8. From m-di-bromo-benzene, 
 OlCOjEt, and Na (Wurster, A. 176, 149). 
 
 Properties. — Crystalline ; very slightly vola- 
 tile with steam ; si. sol. water, v. sol. alcohol. 
 
 Reactions. — 1. Potash-fusion gives m- and 
 a little 0- oxy-benzoio acid (Eichter, Z. 1869, 
 457 ; Barth, A. 159, 236).— 2. The K salt fused 
 with sodium formate gives isophthalio acid 
 (V. Meyer a. Ador, A. 159, 15). 
 
 Salts . — CaA'2 3aq. — BaA'j 4aq : needles. 
 
 Methyl ether MeA'. [32°]. 
 
 Ethyl ether EtA'. (259°). 
 
 Phenyl ether PhA'. [65°]. 
 
 Chloride C„H,Br.COCl. (239°). 
 
 Amide C^H^Br.CONH,. [150°]. 
 
 Nitrile OsH^BrCN. [38°]. (225°). From 
 the amide (Engler, B. 4, 708). Formed also by 
 the action of a hot solution of potassium cu 
 prous cyanide upon to - bromo - diazo - benzene 
 chloride (from TO-bromaniline) (Sandmeyer, B. 
 18, 1496). 
 
 ^ - Bromo - benzoic acid C^HjBr.COjH [1:4]. 
 [251°]. Formation. — 1. By oxidation of p- 
 bromo-toluene (Hubner, A. 143, 247; Jackson a. 
 Eolfe, Am. 9, 84), ^-bromo-ethyl-benzene (Fit- 
 tig a. Konig, A. 144, 283), or jj-bromo-benzyl 
 bromide (Jackson,^™. 1,93).— 2. From^-bromo- 
 aniline vid p-bromo-thio-carbimide, the lattei 
 when heated with copper at 190° giving p. 
 bromo-benzonitrile (Weith a. Landolt, B. 8, 715). 
 
 Properties, — SmaU needles (from ether) or 
 
158 
 
 BROMO-BENZOIO AOID. 
 
 plates (from water). V. b1. boI. water, v. sol. 
 alcohol and ether. — AgA'; 
 
 Ethyl ether EtA' (236° unoor.) at 713 mm. 
 Formed, together with ^-bromo-benzyl-aloohol, 
 by boiling ^-bromo-benzyl bromide with aloo- 
 holio KOH (Bibs, J.pr. [2] 34, 341). 
 
 Phenyl ether FhA.'. [117°]. Scales. 
 
 Pyrogallyl ether GifisA's. [140°]. 
 
 Chloride. [30°]. (246°). Needles. 
 
 Amide C.HjBr.CONH^. [186°]. 
 
 Anilide Cfifit.COIUFhB.. [197°]. Plates. 
 On nitration it gives a dinitro- derivative. [214°]. 
 (Raveill, A. 222, 178). 
 
 Anhydride (G,'R,BrCO)fi. [213°]. From 
 y-bromo-benzoyl chloride and sodium p-bromo- 
 benzoate (J. a. E.). Minute oblong rectangular 
 plates (from CHClj). Insol. water. Converted 
 by hot HOBt into the ethyl ether. 
 
 Di-bromo-benzoic acid Oi^B^BtfiO^^ [1:2:3] 
 [147°]. From (a)-bromo-amido-benzoic acid 
 [1:2:3] by diazo- reaction (Hubner, A. 222, 105). 
 From (1, 2, 3)-di-bromo-toluene (Nevile a. Win- 
 ther, B. 13, 965). Silky needles (from water). 
 V. sol. hot water. Heated with H,,SOj (3 vols.) 
 and HjO (1 vol.) at 225° it gives o-di-bromo- 
 benzene [218-5°]. 
 
 Salts.— BaA'j4iaq. S. (of BaAy 4-44 at 
 1 6°.— Sr A'j 4aq.— A'CuOH.— K A' xaq. 
 
 This acid is perhaps identical with the di- 
 bromo-benzoic acid [148°] prepared from o-nitro- 
 benzoic acid, Br, and water at 200° (Glaus a. 
 Lade, B. 14, 1170). 
 
 Di-bromo-benzoic acid GeUfivfiO.^Ti [1:4:3]. 
 [153°]. From (/3)-bromo-amido- benzoic acid 
 [1:4:3] by passing nitrous acid gas into a mix- 
 ture of the acid, HBr, glacial acetic acid and 
 alcohol (Hubner, A. 222, 108). From nitro-p- 
 di-bromo-benzene and alcohoUo KCy (Eiohter, 
 -B. 7, 1146). From (1, 4, 3)-di-bromo-toluene 
 by oxidation (Nevile a. Winther, B. 13, 963). 
 Long silky needles (from water). Volatile with 
 steam. Heated with H^SOj (3 vols.) and water 
 (1 vol.) at 225° gives ^-di-bromo-benzene [89°]. 
 
 Salts.— BaA'j lAaq.— SrA'24aq.— ZnAV — 
 OaA'jSJaq.- KA'aq. 
 
 This acid is probably identical with the di- 
 bromo-benzoic acid [153°] from o-nitro-benzoic 
 acid, Br, and water at 200° (Glaus a. Lade, B. 
 14, 1170). 
 
 Di-bromo-benzoic acid CjHjBrjCOjH [1:3:2]?. 
 [150°-167°]. By oxidising di-bromo-toluene 
 from di-bromo-m-toluidine, [35°] (Nevile a. 
 Winther, C. J. 37, 441). 
 
 Di-bromo-benzoic acid OgRsBrfiO^U [1:3:4]. 
 [169°]. By oxidising di-bromo-toluene from di- 
 bromo-m-toluidine [76°] (NevUe a. Winther, 
 C. J. 37, 441). 
 
 Di-bromo-benzcic acid GsHsBr^CO^H [1:3:5] 
 [207°-210°] (N. a. W.); [209°] (E.) ; [214°] (H.). 
 
 Formation. — 1. By oxidation of di-bromo- 
 toluene [39°] from di-bromo-^J-toluidine [73°] 
 (Nevile a. Winther, O. J. 37, 437).— 2. From 
 »n-di-bromo-benzene by nitration and treatment 
 with alcoholic KGy at 250° (V. v. Eiohter, B. 8, 
 1423). — 3. From di-brominated ^J-amido-benzoio 
 acid (BoDstein a. Geituer, A. 139, 4).— 4. From 
 C,H,Br(NH,)C02H, aqueous HBr (S.G. 1-48), 
 glacial acetic acid and NjOg at 15° (Hesemann 
 a. Kohler, A. 222, 171). 
 
 Pnperties. — Plates (from aloobol) . Needles 
 (from other solvents). 
 
 Salts.— BaA'2 4aq. - CaA'j 5aq — OdA'j4afl^ 
 — CaA'j 6aq. — NaA' aq.— CdA'j 4aq. 
 
 Di-bromo-benzoic acid CsHaBrjCOjH [l:3:a!]. 
 [223°-227°]. Formed by heating benzoic acid 
 with Br and water at 220° (Angerstein, A. 
 158, 10). Needles.— BaA'2 2aq. 
 
 Di-bromo-benzoic acid C8HaBr2C0,jH [1:2:4]. 
 [229°-230°] (B.) ; [238°] (N. a. W.). 
 
 Formation.—!. CsHaBr(NH;)C02H [4:3:1] is 
 treated with ether and N^Oj and the diazo- deri- 
 vative treated with HBr (Burghard a. Beutnagel, 
 
 A. 222, 184).— 2. By oxidising the corresponding 
 di-bromo-toluene from brominated jp-toluidine 
 (Nevile a. Winther, 0./. 37,439).— 3. A product 
 of the action of Br on^-nitro-benzoic, or (1, 2, 4)- 
 di-nitro-benzoic, acid (Halberstadt, B. 14, 908, 
 2215). 
 
 Properties. — Colourless needles (from water), 
 tables (from alcohol). 
 
 S alts.— BaA'2 4aq.— SrA'2 4aq.— HOCuA'.— 
 AgA'.— KA'Kaq. 
 
 Ethyl ether EtA'. [38°]. 
 
 Amide G^B^BrfOlSB^. [151°-152°]. 
 
 Tri-bromo-benzoic acid CjH2Br3(C02H). 
 [235°]. From m-bromo-benzoio acid and Br 
 (Eeineoke, Z. [2] 5, 110). Tufts of slender silky 
 needles; v. si. sol. water. — NHjA'. — CaA'^Saq. 
 
 Tri-bromo-benzoic acid CsHjBraCOjH. 
 [1:3:5:6]. [187°]. Fromtri-brominatedm-amido- 
 benzoic acid (Vollbreoht, B. 10, 1708). Needles. 
 — BaA'2 SJaq. 
 
 Tri-bromo-benzoic acid CjH^BrsCOjH. [195°]. 
 From (1, 2, 4) -di-bromo-benzoic acid [229°] by 
 nitration, reduction, and diazotisation (Smith, B, 
 10, 1706). Needles (from alcohol).— BaA'2 5aq. 
 
 Tri-bromo-benzoic acid OsH^Brs.COjH. [178°]. 
 From(l,4,5)-bromo-amido-benzoio acid (Lawrie, 
 
 B. 10, 1705). Needles.— BaA'j3aq. 
 Feuta-bromo-beuzoic acid CjBraOO^H. [235°]. 
 
 From tri-bromo-benzoio acid and Br at 200° 
 (Reinecke, Z. [2] 5, 110). Thin plates or flat 
 needles (from alcohol) ; thick needles (from benz- 
 ene) ; V. si. sol. water. — NHjA'. — OaA'^ 6aq. 
 
 Nitrile CfivfiT^i. [above 300°]. Obtained 
 by brominating benzonitrile (Merz a. Weith, B, 
 16, 2892). 
 
 o-BBOMO-BENZOIG ALDEHYDE 
 CjHjBr.CHO [1:2]. A heavy oil; formed by 
 boiling o-bromo-benzyl bromide with aqueous 
 lead nitrate (Jackson a. White, Am. 3, 33 ; P. Am, 
 A. 15, 269). 
 
 w-Bromo-benzoic aldehyde CjH^Br.CHO [1:3]^ 
 Oil (J. a. W.). 
 
 p-Bromo-benzoic aldehyde CjHjBr.GHO [1:4]^ 
 [57°] (Jackson a. White, B. 11, 57). 
 
 BBOMO-BENZOIC SULFHINIDE v. Bbomo. 
 
 SDLPHO-BENZOIC ACID. 
 
 BROMO - BENZOPHENONE G,.,l^BiO i.e. 
 CaH,.CO.GjHjBr. [81-5°]. From benzoic acid, 
 bromo-benzene and PjOj at 190° (KoUarits a. 
 Merz, B. 6, 547). 
 
 BROMO-BENZOYL CHLORIDE v. Chloride oj 
 
 BbOMO-BENZOIO AOID. 
 
 BROMO-DI-BENZYL v. Bromo-di-ehenxl- 
 
 ETHANE. 
 
 O-BROMO-BENZYL ALCOHOL C,H,BrO i.e. 
 C,H,Br.GH2.0H. [80°]. Prepared by digesting 
 o-bromo-benzyl acetate with aqueous ammonis 
 at 160°. Crystallises in white needles. SoL 
 hot water, ligroiu, alcohol, ether, benzol, and CS- 
 
BROMO-BUTANE. 
 
 65S 
 
 Volatile with steam (Jackson a. White, Am. 2, 
 316; J?. 13, 1218). 
 
 TO-Bromo-benzyl aloohol CjH^Br.CHjOH. 
 From m-bromo-benzyl bromide and water at 130° 
 (J. a. W.). 
 
 p-Bromo-benzyl alcohol OgHjErCHjOH. [77°]. 
 Prepared by boiling ^-bromo-benzyl bromide 
 with water for 3 days. Long elastic trans- 
 parent needles. Sol. aloohol, ether, benzene, and 
 CSj (Jackson a. Lowery, Am. 3, 246 ; B. 10, 1209). 
 
 o-BROMO-BENZYL-AMINECBH^Br.CHiNHj. 
 Prepared by acting on o-bromo-benzyl bromide 
 with alcohoUo ammonia at 100° for 2 hours 
 (Jackson a. White, Am. 2, 318). Colourless oil ; 
 sol. ether. Salts.— B'HCl : [208°]; needles.— 
 B'jHjPtCle.— B'jHjCOa. [95°]. 
 
 p . Bromo - benzyl - amine CuHjBr.CH^NHj. 
 From p-bromo-benzyl bromide and cold alco- 
 hoUo NHj (Jackson a. Lowery, Am.S, 251). Oil ; 
 volatile with steam.— B'HCl [160°].— B'jH^PtCl,. 
 — B'jHsCOa [131°-133°J : small prisms. 
 
 Bi-o-bromo-di-benzyl-amiue 
 (C8H,Br.CH2)2NH. [36°]. From o-bromo-benzyl 
 bromide and alcoholic NH3 at 100°. Trimetrio 
 crystals; insol. water (Jackson a. White, Am. 
 2, 318 ; B. 13, 1219).— B'HCl [166°].-B'2H2PtCl„. 
 
 Di-p-bromo-di-benzyl-amine 
 (CeHjBr.CHj)j,NH. [50°]. — B'HCl [183°].— 
 B'jHjPtCl. (J. a. W.). 
 
 Tri-o-bromo-trl-benzyl-amine(CjH4Br.CH2)3N. 
 [122°]. From o-bromo-benzyl bromide and al- 
 oohoUc NH3 at 100° (J. a. W.). Small prisms.— 
 B'jHjPtCl,. 
 
 Tri-p-bromo-tri-benzyl-amine(CsHjBr.CH2)3N. 
 Crystals (from ligroin) [92'] ; (from ether) [78°]. 
 Slender needles ; the hydrochloride could not 
 be obtained.— B'HBr. [270°]; insol. water.— 
 B'jH^PtCla (Jackson a. Lowery, Am. 3, 252). 
 
 o-BBOKO-BENZYL BBOMIDE 
 CsH^Br.CHjBr [1:2]. [30°]. (250°-260°). Di- 
 bromo-toluene. Prepared by brominating 0- 
 bromo-toluene (Jackson, Am. 1, 93 ; 2, 315 ; B. 
 13, 1218). Very pungent ; volatile with steam. 
 Converted in ethereal solution by Na into an- 
 thracene, phenanthrene, s-di-phenyl-ethane, and 
 other products. 
 
 m-Bromo-benzyl bromide CjH^Br.OHjBr [1:3]. 
 [41°]. From jre-bromo-toluene and Br (Jackson, 
 Am. 1, 93 ; B. 9, 932). Pungent plates ; slightly 
 volatile with steam ; very volatile with ether- 
 vapour. 
 
 jp-Bromo-benzyl bromide CsHjBr.CHjBr [1:4]. 
 [62°]. Formed by brominating ^-bromo-toluene 
 or benzyl bromide (Jackson, Am. 1,93; Schramm, 
 B. 17, 2922 ; 18, 350). Needles (from alcohol) ; 
 volatile with steam; very pungent. Alcoholic 
 KOH forms ^-bromo-benzyl aloohol and p- 
 bromo-benzoio ether (Elbs, J. pr. [2] 34, 840). 
 
 BEOMO-BENZYL CYANIDE v. Nitrile of 
 
 BnOMO-PHENYL-ACETIO ACID. 
 
 BBOMO-BENZYIIDENE-PHTHAIIMIDINE 
 CijHioONBr. PMhaUmidyl-hromo-benzyl. [210°]. 
 Glistening needles. Formed by the action of 
 bromine upon deoxybenzoin-oarboxylamide 
 CsHiCO.NH2).CO.CH,.CBH5 dissolved in chloro- 
 form (Gabriel, B. 18, 2435). 
 
 TETBA-BBOMO-BENZYLIDENE-DI-TOLYL- 
 DL4MINE (PhCH)j(NCsH^rjMe)2. [160°-165°]. 
 From benzylidene-di-2)-tolyl-diamine and Br 
 (Mazzara, G. 10, 370). 
 
 jj-BBOMO-BEMZYI MEBCAPTAN 
 C^H^Br. CH,SH. [25°]? From ^-bromo-benzyl 
 bromide and alcoholic KHS (Jackson a. Harts- 
 horn, Am,. 5, 268). Crystalline mass ; insol. 
 water and glacial HOAc ; sol. alcohol, ether, and 
 benzene.— Hg(SC,H|iBr)j: sol. hot alcohol. 
 
 DI-BEOMO-BENZYL-PHENOL C.jHJJrj.OH. 
 [175°]. From benzyl-phenol in CS^ and Br 
 (Paterno a. Fileti, &. 3, 254). Amorphous. 
 
 BBOMO-o?-BENZYL-PHENOL STILPHONIC 
 ACID C,H,.0sH2(0H)BrS0,H. Salt .— KA'.From 
 Br and C,H,.C,H3(OH)S03K(Eennie, 0.7.49,409). 
 
 Bromo.^-benzyl-phenol sulphonic acid 
 C,H,.C5Hi,(0H)Br.S03H [l:4:x:2]. 
 
 Salt.— KA' (Eennie, C. J. 41, 35). 
 
 p-BBOmO-BEITZYL STTLPHIDE 
 (OsH4BrCH2)3S. [59°]. Prepared by boiling 
 jp-bromo-benzyl bromide with alcoholic Na^S. 
 Large thin plates. Aromatic odour. Insol. 
 water. Sol. ether, benzene, and CS^ (Jackson 
 a. Hartshorn, Am. 5, 267). 
 
 p-Bromo - benzyl disulphide (C5H4BrOH2)2S2 
 [88°]. Prepared by exposing the mercaptan to 
 air, and also by acting on ^- bromo -benzyl 
 bromide with alcoholic Na^S. Needles. Insol. 
 water ; sol. ether, benzene, and CSj (Jackson a. 
 Hartshorn, Am. 5, 269). 
 
 j)-BB0M0-BENZYL SULPHOCYANIDE 
 CsHjBr.SCN. [25°]. From p-bromo-benzyl 
 bromide and potassium sulphocyanide. Xhe 
 o-isomeride is an oil (Jackson a. Lowery, B. 10, 
 1209 ; Am. 3, 250). 
 
 DI-p-BROMO-DI-BENZYL STJLPHONE 
 (CjHjBr.CH2)2S02. [189°]. From the sulphide 
 and CrO, in HOAc. Needles (Jackson a. Harts- 
 horn, Am. 5, 269). 
 
 BBOMO- BENZYL SULFHONIG ACID v. 
 
 BbOMO-TOLUENE SCIiPHONIO AOID. 
 
 DI-BROmO-BETORCIN CsBr2Me3(0H)j[155°] . 
 From tetra-bromo-betoroin and HI. Also by 
 boiling a mixture of betorcin (3 pts.), bromine 
 (8 pts.) and CSj (100 vols.). The product is re- 
 crystallised from light petroleum (Stenhouse a. 
 Groves, C. 3. 37, 401). Long needles. 
 
 Tetra-bromo-betorcin CsBr2Me2(0Br)2. [101°]. 
 From bromine (5 pts.), water (100 vols.) and 
 betorcin (1 pt.). Dissolved in water (50 pts.). 
 Crystallised from light petroleum (S. a. G.). 
 
 Large colourless prisms. V. sol. ether, benz- 
 ene and OS2, less so in petroleum. 
 
 BROMO - BBASILIN CisHuBrOj. Obtained 
 by brominating acetyl-brasUin and saponifying 
 the product. Glistening red plates. V. sol. 
 water. Dissolves in KOH with a red colour. 
 
 Tetra-acetyl derivative 
 C,„H3Br(OAc)40. [204°] (Buchka a. Erok, B. 
 17, 685 ; 18, 1140). 
 
 Tri-bromo-brasilin CuHnBrsOj. 
 
 Tetra-acetyl derivative 
 C,5H,Br3(OAo)40. [147°]. Small white needles ; 
 very oxidisable (B.a. E.). 
 
 Tetra-bromo-brasilin C,sH,„Br,05. Slender 
 red needles. Dissolves in alkalis with a violet 
 colour. Obtained by bromination of brasilin. 
 
 Tetra-acetyl derivative 
 0,3H,Br,(0Ac)A [222°] (B.a. E.). 
 
 BBOUCO-BUTANE v. Butyl beomide. 
 
 M-o-Di-bromo-butane C^HgBr^ i.e. 
 CH2Br.CHBr.CH2.CHs. Butylenehrcmide. (166°). 
 S.G. =5" 1-820. Formed by the action of Br on «- 
 butylene or w-butyl bromide (Wurtz, A. 162, 23, 
 
500 
 
 BROMO-BUTANE. 
 
 Linnemann, A. 161, 199; Grabowsky a. Saytzeff, 
 
 A. 179, 332). Na forms CH^iCH.OH^CH,. 
 o/8-Di - bromo - butane OH3.OHBr.CHBr.CHs. 
 
 (158°). S.G.21-82. From CHj.CH-.CH.CH, and 
 Br. Converted by PbO and excess of water at 
 150° into methyl ethyl ketone (Wurtz, A. 144, 
 236 ; Eltekoff, J. B. 10, 219). 
 
 Di-bromo-isobutane (OH3)jOBr.CH2Br. Iso- 
 butylene bromide. (149°). S.G. 14 1-8; if 
 1-7434 ; If 1-7308. M. M. 11-890 at 14-7° 
 (Perkin). From isobutyleue and Br (Linne- 
 mann, A. 162, 36). By heating with excess of 
 water at 150° it is converted into isobntyric 
 aldehyde ; if PbO is also present some di-oxy- 
 isobutane is also formed (Eltekoff, J. B. 10, 214). 
 
 Di - bromo - butane C^HsBrj. (155°-162°). 
 Formed by brominating butane (Carius, A. 126, 
 215). 
 
 Tri-bromo-isobntane OjHiBra i.e. 
 (CHjBr)2CBr.CH3. (178°-183°) at 235 mm. 
 S.G. }| 2-15. From isobutylene and Br (Norton 
 a. Williams, Am. 9, 88). 
 
 Tri-bromo-isobutane C4H,Br3 i.e. 
 (CHjj^CBr.CHBr,. (155°-161°) at 235 mm. 
 From (CH3)2C:CHBr and Br (N. a. W.). 
 
 Tri - bromo - butane C^HjBrj. (208°-215°). 
 From bromo-butylene (82°-92°) (Caventou, A. 
 127, 93). 
 
 Tetra-bromo-butane 
 C,HsBr4i.e.CHjBr.CHBr.CHBr.CH2Br.BM<me)ie- 
 or pyrrdlylene- tetra-bromide. [119°]. Formed 
 by combination of bromine with the bntinene 
 from di-methyl-pyrrolidine or from erythrite. 
 From erythrite, vinyl-ethylene, or gas oils (Caven- 
 tou, A. 127, 95 ; B. 6, 70; Henninger, B. 6, 70 ; 
 Grimaux a. Cloez, C. B. 104, 1446; Bl. [2] 
 48, 81). From the gas obtained by passing 
 acetylene mixed with ethylene through a red-hot 
 tube (Prunier, Bl. [2] 20, 72). On distillation it 
 is partially converted into the following body. 
 Colourless needles (from alcohol). Insol. cold 
 petroleum-ether (Ciamician a. Magnaghi, B. 19, 
 669). 
 
 Tetra-bromo-butane CH3.CBr2.CBr2.CH3 (?) 
 [40°]. Erythrene isobromide. Erythrite tetra- 
 bromhydrin. Formed, together with the iso- 
 meride [119°], by combining butinene from 
 erythrite with bromine. Large colourless tri- 
 metric prisms or tables, a:6:c = -9776:1:1-682 
 (Ciamician a. Magnaghi, B. 19, 569). V. sol. 
 ether, alcohol, and petroleum-ether. Alcoholic 
 KOH converts both this and the preceding into 
 the same di-bromo-butinene C^HjErj, which 
 rapidly polymerises. The latter absorbs Br, 
 forming C^H^Br^ [67°] and C^H^Br^ [170°]. 
 
 Tetra-bromo-butane CjHjBr,. From Br and 
 di-bromo-butylene (140°-150°) from fusel oil 
 vid butylene (Caventou, A. 127, 93). Crystalline ; 
 decomposes at 200°. 
 
 Tetra-bromo-butane CHs.CHj.CBrj.CHBrj. 
 From butinene prepared from methyl ethyl 
 ketone by successive treatment with PCI, and 
 alcoholic KOH. Sublimes at 105° (Bruylants, 
 
 B. 8, 410). 
 
 Tetra-bromo-isobutane CjHjBr,. [205°]. 
 From di-bromo-isobutylene (155°) (Norton a. 
 Williams, Am. 9, 87). 
 
 Hexa-bromo-butane C^H^Br^. [109°]. Ob- 
 tained by brominating isobutyl bromide at 170°. 
 The yield ia 90 p.c. of the theoretical (Merz a. 
 VVeith, B. XI, 3245). 
 
 Hexa-tromo-butane 0,HjBrj i.s. 
 Br3.CHBr.CHBr.CH2Br. S.G. 1^ 2-9. Formed, 
 together with the following, by heating erythrits 
 tetrabromhydrin with Br at 180° (Colson, Bl. 
 [2] 48, 52). Liquid; v. sol. ether, si. sol. 
 alcohol. Dilute KOH at 130° converts it into 
 potassium erythrate. 
 
 Hexa-bromo-butane CjH^Brs. [170°]. S.G. 
 3-4. Formed in small quantity as above (C). 
 Pearly scales, si. sol. ether and alcohol. Fuming 
 HNO3 forms an oil C4H3(NO,)Br2(NO,)j, S.G. 1-81. 
 
 Di-BROMO-BITTYL ALCOHOL C^HsBr^O., i.e. 
 CHj.CHBr.CHBr.CHsOH. Oil. From butenyl 
 alcohol CH3.CH:CH.CH20H and Br (Lieben a. 
 Zeisel, M. 1, 828). Boiling water forms tri-oxy- 
 butane. 
 
 eoa-DI-BROMO-n-BUTYL-BENZENE 
 C,„H,2Brj i.e. CeHs.CH^.CHj.CHBr.CHjBr. From 
 phenyl-butylene and Br (Aronheim, A. 171, 229). 
 Oil. Reactions. — 1. Bed-hot soda-lime forms 
 naphthalene. — 2. HNO, forms a little bromo- 
 phenyl-propionio acid. 
 
 187-Di-bromo-jt-butyl-benzene 
 OsH5.CHBr.CHBr.CH2.CHs. [67°]. From 
 butenyl-benzene and Br (Perkin, 0. /. 32, 668). 
 
 •)T-Di-bromo-«-butyl benzene 
 CeH5.CBr2.CH2.CHj.CH3 (?). From butyl-benz- 
 ene and Br in sunlight. Unstable oil (Schramm, 
 B. 18, 1276). 
 
 Di-bromo-n-butyl-benzene CjjHijBrj. [70°]. 
 From ra-butyl-benzene and Br first in sunlight, 
 then heated in the dark (Badziszewski, B. 9, 
 261). 
 
 a^-Bl-bromo-isobutyl-benzene 
 CsHs.CHBr.CBrMej. From phenyl-isobutylene 
 and Br (Perkin, C. J. 35, 138). 
 
 Tri-bromo-lsobutyl benzene C,„H,iBr3. [64°]. 
 From the preceding by successive treatment 
 with alcoholic KOH and Br (P.). 
 
 BROMO-BTTTYLEHE C,H^r i.e. 
 (CH3)2C:CHBr. (91°). Isocrotyl bromide. From 
 isobutylene bromide and alcoholic KOH 
 (Butlerow, Z. 1870, 524). AlcohoUc KOH at 
 170° forms (CH3)2C:CH.OEt. Moist Ag20 at 
 100° gives isobutyric acid. NHj has no action. 
 
 Bromo-butylene C^HjBr. (82°-92°). From 
 fusel oil butylene by successive treatment with 
 Br and alcoholic KOH (Caventou, A. 127, 93). 
 
 Bromo-butylene C,H,Br. .(87° i.V.). From 
 di-bromo-methyl-ethyl-aoetio acid and aqueous 
 Na,COs (Jaff6, A. 135, 300 ; Pagenstecher, A. 
 195', 126). 
 
 Bromo-butylene C^HjBr. (97°). Formed by 
 boiling the di-bromide of angelic acid with water 
 (Jaii6, A. 135, 300). 
 
 Di - bromo - iso - butylene CjHjBr2. (155°). 
 From tri - bromo - iso - butane (165°-161°) at 
 235 mm. (Norton a. Williams, Am. 9, 87). 
 
 Di-bromo-butylene G,B.^Bi:^. (140°-150°). 
 From tri-bromo-butane (208°-215°). Forms a 
 crystalline di-bromide CjH^Brj which decomposes 
 without melting at 200° (Caventou, A. 127, 93). 
 
 Di-bromo-butylene C,H„Brj. (148°-158°). 
 From orotonylene and Br (Caventou, A. 127,349). 
 
 Di - bromo - butylene CjHjBrj. From tetra- 
 bromo - butane [119°] (from erythrite) and alco- 
 holic KOH. Eapidly polymerises. Combines 
 readily with bromine (Grimaux a. Cloez, Bl. [2] 
 48, 31). 
 
 Di - bromo - butylene C^RJiv^ i.e. 
 CH2:CH,CHBr.CH2Br. (190°-200°). From the 
 
BROMO-CARBANTLIC ACID. 
 
 661 
 
 oilB deposited by compressed gas, by adding 
 less than the calculated quantity of Br and 
 fractionally distilling. Combines readily with 
 Br, forming C,H,Br^ [119°] (G. a. C). 
 
 Hexabromobutylene CBr^Hj. [53°]. Pre- 
 pared by further bromination of hexabrom- 
 isobutane (Merz a. Weith, B. 11, 2240). 
 
 o-BROMO-n-BUTYEIC ACID C.HjBrOj i.e. 
 CH,.CH,.CHBr.C02H. (214°-217°). (110°) at 
 3 mm. S.G.15 1-54. S. 7. 
 
 Formation.— 1. By heating butyric acid with 
 Br at 140°; or by the action of Br on silver 
 butyrate (Friedel a. Machuca, A. 120, 279 ; 
 Suppl. 2, 70 ; Gorup-Besanez a. Klinksieck, A. 
 118, 248; Naumaun, A. 119, 115; Ley, J. R. 
 9, 129 ; Urech, A. 165, 93 ; TupolefE, A. 171, 
 249). — 2. From crotouio acid and HBr. — 
 3. From the bromide and water (Easchirski, 
 C. C. 1881, 278). 
 
 Properties. — Oil ; mixes with alcohol and 
 ether. NEtj, whether dry or in aqueous solu- 
 tion, forms a-oxy-butyrio acid (Duvillier, Bl. [2] 
 48, 3). NaOHAq acts similarly. 
 
 Salts .— PbA'j.— PbA',. 2PbO.— AgA'^. 
 
 Methyl ether MeA'. (165°-172°). 
 
 Ethyl ether EtA'. (178°) (Lov6n, /. pr. 
 [2] 33, 102). S.G. la 1-345. Dry NaOEt forms 
 an ether CsHi^OiOEt). (252°) (Krestownikoff, 
 
 A. 208, 348). 
 
 Bromide CHsBrO.Br. (173°). From 
 butyryl bromide and Br. 
 
 3-Bromo-butyric acid CH3.CHBr.CH2.COjH. 
 Formed in small quantity in the preparation of 
 the a- acid from crotonio acid and HBr (Hemi- 
 lian, A. 174, 325). 
 
 7-Bromo-butyrio acid OHjBr.CHj.CH.i.COjH. 
 [33°]. From butyro -lactone and HBr (Henry, 
 O. B. 102, 368). Tables or plates; si. sol. 
 water, v. sol. ether. 
 
 Methyl ether MeA'. (187°). S.G.si-45. 
 
 Ethyl ether 'E.ik'. (197°). S.G.si-36. 
 
 o - Bromo - isobutyric acid (CH3)2CBr.C02H. 
 [48°]. (199°). S.G. |2 1-52. From isobutyric 
 acid and Br (Markownikoff, A. 153, 229 ; Hell 
 a. Waldauer, B. 10, 448). Tables. Boiling 
 water converts it into a-oxy- isobutyric acid, 
 KHS acts similarly (Lovfo, J. pr. [2] 33, 105) ; 
 boiling baryta-water forms also CHjiCMe.COjH 
 (Engelhom, A. 200, 68). 
 
 Ethyl ether MA.'. (164° cor.). S.G.21-13. 
 Oil; smelling of raspberries and peppermint 
 (Markownikoff, A. 182, 336 ; Hell a. Wittekind, 
 
 B. 7, 320 ; Lovto, J. pr. [2] 33, 106). 
 Bromide (CH3)jCBr.C0Br. (163°). 
 fl.Bromo-isobutyric acid CHjBr.CHMe.COjH. 
 
 [22°]. From a -methyl -acrylic acid and cold 
 cone. HBr. Crystals (from CSj). Boiling 
 alkalis convert it into a- methyl -aoryUo acid 
 and a little propylene (Fittig a. Engelhom, A. 
 200, 65). 
 
 aa-Di-bromo-butyric acid 
 CH3.CHj.CBrj.COjH. (140°) at 8 mm. S. 3. 
 S.G. 1'96. From bromo-butyrio acid and bro- 
 mine (Schneider, J. 1861, 458 ; Michael a. 
 Norton, Am. 2, 15 ; Otto a. Fromme, A. 239, 
 275). Thick oil. Water or baryta-water at 
 120° forms o-bromo-crotonio acid (Erlenmeyer 
 a. Miiller, B, 15, 49). Converted by reduced 
 silver into di-ethyl-maleio or xeronio acid 
 C0jH.CEt:CEt.C0jH, butyric acid being formed. 
 
 Vop. I. 
 
 a^-Bi-bromo-butyrio aoid 
 CH3.CHBr.CHBr.COjH. [87°]. 
 
 Prepa/ration.— ¥1010. Br and crotonio or iao< 
 crotonio acid dissolved ia CSj (KOrner, A. 137, 
 2.S4 ; Michael a. Norton, Am. 2, 12; B. 14, 1202; 
 0. Kolbe, J.pn 133,386). 
 
 Properties. — Large transparent prisms (from 
 OSj) ; sol. alcohol, ether, and hot water. 
 
 Reactions. — 1. Boiled with water or NajOO, 
 it gives i3-bromo-propylene, bromo-oxy-butyrio 
 acid, di-oxy-butyric aoid, and bromo-orotonio 
 aoid. Water gives chiefly bromo-oxy-butyrio 
 acid ; NajCOj gives more bromo-propylene, but 
 no propionic aldehyde. — 2. Warmed with a 
 solution of NaOH it gives bromo-crotonio aoid. 
 
 Di-bromo-iso-butyric acid 
 CHjBr.CBrMe.OOjH. [48°]. 
 
 Preparation,. — By adding Br to methacrylio 
 aoid dissolved in CSj (C. Kolbe, /. pr. [2] 25, 
 373). Long prisms (from CSj). Boiling with 
 water or NajCOj produces COj, acetone, some 
 propionic aldehyde, a very little bromo-meth- 
 aorylic acid [63°],andbromo-oxy-iso-butyrio acid 
 (q.v.). Warmed with solution of NaOH it gives 
 bromo-methacrylic acid and HBr. 
 
 Tri-bromo-butyrio aoid GJH^BTsO^ i.e. 
 CH3.CBr2.CHBr.COjH? [114°]. From i8-bromo. 
 crotonio acid in CSj and Br (Michael a. Norton, 
 Am. 2, 14). Ehombio plates ; sol. alcohol and 
 hot water ; sublimes readily. 
 
 Tri-bromo-bntyric acid C4HjBr30j i.e. 
 CH3.CHBr.CBrj.COjH7 [111°]. From o-bromo- 
 orotonic aoid and Br. V. sol. water and alcohol 
 (M. a. N.). 
 
 Tri-bromo-isobutyric acid CjH^BrjOj. From 
 bromo-o-methyl-acrylic acid and Br (Cahours,.4. 
 Suppl. 2, 349). Prisms. 
 
 Tetra-bromo-butyrio acid OjHjBrjOj. [116°]. 
 From mucobromio acid and Br (Limpricht, A. 
 165, 293). Monoclinio tables ; si. sol. water. 
 
 Tetra-bromo-isobutyric acid CjHjBr.Oj. 
 From di-bromo-a-methyl-acrylio acid and Br(C.). 
 
 BROMO-ISO-BTJTYRIC ^ara-ALDEHYDE 
 ((CH3)jCBr.CH0)„. [129°]. _ When the product 
 of the action of NH, on iso-butyrio aldehyde 
 (q.v.) is distilled a product CjH.sN is got. This 
 must be combined with bromine, and the com- 
 pound, (CH3)jCH.CH:N.CHBr.CBr(CH3)j, after 
 keeping for 3 months, is decomposed by water 
 (Lipp, A. 211, 353). Needles (from alcohol). 
 Insol. water, acids or alkalis, v. sol. ether, m. 
 sol. alcohol. Does not reduce ammoniacal AgNOj. 
 
 BEOMO-CATECHOI v. Bkomo-pirooateobin. 
 
 BROMO-CAFFEINE CgHjBrN^O,. [206°]. 
 Caffeine combines with Br forming the orange- 
 red bromide GgH^„'S fl^BTj., which is decomposed 
 at 150° into HBr and bromo-caiieine (Fischer, 
 B. 14, 639 ; Sohultzen, Z. 1867, 614 ; Maly a. 
 Andreasch, M. 3, 85). Crystals, si. sol. cold water, 
 V. sol. NHjAq. Beduoed by zinc-dust to caffeine. 
 Alcoholic KOH forms ethoxy-caffeine. 
 
 BROMO-CAMPHOR v. Camphoe. 
 
 BROMO-CAMFHORIC ACID v. CAUPHOBia 
 Acm. 
 
 BROMO-CAFRIC ACID v. Bbouo-dhcoic acid. 
 BROMO-CAFROIC ACID v. Bbomo-eexoio 
 
 ACID. 
 
 BROMO-OARBAinLIC ACID v. Fhsn^l-cak- 
 
 BAMIO AOID. 
 
 9Q 
 
662 
 
 BROMO-OARBAZOLE. 
 
 BROMO-CAEBAZOLE C,jH,BrN. [199°]. 
 From its acetyl derivative and alcoholic KOH. 
 Ehombio plates, v. sol. water. 
 
 Acetyl derivative C,jH,AcBrN. [128°]. 
 From acetyl-oarbazole and Br. Laminae, v. sol. 
 alcohol and boiling toluene (Ciamician a. Silber, 
 Q. 12, 276). 
 
 TEI-BEOMO-CARBOPYEROLIC ACID v. Tbi- 
 
 BBOMO-PYKEOIi-CAKEOXTLIC ACID. 
 
 7-BEOMO-CARBOSTYEIL CsH.NOBr i.e. 
 /0(Br):CH 
 CeH,<^ I . (Py. 1, 3)-Bromo-oxy- 
 
 \N: C(0H) 
 quinoUne. [266°J. Formed by boiling o-amido- 
 phenyl-propiolio acid with dilute HBr (Baeyer a. 
 Bloem, B. 15, 2149). Prepared by the action of 
 bromine on carbostyril-ether and saponification 
 of the product by heating with HCl (Friedlander 
 a. Weinberg, B. 16, 2682). Needles ; may be 
 sublimed. The Br is not replaced by boiling 
 with alcoholic KOH, but requires to be fused 
 with KOH at 200°C. 
 
 BEOMO - CARVACROL C.jH.jBrO i.e. 
 OeH2Me(OH)Br(03H,) [l:2:3or5:4]. Frombromo- 
 cymidine and HNOj. Oil (Mazzara, 0. 16, 194). 
 
 BEOMO-CHLOBAL v. Di-ohlobo-bbomo-alde- 
 
 HYDE. 
 
 BEOMO-CHLOEO- v. Chloko-eromo-. 
 
 BROMO-CHLOROrORM v. Diohloko-beomo- 
 uethane. 
 
 BROnO-DICHROMAZIX v. Tbi-amido-phe- 
 voi., p. 172. 
 
 BBOMO-CHRYSENE v. Chbysene. 
 
 BROMO - CHRYSOQTTINONE v. Chbtbo ■ 
 
 OTINONE. 
 
 BROMO-CIKCHONINE v. Cikchonine. 
 
 BROMO-CINNAMENE v. Beomo-styeene. 
 
 DI - BROMO - CINNAMENYL - THIENYL - 
 KETONE V. Thientl- m-BEOMo-STYEYL ketone. 
 
 o-BROMO-CINNAMIC ACID CjHjBrOj i.e. 
 CjHs.CH-.CBr.COjH [131°]. 
 
 Formation. — 1. Together with aZZo-o-bromo- 
 cinnamio acid by the action of alcoholic 
 KOH on the di-bromide of cinnamio acid 
 O3H5.CHBr.CHBr.CO2H (Glaser, A. 143, 325).— 
 2. From ea;o-tri-bromo-;8-phenyl-propionio acid 
 and water at 100° (Kinnicutt a. Palmer, Am. 4, 
 26 ; 5, 386). 
 
 Preparation. — Dibromide of cinnamic acid 
 (SO grms.) is dissolved in hot alcohol and mixed 
 with the calculated quantity (2 equivalents) of 
 potash dissolved in alcohol. The liquid is neu- 
 tralised with HCl and the alcohol boiled off. 
 The solution of the mixed potassium salts is 
 filtered from bromo-styrene [218°]. The two 
 acids are separated by partial precipitation with 
 HCl, the o-aoid coming down first (Barisch, 
 J. pr. 128, 178). 
 
 Properties. — Long needles (from water or 
 chloroform). V. e. sol. alcohol. 
 
 Salts. — NH,|A': arborescent groups of flat 
 needles, si. sol. cold water. — AgA' : si. sol. water. 
 — BaA'2 : thin rhombic laminse. S. "12 at 6°. 
 Insol. alcohol. 
 
 iJeuctiows. — 1. Sodiwm-amalgam, reduces it to 
 fl-phenyl-propionic acid. — 2. Alcoholic KOH 
 gives phenyl-propiolic acid. — 3. Br gives a tri- 
 bromo-phenyl-propionio acid [132°]. — 4. Both a 
 and allo-a-bromo-oiunamic acids may be.reduced 
 by zinc-dust and glacial acetic acid to cinnamio 
 acid, which seems to b» the same in both cases 
 
 (Michael, X pr. [2] 85, 857). — 6. Is not altered 
 by dissolving in HjSO, and pouring into water. 
 
 Methyl ether A'Me : (159°) at 14 mm. 
 Formed by distillation of the isomeric methyl 
 ether corresponding to the acid [120°] under 
 ordinary atmospheric pressure (A. a. S.). 
 
 Ethyl ether A'Et: (290°); (202°) at 30 
 mm.; (160°) at 10 mm.; (188°) at 30 mm. V.D. 
 = 8-715 (obs.) (Michael a. Browne, B. 20, 551). 
 Formed by distillation of the isomeric ethyl- 
 ether corresponding to the acid [120°] under 
 ordinary atmospheric pressure (Anschiitz a. Sel- 
 den, B. 20, 1384). Prepared by passing HCl 
 into a solution of the acid in alcohol (4 pts.) 
 (Barisch, loc. cit.). By cold oonc. H^SO, it is 
 converted into benzoyl-acetic ether (Michael a. 
 Browne, B. 19, 1392). 
 
 Chloride: (153°) at 12 mm.; clear oily 
 liquid. Formed by the action of PCI5 upon salts 
 of the acid [131°] or of its isomeride [120°]. 
 
 Amide: [119°]; very thin pearly plates; 
 si. sol. hot water. 
 
 Anilide: [80°]; small white needles, which 
 change into six-sided plates (A. a. S.). 
 
 JBffio-Bromo-cinnamic acid CgHjBrOj. [134°]. 
 Formed, together with the isomeride [159°] by 
 the addition of HBr to phenyl-propiolic acid. 
 Long needles (from water). Thick rhombic 
 prisms (from chloroform). V. sol. alcohol and 
 hot benzene, si. sol. CS^, hot petroleum-ether 
 and hot water. — A'NH/ : flat needles, sol. hot 
 water, si. sol. cold. — A'jBa : glistening rhombic 
 plates; S. -776 at 6°, m. sol. hot water. It is 
 doubtful whether this acid is a distinpt isome- 
 ride or is identical with the preceding acid ; the 
 solubility of the barium salt appears to point 
 to the former conclusion (Michael a. Browne, B. 
 20, 550). 
 
 .12Zo-a-Bromo-cinnamic acid 
 CjH5.CH:CBr.C0jH. [120°]. Formed, together 
 with o-bromo-cinnamic acid (v. Preparation) by 
 boiling the dibromide of cinnamic acid with 
 alcoholic KOH (Glaser, A. 143, 330). Six-sided 
 laminae (from water) or thick prisms (from 
 ether). V. sol. boiling water. 
 
 Salts. — KA': deliquescent needles.— AgA'. 
 The ammonium salt is deliquescent and v. 
 sol. water (difference from a acid). 
 
 Reactions. — 1. Reactions 1, 2, and 4 described 
 under o-bromo-cinnamic acid are also exhibited 
 by the aUo-a- acid. Reaction 3 gives, however, 
 a different tri-bromo-phenyl-propionio acid 
 [45°-48°].— 2. On dissolving in H^SO, and 
 pouring into water two products are obtained : 
 (a) A substance C,gH,,,04 ; yellow needles [above 
 260°], sol, alkalis, alcohol, ether and benzene. 
 (6) A substance OuHijBrjOj ; large pearly plates 
 [above 260°], insol. alkalis, sol. phenol, nitro- 
 benzene and aniline, insol. most other solvents, 
 forms a crystalline molecular compound with 
 phenol ; on reduction with zinc-dust and acetic 
 acid it gives a substance C„H„02 which forms 
 colourless crystals, [127°], sol. alcohol, si. sol. hot 
 water (Leuckart, B. 15, 16). 
 
 Methyl ether A'Me: (146°) at 11mm.; 
 from A'Ag and Mel ; by distillation at ordinary 
 pressure it is converted into the methyl ether 
 of the isomeric acid [131°] (Anschiitz a. Selden, 
 B. 20, 1383). 
 
 Ethyl ether A'Et: (174°) at 80 mm. ; (177°) 
 »t 30 mm.; V.D. - 8-828 (obs.) (Mioha«l t. 
 
BROMO- COMPOUNDS. 
 
 663 
 
 Browne, B. 20, 561). From A'Ag and EtI. By 
 distillation under ordinary pressure it is con- 
 verted into the ethyl ether of the isomerio acid 
 [131°] (Ansohiitz a. Selden, B. 20, 1384), 
 
 ? ;8- Bromo-cinnamic add 
 C,H,.0Br:0H.C02H (?) [159°]. Formed, together 
 with the acid [184°], by the action of aqueous 
 HBr upon phenyl-propiolio acid at 0?. Long 
 flat needles (from water) ; or rhombic plates 
 (from alcohol). SI. sol. cold alcohol and ben- 
 zene. By cold eonc. KOH or NH, it is at once 
 converted into an indifferent insoluble oil. 
 Heating with HBr forms phenyl-acetic aldehyde 
 and acetophenone. It combines with Br form- 
 ing a tri-bromo-hydro-cinnamic acid [148°]. 
 
 Salts. — NHjA'* : long soluble needles. — 
 BaA'uaq: soluble concentric prisms. — PbA'^: 
 amorphous pp. — CdA',: concentric needles 
 (Michael a. Browne, B. 19, 1378). 
 
 Ethyl ether A'Et: (151°) at 15 mm.; 
 V.D. = 8-948 (obs.) (M. a. B., B. 20, 551). 
 
 Bromo-cinnamic acid [153°]. This was ob- 
 tained by Erlemneyer a. Stockmeier by the 
 addition of HBr to phenyl-propiolic acid. Aque- 
 ous Na^COj converted it into phenyl-acetylene, 
 a-bromo-styrene CgHsCBriCHj, and phenyl-pro- 
 piolic acid. Successive treatment with cone. 
 HjSO, and water gave benzoyl-acetic acid and 
 bromo-acetophenone. Heating with HBr gave 
 acetophenone and a little phenyl-acetic aldehyde 
 (Erlenmeyer, B. 19, 1936). According to 
 Michael a. Browne this acid is a mixture of the 
 two acids [159°] and [184°]. 
 
 o-Bromo-cinnamlc acid [1:2] 
 C5H4(Br).CH:CH.C02H. Bromo-P-phmyl-acrylic 
 acid. [213°]. Formed by diazotising o-amido- 
 cinnamic acid and boiling the diazo- compound 
 with HBr (Gabriel, B. 15, 2294). Flat colour- 
 less needles or scales. Sol. alcohol, ether 
 and acetic acid, si. sol. chloroform, benzene 
 and CSj. 
 
 m-Bromo-cinuamic acid 
 [1:3] CsH,(Br).CH:0H.C02H. [179°]. Formed 
 like the preceding from w-amido-cinnamio acid 
 (Gabriel, B. 15, 2296). Long needles. Sol. 
 alcohol, acetic acid, hot benzene, chloroform, 
 and CSj. 
 
 p-Bromo-ciunamic acid 
 [1:4] 05H,(Br).C2Hj.C0jH. [c. 253°]. Fine 
 needles. From p-amido-oinnamic acid (Gabriel, 
 B. 15, 2800). 
 
 Bi-bromo-cinnamic acids CgH^r^Oj i.e. 
 C8H5.CBr:0Br.COjH. Bromine unites with 
 phenyl-propiolio acid producing di-bromo-cin- 
 namio [189°] and allo-di-bromo-oinnamic acid 
 [100°]. The acid [139°] is not converted into 
 an indonaphthene derivative by cone. H^SO^, 
 
 whereas the acid [100°] forms CeBit<i^^j.^ 
 
 [123°] (whence hydroxylamine forms an oxim 
 [195°], and aniline forms an anilide [170°]) 
 (W. Eoser, B. 20, 1278, 1576). 
 
 a-BKOMO-CINNAMIC ALDEHYDE CgH^BrO 
 i.e. 0,H5.CH:CBr.CH0 [73°]. Formed from 
 cinnamic-aldehyde-di-bromide by splitting ofE 
 HBr (Zinoke a. Hagen, B. 17, 1815). Thick 
 tables or large monocUnio prisms. CrO, gives 
 bromo-cinnamic acid [131°]. 
 
 Phenyl-hydraiide 
 OA-C8HBr.OH:NsHC^,X130''],gliBtonlngyollow 
 plates. 
 
 BROMO- CITEACOKIC ACID O.H.BrO. U. 
 0H3.C(COjH) :CBr.C02H(?), 
 
 Formation. — 1. From its anhydride by boil- 
 ing with water. — 2. From cifo-a-di-bromo-pyro- 
 tartario acid, water, and Ag^O in presence of a 
 trace of HCl : CsHsBrjOi = HBr + CsH^BrO^ (Bour- 
 goin, C. B. 88, 342 ; 89, 418 ; A. Oh. [5] 19, 285). 
 
 Properties. — ^Very unstable, giving off water 
 even over H^SOj and changing to the anhydride. 
 
 Beactions, — 1. Sodium amalgam forms pyro- 
 tartario acid. — 2. Boiling KOH forms a syrupy 
 dibasic acid CjHjO,. — 3. Evaporation of its solu- 
 tion produces bromo-citraconio anhydride and, 
 at a low temperature, the acid CsH^Oj, but 
 at a high temperature ' bromo-oitronio acid ' 
 GjH5Br02 (B.). — 4. The aqueous solution treated 
 with the equivalent of aniline gives a crystalline 
 pp. of the acid aniline salt. [121°]. Standing 
 under water for a few hours, or heating the 
 aqueous solution for a minute, converts itinto the 
 
 0(CH,)-CO. 
 phenylimide II >NPh. [145°]. This 
 
 CBr CO / 
 
 forms stellate groups of prismatic needles. SI. 
 sol. hot water ; v. sol. hot alcohol ; insol. dilute 
 HCl (Michael, Am. 9, 180). An intermediate 
 body is the acid aniUde C,H3Br(C02H).CONPhH 
 [212°] (Michael, B. 19, 1373). 
 
 Salts.— (NHJ^A". — K,A". — CaA" 2aq.— 
 CaA" IJaq. — BaA" aq. — AgjA"- Decomposed by 
 water at 130° giving off COj, and allylene. 
 
 Anhydride O^HjBrO,. [100°]. (220°). 
 S.G. "£ 1-935 (Kekul6, A. Suppl. 1, 130 ; 2, 97; 
 Lagermark, Z. 1870, 299 ; Fittig a. Krusemark, 
 A. 206, 19; Bourgoin, Bl. [2] 31, 252; 32, 888). 
 Formation. — 1. From citraconic anhydride and 
 Br at 140°.— 2. By distilling ciira-dibromo-tar- 
 tario acid. — 3. From pyrotartaric acid, Br, and 
 water at 120°. Properties. — Laminse (from CS2); 
 si. sol. cold water, v. e. sol. alcohol and ether ; 
 volatile with steam. 
 
 Imide CjHjBrOjNH. [0. 181°]. From 
 pyrotartrimide or oitraconimide and Br at 150° 
 (Mendini, G. 15, 182). Lamina ; may be sub- 
 limed.— CjHaBrOjNAg. 
 
 Dl-bromo-citraconic acid. Imide. 
 CsHjBrjOjNH. [144°]. From pyrotartrimide 
 or oitraconimide and Br (M.). LamincB ; may 
 be sublimed.— CsHjBrjOjNAg. 
 
 BBODIO-CODEIXE v. Codeini!. 
 
 DI - BKOMO - COLLIDINE v. Di-bbomo-tbi- 
 
 METHYl-PYErDINE. 
 
 BBOMO- COMPOUNDS. Bromine unites 
 directly with most unsaturated compounds, 
 but there are some oases in which it does 
 not combine with them in the cold, e.g. 
 fumaric, mesaconio, teraconio, terebilenio, 
 aconic, 0- andp- coumaric, and (fl)-hydropiperic 
 acids (c/. Fittig, A. 227, 29). Aromatic com- 
 pounds combine with great difficulty with bro- 
 mine, but when reduced to their di- or tetra- 
 hydrides they take up bromine as readily as the 
 ordinary unsaturated compounds. Bromine dis- 
 places hydrogen in saturated compounds, the 
 displaced hydrogen being given off as HBr ; this 
 reaction usually requires the aid of heat: the 
 substance is generally heated with bromine and 
 a little water in a sealed tube, 
 
 Bydroxyl may be displaced by bromine by 
 treatanent with HBr or PBij; instead of PBr, 
 
 008 
 
661 
 
 BROMO- COMPOUNDS, 
 
 red phosphorus and bromine may be used, one 
 ol the two being added gradually. 
 
 Ghlorifie may be displaced by bromine by 
 treatment with the bromide of K, Mg, Ca, Sr, 
 Ba, Al, Mn, or Co (Kohnlein, A. 225, 194). 
 CdBr^, SbBrj and AsBrj sometimes act similarly ; 
 thus AsBrj at 145° completely converts ohloro- 
 acetic acid and benzyl chloride into bromo- 
 Boetic acid and benzyl bromide respectively. 
 
 Iodine may be displaced by bromine by 
 means of the bromides of Cu, Ag, Hg, Sn, Pb, 
 As, and Sb. BiBrs at 160° only partially con- 
 verts EtI into EtBr. Bromine itself can dis- 
 place iodine (E. Meyer, J. pr. [2] 34, 104). 
 
 Amidogen may be displaced by bromine 
 by using the diazo- reactions (p. 399). In aro- 
 matic compounds it is sufficient to add HNO3 to 
 a hot solution of the amine in HBr (Losanitsch, 
 B. 18, 39, V. also AminksV 
 
 Carriers. — The displacement ol hydrogen by 
 Br is assisted by the presence of carriers which 
 first combine with the bromine, and then pass it 
 on to the organic body. The most suitable 
 carriers for bromine are : iodine ; ALBr^ (Gus- 
 tavson, B. 10, 971) for benzene and homologues ; 
 amorphous P for fatty acids (Hell a. Gautter, 
 B. 14, 891), SbBrj, Fe^Brj, FeBr^, and, better 
 still, FeClj (Soheufelen, A. 231, 154 ; cjf. Will- 
 gerodt, J.pr. [2] 34, 2G4). 
 
 Bromination of organic acids. The follow- 
 ing is a very convenient method, which depends 
 upon the fact that the acid bromides and an- 
 hydrides are much more easily brominated than 
 the acids themselves. The acid is mixed with 
 amorphous phosphorus in quantity sufficient to 
 convert it into the bromide or anhydride, and 
 the corresponding quantity of bromine added 
 together with the extra amount required for 
 bromination. The mixture is heated to 100° 
 till decolourised, when the reaction is complete 
 (Hell, B. 14, 891). The bromination of fatty 
 acids may also be readily effected by boiling 
 their chlorides with Br and CS2 (Michael, J. pr. 
 [2] 35, 92). Alkalis or water acting upon a- 
 bromo- acids usually produce a-oxy- acids, with ;3- 
 bromo- acids they form unsaturated acids, while 
 7-chloro- acids become lactones (Fittig, A. 195, 
 169; Erlenmeyer, B. 14, 1318 ; 15,49). 
 
 Bromination of aromatic hydrocarbons. 
 Bromine in presence of a carrier enters the 
 benzene nucleus ; bromine alone, or in presence 
 of too little iodine, enters the side-chains of 
 boiling hydrocarbons. Sunlight promotes sub- 
 stitution in the side-chains (Schramm, B. 17, 
 2922 ; 18, 850, 1272 ; 19, 212). 
 
 Bromination of aromatic amines. Bromine 
 goes first into a position p to the NHj, and then 
 into the 0- positions, but not into a m- position 
 (Nevile a.Winther, B. 13, 962 ; u.also Ajiomatio 
 COMPOUNDS, p. 299). 
 
 Stabilityofbromo- compounds. Bromo- com- 
 pounds are less stable than the corresponding 
 chloro- compounds; thus bromo-aoetic and 
 bromo-propiouio acids may be converted by 
 reduced silver into succinic and adipio acids 
 respectively, in this they differ from the corre- 
 Bponding chloro- but resemble the iodo- acids. 
 The relative stability of the alkyl bromides de- 
 pends upon the reagents attacking them ; thus 
 Zn and H^SO, reduces iso-propyl bromide more 
 quickly than propyl bromide, the order being 
 
 isopropyl, iaoamyl, butyl, propyl, ethyl ; on the 
 other hand, alooholio NaOH attacks propyl 
 bromide more vigorously than isopropyl bromide, 
 the order being ethyl, propyl, isoamyl, butyl, 
 isopropyl (Eemsen a. Hillyer, Am. 8, 251). 
 
 Other characteristics of bromo- compounds 
 may be inferred from the article on Chlobo- 
 coMPOUNDs; the bromo- compounds resemble the 
 ohloro- compounds in almost every respect. 
 
 BROMO-CONIlNE v. CoNnua. 
 
 BROMO - COUMARIC ACID 0,H,BrO,. 
 Bromo -o-oxy-cinnamic acid. Methyl deri- 
 vative MeO.CjH^.OjHBr.COsH. [171°]. S. 
 (CSj) -32 at 14°. From the methyl deri- 
 vative of o- or J3- di-bromo-melilotio acid 
 MeO.C8H4.C2H2Brj.COjH and aqueous KOH (Per- 
 kin, O. J. 39, 422). Small prisms (from CSj) j 
 si. sol. boiling water, v. sol. alcohol. BoiUng 
 dilute KOH forms the methyl derivative of 
 cumarilio acid MeO.CjHj.Oj.COjH. 
 
 Ethyl derivative EtO.OeH^.CjHBr.COjH. 
 [164°]. From EtO.0BH4.O2H2Br2.CO2Bt and 
 cold alcoholic KOH (P.). Flat prisms ; si. sol. 
 boiling water, m. sol. CSj, v. sol. alcohol. 
 
 (o)-BBOMO-COUMAKIN CpHsBrOj. [110°]. 
 From coumarin dibromide and alcoholio KOH 
 (Perkin, G. J. 23, 368). Prisms ; converted by 
 alcoholic KOH into cumarilio acid. 
 
 (i8) - Bromo - coumarin OsHjBrOj. [160°]. 
 From sodium bromo -o-oxy- benzoic aldehyde 
 and ACjO. Bhombic prisms (from alcohol) 
 (Perkin, C. J. 24, 37). 
 
 (o)-Di-bromo-coumarin CH^BrjOj. [183°]. 
 From coumarin, Br, and I (P.). Needles ; alco- 
 hoUc KOH forms bromo-cumarilic acid. 
 
 (j8)-Di-bromo-coumarin OBH^BrjOj. [176°]. 
 From sodium di-bromo-o-oxy-benzoio aldehyde 
 and AC2O. Needles (P.). 
 
 BROMO-o-CBESOL 0„H3MeBr(0H) [1:3 ?:6]. 
 [89°]. From bromo-o-toluidine (Wroblewsky, 
 A. 168, 165). Golden needles; y. el. sol. water; 
 the aqueous solution is turned green by FojOlj. — 
 KCjHjBrO aq : red scales. 
 
 Bromo - m ■ eresol CjH3MeBr(0H) [1:3:5]. 
 [57°]. From s-bromo-toluidine by diazo- reaction 
 (NevUe a. Winther, C. J. 41, 421). 
 
 Bromo -J) - cresoI CeHs(CHj)Br.OH [1:3:4]. 
 (214°). S.G. 25=1-5468. Liquid. Formed by 
 the action of dry bromine upon sodium-^-cresol. 
 
 Methyl ether C8H3MeBr(OMe) : (226°); 
 S.G. I 1-418 ; liquid (SchaU a. DraUe, B. 17, 
 2530). 
 
 Di-bromo-o-oresol C„H2MeBr2(0H). [57°]. 
 From o-cresol and Br. Volatile with steam 
 (Werner, Bl. [2] 46, 278). 
 
 Di-bromo-p-cresol OeH2(CH3)Br2.0H [1:3:5:4]. 
 [49°]. Large crystals. V. sol. alcohol, v. si. sol. 
 water. Excess of Br forms 08H2Br3(OBr) (W.). 
 
 Benzoyl derivative CBH.,MeBr2(0Bz) 
 [91°], white needles (Sohall a. Dralle, B. 17, 
 2632 ; Werner, Bl. [2] 46, 278). 
 
 Tri-bromo-OT-cresol CeHMeBr3(0H). [82"]. 
 From m-cresol (W.). Needles (from alcohol). 
 
 Tetra-bromo-p-cresol C8Br4Me(OH). [109°], 
 From j)-cresol (Baumann a. Brieger, B. 12, 804). 
 Plates ; slowly decomposed by cold bromine- 
 water into COj and tri-bromo-phenol. 
 
 BROMO-CBESOI SVLFHONXC ACID 
 C„H2MeBr(0H)(S0aH) [l:2or6:5?:8]. From 
 o-bromo-toluene by sulphonation, oitration, re- 
 
BEOMO-OUMENE. 
 
 56fi 
 
 duction, and diazotisation (Sohafer, A, 174, 361). 
 — BaA',4iaq.— BaA'j 3aq.— PbA'2 2aq. 
 
 Biomo-cresol salphonic acid 
 C„K,MeBr(OH)(SO,H) [1:4:5?:3]. From (3,1,2). 
 bromo-toluene sulphonio acid by nitration, re- 
 duction, and diazotisation (S.). — BaA'j 3aq. 
 
 Bromo-cresol snlphanic acid 
 C,H,MeBr(0H)(S03H) [1:4:?:2]. From (4,1,2)- 
 hromo-toluene sulphonio acid in a similar way. 
 — BaA'2 aq. 
 
 Si-bromo-cresol snlphonic acid 
 CsHMeBrj(OH)(SOaH). From (2,1,4) - amido- 
 toluene sulphonio acid and Br (Hayduck, A, 
 174, 353).-KA'aq. -BaA'jS^aq. 
 
 o-BEOMO-CaOTONIC ACID C.H^BrOj i.e. 
 CH,.CH:CBr.C02H. [106-5°]. 
 
 Formation. — 1. From ao-di-bromo-w-bntyrio 
 acid and alcoholic KOH, NH,, baryta- water, or 
 AgjCOj (Michael a. Norton, Am. 2, 15 ; Erlen- 
 meyer a. MiUler, B. 15, 49).— 2. From aj3-di- 
 brorao-butyric ether and alcoholic KOH (Michael 
 a. Browne, Am. 9, 280).— 3. Together with bromo- 
 pyrotartario acid by the action of bromine on 
 propane tri-carboxylio acid (Bisohoff a. Guthzeit, 
 B. 14, 616). 
 
 Properties. — ^Long needles (from water) ; 
 needles (from ligroin) ; m. sol. cold, y. sol. hot, 
 water. — AgA' : white needles, quickly affected by 
 light.— BaA'j 2aq. 
 
 ^ZZo-a-Bromo-crotonic acid 
 CHa.CHiCBr.COjH. [90°] (K.) ; [92°] (M. a. N.). 
 From o;3-di-bromo-butyrio acid (dibromide of 
 crotonic acid) by treatment with alcoholic KOH 
 (Michael a. Norton, Am. 2, 15) or NaOHAq (0. 
 Kolbe, X^jr. [2]25, 394). 
 
 Properties. — Long needles (from water) ; 
 needles (from ligroin) ; m. sol. hot water. — AgA' : 
 needles, little affected by light. — BaA'^ 3^aq. — 
 CaA'2 3aq. 
 
 /3-Bromo-crotonic acid CH^.CBrtCH.COoH. 
 [95°]. From tetrolic acid and cone. HBrAq at 
 0° (Michael a. Browne, Am. 9, 277 ; J. pr. [2] 35, 
 258). Flat needles (from water) ; feathery 
 groups of tough needles (from ligroin) ; si. sol. 
 cold water, m. sol. hot water. — AgA' : amorphous, 
 readily affected by light.— BaA'^ aq.— KA'. 
 
 a;3-Di-broma-crotonic acid 
 CHa.CBriCBr.COjH. [96°]. From tetrolic acid 
 and Br (Pinner, B. 14, 1081).— Boiling with 
 Ag,0 gives (C^HsBr)^. [116°]. 
 
 BBOMO-CUMALIC ACID C5H2Br02(C02H). 
 [176°]. Formed by the action of bromine on 
 cumalio acid in acetic acid solution (Pechmann 
 a. Welsh, B. 17, 2896). Colourless glistening 
 needles. Can be distilled in small quantities. 
 V. sol. alcohol, ether, acetic acid, and chloro- 
 form, more sparingly in benzene, insol. ligroin. 
 
 Methyl ether A'Me : [134°], prismatic 
 needles, sol. alcohol and benzene, si. sol. ether, 
 insol. water. Aqueous NH3 converts it into the 
 methyl ether of brom-oxy-nicotinic acid. 
 
 o-BEOMO-w-CUMENE CjHuBr i.e. C^H^BrPr 
 [1:2]. Bromo-n-propyl-benzene. (222 i. V.). A 
 mixture of this body with the p- isomeride is 
 formed by the action of Br on propyl-benzene 
 in the dark or on ethyl-benzene mixed with I 
 in diffused daylight (Schramm, B. 18, 1274). 
 KMnO. gives o-bromo-benzoio acid. 
 
 ^Bromo-M-cumene OgH^BrPr [1:4]. (220° 
 cor.) From C^HsPr and Br at 0° in presence of 
 1 (Meyer a. MMler, B. 15, 098 ; R. Meyer, J.pr. 
 
 [2] 34, 101). HNO3 (S.a. 1-2) forms p-bromo- 
 benzoic acid. 
 
 3-Bromo-n-cumene CjH5.CHBr.CH2.CH3. 
 Formed in the cold by the action of bromine 
 (1 mol.) upon ji-cumene in direct sunshine. By 
 further bromination in sunlight it gives ;8-di- 
 bromo-Ji-cumene CjHs.CBr^.CHj.CHj, but in the 
 dark at 100° it yields aj8-di-bromo-w-cumene 
 CjH5.CHBr.CHBr.CH3 (Schramm, B. 18, 1275). 
 o;8-Di-bronio-ra-cumeneCjH5.CHBr.CHBr.CH3. 
 From allyl-benzene {c[.v.) and bromine (Eiig- 
 heimer, A. 172, 131 ; Badziszewski, O. B. 78, 
 1153; Perkin, C. J. 32, 668). From w-cumeno 
 and bromine at 160° (Wispek a. Zuber, A. 218, 
 381 ; cf. 8. supra). Silky needles (from alcohol). 
 
 ^;8-Di-bromo-K-cumene CjHj.CBrj.CHj.CHa. 
 Phenyl-ethyl-hetone-di-hromide. Formed in the 
 cold by the action of bromine (2 mols.) upon 
 ji-cumene exposed to direct sunshine (Schramm 
 B. 18, 1275). 
 
 ua;3-Tri-bromo-n-cnmene 
 CjHj.CHBr.CHBr.CHjBr. Stycerin tri-brom- 
 hydrin. [124°]. From oinnamyl bromide and Br, 
 or by the action of HBr on the dibromide of 
 cinnamyl alcohol (Grimaux, Bl. 20, 120). 
 
 Tetra-bromo-ji-cumene CjHjBr,. Liquid 
 (Fittig, A. 149, 327). 
 
 o-Bromo-cumene CjH,BrPr [1:2]. Bromo- 
 isopropyl-bemene. (206° cor.) at 740 mm. From 
 isopropyl-phenol and PBtj (Pileti, G. 16, 131). 
 
 ^-Bromo-cumene CsH^BrPr [1:4]. (217°). 
 S.G. ^ 1-3014. Prepared by brominating 
 cumene at 0' in presence of I (Jacobsen, B. 
 12, 430). With benzene, Na, and CO2 it gives 
 cuminio acid (B. Meyer, J. pr. [2] 34, 93). 
 
 Penta-bromo-cumene CaHjBrj. [97°]. From 
 cumene and Br (Meusel, Z. 1867, 322 ; Fittig, 
 A. 149, 326). Needles ; si. sol. cold alcohol. 
 
 Bromo-if-cumeue C„H2(0H3)3Br [1:2:4:5]. 
 [73°]. (227°). White plates. 
 
 Formation. — 1. By the action of cuprous 
 bromide upon diazo-pseudo-cumene (HaUer, B. 
 18, 93). — 2. By the action of bromine (1 mol.) 
 in the dark upon pseudo-oumene ; the yield is 
 60 p.c. (Beilstein, A. 1.37, 323 ; Fittig, A. 139, 
 188 ; 145, 138 ; Schramm, B. 19, 216 ; Sussen- 
 guth, A. 215, 243). — 3. By the action of bromine 
 upon an aqueous solution of pseudo-cumene- 
 sulphonic acid (1:2:4:5) 76 p.c. is converted into 
 bromo-i^-cumene, the remainder forming bromo- 
 i/z-cumene sulphonio acid C,HMe3Br(S03H) 
 [1:2:4:3:5] (Kelbe a. Pathe, B. 19, 1547). 
 
 Bromo - \fi - cumene C^H^MCgBr [1:2:4:3]. 
 (226^-229'). Colourless oil. Formed by the 
 hydrolysis of the sulphonic acid CjHMe3Br(S0sH) 
 [1:2:4:3:5] by means of superheated steam at 
 200°-210°. By Mel and Na it yields c-tetra- 
 methyl-benzene (Kelbe a. Pathe, B. 19, 1551). 
 
 Bromo-if-cumene GJd^Uefii [1:2:4:6] (237°). 
 Liquid ; still fluid at — 15°. Obtained by hydro- 
 lysis of the sulphonio acid (1:3:4:5:2]. By sul- 
 phonation it is reconverted into the same sul- 
 phonio acid (Jacobsen, B. 19, 1223). 
 
 (B-Bromo-i^-cumene CjH3(CH3)2.CHjCl. Pseudo- 
 cumyl bromide. Liquid. Decomposes on dis- 
 tillation. Formed by the action in direct sun- 
 shine of 1 mol. of bromine upon 1 mol. pseudo- 
 oumene (Schramm, B. 19, 217). 
 
 Di-bromo-i|*-oniaene CjHMejBrj [1:2:4:5:6]. 
 [64°]. (294°). Formed by the action of 1 mol. 
 of bromine upon 1 mol. mono-bromo-pseudo- 
 
506 
 
 BROMO-CUMENE. 
 
 oumene by gaslight, or in the dark (Sohramm, 
 B. 19, 216 ; Jaoobsen, B. 19, 1220). Long flat 
 needles, v. sol. alcohol. 
 
 oii-w^-Di-bromo-^fi-eumene C5H3(CH3)(CH;jBr)2 
 [1:2:4] . Pseudo-cumylene bromide. [97°]. Flat 
 glistening needles (from petroleum-ether). V. 
 sol. alcohol and benzene. Formed by the action 
 of 2 mols. of bromine upon 1 mol. pseudo-cumene 
 in direct sunshine (Sohramm, B. 19, 218 ; Hjelt 
 a. Gadd, B. 19, 867). 
 
 Tri-bromo4-cumene CeMesBra [1:2:4:3:5:6]. 
 [226°] or [233° cor.]. V. sol. hot toluene, si. sol. 
 alcohol. Formed by the action of Br (3 mols.) 
 in the dark upon il'-cumene (1 mol.) (Fittig a. 
 Laubinger, A. 151, 264 ; Schramm, B. 19, 217 ; 
 Jaoobsen, B. 19, 1222). 
 
 BEOMO-i(/-CUMENE-STILPHONIC ACID 
 C,HMe3Br(S0,H) [1:2:4:5:6]. [c. 121°]. _ Formed 
 by dissolving bromo-ij'-oumene [73°] in warm 
 slightly fuming H^SO,. Needles (containing 
 2aq). By treating the Na salt with zinc-dust and 
 aqueous NHj it is debrominated with production 
 of (l,2,4,6)-pseudo-cumene-sulphonio acid. 
 
 Salts. — ^A'Na aq. — A'jCa 3aq. — CuA'^ 4aq. — 
 BaA'2 Jaq. — KA'aq. 
 
 Amide CfiUe.'BiiSO^l/fB.^) : [185°]; smaU 
 needles, v. sol. alcohol, nearly insol. water (Jacob- 
 sen, B. 19, 1218 ; Kelbe a. Pathe, B. 19, 1553). 
 
 Bromo-iJ'-cumene-Bulphonic acid 
 CsHMe3Br(S03H) [1:2:4:6:8]. Formed, together 
 with the di-bromo- acid, by the action of CISO3H 
 upon di-bromo->)'-oumene. — NaA' ^aq. 
 
 Amide C,HMe3Br(S02NH2) : [158°]; thin 
 needles (Jaoobsen, B. 19, 1223). 
 
 Bromo-i|'-cumene-sulphonic acid 
 C,HMe3Br(S03H) [1:2:4:3:5]. [116°]. Colour- 
 less needles. Formed by the action of bromine 
 upon an aqueous solution of pseudo-cumene- 
 sulphonie acid [1:2:4:5] ; 76 p.c. of the pseudo- 
 cumene-sulphonio acid is converted into bromo- 
 pseudo - cumene [73°], the remainder yielding 
 the bromo-sulphonio acid. It is also formed by 
 sulphonation of bromo-pseudo-cumene [1:2:4:3]. 
 The latter body is formed by the action of super- 
 heated steam upon it at 200°-210°. 
 
 Salts. — NaA' aq. — KA' aq. — AgA' aq. — 
 BaA'2 aq.—PbA'jSaq. 
 
 Amide C„HMe3Br(S02NH2) : [188°] ; thin 
 needles (Helbe a. Pathe, B. 19, 1547). 
 
 Di-bromo-i^-cumene-sulphonic acid 
 C3MejBr,(S03H) [1:2:4:5:6:3]. Obtained by sul- 
 phonation of di - bromo - pseudo - cumene with 
 sulphuric ohlorhydrin. 
 
 Salts .—NaA'.— NaA' aq.— BaA'^. 
 
 Amide C,Me3Br2(SOjNHi,) : [above 250°] ; 
 plates (Jaoobsen, B. 19, 1222). 
 
 BROMO -^-CUMENOL C^HMeaBr.OH 
 [1:2:4:3:5]. [35°]. Formed by bromination of 
 pseudo-cumenol in cold acetic acid. Slender 
 yellow needles. Insol. water, v. sol. other sol- 
 vents (Beuter, B. 11, 29 ; Auwers, B. 18, 2657). 
 
 Bromo - iso - eumenol C,H3PrBr(0H) [2:4:1]. 
 [49°]. Brofno-isopropyl-pheTwl. From o-iso- 
 propyl-phenol (o-isooumenol) and Br (Fileti, G. 
 16, 117). Decomposes at 250°. 
 
 Methyl ether C„}i,¥rBv{OMe). (250°). 
 
 Si - bromo - ifi - cumeuol 
 C,Me3Brj.0H [1:2:4:3:6:5]. [149°]. Formed by 
 bromination of pseudo-cumenol dissolved in a 
 small quantity of acetic acid. Long colourless 
 
 prisms or needles. Insol. water, m. sol. alcohol, 
 acetic acid, and benzene, v. sol. ether. 
 
 Methyl ether 03Me3Br2.0Me : [96°]. 
 Formed by methylation of the above or by 
 bromination of pseudo-cumenol-methyl ether. 
 White needles. Insol. water, v. sol. other sol- 
 vents (Auwers, B. 18, 2657). 
 
 Si - bromo - if/ - cumeuol 
 OjMeaBrjOH [1:2:4:3:5:6]. [152°]. From 
 CjHMejBrj [1:8:4:2:6] (Edler, B. 18, 630 ; Jacob- 
 sen, B. 19, 1220). 
 
 Si-bromo-iso-cumenol 
 CsH2i'rBr2(OH) [2:4:6:1]. From o-iso-oumenol 
 and Br (Fileti). Liquid. 
 
 Methyl ether CeH;,PrBrj(OMe). (279°). 
 HNO3 forms a nitro- derivative 
 03H2PrBr(N02)(0H) [2:4:6:1]. [33°]. 
 
 BROMO - CUMINIC ACID 0,„H„Br02 i.e. 
 C<;H3Br(C3H,)C02H. [151°]. Bromo ■ propyl- 
 benzoic acid. From Br and cuminic acid or 
 silver cuminate (Naquet a. Luginin, Z. 1866, 
 333; Gerichten, B. 11, 1719). From bromo- 
 cymene and HNO3 (Fileti a. Crosa, O. 16, 296). 
 
 Bao-bromo-cumiuic acid C3HjBr.C3H4.COjH. 
 From Br and ouminio acid at 120° (Czumpelik, 
 B. 3, 478). 
 
 BBOMO-CUMYI-BUTYEIC ACIS 
 C,3H„Br02 i.e. CsH^Pr.CjH^.CHBr.COjH. [150°]. 
 From oumenyl-crotonic acid and HBr. Prisms. 
 Decomposed by NajCOj giving allyl-isopropyl- 
 benzene (Perkin, C. J. 32, 662). 
 
 BROMO-CUMYL-PROPIONIC ACIS 
 C.jHijBrOj i.e. CjH.Pr.CHj.CHBr.COjH. [87°]. 
 From cumyl-acrylio acid and HBr (Perkin, 0. J. 
 32, 661). Besolved by boiling water into HBr 
 and oumyl-acrylic acid. Na^COaAq forms vinyl- 
 isopropyl-benzene. 
 
 Sl-bromo-cnmyl-propionic acid 
 CjH^Pr.CHBr.CHBr.COjH. [190°]. Fromcumyl- 
 acryhc acid and Br (Widman, B. 19,258). 
 
 BROMO-CUMYI-VALEBIC ACID 
 CnHigBrOj i.e. OjH.Pr.OsHj.CHBr.CO^H. From 
 cumenyl-angelio acid and HBr. Prisms. 
 NajCOjAq gives isopropyl-butenyl-benzene (Per- 
 km, O. J. 32, 663). 
 
 BBOMO - CYAIf - BENZENE v. NitriU of 
 Bromo-benzoio acid. 
 
 BROMO-p-CYMENE C,„H,3Br i.e. 
 C,H3(CH3)(C3H,)Br [1:4:2]. Bromo -p -methyl- 
 n-propyl - benzene. (234° i.V.). S.G. ^11 1-27. 
 
 Formation. — 1. From cymene and Br (Lan- 
 dolph, B. 5, 267).— 2. Together with bromo-p- 
 cymene - sulphonio acid C3H2MePrBr(S03H) 
 [1:4:5:2] by the action of bromine upon a.n 
 aqueous solution of ^'-oymene-sulphonio acid 
 (Kelbe a. Koschitzsky, B. 19, 1730).— 3. The 
 same or the following bromo-cymene is formed 
 by hydrolysis of bromo-^-oymene-sulphonic acid 
 C3H,MePrBr(S03H) [1:4: 5or6 :2] (K. a. K.). 
 
 Bromo-2)-cymene C3H3(CH3)(C3H,)Br [1:4:3]. 
 (232°). From thymol and PBr, (Fileti a. Crosa, 
 O. 16, 287). Formed also by the action of 
 bromine upon an aqueous solution of ^-oymene- 
 sulphonic acid (Me:Pr:S03H = 1:4:3) (Claus a. 
 Christ, B. 19, 2165, v. supra). 
 
 Di-bromo-jp-cymene CjHjMeBrjPr. (272°). 
 S.G. ii 1-596 (Glaus a. Wimmel, B. 13, 903). 
 
 (a)-Bromo-m-isocymeue C3H3Meli'rBr [1:3:6]. 
 (225° cor.). Formed, together with bromo-iso- 
 cymene sulphonic acid, by the action of bromine 
 on m-isocymene sulphonio aoid (Eelbe, A. 310, 
 
BROMO-DURENE. 
 
 56T 
 
 48; 235, 281). Oxidised by dilute HNO, to 
 bromo-toluio acid [210°]. 
 
 (;8)-Bromo-i30oymene OuHaMefPrjBr [1:3:4]. 
 (224°). Got by distilling CeHjMe(Pr)Br(SO,K) 
 [1:3:4:6] with superheated steam (Kelbe a. Czar- 
 nomski, 4. 235, 293). Dilute HNO3 oxidises it to 
 bromo-toluio acid CsHsMeBrCO^H [1:4:3] [153°]. 
 Di-bromo-m-isocymene C,„H,2Brj. (273° 
 uncor.). Obtained by brominating (o)-bromo- 
 m-isooymene sulphonio acid (Kelbe a. Czar- 
 nomski, A. 285, 281). Converted by fuming HNO^ 
 intonitro-bromo-iso-cymene C,|,H,2(N02)Br [83°]. 
 
 Bromo-p-cymene-sulplionic acid 
 CBHjMePrBr(S03H) [1:4: 5or6 :2]. Bromo-p- 
 methyl-n-propyl-bemene-sulphonic acid. Formed, 
 together with bromo-jj-cymene CgH^MePrBr 
 [1:4:2], by the action of bromine upon ^-cymene- 
 Bulphonio acid CjH3MePr(S03H) [1:4:2] in 
 aqueous solution at40°-50° (Kelbe a. Kosohitzky, 
 B. 19, 1730). Formed also from cymldine by 
 Eulphonation and diazotisation (Widman, B. 
 19, 248). Sodium amalgam reduces it to n- 
 cymene sulphonio acid. 
 
 Salts.— KA'aq.—BaA'j2Jaq. S. 1 at 17°.— 
 BaA'jliaq.— CuA'2 12aq. 
 
 Amide O^B.^MeP]:lBx{SO^^B.^) : [152°]. 
 
 Bromo.;2]-cyniene-BalpIiomc acid 
 CjHjMePrBr(S03H) [1:4:2:.'>]. Formed by sul- 
 phonation of bromo-p-cymene (1:4:2) with H^SOj 
 (Kelbe a. Kosehitzsky, B. 19, 1732 ; Glaus a. 
 Christ, B. 19, 2163; Bemsen a. Day, Am. 5, 
 151), or CISO3H (Paterno a. Canzoneri, O. 11, 
 126). Long needles containing 3aq [c. 60°]. By 
 zino-dust and NH3 it is easily debrominated to 
 p-oymene-sulphonic acid (1:4:5)?. 
 
 Salts.— KA'Saq.-PbA'j. S. 2-1 at 30°.— 
 AgA'.— CaA', 8aq.— NaA' 4iaq (E. a. D.).— 
 ZnA'jSaq (E. a. D.).— MgA'2 9|aq (E. a. D.).— 
 CaA'jQiaq (E. a. D.).— CaA'^Baq.- BaA'^g^aq 
 (E. a. D.).— BaA'j 5aq. S. 1-37 at 27°.— CuA'^ 8aq. 
 
 Amide C^B.JiS.ePvBr{SO.,TiiB.i) : [188°] 
 (K. a. K.) [195°] (C. a. C). 
 
 Chloride C^H^MePrBrSO^Cl [82°]. 
 
 Bromo-p-cymene-sulpbonio acid 
 C«H,(CH3)(03H,)Br(S03H) [1:4:5:3]. [180° 
 uncor.]. Formed by bromination of an aqueous 
 solution of p - oymene - sulphonio acid 
 CjH3MePr(S03H) [1:4:3]. Glistening colourless 
 plates (Claus a. Christ, B. 19, 2166). 
 
 (a)-Bronio-iso-cymeue sulpbonic acid 
 C.HjMe(Pr)Br(S03H) [1:3:6:4]. [65°] and [126°]. 
 From (a)-bromo-iso-cymene by sulphonation, or 
 from (j8)-isocymene sulphonio acid by bromina- 
 tion (Kelbe a. Czarnomski, A. 235, 277). Needles 
 containing 3aq (from water). After a week's 
 exposure over H^SO, it melts at 126°. Salts . — 
 BaA'2 7aq.— CuA'2 7aq.— KA' aq.— NaA'2aq. 
 
 Amide C„H,iBr.SOjNHj [171°]. 
 
 (i8)-bromo-TO-iso-cymene sulphonic acid 
 C,„H,^r.S03H i.e. CeH,Me(C3H,)Br(S03H) 
 [1:3:4:6]. [109°]. Formed by brommation of 
 »i-isooymene sulphonio acid (Kelbe a. Czar- 
 nomsld, A. 235, 272). Salts. — PbA'^aq.— 
 BaA',. — CuA'2 4aq. — KA' aq. 
 
 Amide.— G,„B.,,-Bi.SO,^B.^ [162°]. 
 
 BEOMO-CYMENOL C,HjMePrBr(OH) 
 [l:4:3:2or6]. From amido-cymenol by the 
 diazo- reaction. Oil (Mazzara, G. 16, 191). 
 
 Tri - bromo - cymenol C3Me(03H,)Br3(OH) 
 [2!4:1]. [222°]. Glistening golden plates. 
 Formed by shaking an aqueous solution of 
 
 cymenol with a solution of bromine in HBr 
 (Jesurun, B. 19, 1414). 
 
 BEOMO- CYMIDINE C„H.,MeBr(C3H,).NH, 
 From bromo-nitro-oymene. Liquid (Mazzara. 
 a. 16, 193). 
 
 BBOMO-SECAXE v. Decyl bbomide. 
 
 Di-bromo-decane C,„H2„Br2. Decylene brom- 
 ide. Oil. From petroleum decylene (Eeboul a. 
 Truohot, A. 144, 248). 
 
 Di - bromo - decaue C,„H2„Br2. Diamylene 
 bromide. From diamylene and Br (Bauer, A. 
 135, 344). Liquid. Alcoholic KOH gives rutyl- 
 ene C,„H,3 (150°). 
 
 Tri-bromo-deoane C|„H,aBr3. OU. From 
 diamylene and Br (Walz, Z. 1868, 315). 
 Decomposes at 100". 
 
 Tetra-bromo-decane CioHuBr,. Menthene 
 tetrabromide. From menthene and Br (Beckett 
 a. Wright, Report of British Ass. 1875, ii. 88). 
 Oil, split up by distillation into HBr and 
 oymene. 
 
 Tetra-bromo-decane C|„H,8Br,. DecenyUne 
 tetra-bromide. From deciuene (165°) and Br. 
 Oil (Eeboul a. Truohot, A. 144, 249). 
 
 Tetra-bromo-decane CuHuBr^. From allyl- 
 propylidene-propyl-methane (158°) and Br (Ee- 
 formatsky, J. pr. [2] 27, 389). 
 
 SI-BEOMO-BECINENES C„H„Br. Described 
 as hydrobromides of terpenes. V. also Boknyl 
 
 BBOMIDE. 
 
 Di- bromo -decinene CuHuBrj. From di- 
 amylene and Br, p. 211. 
 
 Tetra-bromo-decinene 0,|,H„Br<. Di-bromo- 
 camphilidene dibromide [160°-164°]. From 
 camphor and PClsBr^ (Do la Eoyke, Bl. [2] 88, 
 579). Unctuous tables. 
 
 7-BROMO-DECOIC ACIB C,„H,s;BrOj i.e. 
 C3H,3.CHBr.CH2.CH2.C02H. From decenoio 
 acid (g. v.) and BBr (Schneegans, A. 227, 92). 
 Heavy oil. Na^COa removes HBr forming the 
 lactone of oxydecoic acid. 
 
 Si-bromo-decolc acid C,„H,gBr20j. Di-bromo- 
 capric acid. [135°]. From decenoio ( ' amydecyl- 
 enic ') acid and Br (Hall a. Schoop, B. 12, 194). 
 Monoclinic prisms (from benzene). 
 
 DI-BROMO-DECYL ALCOHOL C^^U^fiifi. 
 Oil. From allyl-di-isopropyl-carbinol and Br 
 (Lebedinsky, J. pr. [2] 23, 22). 
 
 BROMO-DEOYLENE C„H,gBr. (215°). S.G. 
 — 1-109. Oil. From decylene bromide (v. sup.) 
 and alcoholic KOH (Eeboul a. Truchot, A. 144, 
 248). Alcohohc KOH forms C,„H,j (165°) and 
 CioHigOEt. 
 
 Bromo-decylene v. Menthtl beomide. 
 
 Di-bromo -decylene CijHisBrj. Decinene 
 bromide. Oil. From 0,„H,s and Br (E. a. T.). 
 
 Di-bromo-decylene C|„H,sBr2. From ter- 
 pilene hydride and Br (Montgolfier, A. Ch. [5] 
 19, 158). 
 
 Di-bromo-decylene CioHigBr^. From rutyl- 
 ene and Br (Bauer, A. 185, 344). 
 
 DI-BEOMO-DODECANE C.^H^^Brj [-15°]. 
 Dodecylene bromide. Formed by the addition ol 
 Br2 to dodecylene (KrafEt, B. 17, 1871). 
 
 BROmO-ISO-DURENE CjHBrMej [1:3:4:5:6]. 
 (253°). Liquid; solidified by cold (Bielefeldt, A. 
 198, 388). 
 
 Bromo-s-durene CsHMe^Br [1:2:4:5:3]. [61°]. 
 By bromination of durene (Gissmann, A. 216, 
 210). Pearly plates (from alcohol). 
 
608 
 
 BROMO-DURENE. 
 
 Bi-bromo-c-durene C,„H,2Br3 i.e. CaMe^Brj 
 [1:2:3:4:5:6]. Di-bromo-prehnitene. [210°]. From 
 c-durene, Br, and I. Prisms (Jaoobsen, B. 19, 
 1213). 
 
 Si-bromo-iso-durene C,„H,2Br2 [1:3:4:5:2:6]. 
 [209°]. Long fine needles. SI. sol. hot, v. si. sol. 
 cold alcohol. Prepared by bromination of iso- 
 durene (Jaoobsen, B. 15, 1853 ; cf. Jannasch, B. 
 8, 356). 
 
 Di-brcmo-s-durene C^Me^Brj [1:2:4:5:3:6]. 
 [203°]. Needles (from alcohol) (Fittig a. Jan- 
 nasch, Z. 1870, 161 ; Friedel a. Crafts, A. Ch. 
 [6] 1,515). 
 
 BEOMO - DUEENOL C,„H,jBr.OH [118°]. 
 Formed by bromination of durenol in acetic acid. 
 Long prisms. V. sol. alcohol and ether, iusol. 
 water (Jaoobsen a. SchnapaufE, B. 18, 2844). 
 
 DI-BEOMO-ENNANE G^.^Bz,. Nonylene 
 bromide. From Br and ennylene (from paraffin). 
 Alcoholic KOH forms bromo-ennylene CgHuBr 
 (0. 210°) (Thorpe a. Young, A. 165, 18). 
 
 BEOMO-ENNOIC ACID CeH,3.CjH3Br.CO,H. 
 From ennenoio acid CgHjjOj and HBr. Decom- 
 posed by warm aqueous NajCOj forming an oil, 
 probably CeH.j.C^Hj (Schneegans, A. 227, 83). 
 
 BEOMO-EifHYLENE v. Di-bromo-ennane. 
 
 BEOMO-EEUCIC ACID C^^U^BtO^. [34°]. 
 From di-bromo-behenic acid and alooholio KOH. 
 Converted into behenolic acid by alooholio KOH 
 (Haussknecht, A. 143, 50). 
 
 Di-bromo-erucic acid CjaH^BrjOj. [47°]. 
 From behenolic acid and bromine (H.). 
 
 BEOMO-ETHANE v. Ethyl eeomide. 
 
 Bi-bromo-etliane v. Ethylene bkomide and 
 
 ElHYLIDENE BBOMIDE. 
 
 M-Tri-bromo-ethane CHBrj.CH^Br. Bromo- 
 ethylene irormde. (188°) at 752 mm. S.G. -^ 
 2-6189; ?^ 2-6107 (Anschiitz, A. 221, 138). 
 M. M. 12-897 at 11-7°. From CHBr:CH2, water, 
 and Bi (Wurtz, A. Ch. [3] 51, 84). Also formed 
 by the action of Br on ethyl bromide, ethylene 
 bromide, or iodo-ethylene (M. Simpson, P. M. 
 [4] 14, 544 ; Caventou, A. 120, 323 ; Tawildaroff, 
 A. 176, 22 ; Staedel, B. 11, 1741). 
 
 Reactions. — 1. Alcoholic KOH gives M-di- 
 bromo-ethylene, bromo-aoetylene, and acetylene. 
 2. M-Di-bromo-ethylene is also formed by the 
 action of alcoholic KOAc, water and PbO, and 
 NaOEt (Michael, Am. 5, 192).— 3. SbClj gives 
 CH0l2.CH2Br (Henry, BZ. [2] 42,262).— 4. Benz- 
 ene in presence of Al^Clj produces bromo-benz- 
 ene, s-di-phenyl-ethane, and M-di-phenyl-ethaue 
 (Anschiitz, A. 235, 333). 
 
 M-Tetra-bromo-ethane CBra.CHfBr. Acetyl- 
 idenetetrabromide. (1035°) at 13-5 mm. S.G. ^ 
 2-9216. From CBr2:CH2 and Br^ (Anschiitz, A. 
 221, 140; Lennox, C. J. 13, 206; Eeboul, A. 
 124, 270). Also from tri-bromo-ethane and Br 
 (Denzel, B. 12, 2207). Decomposed by heat, 
 giving off Br^ and HBr. Converted by benzene 
 and AljClj into M-di-phenyl-ethane, and s-tetra- 
 phenyl-ethane CHPh^.CHPh, [210°] : bromo- 
 benzene and acetylene dibromide being also 
 formed (Anschiitz, A. 235, 196). 
 
 s-Tetra-bromo-ethane CHBr^.CHBrj. Acetyl- 
 ene tetra-bromide. (114°) at 12 mm. S.G. — 
 2-9629. Acetylene, from C^H^Bi-j and alcoholic 
 KOH is passed directly into bromine. The pro- 
 duct, containing CHBrj.CHjBr, is treated with 
 
 alcohol and zinc-dust and CHBr:CHBr is sepa- 
 rated from CH2:CHBr by fractional distillation, 
 and is then mixed with bromine (Anschiitz, A, 
 221, 138 ; cf. Eeboul, 0. B. 54, 1229 ; Sabanejeff, 
 B. 9, 1441; ^.178,112). 
 
 Properties. — Smells of camphor and chloro- 
 form. Takes up moisture from air, becoming 
 cloudy. At 185° it begins to decompose, giving 
 off Brj and HBr, and leaving C^HBr,. With 
 water and bromine at 185° it gives C^Br, and 
 CjBrj. Boiling alcoholic KOH forms acetylene 
 and bromo-acetylene. Zinc added to its alooholio 
 solution forms acetylene dibromide in the cold, 
 but on warming it forms acetylene. With benz- 
 ene and Al^Clj it forms bromo - benzene, M-di- 
 phenyl-ethane, anthracene, and anthraquinone 
 (Anschiitz, A. 235, 161). AljClj alone forms 
 CHBr2.CH2Br and CjBrj. Toluene and Al^Cl. 
 give di-methyl-anthraoene [225°]. o- to- and 
 p- xylene appear to give tetra-methyl-anthra- 
 cenes. 
 
 Penta-bromo-ethane CBrs.CBr^H. [49°] (S.); 
 [54°] (D.) ; [57°] (B.). (210°) at 300 mm. 
 
 Fonnation.—l. From CHBr:CBr2 and Br 
 (Lennox; Sabanejeff, A. 216, 281). — 2. From 
 bromo-ethylene and Br (Denzel, B. 12, 2208).— 
 3. From bromo-acetylene and Br (Eeboul, A. 
 124, 268). — 4. By spontaneous decomposition of 
 tri-bromo-ethylene exposed to air (Demole, Bl. 
 [2] 34, 204). — 5. From acetylene tetrabromide 
 and Br (Bourgoin, Bl. [2] 23, 173).— 6. From 
 succinic acid, water, and Br (Orlovsky, /. B. 
 9, 280). 
 
 Hexa-bromo-ethane C^Brs. Carbon hexa- 
 bromide. Formed by brominating C^BrsH (Ee- 
 boul). Formed also by the action of Br and Al 
 on CC1„ C2CI4, or OjCla (Gustavson, J. B. 13, 
 287). Also from muoobromio acid, water, 
 and Br at 130° (Delbriick, A. 165, 253). Prisms 
 (from CS2); insol. alcohol. At 200°-210° it 
 decomposes, without previous fusion, into Br 
 and G^^r^. Unlike the latter, it is not volatile 
 with steam. 
 
 BEOMO - ETHEN? L - NAPHTHYIENE-DIA- 
 
 ^^^^ C.CH, 
 
 nh/\n 
 
 .0=0 
 
 \CBr : CH 
 [229°]. Formed by reduction of the acetyl 
 derivative of (l:3:4)-bromo-nitro-(o)-naphthyl- 
 amine with SnCl^. Small white needles. V. sol. 
 alcohol and ether, insol. water. The ethenyl 
 group is very stable. Salts. — B'HCI. — 
 B'.jHjSO," : sparingly soluble needles. — 
 B'HNOj* : fine white sparingly soluble needles 
 (Prager, B. 18, 2160 ; cf. Meldola, C. J. 47, 605). 
 
 BEOMO-ETHOXY- v. Bromo-oxy-. 
 
 BEOMO-ETHYL-ACErO-ACETIC ETHEE v. 
 Beomo-aoeto-aoetio etheb. 
 
 w-Bromo-ethyl-aceto-acetic-ether CgH„Br03 
 i.e. CH3.CO.CH(COjEt).CH,.OH2Br. Heavy yel- 
 lowish oil of camphor-like odour. Not distillable. 
 Formed by dissolving trimethylene-methyl- 
 
 CH,. /CO.OH3 
 ketone-oarboxylic ether | >C^ in 
 
 CH./ \COjEt 
 three times its weight of strongly oooled cone. 
 HBr (1-85 S.G.), allowing to stand 10 mins. at 
 15° and pouring into iced water. By boiling 
 
BROMO-ETHYLENE. 
 
 5S8 
 
 with HOi it ii converted into acetyl propyl alco- 
 hol CH3.OO.CH2.CHj.OH2.OH (v. p. 46) with 
 formation of alcohol, COj, and HBr (Perkin, jun., 
 a. Freer, 0. J. 51, 833, B. 19, 2565). 
 
 BKOMO-ETHYL ALCOHOL v. Oltooi. erom- 
 
 HYDEIN. 
 
 Dibromo-ethyl alcohol CHBrj.OHjOH. (180°). 
 S.G. - 2-35. From bromo-ethylene and dilute 
 HBrO (Demole, B. 9, 49). Beduoes ammoniaoal 
 AgNOj. Alcoholic EOH gives bromo-ethylene 
 oxide. Acetyl derivative OHBr^.CHj.OAc. 
 (194°). S.G. s 1-98. 
 
 BROMO- TBI -ETHYL -AMINE. Ethylo- 
 bromide C2H<Br.NEt3Br. From NEtj and 
 ethylene bromide. Alcoholic EOH forms 
 C2H3.NEt3Br (Hofmann, O. R. 49, 880). 
 
 p-BROMO-ETHYL-AlTILINE C,HjBr.NHEt. 
 From ^-bromo-aniline and EtBr (Hofmann, A. 
 74, 145). 
 
 y-Bromo-dl-ethyl-amline OjHiBr.NEtj. [33°]. 
 (270°). Needles or prisms. Formed by bromi- 
 uation of diethylanUlne (Claus a. Howitz, B. 17, 
 1827). 
 
 p-BEOMO-ETHYL-BENZElfE O^HjErEt 
 
 [1:4]. (204°). S.G. 13:5 1-34. From ^i-ethyl- 
 benzene, Br, and I (Kekul6 a. Thorpe, O. J. 22, 
 366). From CsH^Brj, EtI, and Na (Aschen- 
 brandt, A. 216, 222). Does not solidify at 
 —20°. A mixture of 0- and^- ethyl-benzenes is 
 formed by the action of bromine in the dark 
 upon ethyl-benzene, or by the action of bromine 
 in presence of 3 p. c. of iodine upon ethyl-benz- 
 ene in diffused daylight (Schramm, B. 18, 1272). 
 
 u-Bromo-ethyl-benzene OjHs.CHi.CHjBr 
 (0. 148°) at 30 mm. S:G. ^ 1-311. Formed by 
 direct combination of styrene with HBr (Bernth- 
 sen a. Bender, B. 15, 1983). Formed also by 
 treating a mixture of benzene and bromo-ethyl- 
 ene with AI2CIJ (Hanriot a. Guilbert, 0. B. 98, 
 525). 
 
 a-Bromo-ethyl-benzene CsH5.CHBr.CH3. 
 (37°) at 17 mm. (c. 150°) at 500 mm. From Br 
 and ethyl-benzene at 140° (Eadziszewski, B. 6, 
 492 ; Berthelot, G. B. 67, 328 ; Ansohutz, A. 
 235, 328). Formed also by passing HBr into 
 cooled phenyl-methyl-carbinol (Engler a. Bethge, 
 B. 7, 1125). Partially decomposed by distilla- 
 tion into styrene and HBr. 
 
 v-a-Dl-bromo-ethyl-benzene 
 Ph.CHBr.CH2Br. [74°]. (140°) at 15 mm. 
 Styrene di-bromide. 
 
 Preparation. — 1. From styrene (10 g.), ether 
 (25 g.) and bromine (17 g.) (Blyth a. Hofmann, 
 A. 53, 306 i Zinoke, A. 216, 288).— 2. From hot 
 ethyl-benzene and Br (Eadziszewski, B. 6, 493 ; 
 Friedel a. Balsohn, Bl. [2] 35, 55). 
 
 Properties.-'White plates or needles (from 
 80 p.c. alcohol). V. e. soL ether, benzene and 
 glacial HOAc, v. sol. alcohol or benzoline. 
 
 Beactions. — 1. KOAo and alcohol at 160° 
 gives chiefly ;8-bromo-styrene (150°-160° at 
 75 mm.).— 2. KOAc and glacial HOAc gives 
 chiefly the diaoetate of phenyl-glycol, 
 Ph.CH(OAo)CH2(OAo).— 3. AlcohoUc KOH or 
 water at 190° give a-bromo-styrene (Glaser, A. 
 154, 154).— 4. Gives PhOH(OH).CH2(OH) by 
 treatment with AgOAc, alcohol and AgOBz, or 
 aqueous KjOO,. AgOBz in presence of toluene 
 forms Ph.CH(OBz).CHj(OBz).— 5. Benzene and 
 AI2CI, give j-di-phenyl-ethane (Anschiitz, A. 
 235, 328). 
 
 Tri-bromo-ethyl-benzene OjH,.CHBr.CHKr, 
 [38°]. From oi-bromo-styrene and Br (Fittig a. 
 Binder, A. 195, 142). Acted upon by benzene 
 and AljCl, in presence of CS^, it is converted 
 into s-tetra-phenyl-ethane [209°] (A.). 
 
 Tetra-bromo-ethyl-lienzene OgH^Br,. From 
 di-bromo-ethyl-benzene and Br (Einnicutt a. 
 Pahner, Am. 5, 387). 
 
 Fenta-bromo-ethyl-benzene OgHjErg. From 
 ethyl-benzene, Br, and Al^Br, (Gustavsen, Bl. 
 [2] 30, 22). 
 
 Di-bromo-di-ethyl-benzene 0„Hj(C2H|Br).^. 
 (200°-230°) at 30 mm. From bromo-ethylene, 
 benzene, and AljCl, (Hanriot a. Guilbert, C. B. 
 98, 525). 
 
 Bromo-tetra-ethyl-benzene 0|iH(02H5),Br 
 (284° unoor.). Heavy liquid (GaUe, B. 16, 1745). 
 
 Di-bromo-tetra-ethyl-benzene C|j(C2H5)4Br2. 
 [75°]. (above 330°). Prisms. V. sol. alcohol 
 (Galle, B. 16, 1745). 
 
 BROMO-EIHYL-BBOMIDE «. Di-bkomo- 
 
 ETHANE. 
 
 BROIIO ■ ETHYL BROHO ■ ACETATE v. 
 
 Bkomo-aoetic acid. 
 
 BROMO-ETflYLENE CjHsEr i.e. CHErtOHj. 
 Vinyl bromide. (16°). S.G. y 1-5167 (Anschiitz). 
 Formed by the action of alcoholic EOH upon 
 either di-bromo-ethane (Eegnault, A. Ch. [2] 
 59, 358 ; Eeilstein, J. 1861, 609 ; Gloekner, A. 
 Suppl. 7, 109 ; Semenoff, J. 1864, 480). Formed 
 also from acetylene and HBr (Eeboul, G. B. 
 74, 947). Gas or liquid ; when kept in a sealed 
 tube and exposed to sunlight it changes to an 
 amorphous polymeride, insol. water, alcohol, 
 and ether; S.G. 2-075. This substance carbon- 
 ises when heated (Hofmann, O. J. 13, 68 ; Bau- 
 mann, A. 168, 808) ; it is not aSeoted by boiling 
 alcoholic EOH. Polymerisation is arrested by 
 the presence of Mel or EtI, but not by chlo- 
 rinated or brominated hydrocarbons ; a little I 
 stops polymerisation of the liquid, but not of 
 the gas. Aniline arrests, but SO^ promotes, the 
 change (Lwow, Bl. [2] 35, 169). 
 
 Beactions. — 1. Split up into HBr and acetyl- 
 ene by alcoholic EOH, NaOEt, NaOC^Hn, or am- 
 moniaoal AgNOj (Sawitsch, Bl. 1861, 7 ; A. 119, 
 
 185 ; Miasnikoff, Bl. 1861, 12 ; A. 118, 330) 
 
 2. Cone. HBr at 6° forms s-di-bromo-ethane ; a 
 more dilute acid gives M-di-bromo-ethane (Ee- 
 boul, A. 155, 29, 212).— 3. Fuming HCl at 100° 
 forms CHs.CHBrCl.— 4. Cone. HI at 4° gives 
 CHj.CHBrl; at 100° it forms also 0HjI.CH4Er. 
 (E.). — 6. Aqueous solutions of metallic 
 salts either have no action or split it up 
 into acetylene and HBr (Eutsoheroff, B. 14, 
 1532 ; Linnemann, A. 143, 347 ; Saytzeft a. 
 Glinsky, Z. [2] 3, 675). — 6. Successive treatment 
 with cone. H^SOj and water forms crotonic alde- 
 hyde (Zincke, A. 191, 370).— 7. Aqueous BrOH 
 at 0° gives CHBrj.GH^OH, CHBr^.CHjBr, and 
 CjHjBrOa [40°-45°] (90°) (Demole, B. 9, 49).— 
 7. Dry oxygen at 23° has no action.— 8. ICl 
 forms CHBrl.CHjCl and a less quantity of 
 CH,I.CHBrCl (Henry, O. iJ. 98, 680).— 9. With 
 benzene and AI2CI5 it produces styrene, ethyl- 
 benzene, w-di-phenyl ethane, and di-methyl- 
 anthraoene dihydride (Ansohutz, A. 235, 331). 
 If elevation of temperature be avoided and the 
 AljClj be slowly added the products are 
 CHs.CjHjBr and Cfi,(C^E^Br)^ (Hanriot a. 
 Guilbert, 0. B. 98, 525). 
 
070 
 
 BROMO-ETHYLENE. 
 
 s-Dl-bromo-etliyleua OHBr:CHBr. Acetylene 
 dibromide. (110°-111°). S.G. ip 2-2714 (An- 
 Bchutz, A. 221, 141) ; 2 2-268 (Sabanfeeff, B. 9. 
 1441; Plimpton, O. J. 39, 536) ; ia 2-223 (S.)- 
 V.D. 6-47 (oalo. 6-44).— Formfid by mixing acetyl- 
 ene tetrabromide (100 g.) -with alcohol (20 g.) 
 and adding zinc dust slowly, with cooling (A. ; of. 
 Saban6eff,4.216,252). 
 
 Properties. — Oil ; does not polymerise. 
 
 Reactions. — 1. Heated for several days with 
 50 pts. of water at 135°, it is not affected. — 
 2. Heated with dilate 'K.fiO,, bromo-acetylene 
 is formed, which is spontaneously inflammable. 
 Alcoholic KOH and aqueous KCy also form 
 bromo-acetylene. — 8. Heated with dry KOAo at 
 160° for two days it forms CHBr:CH(OAc), the 
 acetate of bromo-vinyl alcohol (Saban^eff, Bl, 
 [2] 41, 253).— 4. Heated with AgOAc and a 
 little HOAc at 100° it forms a compound 
 C2HjBrj2AgOAo. This is decomposed by HCl 
 with evolution of acetylene. — 5. Combines with 
 AgNOj. — 6. With alcoholic KCN it forms a com- 
 pound which, on saponification, gives an acid 
 C^HjOs [163°-168°]. Its silver salt is C^H^AgA 
 (S.).— 7. Alcoholic KOPh gives CHBr.CHOPh. 
 (0. 228°); S.G. is 1-485.— 8. With alcoholic 
 NMe, at 120° it forms NMeiBr, NMejHBr, 
 NMejHjBr, and carbonaceous bodies : 
 
 2NMe3 + CjHjBrj = 2NMesHBr -h C^ 
 (Plimpton, C. J. 39, 586).— 9. With NEta it 
 acts similarly. — 10. Acts upon benzene in 
 presence of AljCl, forming CHBrj.CHjBr, 
 anthracene, and CHjPh.CHjPh (Ansohiitz, A. 
 235, 153). 
 
 tt-Si-bromo-ethylene CBrjiCHj. AcetyUdene 
 dibromide. (92°) at 754 mm. in COj. S.G. f^ 
 2-1780 (Anschiitz). From CHBr^.CHJBr by 
 treatment with alcoholic KOH, NaOEt, sodium, 
 or solid KOH (Oahours, C. B. 31, 293 ; Fontaine, 
 C. B. 70, 1361 ; Sawitsch, A. 119, 183 ; Eeboul, 
 A. 124,270; Tawildaroff, A. 176,22; Michael, 
 Am. 5, 192). From CBrj.CHjBr by boiling with 
 alcohol and KOAo (Demole, Bl. [2] 29, 205), or 
 by treatment with zinc and alcohol (Sabanfieff, 
 A. 216, 255). Also from CH^CLCHBrj and al- 
 coholic KOH (Henry, Bl. [2] 42, 262). 
 
 Pj-qperfes.— Pungent liquid, attacking the 
 eyes. Eeadily absorbs oxygen, changing to 
 bromo-acetyl bromide. Polymerises with great 
 ease, becoming solid. 
 
 Eeocfcras.— l.HBrOformsCBr3.CO.CHj.CBr3 
 [90°]. S.G. 2 2-88 (Demole, B. 11, 1710).— 2. 
 Benzene and Alfilg give M-di-phenyl-ethylene 
 (Anschiitz, A. 235, 158). 
 
 Tri-bromo-ethylene CHBr:CBrj. (163°-164°). 
 S.G. 5?-5 2-708 (S. a. D.); 2 2-69 (Demole, B. 11, 
 318). From di-bromo-ethylene bromide and 
 alcoholic KOH (Lennox, A. 122, 125). 
 
 Preparation. — Acetylene tetra-bromide (1 
 mol.) is dissolved in twice its weight of alcohol 
 and (somewhat more than 2 mols. of) KOAc and 
 Na^CO, (1 mol.) are added ; the mixture is 
 heated on a water bath 24 hours with inverted 
 condenser (Saban^eff a. Dworkowitsoh, A. 216, 
 280; cf. Sabandeff, A. 178, 122; Bl. [2] 29,207). 
 
 BeacUons. — 1. Alcoholic KOH or Zn and 
 HOEt give a mixture of OjHj and C^HBr. — 
 8. Alcoholic KOPh at 100° forms phenyl di- 
 bromo-vinyl oxide.— 3. Alcoholic KOPh at 170° 
 forms the phenyl derivative of glyoxylic acid. 
 
 PhO.CH3.OOaH.— 4. Eeacts upon benzene ia 
 presence of AljClj producing M-di-phenyl-ethyl- 
 ene and tri-phenyl-methane (Anschiitz, A. 235, 
 336).— 5. Absorbs oxygen, becoming CHBrj.OO.Br 
 (Demole a. Dun, B. 11, 1302). 
 
 Tri-bromo-ethylene (CaHBrs)^.. [174°]. A 
 by-product in formation of CjHjBrj from acetyl- 
 ene (Saban^eft, A. 178, 114). 
 
 Tetra-bromo-ethylene C^Br,. [54°]. (215°). 
 
 Formation. — 1. By the action of Br on alco- 
 hol or ether (Lowig, A. 8, 292).— 2. From 
 CjHBrs and alcoholic KOH (Lennox, A. 122, 
 126).— 3. From CHaOlj and IBr3 (Holand, 4. 
 240, 234).— 4. From CBr, by heating at 220° 
 (H.). — 5. From di-bromo-succinio acid, Br, and 
 water at 190° (Bourgoin, B. 7, 1644). 
 
 Properties. — Plates ; volatile with steam ; no« 
 affected by oxygen even at 216° (D.). 
 
 BBOUO-ETHYL-EXHEB v. Bbomo-eibyl 
 
 OXIDE. 
 
 BBOMO-ETHTL-KAIBIITE v. Ethyl ether 
 
 of Br0M0-(B. 4)-0XI-(B. 4)-ETHyL-QUIN0LINB TB- 
 TBAHYDBHIE. 
 
 7-BSOlIO-ETHYL-MALONIC ACID 
 
 C^HjBrOi i.e. Br.CH3.CH.,.CH(C03H)3. [116°]. 
 From vinaconio (tri-methylene di-carboxylio) 
 acid and HBr (Eoder, A. 227, 19 ; Perkin, jun., 
 0. J. 47, 814). SI. sol. benzene, OS, or light 
 petroleum, sol. chloroform. Boiled vrith water 
 it gives the lactone of 7-oxy-ethyl-malonia 
 acid (g. v.). 
 
 Eromo-ethyl-malonic acid 
 CH3.CHBr.CH(C0jH)2 (?). [141°]. From crot- 
 aconio acid CsHuO^ and HBr (Glaus, A. 191, 79). 
 
 TBIBBOUO- (a) ■ ETHYL- NAPHTHALENE 
 0,„H4Br3.C2Hj. [127°]. Slender needles. Pre- 
 pared by the action of bromine on (a)-ethyl> 
 naphthalene (Oarnelutti, B. 13, 1672). 
 
 BBOMO-EIHYL (;3)-NAPHTHYL ETHEB «. 
 
 (j3)-NAFHTH0L. 
 
 a>a-BSOMO-DI-ETHYL OXIDE 
 CH3Br.CH3.OEt. (128»). S.G. 2 1-371. V.D. 
 5-29 (calc. 5-28). From the iodo- compound and 
 Br (Henry, O. B. 100, 1007). 
 
 Di-a-bromo-di-ethyl oxide CHjBr.CHBr.OEt. 
 From Br and vinyl ethyl oxide. Very unstable 
 liquid. NaOEt gives CH2Br.CH(0Et)j (Wish- 
 cenus, A. 192, 111). 
 
 Tetra-bromo-di-ethyl oxide C^^tfi. A 
 fuming liquid obtained by saturating ethylidena 
 oxychloride with Br at 120° (Kessel, B. 10, 1667). 
 
 Octo-bromo-di-ethyl oxide C^HjBrgO. (0. 134°) 
 at 460 mm. By heating ethylidene oxychloride 
 with Br for 10 hours from 100°-210° (Kessel, B. 
 10, 1667). Fuming oil. 
 
 Eso-exo- DI - BROMO -o -ETHYL - PHENOL 
 OsH3Br(C2H4Br)OH. From o-ethyl-phenol and 
 Br in the cold. Decomposed by distUlation into 
 HBr and CsH,Br(C2H3)OH (Suida a. Plohn, ilf. 
 1, 175). 
 
 Tri-bromo-(a)-ethyl-phenol CsHBrjEt.OH. 
 [55°]. Formed, together with the following 
 body, by treating (a) -ethyl phenol with excess ot 
 Br in the cold (Fittig a. Kiesow, A. 156, 251). 
 
 Eso-exo- Tri-bromo-ethylphenol 
 0„H3Br(0H).CHBr.0H3Br. [108°]. Long white 
 needles. Obtained by the action of alcoholic 
 KOH upon C^3Br(OH).0HBr.CHBr.003H, the 
 product of the action of bromine upon _p-coa- 
 maric acid. 
 
bromo-fluoresoeht. 
 
 671 
 
 Acetyl derivative CeH3Br(OAo).CjH,Brj: 
 [94°] ; needlea (Eigel, B. 20, 2535). 
 
 Tetra-bromo-ethyl phenol CjBriEt.OH [106°] 
 {v. sup.). 
 
 BBOMO- TETRA - ETHYL - PHOSPHONIUM 
 BROMIDE 0BLjBr.0H2.PEtsBr. [235°]. From 
 PEtj and ethylene bromide in the cold (Hofmann, 
 Pr. 9, 287 ; 4. Suppl 1, 154). Bhombio dodeoa- 
 hedra. 
 
 Reactions. — 1. Moist silver oxide gives 
 CH2(0H).CH2PEts.0H (difference from corre- 
 sponding derivatives of AsEtj and NEtj which 
 give vinyl base). — 2. With silver acetate and 
 water at 100° it gives acetate of the vinyl base 
 C2H3PEt3.0Ao.— 3. Zinc and HjSO, give 
 tetra-ethyl-phosphonium bromide. — 4. Alcoholic 
 potash has no effect. — 5. Combines with PEtj, 
 AsEt, and NH, forming di-acid bases. 
 
 Salts.— (C2H4Br.PEt3Cl)2PtCl<. Pale orange 
 monocHnio prisms, si. sol. cold, v. sol. hot, water. 
 — (CjH,Br.PEt3Cl)AuCl3.— CjH^Br.PEtal. 
 
 Hydroxide.— GJB.iBT.FEt30B.. From the 
 sulphate by the action of baryta. Unstable, 
 rapidly changing to CjH40H.PEtaOH. 
 
 BROMO-ETHTL-QTJIITOLINE 
 C9Hj(02H4Br)N. The hydrobromide is formed 
 by heating quinoline with ethylene bromide. — 
 B'HBr: thick needles.— (B'^HaCyPtCl^: orange- 
 yellow needles (Berend, B. 14, 1349). 
 
 DI-BROMO-DI-ETHYL SULPHATE 
 (CH2Br.CH2)2S04. An oil formed by warming 
 AgjSOj with benzene and ethylene bromide 
 (Beilstein a. Wiegand, B. 15, 1369). 
 
 Bromo-ethyl-sulphuric acid 
 CH2Br.CHj.O.S03H. From ethylene bromide 
 and SO3 (Wroblewsky, Z. 1868, 563).— BaA'^.- 
 PbA'2 3aq, scales. Ai isomeric acid appears to 
 be formed by heating ethylene bromide with 
 Ag^SOi and water (B. a. W.). 
 
 BROMO-ETHYL-THIOPHENE 
 C4SH2(C2H5)Br. (195° unoor.). Oil. Formed by 
 shaking ethyl-thiophene with bromine-water 
 (Demuth, B. 19, 684). 
 
 Di-bromo-(j3).ethyl-tliiopheneC,SHBr2(C2H5). 
 Oil. Formed by adding 2 mols. of bromine to 
 1 mol. of (;8)-ethyl-thiophene dissolved in acetic 
 acid (Bonz, B. 18, 550). 
 
 Tri-bromo-(/3)-ethyl-tliiopliene C4SBr3(C2H5). 
 [108°]. White plates. SI. sol. cold alcohol and 
 ether. ■ Formed by complete bromination of 
 (;8) -ethyl-thiophene (Bonz, B. 18, 549). 
 
 BEOMO-o-ETHYL-TOLTJENE OsHaMeEtBr 
 [1:2:4]. (221°). Formed by bromination of o- 
 ethyl-toluene in presence of FejBrj. Liquid. 
 By HNO3 (1-1) at 200° it is oxidised top-bromo- 
 o-toluic acid [118°] (Glaus a. Pieszcek, B. 19, 
 3088). 
 
 Bromo-p-ethyl-toluene CsHsMeBrEt [1:2:4]. 
 Fromp-ethyl-toluene and Br. Oxidised to bromo- 
 y-toluio acid (Morse a. Bemsen, B. 11, 224). 
 
 cga-Di-bromo-OT-ethyl-toluene 
 C,H,.CHBr.CH^r. [45°]. Formed by the 
 combination of w-tolyl-ethylene (m-methyl- 
 styrene) with bromine. Colourless crystals 
 (Miiller, B. 20, 1216). 
 
 Tri-bromo-di-ethyl-toluene OjBrsMeEtj. 
 
 [206°]. From (1, 3, 5)-di-ethyl-toluene (Jaoob- 
 (en, B. 7, 1435). 
 
 TEI-BROMO-ETHYL-XYLEITE CBrjEtMe, 
 [3:5:6:1:2:4]. Tri-bromo-di-methyl-ethyl-bem- 
 
 ine. [91°]. From ethyl-w-xyleno (187°) 
 (AnschStz, A. 235, 824). 
 
 BROMO-EUGENOL 03HsBr(OMe)(OH)C3H,. 
 
 Methyl ether OgH,Br(OMe)2. (190°) at 
 20 mm. S.G. 2 1-396. From the dibromide, hot 
 alcohol, and Zn (Wassermann, C. B. 88, 1206). 
 Di-hromide OaHjBr3(OMe)2. Dimethyl ether 
 ofdi-bromo-di-oxy-propyl-benzene. (78°). From 
 Br and a well-cooled solution of methyl-eugenol 
 in ether. Silky needles. 
 
 Ethyl ether C3H,Br(0Me)(0Et). [48°]. 
 Prepared by the action of alcohol and Zn on its 
 dibromide (Wassermann, A. 179, 385). Di- 
 bromide CsH:^r3(0Me)(0Et). [80°]. From 
 ethyl-eugenol and Br. 
 
 Di-bromo-eugenol C3HBr2(0Me)(0H)(C3HJ. 
 [59°]. Glistening hexagonal prisms. V. sol. 
 alcohol. Formed by boiUng an alcoholic solu- 
 tion of the di-bromide with zinc-dust (Chasa- 
 nowitz a. Hell, B. 18, 824). 
 
 Di-bromide CsHBrj(0Me)(0H)(C3H5Br2). 
 [119°]. Glistening quadratic or trimetric tables. 
 Sparingly soluble in ether and cold alcohol. 
 Formed by bromination of eugenol. 
 
 BROMO-FLTJOREITE '> 
 
 C.jH^Br i.e. <ic^Br>^^- l^^^^'J" ^''°™ 
 fluorene, CHGl, and Br in the cold (Hodgkinson 
 a. Matthews, 0. J. 43, 165). Needles (from 
 alcohol). Y. sol. CHClj. Oxidises to bromo- 
 di-phenylene ketone. 
 {a) -Di-bromo-fluorene 
 
 C.aHsBr^ i.e. ^^q^^^I^CH^. Di - bromo - di - 
 
 phenylene-methane. [165°] (Barbier, A. Ch. 
 [5] 7, 479 ; Hodgkinson a. Matthews, O. J. 
 43, 164). Got by adding bromine to a solution 
 of fluorene in CHCI3. Monoolinic crystals, 
 a:b:c = l-167:l:l-065 ; i8 = 77° 52' (Arzruni, Z. 
 Kryst. 1, 624). Sol. boiling alcohol. Turned 
 yellowish by light. CrOs gives di-bromo-di- 
 phenylene ketone. 
 
 Sulphonic acid C.sHjBrjSOaH. [142°]. 
 Formed by sulphonatiou with ClSOsH in CHCI3. 
 — BaA'j. 
 
 (;8)-Di-bromo-fliiorene C,3H8Br2. [163°]. 
 Formed together with the preceding (Fittig a. 
 Sohmitz, A. 193, 134). Monoclinio crystals ; 
 a:6:c = -563:l:-697. )3 = 78° 21' (A.). Eeadily 
 changes into two isomeric modifications (7) 
 and (S) (Lehmann, Z. Kryst. 1, 626). 
 
 Tri-bromo-fluorene 
 
 C,3H,Br3 i.e. <%^^^^^^^- [162°]. From 
 
 fluorene (1 mol.) in CSj and Br (3 mols.). 
 Oxidised by CrO, to (5)-di-bromo-diphenylene 
 ketone (B.). 
 
 DI-BBOMO-FLTJORESCElN C2„H,„BrA- 
 [260°-270°]. From fluorescein (1 mol.) and Br 
 (2 mols.) in HOAo (Baeyer, A. 183, 1). Eeddish- 
 brown needles with green reflex. Dyes wool and 
 sUk salmon-pink. 
 
 Di-acetyl derivative CjoHjAo^BrjOj. 
 [210°]. 
 
 Tetra-bromo-fluorescem 
 
 02„H3Br40. i.e. 0<^«^^^j°§>C<°'^^>CO. 
 
 Eosin. Formed by adding Br to a solution of 
 fluorescein in HOAc. It is purified by conver- 
 sion into the K salt (Baeyer, A. 183, 38), 
 Prepared by dissolving fluorescein (1 mol.) in 
 
672 
 
 BROMO-FLUORESCEiN, 
 
 NaOHAq, adding a solution of Br (4 mols.) in 
 NaOHAq, and acidifying. Orange needles (con- 
 taining HOEt) (from aloohol), or flesh-coloured 
 crystals OjoHgErjOs (from dilute alcohol contain- 
 ing HCl). Tetra-bromo-fluorescem is v. si. sol. 
 water and benzene ; its alkaline solutions are 
 pink and show strong yellow fluorescence, they 
 dye wool and silk pink. Zinc-dust and NaOH 
 reduce it to a leuoo- compound, which is reoxi- 
 dised by air. Potash-fusion forms di-bromo- 
 resorcin and di-bromo-resorcin-phthalein. Cone. 
 HjSO, forms 0„H,sBr,0,„. POI5 forms 
 CjoHjOljErjOj. Sodium-amalgam forms fluor- 
 escein. Warming with cone. KOH gives a 
 deep blue solution whence HCl pps. unstable 
 
 0<C:^r:lSi!>C(OH).C,H,.CO,H. 
 
 Salts. — K2(C2„H5Br^05) 5aq. S. 50. — 
 K,A"HOEt.— (NH,)^".— BaA"2aq.— CaA"|aq. 
 — AgjA".— (HOPbjjA". 
 
 Methyl ether C^B.,M.eBifts. Methyl 
 erythrin. 
 
 Ethyl ether OjoHjEtBr^Os. Erythrin. 
 Spirit-soluble eosin. From KjA", KEtSO,, and 
 alcohol at 150°. From fluorescein, boiling alco- 
 hol and Br. Bed crystals (from alcohol). 
 Formed, together with a colourless ethyl-eosin, 
 by heating silver eosin with EtI and alcohol at 
 100°.— KCjjHjEtBr^Osaq; dyes a more violet 
 shade than eosin. 
 
 Di-ethyl ether CjjHaEtjBrjOj. From 
 AgjA" and EtI. 
 
 Acetyl derivative CajHjAojBr^Os (?). 
 [278°]. 
 
 BEOMOFOEM OHBrj. Tri-hromo-methane. 
 Mol. w. 253. [8°]. (151°). S.G. | 2-8341 (T.) ; 
 ^ 2-9045 (Perkin, O. J. 45, 533) ; || 2-8842 (P.). 
 C.E. (0°-10°) -000944; (0°-100°) -0010116. 
 S.V. 103-53 (Thorpe, C. J. 37, 203). M.M. 
 11-626 at 17-9° (P.). V.D. 8-63 (oalo. 8-75) 
 (Oahours, A. Oh. [3] 19, 484). 
 
 Occurrence. — In crude bromine (Hermann, 
 A. 95, 211 ; Dyson, O. J. 43, 36). 
 
 Formation. — 1. By the simultaneous action 
 of Br and KOH, or of 'bromide of Ume,' on 
 alcohol or acetone, or by decomposing bromal 
 with alkalis (Lowig, A. 3, 295 ; Dumas, A. Oh. 
 [2] 56, 120 ; Giinther, Ar. Ph. [3] 25, 373).— 
 2. From CHjClj and IBrs (Holand, A. 240, 236). 
 
 Beactions. — 1. Alcoholic KOH forms CO 
 (3 vols.) and ethylene (1 vol.) but no formate 
 (Long, A. 194, 23). — 2. Br in presence of dilute 
 EOH in sunlight forms CBr, (Habermarm, B. 
 6, 549).— 3. Eeduced to CH. by KI, water, and 
 Zn or Cu (Berthelot, A. Oh. [3] 61, 48) or by the 
 copper-zinc couple (Gladstone a. Tribe, C. 3. 
 28, 510). 
 
 BEOMO - riTMAEIC ACID G^:Bx{CO^)^. 
 [178°]. 
 
 EormatkM. — 1. From iso-di-bromo-sucoinio 
 acid by heating at 180° or by boiling with water 
 (Kekul6, A. Swppl. 2, 91 ; A. 130, 1).— 2. From 
 di-bromo-succinic acid and water at 140° 
 (Bandrowski, B. 12, 345).— 3. By dissolving 
 aoetylene-di-carboxylic acid in strong aqueous 
 HBr (Bandrowski, B. 15, 2697).— 4. From (;85). 
 dibromopyromucic acid and from (/3)-bromo- 
 pyromucie acid by dilute HNO, (Hill a. Sanger, 
 A. 232, 82, 64). — 5. From bromo-maleic acid 
 and cold fuming HBr (Fittig a. Petri, A. 
 195, 67) 
 
 Properties. — Laminte; v. e. sol. water, V. 
 sol. alcohol and ether. At 200^ it changes to 
 bromo-maleic acid or its anhydride. Sodium, 
 amalgam forms fumaric acid. Br gives the 
 same tri-bromo-succinic acid as with bromo- 
 maleic acid. Fuming HBr combines slowly in 
 the cold ; at 100° it quickly forms iso-di-bromo- 
 sucoinic acid. With its equivalent of aniline it 
 unites immediately to form the acid aniline salt. 
 This does not give an anilide on standing for 
 weeks in contact with cold water. On boiling 
 its aqueous solution the same substance is 
 obtained as on heating aniline bromo-maleate, 
 viz. C.eH.jNjiOj. [230°] (Michael, Am. 9, 180). 
 
 Salts. — AgjA".— PbA" 2aq.— A"H(NH3Ph) : 
 [154°] (Michael, B. 19, 1373). 
 
 Dimethyl ether k"llle,. [30°] (Anschiitz, 
 B. 12, 2284). 
 
 Sl-bromo-fnmaric acid 
 C02H.CBr:CBr.C02H. [220°]. Colourless crystals. 
 Prepared by the addition of bromine to acetylene- 
 dicarboxylic acid. On distillation it is con- 
 verted into dibromomaleic acid [108°]. 
 
 Salts.— AgjA"iaq.—PbA" (Bandrowski, B. 
 12, 2213). 
 
 (/3)-BE0M0-nrEFUEANE C^HjBrO. (103°). 
 From the corresponding bromo-pyromncio acid 
 by distilling with lime (Oanzoneri a. Oliveri, 0. 
 17, 42). Heavy oil. 
 
 (a)-Di-bromo-farfarane C,H,BroO i.e. 
 HC = CBr. 
 
 I >0- [10°]- (63°) at 15 mm. ; (166°) 
 
 HO = CBr'^ 
 
 at 764 mm. Formed by adding bromine to 
 an alkaline solution of (S)-bromo-pyromucio 
 acid [184°]. On oxidation it gives fumaric and 
 maleic acids. 
 
 Tetra-bromide C^HjErsO: [111°] ; by long 
 boiling with water it yields bromo-f umaric and 
 bromo-maleic acids (Hill a. Hartshorn, S. 16, 
 1132 ; B. 18, 448 ; A. 232, 63). 
 
 (;8)-Di-bromo-furfurane<^^J:^^0.(166°). 
 
 Formed by distilling di-bromo-pyromucic acid 
 (1 pt.) with Ca(OH)j (2 pts.) (Canzoneri a. 
 OUveri, 0. 15, 116). 
 
 Tetra-bromo-furfnrane C^Br^O [65°]. From 
 (;87)-di-bromo-pyromucio acid, or from tri- 
 bromo-pyromucio acid, water and bromine va- 
 pour. Formed also by the action of alcoholic 
 KOH on di-bromo-furfurane tetrabromide (Hill 
 a. Sanger, A. 232, 86, 96; B. 16, 1132; 17, 
 1760). 
 
 Di-bromide C,Br,0. [123°]. Six-sided 
 plates. Y. sol. ether, m. sol. alcohol and benzene. 
 By boiling with water it yields di-bromo-maleio 
 acid (Hill a. Hartshorn, B. 18, 450). 
 
 BEOMO-rUEIL V. Fueil. 
 
 BE0U0-6AILIC ACID v. Bbomo-ibi-oxt- 
 
 BENZOIO ACID. 
 
 TBI-BEOMO-GtrAIACOL C,H,Br,Oj i.e. 
 CjHBr3(0Me)(0H). [102°]. From guaiacol and 
 Br (Tiemann a. Koppe, B. 14, 2017). 
 
 BEOMO-GUANIDIITE CH^BrN,. From 
 guanidine carbonate and Br (Kamenski, B. 
 11, 1600). Needles; detonates just above 100°. 
 
 BEOMO-GUANINE C^H^NsOBr. From 
 guanine and bromine, crystallised from water. 
 White powder. SI. sol. boiling water, insol. 
 cold water, alcohol or ethsr. — ^B^Ol. PrismSi 
 
BROMO-HEXOIO AOID, 
 
 873 
 
 Converted by NaNO, into bromo-zanthine 
 (Fischer a. Eeese, A. 221, 341). 
 
 Tai-BEOMO-HEMIMELLITHOL v. Tm- 
 
 BBOSIO-TKI-MBTHYI,-BENZENl!-(l:2:3:4:5:6). 
 
 BSOMO-HEPTANE v. Hepttl bkomide. 
 Di-bromo-heptane CjHuBrj. Heptylene 
 bromide. S.G. !?!? 1'515. From heptane of 
 paraffin oil. Decomposes at 150' (Thorpe a. 
 Young, A. 165, 12). 
 
 Di-bromo-heptane CjHuBrj (211°). From 
 heptane in the oil of Pimcs sabiniana (Venable, 
 A. a. J. 4, 22). 
 
 Di-bromo-heptane CMej.CMeBr.CHjBr. From 
 penta-methyl-ethyl alcohol and PBrj. Easily 
 fusible solid (Kasohirski, O. G. 1881, 278). 
 
 Di-bromo-heptane 
 CHj.CHj.CHj.CHj.CHj.0H2.CHBrj. Beptytidene 
 bromide. From oenanthol and PCljBrj (Bruy- 
 lants, B. 8, 409). 
 
 Heza-bromo-heptane CjHuBr,;. From hep- 
 tonene and Br. Oil (Saytzeff, A. 185, 144). 
 
 o-BROMO-HEPTOIO ACID CjH.jBrOj i.e. 
 CH3.CHj.CH2.CH2.CH2.CHBr.CO,H.(250°).From 
 Br and heptoio acid (Cahours, A. Sujapl. 2, 83 ; 
 Helms, B. 8, 1168; Hell a. Schule, B. 18, 625). 
 
 Ethyl ether 'EtA'. (o. 225°). S.G. >£.^ 1-211. 
 
 TETEA-BKOMO-HEPTYL ALCOHOL 
 C,H, jBr.O i.e. (CH^Br.CHBr.CHJjCH.OH. From 
 di-allyl-carbinol and Br (M. Saytzeff,4. 185,135). 
 Oil. 
 
 Acetyl derivative C,H„BrjOAc. Con- 
 verted by AgOAc into 0,H„0(0Ac)3, S.G. g 1-180, 
 whence baryta forms a syrup C,H„0(0H)3 
 (Dieft, J.pr. [2] 35, 17). 
 
 BKOMO-HEPTTLENE C,H,3Br. (158°). 
 From the heptylene bromide of Venable. 
 
 Bromo-hep^lene 0,H,sBr. (165°). From the 
 heptylene bromide of Bruylants. 
 
 BBOmO-HEXADECANE v. Cetyi. bbomide. 
 
 Di-bromo-hezadecane Ci^Hj^Br^. Getene bro- 
 mide. [13^°]. Colourless crystalline solid. 
 Formed by addition of Brj to cetene (Krafft, B. 
 17, 1373). 
 
 BKOMO-HEXANE v. Hextl bkomide. 
 
 Di-bromo-hezane CgHi^r^ i.e. 
 CH3.CH2.CH2.CHBr.CHBr.CH3. (196°) at 740 
 mm. S.G. V 1-5809. From the corresponding 
 hezylene (Erlenmeyer a. Wanklyn, A. 135, 141 ; 
 c/. Hecht a. Strauss, A. 172, 69 ; Hecht, B. 11, 
 1423). 
 
 Di-bromo-hezane Me^CBr.CBrMcj. [170°] (K.); 
 [140°] (E.). From Me2C:CMej and Br. Needles 
 (from ether). Converted by heating with water 
 and PbO at 150° into pinacohn (Pawlow, A. 
 196, 124 ; Eltekoff, /. B. 10, 220 ; Kaschirsky, 
 J. B. 13, 84). 
 
 Di-bromo-hezane MejC.CHBr.CHjBr. From 
 MesC.CH:CHj. Crystalline (Friedel a. Silva, Bl. 
 [2] 19, 289). 
 
 Di-bromo-hezane CjHijBrj. (211°). From 
 hexane of petroleum (Pelouze a. Cahours, A. 124, 
 293). 
 
 Tetra-bromo-hezane CaH,„Br4. Diallyl- 
 tetrabromide. [63°]. From diaUyl and Br 
 (Wagner a. ToUens, B. 6, 588). 
 
 Tetra-bromo-hezane OsH.oBrj. [142°]. From 
 iodo-hexylene and Br (Bouohardat, Z. 1871, 
 
 699). , . 
 
 Tetra-bromo-hezane CaHioBrj. From hexi- 
 
 n«B« derived from wannite (Heoht, B. 11, 1054). 
 
 Tetra-bromo-hezane OsH.oBr^. From hezi- 
 nene from di-methyl-allyl-carbinyl chloride 
 (Saytzeff, B. 11, 2152). 
 
 Tetra-bromo-hezane 0„H,i;Br,. [112°]. (318° 
 cor.). From hexinene derived from coal-tar 
 (Sohorlemmer, A. 139, 250). 
 
 Heza-bromo-hezane CgHgBrj. From di- 
 allylene (Henry, Bn. 1, 199). 
 
 Heza-bromo-hezane OsHaBrj. [77°]. From 
 di-bromo-diallyl (Henry, B. 7, 23). 
 
 Heza-bromo-hezane CjHjBrj. [152°]. From 
 sec-hexyl iodide and Br at 130° (Merz a. Weith, 
 5. 11, 2250). 
 
 Heza-bromo-hezane CjHjBrj. From hexane 
 and Br at 125° (Wahl, B. 10, 1234). 
 
 Octo-bromo-hezane CsHjBrj. From hexane 
 and Br (W.). 
 
 Octo-bromo-hezane C^H^Brs. [135°]. From 
 sec-hexyl iodide and Br at 130° (M. a. W.). 
 
 Octo-bromo-hezane C^H^Brs. Dipropargyl 
 octobromide [141°] (Henry, B. 7, 21). 
 
 BEOMO-HEXENOIC ACID C^HsBrA; ■Z>'- 
 bromo-hydrosorbic acid. [95°]. From sorbio acid 
 and Br. LaminsE (Fittig a. Kachel, A. 168, 287). 
 
 DI-BROMO-HEXINENE CXBrj. Di-bromo- 
 diallyl. (210°). S.G.is 1-656. Fromdiallyl-tetra- 
 bromide and solid KOH (Henry, J. pr. [2] 8, 57). 
 
 Tetra-bromo-hexinene CoHsBr^. Propargyl 
 tetrabromide. S.G. 2 2-464. Liquid (Henry, B. 
 6, 959). 
 
 o-BKOMO-ra-HEXOIC ACID 
 CH3.CH2.CH2.CHj.CHBr.CO2H. Bromo-caproia 
 acid. (240°). From caproio acid and Br 
 (Cahours, A. Suppl. 2, 78). 
 
 Ethyl ether EtA' (205°-210°) (Hell, J3. 17, 
 2218). 
 
 7-Bromo-n-hezolc acid 
 CHs.CH2.CHBr.CH2.CH2.CO2H. From hydro- 
 sorbic, or iso-hydrosorbic, acid and HBr. Oil. 
 Sodium-amalgam reduces it to n-hexoio acid. 
 Boiling water converts it into hydrosorbio and 
 oxy-hexoic acids (Fittig, A. 200, 42 ; Hjelt, B. 
 15, 618). 
 
 7-Broma-iso-hezoic acid 
 Me2OBr.CH2.CH2.CO2H. 
 
 Ethyl ether Af'Et. Formed by saturating 
 an absolute alcoholic solution of isocaprolactone 
 with HBr. By distiUatiou it is decomposed into 
 the original lactone and EtBr (Bredt, B. 19, 514). 
 
 Bromo-hezoic acid OeH„Br02. [86°]. From 
 iso-pyroterebic acid and HBr. Prisms. AgA' 
 (Lagermark a. Eltekoff, J. B. 11, 128). 
 
 Bromo-hezoic acid CjH„Br02. [25°]. From 
 ethyl-crotonic acid and cone. HBrAq. Sodium- 
 amalgam forms hydro-ethyl-crotonio acid. 
 Aqueous Na^COsAq even at 0° forms amylene, 
 NaBr, and COj. 
 
 aj3-Dl-bromo-iso-hezoic acid 
 Pr.CHBr.CHBr.CO2H. [99°]. From pyrotere- 
 bio acid and Br (W. C. Williams, B. 6, 1095 ; 
 Geisler, A. 208, 46). Large crystals (from CS2). 
 
 Di-bromo-hezoic acid CjH,jBr202.. [68°]. 
 From sorbio acid and fuming HBr. Boiling 
 water or alkalis produce sorbio acid, and other 
 bodies (c/. Hjelt, B. 15, 620). 
 
 Di-bromo-hezoic acid CeHuBrjOa. From 
 hydrosorbio acid and Br in CSj. Liquid ; de- 
 composed by boiling water, giving oxy-hydro- 
 sorbio acid (Fittig, 4. 161, 814 ; 200, 46; Hjelt, 
 B. 15, 619). 
 
574 
 
 BROMO-HEXOTC AOIT). 
 
 Di-bromo-hezoic acid CjHioBrjOj. From iso- 
 Borbic acid and HBr. Oil (L. a. E.). 
 
 Di-bromo-hezoic acid CHEtBr.CMeBr.COjH. 
 [98°j. From methyl-ethyl-acrylio acid and 
 Br. Monoclinio crystals, a:6:c = -96:l:l*53.3 = 
 94° 36'. Water at 100° forms bromo-amylene 
 CHEt:CMeBr, methyl-ethyl-acrylio acid, di-oxy- 
 hexoic acid, and methyl ethyl ketone (Lieben, 
 B. Zeisel, M. 4, 78). 
 
 Di-bromo-hexoic acid CsHioBrjOj. [81°]. 
 From ethyl-orotonic acid and Br. Decomposed 
 by cold NajCOsAq into bromo-amylene, NaBr, 
 and CO2 (Fittig, A. 200, 35). 
 
 letra-bromo-hezoic acid CjEgBr^Oj. [183°]. 
 From sorbio acid and Br (Fittig, A. 161, 323 ; 
 168, 277 ; 200, 58). Monoclinio crystals (from 
 alcohol). More stable than the preceding acids, 
 not being attacked by water at 100°. — NaA' 2act. 
 — CaA'j 7aq.— BaA'2 IJaq. 
 
 DI-BROMO-HEXOIC ALDEHYDE C^H.^r^O 
 i.e. CH3.CH2.CHBr.CMeBr.CHO. Di-hromo- 
 methyl-joropyl-aeeUc aldehyde. From Br and 
 cold methyl -ethyl -acrolein. Pungent oil. — 
 (CsH,„Br.0)NaHS03 3aq (Lieben a. Zeisel, M. 
 4, 19). 
 
 BKOMO-HEXONENE CsH^Br, Bromo-di- 
 allylene. (150°). From di-bromo-di-allyl and 
 KOH. Pps. ammoniacal AgNOj and cuprous 
 chloride (Henry, B. 14, 400). 
 
 Octo-bromo-hezonene OsBrj. Fromseo-hexyl 
 iodide and Br at 140°. Prisms. At 200° it 
 splits up into Br and hexa-bromo-benzene 
 (Merz a. Weith, B. 11, 2247). 
 
 BEOMO-HEXTL ALCOHOL CjHijBrO i.e. 
 CH3.CHBr.CH(0H).CH2Et. (189°). S.G. 1-3. 
 Liquid. From hexylene oxide and Br (Henry, 
 G. B. 97, 260 ; Bl. [2] 41, 363). 
 
 Di-bromo-hezyl alcohols v. Dihromides of 
 
 HeXENTL AlOOHOIiS. 
 
 DI-BBOMO-HEXYL-BENZENE C,2H,eBrj i.e. 
 Ph.CHBr.CHBr.CH,.CH(CH3)j,. [80°]. From 
 hexyl-benzene (g. v.). Needles or plates. 
 
 BEOMO-HEXYLENE CsH„Br. (138°- 141°) at 
 739 mm. S.G. « 1-2025. From (;8).hexylene 
 bromide and alcoholic KOH (Caventou, A. 135, 
 126; Eeboul a. Truohot, A. 144, 247; Hecht, 
 B. 11, 1424; A. 172, 70). See also Hexbntl 
 
 BROMIDE. 
 
 Di-bromo-hezylene CsH,„Br2. S.G. « 1-698. 
 From hexylene (derived from mannite) and Br 
 (Henry, B. 11, 1054). 
 
 Tetra-bromo-hexylene CjHjBr,. From di- 
 allylene and Br (Henry, 0. B. 87, 171). 
 
 Octo-bromo-hexylene C^H^Brs. [184°]. From 
 s«c-hexyl iodide and Br at 130° (Merz a. Weith, 
 B. 11, 2249 ; Hecht, B. 11, 1420). 
 
 Octo-bromo-hexylene C„H^Brj. From hexane 
 and Br at 125° (Wahl, B. 10, 402). 
 
 BROMO-HIPPTTEIC ACID CjHsBrNO, i.e. 
 C,HjBr.C0.NH.CH2.C02H. From hippnrio acid, 
 alcohol, and Br. Slender needles. Possibly 
 identical with the following acid. — CaA'2 (Mayer, 
 Z. 1865, 415). 
 
 jp-Bromo-hippTiric acid 
 [1:4] C8H4Br.CO.NH.CH2.CO2H. Excreted when 
 p-bromo-toluene is taken with food. Flat needles 
 (from water). Boiling HClAq forms glyooooll 
 andp-oxy-benzoio acid (Prensse, H. 6, 63). 
 
 BBOUO-HTDBATBOFIC ACID v. Bnouo- 
 vexntl-pbofiokio acid. 
 
 SBOIIHVDBIV V. QhVast^. 
 
 Iri-bromhydrin v. Tbi-bkomo-pbopakb. 
 P.BBOMO-HYDEOCABBOSTYBIL CHjBrNO 
 ^C.,H,.CO _ ,- 
 i.e.C.H3(Br)\NH/ [^rjj. [178°]. Long 
 
 flat needles. V. sol. alcohol, ether, benzene 
 and acetic acid. Prepared by reduction of p- 
 bromo-o-nitro-hydro-cinnamio acid with tin 
 and HCl (Gabriel a. Zimmermann, JB. 13, 
 1683). 
 
 BBOMO-HYDEOCINNAMIC ACID v. Bbomo- 
 
 PHENTL-PKOPIOSIO AOID. 
 
 DI.BEOMO-HYDEO-C(ERULIGNON v. Cceeu- 
 
 LIONON. 
 
 BEOMO - HYDEOftUINONE O.H.BrO. i.e. 
 03H3Br(OH)2. [111°]. 
 
 Pcn-mation. — 1. Together with di-bromo-hy- 
 droquinone, by the action of cone. HBrAq on 
 quinone (Wiohelhaus, B. 12, 1504). — 2. From 
 hydroquinone (1 mol.) and Br (1 mol.) in ether- 
 chloroform (Sarauw, A. 209, 99). 
 
 Properties. — Leaflets ; may be sublimed. V. 
 e. sol. water, alcohol, and benzene. FcjCl, 
 forms bromoquinone. 
 
 Di-aceiyl derivative 05H3Br(OAc)2. 
 [73°] . Formed, together with di-acetyl di-bromo- 
 hydroquinone by heating quinone with AcBr 
 (Schulz, B. 15, 655). Needles, sol. alcohol and 
 benzene. 
 
 Di-bromo-hydroquinone CjH2Br2(0H)2. [187°]. 
 
 Formation. — 1. As above (W.). — 2. From 
 hydroquinone and Br in HO Ac (Benedikt, M. 1, 
 345). — 3. From quinone and Br (Sarauw). 
 
 Properties. — Long needles (from water). 
 Converted by FejOlj or bromine-water into di- 
 bromoquinone. 
 
 Di-acetyl derivative C5H2Br2(OAc)2. 
 [161°]. Formed as above (Schulz). Needles, 
 sol. chloroform and ether. 
 
 Methyl ether CeH2Br2(0H)(0Me). From 
 methyl-hydroquinone and Br (B.). 
 
 Di-methyl ether CjH2Br2(0Me)2. [142°]. 
 From di-methyl-hydroquinone and Br in HOAo 
 (Habermann, B. 11, 1036). Methyl-ethyl ether 
 CsH2Br2(0Me)(0Et). [88°]. Prepared like the 
 preceding (Fiala, M. 6, 513). 
 
 Di-isobutyl ether 0sH2Br2(0CjH5)2. 
 From O^B.i{OGi^^)i andBr (Schubert, M. 3, 684). 
 Plates (from HOAc). 
 
 Di-bromo-hydroquiiione05H3Br(OH)(OBr)(?). 
 Bromoxy-bromo-phenol. [87°]. From quinone 
 (Imol.) and Br (1 mol.) in chloroform (Sarauw). 
 Golden tables, si. sol. ether and CHCl,, decom- 
 posed by water into HBr and bromoquinone ; 
 changes slowly to CjHjBr2(0H)2. 
 
 Tri - bromo - hydroquinone CsHBr3(0H)2. 
 [136°]. Formed together with tetra - bromo- 
 hydroquinone, by treating di-bromo-quinone 
 with cone. HBr, or by the action of Br (6 mols.l 
 on hydroquinone (2 mols.) or quinone (3 mols.) 
 (Sarauw, A. 209, 116). Silky needles, sol. alco- 
 hol and benzene, v. sol. boiling water. FejCl,, 
 gives tri-bromo-quinone. 
 
 Tetra - bromo - hydroquinone C3Br4(OH)2. 
 [244°]. Prepared as above (Sarauw). Prepared 
 also by reducing tetra-bromo-quinone (brom- 
 anil) with SOj or HI and P (Stenhouse, A. 91, 
 310 ; Svppl. 8, 20) or by warming it with cone. 
 HBrAq. Slender needles (from HOAc) ; inaol. 
 boiling water, v. sol. alcohol. Fe,Cl, forma 
 tetra-bromo-qninoqe. 
 
BROMO-IODO-ETHYLENB. 
 
 678 
 
 bsomo-htdboqttinone-fhihaleIn v. 
 
 HYABOgriNONE-PHTHAIjEIN. 
 
 SI-BBOUO-HYSBOSOBBIC ACID v. Bbouo- 
 
 BEXENOIO AOID. 
 
 BB0UO-HTDB0-THTMOQ1TINONE 
 C,,H,3BrO, i.e. 0^(0,H,)(CH3)Br(0H),. [58°]. 
 Prom thTmoquinone and HBr (Sohniter, B. 20, 
 1318). Oxidises to biomothymoquinone [45°]. 
 The di-aeetyl derivative is formed by the action 
 of acetyl-bromide on thymoquinone. 
 
 Di-acetyl derivative [91°]. Ehombo- 
 hedral crystals (Schulz, B. 15, 657). 
 
 Di-bromo-hydro-thymoq,mnane 
 0,(C,H,)(OH,)Br,(OH),. 
 
 Di-acetyl derivative [122°]. Colourless 
 tables (Sohulz, B. 15, 658). 
 
 BBOMO-HYDEO-TOLTTftTJINONE 
 CsH,MeBr(OH)j. [o. 160°]. Formed by the 
 action of cold cone. HBr upon tolaquinone. 
 Glistening plates (Sohniter, B. 20, 2286). 
 
 Tri-bromo-hydro-tolnqTiinone 
 CjHsBraO, i.e. C^r3Me(0H)j. [202°]. From 
 tri-bromo-toluquinone and SOj. Needles, sol. 
 water (Canzoneri a. Spioa, G. 12, 471). 
 
 BEOMO - HYPOGJEIC ACID v. Hspoaaiio 
 Acn>. 
 
 DI-BEOMO-ICOSYLENE Gjai^^Br^. OU. 
 From ioosinene and Br (Lippmann a. Haw- 
 liczek, B. 12, 69). 
 
 DI-BEOMO-INDIGO O.oHsBrjN.p, i.e. 
 
 O O 
 
 C.H^r<^>0 = C<°>C,H,Br. Formed by 
 
 H H 
 
 boiling « - di - bromo - m - bromo - o - amido - aceto- 
 phenone [5:2:1] 0eH3Br(NHj).C0.CHBrj or w-di- 
 chloro - m - bromo - o - amido acetophenone 
 [5:2:1] CsH3Br(NHj)C0.CHCl2 or their acetyl 
 derivatives with dilute NaOH and exposure to 
 the air (Baeyer a. Bloem, B. 17, 968). Pre- 
 pared by heating bromo-isatin with PCI, and 
 treating the product with a 10 p.c. solution of 
 HI in aoetio acid and then with aqueous SO^. 
 Some isomeric di-bromo-indipurpurin is formed 
 at the same time (Baeyer, B. 12, 1315). Small 
 black needles, may be sublimed; v. si. sol. 
 most menstrua. May be reduced to a ' vat ' like 
 indigo. 
 
 BEOMO-INDIETJBIN C,sH^rNA- Long 
 needles. Formed by the action of NajCOj on 
 an alcoholic solution containing indoxyl and 
 bromo-isatin (Baeyer, B. 14, 1745). 
 
 ;8/3-BEOMO-IODO-ACEYLIC ACID 
 OaHjIBrOj i.e. CBrI:CH.COjH. [119°]. S. 1-7 
 at 20°. From bromo-propiolio acid and HI 
 (Hill, Am. 3, 175). Scales.— BaA'j 3aq. S. (of 
 BaA',) 16 at 20°.— CaA', S^aq.- AgA'. 
 
 ofl-Bromo-iodo-acrylic acid CHI:CBr.COjH. 
 [96°]. Formed by the addition of HBr to 
 /3-iodo-propiolio acid (Homolka a. Stolz, B. 18, 
 2284). Needles ; si. sol. cold water. By heating 
 in alcoholic solution with AgBr it yields afl-di- 
 bromo-aorylic acid [85°] (Stolz, B. 19, 537). 
 
 j3a-Bromo-iodo-acrylic acid CHBkCI.COjH. 
 [71°]. Colourless crystals. V. sol. water. 
 Formed by boiling propiolio acid with an 
 ethereal solution of BrI (Stolz, B. 19, 536). 
 
 j8;8o-Broino-di-iodo-acrylic acid 
 CBrI:OI.CO^. [160°]. S. 2 at 20°. From 
 bromo-propiolic acid and iodine in ether. Flat 
 six-sided plateB.-BaA',4a^. S. X6-26 at 20°.- 
 
 CaA'j. — KA'.— AgA' (Mabery a. Lloyd, Am. 8, 
 124). 
 
 a;3j3-Bromo-di-iodo-acrylio aoid 
 CIj:CBr.COjH. [182"]. Glistening colourless 
 plates. Formed by the action of iodine bromide 
 upon iodo-propiolio acid in ethereal solution 
 (Homolka a. Stolz, B. 18, 2286). 
 
 ;3;3a-Dl-broiuo-iodo-acrylic acid 
 CBr^rOLCOjE. [140°]. S. 8-5 at 20°. From 
 bromo-propiolio acid and IBr (Mabery a. Lloyd, 
 Am. 4, 94 ; N. Am. A. 17, 94). Monoclinio 
 prisms (from water); a:6:c = "617:1: "581. — 
 BaA'j Siaq. S. 16-7 at 20°.— CaA'j.— AgA'. 
 
 /3a3-Di-bromo-ioAo-acryIio acid 
 CIBr:CBr.C02H. [147°]. Long silky needles. 
 SI. sol. cold water. Formed by the action of a 
 solution of bromine in chloroform upon iodo- 
 propiolio acid IC:C.C02H (Homolka a. Stolz, 
 B. 18, 2285). 
 
 DI-BEOmO-IODO-AI.LYI. ALCOHOL. 
 Ethyl ether OiBifiTj.0 i.e. 
 CIBr:CBr.CHj.OEt. Oil. From iodo-propargyl 
 ethyl ether and Br (Liebermann, A. 135, 286). 
 
 o-BEOMO-IODO-BENZENE CjH^Brl [1:2]. 
 (257°). From o-bromo-aniline or o-iodo-aniline 
 by the diazo- reaction (Korner, O. 4, 339). 
 
 m-Bromo-iodo-benzene C^H^Brl [1:3]. (252°). 
 Similarly prepared (K.). 
 
 ^-Bromo-iodo-benzene CsH^Brl [1:4]. [92°]. 
 (252°). Similarly prepared (Griess, J. 1866, 
 452 ; K.). 
 
 Bichloride CeH,BrI,Clj. [115°-120», with 
 decomposition]. Ppd. as yellow needles when 
 chlorine is passed into a solution of bromo-iodo- 
 benzene in chloroform (C. Willgerodt, J. pr. [2] 
 33, 158). With alcohol it forms aldehyde and 
 CjHjBrl. It converts metallic and alcoholic 
 iodides into chlorides, iodine being separated. 
 
 Tri-bromo-iodo-benzene CgH^r,! [1:3:5:6], 
 [104°]. Obtained by adding cone. HI to a solu- 
 tion of CeHiBr3.N:N.N0a. Colourless needles, 
 sol. hot alcohol (Silberstein, J. pr. [2] 27, 120). 
 
 Tri-bromo-iodo-benzene CgHjIBr, [1:2:4:5]. 
 [165°]. 
 
 Bichloride CjH2lBra,Cl2. ' Formed by dis- 
 solving CjHjIBrj ia CHCI3 and passing in CI, 
 (WiUgerodt, J.pr. [2] 33, 159). 
 
 s-BEOMO-IODO-ETHANE C^H^Brl i.«. 
 CHjBr.CHjI. Ethylene bromiodide. [28°]. (163°) 
 S.G. — 2-516. From bromo-ethylene and cone 
 HIAq at 100° (Beboul, A. 155, 213), also from 
 ethylene and BrI (Maxwell Simpson, Pr. 22, 51). 
 Needles ; si. sol. cold alcohol. Alcoholic KOH 
 gives iodo-ethylene and acetylene (Lagermark, 
 /. B. 5, 334). 
 
 u-Bromo-iodo-ethaue CHj.CHBrl. Ethyl- 
 idene bromiodide. (142°). S.G. is 2-452. From 
 bromo-ethylene and cone. HIAq at 4° (E.), or 
 from M-di-iodo-ethane and IBr (Maxwell Simp- 
 son, Pr. 27, 424). Alcoholic KOH forms bromo- 
 ethylene. 
 
 Di-bromo-iodo-ethane OjHjIBrj. (170°-180°). 
 S.G. ^ 2-86. From bromo-ethylene and IBr 
 (M. Simpson, Pr. 22, 61). AgjO forms C^HsBr. 
 s - BEOMO - lODO - ETHYLENE C^HjIBr. 
 Acetylene bromiodide. [c. 8°]. (150° cor.). S.G. 
 (solid) a 2-750; It? 2-627. Got bypassing acetyl- 
 ene into aqueous solution of BrI, the product 
 being treated with NajSjO, and distilled with 
 Rteam (PUtDFtoD, 0. /. 41, 899 ; SabanejeS, A. 
 
676 
 
 BBOMO-IODO-ETHYLENB. 
 
 216, 266). With alcoholic NaOH it appears to 
 give off OjHBr. 
 
 M-Bromo-iodo-ethylene CHjiCBrl. (129°). 
 S.G. - 2-565. From ohloro-bromo-iodo-ethane 
 and alcoholic KOH (Henry, 0. B. 98, 741). 
 Slowly absorbs oxygen from air. 
 
 Di-bromo-iodo-ethylene OIBr:CHBr. [66°]. 
 Small prisms. Formed by the action of an 
 aqueous solution of bromine upon i'odo-pro- 
 piolic acid ICiCCO^H, CO2 being evolved 
 (Homolka a. Stolz, B. 18, 2285). 
 
 BROMO-IODO-METHANE OH^Brl. Methyl- 
 ene bromiodide. (139°). S.G. J-g 2-926. V.D. 
 9-65. From methylene iodide and Br or IBr 
 (Henry, C. B. 101, 599). 
 
 Di-bromo-iodo-methane CHBr^I. Bromiodo- 
 form. [6°]. From iodoform andBr (SeruUas, A. 
 Ch. [2] 34,225; 39, 97; Bouohardat, /. Ph.23, 10). 
 
 BBOMO-IODO-NAPHTHALENES C,„HjBrI. 
 The three following are obtained from the corre- 
 sponding bromo-naphthylamines by the diazo- 
 reaotion (Meldola, G. J. 47, 523) : 
 
 (aa)-Bromo-iodo-naphtlialene CijHjBrl [1:4]. 
 [84°]. Large flat needles ; insol. water ; sol. 
 alcohol and glacial HOAc, v. e. sol. benzene and 
 ether. 
 
 (aj3)-Bromo-iodo-naphthalene C,gH„BrX [1:3]. 
 [68°]. Needles. 
 
 (a;3)-Bromo-iodo-naphthaleue C,gH„BrI [1:2]. 
 [94°]. Thick needles. 
 
 BBOMO-IOBO-NIIBOBENZENE 
 0,HjBrI(N02) [1:2:5]. [106°]. From CjH.BrI 
 [1:2] and HNO, or from CsHaBr(NHs,)(NO,) 
 [1:2:5] (Korner, O. 4, 383). Needles or prisms. 
 Alcoholic NH3 displaces I by NHj. 
 
 Bromo ■ iodo - uitro - benzene GgH3BrI(N02) 
 [1:4:3]. [90°].From C5H3Br(NHj)(NOj) [1:4:3] (K.). 
 
 Bromo -iodo - nitro - benzene 0„H3BrI(N02) 
 [1:3:4]. [84°]. From 0,H3Br(NH2)(NO,) [1:3:4] 
 (K.). Alcoholic NH3 displaces I by NH^. 
 
 Bromo - iodo - nitro - benzene CeH3BrI(N02) 
 [1:3:6?]. [127°]. Formed, together with the 
 following body, by dissolving m-bromo-iodo- 
 benzene in fuming HNO3 (K.). Alcoholic NHj 
 displaces Br by NHj. 
 
 Bromo - iodo - nitro - benzene C5H3Bi-I(N02) 
 [1:3:2?]. Needles. 
 
 BEOMO-IODO-NITRO-PHENOL 
 O.H2(OH)(N02)BrI [1:2:4:6]. [104°]. From (1,3,4)- 
 bromo-nitro-phenol, KOH, HIO3, and I (Korner, 
 J, 1867, 617). Monoclinic tables a:b:c 
 = ■520 : 1 : -587 ; i8 = 65° 32' (Groth, Z. Kryst. 1, 
 437) ; volatile with steam. — KA'.— NaA'. 
 
 Bromo-iodo-nitro-phenol C8H2(0H) (NOj)Brl 
 [1:4:2:6]. Prom (1,3,6) -bromo-nitro-phenol as 
 above (K.). Prisms (from ether). — KA' : yellow 
 
 11.66 0.16 S 
 
 BBOMO-IODO-NITBO-TOITJENE 
 
 C3H2MeBrI(N0.J [l:3:4:a;]. [118°]. Formed by 
 nitrating (l,3,6)-bromo-iodo-toluene. Needles 
 (Wroblewsky, A. 168, 160). 
 
 Bromo-iodo-nitro-toluene CeH2MeBrI(N02) 
 [1:3:2 or6:a;]. From the corresponding bromo- 
 iodo-tolueue (W.). 
 
 Bi-bromo-iodo-nitro-tolaene 
 C„HMeBr2l(N0j) [1:3:5:4:2]. [69°]. From 
 OjH^MeBrjI by nitration (Wroblewsky, A. 192, 
 210). Large needles. Yolatile with steam. 
 
 Di-bromo- di-iodo-uitro-tolaene 
 g,MeBr2l2(NO,) [1:3:5:4:2:6]. [129°]. From 
 
 CjHMeBrjIj and fuming HNO,. Yields on re. 
 duction by Sn and HCl an amido- compound 
 which is converted by further treatment by Sn 
 and HCl to o-toluidine (W.). 
 
 BEOMO-DI-IODO-PHLOEOGLUCIN 
 Cj(OH)3Brl2. From tri-bromo-phloroglucin and 
 aqueous KI. Decomposed by heat (Benedikt a. 
 Schmidt, M. i, 605). 
 
 BBOMO-IODO-PEOPANE CsH„BrI i.e. 
 CH3.CBrI.CH3. (148°). S.G. 11 2-20. Formed 
 by union of HI with allylene hydrobromide 
 (Reboul, C. B. 74, 669, 944). 
 
 Bromo-iodo-propane CH3.CHI.GH3Br or 
 CH3.CHBr.CHi,I. (160°-168°). From propylene, 
 water, and IBr (M. Simpson, Pr. 22, 51). 
 
 DI-BEOMO-IODO-PBOPYLENE 03H3lBr3 (?). 
 From iodo-allylene and Br. Does not combine 
 with Br (Liebermann, A. 135, 275). 
 
 SI-BBOMO-IOSO-STEABIC ACID 
 C,sHs3BrjI02. From ricinoleio acid CigHj^Os vid 
 CisHaalGj (Claus, B. 9, 1917). 
 
 BBOMO-IODO-TOLUENE 
 OsHjMeBrI [l:2:3or5]. (260^). S.G. is. 2-139. 
 From CjH3MeBr(NHj) (Wroblewsky, A. 168, 164). 
 
 Bromo-iodo-toluene CjHjMeBrI [1:3:4]. 
 (265°). S.G. 22 2-044. From the corresponding 
 bromo-toluidine (W.). 
 
 Di-bromo-iodo-toluene CeH^MeBr^I [1:3:5:4]. 
 [86°]. (270°). From C„H3MeBr(NO,)(NH2) Did 
 CsH2MeBr(N02)I, and CsH3MeBr(NH3)I (Wro- 
 blewsky, A. 192, 209). Also from di-bromo-p- 
 toluidine, C5H2MeBr2(NH2) by diazo- reaction. 
 
 Sl-bromo-di-iodo-toluene CgHMeBr^I^ 
 [1:3:5:4:2]. [68°]. From C5HMeBr2l(NHj) by 
 diazo- reaction (Wroblewsky, A. 192, 212). 
 
 BI-BEOMO-IODO-TOLTJIDINE 
 C,HMeBr2l(NH,) [1:3:5:4:2]. [64°]. By reduc 
 tion of the corresponding nitro- compound (Wro- 
 blewsky, A. 192, 210). Converted by sodium 
 amalgam into o-toluidine. 
 
 Acetyl derivative C5HMeBr2l(NHAo) 
 [121°]. Small white needles. 
 
 BBOMO-ISATIO ACID v. IsAiio acid. 
 
 BBOMO-ISATIM v. Isatin. 
 
 BROMO-ISAIOiiC ACID v. IsAioio ACm. 
 
 BBOMO-ISO- V. Bbomo-. 
 
 BBOMO-ITACONIC ACID CjHsBrO,. [164°]. 
 Formed by the dry distillation of iia-di-bromo- 
 pyrotartaric acid (Swarts, J. 1873, 684). Its 
 anhydride is formed similarly from ito-di-bromo- 
 pyrotartaric anhydride (Petri, B. 14, 1637). 
 Alkalis form aeonic acid ; Sn reduces it to 
 itaconic acid. 
 
 BEOMO-IACTIC ACID v. Bkomo-oxy-sbo- 
 
 PIONIC AOm. 
 
 DI-BEOMO-tADEENE CjoHi^Brj (?) [210°]. 
 From laurene and Br (Montgolfier, A. Ch. [5] 
 14, 93). 
 
 Tri-bromo-laurene 0„H,3Br3? [125°]. From 
 laurene and Br in the cold (Fittig, Kobrioh a. 
 Jilke, A. 145, 149). Cf. Laubene. 
 
 BEOMO-LEVULIC ACID v. Bsouo-ACEini- 
 
 PBOPIONIO ACID. 
 
 BEOMO-LUTIDINE v. Bbouo-di-meieil- 
 
 PYBIDINE. 
 
 BBOMO-MALElC ACID C2HBr(G02H)2 i.e. 
 C02H.CH:CBr.C02H, or COjH.C.CHBr.COjH, 
 
 CBr.C(OH)jx 
 or II >0. or 
 
 OH . C(K 
 
 CH.C(OH)^ 
 
 II >0. [128°]. 
 
 OBy . QQ< 
 
nnOMO-MALONIO ACID, 
 
 577 
 
 Formed by boiling di-bromo-Bucoinio aoid or its 
 Ija salt with water (KekuU, A. Siippl. 1, 367 ; 
 Petri, A. 195, 62). Formed also, together with 
 bromo-fumaric acid {q. v.) by the action of Br 
 and water on succinic acid, at 180° (Kekulfi, j1. 
 130, 1), or fumaric aoid at 100° (Carius, A. 149, 
 264). Deliquescent prisms or needles ; v. b. sol. 
 water, alcohol, and ether, splits up into water 
 and its anhydride on distillation. 
 
 For discussion of formula see Maleio acid. 
 Reactions. — 1. Sodium-amalgam gives suc- 
 cinic acid. — 2. Fuming HBr unites in the cojd, 
 forming di-bromo-suooinio acid. — 3. Electrolysis 
 of its Na salt gives CO and HBr.— 4. Boiling 
 cone, baryta-ioater forms oxalic and acetic 
 acids. — 5. When it is dissolved in water and an 
 equivalent of aniline is added there separates a 
 crystalline pp. C2HBr.(C0,H){C0,H.NH,CBHJ. 
 [128°]. This aoid aniline salt dissolved in 
 water and allowed to stand deposits the acid 
 anjlide C02H.C2HBr.CO.NH05H5 which crystal- 
 lises in prisms ; insol. in dilute HCl. If instead 
 of allowing the substance to react in the 
 cold the solution is heated, the compounds 
 CibHijN^Oj and C„H,jN.^03 are obtained. 
 C(NHPh)— CO. 
 CijHijNA. probably || >NPh, 
 
 CH c(y 
 
 [230°], forms ochre - coloured microscopic 
 needles. Insol. hot, si. sol. cold aq; sol. 
 hot. alcohol, less in cold; CuHuNjOj, pro- 
 
 C(NHPh)— COjH 
 bably || , [176°], forms yellowish 
 
 CH.CO.NHPh 
 indistinct crystals. Sol. hot, m. sol. cold aq. 
 Sol. alkalis : acids pp. the substance unchanged 
 (Michael, Am. 9, 180; B. 19, 1373). 
 
 Baits. — AgjA" : crystalline pp.— CaA"2aq. 
 — CaNa,A"2 4aq.— PbA" aq. 
 
 Dimethyl ether A"Me.,. (238° i.V.). Con- 
 verted by iodine into dimethyl bromo-fumarate. 
 
 Diethyl ether A"Etj. (256° i.V.). 
 
 (140°-150°) at 25 mm. (Anschiitz, B. 12, 2284 ; 
 Schacherl, A. 229, 91). 
 
 Anhydride CjHBrOa. (215° i.V.). Formed 
 as above, and also by heating di-bromo-succinic 
 acid with Ac^O at 130° (Anschiitz, B. 10, 1884). 
 Water forms bromo-maleio acid. 
 
 4mide OjHaBrNA- [168°-175°]. From the 
 imide and NH3. 
 
 Imide (C^HBrOJNH. [151°]. Formed, 
 together with the amide of di-bromo-maleiic 
 acid, by heating succinimide with Br at 160° 
 (Ciamician a. Silber, B. 17, 557 ; Kisielinski, 
 Sitz, B. 74, 561). 
 
 Iso - bromo - male'io aoid is Bbomo-jumaeio 
 ACID (q. v.). 
 
 Bromo-maleio aoid (?) CjHjBrOj. [112°]. 
 From mucobromio acid and baryta (Hill, B. 
 17, 239).— K2A"aq.— BaA" 2aq.— Ag^A". 
 
 Di-bromo-maleic acid C^Br^HjO^. [123°]. 
 Formed, together with bromo-maleic aoid, by 
 brominating succinic acid (Kekul6, A. 130, 2). 
 From (/37)-di-bromo-pyromucic acid and from 
 tri-bromo-pyromucic acid by hot dilute HNO3 
 (Hill a. Sanger, A. 232, 89). Formed also by 
 heating mucobromic and with Br at 140° (Hill, 
 Am. 3, 48 ; B. 13, 734). Slender felted needles, 
 V. sol. water, alcohol, and ether, v. si. sol. benzene 
 and ligroin. An equivalent quantity of aniline 
 added to a solution of the acid in water dissolves 
 
 Vol. I. 
 
 and then deposits the acid aniline salt. When 
 this is allowed to stand under water it gradually 
 forms an anilide. The neutral salt in the 
 same way gives the di-anilide C2Br.^(CO.NHPh)2,. 
 [140°]. By heating the acid (3 pts.), with water 
 (60 pts.) and aniline (2-2 pts.) for 30 minutes 
 C(NHPh)— CO. 
 
 CBr- 
 
 -CO' 
 
 ,/- 
 
 OTh [183°] is obtained in the 
 
 form of flat, yellowish-red prisms; insol. aq. ; 
 m. sol. hot alcohol (Michael, Am. 9, 180). 
 
 Salts.— BaA"2aq. S.6-05 at 20°.— PbA" aq. 
 — Ag^A" : explodes when heated. 
 
 Anhydride CjBr^Oj. [115°]. Prepared by 
 heating the acid. Needles (by sublimation) ; si. 
 sol. cold water. 
 
 CBr.COv 
 
 Imide || >NH. [225°]. Formed by 
 
 CBr.CO'^ 
 heating succinimide with bromine. Monoolinio 
 crystals, a:h:c = -4342:1: -9649 ; /3 = 119° 59'. By 
 boiling with aqueous KOH it is converted into 
 di-bromo-maleio acid (Ciamician a. Silber, B. 
 17,556; G.14,35; c/.Kisielinski,Si(!«.B. 74,561). 
 
 Bromo-male'io-aoid-di-bromide v. Tki-beomp- 
 
 SUCCINIC ACID. 
 
 DI-BROMO-MALEIC ALDEHYDE C^H^Br^O,. 
 [90'']. Got in small quantity from (^y)- dibromo- 
 pyromucic acid and aqueous bromine (Tonnies, 
 B. 12, 1203 ; Hill a. Sanger, A. 232, 87). Long 
 thin prisms (from water). V. sol. alcohol, ether, 
 chloroform, and benzene, m. sol. light petro- 
 leum. In a current of CO2 it may be sublimed. 
 On oxidation it gives mucobromic acid. 
 
 BROMO-MALEYL BROMIDE C^HBr^O.,. [56°] 
 Formed by treating (;35)-di-bromo-pyromucie 
 acid with cold bromine (Hill a. Sanger, A. 232, 
 80). Long prisms (from light petroleum). 
 
 BEOMO-MALIC ACID CjHjBrOs. The so- 
 dium salt NaHA" is formed by the action of 
 NaOEt sodium di-bromo-succinate. Boiling lime- 
 water converts it into calciumraoemate. Sodium- 
 amalgam forms sodium succinate. Pb(OAc)j 
 pps. PbA". 
 
 Ethyl derivative. Sodium salt 
 CO,Na.CH2.CH(OEt).C02Na. Hygroscopic mass ; 
 formed by adding alcoholic NaOEt to sodium 
 di-bromo-succinate (Mulder a. Hamburger, 
 B. T. 0. 1, 154). 
 
 BROMO-MALONIC ACID C^H^BrO, i.e. 
 CHBr(C02H)2. Obtained by reducing the di- 
 brominated acid with sodium amalgam (Petrieff, 
 J. B. 10, 65 ; B. 11, 415). Deliquescent ; moist 
 AgjO forms tatronic acid. — AgHA". — AgjA". 
 
 Di-bromo-malonic aoid CBr, (C02H)2. [c. 126°]. 
 From malonic acid CHCI3 and Br (Petrieff, B, 
 7, 400 ; /. B. 10, 65 ; Van 't Hoff, B. 8, 355). 
 Needles, v. e. sol. water. Boiling baryta-watei 
 forms mesoxalic acid. 
 
 Amide CBx.,{CO^B^).,. [206°]. Formed 
 by adding Br to malonamide in aqueous solu- 
 tion (Freund, B.Xl, 782). Formed also by the 
 action of alcoholic NH3 on the amide of penta- 
 bromo-aceto-acetic aoid CBr3.CO.CBr2.CO.NH2 
 (Stokes a. Pechmann, Am. 8, 380). Needles, 
 prisms, or large octahedra. SI. sol. hot water, 
 
 alcohol, and acetic aoid. — CBr2<f f^f;'^S:^Hg : 
 
 white amorphous powder, insoluble in water and 
 alcohol. 
 
 Methylamide CBr2(CO.NHMe)2: [162°]; 
 
578 
 
 BROMO-MALONIO AOID. 
 
 large white needles or trimetric crystals (Freund, 
 B. 17, 782). 
 
 BEOMO-MAIOPHTHAIIC ACID CsHi.BrO^. 
 From tetra-hydro-phthalio acid and bromine- 
 •water (Paeycr, A. 166, 353). Prisms or tables 
 (containing I aq). Baryta- water converts it into 
 
 BEOMO-MELILOTIC ACID v. Bbomo-oxt- 
 
 PHENYL-PBOPIONIC ACID. 
 
 BBOMO-MESITENE LACTONE 
 
 CsH,Br<;]„Q^. [105°]. From mesitene lactone, 
 
 CS, and Br (v. Aceto-acetio bthee). SI. sol. cold 
 alcobol and water (Hantzscli, A. Ill, 18). 
 
 BKOMO - MESITOL C,H,|BrO i.e. 
 C,HMe3Br(0H). [80°]. Needles (from alcohol) 
 (Biedermann a. Ledoux, B. 8, 59). 
 
 Di-bromo-mesitol C,Me3Br2(OH). [150°]. 
 From mesitol, Br, HOAc, and I (Jaoobsen, A. 
 195, 265). 
 
 BSOMO-MESITYL ALCOHOL v. Bbomo-u- 
 
 0XY-MESIT¥I,ENE. 
 
 j)-BBOMO-MESITYL BEOMIDE «. ji-a-Di- 
 
 BKOMO-MESITTLENE. 
 
 BKOMO-MESITYLENE OsH^McsBr [1:3:5:4]. 
 Bromo-s-iri-methyl-bensene. [ — 1°]. (227° i. V.). 
 S.G. ifi 1-32. Formed by the action of 1 mol. Br 
 upon cold mesitylene in the dark (Fittig a. 
 Storer, A. 147, 6 ; Schramm, B. 19, 212). 
 
 (5:3:l)-ti>-Bromo-mesitylene 
 C,H,(CH3).,(CH2Br) [1:3:5], Mesityl bromide. 
 [38°]. (231°). Prisms. Formed by bromination 
 of mesitylene at 130° (Wispek, B. 16, 1577; 
 Colson, A. Ch. [6] 6, 89 ; C. B. 96, 713). 
 
 eso-Di-bromo-meaitylene CjHMeaBr^. [64°]. 
 (278°). Long needles. Formed by the action 
 of 2 mols. of bromine upon mesitylene in the 
 dark (F. a. S.; Siissenguth, A. 215, 248; 
 Schramm, B. 19, 212). Fuming HNO, gives 
 bromo-di-nitro-mesitylene [194°]. 
 
 p-u-Di-bromo-mesitylene 
 C.H2(CH3)2Br(CH2Br) [5:3:4:1]. p - Bromo - 
 mesityl bromide. Oil, fluid at —19°. Decom- 
 poses on distillation. Formed by the action of 
 bromine (1 mol.) in sunshine upon eso-bromo- 
 mesitylene (Schramm, B. 19, 213). 
 
 ojiu-Di- bromo -mesitylene C5H3Me(CH2Br)2. 
 [66°]. Formed by passing CO^ charged with 
 bromine-vapour into boiling mesitylene (Colson, 
 A. Ch. [6] 6, 92 ; O. B. 96, 713 ; Eobinet, G. B. 
 96, 500). Formed also by treating ww-di-oxy- 
 mesitylene with HBr (Eobinet a. Colson, Bl. [2] 
 40, 111). Long prisms ; decomposed by alcohol. 
 
 Tri-eso-bromo-mesitylene CjMeaBrj. [224°]. 
 Formed by the action of 3 mols. of bromine 
 upon mesitylene in the dark (Schramm, B. 19, 
 213). Triclinic crystals, v. si. sol. alcohol. 
 
 i i»,o)2-Tri-bromo-mesitylene 
 C,H2(CHi)Br(GH2Br)2 [5:4:3:1]. [122°]. Obtained 
 by the action of bromine (1 mol.) in sunshine 
 upon hot ^-ai-di-bromo-mesitylene (p-bromo- 
 jnesityl-bromide) C„Hj,(CH3)2Br(CHj.Br). Very 
 ■slender needles (from alcohol) Schramm, B. 19, 
 215). 
 
 <:-<<i,aij-Tri-bromo-mesitylene 
 C,H2MeBr(CH2Br)2 [5:2:1:3]. [81°]. From 
 bromo- aj,aj2-di-oxy -mesitylene and cone. HBr. 
 Can be formed by brominating mesitylene (Col- 
 son, A. Ch. [6] 6, 101 ; Bl. [2] 41, 362). 
 
 (o-aijajj-Tri-bromo-mesitylene C„H3(CH2Br)3. 
 [94°]. (2ic") at 10 mm. From boiling mesityl- 
 
 ene and Br (3 mols.). Needles, v. sol. boiling 
 
 alcohol (Colson, O. B. 96, 713 ; A. Ch. [6] 6, 96). 
 
 BROMO-MESIXYLENE GLYCOL v. Bbomo- 
 
 DI-OXy-MESITTLENE. 
 
 BEOMO-MESITYLENE STJLPHONIC ACID 
 
 CjHi.BrSOj i.e. CsHMejBr.SCH. Formed by 
 the action of bromine-water on a very dilute 
 solution of mesitylene-sulphonio acid or its Ba 
 salt; formed also from bromo-mesitylene and 
 fuming HjSOj (Eose, A. 164, 56). Deliquescent 
 trimetrio needles (from ether). — BaA'^aq. — 
 PbA'jliaq.— KA'aq.— CuA'^iaq.— NaA'. 
 
 (a)-BE0M0-3IESITYLENIC ACID CeH^BrO^ 
 i.e. C„H2Me2Br(C02H) [1:3:4:5]. [147°]. Formed, 
 together with some of its isomerides, by the slow 
 action of Br on mesitylenio acid in the cold. 
 Formed also from the corresponding amido- 
 mesitylenic acid (Schmitz, A. 193, 172). Tri- 
 metric prisms (from alcohol), a:b:c = -927:1: '470, 
 — BaA'j 4aq : monoclinio, a:b:c = 3-068:1: ■801; 
 ;8 = 63°24'.— CaA'j2aq. 
 
 (/3) -Bromo -mesitylenic acid 
 C8H2Me,Br(CO,H) [1:3:2:5]. [215°] (Sch.) ; 
 [212°] (S.). Formed by oxidising bromo-mesityl- 
 ene (Fittig a. Storer, A. 147, 1), or from the 
 corresponding amido- acid (Sch.). Monoclinio 
 crystals, a:6:c = l-193:l:'760; S = 70° 35'.— BaA',. 
 — CaA'j.— CaA'j 5aq.— KA'. 
 
 Di-bromo-mesitylenic acid CjHBr2Me2(COjH). 
 [195°]. Formed by oxidising di-bromo-mesityl- 
 ene (Siissenguth, A. 215, 250). Needles (by 
 sublimation) . — CaA'2 7aq. — ^BaA'^ 3 Jaq. 
 
 BEOmO-METHACEYLIC ACID C^HsBrO^ i.e. 
 CHBr:CMe.C02H. Bromo-crotonic acid. [63°]. 
 (229°). From citra- or mesa- di-bromo-pyro- 
 tartario acid by treatment with water, NajCOjAq, 
 or KOHAq (KekuU, A. Suppl. 2, 97 ; Cahours, 
 A. Suppl. 2, 347 ; Fittig a. Krusemark, A. 206, 7 ; 
 Friedrich, A. 203, 354). Also from o3-di-bromo- 
 isobutyric acid and NaOHAq (C. Kolbe, J. pr. 
 [2] 25, 382). Flat needles, si. sol. cold water. 
 Reduced by sodium-amalgam to isobutyric acid. 
 Decomposed by heating with alkalis into 
 methane, allyleue, and acetic acid (F.). — 
 CaA'2 3aq. S. (of CaA'^) 5-75 at 11°.— AgA'.— 
 HO.CuA'.— NHjHA', (Morawski, SiU. B. 74, 39). 
 
 Ethyl ether EtA'. (193°) (C). 
 
 Bromo-methacrylic acid 
 CH2:C(CHjBr).C02H. [66°]. Formed, together 
 with the preceding, by boiling mesa-di-bromo- 
 pyrotartario acid with water or NajCOjAq 
 (Krusemark, A. 206, 12). Laminae (from water), 
 V. sol. water; volatile with steam. Eeduced 
 with difiSculty by sodium-amalgam to isobutyric 
 acid.— CaA'2 2aq. S. (of CaA'j) 80 at 5°. 
 
 Di-bromo-methaorylic acid OjHjBrjOj. 
 Needles. From tri-bromo-butyrio acid (dibromide 
 of bromo-methacrylic acid). At 120° it takes up 
 Br forming tetra-bromo-butyrio acid, whence 
 boiling alkalis form 
 
 Tri-bromo-methacrylic acid CiHjBrjO^ 
 Needles (C). 
 
 BEOMO-HETHANE v. Methyl bromide. 
 
 Di-bromo-methane v. Methylene bbomide. 
 
 Tri-bromo-metbane v. Bkomopoem. 
 
 Tetra-bromo-methane CBr,. Carbon tetra- 
 bromide. [92°]. (189°). Occurs in commercial 
 bromine (Hamilton, C. /. 39, 48). 
 
 Formation. — 1. By heating Br with CS2 in 
 presence of I or SbBr, (Bolas a. Groves, C. /. 
 23, 161; 24, 773; A' 156, 60; 160, 160).- 2. 
 
xiJiAA-iiitUfilO-xMETHYLENE-DIPHENYLENE OXIDE. 
 
 670 
 
 From CHjCL, and IBr, (Holand, A. 240, 236).— 
 3. From alcohol and Br (Sohaffer, B. 4, 366).— 
 <!. By exposing a mixture of dilute KOH, bromo- 
 form, and Br to sunlight (Habermaun, A. 
 167, 174). — 5. By heating bromoform or bromo- 
 picrin with SbBrj or BrI at 150°.— 6. From OIj 
 and Br (Gustavson, A. 172, 176).— 7. From 
 CCl, and Al^Br^ at 100° (Gustavson, J.R. 13, 286). 
 8. From CHjBr and Br in presence of animal 
 charcoal (Damoiseau, O. B. 92, 42). 
 
 Preparaticm.— CS^ (2 pts.) is heated with 
 iodine (3 pts.) and Br (14 pts.) for 96 hours at 
 150° (Holand, A. 240, 238). 
 
 Properties. — Tables with faint camphor-like 
 smell ; extremely prone to sublimation. At 220° 
 it splits up into CjBr, and bromine. Boiling 
 alcohol gives bromal, HBr, and aldehyde. Aloo- 
 holie KOH gives K^CO, and KBr. Sodium-amal- 
 gam forms CHBr, and CH^Brj. 
 
 BROMO-METHANE D t-STILPHONIC ACID 
 CHBr(S03H)2. Potassium salt KjA". From 
 bromo-dl-sulpho-aldehyde CBr(S03H)2.CHO by 
 boiling with aqueous KjCOj (Eathke, A. 161, 161). 
 
 I)i-bromo-met}ian.e snlphonic acid 
 CHBr2.SOaH.BariumsaltBaA'2. Thin unctuous 
 plates, foi-med by the action of Br upon barium 
 sulpho-acetate at 130° (Andreasch, M. 7, 157). 
 
 BROMO-PENTA-MErHYL-TEI-AMIDO-Tal- 
 PHENYL-CARBINOL C^jH^JBrNjO. Hydro- 
 bromide C24HjjN33HBr. Formed by heating 
 di-methyl-aniline with Br at 120° (Brandenburg 
 a. Brunner, B. 10, 1845, 11, 697). 
 
 DI-BEOmO-METHYLAMINE MeNBr^ v. 
 Methylamine. 
 
 p-BEOMO-METHYL-ANILINE 
 C,H,(Br)NHMe. [11°]. (260°). Prepared from 
 the nitrosamine. 
 
 Acetyl derivative [99°]. 
 Nitrosamine C„Hj(Br)NMe(NO). [74°]. 
 Long needles. Formed by the action of HNO.^ on 
 p-bromo-di-methyl-aniline (Wurster a. Soheibe, 
 B. 12, 1818). 
 
 TO-Bromo-di-methyl-aniline CjHj(Br)NMe2 
 [1:3]. [11°]. (264° corr.). Prepared by the 
 methylation of TO-bromaniline. By the action 
 of HNOjit gives a nitroso- compound which forms 
 light green needles and melts at [about 148°]. 
 
 Methylo-iodide CsH^Br.NMejI. [201°]. 
 Leaflets (Wurster a. Soheibe, B. 12, 1818). 
 
 2)-Bromo-di.methyl-aniline C|jHj(Br)NMe2 
 [1:4]. [55°]. (264- corr.). 
 
 Preparation. — 1. By bromination of di- 
 methyl-aniline dissolved in acetic acid (Weber, 
 B. 8, 714 ; 10, 763).— 2. By methylation of p- 
 bromaniline. By the action of HNOj it gives 
 a mixture of ^-nitro-di-methyl-aniline and p- 
 bromo-phenyl-methyl-nitrosamine. 
 
 Methylo-iodide CsH^Br.NMeJ. [185°] 
 (Wurster a. Scheibe, B. 12, 1816). 
 
 Ferrocyanide B'2HjFe(CN)s2aq: leaflets. 
 Perricyanide B'4H|;Fe2(CN)„5aq: very 
 soluble yellow crystals (Wurster a. Eoser, B. 12, 
 1825). 
 
 BEOMO-DI-METHYL- ANILINE -PHTHA- 
 LEIN GjjHjjBrjNjOj i.e. 
 
 C„H<'^(^'^^q'^q*^^«)^>. The hydrochloride, 
 
 formed by heating j)-bromo-di-methyl-aniline 
 with phthalyl chloride, crystallises in steel-blue 
 needles. Cone. HGIAq pps. dingy-green B"2HC1 
 (O. Fischer, B. 10, 1623).-B"2H,PtCl5. 
 
 BI-BKOMO-METHYL-ANTHSACENE 
 
 CisHijBrj. [138°-140°]. From methyl-anthra- 
 cene by Br in CSj (Liebermann, A. 213, 35). 
 Yellow needles (from glacial HOAc). 
 
 Tetra- bromo - methyl - anthracene OuHjBrj. 
 Needles (from toluene). Oxidises to di-bromo- 
 methyl-anthraquinone (L.). 
 
 DI-BKOMO - DI - METHYL - ANTHEACENE- 
 DIHYDEIDE C,sH„Br2. From di-methyl-anthrsk- 
 oene dihydride and Br in HOAc (Ansohiitz, A. 
 235, 309). Oxidises to anthraquinone. 
 
 DI-BEOMO-METHYL-ATEOLACTIC ACID v. 
 
 Dl-BKOMO-OXY-TOIiYL-PEOPIONIC ACID. 
 
 TETEA-BEOMO-METHYL-AURINE 
 C^uHj^Br^Os. Formed by brominating methyl- 
 aurine.— B'HBr 2aq (Zulkowsky, M. 3, 471). 
 
 BEOMO - METHYL - BENZENE v. Bromo- 
 
 TOLUENE. 
 
 Bromo-di-methyl-benzene v. BitoMo-XYLENB. 
 
 Tri-bromo-tri -methyl- benzene 0s(CH3)^r5 
 [1:2:3:4:5:6]. Tri-bromo-hemimelUthene. [245°]. 
 Needles. SI. sol. alcohol. Formed by bromina- 
 tion of (l:2:3)-tri-methyl-beuzene (Jacobsen, JB. 
 15, 1858). Other bromo-tri-methyl-benzenea 
 are described as Bbomo-i|'-oumenes and Bbomo 
 
 MESITYIiENES. 
 
 Bromo - tetra - methyl - benzene v. Bbouo- 
 
 DUBENE. 
 
 Bromo-penta-methyl-benzeueCuBrMe5.[161°]. 
 (289°). From C^Ue^B., Br, and I (Friedel a. 
 Crafts, A. Oh. [6] 1, 473). 
 
 Hexa-m-bromo-hexa-methyl-benzene 
 C,(CH,Br)„. [255°] (F. a. C.) ; [227°] (H.). 
 From hexa-methyl-benzene, water, and Br at 
 100° (Hofmaun, B. 13, 1732 ; Friedel a. Crafts, 
 A. Ch. [6] 1, 468). 
 
 BEOMO-METHYL-BENZOIC ACID v. Bbomo- 
 
 TOLUrO ACID. 
 
 Bromo-di-methyl-benzolc acid 
 CjHjBrMeaCOjH. [173°]. Bromo-pseudo-cumenic 
 acid. Bromo-xylyUc acid. From CjHjBrMej 
 [1:2:4:5] by CrOj in HOAc (Siissenguth, A. 216, 
 244). Also from C8H3Me2(C0jH) [1:3:4] and Br 
 (Gunter, B. 17, 1608). Needles (from water). 
 V. e. sol. alcohol. — CaA'j2aq. — BaA'2 6aq. 
 
 Bromo-di-methyl-benzoic acid 
 CjHJBrMejCOjH. [189°]. Bromo-p-xylyUc acid. 
 FromCBH3Me,(COjH) [1:2:4] and Br (Gunter, B. 
 17, 1609). Needles (from dilute alcohol). 
 
 Other isomerides are described as Bbomo- 
 
 MESITYLENIO ACIDS (q. V.). 
 
 ea:o-BEOMO-DI-METHYL-COUMAEIN 
 .C(CH,):CBr 
 C.H,(CH,)< I . Formed by bromina- 
 
 ' "^ "\0 CJO 
 
 tion of di-methyl-coumarin dissolved in CS2. 
 Crystalline solid. SI. sol. alcohol. Converted 
 by hot alcoholic EOH into di-methyl-coumarilio 
 acid (di - methyl -coumarone-carboxylio acid) 
 (Hantzsch a. Lang, B. 19, 1299). 
 
 DI-BEOMO-METHYLENE-DI-PHENYLENE 
 CijHjBrj. [162°]. From methylene-di-phenylene 
 (g. v.). Needles or octahedra (from ether) (Car- 
 nelley, 0. J. 37, 710). 
 
 HEXA-BEOMO-METHYLENE-DI-PHENYL - 
 ENE OXIDE CisH^BrjO. Formed, together 
 with the hepta-brominated compound C,3H,Br,0 
 [136°], by adding Br to o-methylene-di-phenylene 
 oxide suspended in water. Blackens at 0. 225° 
 (Salzmann a. Wichelhaus, B. 10, 1401). 
 
580 
 
 BROMO-METHYLENE-PHTHA LIDE. 
 
 BEOMO-METHTLENE-PHTHAIIDE 
 ^C=CHBr 
 CsHsBrOj j.«. CjH,< >0 . [133°]. Long 
 
 colourless needles. Formed by heating phthalyl- 
 bromo-acetio acid in vacuo ; or by bromination 
 of acetophenone-oarboxylio acid. It combines 
 
 *ith Br, forming C„H,<^g=^(^^'"=^)>0. [118°] 
 
 (Gabriel, B. 17, 2525). 
 
 p-BROMO-METHYL-ETHYL-ANILINE 
 
 CjHijBrN i.e. 0„HiBr.NMeEt. (265°). From 
 methyl-ethyl-aniline and Br. Solidifies below 
 0° (Clans a. Howitz, B. 17, 1327). 
 
 TRI - BROMO - DI-METHYL-ETHYL - BENZ - 
 ENE C,„H„Br3 i.e. C^BraMe^Et. [218°]. (Jacob- 
 sen, B. 7, 1434). 
 
 DI-BEOMO - METHYL - ETHYL - GLYOXA - 
 LINE C3Br2(CH3)(C,H,)N2. Di-bromo-oxal- 
 ethyline. [38°]. Colouriess crystals. Sol. acids. 
 Formed by bromination of methyl-ethyl-glyoxa- 
 line (oxal-ethyline) (Wallach, B. 16, 537). 
 
 HEXA-BROMO-METHYL-ETHYL-KETONE 
 C^H^Br^O i.e. CBr5.CO.CH2.CBr3. [90°]. From 
 it-di-bromo-ethylene and HBrO (Demole, B. 11, 
 1710). Seduced by sodium-amalgam to methyl 
 ethyl ketone. Fuming HNO, gives malonic 
 acid. 
 
 DI-BROMO-(B. 2-Pv. 2)-DI-METHYL-(P2/. 3)- 
 ETHYL-ftTjmOLINECisHijBrjN. [144°]. White 
 needles (Havz, B. 18, 3389). 
 
 TRI-BEOMO-METHYL-GLYOXALINE 
 C3Br3(CH3)N2. TH-bromo-oxalmethylin. [89°]. 
 White crystals. Insoluble in cold water. 
 
 Formation. — 1. By the action of Mel on tri- 
 bromo-glyoxaline-silver. — 2. By bromination of 
 methyl-glyoxaline (oxal-methyline) dissolved in 
 dUute H^SO, (Wallaoh, B. 16, 537). 
 
 BROMO-METHYL-IND ON APHTHENE-CAE- 
 
 BOXYLIC ACID C^H^^^^'^'^^^'^-'^'^^H. [245°]. 
 
 Formed by bromination of methyl-jndonaph- 
 thene in chloroform. Needles. SI. sol. alcohol 
 (Eoser, B. 20, 1575). 
 
 HEXA -BBOMO-DI-METHYL-METHYLENE 
 DIKETONE C.JlJBifiM. CBr3.CO.CH2.CO.CBr3. 
 Hexa-bromo-acetyl-aeetone. [108°]. From the 
 diketone and Br (Combes, A. Ch. [6] 12, 240). 
 Needles ; decomposed by alkalis into tri-bromo- 
 acetone and tri-bromo-acetic acid. 
 
 eso-BROMO-a-METHYL-NAPHTHALENE 
 C,„HjBr(CH3). (298° corr.). Colourless fluid. 
 Formed by the action of bromine on a cold 
 solution of (a) -methyl-naphthalene in CS,. 
 
 Picric acid compound 
 C„H„Br,CeH2(N02)30H. [105°]. Yellow needles 
 (Schulze, B. 17, 1528). 
 
 eso-Broino-/3-methyl-naplitlialene 
 C,„H,Br(CHs). (296°). Colourless fluid. Formed 
 by the action of bromine on a cold solution of 
 (;8)-methyl-naphthalene in CSj. 
 
 Picric acid compound 
 C„H3Br,CeH2(N02)30H [113°], yellow needles 
 (Schulze, B. 17, 1528). 
 
 a!-Bromo-(;8)-methyl-naplithalene 
 C,„H,.CH^r. [56°]. (213° at 100 mm.). White 
 glistening plates. Formed by passing gaseous 
 bromine into (fl) -methyl-naphthalene heated 
 to 240° (Schulze, B. 17, 1529). 
 
 Tri-bromo-di-methyl-naphthalene CjjHjBr,, 
 [228°] (Cannizzaro a. Carnelutti, O. 12, 410 j 
 cf. Giovanozzi, O. 12, 147). 
 
 TRI-BROMO-METHYL-DI-PHENYL-AMINE 
 C,3H,„Br3N i.e. NMe(C„H3Br2)(C,H,Br). [98°]. 
 From methyl-di-phenyl-amine and Br (Gnehm, 
 B. 8, 926). HNO3 forms {0,HjBr(N0i,)j}2NH. 
 
 Tetra-bromo-methyl-di-plieiiyl-ainine 
 (CjHjBrJaNMe. [129°]. Formed at the samn 
 time as the preceding (G.). 
 
 DI-BROMO-DI-METHYL-aUINOL v. Di- 
 methyl- Bkomo-hydkoqtiinone. 
 
 BROMO-METHYL-PIPERIDINE 
 
 CH2<^™''^^^''>NMe. The methylo-bromida 
 
 (B'MeBr) is formed very readily by isomeric 
 change of di-methyl-eS-di-bromo-ra-amyl-amine 
 (so-called ' di-methyl-piperidine-di-bromine '), 
 CHoBr.CHBr.CH^.CHj.CHj.NMej, by warming 
 its "alcoholic solution for a short time (Merling, 
 B. 19, 2630). 
 
 DI-BROMO-METHYL-PYRIDINE CsHjBr.N 
 i.e. CjNHjMeBrj. [109°]. Formed, together with 
 ethylene bromide, from tropidine (g. v.) hydro- 
 bromide and bromine at 165° (Ladenburg, A. 
 217, 145). 
 
 s-Di-bromo-di-methyl-pyridine C^NHMe^Br^ 
 [1:5:2:4]. Di-hromo-lutidine. [65 ]. Formed 
 by the action of bromine upon an aqueous solu- 
 tion of the potassium salt of s-di-methyl-pyri- 
 dine - di - carboxylic acid. — B'2H2Cl2PtClj 2aq : 
 needles (Pfeiffer, B. 20, 1350). 
 
 Di-bromo-s- tri - methyl - pyridine CjNMesBrj 
 [1:3:5:2:4]. Bi-bromo-collidine. [81°]. (262°) at 
 726 mm. Obtained by the action of bromine 
 upon an aqueous solution of the potassium salt 
 of s-tri-methyl-pyridine-di-carboxylic acid; the 
 yield is 50 p.c. of the theoretical. White pearly 
 plates. Very volatile with steam. Weak base. 
 
 Salts. — B'HCl: easily soluble small glis- 
 tening crystals; — B'^HjCl^PtCl, 2aq : orange- 
 yellow needles.— B'2H,Cr20, : [146°] ; needles.— 
 xB'C„H,(N02)30H: [160°] dark-yellow flat 
 prisms, v. sol. hot alcohol, insol. water (Pfeiffer, 
 B. 20, 1345). 
 
 DI - BROMO - TRI-METHYL-PYRIDINE DI- 
 CARBOXYLIC ETHER. Dihromide 
 NCsH,Br2(C02Et)2Br2. [102°]. From the follow- 
 ing body and fuming HN03(Hantzsch, .4. 215, 17). 
 
 Di-bromo-tri-methyl - pyridine di-oarboxylio 
 ether. Di-brom hydride 
 NCsH,Bi^{GO^Et)^B.^BT,. [88°]. From the di- 
 hydride of (1,3,5,2,4) -tri- methyl-pyridine-di - 
 carboxylic ether by Br in CS2 (Hantzsch, A. 
 215,14). Yellow twin crystals. 
 
 DI-BEOMO - DI - METHYL - PYROCATECHIN 
 V. Di-methyl ether of Di-bbomo-pyhooateohin. 
 
 HEXA-BROMO-DI-METHYL TRISTJLPHIDE 
 C2Br5S3 i.e. (CBr3)2S3. Carbotrithiohexabromide. 
 [125°]. S. (alcohol) 6-5 at 78° ; S. (ether) 2-35 
 at 0°. From OS, and Br (Hell a. Urech, B. 15, 
 275, 987 ; 16, 1147). Prisms or tables, insol. 
 water. Hot cone. NaOH gives NaBr, Na2C03, 
 and Na2S3. Decomposed by heat into CBr.„ 
 CS2Br4, SBr^, and a blue substance CgBr^Sj 2aq. 
 
 DI-BEOMO-METHYL-THIOPHENE 
 C4HBr2(CH3)S. (228°). Oil (Meyer a. Kreis, B. 
 17, 787). 
 
 Tri-bromo-(o)-methyl-thiopheneC4Br3(CH3)S. 
 Tri-bromo-{0)-thiotoUne. [86°]. Formed by bro- 
 mination of (/3)-methyl-thiophene (Egli, B. 18, 
 
BROMO-NAPHTllALENE. 
 
 681 
 
 545). Long colourless silky needles. V. sol. ether 
 ftnd hot alcohol. 
 
 Tri-bromo-methyl-tMopliene CjBr3(CH3)S. 
 [39°]. Formed by bromination of the methyl- 
 thiophene from pyrotartario acid. Large colour- 
 less needles (Volhard a. Erdmann, B. J.8, 465). 
 Forms a molecular compound [74°] with the 
 preceding (Gattermann, B. 18, 3005). 
 
 Bromo-di-methyl-thiophene CjH(CHa)jBrS. 
 Bromo-thioxene. (194° unoor.). Formed by bro- 
 mination of thioxene dissolved in CSj. Volatile 
 with steam. Colourless fluid. Heavier than 
 water (Messinger, B. 18, 1687). 
 
 Sl-bromo-di-metliyl-thiopIieBe C4(CH3)2Br2S. 
 Di-bromo-thioxBne. [46°]. (247° unoor.). Long 
 colourless needles. Formed by adding 2 mols. 
 of bromine to cooled thioxene (from coal-tar) 
 (Messinger, B. 18, 563). 
 
 Bi-bromo-di-methyl-thiophene C„(CH3)2Br2S. 
 Di-hromo-thioxene. [47°-50°]. Needles. Vola- 
 tile with steam. Formed by bromination (with 
 2Br2) of thioxene (from aoetonyl-aoetone) (Paal, 
 B. 18, 2253). 
 
 Tri-bromo-di-methyl-thiophene CjHjBrjS i.e. 
 CjBr2(CH3)(CH2Br)S. Tri-bromq-tUoxene. [144°]. 
 Crystallises and sublimes in needles. Formed 
 by the action of an excess of bromine upon the 
 di-bromo- derivative of the thioxene obtained 
 from acetonyl-acetone (Paal, B. 18, 2253).- 
 
 Octo-bromo-di-methyl-thiophene 
 CjBr2(CBrs)j,S. Octo-hromo-thioxene. [114°]. Small 
 needles. Formed by the action of an excess of 
 bromine upon thioxene (from coal-tar) (Mes- 
 singer, B. 18, 565). 
 
 BBOMO-DI-METHYI-o-TOLTJIDINE 
 CjHijBrN i.e. C„H3(CHs) (Br)NMe2. (245°). Pre- 
 pared by bromination of di-methyl-o-toluidine, 
 or by methylation of bromo-o-toluidine (Michler 
 a. Sampaio, B. 14, 2172). Liquid ; sol. alcohol 
 and ether, volatile with steam. 
 
 Bromo-di-metliyl-m-toluidine 
 C,H3(Br)(0H3)NMej [1:2:4]. [98°]. (276°)._ Pre- 
 pared by bromination of di-methyl-m-toluidine. 
 White leaflets. Insol. water, sol. alcohol, ligroin 
 and CjHj (Wurster a. Eiedel, B. 12, 1800). 
 
 Ferrocyanide'B'^^e{OK)si&ri: crystals. 
 
 Ferricyanide B'4H|;Fej(CN),2 9aq. Very 
 soluble yeUow crystals (Wurster a. Koser, B. 
 12, 1826). 
 
 TETKA-BBOMO-MYKISTIC ACID 
 CijHjjBrjOj. From myristolic acid and Br 
 (Masino, A. 202, 176). 
 
 DI-BKOMO-MYRISTOLIC ACID CnH^jBrA- 
 Obtained by gently warming the preceding (M.). 
 
 o-BSOMO-NAPHTHALENE C,„H,Br[l]. [5°]. 
 (277°) ; (280° cor.) (Eamsay a. Young, 0. J. 
 47, 650). S.G. \8 1-4750 ; ll 1-503. Boo 84-9 
 (Nasini, O. 15, 98). 
 
 Formation. — 1. From naphthalene in CSj 
 and Br (Laurent, A. Ch. [2] 59, 196 ; Glaser, A. 
 135, 40; Wahlforss, Z. 1865, 3; Gnehm, B. 
 15, 2721). — 2. From diazo-bromo-naphthalene 
 salts by boiHng with alcohol (Bother, B. 4, 851 ; 
 Stallard, C. J. 49, 188).— 3. From Hg(C,„Hj2 
 and Br (Otto, A. 147, 175). 
 
 Properties. — Liquid, insol. water, miscible 
 with alcohol, ether, and benzene. 
 
 Reactions. — 1. CrO, gives phthaUc acid 
 (Beilstein a. Kurbatow, C. C. 1881, 359).— 2. A 
 solution in CS.j gently heated with A1,,C1, gives 
 (/8)-bromo-naph'thalene as the chief product, to- 
 
 gether with di-bromo-naphthalenes, and naph- 
 thalene (Eoux, Bl. [2] 45, 510).— 3. Toluene in 
 presence of AI^CIb forms bromo-toluene and 
 naphthalene (Eoux). — 4. Eeduced hy sodium- 
 amalgam to naphthalene. — 5. Cl.COjEt and Na 
 give naphthoic acid. 
 
 Picric acid compound 
 C,„H,BrC„H,(N0,)30H. [135^]. Yellow needles 
 (Wiohelhaus, B. 2, 805 ; E.). 
 
 Di chloride C.oH^BrClj: [165°]; tables. 
 0)-Bromo-naphthalene 0,„H,Br [2]. [59°]. 
 (282 cor.). S. (92 p. c. alcohol) 6 at 20°. 
 
 Formation. — 1. By heating (3)-diazo-naph- 
 thalene with a large excess of HBr (Gasiorowski 
 a. Wayss, B. 18, 1941 ; of. Liebermann, A. 183, 
 268). — 2. By running a solution of (/3)-diazo- 
 naphthalene bromide into a hot solution of 
 cuprous bromide ; the yield ig 30 p.c. of theo- 
 retical (Lellmann a. Kemy, B. 19, 811). — 3. 
 From (e)-naphthol and PBr^ (Brunei, B. 17, 
 1179). — 4. From (a)-bromo-naphthalene and 
 AljClj (Eoux, Bl. [2] 45, 513). 
 
 Properties. — Trimetric scales, 7. sol. CS^, 
 CHCI3, benzene, and ether. 
 
 Picric acid compound 
 0,oH,BrC,H,(NO,)30H. [79°] (E.); [86°] (B.) ; 
 S. (alcohol of 92 p.c.) 6 at 20° (R.). 
 
 Di-bromo-naphthalene OioHjBrj. [61°]. 
 Formed in small quantity by brominating naph- 
 thalene (Jolin, Bl. [2] 28, 514 ; not observed by 
 others). 
 
 o-Di-bromo-naphthalene CioH^Brj [1:2]. [68°]. 
 From (1, 2)-bromo-(i8)-naphthylamine by the 
 diazo-perbromide reaction (Meldola, C. J. 48, 5). 
 Oblique rhombic prisms (from alcohol, acetone 
 or petroleum). 
 
 OT-Di-bromo-naphthalene CuH^Br^ [1:3]. 
 [64°]. From di-bromo-(a)-naphthylamine, [119°] 
 by removal of NH^ (Meldola, O. J. 43, 2). 
 Needles. 
 
 Di-bromo-naphthalene CioH^Br^ [2:8] ? 
 [c. 68°]. Formed, together with two isomerides, 
 [81°] and [130°] by the action of Br (2 mols.) 
 on naphthalene (1 mol.) (Guaresohi, G. 7, 24). 
 Also from bromo-(;3)-naphthol and PBr3(Canzo- 
 neri, O. 12, 425). Prisms (from alcohol). 
 
 (a0')-Di-bromo-naphthaleneO,„HBBr2[4:2'or3']. 
 [74°]. From (4, 2'or3',2)-di-bromo-naphthyl- 
 amine by diazo- reaction (Meldola, C. J. 47, 
 513). Silvery scales (from dilute alcohol). 
 
 Tj-Di-bromo-naphthalene C,„H„Br2[l:a;]. [77°]. 
 Formed, together with the isomeride [130°], by 
 brominating naphthalene (a)-sulphonic acid 
 (Darmstadter a. Wiohelhaus, A. 152, 304). 
 
 (/3)-Di-bromo-naphthalene C,„HjBr2 [1:4]. 
 [82°]. (310°). S. (93-5 per cent, alcohol) 1-33 
 at 11-4° ; 6 at 56° (Guaresohi, A. 222, 269). 
 
 Formation.— 1. The chief product of the 
 action of bromine (2 mols.) on naphthalene 
 (Glaser, A. 185, 40).— 2. By distilling (a) -bromo- 
 naphthalene sulphonic acid or nitro-{a)-bromo- 
 naphthalene [85°] with PBr^ (John, Bl. [2] 28, 
 514). — 3. From acetyl- (a) -naphthylamine by bro- 
 minating, saponifying, and treating the resulting 
 C,„H|,Br(NH2) by the diazo- reaction (Meldola, 
 0. /. 43, 4). 
 
 Properties. — Long needles. Oxidised by 
 HNO3 to di-bromo-phthalio and bromo-nitro- 
 phthalic acids and bromo-nitro-naphthaleae. 
 CrOj in acetic acid gives di-bromo-naphtho- 
 quinone and di-bromo-phthalide. Eeacts with 
 
682 
 
 BROMO-NAPHTHALENE. 
 
 Br forming C,„H^Brs [173°] (Guareschi, G. 16, 
 
 ConstituUon. — This follows from the oxida- 
 tion to di-bromo-phthalio acid, coupled with the 
 observation that the bromo-(a)-naphthyIamine 
 from which it may be formed (v. supra) gives 
 (a)-bromo-naphthalene by the diazo- reaction. 
 
 (7) Di-hromo-naphtlialene 
 C,„H^rj [l:l'or4']. [131° oor.]. (326°). S. 
 (93-5 p.c. alcohol) 2 at 56°. 
 
 FormaUon. — 1. By brominating naphthalene 
 (G.; Magatti, 0. 11, 357). — 2. From diazo- 
 bromo-naphthalsne (from bromo-naphthylamine 
 [64°]) by adding bromine-water and warming the 
 pp. with HOAc. — 8. The chief product of the 
 action of Br on naphthalene (o)-sulphonic acid 
 (Darmstadter a. Wiohelhaus, A. 152, 803).— 4. By 
 the action of PBrj on (ii)-di-nitro-naphthalene 
 or bromo-naphthalene (o)-Bulphomo acid (J.). 
 
 Properties. — Tables. HNO, gives bromo- 
 nitro-phthalio acid. CrOj in HOAo gives bromo- 
 phthalio acid [176°]. Does not form a tetra- 
 bromide with Br. 
 
 S-Di-bromo-naphthalene C,„HsBrj. [141°]. 
 From naphthalene (a)-snlphonio acid and PBrj 
 (J.). Thin plates. 
 
 e-Di-bromo-naphthalene C,„H^r2. [160°]. 
 From (o)-bromo-naphthalene sulphonic acid and 
 PBr3 (J.). 
 
 Si-bromo-uaplitlialene tetra-chloride 
 CijHJBrjClj. [156°]. From di - brominated 
 naphthalene (? [82°]) and CI (Laurent). 
 
 Di-bromo-naplithalene tetra-bromide 
 C,„H|iBr„. A mixture of three bodies of this 
 composition, [0. 100°] [120°] and [173°] is formed 
 from naphthalene and Br (G.). 
 
 Tri-bromo-naplithalene C.^HsBrs. [75°]. 
 Formed by brominating naphthalene, or by heat- 
 ing di-bromo-naphthalene tetra-bromide with 
 alcoholic KOH (Laurent, A. Ch. [2] 59, 196; 
 Glaser, A. 135, 43). Needles (from alcohol). 
 
 Tri-bromo-naphthalene CijHjBrj [1:4:1']. 
 [85°]. From di-bromo-nitro-naphthaleue [117°] 
 and PBrs (Jolin). Needles. 
 
 Tri-bromo-naphthalene CioH^Brj [87°]. 
 From di-bromo-naphthalene (;8)-sulphonio acid 
 and PBr^ (J.). Needles. 
 
 Tri-bromo-naphthalene CioHsBrj [l:3:l'or4']. 
 [105°]. From (3, 1' or 4', l)-di-bromo-naphthyl- 
 amine [102°] by diazo- reaction (Meldola, C. J. 
 47, 516). 
 
 Tri-bromo-naphthalene CioH^Brs [l:3:2'or3']. 
 [110°]. From (1, 2' or 3', 3)-di-bromo-naphthyl- 
 amine by the diazo- reaction. Needles (from 
 alcohol) (Meldola, O. J. 47, 513). 
 
 Tri-bromo-naphthalene CuHsBrj [1:2:4]. 
 [114']. From C,„H,(NH,)Brj [1:2:4] by diazo- 
 reaction (Meldola, C /. 43, 4). Formed also by 
 heating C,„H5(NH2)(N02)Br [1:2:4] with cone. 
 HBrAq and glacial HOAo at 130° (Prager, B. 
 18, 2163). White needles (from dilute C^H^OJ. 
 Dilute HNO3 at 180° gives phthalic acid. 
 
 Tetra-bromo-naphthalene CuH^Br^ [1:4:2':3']. 
 [175°]. S. (95 p.c. alcohol) -5 at 78°. From 
 di-bromo-naphthalene tetrabromide [173°] and 
 NaOEt (Guareschi, G. 16, 141). Needles (from 
 alcohol) or plates (by sublimation). CrOa in 
 HOAo gives di-bromo-phthalide [188°] and 
 Jetra-bromo-(o)-naphthoquinone [224°]. 
 
 Tetra-bromo-naphthalene C,„H^Br,. [120°] 
 From di-bromo-naphthalene tetrabromide [100°] 
 and NaOEt (Gu.). Needles (from alcohol). 
 
 Tetra-bromo-naphthalene tetra-bromide 
 CioH^Brj. [173°]. From (1, 4)-di-bromo-naphthaI- 
 ene and Br (Gu.). 
 
 Penta-bromo-naphthalene C,jH3Br5. From 
 CioHjBr, and Br at 150° (Glaser). Granules, 
 insol. alcohol. 
 
 Heza-bromo-naphthaleae C,„H2Br„. [252°]. 
 From naphthalene, Br, and I at 400° (Qessuer, 
 JB. 9, 1505). Also from naphthalene (20 g.), 
 AljCls (15 g.) and Br (300 g.) (Boux, Bl. [2] 45, 
 515). Needles ; easily sublimed. Does not 
 combine with picric acid. 
 
 BKOMO-NAPHTHALENE DI-CABBOXTLIC 
 ACID C,2H,BrO, i.e. C,„H5Br(C0,H)j. [210°]. 
 From bromo-aoenaphthene and CrOj (Blumen- 
 thal, B. 7, 1095). Needles (from benzene). Con- 
 verted by NH3 into the imide C,„HjBr(C0)2NH 
 [above 265°]. 
 
 BROMO -NAPHTHALENE - (/3) - STJLPHINIC 
 ACID CioHeBrSOjH. From naphthalene (,8)- 
 sulphinic acid and Br (Gessner, B. 9, 1503). 
 
 (o)-BKOMO- NAPHTHALENE SULPHONIC 
 ACID C,„H.Br(SO,H) [1:4]. [139°]. Formed by 
 sulphonating (a)-bromo-naphthalene (Laurent, 
 Gompt. chim. 1849, 392 ; Darmstadter a. 
 Wiohelhaus, A. 152, 303 ; Otto, A. 147, 184). 
 Flat needles. Oxidised by KMnOj to phthalic 
 acid (Meldola, B. 12, 1964). Potash-fusion 
 gives no bromo-naphthol (M.). Br gives chiefly 
 C.jHsBrj [82°]. — CaA'j 8aq. — BaA'^ 2aq. — 
 PbA'j liaq. 
 
 0;tJoriie C,„H,Br(S02Cl). [87°]. (Jolin,B2. 
 28, 516). In its preparation there is also formed 
 C,„H,Cl(SO.^r) [116°] (Gessner, B. 9, 1504). 
 
 Bromide C,„H,Br(S02Br) [115°] (J.). 
 
 Amide C,„B.fii{SO^N'E^) [190°] (J.); [195°] 
 (0.). 
 
 Bromo-naphthalene (a)-salphonic acid 
 C,„H5Br(S03H). [104°]. Formed by bromina- 
 ting naphthalene (a)-sulphonio acid (D. a. W.). 
 PBrj gives di-bromo naphthalene [131°]. — KA.'. 
 
 Chloride C,„H,Br(SO,Cl) [90=] (J.). 
 
 Amide C,„HsBr(S02NH„) [205°] (J.). 
 
 Bromo-naphthalene (/3) -sulphonic acid 
 C,„HjBr(S03H). [62°]. Formed by brominating 
 naphthalene (/3) -sulphonic acid (D. a. W.). 
 Crystalline mass, sol. ether (difference from the 
 two preceding acids). — KA.'. 
 
 Bromo-naphthalene sulphonic acid 
 C,„H„3r(S0.,H). Formed in small quantity in 
 preparing its isomeride [139°] by sulphonating 
 (o) -bromo-naphthalene with H2SO4 or CISO3H 
 (Armstrong a. Williamson, G. J. Proc. 1, 234). 
 
 Ghloride C,„H,BrSO,Cl [151']. 
 
 Di-bromo-naphthalene (|3) -sulphonic acid 
 C,„H5Br2(S03H). Formed by brominating naph- 
 thalene (;8)-sulphonio acid (J.). Crystalline. 
 PBrs gives tri-bromo-naphthalene [87°]. 
 
 Chloride C,„H5Br2(SO.,Cl) [109°]. 
 
 Amide C,„H,Br5(S0,NHJ [238°]. 
 
 Di-bromo-naphthalene sulphonic acid 
 C,„H,Br2(S03H). Got by sulphonating di- 
 bromo-naphthalene (Laurent, A. 72, 299). — KA'. 
 — BaA'j. 
 
 BaOMO-NAPHTHALIC ACID v. Bbomo-oxt- 
 
 (o)-NAPHIHOQDINONE. 
 
 BROMO-(o)-NAPHTHOIC ACID 
 C„H,Br02 i.e. 0,„H,Br.C0jH [1:4']. [246°] (Ek. 
 
BROMO-NAPIITIIOQUINONE. 
 
 58a 
 
 •traud, B. 19, 1135). Produced from its nitrile 
 or by bromiuating (o)-naphthoio acid (Haasa- 
 mann, B. 9, 1516). White needles (by subli- 
 mation).— KA'Jaq.—CaA'j llaq. S. 1-5 at 20°.— 
 BaA'^Saq. S. 1-7 at 21°.— AgA'. 
 
 Amide C.oHjBr.CONH^: [241°]; flat needles. 
 
 Nitrile Cj„H^r.CN. [147°]. From («)- 
 uaphthonitrile in CSj and Br. 
 
 Bromo-(/3).naphthoic acid 0,„H„Br.CO,H. 
 [256°]. From (j3) -naphthoic acid and Br (H.). 
 Needles (by sublimation).— KA' 2 |aq.— CaA'^ 3aq. 
 S. -02 at 20°.— BaA'i, 3aq. S. -023 at 21°.— AgA'. 
 
 Nitrile 0,„HsBr.CN: [149°]; flat needles. 
 
 Tii-bromo-((3)-naphthoic acid C,„HjBr3.C0..H. 
 [270°]. From (j8)-naphthoio acid (1 mol.),"Br 
 (3 mols.), and I at 350°. Needles (by sublima- 
 tion).— BaA'^ (H.). 
 
 Tetra-brorao-(a)-naphtlioic acid 
 C,„H3Brj.C0,H. [239°]. From (o)-naphthoio 
 acid (1 mol.) and Br (4^ mols.) at 350' (H.). 
 Granules (from alcohol) or needles (by sublima- 
 tion). — BaA'j. 
 
 Tetra-bromo-(/3)-napIithoic acid 
 OijHaBrj.COjH. [260°]. Preparation and proper- 
 ties similar to those of the preceding acid (H.). 
 
 BE0MO-(a)-NAPHTH0L. Ethyl ether 
 C,„HJBr(OEt). [48°]. From ethyl bromo-(a)- 
 naphthol and Br (Marchetti, C. N. 40, 87). 
 Prisms, v. sol. ether. 
 
 Bromo-(;8) -naphthol C,„H;Br(OH) [3:2] ?. 
 [84°]. Prepared by adding Br in glacial acetic 
 acid slowly to naphthol in glacial acetic acid 
 (A. J. Smith, O. J. 35, 789). Needles. Sol. 
 alcohol, ether, light petroleum and benzene. At 
 130° it begins to decompose, giving off HBr. 
 Oxidised by alkaline KMnO, to phthalic acid. 
 PBrj gives di-bromo-naphthalene [68°] and (;3)- 
 bromo-naphthalene (Canzoneri, G. 12, 424). 
 
 Acetyl derivative 0,(,H:sBr(OAo). (215°) 
 at 20 mm. (C). 
 
 Nitroso- derivative C,oH5(NO)Br(OH). 
 [65°] : green needles. 
 
 Di-bromo-(a)-naphtliol C,„H5Br2(0H) [1:3:4]. 
 [106°] (Fittig, A. 227, 244). Formed by bromi- 
 nating (a)-naphthol in HOAc (Biedermanu, B. 6, 
 1119) and in small quantity from di-bromo-(o)- 
 naphthylamine by the diazo- reaction (Meldola, 
 C. J. 45, 161). Long needles (from alcohol). 
 Powerful oxidising agent. 
 
 Reactions. — 1. KMnOj gives phthalic acid. — 
 
 2. AlcohoUc KOH gives tri-oxy-naphthalene. — 
 
 3. Combines with aniline forming a white crys- 
 talline salt. If this is heated for 10 minutes 
 at 200°, and then allowed to cool, crystals of 
 
 0,„H3(NPhH)<§^^ or (/3) -naphthoquinone di- 
 
 anilide (^-v.) are got (Meldola, 0. J. 45, 156). — 
 
 4. p-Toluidine formsVae corresponding (;8)-naph- 
 thoquinono di-toluide {q.v.). — 5. (fi)-naphthyl- 
 amine forms the corresponding (iS) -naphtho- 
 quinone di-naphthalide (g. v.). 
 
 Tetra-bromo-(i8)-naphtholC,„H3Br,OH.[156°]. 
 Prepared by adding excess of bromine to (;8)- 
 naphthol dissolved in glacial acetic acid (A. J. 
 Smith, O. J. 35, 791). White needles (from 
 glacial acetic acid). Sol. OS,, benzene and 
 alkalis. Oxidised by KMnOj and KOH to bromo- 
 phthalio acid (anhydride [125°]). Hence it is 
 CBHBr3(C,H^rOH). 
 
 Penta-broma-{o)-naphtliol C,„HfBr5.0H 
 [2:4:1':3':4':1]. [239°]. Formed by bromination 
 
 of (o)-naphthol in presence of AL^Br^, Slender 
 felted needles. SI. sol. benzene, xylene, and cu- 
 mene, nearly in sol. alcohol and ether. Dissolves 
 in alkalis. By dilute HNO3 at 100° it is oxidised 
 to tetra-bromo-(a)-nai3hthoquinone [265°] ; at 
 150° it is oxidised to di-bromo-phthalic acid 
 [206^.- C,„H2Br,.0Na: long easily soluble 
 needles.— C|„H.,Br ..OK: small colourless needles 
 (Bliimlein, B. 17, 2485). 
 
 Penta - bromo - (;S)- naphthol C,„H,Br5(0H). 
 [237°]. Formed by bromination of (0)-naphthol 
 in presence of Al^Br^. White needles. Insol. 
 alcohol, si. sol. benzene. It is oxidised by HNO, 
 to tetra-bromo-(8)-naphthoquinone ; on further 
 oxidation it yields tri- bromo -phthalic acid 
 0,„H2Br,(0Na) : long white silky needles (Plessa, 
 B. 17, 1479). 
 
 Bromo- (3) -naphthol (a)-suIphouic acid 
 C,„H,Br(0H)S03H. [3:2:1]? 
 
 Salts. — Formed by adding the calculated 
 quantity of bromine to saturated solutions of 
 the salts of (;3)-naphthol (a)-sulphonio acid 
 (Armstrong a. Graham, G. J. 39, 137).— KA'. 
 S. '4 at 15°. Boiling HNO3 forms phthalic acid. 
 — CaA'j saq. 
 
 BBOMO-(a)-NAFHTHOaXriNONE 
 
 Anilide C,„H,Br(NHCeH5)0j. [166°], 
 Formed by the action of aniline on bromo-oxy- 
 (o) -naphthoquinone [197°] in acetic acid solution. 
 Bed prisms. Sol. hot alcohol and hot acetic 
 acid. By cold aqueous NaOH it is split up into 
 its constituents (Baltzer, B. 14, 1902). 
 
 An isomeric anilide C,„H4Br(NPhH)0, 
 [2:3:4:1] [194°] is formed by boiling dibromo- 
 (a)-naphthoquinone [218°] with an alcoholic solu- 
 tion of aniline. It is converted by KOH into 
 bromo-oxy-(a)-naphthoquinone [202°] (Miller, Bl. 
 [2] 43, 125). 
 
 p-Bromo-anilide C,„HjBr(NHC,HjBr)0.,. 
 [240 ']. Prepared by bromination of (a)-naphtho- 
 quinone-anilide, or by boiling a mixture of p- 
 bromo-aniline and bromo-oxy-(a)-naphthoquin- 
 one with acetic acid. Bed needles. Sol. benzene, 
 si. sol. alcohol. By alcoholic H^SO^ it is decom- 
 posed into bromo-oxy-(a).naphthoquinone and ^- 
 bromo-aniline (Baltzer, B. 14, 1901). 
 
 Bromo-(i3)-iiaphtlioquinoneC.H,<^^°-.^^j.>. 
 
 [178°]. Obtained by bromination of (3)-naphtho- 
 quinone in acetic acid. Bed needles or prismatic 
 crystals. M. sol. warm alcohol, benzene, and 
 acetic acid. Sublimable. Dissolves in dilute 
 caustic alkalis with a brownish-red colour, form- 
 ing bromo - oxy - (a) - naphthoquinone [196°] 
 (Zincke, B. 19, 2495). 
 
 Di-bromo - (o)- naphthoquinone CuH^BrjO,. 
 [151°]. S. (alcohol) -98 at 13°. Formed by the 
 action of Br (7 pts.) and I (2 pts.) on (o)- 
 naphthol (1 pt.) in presence of water (Diehl a. 
 Merz, B. 11, 1065). Yellow needles; may ba 
 sublimed. Alkalis from HBr and bromo-oxy- 
 naphthoquinone. 
 
 Di - bromo - naphthoquinone CioH^Br^Oj. 
 [171°-173°] [1:4:1':4'] ? S. (95 p.c. alcohol) -at 
 at 16°. From di-bromo-naphthalene [82° J, 
 CrOj and glacial acetic acid (Guaresohi, A. 222, 
 279). YeUow needles (from alcohol). Insol. 
 water. Cannot be sublimed. Volatile with 
 steam. CrOj does not oxidise it to di-bromo- 
 phthalide. 
 
584 
 
 BROMO-NAPHTHOQUINONE. 
 
 Di-bromo-(;8)-naplithoquinone CioHjBr^Oj 
 [1:2:3:4]. [174°]. Obtained by the action of 
 bromine upon bromo-(;8)-naphthoqiiinone in hot 
 acetic acid, or better upon (a)-amido-(/3)-naphthol 
 or its sulphate. Thick red plates or tables. SI. 
 sol. alcohol and ether (Zincke, B. 19, 2496). 
 
 Di-bromo-naphthoquinone C,„HjBr.p2- [218°]. 
 Prom (a) -naphthoquinone, Br, and I (Miller, Bl. 
 [2] 38, 138). Prisms. Converted by KOH into 
 bromo-oxy-naphthoquinone [200°]. 
 
 Anilide [194°]. 
 
 Tetra-bromo-(a)-naphtlioquiiione C,„H.^rjO,. 
 [265°]. Yellow plates. SI. sol. alcohol. Formed 
 by oxidation of penta-bromo-(o)-naphthol with 
 dilute HNO3 at 100°. By further oxidation at 
 150° it yields di-bromo-phthalio acid [206°] 
 (Bliimlein, B. 17, 2488). 
 
 Tetra-bromo-[a]-iiapttlioquinone C,^.firfi^ 
 [l':4':2:3:l:4]. [224°]. Formed by oxidising tetra- 
 bromo - naphthalene [173°]. Orange - yellow 
 prisms, v. sol. hot water (Guaresohi, O. 16, 149). 
 
 Tetra-bromo-(i8) -naphthoquinone G^^'R.firfi^. 
 [164°]. Red granular crystals. SI. sol. alcohol. 
 Formed by oxidation of penta-bromo-(/3)-naphthol 
 with dilute HNO3. By further oxidation it is 
 converted into tri-bromo-phthalic acid (Flessa, 
 B. 17, 1481). 
 
 BBOMO-NAPHTHOSTYRIL v. Inner anhy- 
 dride of Bbomo-amido-naphthoic acid. 
 
 DI-BBOMO-(oa)-DIlTAPHTHYl CjoH.^Br^. 
 [215°]. From di-naphthyl and bromine-vapour 
 (Lossen, A. 144, 77). Monoclinic prisms ; v. si. 
 3ol. alcohol. 
 
 Hexa-brcimo-(aa)-diiiaplithyl CjuHaBr^. Resin. 
 
 Hepta-bromo-(/3;8)-dinaphthyl CjjHjBr,. 
 
 Amorphous (Smith a. Poynting, C. J. 27, 854). 
 
 BK0M0-NAPHTHY14MINE C,(,HJBr(NH,). 
 By reduction of bromo-nitro-naphthalene [85°] 
 of Jolin, itself got from (a)-bromo-naphthalene 
 by nitration. An oil. May be distilled with 
 steam. FCjClj gives a violet colour in its aqueous 
 solution. Reduces AgNOj (Guaresohi, A. 222, 
 299). Possibly identical with Bother's (1, 4)- 
 bromo-naphthylamine [94°]. 
 
 jTO-Bromo-(a)-naphthylamine C,„HjBr(NH2) 
 [3:1]. [62°]. From the nitro- compound, zinc- 
 dust, andHOAc (Meldola, O. J. 47, 509). Needles 
 (from dilute alcohol). 
 
 Acetyl derivative C,„H;,3r(NHAc) [187°]: 
 needles. 
 
 o-Bromo-(i8)-naphthylamlne C,„Hj(Br)NH2 
 [1:2]. [63°]. Got by saponification of the acetyl 
 derivative obtained by bromination of acetyl 
 (/3)-naphthylamine [131°]. Small white needles. 
 Volatile with steam. It is a neutral body. Dilute 
 HNO3 gives phthalic acid (Meldola, C. J. 43, 6). 
 When NH2 is displaced by H (o)-bromo-naph- 
 thalene results (M.). 
 
 Acetyl derivative C||,H5Br.NH(Ac) 
 
 [135°]. Needles (Cosiner, B. 14, 59). 
 
 Bromo-(o)-uaplithylamine C|„H„Br(NHJ 
 [1 : 1' or 4']. [64°]. From bromo-nitro-naph- 
 thalene [122-5°] (Guaresohi,^. 222,297). Volatile 
 with steam. Plates (from boiling water). May 
 be sublimed. KMn04 forms c-bromo-phthalio 
 acid [165°-172°].— B'HCl. 
 
 wi-Bromo-(i8)-naphthylamine C,„H„Br(NHj) 
 [1:3]. [72°]. From Liebermann's bromo-nitro- 
 naphthalene by reduction (Meldola, G. J. 47, 
 509). Converted into (1, 3)-di-bromo-naphthal- 
 ene by the diazo- reaction. 
 
 Acetyl derivative C,„H,Br(NH.Ac). 
 
 [187°] : needles. 
 
 2)-Bro!no-(a)-naphthylamine C,„HjBr(NH2) 
 [1:4]. [94°]. From its acetyl derivative and 
 KOH (Bother, B. 4, 850 ; Meldola, B. 12, 1961). 
 Needles. On oxidation it gives phthalic acid. 
 By diazo- reaction it gives (o)-bromo-naphtha- 
 lene. Br gives di-bromo-naphthylamino [119°]. 
 
 Acetyl derivative C,„H„Br.NHAo. [192°]. 
 Prepared by slowly adding HCl to a solution of 
 bromine in NaOH in which is suspended aeetyl- 
 (o)-naphthylamine. White needles (Prager, B. 
 18, 2159). 
 
 Di-bromo-(a)-naphthylamiiie C,|,H5Br2(NH2) 
 [3:2'or3':l] ? [102°]. From its acetyl deriva- 
 tive. Needles ; sol. boiling dilute acids. Re- 
 moval of NHj gives di - bromo - naphthalene 
 [74°] (?[1:1']). 
 
 Acetyl derivative C,„H5Br2(NHAo) 
 221°]. From acetyl-(3, l)-bromo-naphthylamine 
 and Br (Meldola, 0. J. 47, 514). 
 
 Di-bromo-(a)-iiaphthylamiiie 
 C,„H3Br2(NHj,) [l':3:l]. [105°]. From its acetyl 
 derivative. Needles. Oxidised by dilute HNO, 
 to c-bromo-phthalio acid [174°]. Converted into 
 di-bromo-naphthalene [74°] by diazo- reaction. 
 
 Acetyl derivative C|„H5Br2(NHAc). 
 [222°]. From bromo-naphthylamine [62°] by 
 acetylation and bromination (Meldola, C J. 47, 
 512 ; 0. J. Proc. 1, 173). 
 
 Dibromo-(a)-naphthylamiiie 
 C,„H,Br2(NHJ [1:3:4]. [119°]. From the acetyl 
 derivative by hot aqueous KOH. Needles ; 
 does not combine with acids. Oxidation gives 
 phthalic acid ; the diazo- reaction gives (1, 3)- 
 di-bromo-naphthaleiie. 
 
 Acetyl derivative C,„H5Brj(NHAc). 
 [225°]. Formed by bromination of acetyl-(a). 
 naphthylamine (Meldola, B. 12, 1961). 
 
 Di-bromo-(/3)-naphtliylamine C,„H5Br2(NH2) 
 [121°]. Long colourless needles. Formed bj 
 the action of bromine in acetic acid solution 
 upon (/3)-naphthalene-azo-(;8)-naphthylamine. 
 
 Acetyl derivative: [208°] (Lawson, JB. 
 18, 2424). 
 
 Tetra-bromo-naphthylamine 
 
 Acetyl derivative CioHjBr^NHAc. [188°]. 
 Formed by brominating acetyl-(l,2)-bromo-(3)- 
 naphthylamine in acetic acid solution (Meldola, 
 C. J. 43, 8). Minute needles (from alcohol- 
 Could not be saponified. 
 
 BROMO-NAPHIHALENE-DIAMINE. 
 
 Acetyl derivative C,„H5Br(NH2)(NHAo) 
 [2:4:1] Tc. 222°]. From bromo-nitro-acetnaph- 
 thalide. " Is not basic (Meldola, C. J. 47, 499). 
 
 Di-bromo-(l : l'or4')-naphthylene-diamine 
 C,|,H5Br(NHj)2. From naphthylene -diamine 
 hydrochloride (from (oi)-di- nitro -naphthalene) 
 and bromine-water (Hollemann, Z. 1866, 566). 
 
 DI-BROMO.(a)-DmAPHTHYLENE.OXIDE 
 C^nH.oBrjO. [287°]. Light-yellow crystals. SI. 
 sol. benzene and acetic acid. Prepared by the 
 action of Br on a CSj solution of (a)-dinaphtliyl- 
 ene-oxide (Kneoht a. Unzeitig, B. 13, 1725). 
 
 Di-bromo-(j3)-dinaphthylene-oxide 
 C2„H,„Br20. [247°]. Yellow needles. Prepared 
 by the action of bromine on a CS3 solution cf 
 (iKj-dinaphthylene-oxide (K. a. U.). 
 
 DI-BEOHO-DI-NAPHTHYL-METHANE 
 C2„H,jBr2. [193°]. From di-naphthyl-methane 
 and Br (Grabowski, B. 7, 1605). Needles (from 
 
BROMO-NITRO-ANILINE. 
 
 685 
 
 alcohol-benzene) ; not affected by boiling aloo- 
 iholic KOH. 
 
 BROMO-NICOTINE v. Nicotine. 
 
 BKOMO-o-NITRO- AC ETOPHENONE 
 ■C8H5BrN03i.e. [2:1] C„H^(N02).C0.CH,Br. [56°]. 
 By brominatiou of CsH^(N02).C0.M6 (Gevekoht, 
 A. 221, 327). Needles (from benzoline). 
 
 Bromo-m-nitro-acetophenone 
 ;[3:l]C„H,(N0,).C0.CH,Br. Nitro-phenyl bromo- 
 methyl ketone. [96°]. Formed by nitrating 
 bromo - acetophenone. Needles (from dilute 
 :alcohol) ; v. s). sol. ether. Oxidation gives m- 
 nitro-benzoio acid (Hunnius, B. 10, 2008). 
 
 Di-bromo-o-nitro-acetophenone 
 ■C„Hj(N02).C0.CHBr2. [86°]. Prepared like the 
 above (G.). Attacks the eyes. Prisma (from 
 benzoline). 
 
 ai-Di-bromo-m-nitro-acetophenone 
 'CJS,(N02).C0.CHBr,. m-Nitro-phenyl di-bromo- 
 ■methyl ketone. [59°]. Formed by careful nitra- 
 tion of (B-di-bromo-acetophenone ; or by further 
 'bromination of u-bromo-m-nitro-acetophenone. 
 Yellowish tables. V. sol. most solvents (Engler 
 a,. Hassenkamp, B. 18, 2240). 
 
 BBOMO-NITRO-o-AMIDO-BENZOIC ACID 
 •CeH3Br(N02)(NH,)C02H [1:2?:4:5]. [272°]. 
 Formed by treating nitro-isatoio acid at 100° 
 ■with bromine dissolved in glacial acetic acid 
 •^Dorsch, J.pr. [2] 33, 40). Long yellow needles. 
 - Sol. hot water, acetone, alcohol, glacial acetic 
 racid and ether. Insol. chloroform and benzene. 
 
 Di-bromo-nitro-o-amido-benzoic acid 
 ■C,HBr2(N0,)(NHj)C02n. [c. 203°]. Fromnitro- 
 isatoic acid and bromine in glacial acetic acid 
 at 100° (D.). Plates. Sol. acetone, alcohol and 
 glacial acetic acid, less sol. benzene, chloroform, 
 and ether, insol. water. 
 
 Iri-bromo-nitro-o-amldo-benzoic acid 
 ■C,Br3(NO.J(NH2)(COjH). [196°]. From nitro- 
 isatoio acid and bromine (D.). Needles (ppd. by 
 adding water to its solution in acetone). V. sol. 
 acetone, alcohol, ether, glacial acetic acid, chloro- 
 form and benzene. 
 
 (3:5:4:1) - BROMO-NITSO-AMIDO-PHENTL- 
 ACETIC ACID C5H2(Br)(N02)(NHJ.CH,.C0,H 
 [3:5:4:1]. [192°]. Prepared by saponification of 
 the acetyl derivative of (3:5;4:l)-bromo-nitro- 
 amido-benzyl cyanide (Gabriel, B. 15, 1994). 
 Long yeUow needles. Sol. hot alcohol, ether and 
 acetic acid, si. sol. cold water, benzene, and 
 ■chloroform. 
 
 Nitril& 
 C,H,(Br)(N02)(NHj).CH2CN [3:5:4:1]. Bromo- 
 mitro-amido-henzyl cyamde. Acetyl derivative : 
 [191°]. Formed by nitration of t'-ie licetyl deri- 
 vative of (3:4:1) bromo - amido - phenyl - aceto - 
 nitrile (Gabriel, B. 15, 1992). Slender yeUow 
 needles, sol. alcohol and acetic acid, si. sol. cold 
 water, v. si. sol. ether and OS.,. 
 
 BROMO-NITRO-ANILINE 
 C6H3Br(N02)(NHJ [1:3:6]. [104°]. Formed by 
 heating CjH3Brj(N02) [59°] with alcoholic 
 NH3 at 190° (Korner, G. 4, 371). Yellow 
 needles ; gives jre-bromo-nitro-benzene by diazo- 
 reaction. Br forms di-bromo-j)-nitro-aniline 
 
 [203°]. 
 
 Benzoyl derivative CBH3Br(N0J(NHBz). 
 [160°]. From benzoyl-^-nitro-aniline and Br 
 (Johnson, B. 10, 1709). 
 
 Bromo-nitro-aniline C,H3Br(N02)(NH2)[l:3:4]. 
 [1U=]. S. -014 at 20° ; S. (alcohol) 10'4. 
 
 Formation. — 1. From nitro-p-di-bromo-benz- 
 ene and alcoholic NH, at 165° (K. ; Meyer a. 
 Wurster, A. 171, 59). — 2. By nitrating p-bromo 
 aniline in glacial HOAc (Hiibner, A. 209, 357). 
 3. By the action of alcoholic NH3 on the methyl 
 derivative of (1,3,4) -bromo-nitro-phenol. 
 
 Properties. — Orange needles ; may be sub- 
 limed ; scarcely basic. Converted by diazo- re- 
 action into m-bromo-nitro-benzeue [56°]. 
 
 Acetyl derivative C.HjBr(N02)(NHAo). 
 [103°]. Formed by nitrating acetyl-p-bromo- 
 aniline (H.). Ammonia and zinc-dust reduce 
 it to CsH3Br(NHAc).N2.C,H3Br(NHAc) [282°J 
 (Matthiesseu a. Mixter, Am. 8, 347). 
 
 Benzoyl derivative GjH3Br(N0„)(NHBz). 
 [138°]. Formed by nitrating benzoyl-p-bromo- 
 aniline or brominating benzoyl-o-nitro-aniliue 
 (Meinecke, B. 8, 564; Johnson, B. 10, 1710). 
 
 Bromo-nitro-aniline 
 C„H3Br(N02)(NH2) [1:2:4]. [132°]. Formed by 
 nitration of p-bromaniline dissolved in 10 pts. 
 of HjSO,. Flat plates. V. sol. alcohol, ether, 
 acetic acid, and chloroform, v. sol. water. By 
 further bromination it yields tri-bromo-nitrani- 
 line [103°] (Nolting a. Collin, B. 17, 266). 
 
 Bromo-nitro-aniline 
 C,H3Br(N02)(NH3) [1:4:5]. [151°]. Formed by 
 the action of alcoholic NH, upon (1,5,4) -di- 
 bromo-nitro-benzene [62°] or on (l,4,5)-bromo- 
 di-nitro-benzene [56°] (K.; Wurster, B. 6, 1542). 
 Orange needles. Gives by diazo- reaction^-bromo- 
 nitro-benzene. Is not basic. Dilute HNO3 (S.G. 
 1-38) slowly forms bromo-di-nitro-phenol [81°]. 
 
 Bromo-di-nitro-aniliue 
 0,H2Br(NO„),(NH2) [1:3:5:6]. [154'=] (L.) ; [144°] 
 (K.). j?ormed by brominating di-uitro-aniline 
 (K.), or by heating di-nitro-methyl-aniline with 
 HOAc and Br (Leymaun, B. 15, 1234). Yellow 
 needles. Converted by boiling KOH into bromo- 
 di-nitro-phenol [118"]. 
 
 Bromo-di-nitro-aniliue CsH2Br(N02)2(NH2). 
 [160°]. From di-bromo-di-nitro-benzene [100°] 
 and alcoholic NH3 at 100° (Austen, B. 9, 919). 
 Orange scales. 
 
 Bromo-di-nitro-aniline C5H^r(NO,)o(NH2). 
 [178°]. From di-bromo-di-nitro-benzene [117°] 
 and alcoholic NH3 (K.). 
 
 Bromo-di-nitro-aniline. Benzoyl deri- 
 vative C„HjBr(N03)2(NHBz) [1:3:5:4]. [221°]. 
 Small needles ; formed by nitrating benzoyl 
 bromo-nitro-aniline C.H3Br(N0„)(NHBz) [1:3 4], 
 or benzoyl di-bromo-aniline (Johnson, B. 10, 
 1710). 
 
 Bromo-di-nitro-aniline. Benzoyl deri- 
 vative C,H3r(N02)2(NHBz). [196°]. Formed 
 by nitrating benzoyl-^-bromo-aniline (Meinecke, 
 B. 8, 564), is probably identical with the pre- 
 ceding. 
 
 Di-bromo-nitro-aniline CjH.J3r2(N02) (NH^). 
 [75°]. From di-bromo-di-nitro-ienzene [159°] and 
 alcohoUo NH3 at 100° (Austen, B. 9, 622). Bed 
 needles. 
 
 Di-bromo-o-nitro-aniline C^H2Br2(N02) (NH ) 
 [1:3:5:6]. [:127°] (Heutsohel, ). pr. [2] 34, 426). 
 
 Formation. — 1. By brominating o-nitro-ani- 
 line or (1,3,4) -bromo-nitro-aniline. — 2. By the 
 action of alcoholic NH3 on (l,3,4,5)-tri-bromo- 
 nitro-benzene or the methyl ether of (1,3,5,6) -di- 
 bromo-nitro-phenol (K.). 
 
 Properties. — Orange needles. 
 
 Acetyl derivative C|,H^Br2(NOJ(NHAo). 
 
686 
 
 BROMO-NITKO-ANILINE. 
 
 [209"]. From aoetyl-di-bromo-aniline by nitra- 
 tion. Needles, v. sol. alkalis (Bemmers, B. 
 7, 348). 
 
 Benzoyl derivativeOs^^T^(^0;)(^n'B7.) 
 [1:3:5:6]? [195^. Formed by brominatiug 
 benzoyl-o-nitro-aniline (Johnson, B. 10, 1710). 
 Yellow needles. 
 
 Di-bromo-p-nitro-aniUne G^B^t^T^O.^ (NH^) 
 [1:3:5:2]. [207°] (L.) ; [203°] (K.). 
 
 Formation. — 1. By brominating ^-nitro-ani- 
 line or (l,3,6)-bromo-nitro-aniline.— 2. By the 
 action of alcoholic NH3 on tri-bromo-nitro-benz- 
 ene [112°] or the methyl ether of (l,3,5,2)-di- 
 bromo-nitro-phenol (K.). — 3. Prom tri-bromo- 
 aniline in HOAc by warming with cone. HNO3 
 for a short time (Losanitsch, B. 15, 474). 
 
 Properties. — Thin yellow needles. Displace- 
 ment of NH2 by H gives tri-bromo-benzene [112°]. 
 
 Tri-bromo-nitro-aniline CjHBr3(N02)(NH2) 
 [1:3:5:4:6]. [103°]. From TO-nitro-aniline and 
 bromine-vapour (K.), or from (l,2,4)-bromo- 
 uitro-aniline and Br in HOAo (Nolting a. Collin, 
 B. 17, 266). Pale greenish-yeUow needles in 
 stellate groups ; v. sol. alcohol. Converted by 
 diazo- reaction into (1,3,5,4) -tri-bromo-nitro- 
 benzene. 
 
 Tri-bromo-nitro-aniline CjHBr3(N02) (NH ,) 
 [1:3:5:4:6]? [215°]. From its acetyl deriva- 
 tive (Remmers, B. 7, 351). Flat yellowneedles ; 
 si. sol. alcohol. This body might be expected to 
 be identical with the preceding. 
 
 Acetyl derivative CBHBr3(N02)(NHAo)r 
 [232°]. From acetyl-(l,3,5,6)-tri-bromo-aniline 
 (K.). Needles. 
 
 Di-acetyl derivative 05HBr3(N02l(NAc2). 
 Formed by nitrating di-acetyl-tri-bromo-aniline. 
 
 Tri - bromo-nitro - aniUue C„HBr,(NO,) (NHJ 
 [1:2:3:5:6]. [161°]. From (1,2,4) -bromo-nitro- 
 aniline [151°] and bromine vapour (K.), Lemon- 
 yellow needles (from alcohol). Converted by 
 diazo- reaction into (l,2,3,5)-tri-bromo-mtro- 
 benzene [112°]. 
 
 BBOMO-KITRO-ANTHSAQUINONE 
 C,4Hs(N02)(Br)02. [261° uncor.]. Prepared by ni- 
 tration of tetra-bromo-anthracene.Whiteneedles. 
 Sublimable. Sol. acetic acid, si. sol. alcohol, 
 ether, and chloroform. On reduction it gives 
 amido-anthraquinone (Glaus a. Hertel, B. 14, 980) . 
 
 Bromo-di-nitro-anthraquinone 
 CuH5Br(N02)202. [213° uncor.]. Prepared by 
 nitration of tri -bromo-anthracene with a mixture 
 of fuming HNO3 and fuming HjSO,. Yellow 
 needles. Sol. benzene, chloroform, and acetic 
 acid, m. sol. alcohol and ether (Claus a. Diern- 
 fellner, B. 14, 1333). 
 
 Si-bromo-nitro-antliraqiiinone 
 C„H3Br2(N02)02. [245° uncor.]. Prepared by 
 nitration of tetra-bromo-anthracene. Sublimable. 
 Fine yellow needles. V. sol. hot acetic acid, 
 less in alcohol and ether. On reduction with 
 sodium-amalgam it gives amido-anthraquinone. 
 
 Di-bromo-di-uitro-anthraquinone 
 C„HjBr2(NOJ^02. [239° uncor.]. Prepared by 
 nitration of tetra-bromo-anthracene with a 
 mixture of fuming H^SOj and fuming HNO3. 
 Needles. Sol. acetic acid, benzene and chloro- 
 form, si. sol. alcohol and ether (C. a. D.). 
 
 Tetra-bromo-di-uitro-anthraquinone 
 CnH2(NOj)2BrjO.. [105°]. Prepared by nitra- 
 tion of dibromo-anthracene-tetrabromide. Sol. 
 alcohol, ether, benzene, and acetic acid. Not 
 
 sublimable. On reduction it gives (a)-diamido- 
 anthraquinoue (Claus a. Hertel, B. 14, 981). 
 
 17.BROM3.0-NITRO-BENZAI.DOXIM 
 C,H3N,0.;Br i.e. [2:4:1] C,H,(NO.)(Br)(0H:NOH) 
 [153°]. Prepared by heatmg o-nitro-^-diazo- 
 benzaldoxim with HBr (Gabriel a. Meyer, B. 
 14, 827). Fine needles. Sol. alcohol, ether, 
 acetic acid, and hot benzene. 
 
 o-BROMO-NITBO-BENZENE C,H^Br(NO,) 
 [1:2]. Mol. w. 202. [41°] (F. a. M.) ; [43°] (K.). 
 (261° i.V.). Formed, together with a much 
 larger quantity of the ^-isomeride, by nitrating 
 bromo-benzene (Hiibner a. Alsberg, A. 156, 316 ; 
 Z. [2] 6, 369; Walker a. Zinoke, B. 5, 114; 
 Fittig a. Mager, B. 7, 1179). Yellow needles, 
 more sol. alcohol than the p-isomeride. 
 
 Beactions. — -1. SuClj reduces it to o-bromo- 
 auiline. — 2. Alcoholic NH, at 190° gives o-nitro- 
 aniline (W. a. Z.). — 3. HNO3 gives bromo-di- 
 nitro-benzene [72°]. — 4. KCN and alcohol at 
 190° gives CjH^Br.CN.— 5. Heating with KOHAq 
 gives o-bromo-phenol. 
 
 TO-Bromo-nitro-benzene CjH^Br(N02) [1:3]. 
 [56°]. (257° i.V.). 
 
 Formation. — 1. From m-nitro-aniline by the 
 diazo- reaction (Griess, T. 1864 [3] 712).— 
 
 2. From (1, 3, 4)-bromo-uitro-aniline (Wurster, 
 B. 6, 1543; 7, 416).— 3. From nitre-benzene 
 (lOg.), Fe^Cls (1 g.), bromine (13 g.) in sealed 
 tubes for 12 hours at 70° (Scheufelen, A. 231, 
 165). The yield is 80 p.o. of the theoretical.- 
 
 4. By the action of a hot solution of cuprous 
 bromide upon w-nitro-diazo-benzene sulphate 
 (from 7n-nitrauiline) (Sandmeyer, B. 18, 1495). 
 
 Properties. — Yellow trimetrio plates. Not 
 attacked by KOHAq or alcoholic NHj. 
 
 jj-Bromo-nitro-benzene C^H^BrfNOj) [1:4]. 
 [126°]. (256° i.V.). 
 
 Formation. — 1. The chief product obtained 
 by dissolving bromo-benzene in fuming HNO3 
 (Couper, A. 104, 226). — 2. From ^-nitro-aniline 
 by the diazo- reaction. — 3. From bromo- nitro- 
 aniline [151°]. — 4. From bromo-benzene ^'-sul- 
 phouic acid and HNO3 (Spiegelberg, A, 197, 257). 
 
 5. Formed by the action of precipitated Cu^O (1 
 mol.) upon p-bromo-diazo-benzene nitrite (Imol.) 
 obtained by adding slowly a solution of 15 g. of 
 NaNOj in 50 0.0. of water to a mixture of 17 g. of 
 j)-bromo-aniline, 20 g. HNO3 (1'4), and 50 c.o. of 
 water. The yieldis small (Sandmeyer, B. 20, 149G). 
 
 Properties. — Long white needles, si. sol. 
 HOEt. 
 
 Beactions, — 1. Eesembles o-nitro-aniline in 
 reactions 1 and 2. — 2. Alcoholic KCN at 190" 
 gives TO-bromo-benzonitrile (Eiohter, B. 4, 462). 
 
 3. Br at 250° gives ^-di-, u-tii-, and s-tetra- 
 bromo-benzenes (Ador a. SlUiet, J. 1876, 370). 
 
 Bromo-di-nitro-benzene C^HjBr(N02)2 [1:3:4]. 
 [59°]. From m-bromo-nitro-benzene, HNO3 and 
 HjSOj (Korner, J. 1875, 332). Monoolinic plates 
 (from ether-alcohol). Alcoholic NH3 at 180° 
 forms C,H,Br(NOJ(NH,) [1:4:3] [151°]. Boiling 
 NaOHAq (S.G. 1-135) gives CeH3Br(N0,)(0H) 
 [1:4:3] andalittle 0„H ,Br(NO,) (OH) [1:3:4] (Laa- 
 benheimer, B. 11, 1159). 
 
 Bromo-di-nitro-benzene C5H3Br(N02)2 [1:2:4]. 
 [72°]. From bromo-benzene, fuming HNO,, and 
 HjSOj in the cold (Kekul6, A. 137, 167 ; Spiegel- 
 berg, A. 197, 257). Large yellow prisms. Alco- 
 holic NH3 forms di-nitro-aniline. KOHLAq forma 
 di-nitro-phenol [114°]. Sn and HCl gives )«- 
 
BROMO-NITRO-BENZENE SULPHONIC ACID. 
 
 587 
 
 phenylene-diamine (Zinoke a. Sintenis.B 5,791). 
 Crystallises with benzene as (CaH3Br(N02)2)2C^Hj 
 [65°]. 
 
 Bromo-di-nitro-benzene CBH3Br(N02)2. [87°]. 
 Di-bromo-di-nitro-benzene [158°] is treated with 
 alcoholic NH, at 100° and in the resulting 
 CsH2Br(N02)j(NH2) hydrogen is substituted for 
 NHj by the diazo- reaction (Austen, B. 8. 1183). 
 Not affected by alcoholic NH3. 
 
 Di-bromo-nitro-benzene C„H3Br2(N02) [1:2:4]. 
 Mol. w. 281. [59°]. From o-di-bromo-benzene 
 and HNO3 (Eiese, A. 164, 179). Mouoolinio 
 tables (Groth a. Bodewig, B. 7, 1563). May be 
 reduced to di-bromo-aniline [80°]. 
 
 Di-bromo-nitro-benzene CsH3Br2(N02) [1:8:4]. 
 [62°]. Formed by nitrating m-di-bromo-beuz- 
 ene (Meyer a. Stiiber, A. 165, 176). Triclinio 
 prisms (by sublimation, G. a. B.) ; volatile with 
 steam. Converted by alcoholic NH, at 190° 
 into (1,4,3) -bromo-nitro-aniline. Eeduotion 
 gives (l,3,4)-di-bromo-amline. Alcoholic KCN 
 at 250° gives the nitrile of di-bromo-benzoic 
 acid [209°] (E.). 
 
 Di-bromo-nitro-benzene C,H3Br2(N02) [1:3:2]. 
 [83°]. Separates from the aloohoUo mother- 
 liquors from which the preceding has crystal- 
 lised. Prisms or laminse. Alcoholic NH3 at 
 190° gives nitro-TO-phenylene-diamine (Korner, 
 G. 4, 360). 
 
 Di-bromo-nitro-benzene C3H3Br2(N02) [1:4:5]. 
 [85°]. From ^-di-nitro-benzene by nitration 
 (Bicdie a. B6rard, A. 133, 51). From OT-bromo- 
 nitro-benzene (14 g.), Br^ (11-2 g.), and Fe^Clj 
 (4 g.) at 80° for 12 hours (Soheufelen, A. 231, 
 169). Yellowish-green tablets (from ether- 
 aloohol). Alcoholic NH3 at 210° gives (1,3,4)- 
 bromo-nitro-aniline. Sn and HOI gives p-Ai- 
 bromo-anUine [51°]. Alcoholic KCN gives the 
 nitrile of di-bromo-benzoic acid [152°]. 
 
 Di-bromo-nitro-benzene C8H3Br2(N02) [1:3:5]. 
 [105°]. From (1,5,3,6) or (1,5,3,2) di-bromo- 
 nitro-anilinebydiazo- reaction (Korner). Prisms 
 or tablets (from ether). May be reduced to di- 
 bromo-anUine [57°]. 
 
 Di-bromo-di-nitro-benzene CBH2Br2(N02)2. 
 [117°]. Formed by nitrating TO-di-bromo- 
 benzene (Korner). Greenish-yeUow needles, 
 volatUe with steam. Heating with KOHAq 
 gives bromo-di-nitro-phenol [92°]. 
 
 Di-bromo-di-nitro-benzene CsH2Br2(N02)2. 
 [58°]. Formed by nitrating o-di-bromo-benzene 
 (Austen, B. 8, 1182). Prisms (fromHOAc). By dis- 
 placement of Br by NHj andH successively it may 
 be converted into bromo-di-nitro-benzene [87°]. 
 
 Di-bromo-di-nitro-benzene C5H2Br2(N02)2. 
 [120°]. Formed in small quantities in the pre- 
 paration of the preceding body (A.). 
 
 Di-bromo-di-nitro-benzene C^H2Br2(N02)2. 
 [159°]. Formed by nitrating^-di-bromo-benzene 
 (Austen, B. 9, 621). Small nfedles. Alcoholic 
 NH3 forms di-bromo-nitro-aniUne [75°]. 
 
 Di-bromo-di-nitro-benzene 
 G,B.Bi,{^O^h [1:4:2:6J. [100°]. Formed in 
 preparing the preceding (A.). Alcoholic NHj 
 converts it into bromo-di-nitro-aniline [160°]. 
 
 Tri - bromo - nitro - benzene C5H2Br3(N02) 
 [1:8:4:6]. Mol. w. 360. [94°]. Formed by ni- 
 trating M-tri- bromo -benzene (Mayer, A. 137, 
 226). Pale yellowish-green needles (from alco- 
 hol). Alcoholic NH3 gives bromo-nitro-iJ- 
 phenylene-diamine. 
 
 Tri-bromo-nitro-beuzene 
 C,H2Br3(N02) [1:2:8:5]. [112°]. From (1,5,3,6)- 
 di- bromo -nitro -aniline [203°] by displacing: 
 NH2 by Br, or from (1,2,3,5,4) tri-bromo-nitro- 
 aniline by displacing KH2 by H (Korner). Tri- 
 clinic crystals; a:6:o = 1-005:1: -4823 (La Valle,^ 
 G. 10, 1). Beduction gives tri-bromo-aniline. 
 Alcoholic NH3givesdi-bromo-nitro-anLline[203°]. 
 
 Tri-bromo-nitro-benzene 
 C,H2Br3(N02) [1:2:4:6]. [120°]. From (2,4,6,1). 
 di-bromo-nitro-aniline by diazo- reaction (Knr- 
 ner). Needles (from HOAc). Alcoholic NH, 
 gives the parent di-bromo-nitro-aniline. 
 
 Tri-bromo-nitro-benzene 
 C,H.2Br3(N02) [1:3:5:2]. [125°]. (177°) at 11 mm. 
 Prepared by nitration of s-tri-bromo-benzene 
 withHNOa (1-5) (Wurster a. Beran, B. 12, 1821 ; 
 cf. G. L. Jackson, B. 8, 1172). Formed also by 
 diazo- reaction from (l,3,5,2,4)-tri-bromo-nitro- 
 aniline (Korner, G. 4, 422). Monoclinio prisms ; 
 a:b:c = -6518:1: -8695 ; v = 99°46' (Panebianco, G.- 
 9, 354). Tin and HCl reduce it to ordinary tri- 
 bromo-aniline. Alcoholic NH3 at 170° gives 
 (l,4,3,5)-bromo-nitro-phenylene-diamine. 
 
 Tri-bromo-nitro-benzene 
 C(iH2Br3(N02) [1:3:4:2]. [above 187°]. Formed 
 in small quantity in preparing the isomeride 
 [94°]. SubUmes at 187°. 
 
 Tri-bromo-di-nitro-benzene 
 C„HBr3(N02)2 [1:2:4:3:5?]. [135°]. Formed by 
 nitrating the preceding body (Mayer). Triclinic 
 crystals; a:6:c = -455:1: -457 (Panebianco, G. 9„ 
 355). Alcoholic NH3 gives bromo-di-nitro- 
 phenylene-diamine. 
 
 Tri-bromo-di-nitro-benzene 
 0eHBrs(N02)2 [1:3:5:2:6]. [192°]. Glistening, 
 needles. Prepared by nitration of s-tri-bromo- 
 benzene with HNO3 and H^SO^ (Wurster a- 
 Beran, B. 12, 1821). 
 
 Tetra-bromo-nitro-benzene 
 CsHBrj(N02) [1:3:4:5:6]. [96° after several fu- 
 sions]. Slender needles, [60°] (from alcohol). From. 
 M-tetra-bromo-benzene by nitration. Formed 
 also by heating C„(N02)Br4S03H with HCl (V. v. 
 Biehter, B. 8, 1427 ; Langfurth, A. 191, 202). 
 
 Fenta-bromo-nitro-benzene CaBr5(N O2) . 
 
 [228°]. From u - tetra - bromo - benzene and. 
 fuming HNO3 (B.). Monoclinic prisms (from 
 benzene). 
 
 BROMO - NITBO - BENZENE SULPHONIC 
 ACID C,H3Br(N02)(S03H) [1:4:2]. [130°-135°]> 
 From bromo-benzeue o-sulphonio acid and cone. 
 HNO3 (Bahlmann, A. 186, 315). From^-bromo- 
 nitro-benzene and fuming H2SO4 (Augustin a. 
 Post, B. 8, 1559). Flat yellow columns, v. e.. 
 sol. water. Beduction gives amido-benzene m- 
 sulphonic acid ; exchange of NOj for Br gives 
 p-dl-bromo-benzene sulphonio acid. — AgA'. — 
 BaA'2 5aq. S. (of BaA'2) 5-3 at 16°.— CaA'j 4aq.- 
 — CaA'2 6|aq (A. a. P.). -KA'. — NaA'.— NH^A'. 
 PbA'2 5aq.— Zn A'2 7aq. 
 
 O;iiori(ZeCsH3Br(N02)(S02Cl):[92°];tables.. 
 
 Amide C,H3Br(N02)(S02NH2). [205°]. 
 
 Bromo-nitro-benzene snlphonic acid 
 C„H3Br(NO.J(S03H) [1:6:2]? Formed in smaU, 
 quantity in preparing the above by nitrating: 
 bromo-benzene o-sulphonio acid (B.). — BaA'j.. 
 S. ■156at8°.— KA'. 
 
 CfeZori(?eC,H3Br(N02)(S02Cl): [97°]; tables^ 
 
 Amide C,H3Br(NO.,)(S02NH2). [215°}. 
 
588 
 
 BROMO-NITRO-BENZENE SULPHONIO ACID. 
 
 Bromo-nitro-benzene-sulphonic acid 
 Cj,a3r(N0,)(S03H) [1:3:6]. Formed by heating 
 nitro-diazo-benzene-sulphonio acid (1:3:6) with 
 HBr (Limpricht, B. 18, 2186). 
 
 Chloride : [75°], large yellow tables. 
 
 Amide: [166°], small white tables. 
 
 Bromo-uitTo-benzene snlphonlc acid 
 <!,H3Br(NO,)(S03H) [1:4:3]. Formed by nitra- 
 ting bromo-benzene m-sulphonio acid (Berndsen, 
 A. 177, 95 ; Thomas, A. 186, 124). Beduoed to 
 ami do-benzene o-sulphonio acid. Exchange of 
 NO.^ for Br gives ^-di-bromo-benzene sulphonio 
 .aoid.^AgA' IJaq.— BaA', 3aq. S. 2-4 at 7°.— 
 CaA'^ Gaq.— KA'.— NH,A'.— PbA'j 3aq. 
 
 Chloride C„H3Br(N02)(SO.,Ci). [83°]. 
 
 Amide C,H3Br(N02)(S02NH,). [170°]. 
 
 Bj omo-nitro-benzene sulphonio aci.4 
 .C„H3Br(N03){S03H) [1:2:4]. Formed by nitra- 
 ■ting bromo-beazeue ^-sulphonio aoid (Goslioh, 
 A. 180, 93; Limpricht, JS. 8, 456). Formed 
 ^Iso by sulphonating o-bromo-nitro-benzene 
 {A. a. P.; Andrews, 5. 13, 2127). Eeduction 
 by HI at 120° gives amido-benzene rra-sulphonio 
 acid.— BaA'.aq. S. (of BaA'J 1-71 at 15° (A.). 
 --BaA'j,l|aq. S. (of BaAy 1-46 at 9° (G.).— 
 ■C!aA'2 2aq (A. a. P.).— CaA'^ 2iaq. S. (of CaAy 
 4-71 at 9° (G.).— CuA'j9iaq.— KA'. S. 1-02 at 
 9° (G.).— NH4A'. S. 5-96 at 9°.— PbA'^ 2aq.— 
 •ZnAjSaq. 
 
 Chloride C3H3Br(NO,){SO,Cl). [40°-50°] 
 .(A.); [57°] (G.). 
 
 Amide CjH3Br(N02) (SO^NHJ: [177°] ; plates. 
 
 Bromo-nitro-benzene di-sulphonic acid 
 CI„H2Br(NOj)(S03H)„. From nitro-benzene m- 
 sulphonic aoid vid di-nitro-benzene di-sulphonic 
 acid and amido-nitro-benzene disulphonic aoid 
 (Ijimprioht, B. 8, 289). Trimetric tables (oon- 
 itaining aq). 
 
 Si-bromo-nitro-benzene sulphonio acid 
 C„HjBr3(N03)(S03H) [1:2:4:6]. _ From o-di- 
 bromo-benzene sulphonio acid and fuming 
 HNO3 (Goslioh, A. 186, 152). Eeduction gives 
 di-bromo-aniline sulphonio acid. — BaA'2 3aq. 
 S. -9 at 7°.— CaA'„4aq.— CaA'2 6aq.— KA'.— 
 NHjA'.— PbA'j3aq. S. -8 at 11°. 
 
 Chloride G,'a^Bi^(SO.,)SOfil. [99°]. 
 
 Amide C,HJBr,(N0j)S02NH2. [211°]. 
 
 Di-bromo-nitro-benzeue sulphonio aoid 
 C„H^r3(N02)(S03H) [1:4:3?:5]. From (1,4,5)- 
 -di-bromo-benzene sulphonio acid and HNO3 
 <Borns, A. 187, 358 ; Hiibner a. Williams, A. 
 167, 121). Hygroscopic prisms which blacken 
 At 100°.— BaA'2 aq.— BaA'j l|aq.— BaA'^ SJaq.— 
 .BaA'2 6aq. — BaA'2 9aq. — CaA'2 3aq.— CuA'jaq. — 
 JKA'aq.- KA' 2|aq.— NH^A'iaq.— PbA'^ 2aq.— 
 PbA'2 3aq. S. 10-3 at 10°. 
 
 Chloride C„H2Br2(N02)(SO,Cl). OU (?). 
 
 Amide CeH2Br2(N03)(B02NH2). [178°]. 
 
 Di-bromo-uitro-benzene sulphonio aoid 
 O.H2Br2(N02)(S03H) [1:3:4:5]. From s-di- 
 •bromo-benzene sulphonio aoid and HNO3 (Lenz, 
 A. 181, 32). Tablets (containing a;aq) ; not 
 hygroscopic. By exchanging NO2 for Br it is 
 converted into (l,3,4,5)-tri-bromo-benzene sul- 
 a)honio aoid. — BaA'2 l-Jaq- S. -73 at 20°.— 
 BaA'2 4aq.— CaA'2 3aq.— KA'aq. S. 1-09 at 20°. 
 — NH,A'.— PbA'2 5aq. S. -120 at 20°. 
 
 Chloride C„H2Br2(NO.J(S02Cl). [121°]. 
 
 Amide C^'H.^i,{^0^(80,T!iE.^. Blackens 
 «t 300°. 
 
 Di-bromo-nitro-benzene sulphonio acid 
 CsH2Br2(N02)S03H [1:3:4:6] [above 200°]. Formed 
 by nitrating OjHjBrjSOsH [1:3:4] (Bassmann, A. 
 191, 235). Deliquescent needles or prisms (con- 
 taining a;aq).— KA'. S. 1-4 at 21-5°.— BaA'2 aq. 
 S. (of BaA'2) 1-06 at 24°.— CaA'jeaq.— PbA'2 4aq. 
 
 Chloride C„H2(N02)Br2S02Cl. [115-5°]. 
 
 Amide C,II ,(N02)Br2S02NH2. Minute 
 tablets. Not melted at 240°. 
 
 Tri-bromo-ultro-benzene sulphonic aoid 
 CeHBr3(NOJSOsH2aq [1:3:5:2:6]. [0. 100°]. 
 Formed by nitrating C,H2Br3S03H (Langfurth, 
 A. 191, 196 ; Eeinke, A. 186, 282 ; Bassmann, 
 A. 191, 216). Hygroscopic, monoclinic prisms. 
 Cone. HCl at 180° gives H^SO^ and 
 CsH.,Br3(N02) [125°].— KA'. S. -76 a't 5° (B.) ; 
 1-33 at 11° (L.).— BaA'jaq. S. (of BaA'j) -207 
 at 1-5° (B.) ; -331 at 15° (L.). BaA'2 Isaq.— 
 CaA'2 2aq.— PbA'2 9aq. S. (of PbA'j) -63 at 7° 
 (B.); -gSatlO" (L.).— PbA'jlJaq.— PbA'2Pb07aq. 
 — PbA'2PbO 6aq.— NH^A'. 
 
 Chloride C„HBr3(N02)S02Cl. [145°]. 
 
 Amide 03HBr3(N02)S02NH2. 
 
 Tri-bromo-nitro-benzeue sulphonic acid 
 C„HBr3(NO.)(S03H) [1:2:3:4:5]. From (1,2,3,5). 
 tri-bromo-benzene sulphonio aoid by nitration 
 (Limpricht a. Lenz, B. 8, 1072, 1482 ; A. 181, 
 41). Laminse.— BaA'2 4aq, S. -074 at 18°.— 
 CaA'jSaq. S. 1-05 at 20°. — KA' aq. S. -16 
 at 18°.— NH,A'aq.— PbA'2aq. S. -14 at 20°. 
 
 Chloride C3HBr3(N02)(S02Cl). [116°]. 
 
 Amide C„HBr3(N02)(S02NH2). [202°]. 
 
 Tri-bromo-nitro-benzene sulphonic aoid 
 C„HBr3(N02)(S03H) [1:3:4:2:6]. [125°] or, anhy- 
 drous, [141°]. From (l,2,4,5)-tri-bromo-benz- 
 ene sulphonio acid and HNOj (Spiegelberg, A. 
 197, 284) columns (aontaining 3aq). — AgA'aq. 
 S. (of AgA') -45 at 7°. BaA'2 3aq. S. (of BaA'2). 
 •669 at 9°.— CaA'2 4iaq. S. (of CaA'2) 1-95 at 
 8°.- EA'. S. 1-19 at 8°.— NH,A'. S.1-68 at 6-5°. 
 — PbA'2 6aq. S. (of PbA'2) -853 at 7°. 
 
 Chloride C,HBr3(N02)(S02CI). [143°]. 
 
 Amide C.HBr3(N02)(S02NH2). Blackens 
 at 250°. 
 
 Iri-bromo-di-nitro-benzene sulphonic acid 
 C3Br3(N02)2SOsH [1:3:5:2:4:6]. [216°]. From 
 C3H2Br3S03H and cone. HNO3 at 100° (Bass- 
 mann, A. 191, 239). Colourless columns (con- 
 taining 3aq). Not hygroscopic, but v. sol. 
 water, sol. alcohol.— With water at 230° it gives 
 C„HBr3(N02)2 and H.SO^. Eeduced by Sn and 
 HCl to C,H2Br(NH2)2S03H.—NH,A'aq.— KA'aq. 
 S. (of KA') -48 at 24°.— BaA'j 9aq. S. (of BaA'j) 
 •83 at 21°.— CaA'2 7iaq.— PbA'2 9aq. S. (of PbA'j) 
 1-02 at 19-5°. 
 
 Chloride C^r3{N02)2S02Cl. [203°]. 
 
 Amide C,Br3(N02)2S02NH2. [260°]. 
 
 Tetra-bromo-nitro-benzene sulphonio acid 
 C„Brj(N02)S03H [1:2:3:5:4:6]. Got by nitrating 
 CaHBrjSOjH. Crusts of needles (containing 4aq). 
 V. sol. alcohol and water (Beckurts, A. 181, 220 ; 
 Langfurth, A. 191, 202). With cone. HCl at 
 200° it gives C„HBr.,(N02) and HjSO^.- KA'l|aq. 
 S. (of KA') ^57 at 10^5°.- BaA'jgaq. S. (of BaA'2) 
 ■36 at 11° (B.); -100 at 14^5° (L.).— NH^A'aq. 
 S. (of NH^A') 1-01 at 11°.— CaA'2 8aq. S. (of 
 CaA'2) •le at 6°.— PbA'2 9aq. S. (of PbA'j) •OB 
 at 6°. 
 
 Chloride C^r,(N02) SOjCl: [147^o°]; tablets. 
 
 Amide: crystalline powder. 
 
BROMO-NlTRO-CmNAxMlO ACID. 
 
 Tetra-bromo-nitro-benzene sulphonio acid 
 C,J3r,(N0,)S0,H [1:2:3:4:5:6]. [173°]. From c 
 tetra-bromo-beuzene sulphonio acid and HNO, 
 (Spiegelberg, A. 197, 297). Slender needles (eon: 
 taming aq).—BaA'i,4aq. S. (of BaAy -22 atl2°.— 
 BaA'j 9aq.— CaA'j aq. 8. (of CaA' ) 2-8 at 13°.— 
 KA'aq. S. (of KA') -17 at 11°.— NH,A'. S. -46 
 at 11°.— PbA'.,2aq. S. -042 at 11°. 
 
 Chloride C,3r,(N0,)(S0,Cl): [173°]; prisms. 
 Jrnide C^r,(N02)(SO,NH2). Blackens at 
 
 BROMO-NITRO-BENZOIC ACID 
 
 C,H3Br(N0JC02H [1:4:3]. [141°]. Formed, 
 together with the isomeride [250°] by nitrating 
 jn-bromo-benzoio acid (Hubner a. Ohly, Z. [2] 
 1, 547; 2, 241; A. 143, 230; 222, 102). 
 Monoclinio prisms.- NaA' 3aq. — NaA' 2| aq. — 
 KA' 2aq. — BaA'^ 4aq. — CaA'^ 2aq.— MgA', 4aq .— 
 PbA'„.— CuA^ - AgA'. 
 
 Ethyl etherMA': [55°]; monoclinicprisms. 
 
 Bromo-nitro-benzoic acid C5H.Br(N0,)C0.,H 
 [1:3:5]. [161°]. S. -057 at 11°. Formed from 
 CeH:,(NH,)(N0j)C02H, glacial acetic acid, HBr 
 (S.G. 1-49), and nitrous acid gas (Hesemanu a.. 
 Eohler, A. 222, 166). Long needles (from water, 
 benzene, ether, or CSj), whetstone - shaped 
 crystals (from glacial acetic acid) or thin six- 
 sided plates (from alcohol). — EA' Aaq. — 
 BaA'j 5|aq.— CaA'j aq.— MgA'^ aq. — ZnA*^, 4iaq. 
 — CdA', 4|aq.- Sr A',.- AgA'.— PbA',. 
 
 Bromo-nitro-benzoic acid CjH3Br(N02)C02H 
 [1:3:6]. [164°]. Formed by oxidation of 
 C„H3Br(N02)Me by dUute HNO, (Scheufelen, A. 
 231, 173). V. sol. ether and dilute alcohol. SI. 
 sol. water. Beduced by Sn and HCl to m-bromo- 
 aniline, COj going off. — ^AgA'. 
 
 Bromo-nitro-benzoic acid C5H3Br(N02)(C02H) 
 [1:4:6]. [180°]. From C,H3MeBr(N02) [1:2:5] and 
 dilute HNO3 (Scheufelen, A. 231, 181) or by 
 nitrating o-bromo-benzoic acid (Burghard, B. 8, 
 560). Almost insol. cold water, si. sol. hot water, 
 V. sol. ether and dilute alcohol. Alcoholic NH, 
 at 130° gives ^-nitro-aniline and (1, 4, 6)-amido- 
 nitro-benzoic acid. — BaA'^oiaq. 
 
 Ethyl ether EtA' : [66°]; needles. 
 
 Bromo-nitro-benzoic acid 
 CsHsBr(N02)C02H [1:2:4]. [199°]. Formed by 
 nitration of ^-bromo-benzoic acid [248''] (Hub- 
 ner, A. 143, 248 ; Eaveill, A. 222, 177) and by 
 oxidation of the corresponding bromo-nitro- 
 toluene (Scheufelen, ^. 231,183). Long needles 
 (from water) or plates (from dilute alcohol) ; v. 
 sol. ether, si. sol. water. Eeductiou gives m- 
 amido-benzoic acid. 
 
 Salt s.— AgA'.— BaA'2 4aq.— MgA'2 6aq. 
 
 Ethyl ether EtA': [74°]; prisms. 
 
 Bromo-nitro-benzoic acid 
 C„H3Br(N02)COjH [1:2:3]. [250°]. From m- 
 bromo-benzoio acid by nitration. Separated 
 from its isomeride [141°] by being less soluble in 
 water (Hiibner, A 143, 284 ; ^.222,101). Mono- 
 clinic octahedra (from ether). — NaA' aq. — 
 BaA'2 4aq. — MgA'2 6aq. 
 
 Ethyl ether EtA': [80°]; prisms. 
 
 Si-bromo-nitro-benzoic acid 
 C„H2Br2(N02)CO.,H [3:4: 2or6 : 1]. [162°]. 
 From di-bromo-benzoic acid [230°] by nitration 
 (B. F. Smith, A. 222, 188). Colourless needles ; 
 reduction gives anthranihc acid. 
 
 Salt s.— PbA'j.— NaA' 3aq.— KA'.— BaA'^ aq. 
 -CaA'2 3^aq.— MgA',. 
 
 6b5> 
 
 Di-bromo-nitro-benzoic acid 
 C^H^Br (N0.J(C02H). [162°]. Formed by nitra- 
 ting_ the di-bromo-benzoic acid [223°-227°l 
 obtained by brorainating benzoic acid (Anger- 
 stein, A. 158, 13). Needles (from water). Ee- 
 duotion gives di-bromo-amido-benzoio acid 
 [196°] and then anthranihc acid.— NaA' 3aq.— 
 BaA'2 2aq. This acid is perhaps identical with 
 the preceding. 
 
 Di-bromo-nitro-benzoie acid 
 CsH2Br2(N02)CO,,H [3:5:2:1]. [233°]. Formed by 
 nitration of CjH3Br2C02H (Hesemanu a. Kohler, 
 A. 222, 173). Long colourless needles ; may bo 
 subhmed.— BaA',4aq.— CaA'2.— AgA'.— KA'. 
 
 BEOMO-NITBO-o-BENZYL-PHElTOL 
 C,3H,„BrN02. [105°-110°]. From potassium 
 nitro-o-benzyl-phenol sulphonic acid and Br 
 (Eennie, C. J. 49, 410). Yellow scales (from 
 alcohol).— KA'. 
 
 Bromo-nitro-jj-benzyl-phenol 
 Ph.CH2.C„H2Br(N02)0H [1:3:5:4]. [65°]. 
 
 Formation. — 1. From potassic bromo-benzyl- 
 phenol sulphonate and dilute HNO, (1:1) 
 (Eennie, C. J. 41, 223).— 2. Prom potassic nitro- 
 benzyl-phenol sulphonate, C2H.,02, and Br.— 
 
 3. From nitro-benzyl-phenol, C^fi^, and Br.— 
 
 4. From benzyl-phenol by first brominating 
 and then nitrating. 
 
 Properties.— Crystalline scales (from alcohol). 
 — KA'. Bed scales. HNO3 oxidises it to bromo- 
 di-nitro-phenol, CsH2Br(N02)20H [1:2:3:5] [118°]. 
 
 BROMO-iriTRO-BUTANB C^HgBrNOj i.e. 
 C3H,.CHBr(N02). (181° cor.). From nitro- 
 butane, potash, and Br (Ziiblin, B. 10, 2085). 
 The three following compounds are prepared in 
 a similar way (Z.). 
 
 Di-bromo-nitro-butane 03H,CBr2(N02). (204° 
 cor.). 
 
 Bromo-di-nitro-butane C3H,CBr(N02)j. Not 
 volatile. 
 
 Bromo-di-nitro-iso-butane 
 (CH3),CH.CBr(N02)2. [38°]. Solid resembling 
 camphor. Volatile with steam. Eeadily decom- 
 posed by alkaUs forming dinitro-isobutane. 
 
 BEOMO-m-KITEO-CIlfNAmiC ACID 
 [3:l]C,H,(N02).C2HBr.C02H. [212°]. Formedby 
 heating the dibromide of m-nitro-benzylidene- 
 malonic acid (Stuart, G. J. 49, 361). 
 
 Bromo-p-nitro-cinnamic acid 
 [4:l]CsHj(N02).C2HBr.C02H. [146°]. V.sol.alco- 
 hoi, ether, chloroform. SI. sol. hot CS.^. More 
 sol. in cold water than its isomeride [205°]. 
 
 Salt. — BaA'j. Boiled with water gives nitro- 
 phenyl-aoetylene, COj and BaBr.,. 
 
 Ethyl ether EtA'. [63°]. 'Prisms. From 
 C„Hj(N02)CHBr.CHBr.C02EtandalcoholicKOH 
 (C. L. Muller, A. 212, 131). 
 
 Bromo-p-uitro-cinnamic acid 
 [4:1] C5H^(N02).C2HBr.C02H. [205°]. Slender 
 silky needles (from water). SI. sol. cold water, 
 insol. cold CSj. V. sol. alcohol, ether, chloro- 
 form, or benzoline. 
 
 Salt. — ^BaA'2. Decomposed by boUing into 
 nitro-phenyl-acetylene, CO2 and BaBrj. 
 
 Ethyl etherMA.'. [93°]. Needles. From 
 di-exo-bromo-^-nitro-phenyl-propionic ether by 
 alcoholic KOH (C. L. MiiUer, A. 212, 131). 
 
 Dl-bromo-2)-nitro-ciuuamic acid 
 [4:1] CsHXN0,).CBr:CBr.C02H. [c.l80°]. From 
 ^-nitro-phenyl-propiolic acid and Br (Drewson, 
 A. 212, 167). 
 
590 
 
 BKOMO-NITRO-CINNAMIO ACID. 
 
 Ethyl ether 'EtA.'. [8(5°]. V. sol. benzene, 
 ehloroform or glacial HOAc, si. sol. benzoline. 
 
 BROMO-NITBO-CXNNAMIC ALDEHYDE 
 C„H,(NOJ.CH:CBr.CHO. [97°]. Long yellowish 
 needles. Formed together with the isomeride 
 £136°] by nitration of o-bromo-cinnamio alde- 
 hyde. 
 
 Phenyl-hydrazide. [134°]. Large yellow 
 plates (Zincke a. Hagen, B. 17, 1816). 
 
 Sromo-uitro-ciuoamic aldehyde 
 C,Hj(N02).CH:CBr.CH0. [136°]. Yellowish 
 needles. Formed as above. 
 
 Phenyl-hydrazide. [154°]; red crystal- 
 line solid, si. sol. alcohol (Z. a. H.). ' 
 
 DI-BEOMO-NITRO-o-CEESOL 
 CjH(CH,)(N02)(Br)2(OH) [l:4:a;:2] [92°]. 
 Formed by bromination of nitre -o- cresol 
 C„Hs(CH3)(N02)(0H) [1:4:2]. Yellowish needles. 
 V. sol. alcohol and ether, nearly insol. water 
 (Nolting a. Collin, B. 17, 270). 
 
 Di-bromo-nitro-p-cresol 
 C„HMe(N0.J(0H)Br2 [1:2:4:?:?]. [83°]. From 
 aqueous nitro-cresol, [78°], and bromine-water. 
 Long yellow needles (from alcohol). Insol. cold 
 water, v. si. sol. hot water, v. sol. alcohol or 
 ether (E. Kneoht, A. 215, 89 ; B. 15, 1071). 
 
 Salts. — C„HMe(NO,)(ONa)Br22iaq. Eed 
 needles (from alcohol).— C„HMe(N02)(OK)Br2aq. 
 
 DI-B ROMO-NITBO-CTTME NE 
 C A.CHBr.CBr(N02).CH3. Di - bromo - nitro • 
 phenyl - propylene. [77°-78-5°]. From 
 Ph.CH:C(N02).CHa and Br (Priebs, A. 225, 362). 
 Colourless prisms (from light petroleum). Not 
 decomposed even by hot aqueous NaOH, thus 
 differing markedly from the corresponding di- 
 bromo-nitro-ethyl-benzene. 
 
 Bromo-nitTO-if'-ciimeue 
 C.HMe3Br(N0j) [l:2:4:5:a;]. [192°]. Formed by 
 nitration of bromo-pseudo-cumene [73°] by 
 fuming HNOj. Needles. Sol. benzene, si. sol. 
 alcohol (Kelbe a. Pathe, B. 19, 1548). 
 
 Bromo-di-iiitro-;f'-cumene 
 C,Me3Br(N02)j [1:2:4:3:5:6]. [181°]. Formed by 
 nitration of bromo -pseudo -cumene [1:2:4:3]. 
 Long yellowish needles. SI. sol. hot alcohol, 
 nearly insol. cold (Kelbe a. Pathe, B. 19, 1551). 
 
 Bromo-di-nitro-i/'-cumeue 
 C,Me3Br(N02)2 [1:2:4:5:3:6]. [214°]. Formed by 
 nitration of bromo-pseudo-cumene [73°] with 
 fuming HNO3 and cone. H^SO^. Microscopic 
 tables. Sol. benzene, si. sol. hot alcohol, nearly 
 insol. cold alcohol (Fittig, A. 147, 14 ; Kelbe a. 
 Pathe, B. 19, 1648). 
 
 BEOMO-NITEO-iso-CTTMENOI C,H,„BrNO, 
 i.e. 05Hj,(C8H,)Br(NOJ(OH) [1:5:3:2]. Bromo- 
 nitro-isopropyl-pkenol. [33°]. From bromo-iso- 
 propyl-phenol and HNO3 (Fileti, &. 16, 123). 
 Pale yellow needles (from dilute HOAc). 
 
 Bromo-nitro-iso-cumenol 
 C,HjPrBr(N02)(0H) [1:3:5:2]. [88°]. Fromnitro- 
 isopropyl phenol and Br (F.). Nacreous tables 
 (from dilute alcohol) ; volatile with steam. 
 
 BEOMO-NITEO-CUMYL-PEOPIONIC ACID 
 CiaH.jBrNOj i.e. 
 
 CaH3(C3H,)(NOJ.CHBr.CHj.COjH. [127°]. 
 From o-nitro-eso-propyl-oinnamio acid and HBr 
 (Einhorn a. Hess, B. 17, 2020). 
 
 Di-bromo-nitro-cnmyl-propionic acid 
 C,H3(C3H,)(N02).CHBr.CHBr.COjH. [171°]. 
 
 From o-nitro-6.'io-propyl-oinnamic acid and Br 
 (Widman, B. 19, 260). 
 
 Di-bromo-nitro-cumyl-propionic acid. [184°], 
 From m-nitro-eso-propyl- cinnamio acid and Br 
 (Widman, B. 19, 418). 
 
 BROMO-NITEO-CYMENE C,„H,3rN02 i.e. 
 C„H2Me(C3H,)Br(NOj) [l:4:3:a!]. Formed by 
 nitrating the bromo - oymene derived from 
 thymol (Mazzara, Q. 16, 193). Oil, volatile 
 with steam. 
 
 Bro mo-di-nitro-cymene 
 C„HMePrBr(N0j2 [1:4:2?:?:?]. [98°]. Formed 
 by nitrating bromo-cymene (229°). Monoclinia 
 prisms (Gerichten, B. 11, 1092). May be iden- 
 tical with the following. 
 
 Bromo-di-nitro-cymene 
 CsHMePrBr(N03)j [1:4:3:?:?]. [94°]. Formed 
 by nitrating the bromo-oymene derived from 
 thymol (M.). Slender yellow needles. 
 
 Bromo-nitro-isooymene 
 C,H,(03H,){CH3)(Br)(N02) [4:2:1:?]. _ [121°]. 
 Long red needles. Prepared by nitration of 
 (l:2:4)-bromo-isocymene (Kelbe, B. 15, 40). 
 
 Bromo-nitro-m-isocymene (?) C,„H,2(N0j)Br. 
 [83°]. From di-bromo-m-isooymene by nitra- 
 tion (Kelbe a. Czarnomski, A. 235, 284). 
 
 Bromo-di-nitro-isocymene 
 C,H(C3H,)(CH3)(NOJ,(Br). [53°]. Short thick 
 needles. Prepared by nitration of (i8)-bromo- 
 isocymene (Kelbe, B. 15, 42). 
 
 BEOMO-NITRO-ETHANE C^HjBrNOj i.e. 
 CH3.CHBr(N02). (147°). Formed by dissolv- 
 ing nitro-ethane (q_.v.) in aqueous caustic potash 
 and adding bromine: CH3.CHK(N02) -l-Brj = 
 CH3.CHBr(N02) + KBr (Meyer a. Wurster, B. 6, 
 94; Tscherniak, B. 7, 916; 4.180, 126).- Pun- 
 gent oil. Forms unstable salts. 
 
 Bromo-di-nitro-etliane CH,.CBr(N02)2. From 
 Br and potassium dinitroethane (Ter Meer, A. 
 181, 15). — Oil, volatile with steam ; decomposed 
 by K2CO3 which forms CH3.CK(N02)2. 
 
 Di-bromo-tetra-nitro-ethane 
 CBr(NO.j2.CBr(N02)2. Jrom ethylene bromide 
 and fuming HNO3, or from C,(NO.J,Kj and Br. 
 Unstable liquid ; forms with potash a compound 
 C2Br2(N02)42KOH, m. sol. hot water, which ex- 
 plodes at about 180°. Ammonium sulphide con- 
 verts it into C2K.,(N03)4. SO^ forms NH3, HBr, 
 and HON. Aqueous EgSO, forms yellow crys- 
 tals G.,(NOj)4Kj3K2S04 (Yilliers, O. B. 94, 1122; 
 98, 431). 
 
 Di - bromo - nitro-ethane CH3.CBrj(N02). 
 (165°). Formed by adding potash to a mixture 
 of nitro-ethane (3. v.) and the calculated quan- 
 tity of bromine (V. Meyer, B. 7, 1313). Indif- 
 ferent oil, insol. KHO. 
 
 BEOMO-NITEO -ETHEHYL - NAPHTHYL- 
 ENE-DIAMINE 
 
 C„H,Br(N02)<^H>C.CH3 [4.:x:\]. [242°]. 
 
 Formed by nitration of ethenyl-(4:2:l)-bromo- 
 naphthylene- diamine (Prager, B. 18, 2162), 
 Yellow needles si. sol. alcohol, v. sol. HN03Aq. 
 
 Bo-DI-BHOMO-o-NITEO - ETHYL - BENZENE 
 CgHjBr^NOj i.e. [2:1] C„Hi(N02).CHBr.CH.jBr. 
 o-nitro-styrene dihromide. [52°]. From o-nitro- 
 Rtyrene and Br (Einhorn, B. 16, 2213). 
 
 wa-Di-bromo-TO-nitro-ethyl-benzene 
 [3:1] C„Hj(N02).CHBr.CH2Br. [79°]. From «. 
 nitro-styrene and Br (Prausnitz, jB. 17, 598). 
 
 aio-Di-bromo-p-nitro-ethyl-benzene 
 [4:1] C„H,(N03).CHBr.CH2Br. [73°]. From p- 
 nitro-styrene and Br (Basl'er, B. 16, 8006). 
 
JiRuMO-NlTRO-NAPHTHALENE. 
 
 CBl 
 
 ttfa-Si-bromo-co-iutro-ethyl-benzeiie 
 C„H5.CHBr.CHBrN02. [86°]. FromM-nitro- 
 phenyl-ethylene and Br (Brdmann, B. 17, 414). 
 Also from ai-nitro-ethyl-benzene and Br (Priebs, 
 A. 225, 341). Mouoolinio crystals, a:6:c = 
 l;257:l:l-396; L = 83° 54'. Cold aqueous NaOH 
 gives bromo-nitro-styrene. 
 
 <t)a-Di-bronio-ao-di-iiitro-ethyl-benzene 
 [2:1] C„H,(N0,).CHBr.CHBrN02. [91°]. Prom 
 eoo-di-nitro-phenyl-ethylene and Br (Priebs, A. 
 225, 352). White needles, v. si. sol. ligroin. 
 
 oia-Di-bromo-oip-di-nitro-ethyl-benzene 
 [4:1] C„H,(N02).CHBr.CHBrN0,. [103°]. From 
 aip-di-nitro-phenyl-ethylene and Br (P.), Plates. 
 
 DI-BEOMO-KITEO-ETHYLENE 
 02HBrj(NOJ. [112°]. From sodium tri-nitro- 
 resoroin 0„a(N0j3{0H)(0Na) in aqueous solu- 
 tion, and bromine vapour (Merz a. Zetter, B. 12, 
 2046). Prisms (from CHCI3) ; does not combine 
 with Br. Zn and HCl give ethylamine. 
 
 DI-BKOMO-DI-NITilO-FIiUOSESCEitN 
 02i,HsBr2(NO2)2O5. From di-bromo-fluoresoein 
 and HNO3, or from di-nitro-fluoresoein and Br. 
 Yellow needles ; is not fluorescent. 
 
 Acetyl derivative [256^] (Baeyer, A. 
 183, 61). 
 
 BHOlIO-NirBOrORM V. Bkomo-ibi-niibo- 
 
 IIEIHANE. 
 
 BBOMO-NIiaO-HYDKOCINNAMIC ACID v. 
 
 BaoMO-NITKO-PHENYL-PItOPIOXIC ACID. 
 
 BEOMO-NITaO-MESirYLESE" CjH,„BrN02 
 i.e. C,HBrlIe3(N02). [54°]. Formed by nitrating 
 bromo-mesitylene (Fittig a. Storer, A. 147, 7). 
 
 Broma-di-nitro-mesitylene C^BrMe3(NOj)2- 
 [194°]. From di-bromo-mesitylene by fuming 
 HNO3. Needles (Siissenguth, A. 215, 248). 
 
 BBOMO-NITEO-MEraANE 0H,Br(N02). 
 (144^). Formed by the action of bromine on 
 sodium nitro-methane (Tsoherniak, B. 7, 916 ; 
 A. 180, 128 V. Niibo-methane). Pungent oil. 
 The bromine and nitroxyl render its hydrogen 
 displaceable by sodium : it is a strong acid. 
 
 Bromo-di-aitro-methane 0HBr(N02)2. From 
 di-bromo-di-nitro-methaue and alcoholic KOH 
 (Villiers, Bl. [2] 37, 452; Losanitsch, B. 16, 
 51) ; or from (a)-di-bromo-oamphor and cone. 
 HNO3 (Kaohler a. Spitzer, M. 4, 558). Oil. 
 
 Salt.— CKBr(N0.,)2: S.G. Ai 1-25; triclinic 
 crystals which explode at about 147°. Reduc- 
 tion by sodium-amalgam gives HON, HBr, and 
 NH3 (Villiers, Bl. [2J 41, 282). Ammonium 
 sulphide gives di-nitro-methaue. 
 
 Bromo-tri-nitro-methane CBr(N02)3. Bromo- 
 nilroform. [about 12°]. S.G. 2-8. From 
 nitroform and Br in sunlight ; or from mercuric 
 nitroform and Br (Schischkoff, A. 119, .247). 
 Decomposes at 140°, but volatile with steam. 
 
 Di-bromo-nitro-methane CHBr2(N02). 
 (155,°-160°). Formed by adding bromine to 
 potassio bromo-nitro-methane : 
 
 CHKBr(NO,,) + Br2= CHBr2(N0J + KEr. 
 Bromopicrin, insoluble in potash, is formed at 
 the same time (Xsoherniak, A. 180, 130). Very 
 pungent oil, volatile with steam, soluble in 
 caustic soda. 
 
 Di-bromo-di-nitro-methane CBr2(N02)2. 
 [0. 0°]. Formed by the action of cone. HNO3 
 on tri-bromo-aniline, ethylene bromide, bromo- 
 phenol, or di-bromo-j7-toluidine (Losanitsch, B. 
 15. 472 ; VilUers, Bl. [2] 37, 452). Greenish- 
 
 yellow, pungent oil, volatile with steam. Alkalis 
 form salts of bromo-di-nitro-methane. 
 
 Tri-bromo-nitro-methane 0Br3(NO,). Bromo- 
 picrin [10°]. S.G. ia : 2-811. 
 
 Formation. — From nitro-methane, bromine, 
 and KOH (V. Meyer a. Tsoherniak, A. 180, 122). 
 
 Preparation. — CaO (4 pts.), H^O (50 pts.), 
 Brj (6 pts.) and picric acid (1 pt.) are mixed in 
 the order named and the product is distilled 
 (Stenhouse, P. M. [4] 8, 36; Groves a. Bolas, A. 
 155, 253 ; G. J. 23, 153). 
 
 Properties.— Pungent prisms, may be dis- 
 tilled m vacuo. Converted by Br into OBr,. 
 
 BEOMO-DI-iriTRO-METHYL-AHILINE 
 C„H2Br(N02)2NHMe [1:3:5:6]. [147°]. From 
 di-nitro-methyl-anUine and Br. Yellow crys- 
 tals ; boiling aqueous KOH gives bromo-di- 
 nitro-phenol (Norton a. Allen, B. 18, 1996). 
 
 Bromo-nitro-di-methyl-aniline 
 C,H3Br(N02)NMe2 [4:3:1]. [72^. Long crystals. 
 Formed together with other products by the 
 action of nitrous acid upon p-bromo-di-methyl- 
 aniline (Koch, B. 20, 2460). 
 
 BEOMO-DI-NITEO-METHYL-DI-PHENYL- 
 AMINE C,3H,„NBr(N02)2. [194°]. Light yellow 
 tables. Formed by bromination of di-nitro- 
 methyl-di-phenyl-amine (Leymann, B. 15, 1286). 
 
 BROMO-NITEO-NAPHTHALENE 
 0„H,Br(N02) [1:4]. [85°]. From (a) biomo- 
 naphthalene and HNO3. Yellow needles. PBr, 
 gives C,„HjBr2 [81°] (Jolin, Bl. [2] 28, 515). 
 
 Bromo-nitro-naphtlialene 
 C,„H,Br(N02) [l:l'or4']. [122-5°]. S. (93 p.o. 
 alcohol) -337' at 15-7°. From (o)-nitro-naphtha- 
 leue and bromine (Guaresohi, A. 222, 291). 
 Yellow needles (from alcohol). KMnO, gives 
 bromo-phthalic acid [174°-176°]. 
 
 Bromo-nitro-naphthalene 0,„H5Br(N02) [3:1]. 
 [131°]. From (2,4,l)-bromo-nitro-(a).naphthyl- 
 amine by the diazo- reaction (Liebermann a. 
 Soheiding, A. 183, 262 ; Meldola, C. J. 47, 508). 
 Straw-coloured needles. Exchange of NO, for 
 Br gives (l,3)-di-bromo-naphthalene [64°]. 
 
 Bromo-nitro-naphthalene C,„H^Br(NOj) [1:3]. 
 [132°]. From (a)-naphthylamine by bromina- 
 tion, nitration, diazotisation &c. (Liebermann, 
 B. 8, 1108; A. 183, 202). Yellow needles; Sn 
 and HCl give (;3)-naphthylamine. 
 
 Bromo-di-nitro-naphthalene 
 C,„H5Br(NOj2. [170°]. Long glistening needles. 
 Formed together with the following isomeride by 
 nitration of (a)-bromo-naphthalene with fuming 
 HNO3 (1-5). Not attacked by boiling with 
 aqueous NaOH. On oxidation with dilute HNO, 
 it gave a small quantity of (a)-nitro-phthalio 
 acid (Merz a. Weith, B. 15, 2710). 
 
 Bromo-di-nitro-naphtlialene 
 C,„H3Br(N02)j. [143°]. Tables or prisms. Formed 
 as above. Not attacked by boiling aqueous NaOH. 
 On oxidation with dilute HNO3 it gave a little (a), 
 nitro-phthalic acid (Merz a. Weith, B. 15,2710). 
 
 Bromo-tetra-nitro-naphtlialene 
 C„H3Br(N02)j. [190°]. Needles. S. (benzene 
 at 18°) 3-7. Formed by further nitration of 
 bromo-di-nitro-naphthalene [170°] by heating 
 with a mixture of HNO3 and H^SOj. It dissolves 
 in caustic alkalis forming tetra-nitro-naphthol. 
 NH3 converts it into tetra-nitro-naphthylamine, 
 and aniline gives the phenyl derivative of the 
 latter. On oxidation with dilute HNO, it givM 
 
692 
 
 BEOMO-NITRO-NAPHTHALENE. 
 
 di-nitro-plithalio acid [227°] (Merz a. Weith, B. 
 15, 2712). 
 
 Brouio-tetra-nitro-naphthalene 
 C,oH3Br(N02)4. [245°]. White glistening needles. 
 Nearly insol. ordinary solvents. Formed by 
 nitration of bromo-di-nitro-naphthalene [143°] 
 with a mixture of HNO, and H^SO^. It is at- 
 tacked by alkalis with difficulty. NH, converts 
 it into tetra-nitro-naphthylamine and aniline 
 gives the phenyl derivative of the latter. On 
 oxidation with dilute HNO3 it gives di-nitro- 
 phthaHe acid [200°] (Merz a. Weith, B. 15, 
 2718). 
 
 Di-bromo-nitro-naphthalene Ci„H5Br2(N02). 
 [96-5°-98°]. One of the products of action of 
 Br on nitro-naphthalene. Small yellow needles 
 (from alcohol) (Guareschi, A. 222, 286). 
 
 Si-bromo-nitro-naphthaleue 
 C,„H5Br2(NOj) [1:4:1']. [116-5°]. From (1,4)- 
 di-bromo-naphthalene and HNO3 (S.G. l4) in 
 the cold (Jolin, Bl. [2] 28, 515). POI5 gives tri- 
 bromo-naphthalene [85°]. 
 
 Di-bromo-nitro-naphthaleae C,„H.Br2(N02). 
 [100°-105°]. From di-bromo-naphthalene [68°] 
 and HNO3 (S.G. 1-4) (Canzoneri, G. 12, 427). 
 
 Tri-bromo-di-nitro-naplithalene 
 C,„H3Br3(N02)2. From (1, 2, 4)-tri-bromo-naph- 
 thalene and fuming HNO3 (Prager, B. 18, 2164). 
 BEOMO - NITRO - (a) - NAPHTHOIC ACID 
 C,„H5Br(N02)C02H [1:4:4^. [260°]. Formed by 
 nitration of bromo- (a) -naphthoic acid [246°]. 
 Small yellowish prisms (from alcohol). Its am- 
 monium salt forms glistening plates, si. sol. 
 cold water (Ekstrand, B. 19, 1135). 
 BROMO-NITRO.(o)-NAPHTHOL 
 C,„H,Br(N02)(0H) [2:4:1]. [136°]. From (2,4,1)- 
 bromo-mtro-acetyl-(o)-naphthylamine and oono. 
 NaOH. Silky needles (from alcohol) ; oxidation 
 gives phthalie acid. 
 
 Salts.— C,„H5Br(N02)(ONa)aq : redneedles. 
 — (C,„H5Br(N02)0)2Ba 3aq. 
 
 Methyl ether G,„H5Br(N02)(OMe). [115°]. 
 Pale yellow silkyneedles (Meldola, 0. J. 47, 497). 
 Bromo-nitro-(o)-naphthol Ci„H5Br(N02)OH. 
 [142°]. From acetyl-bromo-(a)-naphthylamiue 
 by nitration and saponification (Biedermann a. 
 Eemmers, B. 7, 538). 
 
 BEOMO-NITRO-(a) -NAPHTHYLAMINE 
 C,„H5Br(N02)(NHj) [2:4:1]. _ [197°]. From the 
 acetyl derivative by dissolving in cone. H^SOj 
 and ppg. with water. Orange needles ; gives 
 phthalie acid on oxidation (Meldola, 0. J. 
 47, 497 ; 43, 9). 
 
 Acetyl derivative C„HjBr(N02)(NHAc). 
 [225°]. From acetyl-(o)-naphthylamiue by 
 nitration and bromination. Pale ochreous 
 needles. 
 
 Bromo-nitro-(a)-napIithylamiue 
 C,„H,Br(N02)(NH2) [4:2:1]. [200°]. _ From 
 acetyl-(a)-bromo-(o)-naphthylamine by nitration 
 and saponification (Liebermann a. Scheiding, 
 A. 183, 258). Oxidised by dilute HNO3 to 
 phthalie acid. Elimination of NH., gives bromo- 
 nitro-naphthalene [132°]. Cone. HBrAq at 130° 
 gives (1, 2, 4)-tri-bromo-naphthalene. 
 
 Acetyl derivative C,„HsBr(N02)(NHAc). 
 [232°]. 
 
 DI-BKOMO-NITSO-OECIN CjE^Br^NO^ i.e. 
 C„MeBr,(N02)(OH)2. [112°]. From (S)-nitro- 
 orcin and Br. Yellow laminee (from alcohol). — 
 
 Ba(C,H,Br2N0 J2 2a(i : red needles (Weselsky^ 
 B. 7, 444). 
 
 BROMO-NITRO-o-OXY-BENZOIC ACID 
 
 C„H2Br(N02)(OH)C02H [5:3:2:1]. Bromo-nitro- 
 salicylic acid. [175°]. Yellow needles. Formed! 
 by nitration of bromo-salioylio acid in acetic 
 acid solution. — A'jCa xaq : V. sol. water. — A'jBa:: 
 
 yellow needles.— 0„H2Br(NO2X*^Q*^^Ba2aq: 
 
 red crystals.— C„H2Br(N02)<^'^Q*^)>Pb : nearly- 
 insoluble pp. (Lellmann a. Grothmann, B. 17,. 
 2729). 
 
 Bromo-nitro-o-oxy-benzoic acid 
 CeH2Br(N02)(OH)C02H [3:5:2:1]. [222°]. Colour- 
 less needles. V. sol. alcohol, ether, and hot. 
 water. Formed by bromination of nitro- sali- 
 cylic acid in acetic acid solution. 
 
 Salts. — A'2Ba4aq: long yellow needles. — 
 A'jCa 6aq : yellow prisms (Lellmann a. Groth- 
 mann, B. 17, 2724). 
 
 Bromo-nitro-o-ozy-benzoic acid. Methyl 
 derivative CsH2Br(N02)(OMe)(C02H). From 
 methyl bromo-isopropyl - phenyl oxide and 
 HNO3 (S.G. 1-3) (Peratoner, G. 16, 420). A di- 
 bromo-nitro-o-oxy-benzoic acid is also formed. 
 
 Bromo-nitro-p-oxy-benzoic acid. Methyl 
 derivative CeH2Br(N02)(0Me)(C02H) [1:3:2:5], 
 [182°]. Bromo-nitro-anisic acid. Formed by 
 nitrating bromo-anisic acid. 
 
 Ethyl ether 'EtA.'. [85°] : needles (Balbi- 
 ano, G. 14, 241). 
 
 DI-BROMO-DI-NITRO-DI-OXY- DI- PHENYL 
 SUIPHONE 
 
 Ci2H3Br2N2S0e i.e. (CsH2(N02)(0H)Br)2S02. 
 [285°]. From di-nitro-di-oxy-di-phenyl sul- 
 phone in CSj and Br (Annaheim, B. 9, 660). 
 Yellowish needles. — C,2H4Na2Br2N2SOj 2aq : 
 orange needles. 
 
 BROMO-NITRO-OXY- PIPEEIDINE - v - CAB- 
 BOXYLIC ETHER C5H,(Br)(N02)(OH)N.C02Et 
 [157°]. Colourless prisms ; sol. alcohol. Formed 
 by the action of Br in HOAo on nitro-dehydro- 
 piperidine-v-earboxylio ether (Sehotten, B. 16, 
 646). 
 
 BROMO-NITRO-PHENANTHRENE v. Pheh- 
 
 ANTHRENE. 
 
 BROMO-0-NITRO-PHENOL 
 C„H3Br(N02)(OH) [1:4:3]. [44°]. Formed, to- 
 gether with the following body [88°] by boiling 
 (1, 3, 4)-bromo-di-nitro-benzene with aqueous 
 KOH (Laubenheimer, B. 11, 1160). Prisms; 
 volatile with steam. — NaA' : scarlet needles.— 
 BaA'2 aq : red needles, si. sol. water. — CaA'2 2aq. 
 AgA'. 
 
 Bromo - - nitro - phenol C5H3Br(N02)(0H) 
 [1:3:4]. [88°]. 
 
 Formation, — 1. From ^-bromo-pheuol and 
 HNO3 (Hubner a. Brenken, B. 6, 170 ; Korner, 
 G. 4, 388).— 2. From o-nitro-phenol (45g.) and 
 Br (52g.) (Brunck, Z. 1867, 203).- 3. From 
 bromo-di-nitro-phenol (v. sup.). 
 
 Properties. — Yellow monoclinio lamincB (from 
 alcohol) a:6:c = 2-941:l:l-625. j8 = 64° 2' (Arzruni, 
 Z. Kryst. 1, 436) ; may be sublimed ; v. sol. 
 alcohol and ether, slightly volatile with steam. 
 Eeduced by Sn and HCl to bromo-amido-phenol 
 (Sohiitt, Xi)r. [2] 32,61). 
 
 Salts.- Na(C8H3BrNOs): red needles with 
 golden-green lustre, v. sol. watei-. — KA' 2aq.— 
 BaAV— AgA'. 
 
BROMO-NITRO-PHENOL. 
 
 693 
 
 Methyl ether CjHjBrlNOjjOMe. [88°]. 
 From the silver salt and Mel by builing; or from 
 the potassium salt, MeOH and Mel at 110°. 
 Needles. V. sol. hot alcohol or hot ether, v. si. 
 sol. water (Staedel, A. 217, 55 ; B. 11, 1750). 
 
 Ethyl eUerC,H3Br(N02)OEt. [43°] (S.) ; 
 [47°] (H.). From the potassium salt, EtI and 
 alcohol at 100°. Formed also by nitrating o- 
 bromo-phenetol. 
 
 Benzyl derivative 
 C„H3Br(N0J(0C,H,). [84°]. YeUow needles. 
 Insol. water, v. sol. alcohol and glacial acetic 
 acid, si. sol. benzene, ether or chloroform (EoU 
 a. Holz, J. pr. [2] 32, 67). Beducedto bromo- 
 amido-phenol, when treated with Sn and HCl, 
 benzyl chloride splitting off. 
 
 Bromo-m-nitro-phenol CjH3(Br)(N0,){0H) 
 [?:3:1]. [147°] (L.) ; [110°] (P.). Prepared by bro- 
 mination of TO-nitro-phenol (Pfaff, B. 16, 612 ; 
 Lindner, B. 18, 612). Yellow needles. Sublim- 
 able. SI. sol. hot water, CSj and petroleum- 
 ether, insol. cold water. On reduction with tin 
 and HCl it gives ra-amido-phenol, the Br atom 
 being eliminated. — KA' 2aq : red crystals, sol. 
 water and alcohol. — NaA' aq : yellowish - red 
 crystals, sol. water and alcohol. — BaA'2 4aq. 
 
 Methyl ether A'Me: [104°]; white 
 needles, v. sol. alcohol and ether, on reduction 
 with tin and HCl it gives m-anisidine. 
 
 Ethyl ether EtA'. [57°] : prisms. 
 
 Bromo-p-nitro-phenol CsH3Br(N02)(OH) 
 
 [1:3:6]. [102°]. Formed by brominating p- 
 nitro-phenol (Brunck, Z. 1867, 204). Satiny 
 needles (from ether or alcohol) ; m. sol. water. — 
 Ba(C„H;fBrN03)2 6aq : orange needles, m. sol. 
 water. 
 
 Methyl ether MeA'. [106°]. From the 
 potassium salt, Mel and MeOH at 110°. White 
 needles (from alcohol). V. sol. hot alcohol or 
 ether, m. sol. hot water (Staedel, A. 217, 66). 
 
 Ethyl ether EtA'. [98°] (S.) ; [55°] (H.). 
 Formed like the preceding (S.). From^-nitro- 
 phenetol and Br (Halloch, B. 14, 37). Yellow 
 needles (from alcohol). V. sol. alcohol or ether. 
 
 Benzyl ether CeH3Br(N0J(0C,H,). [126°]. 
 Nearly colourless plates (from alcohol). Insol. 
 water, sol. alcohol and ether (R. a. H.). Eeduced 
 by Sn and HCl to bromo-^-amido phenol and 
 CfEjCl. 
 
 Bromo-di-nitro-pheivol CjH2Br(N02)2(OH) 
 [1:3:5:4]. [86°] (K.) ; [71°] (Austen); [76°] 
 (Armstrong). Formed by nitrating ji-bromo- 
 phenol in HOAc, or by brominating and nitrat- 
 ing o-nitro-phenol (Korner, A. 137, 205 ; Arm- 
 strong a. Prevost, B. 7, 922). Formed also by 
 brominating di-nitro-phenol [64°] (Korner, O. 
 4, 305) ; and by boiling di-nitrated jj-di-bromo- 
 benzene with aqueous KNOj (Austen, Am. S. [3] 
 16, 46). Yellow monoclinic prisms, a:b:c = 
 2-795:l:l-778 ; J3 = 67°53' (Arzruni, loc. cit). 
 Water and Br at 100° change it into the iso- 
 meride [118°] (Armstrong, C. J. 28, 520). HNO3 
 forma picric acid. 
 
 Salts.— NH.,A': silky red needles ; sol.boil- 
 ing water and alcohol.— NH^A' aq.—BaA'j : yel- 
 low needles, sol. hot water.— CuA'2 : short brown 
 needles, insol. water.— KA' : long red needles, si. 
 sol. water. — AgA'.— CaA'2 8aq. 
 
 Ethyl ether EtA' [66°]: small needles, 
 sol. alcohol and hot water ; saponified by cold 
 
 Vol. I. 
 
 NaOHAq (Sohoonmaker a. Van Mater, Am. 3, 
 187). 
 
 Bromo-di-nitro-phenol CsH,^r(N02)2(OH). 
 [91'5°]. Formed by nitrating m-bromo-phenol, 
 and also from di-bromo-di-nitro-phenol [117°j 
 and boiling aqueous KOH (Korner, 6. 4, 305). 
 Prisms (from alcohol or ether). The K salt 
 forms yellow needles. 
 
 Methyl ether MeA' [109°]. 
 
 Bromo - di - nitio - phenol CsH2Br(N02)203 
 [1:3:5:6]. [118°]. 
 
 Formation. — 1. From (l,3,4)-di-nitro-phenol 
 and Br (Laurent, Bev. Scient. 6, 65).— 2. By 
 nitrating o-bromo-phenol (Korner, G. 4, 394). — 
 3. From o-nitro-phenol by bromination and 
 nitration. — 4. By jboihng bromo-di-nitro-aniline 
 [144°] with aqueous KOH (Korner).— 5. By 
 nitrating brominated phenol disulphonio acid or 
 di-brominated phenol ^-sulphonic acid (Arm- 
 strong a. Brown, 0. J. 25, 861, 865).— 6. By 
 warming the isomeride [c. 76°] with Br and 
 water (Armstrong, C. J. 28, 520).— 7. From 
 picric acid, water, and Br (Armstrong, B. 6, 650). 
 8. By nitrating tri-bromo-pheuol (Armstrong a. 
 Harrow, 0. J. 29, 477).— 9. From bromo-nitro- 
 benzyl-phenol in HOAc by HNO5 : benzyl being 
 displaced by NO^ (Rennie, C. /. 41, 225). 
 
 Properties. — Yellow prisms. Needles (from 
 alcohol). 
 
 Salts. — KA'aq : flat yellow needles, si. sol. 
 cold water. — KA' Ijaq. — BaAj' 34aq. — BaA'2 4aq. 
 — BaA'2 5aq: yellow needles, si. sol. water. — 
 — CaA'2 7aq. — CaA'2 8aq. — CaA'j 12aq. — 
 NHjA' 2aq.— NaA' Ifaq.— PbA'j 2aq. 
 
 Methyl ether MeA.'. [48°]. From bromo- 
 anisio acid and HNOj. Yellow prisms, sol. alco- 
 hol and ether, insol. water (Balbiano, G. 14,285). 
 
 Di-bromo-o-nitro-phenol C,H2Br„(N02)(0H)^ 
 [1:3:5:6]. [117-5°]. 
 
 Formation. — 1. From o-nitro-phenol and Br 
 (Brunck, Z. 1867, 203 ; Korner).— 2. From. 
 (1,3,4,) -di-bromo-phenol by nitration (K.). — 3. 
 By nitrating di-bromo-phenol sulphonio acid 
 (Armstrong a. Brown, C. J. 25, 863). 
 
 Properties. — Golden monocHuic prisms (from^ 
 alcohol); a:6:c = -515:l:-591; |8 = 65°23' (Arz- 
 runi, Z. Kryst. 1, 436). Volatile with steam ; 
 may be subHmed ; v. si. sol. water. Heatedi 
 with bromine at 100° it gives some of the iso- 
 meride [141°] together with tetra-bromo-quinone 
 and (l,3,6)-bromo-nitro-phenol (Ling, O. J. 51, 
 147). 
 
 Salt. — KA' : scarlet needles, v. si. sol. cold 
 water. 
 
 Methyl ether MeA'. [77°]. From the 
 silver salt and Mel ; alcoholic NHj converts it 
 into di-bromo-nitro-aniline [127°] whence HNOj 
 gives di-bromo-nitro-benzene [105°] (K.). 
 
 Ethyl ether EtA'. [46°]. From the silver 
 salt, EtI and alcohol at 100° (Staedel, A. 217, 
 58). V. sol. benzene, alcohol or ether, insol. 
 wflitGr 
 
 Benzyl ether C„H2Br2(N02)(0C,H,). [65°]. 
 Yellow crystals (from ether). Sol. benzene, 
 chloroform, and glacial acetic acid, insol. water 
 (E. a. H., J. pr. [2] 32, 57). Eeduced by Sn and 
 HCl to di- bromo -amido- phenol and benzyl 
 chloride. 
 
 Di- bromo-m-nitro-phenol C8H2Br2(N02)OH, 
 [91°]. Formed by heating m-nitro-phenol (1 
 
 QQ 
 
«94 
 
 BROMO-NITRO-PHENOL. 
 
 «nol.) with bromine (2 mols.). Yellowish plates. 
 V. aol. alcohol, al. sol. water. 
 
 Salts. — KA'aq: easily soluble orange-red 
 needles. — AgA' : sparingly soluble red powder. — 
 BaA'^Caq : very soluble red needles. 
 
 Ethyl ether C,H2Br.,(N0,)0Et: [110°]: 
 yellowish needles, sol. hot alcohol (Lindner, B. 
 18, 613). 
 
 Di-bromo-p-nitro-phenol C|,HjBr2(N02) (OH) 
 11:5:3:6]. [142°] (Lellmann a. Grothmann, B. 
 17, 2731). 
 
 Formation. — 1. By brominating ^-nitro- 
 phenol or its sulphonic acid (Brunok, Z. 1867, 
 204 ; Post a. Braokebusoh, A. 205, 94).— 2. By 
 nitrating tri-bromo-phenol dissolved in HOAo 
 (Armstrong a. Harrow, loc. cit.).—Z. In small 
 quantity by heating the isomeride [117°] with 
 Br (Ling, O. /. 51, 147). 
 
 Properties. — Prisma, si. sol. water, v. sol. 
 alcohol and ether. 
 
 Salt.— BaA'2 10 aq : yellow needles, efferves- 
 cing to a red powder. — BaA'^SIaq.— AgA'. 
 
 Methyl ether MeA': [123°] (Komer, G. 4, 
 390). From di-bromo-anisic acid and HNO3, 
 the COjH being displaced by NO^ (Balbiano, O. 
 14, 9). Pyramidal needles; converted by NHj 
 into di-bromo-^-nitro-aniline [203°]. 
 
 Ethyl ether [108°]. Long quadratic 
 columns (Staedel, A. 217, 67). 
 
 Benzyl ether C„H2Brj(N0.,){0C,H,). [94°]. 
 Kearly colourless needles (from alcohol). Insol. 
 water, si. sol. alcohol, ether, benzene, ohloro- 
 iorm, and glacial acetic acid (E. a. H.). Eeduced 
 3>y Sn and HCl to di-bromo-jj-amido-phenol {^. v.) 
 and benzyl chloride. 
 
 Tri-bromo-nitro-phenol C .HBr3(N0,;) .OH 
 16:4:2:3:1]. [85°] (L.) ; [89°] (D.). Formed by heat- 
 ing ??t-nitro-phenol with Br (3 mols.) at 100° 
 •(Lindner, B. 18, 614). Colourless crystalline 
 powder ; v. sol. alcohol, ether, and benzene, v. 
 «1. sol. hot water. 
 
 Salts. — A'NH, : sparingly soluble micro- 
 scopic needles. — A'Kaq : v. sol.water. — A'jBa 8aq: 
 sparingly soluble orange-yellow crystals. — 
 A'2Ba aq. — A'jMgx : easily soluble red plates. 
 
 o-Nitro-henzoyl derivative 
 C5HBr3(N02)O.CO.CjHj{NO,): [129° cor.]; very 
 email colourless needles. 
 
 m-Nitro-bensoyl derivative 
 C,HBr3(NO,)O.CO.C5H,(NOJ: [154° cor.]; glis- 
 tening colourless needles; S. (90 p.o. alcohol) 
 -253 at 14° (Daccomo, B. 18, 1167). 
 
 Ethyl ether EtA': [79°]; prisma. 
 
 BBOMO-NITEO-PHENOL SULPHONIC ACID 
 C,H,BrNS0„t.fl.C,H^r(N0J(0H)S03H [1:3:6:5]. 
 Formed, together with di-bromo-nitro-phenol, 
 by brominating (1, 4, B)-nitro-phenol sulphonic 
 acid (Post a. Brackebusch, 4. 205, 92). — CaA'^ 3aq. 
 — BaA'2 Saq.— C„H2BrNSOe(PbOH)3 2iaq. 
 
 Bromo-phenol sulphonic acids have been 
 "obtained by Armstrong (C. J. 25, 857 ; B. 
 "7, 404, 924) and Post {B. 7, 169) by the action of 
 initrio acid on various brominated phenol sul- 
 fphonio acids, and by the action of bromine on 
 t?l, 2, 5) -nitro-phenol sulphonic acid. 
 
 BBOMO-N ITRO-DIPHENYL C.^HsBrNO^ i.e. 
 114:1] CeH,Br.C„H^(N02) [1:4]. [173°]. (above 
 360°). Formed by heating diphenyl (1 pt.) with 
 «!onc. HNO3 (1 pt.), or from amido-nitro-diphenyl 
 by the diazo- reaction (Sohultz, A. 174, 218). 
 IJong white needles (from toluene). CrO, gives 
 
 p-bromo-benzoic acid and a littlep-nitro-benzoio 
 acid. 
 
 Bromo-nitro-diphenyl C,2HjBrN02 i.e. 
 [4:1] C«H,Br.0,H,(N02) [1:2]. [65°]. (c. 360°). 
 Formed together with the preceding. Monoclinio 
 columns. CrO, gives p-bromo-benzoic acid 
 (Sehultz, A. 207, 348). 
 
 Bl-bromo-nitro-diplienyl 
 CaH,Br.C„H3Br(N02). [127°]. Formed by nitra- 
 tion of di-bromo-diphenyl in acetic acid solution 
 (Lellmann, B. 15, 2837). Yellowish crystals; 
 V. sol. alcohol, benzene, and acetic acid. 
 
 Di-bromo-di-nitro-diphenyl C,2H|jBr2(N02)j. 
 From 5)p-di-bromo-diphenyl and fuming HNO, 
 (Fittig, A. 132, 206; S.). Hair-like crystals 
 (from benzene). Sn and HCl give di-bromo-di- 
 amido-diphenyl [89°]. 
 
 Bi-bromo-tri-nitro-diphenyl 
 C,H3Br(N02).CeH2Br(N02)3. [177°]. Formedby 
 nitration of di-bromo-diphenyl with cold fuming 
 HNO3 (1-55) (LeUmann, B. 15, 2838). Small 
 colourless needles. Sol. benzene, si. sol. alcohol. 
 
 BROMO-NITBO-PHEHYL ACETIC ACID 
 CeH,Br(N02)CH3C02H [1:2:4]. [114°]. Formed 
 by nitration of a mixture of 0- and ^-bromo- 
 phenyl-acetio acids (Bedson, C. J. 37, 97). Flat 
 greenish-yellow needles. Sol. hot, insol. cold 
 water. V. sol. alcohol and ether. KjCrjO, and 
 KjSO^ give C„HBr(N02)C02H [199°]. 
 
 Salts. — BaA'2 aq. Its aqueous solution gives 
 white pps. with AgNOj, Pb(0Ac)2, and a blue 
 pp. with Cu(0Ac)2. 
 
 Methyl ether. MeA'. [41°]. Needles. 
 
 Ethyl ether. Oil. 
 
 (a)-Bramo-nitro-phenyl-acetic acid 
 C„H3Br(N02)CH2.C02H. [169°]. Formed by 
 nitration of mixture of o- and p-bromo-phenyl- 
 acetic acids (Bedson). Yellowish-white, branch- 
 ing needles. V. sol. alcohol and ether, insol. 
 cold, sol. hot water. 
 
 Salt. — BaA'2 4aq. K^ aqueous solution gives 
 white pps. with AgNOj and Pb(OAo)2, but fi 
 green pp. vrith Cu(OAo)2. 
 
 Methyl ether [6S°]. Flat needles. 
 
 Ethyl ether. Yellowish needles. 
 
 (;3)-Bromo-nitra-pIienyl-acetic acid 
 C,H3Br(N02)CH2.C02H. [162°]. Formed toge- 
 ther vrith the two preceding (Bedson). Small 
 yellow prisms. 
 
 BEOMO-DI-NITEO-DI-PHENYL-AMINE 
 C,2H8BrN,0,i.e.C3H2Br(N02)2.NH.C8H5.P;smyZ- 
 bromo-nitro-phenyl-amine. [120°]. Formed by 
 warming bromo-di-nitro-benzene [100°] with 
 aniline (Austen, B. 9, 920). Orange hair-like 
 needles (from alcohol). 
 
 Bromo-di-nitro-di-phenyl-amine 
 C8HiBr.NH.CjH3(N02)2. Bromo-phenyl-di-mtro- 
 phenyl-amine. [153°]. From (1, 2, 4)-bromo- 
 dinitro-benzene and di-p-bromo-di-phenyl-urea 
 at 170°. Yellow needles (from ether) (Willge- 
 rodt, B. 11, 602). 
 
 Bromo -tri-nitro-di-phenyl-amine 
 C,H2Br(N02)2.NH.C.H4N02. [158°]. From bromo- 
 di-nitro-di-phenyl-amine [120°] and HNO3 (A.). 
 
 Di-bromo-di-nltro-di-phenyl-amine 
 C,2H,Br2(N02)2N. [196°]. Formed by bromina- 
 tion of di-uitro-di-phenyl-amine (Leymann, B. 
 15, 1236). 
 
 Di-bromo-tetra-nitro-di-phenyl-amine 
 C5HjBr(N02)2.NH.C,H,Br(NOs),. [235°-242°]. 
 
BEOMO-NITRO-PHENYL-PEOPIONIC ACID. 
 
 695 
 
 From NMe(C,HjBr3)(C.H^Br) and HN03(Gnehm, 
 
 B. 8, 929). Laminse (from HOAo). 
 Tri-bromo-di-nitro-di-phenyl-amine 
 
 C,2H;Br3(N02)2N. [210°]. Formed by nitrating 
 tetra - bromo - di - phenyl - amine (CjHgBrJ^NH 
 (Gnehm a. Wyss, B. 10, 1323). 
 
 BEOmO-NITRO-PHENYL BEKZYL OXIDE 
 V. Bhoho-nitko-phenol, Benzyl ether. 
 
 DI - BBOMO - NITRO- PHENYL -CARBAMIC 
 ACID. Methyl ether 
 
 [1:3:4] 0,HjBr,{N02).NH.C0,Me. [152°]. From 
 methyl-(l,3,4)-di-bromo-phenyl-oarbamate and 
 HNOj (Hentsohel, J. pr. [2] 34, 425). Prisms 
 (from alcohol). NHj forms (1,3,4) -di-bromo- 
 aniline. 
 
 BEOMO-NITRO-jjiPHENYLENE -DIAMINE 
 CjHsBrNsOj i.e. CsHjBr(N02)(NH2)2 [1:2:3:5]. 
 From tri-bromo-nitro-benzene and alcoholic NHj 
 for some days at 175° (Korner, G. 4). Orange 
 needles ; decomposes at 163°. Converted into 
 p-bromo-benzene by the diazo- reaction. 
 
 Bromo-uitro-^-phenylene-diamine 
 C„H,3r(N02)(NHj)j [1:4:2:5]. [156°]. From tri- 
 bromo-nitro-benzene [94°] and alcoholic NH3 at 
 110° (Korner, O. 4). Pyramidal needles. Con- 
 verted by diazo- reaction into ^J-bromo-benzene. 
 
 BROUO - NITRO - PHENYL - ETHANE v. 
 Bbomo-niteo-ethyl-benzene. 
 
 Di-bromo-di-nitro-5-di-phenyl-ethane 
 CjH,(NOj).CHBr.CHBr.C,H^.NOj. [above 300°]. 
 Di-bromide of di-p-nitro-stilbene. Split up by 
 heat into 2HBr and di-nitro-tolane (Elbs a. 
 Bauer, J. pr. [2] 34, 345). 
 
 Di-bromo-di-nitTO-s-di-phenyl-etiiane 
 
 C, 4H|„Brj(N02)2. Di-bromo-di-nitro-di-bemyl, 
 [205°]. Formed by nitrating di-^-bromo-di- 
 benzyl (Fittig a. Stelling, A. 137, 260). Sword- 
 shaped crystals (from benzene). 
 
 BEOMO-NITRO-PHENYL ETHYL OXIDE v. 
 
 Ei%Z-BR0M0-KITK0-PHEN0L. 
 
 oo-DI - BROMO - mil - DI-NITRO - to - PHENYL- 
 METHYL-CARBINOL. 
 
 Ethyl ether CBrj(NOj).CH(C,H,NOJ.OEt. 
 [99°]. — 1. From the compound of alcohol with 
 cjra-di-nitro-cinnamic ether (2. u.) by simultaneous 
 treatment with aqueous NaOH and Br (Fried- 
 lander a. Lazarus, A. 229, 237). — 2. From a>-m- 
 di-nitro-styrene, alcohol, aqueous NaOH and Br. 
 White plates (from dilute alcohol). Insoluble 
 in aqueous NaOH. 
 
 Methyl ether CBry(NOJ.CH(C,H,NO,)OMe. 
 [146°]. Formed in a similar way from the com- 
 pound of methyl alcrfhol with the same body, or 
 from oj-TO-di-nitro-styrene, methyl alcohol, Br^ 
 and aqueous NaOH. White plates. 
 
 BROMO - NITRO - PHENYL . METHYL- 
 KETONE V. Bbomo-nitko-acbtophenone. 
 
 rj-BROMO-o-NITRO-fl-PHENYL-PROPIONIC 
 ACID C,H3(Br)(NOj,)C,H4.CO,H [4:2:1]. Bronw- 
 mtro-)i/ydrocinnamic acid. [142°]. Prepared by 
 the action of HBr on the diazo- compound from 
 p-amido-o-nitro-hydrocinnamic acid. Formed 
 together with the (4,3,l)-isomeride by nitration 
 of ^-bromo-hydrocinnamic acid. Flat feathery 
 crystals. By reduction with tin and HCl it 
 gives p - bromo - hydrocarbostyril (Gabriel a. 
 Zimmermann, B. 13, 1682). 
 
 jo-Bromo-m-nitro-jS-phenyl-propionic acid 
 C,H3(Br)(N0,).CjH,.C0,H [4:3:1]. [90°-95°]. 
 Long glistening needles. Prepared as above. 
 On reduction with tin and HCl it gives ^-bromo- 
 
 TO-amido-hydrociunamic acid (Gabriel a. Zim- 
 mermann, B. 13, 1683). 
 
 /3-Bromo-o-nitro-/3-phenyI-propionic acid 
 OsH,(NO,).CHBr.CH2.CO,H. [140°]. From 0- 
 nitro-cinnamic acid, HOAo, and HBr at 100° 
 (Einhorn, B. 16, 2208). Monoolinic crystals; 
 V. sol. ordinary solvents, si. sol. benzene. 
 
 Reactions. — 1. Boiling water forms indoxyl. 
 2. NaOHAq forms uitro-cinnamic acid.— 3. Cold 
 Na2C03Aq forms the lactone of o-nitro-j3-oxy- 
 phenyl-propionic acid. — 4. Hot Na^COjAq gives 
 nitro-oinnamio acid, nitro-oxy-phenyl-propionia 
 acid, and o-nitro-styrene. 
 
 j8-Bromo-TO-nitro-/3-phenyl-propionic acid 
 C„H4(N0j).CHBr.CHj.C0,H. [96°]. Prepared by 
 heating an acetic acid solution of m-nitro-cin- 
 namic acid with HBr at 100°. V. sol. alcohol, 
 si. sol. toluene, insol. petroleum-ether. 
 
 Reactions. — 1. By boiling with water it 
 chiefly gives m-nitro-styrene. — 2. An excess of 
 alkali converts it back into »i-nitro-oinnamio 
 acid. — 3. By adding the powdered acid to an 
 aqueous solution of \ mol. of Na^COa, it yields 
 30 p.o. of nt-nitro-styrene, 20 p.o. of m-nitro- 
 einnamio acid, and 10 p.c. of m-nitro-;8-oxy-;8- 
 phenyl-propionic acid. If the powdered acid is 
 added to a cold solution of Na^COj the /S-lactone 
 is formed (Prausnitz, B. 17, 595). 
 
 jS-Bromo-jp-nitro-pheuyl-propionic acid 
 C,H,(NOj).CHBr.CH2.C02H. [172°]. Prepared by 
 heating p-nitro-cinnamio ether with HBr at 
 100°. Prisms ; sol. hot alcohol, si. sol. water 
 and benzene. 
 
 Reactions. — 1. Long boiling with dilute 
 HjSO, (25 p.o.) reconverts it into ^'-nitro. 
 •jinnamic acid. — 2. Heated with water it yields 
 p-nitro-;3-oxy-phenyl-propionic acid (72 p.c.) and 
 p-nitro-styrene (28 p. 0.). — 8. Cold aqueous KOH 
 gives p-nitro-oxy-phenyl-propionic acid and its 
 lactone. Alcoholic KOH yields almost entirely 
 p-nitro-cinnamio acid.— 4. Aqueous NH3 yields 
 the lactone which by excess of NH3 is converted 
 into the corresponding amido- acid. 
 
 Ethyl ether h.''EA. [81°]; colourless plates 
 (Easier, B. 16, 3001). 
 
 Di-bromo-o-nitro-phenyl-propionic acid 
 CBH4(N0j)CHBr.CHBr.C0jH. Dibromide of o- 
 nitro-cinnamic acid. [0. 180°]. From Br and 
 o-nitro-cinnamic acid (Baeyer, B. 13, 2257). 
 Needles or plates; sol. hot water. NaOHAq 
 gives o-nitro-phenyl-propiolio acid. Zino-dugt 
 and NaOH give indole. 
 
 Methyl ether MeA'. [99°]. 
 
 Ethyl ether EtA'. [71° uncor.] (M.) 
 From o-nitro-cinuamic ether and Br (Miiller, A. 
 212, 130). Alcoholic KOH converts it into 0- 
 nitro-phenyl-propiolic acid. Heated with water 
 at 120° it gives o-nitro-oinnamic acid. 
 
 Di-bromo-^-nitro-phenyl-propionicacid 
 C,H4(N02)CHBr.CHBr.COjH. [218°]. From^j- 
 nitro-cinnamic acid and Br (Drewson, A. 212, 
 151). Bhombic prisms (from glacial HOAc). 
 M. sol. water or glacial HOAo, v. sol. alcohol or 
 ether, si. sol. benzene, V; si. sol. benzoline. 
 Aqueous NaOH forms jp-nitro-cinnamio and p- 
 nitro-phenyl-propiolic acids. — CaA',. 
 
 Ethyl ether EtA'. [111°]. From^-nitro- 
 cinnamio ether and Br in CS2 (C. L. Miiller, A. 
 212, 129). Columns (from CSj) ; v. sol. hot al- 
 cohol, ether, or benzoline. Alcoholic KOH con- 
 verts it into a mixture of two isomeric bromo-p- 
 
 QQ2 
 
cue 
 
 BROMO-NITRO-PHENYL-PROPIONIC ACID. 
 
 nitro-einnamic ethers, and ^-nitro-plienyl-pro- 
 piolio acid. Heated with water at 120° it gives 
 p-nitro-oinnamio acid. 
 
 BROMO-NITBO-PHTHALIC ACID 
 C„H2Br(N02)(COj,H)2 [1:4:2:3]. From di-bromo- 
 naphthalene [82°] and HNO3.— Na^A" (Guares- 
 olii, A. 222, 277). 
 
 a-BEOMO-a-NITKO-PBOPANE 
 CH3.CH2.0HBr(NO,). (0. 160°). Formed to- 
 gether with di-bromo-nitro-propane by the action 
 of potash and Br on nitro-propane (V. Meyer a. 
 Tscherniak, A. 180, 116). Oil, sol. potash. 
 
 a-Bromo-a-nitro-propane CH3.CBr(N02).CH3. 
 (150°). From CH3.CH(N02).CH3. Insol. potash. 
 
 Di-bromo-nitro-propane CH3.CH2CBrj{N02). 
 (184°-186°). From bromo-nitro-propane, Br, and 
 potash. An oil, insol. potash. 
 
 TEI-BEOMO-DI-NITEO-PEOPIONIC ACID 
 C3HBr3NA i.e. CBr3.C(NOj,)2.CO,H. From tri- 
 bromo-phloroglucin and cone. HNO3 (Benedikt, 
 A. 184, 255). Silky scales, insol. cold water, 
 V. e. sol. alcohol and ether; decomposed by boil- 
 ing water. 
 
 BEOmO-NITEO-PEOPYL. BENZENE v. 
 Bkomo-nitko-cumene. 
 
 BEOMO-NITEO-PEOPYL-PHENOL v. Bbomo- 
 
 CCMENOL. 
 
 DI-BEOMO-DI-NITEO-PYEEOL 
 
 CBr:C(NOJv 
 C,HBrjN30< i.e. | >NH. [169°]. 
 
 CBr:C(N02)'^ 
 Formed by dissolving di-bromo-nitro-pyrryl 
 methyl ketone [206°] in a mixture of fuming 
 HNO3 and cone. H^SOj at —18°, and precipita- 
 ting in water. Silky leaflets (containing aq). At 
 the ordinary temperature it is converted into di- 
 bromo-maleimide (Ciamician a. Silber, B. 20, 
 699 ; G. 17, 262). 
 
 DI-BEOMO-NITEO-PYEEYL METHYL KE- 
 CBr:C(N02) 
 TONE I >NH . [206°]. Long needles. 
 
 CBr:C— CO.CH3 
 Formed by the action of cold nitric acid 
 upon di-bromo-pyrrylene-di-methyl-di-ketone 
 CBr:C— CO.CH3 
 
 I >NH , [171°], which is formed by 
 
 CBr:C-CO.CHs 
 
 passing bromine- vapour into pyrrylene di-methyl 
 di-ketone (Ciamician a. Silber, B. 20, 699). 
 
 Di-bromo-nitro-pyrryl methyl ketone 
 CBr : CBr 
 
 I >NH . [175°]. From nitro-pyrryl 
 
 C(N02):C— CO.CH3 
 methyl ketone [197°] and Br. Needles. 
 
 BEOMO-NITEO-dTJIKOIINE C3H5N(Br) (NO^) 
 [133°]. Formed by nitration of bromo-quinoline. 
 Long glistening needles. Volatile undecom- 
 posed. Sol. alcohol and ether, si. sol. water. 
 Weak base. — B'jHjCljPtClj : short orange-yellow 
 prisms (La Coste, B. 16, 1918). 
 
 DI-BROMO-NITEO-ftUINONE 
 CaHBrj(N02)03 [6:2:3:4:1]. [246°]. Yellow plates ; 
 v. si. Bol. hot water and cold alcohol. Formed 
 by the action of a mixture of HNO3 and H^SO, 
 upon the propionyl derivative of tri-bromo- 
 phenol (Guareschi a. Dacoomo, B. 18, 1174). 
 
 BEOmO-NITEO-EESORCIW Ethyl ether 
 C,H2Br(N02)(OH)(OEt). [114°]. From ethyl 
 (1, 2, 4)-nitro-resorcin and Br (Weselsky, M. 
 1, 898). 
 
 Di-bromo-nitro-resorcin CjHjBrjNO^ i.e. 
 CsHBr2(N03)(OH)2. [147°]. From'(l, 2, 4)-nitro- 
 resorcin [115°] in ether and Br (Weselsky, A. 
 164, 7). Golden laminw.— Ba(C,H,Br2NOj2 4aq. 
 
 Ethyl ether C3HBr2(Nb2)(0Et)(0H) 
 [1:5:8:2:6]. [69°]. From ethyl nitro-resorcin and 
 Br (W.). 
 
 Di-bromo-nitro-resorcin CsHBr2(N0j)(0H)j 
 [1:3:5:4:6]. [117°]. From (1, 2, 6) -nitro-resorcin 
 and Br (W.). 
 
 Bromo-di-nitro-resorcin C5HBr(N02)j(0H)j. 
 [193°]. Formed by nitrating di-bromo-nitroso- 
 resorcin or by brominating di-nitro-resoroin 
 (FSvre, Bl [2] 39, 590 ; C. B. 96, 790 ; Typke, 
 jB. 16, 555). Orange needles ; si. sol. boiling 
 alcohol. — K2A"|aq: red needles. — Na2A"2aq. — 
 BaA" 3aq.— (NH,)jA"aq. 
 
 Acetyl derivative: [185°]; prisms. 
 
 BEOMO-NITEO-SAIICYIIO ACiD v. Beomo- 
 
 NITBO-OXY-BENZOIO ACID. 
 
 DI-BBOMO-NITEOSO-RESOECIN 
 
 C8HBr2(NO)(OH)2. From nitroso-resoroin and 
 Br (F^vre, Bl. [2] 39, 591). Yellowish needles 
 (containing 2aq) which turn brown at 138° and 
 decompose at 150° ; insol. benzene, si. sol. cold 
 water, v. e. sol. alcohol. 
 
 BEOMO-NITROSO-THYMOL 
 OjHMePrBr(NO)(OH). [c. 135°]. Fromnitroso- 
 thymene andBr(Mazzaraa.Descalzo, G.16,196). 
 
 BBOMO-NITEO-STYEENE Ph.CBr:CHN02. 
 [68°]. From di-bromo - nitro - phenyl - ethane 
 PhCBrH.CHBrN02 and aqueous NaOH (Priebs, 
 A. 225, 343). Golden needles or plates (from 
 light petroleum). Smells something like hay ; 
 when freshly ppd. from alcoholic solution by 
 water it is soluble in alkalis, hence its consti- 
 tution is as above, rather than Ph.GH:CBr(N02). 
 
 DI-BBOMO-DI-NITilO-THIOPHENE 
 C4SBr2(N02)2. [134°]. Light-yellow crystals. 
 V. sol. hot alcohol. Formed by nitration of di- 
 or tri-bromo-thiophene (Kreis, B. 17, 2074 ; 
 Eosenberg, B. 18, 3029). 
 
 TBI-BEOMO-NITKO-THIOPHENE 
 C,SBr3(N02). [106°]. Formed by nitration oJ 
 tri-bromo-thiophene. Felted yellow needles. V. 
 sol. ether, si. sol. alcohol (Eosenberg,B.18,3028). 
 
 BEOMO-NITEO-THYMOL 
 CsHMePrBr{N0J(0H). [101°]. From bromo- 
 nitroso-thymol and KjFeCyj (Mazzara,ff. 16, 196). 
 
 BBOMO-NITEO-TOLTJENE 
 CsH3Me(N02)Br [1:2:3]. Oil. From bromo-nitro- 
 );i-toluidine by nitrous gas and alcohol (NevUe 
 a. Winther, O. J. 37, 630). 
 
 Bromo-nitro-toluene C3H3Me(N02)Br [1:3:4]. 
 [32°]. (256°). S.G. ifi 1-631. From the corre- 
 sponding nitro-toluidine bythe diazo-perbrgmide 
 reaction (Nevile a. Winther, C. J. 37, 442). 
 Formed also by nitrating ^-bromo- toluene 
 (Wroblewsky, A. 168, 176) and by treating m- 
 nitro-toluene with Br and FeBrj at 70° (Soheu. 
 felen, A. 231, 180). 
 
 Bromo-nitro-toluene C3H3Me(N02)Br [1:2:4]. 
 [45°]. (257°). From the corresponding nitro- 
 toluidine [78°] by the diazo-perbromide reaction 
 (Beilstein a. Kuhlberg, A. 158, 340 ; Nevile a. 
 Winther, G. J. 37, 441). Formed also, together 
 with the preceding, by nitrating j)-bromo-toluene 
 (W.). Large monoclinic tables. 
 
 Eromo - nitro - toluene CjH3Me(N0j)Br 
 [1 : 2or6 : 3]. [55°]. (267°). Formed by nitrating 
 m-bromo-toluene (W. ; Grete, A. 177, 240). 
 
BROMO-NITRO-TOLUENE SULPHONIC ACIDS. 
 
 607 
 
 Trimetrio crystals; on reduction it gives bromo- 
 toluidine. 
 
 Bromo-nitro-toluene CeHjMe(N02)Br [1:4:2]. 
 [77°]. From C5H2(CH,)Br(N02)(NH,) [1:2:4:5] 
 (Nevile a. Winther, C. J. 39, 85) . From ^-nitro- 
 toluene, FeBr^, and bromine (Soheufelen, A. 231, 
 171). Also from diazo-nitro-toluene piperidide 
 C„H3Me(NOj).Nj.NC5H,„ and boiling HBrAq 
 (Wallach, A. 235, 248). Needles. 
 
 Bromo-nitro-toluene CsH3Me(N02)Br [1:3:6]. 
 [78"]. From jre-nitro -toluene, FeBrj, and bromine 
 (Soheufelen, A, 231, 179). From (8, 1, 6)-nitro- 
 o-toluidine (N. a. W.). 
 
 Bromo-nitro-toluene C„H3Me(N02)Br [1:3:5]. 
 [81°]. (N. a. W.) ; [86°] (W.) ; (270°). Formed 
 (a) from bromo-nitro-^-toluidine [65°], (6) from 
 nitro-(5, 1, 2)-bromo-o-toluidine [143°], or (c) 
 from bromo-uitro-o-toluidine [181°] by the usual 
 methods (Nevile a. Winther, O. J. 37, 431; 
 Wroblewsky, A. 192, 203). Hence it can be 
 prepared from a mixture of acetyl o- and p- 
 toluidines by successive bromination, nitration^ 
 saponification, and diazotisation. 
 
 Bromo-di-nitro-toluene CjH2Me(N02)2Br. 
 [104°]. From ?ra-bromo-toluene and fuming 
 HNOj (Grete, A. 177, 258). 
 
 Bi- bromo-nitro-toluene CjH^Me (N02)Br j 
 [l:4or6:2:3]. [o. 57°]. From CeHjlCHJBr^ [2S°] 
 by nitration (Nevile a. Winther, C. J. 37, 434). 
 
 Di-bromo-nitro-toluen e CsH2Me(N02)Br2 
 
 [1:4:2:6]. [58°]. From CaH(OH3)(NH2)(N02)Br2 
 [124°-130°] by ethyl nitrite (Nevile a. Winther, 
 C. J. 37, 445). Also from (2,4,l)-bromo-nitro- 
 toluene, FeBrj, and Br (Soheufelen, A. 231, 178). 
 
 Di-bromo-nitro-toluene C5H2Me(N02)Br2 
 [1:5:3:4]. [63°]. From bromo-uitro-toluidine, 
 C„Hj(CH3)(N02)(NH2)Br [1:5:4:3] by diazo-per- 
 bromide reaction (Nevile a. Winther, O. J. 37, 
 447). Colourless plates (from alcohol). 
 
 Bi - bromo - nitro - toluene CsH2Me(N02)Br2 
 [1:3:2:5]. [70°]. From bromo-nitro-o-toluidine, 
 [143°], by diazo-perbromide reaction (Nevile a. 
 Winther, O. /. 37, 448). 
 
 Di - bromo - nitro - toluene CBH2MeBr2(N02) 
 [1:4:6:2 ?]. [80^]. By nitrating di-bromo-toluene 
 from di-bromo-TO-toluidine, [75°] (Nevile a. 
 Winther, O. /. 37, 441). 
 
 Di - bromo - nitro - toluene CeH2Me(N02)Br2 
 [1:6:3:4]. [87°]. Formed by nitrating the cor- 
 responding di-bromo-toluene. Converted by 
 reduction and diazo- reaction into (2, 4, 5, 1)- tri- 
 bromo-toluene [113°] (Nevile a. Winther, O. J. 
 39, 83). 
 
 Di - bromo - nitro - toluene C8H2Me(N02)Br2 
 [1:4:2:5]. [88°]. From C,H2(CH3){N02)(NH2)Br, 
 [181°] by the diazo-perbromide reaction. Formed 
 also by nitrating C,H,(CH3)Br2 [1:2:5]. Con- 
 verted by reduction and diazotisation into (2, 4, 
 6, 1)- tri-bromo-toluene [113°] (Nevile a. Win- 
 ther, O. 3. 37, 445 ; 39, 83). 
 
 Di - bromo - nitro - toluene CsH2Me(NOJBr2 
 [1:3:5:6]. [106°]. From bromo-nitro-o-tolui- 
 dine, [181°], by exchange of NH2 for Br (Nevile 
 B. Winther, O. J. 37, 433). 
 
 w-Di-bromo-nitro-toluene C8H5.CBr2(N02). 
 Phenyl-di-bromo-niiro-methane. Colourless oil. 
 Formed by the action of bromine upon an 
 aqueous solution of the di-sodium salt of nitro- 
 benzylidene-phthalide 
 
 /C(0Na);^CNa(N02).C,H5. 
 C,H4< >0 Volatile with 
 
 ^ CO / 
 steam (Gabriel a. Eoppe, B. 19, 1145). 
 
 Di-bromo-di-nitro-toluene C||HMe(N02)2Br2. 
 [158°]. Formed by nitrating CsH3(CHs)Br2, [39°] 
 (Nevile a. Winther, G. J. 37, 437). 
 
 Di-bromo-di-nitro-toluene CjHMe{N02)2Br2 
 [105°]. Formed at the same time as the pre- 
 ceding (N. a. W.). 
 
 Di-bromo di-nitro-toluene C5HMe(NO.,)2Br.. 
 [1:?:?:2:6]. [161°]. By nitration of (2, 6, 1)- 
 di-bromo-toluene (N. a. W.). 
 
 Tri - bromo - nitro - toluene CsHMe(N0JBr3 
 [1:4:2:5:6]. [106°]. From di-bromo-nitro-m- 
 toluidine, [125''-130°], by the diazo-perbromide 
 reaction. White needles (Nevile a. Winther, 
 C. J. 39, 85). 
 
 Tri - bromo - nitro - toluene C|iHMe(N02)Br3. 
 [107°]. [l:!c:2:3:4]. Formed by nitrating tri- 
 bromo-toluene, [44°] (N. a. W.). 
 
 Tri - bromo - nitro - toluene CeHMe(NOJBr, 
 [1:3:2:4:6]. [215°]. Formed by nitrating tri- 
 bromo-toluene [70°] (Wroblewsky, A. 168, 195). 
 
 Tri - bromo-di - nitro -toluene C5Me(N02)2Brj 
 [1:?:?:2:3:4]. [217°-220°]. Formed by nitrating 
 tri-bromo-toluene [44°] (Nevile a. Winther, B. 
 13, 975). 
 
 Tetra-bromo-nitro-toluene C5Me(N02)Br, 
 [1:4:2:3:5:6]. [213°] (N. a. W.) ; [227°] (S.). 
 Formed by nitration of C„H(CH3)Brj, [117°] 
 (Nevile a. Winther, G. /. 37, 450). From (2,4,1)- 
 bromo-nitro-toluene, bromine, andFeBr^ (Soheu- 
 felen, A. 231, 179). 
 
 Tetra-bromo-nitro-toluene CBMe(N02)Br, 
 [1:2:3:4:5:6]. [212°]. From tetra-bromo-toluene, 
 [111°]. 
 
 Tetra-bromo-nitro-toluene 05Me(N02)Brj 
 [1:5:2:3:4:6]. [216°]. By nitration of tetra- 
 bromo-toluene, [108°]. 
 
 BROMO - NITRO - TOLUENE SULPHONIC 
 ACIDS C5H2MeBr(N02)S03H. The six following 
 acids of this constitution have been described. 
 
 I. Formed by nitrating o-bromo-toluene sul- 
 phonio acid (Mailer, A. 169, 42 ; Pagel, A. 176, 
 299). Deliquescent. — PbA'22aq. — NaA'aq. — 
 KA'.— BaA'2 2aq. 
 
 II. By the action of fuming HNO3 on (2,1,4)- 
 bromo-toluene sulphonic acid or on (2,l,4)-o- 
 toluidine sulphonic acid : in the latter case the 
 resulting diazo-nitro-toluene sulphonic acid is 
 boiled with HBrAq (Hayduok, A. 172, 219 ; 174, 
 347). Minute needles ; may be reduced to 
 (l,3,4)-m-toluidine sulphonic acid. — BaA'., 3aq. 
 
 Chloride CsH2MeBr(N02)S02Cl. [220°]. 
 Amide C,H2MeBr(N02)(S02NH2). Does not 
 melt below 200°. 
 
 III. From m-bromo-toluene sulphonic acid and 
 HNO3 (Wroblewsky, A. 168, 169).— CaA'24iaq. 
 — BaA'23|aq.— PbA'jSaq. 
 
 IV. Formed by nitrating (3, 1, 2 or 6)-i»- 
 bromo-toluene sulphonic acid (Weokwarth, A. 
 172, 200).— NaA'.— CaA-'o 3aq.— BaA'2 3iaq. 
 
 V. Formed by nitrating (4,1,2) -p-bromo- 
 toluene sulphonic acid (Hasselbarth, A. 169, 22), 
 Deliquescent laminse. — AgA'. — BaA'2 2aq. — 
 CaA'2 6aq.-PbA'2 3aq.— SrA'j 7aq. 
 
598 
 
 BEOMO-NITRO-TOLUENE SULPHONIO ACIDS. 
 
 VI. Formed by nitrating (4,l,3)-2'-''romo- 
 toluene sulphonio acid (H.). Deliquescent 
 needles.— BaA'^aq. — PbA'j2iaq. — SrA'^Saq. 
 
 Di-bromo-nitro-toluene-dl-sulplionic acid 
 OjHBr2(N02)Me.S03H. From ^-bromo-toluene 
 di-sulphonio acid and boiling fuming HNO3 
 (EornatzM, A. 221, 197).— KA' aq.— BaA'^ SJaq. 
 
 BEOMO-NITRO-m-TOLTJIC ACID CsHsBrNOa 
 i.e. C„H2MeBr(N0J(C0jH). [176°]. From 
 bromo-m-toluio acid and HNO3 (Fittig, A. 147, 
 34). — CaA'j 3aq.— BaA'2 3aq. 
 
 Bromo-nitro-p-toluic acid 
 CeH2MeBr(N02)(C02H) [4:2:!!;:1]. [200°]. S. 
 ■1 at 15°. Formed by boiling bromo-cymene 
 (from thymol) with HNO3 (S.G. 1-3). Laminss. 
 — BaA'2 4aq (Fileti a. Crosa, (?. 16, 297). 
 
 Sromo-nitro-p-toluic acid 
 C,H2MeBr(N02)(CO,H) [4:3:a;:l]. [170°-180°]. 
 From bromo-p-toluic acid and fuming HNO3 
 (Landolph, B. 5, 268). Needles (from water).— 
 EaA'^aq. 
 
 BROMO-NITBO-o-TOlTJIDINE 
 C,H2Me(NHj)(N02)Br [1:2:3:5]. [139°] (W.); 
 [143°] (N. a. W.). Formed by nitrating bromo- 
 aoetyl-o-toluidine, C!sH3Me(NHAo)Br [1:2:5], and 
 removing acetyl (Wroblewsky, A. 192, 206 ; 
 Nevile a. Winther, G. J. 37, 431). Gives, by 
 nitrous gas and alcohol, C„H3Me(N02)Br, [81°] 
 whence 0,H3Me(NHJBr, [35°]. 
 
 Bromo-nitro-o-toluidine 
 C3H2Me(NH2)(N02)Br [1:2:5:3]. [181° cor.]. By 
 brominating C„H3Me(NHi,)(N02) [1:2:3], [128°] 
 (N. a. W.). Converted by nitrous gas and 
 alcohol into CjH3Me(N02)Br, [81°] whence 
 CeH3Me(NH2)Br [36°]. 
 
 Bromo-nitro-?re-toluldine 
 CeH2Me(NHJ(N02)Br [1:3:6:5]. [88°]. Formed 
 by nitrating bromo-acetyl-OT-toluidine, and then 
 removing acetyl by H^SO, (2 vols.) and water 
 (1 vol.) (Nevile a. Winther, O. J. 37, 630). 
 
 Bromo-nitro-m-toluidine 
 C3H3Me(NH,)(NOJBr [1:3:2:6]. [103°]. Isformed 
 in small quantity in the preparation of its iso- 
 meride [181°]. 
 
 Bromo-nitro-m-toluidine 
 CeH,Me(NHJ(NO;)Br [1:5:4:2] [181°]. From 
 the acetyl derivative by saponification. 
 
 Acetyl derivative [110°-121°]. Formed 
 by nitration of bromo-acetyl-)»-toluidine (Nevile 
 a. Winther, C. J. 37, 444). 
 
 Bromo-nitro-p-tolnidine 
 C3H,Me(NHj)(N0JBr [1:4:3:5]. [64-5°]. Got by 
 saponifying its acetyl derivative. Orange needles. 
 Converted by nitrous gas and alcohol into bromo- 
 nitro-toluene [86°] (c/. Hand, A. 234, 157). 
 
 Acetyl derivative [211°]. From bromo- 
 acetyl-2)-toluidine and HNO3. Or from acetyl-y- 
 toluidine by successive nitration and bromina- 
 tion (N. a. W.). White needles (from alcohol or 
 dilute acetic acid) (Wroblewsky, A. 192, 202). 
 
 Di-bromo-nitro-m-toluidine 
 C3HMe(NH2)(NOj)Br2 [1:5:4:2:6]. [124°-130°]. 
 From the acetyl derivative of bromo-nitro-m- 
 toluidine [181°] by heating with H^SO, (2 vols.) 
 and water (1 vol.) and subsequent treatment 
 with bromine (Nevile a. Winther, C. J. 37, 444). 
 
 BEOMO-NITKO-m-XYlENE C3H2Me2(N02)Br. 
 (200°-265°). From bromo-m- xylene and cold 
 iuming HNO3. Liquid (Fittig, A. 147, 31). 
 
 Di-bromo - nitro - - xylene C5HMe2(N02)Br, 
 [1:2:3:4:5]. [141°]. Obtained by nitration oj 
 di-bromo-o-xylene G^(CB.^)^x^ [1:2:4:5] with 
 cold fuming HNO3. Colourless needles (from 
 alcohol) (Tohl, B. 18, 2561). 
 
 Di-bromo-nitro-m-xylene 08HMe2(N02)Bri,. 
 [108°]. From di-bromo-m-xylene and HNO,. 
 Needles (F.). 
 
 Di - bromo - nitro -p - xylene C3HMe2(N02)Brj, 
 [112°]. From di-bromo-p-xylene and fuming 
 HNO3 (F.). Needles. 
 
 Di-bromo-di-nitro-o-xyleneC5(CH3)2Br2(N02)j 
 [1:2:4:5:3:6]. [0. 250°]. SmaU needles. Nearly 
 insol. cold alcohol. Formed by nitration of di- 
 bromo-o-xylene CsH2(CH3)^r2 [1:2:4:5] (Tohl, 
 B. 18, 2561). 
 
 BEOMO-NITEO-XTLENE STJLPHONIC ACID 
 C3HMe^r(N02)(S03H) [l:3:6:a!:4]. From nitro- 
 m-xyUdine sulphonio acid by diazo- reaetioa 
 (Sartig, il.230,341;B.18,2190). Ehombio plates, 
 V. sol. water and alcohol. — BaA'23|aq. — KA'aq. 
 
 BEOMO-NONYLIC ACID v. Beomo-ehnoio 
 
 ACID. 
 
 DI-BROMO-OCTADECANE C.sHssBrj. Octa- 
 
 decylene bromide. [24°]. Silvery plates. SI. 
 sol.aloohol. Formedbythe addition of Br (Imol.) 
 to octadeoylene (Krafft, B. 17, 1373). 
 
 BEOMO-OCIANE v. Ooiyl bromide. 
 
 Di-bromo-ootane CsHuBrj. Octylene bromide. 
 From Br and octylene derived from castor oil 
 (Eubien, A. 142, 297) or that from paraffin 
 (Thorpe a. Young, Pr. 21, 193). Non-volatile oil. 
 
 Tetra-bromo-octane CsHjjBr^. Caprylidene 
 tetra-bromide. Frombromo-octyleneandBr. Oil. 
 
 BKOMO-OCTONENE CsHi.Br. (204°). From 
 CaHijBrj (v. supra) and alcoholic KOH (E.). 
 
 BEOMO -OCTYI -BENZENE C3H,(CsH„)Br. 
 (285°-287°). Formed by bromination of octyl- 
 benzene. Oil (Ahrens, B. 19, 2719). 
 
 BROMO-OCTYLENE CsHi^Br. (185°). From 
 di-bromo-octane and alcoholic KOH (Eubien, A. 
 142, 297). With Br it gives an oily tri-bromo- 
 decane. 
 
 Di-bromo-octylene C,H,jBr2. S.G. IS 1-568. 
 Conylene bromide. From conylene and Br 
 (Wertheim, A. 123, 182). 
 
 BEOMO-OCTYI-THIOPHENE 
 C4SH2(C8H„)Br. (285°-290°). Colourless oil 
 solidifying to plates at 5°. V. sol. ether, insol. 
 water. Formed by shaking ootyl-thiophene with 
 bromine-water (Sohweinitz, B. 19, 644). 
 
 BKOMO-OLElC ACID CisHjjBrO^. From di- 
 bromo-stearic acid and alcoholic KOH (Over- 
 beck, A. 140, 47). 
 
 Di-bromo-oleic acid CisHj^BruOj. From 
 stearolic acid and Br (0.). 
 
 BEOMO-ORCIN C^B^Ue(OiH)g&r. [135°]. 
 From orcin and bromine-water (Lamparter, A. 
 134, 258). Crystals ; m. sol. hot water, v. e. sol. 
 alcohol and ether. Solutions are ppd. by lead 
 subacetate. 
 
 Di-bromo-orcin 
 
 Methyl derivative 
 CsH(CH3)(0Me)(0H)Brj. [146°]. White needles. 
 Prepared by bromination of the mono-methyl 
 ether of orcin (Tiemann a. Strong, B. 14, 2002). 
 
 Di-methyl derivative 
 CBH(CH3)(0Me)jBrj. [160°]. Colourless plates. 
 Sol. alcohol, ether, and benzene, insol. water 
 and ligroin. Prepared by bromination of the 
 di-methjl ether of orcin (B. 14, 2001). 
 
BROMO-OXY-BENZOIO ACID. 
 
 59» 
 
 Tritromo-oroin C„iCH3)Br3{OH)2. [103°]. 
 From oroin and Br (Stenhouse, Tr. 1848, 87 ; 
 Laurent a. Gerhardt, A. Ch. [3] 21, 317 ; Lam- 
 parter, 4. 134, 257 ; Hesse, A. 117, 311; Sten- 
 house a. Groves, A. 203, 298). Is formed by 
 heating penta-bromo-oroin with formic aoid. 
 Needles ; insol. water, sol. aloohol and ether. 
 
 Diaeetyl derivative [143°]. White 
 needles. Formed by the action of Ao^O on 
 penta-bromo-orcin (Claassen, B. 11, 1440). 
 
 Fenta - bromo - orcin OiHaBr^Oj i.e. 
 08MeBr3{0Br)2 ? [126°]. Prom orcin and excess 
 of bromine- water. Triolinic crystals (from CSj). 
 At 160° it gives off Br^, leaving C.B.^Bxfi^ (Sten- 
 house, A. 163, 180 ; Liebermann a. Dittler, A. 
 169, 252). 
 
 Bronio-3-orcin v. Bbomo-betokoin. 
 
 DI-BROMO-OXAL-ETHYLINE v. Di-bbomo- 
 
 METHYL-ETHYL-GLyOXALINE. 
 
 BEOMO-OXINDOLE v. Oxindole. 
 
 BKOMO-OXY-ACEYLIC ACID. Phenijl 
 derivative O.HjBrOjle. CHBr:C(0Ph).C02H. 
 [138°]. From phenyl - oxy - mucobromic aoid 
 CHO.CBr:C(OPh).COjH and KOH (Hill a. 
 Stevens, Am. 6, 190). Needles (from water) ; 
 V. e. sol. alcohol and ether. — KA'. — BaA'^ Saq. — 
 CaA'2 5aq. — AgA'. 
 
 BEOMO - OXY - AMIDO - BENZOIC ACID. 
 Methyl derivative CuHgBrNOj i.e. 
 C5H2Br{OMe)(NH2)C02H. [185°]. Bromo-amido- 
 anisic acid. From the corresponding nitro- acid. 
 Needles, si. sol. water.— CaA'2 5|aq.— BaA'2 2a(i. 
 — HA'HCl [186°] (Balbiano, G. 14, 245). 
 
 BROMO-DI-OXY-ANTHEAftTJINONE 
 CnH^rOi i.e. 0„H502(0H)2Br. Bromo-alizarin. 
 From alizarin (3 pts.) and Br (2^ pts.) in CS^ at 
 190° (Perkin, O. J. 27, 401). Tufts of orange 
 needles; may be sublimed. KOHAq forms a 
 blue solution, exhibiting the same absorption 
 bands as aUzarin. HNO3 forms phthalic acid. 
 The same bromo-alizarin, or an isomeride, is 
 formed bytreatingtri-bromo-anthraquinone with 
 KOH. It melts at 280° (Diehl, B. 11, 190). 
 
 Bromo-tri-oxy-anthraquinone 
 C,,,H,02(OH)3Br. Bromo - purpurin. [276°]. 
 From Br and purpurin, or its carboxylio acid, 
 or by warming di-bromo-purpurin {v. infra) 
 with cone. H^SO,. Eed needles (Plath, B. 10, 
 615, 1619 ; Sohunok a. Koemer, B. 10, 554). 
 
 (B. l,3,2)-Di-bromo-oxy-aiitliraquinone 
 cAsrA i-e- C,H,:(C,0,):C,HBr,(OH). [208°]. 
 Formed, together with di-bromo-pbenol by heat- 
 ing tetra-bromo-phenol-phthalein with excess of 
 H,SO, at 150° (Baeyer, A. 202, 136). Slender 
 yellow needles; its alcoholic solution shows 
 reddish fluorescence. Its solution in alkalis is 
 reddish-brown. NaOH at 200° gives ahzarin. 
 
 Acetyl derivative CuHsAcBr^O.,. [190°]. 
 
 Di-bromo-di-oxy-anthraquinone 
 C,4H402(0H)2Br2. Di-bromo-alizarin. [170°]. 
 Prepared by the action of Br in presence of I on 
 alizarin. Small brownish-red needles. Com- 
 bines with mordants (Diehl, B. 11, 190). 
 
 Di-bromo-di-oxy-anthraquinone 
 C,,H,0,(OH)2Br2. Di-bromo-purpurozanthin. 
 r227°-230°] (P.) ; [231°] (S. a. R.). From pur- 
 puroxanthin and Br (Plath, B. 9, 1205). From 
 muniistin and Br (Sohunok a. Eoemer, C J. 33, 
 424). Orange needles (from HOAc). Warm 
 cone. H^SOj forms bromo-purpurin. 
 
 Sftlt.-(NHJ»A". 
 
 Tri-bromo-tri oxy-anthraquinono 
 C„H202(OH)3Br3. Tri-hromo-flavopurpurirt. 
 
 [284°]. From flavopurpurin in HOAo and Br. 
 Orange needles. Its alkaline solutions are orange 
 (Sohunck a. Eoemer, B. 10, 1225). 
 
 Tetra-bromo-di-oxy-anthraquinoue 
 C,4H202(OH)2Br4. Tetra-bromo-alizarin. From 
 alizarin and excess of iodine bromide at 180°. 
 Does not combine with mordants (Diehl, B. 11 „ 
 191). 
 
 BEOMO-o-OXY-BENZOIC ACID C^H^BrOjle. 
 C„H3Br(OH)C02H [3:2:1]. Bromo-salicylic acid. 
 [184°] (L. a. G.); [220°] (H. a. E.). From the 
 corresponding bromo-amido-benzoic acid by ex- 
 change of NHj for OH (Hiibner a. Emmerling, 
 Z. 1871, 709) or from (3, 5, 2, l)-bromo-amido- 
 oxy-benzoic acid by eliminating NHj (Lellmann 
 a. Grothmann, B. 17, 2725). Needles, v. si. sol. 
 cold water, v. e. sol. alcohol. FojCl^ gives a 
 violet colouration. — CaA'^ 12aq : v. sol. water. — 
 BaA'23iaq : prisms.— PbA'^ (H.).— PbCjHjBrO,. 
 
 Bromo-o-oxy-benzoic acid C3H3Br(OH) (CO^H) 
 [5:2:1]. [165°]. From salicylic acid and Br or 
 PBrj (Gerhardt, A. Ch. [3] 7, 217; Cahours, A. 
 
 06. [3] 10, 341; 13,99; Henry, B. 2, 275; H.a.E.). 
 Also from the corresponding amido-m-bromo- 
 benzoio aoid (H. a. E.). Needles (from water). 
 Fe^Clj gives a violet colouration. — BaA'2 3aq. — 
 PbA'j.— PbC,H3Br03.— CuA'j.— AgA'. 
 
 Methyl ether MeA'. [38°] (Henry) ; [61°J 
 (Peratoner, G. 16, 405). (265°). From methyl 
 salicylate and Br or PBrj. Trimetrio prisms or 
 needles. Coloured violet by FejClj. 
 
 Methyl derivative CsH3Br(0Me)C0..H.. 
 [119°]. — BaA'2 3aq. — CaA'j4aq. — AgA' aij. 
 Methyl ether CjH3Br(OMe)C02Me. [J0°J^ 
 (295°) (P.). 
 
 Ethyl derivative CsH3Br(OEt)C02H.. 
 [130°].— BaA'24aq.— CaA'22aq. Methyl ethet- 
 C„H3Br(0Bt)C02Me. [49°]. (301°). 
 
 Propyl derivative CsHsBr(0Pr)C0.,H. 
 [62°]. Methyl ether C3H3Br(0Pr)C0,,Me. 
 (323°). 
 
 Isopropyl derivativeG^S.3Bi(0ii)C0.^. 
 [101°]. Methyl ether (304°). 
 
 Bromo-ji-oxy-benzoic acid. Methyl deri- 
 vative GjH3Br(OMe)C02H [3:4:1]. Brmno- 
 anisicacid. [214°]. [218° cor.]. 
 
 Formation. — 1. From anisic acid and Br 
 (Laurent ; Cahours, A. 56, 311 ; Salkowski, B. 
 
 7, 1013). — 2. By oxidising the methyl ether o£ 
 bromo-^-oresol (Schall a. Dralle, B. 17, 2531). 
 
 Properties. — Needles ; may be distilled or 
 sublimed. Insol. water. 
 
 S a 1 1 s. — Ag A'. — BaA'2 3|aq. —BaA'2 4aq. — 
 CaA'2 6aq.— CuA'22|aq.— MgA'2 5aq.— NaA'2 2aq. 
 — PbA'» baq.— ZnA'j 3aq. 
 
 Ethyl ether C„H3Br(0Me)(C02Et). [74°] 
 (Crespi, G. 11, 419). 
 
 Amide C„H3Br(0Me)(C02NH2). [186°]; 
 insol. water. 
 
 Bromo-j)-oxy-benzoic aoid. Methyl deri- 
 vative C,H3Br(OMe)C02H. [212°]. Ethyl bromo- 
 anisate [74°] is converted into an isomeride 
 [60°] by heating with NaOEt at 180° for 20 
 hours ; on saponification it yields the aoid which 
 crystallises in needles, si. sol. water. Potash 
 fusion forms protocateohuio acid. HNO3 gives 
 the methyl ether of (2,4,6,1)- bromo -di- nitro- 
 phenol. 
 
 Salt.— ZaA'2 4aq (Balbiano, 0. 11,409). 
 
600 
 
 BROMO-OXY-BENZOIC ACID. 
 
 Ethyl ether mk'. [60°] {v. stipra). This 
 acid is possibly identical with the preceding. 
 
 Browo-di-oxy-benzoic acid. Methyl deri- 
 vative C5H2Br(OH)(OMe)CO,H [a;:4:3:l]. 
 Bromo-vanillic acid. [193°]. From its acetyl 
 derivative. Needles (containing aq). Acetyl 
 derivative CABr(0Ac){0Me)C02H. [167°]. 
 From acetyl- vanillic acid and Br (Matsmoto, B. 
 \1, 138). 
 
 Di-methyl derivative 
 0„H,Br(OMe)2CO2H [a;:4:3:l]. Bromo-veratric 
 acid. [184°]. From veratric acid and Br (M.). 
 
 Methylene derivative 
 C„H^r(02CHj)C0,H or CjH3(0jCHBr)C0,H. 
 Bromo-piperonylic acid. [205°]. From bromo- 
 piperonal and KMnO, (Fittig a. Mielck, A. 172, 
 158). 
 
 Bromo-di-ozy-benzoic acid 
 G,B.fir{OB.).fi0^n [a;:l:3:5]. [253°]. From 
 s-di-oxy-benzoic acid and bromine water (Barth 
 a. Senhofer, A. 164, 115). Needles (containing 
 aq). Potash-fusion forms gallic acid. Fefil^ 
 gives a yeUowish-brown colour. — CaA'j 8aq. — 
 Ag^". 
 
 Bromo-di-ozy-benzoic acid C5H2Br(OH)2C02H 
 [a;:2:6:l]. [184°, anhydrous]. From c-di-oxy- 
 benzoic acid in ether and Br (Zehenter, M. 2, 
 480). Prisms (containing aq). Fe2Clj gives a 
 violet colour to its aqueous solution. — AgA'aq. 
 BaA'2 74aq.— CuA'24iaq.— PbA'j 3aq.— KA.'l^aq. 
 
 Bromo-tri-ozy-benzolc acid 
 C5HBr(OH)aC02H. Bromo-gallic acid, [above 
 200°]. Prom galUe acid and Br (Hlasiwetz, A. 
 142, 260 ; Grimaux, ^. 1867, 431). Monoclinio j 
 si. sol. water. 
 
 Di-bromo-o-ozy-benzoio acid 
 CeHjBr2(OH)C02H [5:3:2:1]. Di-bromo-salicylic 
 acid. [219°] (R.); [223°] (L. a. G.). Fromsalicylio 
 acid and Br or from (3,5,2,l)-bromo-amido-sali- 
 cylic acid by the diazo- reaction (Cahours, A. 
 Ch. [3] 10, 339 ; 13, 102 ; EoUwage, B. 10, 1707 ; 
 Lellmann a. Grothmauu, B. 17, 2727). Gives 
 a violet colour with Fe^Cls. Heated with dilute 
 HjSO, it gives (3,5,2)-di-bromo-phenol [36°].— 
 BaA'2 4aq. 
 
 Methyl ether GsB.^i^{OB.)CO.,Me: [149°]; 
 from methyl salicylate and Br (Peratoner, G. 
 16, 405). Long needles, si. sol. alcohol. 
 
 Methyl derivative C,H2Br2(OMe)CO.,H : 
 [194°]. — Salt BaA'22|aq. Methyl ether 
 CsH2Br2(OMe)C02Me : [53°] ; needles. 
 
 Ethyl derivative CsH.J3r2(OEt).C02H: : 
 [156°]; white needles. Methyl ether 
 C,H.,Br2(0Et).C0jMe: [43°]; needles. 
 
 Di-bromo-o-oxy-benzoie acid 
 CeH^Brj(0H)C02H [4:3:2or6:l]. [218°]. From 
 (4,3,1) -di-bromo-benzoic acid [229°] by nitra- 
 tion, reduction, and diazotisatiou (Smith, B. 10, 
 1706). Gives a violet colour with FejClj. 
 
 Si-bromo-o-ozy-benzolc acid 
 CsH2Br2(OH)C02H. [221°]. Formed as a by- 
 product in converting (5,2,l)-bromo-nitro-benzoic 
 acid [250°] into di-bromo-benzoic acid by the 
 diazo- reaction (Hiibner a. Lawrie, B. 10, 1706). 
 Fe^Clu gives a violet colour. 
 
 Di-bromo-p-oxy-benzoio acid 
 C„H2Br2(0H)C02H. [268°]. From di-bromo- 
 anisio acid and cone. HI (Aleoci, O. 15, 242). 
 One of the products of the dry distillation of 
 sodium di-bromo-anisate (Balbiano, G. 13, 69). 
 fjong needles, insol. water, sol. alcohol and ether. 
 
 FejClj turns its solutions yellowish-red. Sodium, 
 amalgam forms ^-oxy-benzoic acid. — GaA'oSaq. 
 
 Methyl derivative 0„H.,Br2(0Me)C0jH 
 [3:5:4:1]. Di-6ro?)io-anisic acid [207°] (E.) ; [214°] 
 (C). From anisic acid, Br, and water at 120° 
 (Eeinecke, Z. 1866, 366 ; Crespi, G. 11, 425). 
 Converted by prolonged action of Br and water 
 into tri-bromo-anisol [87°]. — NaA' 3aq. — AgA'. — 
 BaA'jiiaq. Ethyl ether C„H2(0Me)(C02Bt): 
 [88°] ; plates. 
 
 Di bromo-di-ozy-benzoic acid 
 C,HBr2(OH)2C02H. [214°]. From (3, 2, 1)- di- 
 oxy-benzoio acid and Br (Zehenter, M. 2, 475). 
 Needles (containing aq) ; m. sol. hot water. 
 Fe^Clj turns its solution violet ; cone. H^SOi 
 gives a green colour. Heating with water forma 
 di-bromo-resorcin. — KA' 35aq. — CaA'^ 8|aq. — 
 PbCjE^Br^Oj. -CuA'^aq.- AgA'. 
 
 Si-bromo-tri-ozy-benzoic acid 
 CjBr2(OH),C02H. Di-bromo-gallic acid. [140°] 
 (G.); [150°] (E.). From gallic acid and Br 
 (Grimaux, Z. 1867, 431; Etti, B. 11, 1882). 
 FCjClg gives a. blue-black colour in its aqueous 
 solution. 
 
 Tri-bromo-o-ozy-benzoic acid 
 C|jHBrs(0H)C02H. Tri ■ bromo - salicylic acid. 
 From Br and salicylic acid. Small prisms, insol. 
 water (Cahours, A. Ch. [3] 13, 104). 
 
 Tri-bromo-m-ozy-benzoic acid 
 CeHBr3(OH)C02H. [147°]. From m-oxy-benzoio 
 acid (1 mol.) and Br (3 mols.) (Werner, Bl. [2] 
 46, 276). 
 
 Tri-bromo-di-ozy-benzolc acid 
 C,Br,(0H),,C02H. [183°]. From (5, 3, 1). di- 
 oxy-benzoic acid and Br (Barth a. Senhofer, A. 
 159, 225). Tables (from water). Potash-fusion 
 reproduces s-di-oxy-benzoio acid. 
 
 BEOMO - - OXY - BENZOIC ALDEHYDE 
 CjH^BrOj i.e. C5H3Br(OH)CHO. Bromo - sali- 
 cylic aldehyde. [99°]. From salicylic aldehyde 
 and Br or PBr^ (Lowig, P. 46, 57, 383 ; Piria, 
 
 A. Ch. [2] 69, 281 ; Henry, B. 2, 275). Laminte; 
 insol. water, sol. alcohol and ether. Combines 
 with KHSO3. 
 
 Methyl derivative OBH,Br(OMe)CHO. 
 [114°]. _ From methyl-salicylic aldehyde and Br 
 (Perkiri, A. 145, 304). Flat prisms (from alcohol). 
 
 Ethyl derivative CjH3Br(0Et)CH0 : 
 [68°]; prisms. 
 
 Bromo-p-oxy-benzoie aldehyde 
 C,H3Br(0H)CH0. [180°]. From^J-oxy-benzoio 
 aldehyde and Br. V. sol. alcohol and ether, v. 
 si. sol. water : Combines with KHSO3 (Herzfeld, 
 
 B. 10, 2198). 
 Di-bromo-o-ozy-benzoic aldehyde 
 
 C5H„Br2(OH)CHO. Di-bromo-salicylic-aldehyde. 
 Prisms. From salicyKo aldehyde andBr (Heerlein, 
 J.pr.Z2,65). 
 
 Phenyl-hydrazide 
 C,H2Br2(0H)CH:N2HPh : [148°] ; v. sol. alcohol, 
 benzene, ether, and CHCI3, insol. water. The 
 mono-acetyl-derivative CjH2Br2(OAo)CH:N2HPh 
 forms fine needles [188°], nearly insoluble in ether. 
 Thedi-acetylderivativeC,H2Br2(OAc)GH:N2AcPh 
 crystallises in white needles, [ISS"'], easily soluble 
 in ether; it is formed by brominating the di 
 acetyl derivative of the phenyl-hydrazide of 
 salicyUo aldehyde (Eossing, B. 17, 3008). 
 
 Di-bromo-^-ozy-benzoic aldehyde 
 C(HjBr2(0H)CH0. [181°]. From ^j-oxy-benzoio 
 
BROMO-OXY -NAPHTHOIC ANHYDRIDE. 
 
 60\ 
 
 aldehyde (1 mol.) and Br (2 mols.) (Werner, Bl. 
 [2] 46, 277). 
 
 BBOMO-OXY-BTTTYEIC ACID C^HjErOj. 
 [102°]. Prom di-bromo-butyrio acid and baryta. 
 LaminsB (Petrieff a. Eghis, J. B. 7, 179).— 
 BaA'j.— AgA'. 
 
 Bromo-oxy-bntyric acid 
 
 CH,.CHBr.CH(OH)CO.,H or 
 CH3.CH(0H).CHBr.C0,H. An unorystallisable 
 syrup obtained as a residue when a;8-di-bromo- 
 butyric acid Is distilled with water (C. Eolbe, J. 
 pr. 133, 389 ; cf. Erlenmeyer a. Miiller, B. 15, 49). 
 
 Bromo-oxy-butyrio acid 
 
 CH3.CHBr.CH(0H).C0.,H or 
 CH,.CH(OH).CHBr.CO,H. [90°]. From ;8. 
 
 raethyl-glycidic acid O'^^^'^q "jj and HBr 
 
 (Melikoff, Bl. [2] 43, 116). " Prisms. Probably 
 identical with the preceding. 
 
 Bromo-oxy-iso-batyric acid 
 CIIiBr.C(0H)Me.C02H. [101°]. Formed by boiling 
 di-bromo-iso-butyrio acid with water, and ex- 
 tracting with ether (K.). Also from HBr and 
 
 o-methyl-glyoidio acid 0<^a^ qq tt Needles ; 
 
 sol. hot benzene, insol. CHCI3 and CSj. Not 
 aiiected by boiling water. Reduced by the action 
 of sodium amalgam on its aqueous solution, kept 
 neutral by H^SOj, to oxy-iso-butyrio acid, [79°]. 
 BKOMO-OXY-CINNAMIC ACID v. Beomo- 
 
 COUMAKIC ACID. 
 
 BROMO-(B. 4)-OXY-(P2/. 4)-ETHYL-QUIN0- 
 LINE TETEA-HYDRIDE C„HaBr(OH)EtN. 
 
 Ethyl ether [85°] ; long monoclinic prisms, 
 a:b:c = 0-7902:l:0-5828. Formed by bromination 
 of ethyl-kairine (ethyl ether of oxy-ethyl-quino- 
 line-tetra-hydride), or by ethylation of the ethyl- 
 ether of bromo-oxy-quinoline-tetra-hydride. The 
 picrate forms yellow needles [174°] (Fischer a. 
 Eenouf, B. 17, 762). 
 
 DI-BEOMO-OXY-INDONAPHTHENE 
 
 CsH^Br^O i.e. C,n,<^^^^CBi. Plienylene-di- 
 
 bromo-acetylene ketone. [123°]. Obtained by heat- 
 ing di-bromo-cinnamic acid CBH5.CBr:CBr.C02H 
 with cone. HjSO,. Yellow needles. 
 
 Oxim CaH4Br2(NOH) : [195°] ; yellow needles. 
 
 Anilide: [170°]; red needles. 
 
 Di-bromide CsBfiBT,: [124°]; prisms 
 (Eoser, B. 20, 1273). 
 
 BEOMO-OXY-MALEIC ACID Phenyl cZeri- 
 vaiive CO^'B..GBt:C(OV}i).GO^B.. [104°]. From 
 the phenyl derivative of oxy-mucobromio acid 
 and AgjO (Hill a. Stevens, Am. 6, 187). Needles. 
 
 ^CT A". 
 
 p-BROMO-u-OXY- MESITYLENE CsH„BrO 
 i.e. G^S.J,CB.,)^Br{CS^.OB.) [5:3:4:1]. p-Bromo- 
 mesityl alcohol. [66°]. Obtained from ^-w-di- 
 bromo-mesitylene (p-mesityl bromide) by treat- 
 ment with KOAc and saponification of the 
 acetate. Pointed needles. V. e. sol. alcohol, 
 ether, and benzene, si. sol. cold petroleum-ether, 
 insol. cold water. Decomposes on distillation 
 with separation of H^O and formation, amongst 
 other products, of ^-bromo-mesitylenic aldehyde 
 CsHj(CH3).;Br(CH0). By oxidising agents it is 
 readily converted into p-bromo-mesitylenio acid 
 [214°] (Schramm, B. 19, 213). 
 
 eso-Bromo-a),m„-di-oxy-inesitylene 
 f!,H^r(CH3)(CH,0H),. [121°]. S. 3^ at 100°. 
 from the corresponding tri-bromo-mesitylene 
 
 (200°-215°) by boiling with water and PbCO, 
 (Colson, A. Ch. [6] 6, 98 ; C. B. 97, 177). 
 Pearly scales ; v. si. sol. cold water, m. sol. alco- 
 hol. Boiling HOlAq forms C„H2Br(CH3)(CH.,Cl), 
 
 BEGMO-OXY-jS-METHYL-CUMARILIC ACID 
 
 (1) 
 (4) /CMev 
 CBH3Br(0H)< (2) ^C.COjH. [221°]. Formed 
 
 ^ / 
 by boiling bromo-i3-methyl-umbelliferon-di- 
 CMeBr.CHBr 
 
 with aloo- 
 
 bromide CBH2Br(0H)^ 
 
 
 I 
 -CO 
 
 holio KOH. Colourless needles. V. sol. alco- 
 hol and ether, si. sol. benzene, insol. water. 
 Cold H^SOj gives a colourless solution which 
 becomes violet on heating. Fe2CIs gives a 
 yellow colouration with the alcoholic solution 
 (Pechmann a. Cohen, B. 17, 2134). 
 
 BEOMO - OXY-METHYL-ETHYL-PYEIMID - 
 
 INE C^Hj.C^^-.^l^g'^^CBr. [195°]. Formed 
 
 by bromination of oxy-methyl-ethyl-pyrimidine. 
 Long colourless glistening needles. SI. sol. water. 
 C,H8N2Br(0H) aq : very soluble long white needles 
 (Pinner, B. 20, 2362). 
 
 BEOMO-OXY-DI-METHYL-PYEIMIDINE 
 
 CH3.C<^^:^|^^) ^CBr. Formed by bromina- 
 tion of oxy-di-methyl-pyrimidine. The hydro- 
 bromide (B'HBr) forms colourless needles, m. 
 sol. water, v. sol. alcohol (Pinner, B. 20, 2361). 
 
 (P2/.2,3,l)-BEOMO-OXY-METHYI-QiriNOL- 
 INE 
 
 .CMe:CBr 
 CjoHsNOBr i.e. C^H^^ | ? Bromo- 
 
 \n : C.OH 
 oxyquinaldine, or hromo-guinoxyl. [c. 258°]. 
 Formed by the action of cold cone. HjSOj 
 upon the anilide of bromo-aceto-acetio acid 
 CH3.C(0H):CBr.C0NHPh. Also from (Py. 3, 1)- 
 oxy-methyl-quinoline and bromine-water (Knorr, 
 B. 17, 2875 ; A. 236, 91). Fine silky needles. 
 SI. sol. alcohol, ether, and chloroform. Dis- 
 solves in aqueous acids and alkalis. 
 
 Tri-bromo - (Py.V) - oxy- (Pj/. 3) -methyl-quinol- 
 ine C3H.,MeBr3(OH)N. [275°]. Formed by 
 bromination of (Py. 1, 3)-oxy-methyl-quinoline. 
 Insol. alcohol (Conrad a. Limpach, B. 20, 949). 
 
 Bromo-(P2/.3)-oxy-(P2/.l,4)-di-methyl-quinol- 
 ine C„H,„BrNO. Bromo-methyl-lepidone. [172°]. 
 From the corresponding oxy-dimethyl-quinoline 
 and bromine-water (Knorr, .4. 236, 110). Spheri- 
 cal aggregates of needles (from alcohol). Insol. 
 water and NaOHAq, v. sol. dilute acids. 
 
 BEOMO-OXY-(o)-NAPHTHOICANHYDEIDE 
 CO 
 
 0„H5Br03i.e.C,„H,Br< 
 
 ./l 
 
 bromination 
 -CO 
 
 of 
 
 ^0 
 
 oxy- naphthoic 
 
 [192°]. Formed by 
 anhydride 
 
 C,.H,< 
 
 f I dissolved in 
 
 \, 
 
 CS,. Small, white 
 
 
 
 needles (Ekstrand, B. 19, 1139). 
 Bromo-oxy-(c[)-naphthoquinone 
 ,CO.C(OH) 
 
 C.H,< 
 
 / 
 
 [197°]. 
 
 '\cO.CBr 
 
 Formation. — 1. From di-bromo-(o)-naphtfeo- 
 qninone [151°] by boiling with aqueous NaOH 
 
tIOZ 
 
 BROMO-OXY-NAPHTHOIO ANHYDRIDE. 
 
 or NajCOj ; the yield being 60 p.c. of the theo- 
 retical (Diehl a. Merz, B. 11, 1064).— 2. From 
 oxy- (a). naphthoquinone and Br. — 3. Prepared 
 by the action of alcoholic HjSOj on di-bromo-(a)- 
 naphthoquinone-anilide, ^-bromo-aniline being 
 eimultaneously produced (Baltzer, B. 14, 1901). 
 
 4. By the action of alkali upon bromo-;3-naph- 
 thoquinone (Zincke a. Gerland, .B. 20, 1515). — 
 
 5. By boiling bromo-amido-(o)-naphthoquinone 
 
 C5H,<^^-^^^^) with dilute alkalis (Z.).— 
 
 6. From bromo-oxy-(a)-naphthoquinone-imide 
 
 •^"^^^cJNHi.CBr^' ^y ''°'^™S with cone. HCl or 
 by treatment with alcoholic NaOH (Z.). 
 
 Properties. — Yellow needles ; v. si. sol. water, 
 si. sol. ether, v. sol. alcohol. Oxidation gives 
 phthalio acid. 
 
 Salts.-- KA'aq: red needles. — BAV S.-07 
 at 13°.— AgA'. 
 
 Bronio-oxy-(o)-iiaphthoquinone. [202°]. Prom 
 the anilide [197°] of di-bromo-naphthoquinone 
 [218°] by boiling with aqueous NajCO, (Miller, 
 Bl. [2] 43, 125). Oxidises to phthalic acid ; it 
 should therefore be identical with the preceding. 
 
 BROMO - OXY - (o) - NAPHTHOQTJINOITE - 
 .00 — C(OH) 
 IMIDE CsHX I . [c. 265°]. Formed 
 
 \C(NH).OBr 
 by boiling bromo-amido-(a)-naphthoquinone- 
 
 imide C,H4<^° £> cS^'' ^'^^ ^'^"*^ TfiaOK. 
 Formed also by the action of NHj upon bromo- 
 (;8) -naphthoquinone. Brownish - red glistening 
 needles. By boiling with cone. HCl or by treat- 
 ment with alcoholic NaOH it is converted into 
 bromo-oxy-(o) -naphthoquinone. The sodium- 
 salt forms red needles ; the salts of the heavy 
 metals are sparingly soluble pps. 
 
 Acetyl derivative: [270°]; red hair-Uke 
 needles (Zincke a. Gerland, B. 20, 1514). 
 
 BROMO- OXY -NAPHTHOaUINONE STJL- 
 PHONIC ACID CioHjBrSO, i.e. 
 C,„H30jBr(OH)(S03H). From (;8)-naphthol sul- 
 phonic acid and Br, di-bromo-oxy-naphtho- 
 quinone being also formed in small quantity 
 (Armstrong a. Graham, O. J. 39, 138 ; Arm- 
 strong a. Streatfeild, G. J. Proc. 1, 232).— 
 BaCioHsBrSOs. 
 
 BROMO-OXY-NICOTINIC ACID v. Bbomo- 
 
 OXY-PTKIDINE CAKBOXYLIO ACID. 
 
 BROMO-OXY-OCTOIC ACID CsH.sBrOa i.e. 
 CHs.CHBr.CH2.CH(CO,H).CH,.CH(OH).CH3. 
 Bromo-oxy-di-propyl-acetic acid. 
 
 ^GH^.CH.GHg 
 iac<ojteCHj.CHBr.CH2.CH<f | 
 \ CO.O 
 S.G. ii 1-394. From di-allyl-acetic acid and 
 HBr, the compound (CH3.CHBr.CHi,)i,CH.C02H 
 being probably first formed (Hjelt, A. 216, 73). 
 Oil. Insol. cold water, v. si. sol. warm water. 
 Insol. cold NaOH. Boiled for a long time with 
 water or aqueous NajCOs it appears to form the 
 
 .CHj-CHMe 
 lactone CH2:CH.CHj.CH/ | v. Oxt- 
 
 \co.o 
 
 OCIBNOIO ACID. 
 
 Tri-bromo-oxy-octoic acid. Lactone 
 .CHj.CH.CHoBr 
 CHjBr.CHBr.CHj.CH< | Prom 
 
 \co.o 
 
 di-aUyl-acetic acid and bromine in chloroform 
 (Hjelt, A. 216, 76). Oil. V. sol. ether. Insol. 
 cold NaOHAq. Boiled with aqueous NajCOj it 
 forms (CH3(OH).CH(OH).CH2)2CH.C02Na. 
 
 Tri-bromo - di - oxy - octoio acid. Lactont 
 CgHiiBrjOj i.e. 
 CHjBr.CHBr.CH2.C(OH).CH2.CH(CH2Br).O.CO. 
 
 From so-called ' di-allyl-oxalio acid ' and bromine 
 {v. OxY-ooTiNoio Acm) (Sohatzky, J. jar. [2] 
 34, 485). 
 
 Tetra-bromo-oxy-ootoic acid CJ3.,fiifi, i.e. 
 (CH2Br.CHBr.CH2).,C(0H).C02H. From so- 
 caUed ' di-allyl-oxaho acid' and Br (Saytzeff, A. 
 185,189). Oil: readily splits up into HBr and 
 the preceding lactone. 
 
 Ethyl ether EtA'. Oil (Schatzky, J. E. 
 17, 73). 
 
 DI - BROMO - HEXA - OXY - DIPHENYL. 
 Methyl ether C,jH2Br2(OMe)e. [140°]. Prom 
 the methyl ether of hexa-oxy-diphenyl and Br 
 (Ewald, B. 11, 1623). Needles (from alcohol or 
 HOAc) ; cone. H^SO^ forms a blue solution. 
 
 Tetra-bromo-dl-oxy-diplienyl C^fiJBifi^ i.e. 
 C,U^v.,(OB.).C^B.^Bi^{OU). [264°]. From di- 
 oxy-diphenyl and Br (Magatti, B. 11, 2267 ; 13, 
 225). Also by reduction of bromo-rosoquinone 
 (Baeyer, B. 11, 1801). Fuming HNOj forms 
 brownish-red scales of (OjH2BrjO)2. 'Teira- 
 bromo-diphenyl-quinone.' 
 
 Acetyl derivative CuHjAo^Br^Oj. [245°]; 
 needles. 
 
 Tetra-bromo-tetra-oxy-diphenyl 
 0,2H2Br4(OH)4. Tetra-bromo-diresorcin. From 
 tri-bromo-resoquinone CuHBr^O^f?) and HjS or 
 Sn and HCl. Needles (from HOAc). Turns brown 
 at 230° and decomposes at 280°. Insol. water, 
 V. sol. alcohol and ether. Sodium- amalgam 
 gives diresorcin. Eed-hot zinc-dust gives di- 
 phenyl. 
 
 Acetyl derivative C,2H2Br,(OAc)4 : 
 [195°] i needles (from alcohol) (Benedikt, M. 1, 
 352 ; B. 11, 2170). 
 
 Deca-bromo-tetra-oxy-diphenyl C,2Brj(0Br) ,. 
 Formed by adding Br and HCl to a solution of 
 diresorcin in aqueous potash (Benedikt a. Julius, 
 M. 5, 179). Unstable crystals, gives off Br 
 (2 mols.) at 185°. SO^ reduces it to C,2Br„(0H)j. 
 
 BROMO-^-OXY-PHENYL-ACETYLENE. 
 Methyl derivative C8H3Br(OMe).C-CH. 
 [75°]. Formed by beating the methyl derivative 
 of tri - bromo -p- oxy - phenyl - propionic acid 
 C,H3Br(0Me).CHBr.CHBr.C0jH with aqueous 
 KOH (30 p.c.). Plates. Gives an unstable 
 greenish-yellow compound with ammoniaoal 
 CuClj (Eigel, B. 20, 2538). 
 
 DI-BROMO-DI-OXY-DI-PHEinri-AMINE 
 CeH,(OH).NH.CeH2Br2.0H [4:6:2:1]. Leuco-di- 
 hromo-quinone-pheiwl-imide. [170°]. Colour- 
 less prisms. V. sol. all ordinary solvents, except 
 water. Formed by reduction of di-bromo-quin- 
 one phenol-imide (Mohlau, B. 16, 2848). 
 
 a.$.eso-eso- TETRA - BROMO - o - OXY ■ ;8- 
 PHENYL-BTJTYRIC ACID. Methyl derivative 
 CjHjBrj(0Me).CHBr.CMeBr.C02H. [c. 200°]. 
 From (o) or (;8) methoxy-phenyl-crotonic acid 
 and bromine vapour (Perkin, C. J. 39, 434). 
 Crystalline powder (from chloroforml. 
 
 Tetra-bromo-di-oxy.di-plienyl-metliane 
 G.^TL^BTfi^ i.e. CHj(C,H2Br2.0H)j. [225°]. From 
 di-oxy-di-phenyl-methane and bromine-watar 
 
BROMO-OXY-PHENYL-PEOPIONIO ACID. 
 
 80S 
 
 In ethereal solution it forms an unstable crystal- 
 Une compound with hydrio bromide C,,H.Br50j 
 (Beck, B. 10, 1837). 
 
 BROMO-OXY-PHENYI,-METHYL-PYBAZOI.E 
 CjH5.N<^j;f_Qjjg ^. Bromo-phenyl-methyl- 
 
 pyrazolone. [o.l30°]. From oxy-phenyl-methyl- 
 pyrazole and Br in glacial acetic acid (Kuorr, 4. 
 238, 176). Sol. alkalis, and dilute acids ; insol. 
 water. SI. sol. ether, v. sol. glacial HOAc and 
 chloroform. In alcoholic solution it slowly 
 forms pyrazole-blue. FejCls forms pyrazole- 
 blue. 
 
 Di-bromo-oxy-plienyl-methyl-pyrazole 
 0,„H8N,0Br,i.«. PhN<^2=7lM^'''>- ^i-bromo- 
 phenyl-methyl-pyrazolone. [80°]. From oxy- 
 phenyl-methyl-pyrazole (Ipt.) and Br (2 pts.) in 
 acetic acid solution (Knorr, A. 238, 177). Sol. 
 alcohol, HOAe, ether, and CHCI3 ; insol. water, 
 alkalis, and acids. Kot attacked by Fe^Cls. 
 Eeduced by Sn and HCl or fuming HI to oxy- 
 phenyl-methyl-pyrazole. 
 
 BEOMO-OXY-PHENYL-METHYL-PYRIMID- 
 
 INE 0„H,H^rO i.e. OA.<^:^j°gJ)>CBr. 
 
 [260°]. Formed by bromination of oxy-phenyl- 
 methyl-pyrimidine. Glistening needles (Pinner, 
 B. 20, 2361). 
 
 BBOMO-o-OXY-PHENYL-PKOPIOLIC ACID. 
 
 Methyl derivative 
 C,H3(OMe)Br.C:C.C02H. [168°] (with decom- 
 position). From the methyl derivative of tri- 
 bromo-oxy-phenyl-propionic acid (c[.v.). Short 
 white needles (from benzene). 
 
 BEOMO - o - OXY - i8 - PHENYL - PROPIONIC 
 ACID CjH,BrOj i.e. CeH3Br(OH).CH2CH„CO,H. 
 Bromo-melilotic acid. [142°]. From its anhy- 
 dride by boUing with water. Bectangular tables 
 (from chloroform). Sol. alcohol, si. sol. water. 
 Changes on melting into its anhydride. 
 
 Anhydride CeH3Br<^(,jj^jj >CO.[106°]. 
 
 From melilotic anhydride and Br in CSj in the 
 cold (Fittig a. Hochstetter, A. 226, 361). Thick 
 prisms (from chloroform). Bromine is not taken 
 out by boiling alkalis. Sol. alcohol and chloro- 
 form, si. sol. OS2. Slowly converted by boiling 
 water into bromo-meUlotic acid. 
 
 a-Bramo-/3-oz7-0-phenTl-propionic acid 
 CeH5.CH(0H).CHBr.C02H. [122°]; [125°, an- 
 hydrous]. From a/3-di-bromo-;8-phenyl-propionic 
 acid by boiling with water (Glaser, A. 147, 84). 
 Thin laminaa (containing aq). Boiled with very 
 dilute NaoCOa it gives phenyl-acetic aldehyde : 
 Ph.CH(0H).CHBr.C02H = 
 Ph.CH. CH.COjH + HBr = 
 
 Ph.CH.CH(OH) + HBr = 
 I I 
 0.00 
 
 Ph.CH:CH.OH + 00^ + HBr = 
 Ph.CHj.CHO + CO2 + HBr. 
 The yield is 75 p.c. of the theoretical, but some 
 phenyl-glyceric acid is also formed : 
 Ph.CH.CH.C02H + HjO = 
 
 \o/ 
 
 Ph.CH(OH).CH(OH).COjH 
 (Erienmeyer, B. 13, 308). S a 1 1.— AgA'. 
 
 3;8-Bromo-o-oxy-o-plienyl-propionic acid 
 CHBr2.CPh(OH).C02H. Di - bromo - atrolactit 
 acid. [167°]. Prepared by dissolving di-bromo- 
 pyruvio acid and benzene in cold H^SO,. Long 
 needles or four-sided tables. Sol. benzene and 
 CS2, si. sol. cold water. By boiling with water 
 it decomposes into CO2, HBr, and m-brom- 
 acetophenone (CBHs.GO.CHjBr). On reduction- 
 it gives atrolactic acid (Bottinger, B. 14, 1235). 
 Bromo-di-oxy-phenyl-propionic acid 
 Methylene ether OijHjBrO, or 
 
 CH2 <^>CaH2Br.CH2.CH2.C02H. Bromo- 
 
 pipero-jpropionic acid. [140°]. From sodiunr 
 bromo-(;8)-hydro-piperate and KMnO, (Wein- 
 stein, A. 227, 44). Monoclinic crystals (from, 
 ether) sol. alcohol, si. sol. water. — CaA'j. 
 
 Di-bromo-o-oxy-pheuyl-propionic acid 
 CjHjBrjOj. Di-bromo-melilotic acid. [115°]. 
 From melilotic acid and Br (Zwenger, A. Suppl. 
 5, 116). Needles; may be distilled. — BaA'^Sa^ 
 
 o-;3-Di-bromo-o-oxy-phenyl-propionic acid. 
 
 Di-bromide of coumaric acid. 
 
 Methyl derivative 
 OeHj(OMe).CHBr.CHBr.C02H. [162°]. 
 S. (CHCI3) 2-7 at 17°. From the methyl deriva- 
 tive of coumaric acid CsH4(0Me)CH:CH.002H 
 and Br. V. sol. ether. Decomposed by aqueous 
 alkalis. With bromine vapour it gives rise ta 
 C,HjBr2(0Me)CHBr.CHBr.C0,H [c. 202°]. Crys- 
 tals (from benzene) (Perkin, C. J. 39, 420 p 
 Fittig a. Ebert, A. 216, 157). Strong potash 
 (1:1) forms 0„H,(0Me)C2HBr.C02H [171°]. 
 
 Di-methyl ether 
 C,H,(0Me)CHBr.CHBr.C02Me. 
 
 (a) -compound [125°]. S. (CS^) 3-4. 
 (18). compound [68°]. S. (CS^) -4. 
 These two compounds are formed together by 
 acting on the isomeric methoxy-phenyl-acrylates 
 of methyl with bromine in CS2. But the (a), 
 isomeride gives chiefly that melting at 125*^ 
 while the (j8) -isomeride forms chiefly the other 
 (Perkin, G. J. 89, 424). Alcoholic potash con- 
 verts both into methoxy-phenyl-bromo-acrylios 
 acid. 
 
 Ethyl derivative 
 C5H,(0Et).0HBr.CHBr.C02H. [155°]. S. (CS^)" 
 1-03 at 18°. From the ethyl derivatives of 
 coumaric and of coumarinic acids by Br (F. a. E.).. 
 Small crystals (from CSj^ 
 
 Di-ethyl ether 
 CeHj(0Et)CHBr.CHBr.C02Et. [78°]. Prom. 
 CeH,(0Et)CH:CH.C02Et and Br in CS^ (P.). 
 
 eso-Di-bromo-p-oxy-3-phenyl-propionic acid 
 H0.C5HjBr2.CHj.CIL,.C02H. Di-bromo-hydro- 
 p-coumaric acid. [108°]. From aqueous hydro- 
 5)-coumario acid and cold bromine-water (Stohr,, 
 A. 225, 64). Needles (from acetic acid). 
 
 Salts.-(NHj2C,H„BrA.-Ag2C3H,Br20,. 
 
 0,8-Di-bromo-p-oxy-phenyl-propionic acid 
 C5Hj(0H).CHBr.CHBr.C02H. p ■ CoiLinaric- 
 acid-di-bromide. 
 
 Methyl derivative 
 C,H,(OMe).CHBr.CHBr.COjH : [149°] ; colour- 
 less crystals. Formed by combination of the- 
 methyl derivative of p-coumaric acid with Br. 
 
 Di-methyl ether 
 C5H,(0Me).CHBr.CHBr.C02Me : [118°] ; m. 
 sol. ether and chloroform. Formed by com- 
 bination of the di-methyl ether of ^'-coumaric 
 acid with bromine. When boiled with aqueousi 
 
«04 
 
 BROMO-OXY-PHENYL-PEOPIONIO AOID. 
 
 potash solution (30 p.c.) it i3 converted into 
 the methyl derivative of m-bromo-^-viuyl-pheuo 
 <:!,H^(OMe).CH:CHBr (Valentini, (?. 16, 424 
 Eigel, B. 20, 2536). 
 
 Di - bromo - di- eso-oxy-aa-di-phenyl-propionic 
 acid CisHj^Br^Oj. Di-bromo-di-phenopropionic 
 acid. Formed by bromination of di-pheno-pro- 
 (pionio acid CH3.C(CsHjOH)2.C02H. Amorphous 
 povfder. Sol. alcohol, insol. water. 
 
 Di. acetyl derivative C,5H,|,Br2(OAo)202; 
 insoluble light yellow powder (Bottinger, B. 16, 
 ■2073). 
 
 Tri-bromo-^-oxy -phenyl-propionic acid 
 C,H3Br(OH).CHBr.CHBr.C02H. Bramo - p- 
 
 ■coumaric-acid-di-bromide. [188°]. Obtained 
 by the action of bromine upon p-ooumario 
 acid. Needles. By alcoholic KOH it is con- 
 verted into tri - bromo - oxy - ethyl - benzene 
 'C„H3Br(OH).CHBr.CH2Br. 
 
 Methyl derivative 
 'C„H3Br(0Me).CHBr.CHBr.C02H : [162°] ; 
 needles. Formed by the action of bromine 
 upon the methyl derivative of p-ooumaric acid 
 ■C„Hj(0Me).CH:CH.C02H. By heating with 
 aqueous KOH (30 p.c.) it is converted into bromo- 
 methoxy- phenyl -acetylene C|jH3Br(0Me).C:CH 
 <Eigel, B. 20, 2534). 
 
 o-a-;8-tri-bromo-o-oxy-phenyl-propionio acid 
 
 Methyl derivative 
 *„H3Br(0Me)CHBr.CHBr.C02H. [185°-188°]. S. 
 {chloroform) -42. From methyl-o-coumario acid 
 -and bromine vapour (Perkin, O. J. 39, 417). 
 White nodules (from benzene). 
 
 Boiled with sodium acetate it gives off COj 
 forming the methyl derivative of o-eso-dibromo- 
 o-vinyl-phenol, CjH3Br(OMe)C2H2Br, a viscid 
 oil. Strong KOH (1:1) gives the methyl deriva- 
 tive of bromo-oxy-phenyl-propiolic acid (q.v.). 
 
 Tetra-bromo-o-oxy-phenyl-propionic acid 
 
 Methyl derivative 
 <!sH2Br2(0Me).CHBr.CHBr.C02H. [202°]. From 
 the preceding and Br (P.). 
 
 DI - BEOMO - DI - OXY - DI - PHENYL SUL- 
 PHIDE. S(CeH3Br.OH)2. [173°]. From p- 
 tromo-phenol and SCl^ in CSj (Tassinari, (?. 17, 
 91). Amorphous, reduced by zinc-dust to 
 •S(C,H,OH),. [128°]. 
 
 DI - BROMO - DI - OXY - DI - PHENYL - SUL - 
 PHONE. JDi-methyl derivative 
 S02(OeH3(OMe)Br),. [166°]. From SO,(C,Hj.OMe)j 
 .and Br. Small plates, v. sol. boiling alcohol 
 (Annaheim, A. 172, 48). 
 
 Di-ethyl-derivative S02(CoH3(OEt)Br)2. 
 {183°]. 
 
 Di-isoamyl derivative 
 .-S02(C„H3(OC,H„)Br),. [100°]. 
 
 Tetra-bromo-di-oxy-di-phenyl sulphone 
 .S02(CBH2Br2.0H)2. [279°]. From di-oxy-di- 
 jphenyl-sulphone and Br. Thick monoclinio 
 prisms (from alcohol). 
 
 TETRA - BROMO - OXY - PHENYL-VALEEIC 
 ACID. Methyl derivative 
 'C5H2Br2(OMe)CHBr.CEtBr.C02H. [159°]. From 
 (a) and (;8) methoxy-phenyl-angelic acids and 
 bromine vapour. Crystallised from light petro- 
 leum (Perkin, 0. J. 39, 437). 
 
 Di-bromo-di-oxy-phenyl-valeric acid 
 
 Methylene derivative CijHijBrjO, i.e. 
 
 •CHj<;Q>CsH3.C4H5Br2.COjH. Bi-hromo-pvper- 
 ^ydrmii.'. acid. [136°-140°]. From (a)-hydro- 
 
 piperio acid and Br (Fittig a. Mielck, A. 172, 159 ■, 
 Weinstein, A. 227, 33). Warm NaOHAq givea 
 piperio acid. Sodium-amalgam gives hydro- 
 piperio acid. 
 
 Tetra-bromo-di-oxy-phenyl-valeric acid 
 
 Methylene derivative 
 
 CHj<^>0eH3.CHBr.0HBr.CHBr.CHBr.C0,H. 
 
 Tetra-brcnno-piperhydronic acid. [160°-165°]. 
 From piperic acid and Br (F. a. M.). Alkalis 
 give HBr and piperonal CHjOj.CjHj.CHO. Boil- 
 ing water produces HBr and 'di-bromo-piper- 
 inide ' O^JlaBrfit [136°] ; this body crystallises 
 from alcohol in prisms, insol. water and alkalis, 
 converted into piperonal by boiling aqueous 
 Na^COs. Further treatment with water con- 
 verts di-bromo-piperinide into bromo-oxy-piper- 
 inide OjjHjBrOs [132°], which separates from 
 alcohol in monoclinio crystals, insol. aqueous 
 Na2C03. 
 
 BEOMO-DI-OXY-PHTHALIDE. Di-m ethyl- 
 derivative CjoHgBrOj i.e. 
 
 0,H3Br(0Me)2<^£^>0 [a!:6:5:f]. 
 
 Bromo-pseudo-meconine. [142°]. White flooou- 
 lent solid (Salomon, B. 20, 887). 
 
 BEOMO-OXY-PIPERINIDE v. Tetra-beomo- 
 
 DI-OXT-PHENTL-VALEEIC ACID. 
 
 a-BR0M0-|8-0XY-PR0PI0NIC ACID 
 
 C3H,BrOs i.e. CH2(OH).CHBr.C02H. Bromo- 
 hydracrylic acid. Formed by warming silver 
 a;8-di-bromo-propionate with water (Becturts a. 
 Otto, B. 18, 286). Syrup ; converted by moist 
 AgjO into glyceric acid. Salt. — ZnA'^. 
 
 ;8-Bromo-a-oxy-propiouic acid 
 CH2Br.OH(OH).C02H. $-Bromo-lactic acid. 
 [90°]. From oxy-acrylic acid and HBr (Melikoff, 
 B. 13, 958). Prisms (from ether) ; miscible 
 with water. 
 
 Di-ethyl ether CH2Br.CH(OEt).C02Et. 
 From CHjBr.CHBr.COjEt and NaOBt (Michael, 
 J.pr. [2] 35,136). 
 
 a;3-Di-bromo-a-oxy-propionic acid 
 CH2Br.0Br(OH).CO2H. Di-bromo-lactic acid. 
 [98°]. From acrolein dibromide and cold dilute 
 HNOj (Linnemann a. Peni, B. 8, 1101). 
 
 ;3i3-Di-bromo-a-ozy-piopionic acid 
 CHBr2.CH(OH).C02H. Di-bromo-lactic acid. 
 From the nitrile and HClAq. Syrup. 
 
 Nitrite CHBr2.CH(0H).CN. From di- 
 bromo-aldehyde and HON. Oil (Pinner, A. 
 179,71; B. 7, 1501). 
 
 ;8;8;3-Tri-bromo-oxy-propionic acid 
 CBr3.CH(OH).C02H. Tri-bromo-laciic acid. 
 [143°]. From bromal, HON, and HCl (Pinner, 
 B. 7, 1501 ; WaUach, A. 193, 50). 
 
 Ethyl ether EtA' [46°] ; prisms. 
 
 Nitrile CBr3.CH(0H).CN. From bromal 
 hydrate and cone. HCNAq. Prisms, v. sol. water, 
 
 Tri-bromo-ethylidene ether v. Bbo- 
 
 MALIDE. 
 
 Tri-chloro-ethylidene ether 
 CC],.CH(C3HBr303)j. [184°]. Formed by heating 
 tho acid with chloral. 
 
 DI-BROMO-DI-OXY-PEOPYL-BENZENE v. 
 Bromo-kugenol. 
 
 Di-bromo-tri-oxy-propyl-benzene. Di-bromo- 
 propyl-pyrogallol. 
 
 Di-methyl derivative C„H,4BrjOs t.«. 
 C,(C3H,)Brj(0H)(0Me)2. [109°]. Acetyl deri- 
 vatlve Cs{C,H,)Brj(OAc){OMe)j [102°]. 
 
BROMO-OXY-VALERIO ACID. 
 
 6U5 
 
 Methyl di-aeetyl derivative 
 C«(CaH,)Br2(OAo)2(OMe). [79°]. These com- 
 pounds are formed by brominating the corre- 
 sponding derivatives of tri-oxy-propyl-benzene 
 (Hofmann, B. 11, 331; Brezina, M. 4, 492; 
 Pastrovich, M. 4, 185). 
 
 DI-BEOMO-DI-OXY-DI - PROPYL - MALONIC 
 ACID (CH^r.CH(0H).CHJ,C(C0,H)2. 
 
 Di-lactone 
 OBtBr.CH.CHj,. XHj.OH.CH^Br. 
 
 O.CO ^ \co .0 
 
 [130°]. 
 
 From di-allyl-malonio acid in glacial HOAc by 
 Br (Hjelt, B. 15, 625 ; A. 216, 61). The tetra- 
 bromide (CH2Br.CHBr.CH2)jC(G02H)j is first 
 formed, but splits off 2HBr. Small plates (from 
 alcohol). Insol. cold water, si. sol. boiling 
 water, v. sol. warm alcohol, si. sol. ether. 
 When boiled with baryta it ought to form 
 Ba(C02)jC{CHjj.CH(0H).CH20H)j but this sphts 
 ofi BaCOj forming the lactonic acid : 
 
 ch;jOh.ch.ch2v 
 
 I >CH.CH2.CH(0H).CH.,0H. 
 
 o-cq/ 
 
 DI-BEOMO-OXY-PYRIDINE C.HjBr.NO i.e. 
 C5H2Br2(OH)N. Prepared by heating piperidine 
 with Br and water to 200° (Hofmann, B. 12, 984). 
 Glistening scales. SI. sol. water, ether, and 
 alcohol. Sol. aqueous acids and alkalis. — 
 (B'HCl)2PtCl, : long needles.— OsKjAgBrjON: 
 white pp. 
 
 Methyl derivative: [193°]; longneedles. 
 
 Di - bromo - oxy - pyridine C5HjBrj(0H)N. 
 [207°]. Long white needles. Formed by add- 
 ing bromine- water to a solution of oxy-pyridine 
 [107°] (Konigs a. Geigy, B. 17, 591). 
 
 Di-bromo-oxy-pyridine C5H2Br2(OH)N. 
 
 [o. 200°]. Formed by the action of bromine- 
 water upon (j3)-oxy-pyridine [125°]. Colourless 
 needles. V. sol. water and alcohol, nearly insol. 
 benzene. Fe^Clj gives a violet colouration. 
 
 Salts. — BTDBr: small white silky needles. 
 B'jH^SO/ : easUy soluble plates.— B'^HjC^O/ : 
 needles si. sol. alcohol. The picrate forms yel- 
 low needles (Fischer a. Benouf, B. 17, 1898). 
 
 BEOMO - OXY - PYRIDINE - CAEBOXYLIC 
 ACID C5HjN(Br) (OHjCOjH [l:a;:2:5]. Bromo-oxy- 
 rdcotimc acid. [296°]. Obtained by saponifica- 
 tion of the methyl-ether, which is formed by the 
 action of aqueous NHj upon the methyl-ether of 
 bromo-cumalio acid. SI. sol. hot water, nearly 
 insol. ether, idcohol, and acetic acid. 
 
 Methyl ether C5HjN(Br)(OH)C02Me. 
 [222°]. Slender glistening needles. Sol. hot 
 water and hot alcohol. 
 
 Phenyl derivative of the methyl-ether 
 C5H2N(Br)(0Ph)C02Me. [183°]. Formed by the 
 action of aniline on the methyl-ether of cumalio 
 acid in alcoholic solution. Distils without de- 
 composition ; white glistening needles, sol. al- 
 cohol and ether, insol. water (Pechmann a. 
 Welsh, B. 17, 2398). 
 
 DI-BEOMO-OXY-ftUINOLINE 
 C,H4Brj(0H)N. [195°]. Prepared by the action 
 of bromine-water on a solution of oxy-qumohne 
 (Bedall a. Fischer, B. 14, 1367). Wh.te silky 
 needles. Sol. alcohol, ether, benzene, CS^, ;n3ol. 
 water, ligroin, and dilute acids. 
 
 V. also Bbomo-oabbostybii. 
 
 BEOMO- (B.4)-0XY-aiIIN0LINE TETEA- 
 EYDEIDE. Ethyl ether C,H8Br2(OEt)N. 
 
 [43°]. Obtained by adding bromine to a coolej 
 chloroform solution of {B. 4)-ethoxy-t5tra-hydru- 
 quinoline. Long triclinic crystals. The hydro- 
 chloride crystallises in felted needles, the sul- 
 phate in colourless plates, and the oxalate in 
 prisms. The picrate forms sparingly soluble 
 yellow needles [108°]. The nitrosamine forms 
 glistening plates [86°] (Fischer a. Benouf, B, 
 17, 760). 
 
 DI-p-BEOMO-DI-OXY-ftTJINONE 
 CsBr2(0H)202 [1:4:2:5:3:6]. Bromanilic acid. 
 
 Formation. — 1. By dissolving di-, tri-, or 
 tetra-bromo-quinone in potash (Stenhouse, A. 
 91, 311; Sarauw, A. 209, 115).— 2. By heating 
 the sodium salt of di-oxy-quinone-di-^-carbo- 
 xylic acid with cono. HBr. — 3. Together with 
 tetra-bromo-quinone by heating (l,3,5,2)-tri- 
 bromo-phenol with pyrosulphurio acid at 115° ; 
 the reaction is anomalous as the two Br should 
 remain m to one another (Salzmanu, B. 20, 
 1997), V. also Di-ohiobo-di-oxy-quinonb. 
 
 Properties. — Monosymmetrical dark-red 
 needles or bronzy plates. Converted by Br into 
 hexa-bromo-acetone. A neutral solution of the 
 Na salt gives the following reactions : — CaOlj : 
 brown pp. — BaClj : yellowish-brown pp. — FeSO, 
 and NiSOj: greenish-grey pp. — Fe^Olj: brown- 
 ish-black.— Co(NOs)j: brown.— Pb(0Ac)2 : red- 
 dish-brown. — CuSOj : greenish-brown. — AgNO, 
 and Hg2(N03)2 : red. — HgClj : no pp. 
 
 Salts. — Na2A"4aq: asymmetric crystals. — 
 KjA" 2aq : asymmetric crystals. — KjA" acj 
 (Hantzsch, B. 20, 1303; Hantzsch a. Sehniter, 
 B. 20, 2040, 2279). 
 
 Di-bromo-di-ozy-qxiinone: Di-methyl de- 
 rivative CeBr2(OMe)202. [175°] (Hofmann,.B. 
 11, 332). 
 
 Tri-bromo-oxy-quinone Ce(0H)Brs02. [207°]. 
 From oxy - hydroquinone and Br (Barth a. 
 Schreder, M. 5, 593). Orange grains ; sol. a.lco- 
 hol and CHCI3. 
 
 DI-BEOMO-OXY-TOLUIC ACID. Methyl 
 ether CsHBr2Me(0Me).C0»H [?:?:4:2:1]. [194°]. 
 From the methyl derivative of di-bromo-thymol 
 by oxidation (Patern6 a. Canzoneri, Q. 10, 238). 
 
 DI-BEOmO-OXY-TOLUQTTmONE 
 CeMeBrj(0H)02. [197°]. Formed in small 
 quantity by the action of dilute EOH on tri- 
 bromo-toluquinone (Spica a. Magnanimi, O. 13, 
 312). 
 
 BEOMO - OXY - TOLYL- PHENYL - KETONE - 
 CAEBOXYLIC ACID 
 
 C,H,(C0:^).C0.C,H2(CHJ(Br)0H. [228°]. Pre- 
 pared by the action of Br and acetic acid on an 
 alcoholic solution of o-cresol-phthalein. Small 
 prisms. By heating with HjSO, to 130° it is 
 readily converted into bromo-oxy-methyl-anthra- 
 quinoue. 0/iZoride [208°] (Fraude, .B.12,239). 
 DI - /3 - BROMO-a-OXY-o-TOLYL-PEOPIONIC 
 ACID CioHioBr^Oji-e. CHBr2.C(C,H,)(OH).C02H. 
 Di- bromo -eso- methyl -atrolactic acid. [163°]. 
 Prisms or needles. Prepared by dissolving 
 di-bromo-pyruvic acid and toluene in HjSO^at 0°. 
 By hot water it is decomposed into COj and 
 tolyl bromo-methyl ketone C,H,.CO.CHjBr. On 
 reduction it gives eso-methyl-atrolactio acid 
 (Bottinger, B. 14, 1597). 
 
 BEOMO-OXY-VAIEEIC ACID. Lactone. 
 CH,.CH.CHBr.CH2.C0.0. From ;8y-di-bromo. 
 
 valeric acid by boiling with water (Messer- 
 
606 
 
 BROMO-OXY-VALERIO ACID. 
 
 Schmidt, A. 208, 102). Non-volatile oil ; con- 
 verted by boiling baryta-water into di-oxy- 
 valeric acid. 
 
 Di-bromo-oxy-valeric acid. 
 
 Lactone CHjBr.CBr.CHa.CHj.CO.O or 
 
 I I 
 
 CH3.CBr.CHBr.CH2.CO.O. [78°-81°]. From 
 
 <a)-angelico-laotone and bromine. Thick white 
 hygroscopic needles (from CS^). Water con- 
 verts it into HBr and bromo-levulic acid (Wolff, 
 A. 229, 264). 
 
 DI-BEOMO-PALMITIC ACID C.sHjnBrjOa. 
 [29°]. From hypogseio acid and Br (Schroder, 
 A. 143, 24). Amorphous and insol. water. 
 Alcoholic KOH converts it into bromo-hypogseio 
 and pahnitolic acids. Aqueous alkalis form di- 
 oxy-palmitic acid. 
 
 Di-bromo-palmitic acid G^^^firfip Prom 
 fiaiolic acid and Br. Crystalline ; converted by 
 alcoholic KOH into palmitolio acid (S.). 
 
 Tri-bromo-palmitio acid CisHjaBrsOj. [39°]. 
 From bromo-hypogseio acid and Br. Amor- 
 phous (S.). 
 
 Tetra-bromo-palmitic acid. Ci^^ifl^. 
 Yellow crystals. 
 
 BEOMO-PAIMITOLIC ACID C.eH^iBrOj. 
 [31°]. From tri-bromo-palmitic acid (v. sup.) 
 and alcoholic KOH (S.). 
 
 BEOMO-PENTANE v. Airaii bkomide. 
 
 a;3-Di-bromo-pentane CsHnjBrj i.e. 
 CH3.CH2.CHBr.CHBr.CH3. Aviylene bromide. 
 (178°). S.G.V*1'6868. From the corresponding 
 amylene and Br (Wagner a. Saytzeff, A. 179, 
 307). 
 
 aiM-Di-bromo-isopentane Pr.CHj.CHBrj. 
 
 Isoamylidene bromide. (170°-180°). From iso- 
 valeric aldehyde and PCljErj (Bruylants, B. 8, 
 406). AlcohoUc KOH gives PrCH:CHBr (111°) 
 andPr.C-CH. 
 
 aa-Di-bromo-pentane Pr.CBrj.CHj. From 
 methyl propyl ketone and PCljBrj (B.). Split up 
 by distillation into HBr and Pr.CBr:CH2 (123°). 
 
 a/3-Di-bromo-iBopentane 
 (CH3)2.CBr.CHBr.CH3. (170°-175°). S.G. ^5- 
 1-6870. M.M. 12-947 at 12-6°. From tri- 
 methyl-ethylene and Br (Wurtz, A. Ch. [3] 35, 
 458; Bauer, Bl. 2, 149). Converted by water 
 (20 vols.) and PbO at 150° into methyl iso- 
 propyl ketone (Eltekoff, J. B. 10, 215). 
 
 Isoamylene dibromide, formed by combina- 
 tion of Br with isoamylene from crude fusel oil, 
 is a mixture of several of the preceding di- 
 bromo-pentanes (Cahours, C iJ. 31, 291 ; Wurtz, 
 A. Ch. [3] 4, 458 ; A. 123, 202 ; Beboul, O. B. 
 58, 1058 ; A. 133, 84 ; Bauer, Bl. 1860, 148 ; 
 A. 120, 167 ; Z. 1861, 590 ; Golowkinsky, A. 
 Ill, 252 ; Olevinsky, Z. 1861, 674). 
 
 Valerylene dihydrobromide (170°-175°), 
 formed by the union of HBr with crude valeryl- 
 ene is also a mixture of di-bromo-pentanes. 
 
 Tri-bromo-pentane CsHgBrj. From bromo- 
 isoamylene and Br. 
 
 Tetra-bromo-pentane C^'H.g'Br^. Valerylene 
 tetrabromide. [ — 10°]. From crude valerylene 
 and Br (Eeboul, A. 132, 119 ; 135, 372). 
 
 Tetra-bromo-pentane C^B.fir,. Pvperylene 
 tetrabromide. [115°]. From piperylene and 
 Br (Hofmaim, B. 14, 664). A liquid isomeride 
 is also formed (Magnanimi, G. 16, 390). 
 
 Tetra-bromo-pentane CjHsBrj. Isoprene 
 tetra-bromide. From isoprene (Tildeu, G. N. 
 46, 120). 
 
 Penta-bromo-pentaae CjHjBr^. Two bodies 
 of this composition are formed by the action of 
 Br on valerylene in sunlight (B.). 
 
 BEOMO - PENTENYL ALCOHOL Ethyl 
 ether C,H,3BrO i.e. C^HsBr.OEt. (177°-180°). 
 S.G. i2 1-23. From tri-bromo-pentane and alco- 
 holic KOH (Beboul,^. 133, 84). 
 
 BEOMO-PEMTINENE v. Beomo-vaiekylene. 
 
 BEOMO-PHENANTHEAQTJINONE v. Phen- 
 
 ANTHRAQUINONE. 
 
 BEOMO -PHENANTHRENE v. Phbnan- 
 
 THEENE. 
 
 BROMO-DI-PHENIC ACID 
 
 C0,H.CsH4.C5H3Br.C02H. [236° uncor.]. Formed, 
 together with its di-bromide, by heating diphe- 
 nic acid with bromine at 80°-100°. Small 
 white prisms. Sublimes with difficulty. Not 
 volatile with steam. V. sol. alcohol, ether, and 
 acetic acid, si. sol. benzene, chloroform and CS^, 
 insol. cold water. 
 
 Salts. — A"Na2: white v. sol. amorphous 
 powder. — A"Ba3aq: sparingly soluble needles. — 
 A"Ag2: white insol. pp. — A"Cu: si. sol. amor- 
 phous green powder. 
 
 Di-ethyl ether A''Et2: [65°]; crystals 
 (Glaus a. Erler, B. 19, 3149). 
 
 Bromo-di-phenic-acid-di-bromide 
 C,2H,Br3(C02H)2. [256° uncor.]. Formed in 
 small quantity (15 p.c.) by heating diphenio acid 
 (1 mol.) with bromine (2 mols.) for 8 days at 
 100°. Glistening colourless needles (from hot 
 alcohol). SI. sol. ordinary solvents. Its alka- 
 line solution decomposes very easily on heating, 
 forming salts of di-bromo-di-phenic acid. It 
 has a very bitter peculiar taste. — A"Na : soluble 
 silky plates (Glaus a. Edler, B. 19, 3152). 
 
 Bromo-di-phenic acid 
 [4:1] C3H,(C00H).CsH3Br.C00H [1:4:2]. [208°]. 
 Formed by oxidation of the liquid (1,4,1',4',2') 
 mono-bromo-ditolyl with CrOj and acetic acid 
 (Carnelley a. Thomson, 0. J. 47, 590). 
 
 Di-bromo-di-phenic acid O^fLfivfi^. [296°]. 
 From di-bromo-phenanthraquinone, K^CrjO-, and 
 H2SO4. Geodes of small crystals, v. si. sol. hot 
 water, insol. alcohol and ether (Ostermayer, B. 
 7, 1091). 
 
 Di-bromo-di-phenic acid C,2H5Br2(C02H)2. 
 [245° uncor.]. Formed by heating di-phenic 
 acid (1 mol.) with bromine (2 mols.) at 200°, or 
 by heating aqueous solutions of salts of mono- 
 bromo-di-phenic-aoid-di-bromide. Small glisten- 
 ing needles. Not volatile with steam. Sublimes 
 with difficulty. SI. sol. benzene, chloroform, 
 acetone, CSj, and hot water, nearly insol. cold 
 water, v. sol. alcohol, ether, and acetic acid. 
 
 Salts. — The alkaline salts are very soluble 
 amorphous glassy masses. — A"Ag2 : white 
 amorphous pp. — A"Ca Baq; easily soluble plates. 
 — A"Pb : si. sol. microorystalline powder. 
 
 Di-ethyl ether M'm,^: [106° uncor.] 
 crystals (Glaus a. Edler, B. 19, 3149). 
 
 o-BEO MO-PHENOL CsH^BrO i.e. G.H,Br(OH) 
 [1:2]. (195°). From o-bromo-aniline by tha 
 diazo- reaction (Fittig a. Mager, B. 8, 362 ; 
 Korner). Formed in small quantity in bromi- 
 nating phenol (Hiibner a. Brenken, B. 6, 171). 
 Oil; volatile with steam. Potash- fusion gives 
 
BEOMO-PHENOL. 
 
 607 
 
 re?oroia. HNO3 forms bromo-di-nitro- phenol 
 [118°]. 
 
 Methyl e<fc«r CjH^Br.OMe. (223°). From 
 the methyl ether of o-amido-phenol by Sand- 
 meyer's reaction (Wallaoh a. Hensler, A. 243, 
 238). 
 
 nt-Bromo-phenol CsH^BrlOH) [1:3]. [33°]. 
 (236°). From Jre-bromo-aniline by the diazo- 
 reaction (Korner, G. i, 389 ; Wurster a. Nolting, 
 B. 7, 905; F. a. M.j. Crystalline. Potash- 
 fusion gives resoroin. HNO3 gives bromo-di- 
 nitro-phenol [92°]. 
 
 ^-Bromo-phenol C8H,Br(0H) [1:4]. [64°]. 
 (237°). S.H. (18°-77°) -3157. S. 1-422 at 15°. 
 
 Formation. — 1. By distilling bromo-o-oxy- 
 benzoic acid with BaCOj (Cahonrs, A. Ch. [3] 
 13, 102). — 2. By passing air saturated with Br 
 (160 pts.) into cooled phenol (94 pts.) (K5mer, A. 
 137, 197).— 3. Bromine (l60g.) is dissolved in 
 glacial HO Ac (200 g.) and added to phenol (94 g.) 
 dissolved in HOAc (300 g.) (Hiibner a. Brenken, 
 B. 6, 171). — 4. From ^-bromo-aniUne by the 
 diazo- reaction (E. ; F. a. M.). 
 
 Properties. — Large crystals (from chloro- 
 form) ; si. sol. water, v. sol. alcohol. Dimetric ; 
 a •.0 = 1: 1-46. Its heat of neutralisation has 
 been determined by Werner (C. R. 98, 1333; 
 Bl. [2] 46, 281). Nitration gives bromo-di-nitro- 
 phenol [76°]. Potash-fusion gives resorcin. SCl^ 
 forms S(CsH3Br.OH)2 [176°] (Tassinari, Q. 17, 
 83). 
 
 Methyl ether CjHjBr.OMe. Bromo-anisol. 
 (223° cor.). S.G. s 1-494. 
 
 Ethyl ether C^H^Br.OEt. (233°). 
 
 IsQjgropyl ether C^;&Ti.OSv. (236°). S.G. 
 - 1-981. ftD 1-553. From isopropyl phenol and 
 Br (Silva, Bl. [2] 13, 27). 
 
 Benzoyl derivative CjH^Br.OBz. Crys- 
 talline. 
 
 Bromo-phenol (Fourth). (236°-238°) (Fittioa, 
 J. pr. [2] 28, 176 ; B. 19, 2632 ; A. Ch. [6] 4, 561). 
 
 Preparation. — Phenol (10 g.), alcohol (10 g.) 
 and amorphous phosphorus (3 g.) arp mixed and 
 cooled while bromine (17 g.) is added through a 
 capiUary tube. The product is washed with 
 dilute NajCOj, dried and distilled. It contains 
 di-bromo-phenol and the new body. This can 
 only be distilled when in small quantities, in 
 larger masses it undergoes carbonisation. 
 
 Properties. — Not solid at 10°. 
 
 Nitration. — Bromophenol (1 pt.), glacial 
 acetic acid (3 pts.), and HNO3 (S.G. 1-4) added 
 gradually form crystals of a molecular compound 
 C5H,Br(N0j)0H.C.HjBr(N0,),0H which crystal- 
 lises from alcohol and melts at [60°-65°]. 
 Fuming HNO, converts this into a bromo-di- 
 nitro-phenol [i08°-H0°], isomeric with those 
 known. By the action of baryta on the above 
 molecular compound a second such body 
 (CeH3Br(N02)OH)AH2Br(NO,)20H is got. 
 
 The existence of four bromo-phenols would 
 be contrary to the general rule that only three 
 isomeric di- derivatives of benzene can be ob- 
 tained; according to Hand {A. 234, 129) the 
 fourth bromo-phenol is merely ^-bromo-phenol 
 of which the melting-point is lowered by a trace 
 of moisture. 
 
 Di-bromo-phenol C,H,Br,(OH) [1:3:4]. [40°]. 
 S.H. (18°-73°) -2436. S. -194 at 15° (W.). 
 
 Formation.—!. By distilling di-bromo-sali- 
 eylJo acid with baryta (Cahours, A. 52, 329), or 
 
 by heating with dilute HjSO^ at 230° (Peratoner, 
 (?. 16. 402).— 2. By passing bromine-vapour (2 
 mols.) into cold phenol (1 mol.) (Korner, A. 137, 
 205). 
 
 Properties. — Crystalline mass, v. si. sol. 
 water, v. sol. ordinary solvents. HNO3 forms 
 picric acid. Its heat of neutralisation has been 
 determined by Werner (O. B. 98, 1333). Heated 
 with dilute H^SOj in sealed tubes, it is converted 
 into mono- and tri-bromo-phenol (Peratoner, 
 G. 16, 403). 
 
 Methyl ether CeH3Br2(0Me). [59°]. (272°). 
 From di - bromo - phenol, NaOH, and Mel. 
 Formed also by brominating anisol (C). 
 
 Nitro-henzoyl derivative 
 CsHjBr^O.CO.CsH^NOj. [90°-100°]. From ben- 
 zoyl-phenol by bromination followed by ni- 
 tration. 
 
 Di-bromo-phenol C5H3Brj(OH) [6:2:1]. [56°]. 
 Formed by distilling tetra-bromo-phenol-phtha- 
 leiin with cone. HjSOj (Baeyer, A. 202, 138). 
 Also from di-bromo-^^-amido-phenol by displacing 
 NHj by H (Mohlau, B. 15, 2494). Mass of thin 
 needles (from water). 
 
 Di - bromo - phenol C,H2Br2(OH) [1:3:5]. 
 [76-5°]. Formed, together with its methyl ether, 
 by heating s-tri-bromo-benzene with NaOMe 
 (Blau, M. 7, 621). Converted by potash-fusion 
 into phloroglucin. 
 
 Methyl ether C^^rJiSMe) : [38°]. 
 Ethyl ether C^^Br^iO'E^t). (268°). Formed 
 by boiling di-bromo-o-di-azo-phenetol nitrate, 
 CsHjBr„(0Et)NjN03, with water (Mohlau a. 
 Oehmichen, J.pr. 132, 482). 
 
 Tri - bromo - phenol CsH2Br3(0H) [2:4:6:1]. 
 [92°] (Wilsing, A. 215, 235) ; [95°] (Korner). S. 
 -007 at 15 (W.). 
 
 PormaUon. — 1. From i^henol and Br (Lau- 
 rent, A. Ch. [3] 3, 211 ; Korner, A. 137, 208).— 
 2. By distilling tri-bromo-salicylic acid with 
 sand and baryta (C). — 3. By treating indigo with 
 bromine-water. — 4. From potassium phenol di- 
 sulphonate and Br (Schmidt, B. 11, 852). 
 
 Properties. — Long silky needles (from dilute 
 alcohol) ; may be sublimed. V. si. sol. water, v. 
 sol. alcohol. Its heat of neutralisation has been 
 examined by Werner and Berthelot (0. B. 98, 
 1333; A. Ch. [6] 3, 552). 
 
 Beactions. — 1. Nitric acid forms di-bromo- 
 nitro-, bromo-di-nitro-, and_ tri -nitro- phenol 
 (Armstrong a. Harrow, C. J. 29, 476).— 2. CrOj 
 and HOAc give tetra-bromo-quinone and amor- 
 phous insoluble G^Jlfirfi2 (Benedikt, A. 199, 
 134).— 3. Bromine-water forms CaH^BrjOBr (?) 
 [118°] which forms yellow plates, insol. water, 
 ether, and alcohol ; it exhibits the following re- 
 actions : (a) At 130° it splits up into Br and the 
 compound Gf^fitfi^. (b) Aniline forms tri- 
 bromo-phenol and tri-bromo-aniline. (c) Phenol 
 forms tri-bromo-phenol. (d) It is also reduced 
 to tri-bromo-phenol by boiling alcohol or by Sn 
 and HCl (Benedikt, B. 12, 1005; M. 1, 360; 
 Werner, Bl. [2] 43, 373). 
 
 Ethyl ether C^H^Brs.OEt. [69°]; prisms 
 (Purgotti, G. 16, 526). 
 
 Propionyl derivative CjHjOjCjH^Br, 
 [65°] (Guaresohi a. Daccomo, B. 18, 1174). 
 
 Benzoyl derivative CjHjBrjOBz: [82°]; 
 small colourless prisms ; soluble in alcohol and 
 ether, nearly insol. water (Daccomo, B. 18, 1168). 
 
608 
 
 BROMO-PHENOL. 
 
 Tri-liTomo-plienol 
 
 Ethyl e«/ier CsHjEra-OEt. [73°]. Prepared 
 Irom tri-bromo-di-azo-plienetol by boiling with 
 water and extracting the product with ether 
 (Mohlau a. Oehmichen, J. pr. [2] 24, 484). 
 
 Tetra-bromo-phenol OsHBr^OH [2:3:4:6:1]. 
 [120°]. From tri-bromo-phenol and Br at 180° 
 (K.). Formed also by warming CsH^BraOBr (v. 
 sup.) with cone. HjSOj. Needles (from alcohol) ; 
 may be sublimed. Bromine converts it into 
 CjELBr^OBr [121°] which separates from chloro- 
 form in monoclinic crystals and is reduced by 
 boiling alcohol or by Sn and HOI to tetra-bromo- 
 phenol (Benedikt, M. 1, 361). 
 
 Penta-bromo-phenol CjBrj.OH. [225°]. Ob- 
 tained by heating tri- or tetra- bromo-phenol 
 with excess of Br at 220° for some days (Korner, 
 A. 137, 210). Formed also by heating CsHBr.OBr 
 with cone. H^SO^ (Benedikt, M. 1, 360). Adaman- 
 tine needles (from CS2) ; may be sublimed. 
 Cone. HNO3 forms bromopicrin and tetra-bromo- 
 quinone. PBrj forms OjBrj (Gessner, B. 9, 1505 ; 
 Buofl, B. 10, 1234). 
 
 Hexa-bromo-phenol O^BrjOBr. [128°]. Pre- 
 pared by heating tri-bromo-phenol with excess of 
 bromine in sealed tubes at 220°- Yellow crystals 
 of trimetrio system (a:6:c=l:*82:-114), insol. 
 cold alcohol, but decomposed by boiling into 
 penta-bromo-phenol. On heating with aniline 
 it yields penta-bromo-phenol and tri-bromo- 
 aniline (Benedikt, M. 1, 363). 
 
 TETBA-BBOUO-p-DIFHEirOL v. Teiiia- 
 
 BKOMO-DI-OXT-DIPHENYL. 
 
 TETBA-BBOMO-PHENOL-PHTHALEitN v. 
 
 Phenol-phthalexn. 
 
 BEOMO-PHENOL o-STJLPHONIC ACID 
 
 C5H3Br(OH).SOsH. The K salt is formed by 
 adding Br (1 mol.) to an aqueous solution of 
 potassium phenol o-sulphonate. The free acid 
 is very deliquescent. — KA': pointed needles — 
 BaA'j.— CuA'j (Senhofer, A. 156, 114). 
 
 Bromo-phenol ^-sulphonic acid 
 CsH3Br(0H)(S0sH) [2:1:4]. Formed as in the 
 preceding case (S.), or by passing bromine- 
 vapour into a cold cone, solution of phenol p- 
 Bulphonio acid (Le Canu, C. B. 103, 385). Deli- 
 quescent needles (containing 2aq). — KA'. 
 
 Bromo-phenol sulphonic acid. 
 
 Ethyl derivative CeH3Br(OEt)(S03H). 
 From potassium phenetol sulphonate and Br 
 (Lippmann, J. 1870, 739). Deliquescent mass 
 (containing 4aq). — KA'. 
 
 Bromo-phenol disulphouic acid 
 CeH2Br(0H)(S03H)2 [2:1:4:6]. From an aqueous 
 solution of potassium phenol disulphonio acid 
 (1 mol.) by adding Br (1 mol.) (Armstrong, C. J. 
 25, 865 ; Schmidt, B. 11, 852). CrystaUine ; v. 
 Bol. alcohol, m. sol. ether. Fe^Clj gives a red 
 colour. HNO3 forms bromo-nitro-phenol sul- 
 phonic acid, bromo-di-nitro-phenol, and tri- 
 nitro - phenol. — BaA" 2aq. — K^A". — PbA". — 
 
 Bi-bromo-phenol o-snlphonic acid 
 CeHjBrj(0H)(S03H) [2:4:1:6]. [120°]. Formed 
 by brominating potassium phenol o-sulphonate 
 or bromo-phenol o-sulphonic acid (Armstrong, 
 C. J. 25, 867; Senhofer, 4. 156, 110; Schmidt, 
 B. 11, 855). Concentric needles ; deliquescent. 
 The aqueous solution is coloured violet by FCjClj 
 and is ppd. by Pb(0Ac)2. — HNO3 forms di- 
 bromo-o-nitro-phenol[117°]. Ba(C„H^raS04)j.— 
 
 BaCjHjBrjSOi. — CdOsH^Br^SO, IJaq. — 
 KCcHsBrjSO,.— K,C„H2BrjS0..— PbCjHjBrjSO,. 
 
 Si-bromo-pheuol ^-sulphonic acid 
 CeH2Brij(OH)(S03H) [2:6:1:4]. From potassium 
 phenol 5)-suiphonate (1 mol.) and Br (2 mols.) 
 (Senhofer, A. 156, 103 ; Armstrong a. Brown, 
 C. J. 25, 857) ; or by passing bromine-vapour 
 into an aqueous solution of phenol ^-sulphonio 
 acid (Le Canu, C. B. 103, 385). Formed also by 
 diazo- reaction from di-bromo-sulphanilic acid 
 (Sohmitt, A. 120, 161). Eectangular scales 
 (containing aq). The solution is coloured violet 
 by FcjCle but is not ppd. by Pb(0Ac)2.— 
 KCABr^SOjaq.— KjOsHjBrjSOi 2aq.— 
 
 Ba(C,H3Br2S0,)j 2aq.— BaC.H^BrjSO, 4aq. 
 
 BKOMO-PHENOXY-ACETIC ACID v. Brcmo- 
 phenyl derivative of Glyoollio acid. 
 
 BEOMO - PHENOXY - PKOPIOITIC ACID v. 
 Bromo-phenyl derivative of Lactic acid. 
 
 o-BEOMO-DIPHEHYI O.jHaBr i.e. 
 CsH5.0,H,Br [1:2]. (298°). Formed by decom- 
 posing o-diazo-diphenylperbromide with alcohol 
 (Schultz, Schmidt, a. Strasser, A. 207, 353). Oil, 
 smelling of oranges ; oxidised by CrOj to o-bromo- 
 benzoic acid. 
 
 p-Bromo-diphenyl OsHj.CeHjBr [1:4]. [89°] 
 (310° i. v.). Formed by adding Br to a solution 
 of diphenyl in CSj. Laminse ; v. sol. hot alcohol 
 and HOAc, v. e. sol. ether. Smells like oranges. 
 Chromic acid oxidises it to ^-bromo-benzoic acid 
 (Schultz, A. 174, 207). 
 
 jjjp-Di-bromo-diphenyl [4:1] CeHjBr.CjH^Br 
 [1:4]. [164°] (G.; F.) ; [162°] (0. a. T.). (c.358°). 
 Formed by heating diphenyl dissolved in CSj 
 with bromine at 100° (Fittig, A. 132, 204; 
 Carnelley a. Thomson, 0. /. 47, 588). Also from 
 benzidine by the diazo- reaction (Griess, Pr. 13, 
 383). Prisms and octahedra (C. a. T.) ; v. b1. 
 sol. hot alcohol, slightly volatile with steam. 
 Smells like oranges. Oxidised by CrO, to 
 2)-bromo-benzoic acid. 
 
 Tri - bromo - diphenyl [4:1] CBHjBr.CsH3Brj. 
 Formed by the action of bromine on a mixture 
 of diphenyl and 2)-tolyl-benzene (Carnelley a. 
 Thomson, C. J. 47, 587). Colourless sUky 
 needles, si. sol. alcohol, not volatile with steam. 
 CrOj in HOAc gives jp-bromo-beuzoio acid. 
 
 DI-BEOMO-DI-PHElfYL-ACETAMIDINE 
 C.^H.^Br^Nj i.e. CH3.C(NHCeH,Br):NCsH,Br. 
 From ^-bromo-anUine, HOAc, and PCI3 (Denn- 
 stedt, B. 13, 233).— E'ECL-B'^H^PtCls. 
 . o-BEOMO-PHENYL-ACETIC ACID CjHjBrO^ 
 i.e. [2:1] CjH4Br.CHjC02H. [104°]. From phe- 
 nyl-acetic acid, bromine and HgO. Separated 
 from the^J-compound by its more soluble barium 
 salt (Bedson, C. J. 37, 95). Flat needles (from 
 water). Monoclinic tablets (from glacial acetic 
 acid).— a:6:c = l: •657:1-767; = 99° 44'. KMnO, 
 oxidises it to o-bromo-benzoio acid. — CaA'.. — 
 
 Nitrile CjH^Br.CHj.CN. Oil (Jackson a. 
 White, Am. 2, 316). 
 
 m-Bromo-phenyl-acetic acid 
 [3:1] C„H,Br.CH,.C02H. [97°] (J. a. W.) ; [100°] 
 (G.). From (3, 4, 1)- bromo-amido-phenyl-acetio 
 acid by removing NHj (Gabriel, B. 15, 841). 
 
 Nitrile CsH^Br.CHj.CN. Oil (Jackson a. 
 White, P. Am. A. 16, 256). 
 
 ^-Bromo-phenyl-acetic acid 
 [4:1] C3H,Br.CH,.C0aH. [115°]. Prepared by 
 treating phenyl-acetic acid with bromine and 
 
BEOMO-PHENYL-BENZENE. 
 
 609 
 
 HgO (Bedson, G. J. 37, 94).— Long flat needles; 
 may be sublimed. Oxidation gives o-bromo- 
 benzoic acid. 
 
 Salts.— AgA'.-NH,A' — BaA',. — CaAV— 
 CnA'j. 
 
 Nitrile OeH4Br.CHj.CN. [47°]. Prepared 
 by boiling^-bromo-benzyl bromide with alooholio 
 KCN (Loring Jackson a. Lowery, B, 10, 1210 : 
 4m. 3, 248). 
 
 o-Bromo-phenyl-acetic acid OjH5.CHBr.CO2H. 
 [84°]. From mandeUo acid and oono. HBrAq at 
 130° (Glaser a. Eadziszewski, Z. 1868, 142). 
 Formed also by brominating phenyl-aoetio acid 
 at 160° (Eadziszewski, B. 2, 208). Monoolinio 
 crystals (from CS^). Beduced by sodium- 
 amalgam to phenyl-aoetio acid. Boiling NaOHAq 
 gives mandelio acid C8H5.CH(OH).C02H. 
 Alcoholic EOH gives 0eH5.0H(OEt).CO2H. The 
 ethyl ether is converted by alooholio KCy into 
 C0jEt.CHPh.CHPh.C0^t, and by Na into 
 C0jEt.0Ph:CPh.00jEt. 
 
 Nitrile OsH5.CHBr.GN. Is the chief pro- 
 duct of the action of bromine on benzyl cyanide 
 at 120°. Sol. alcohol and ether. On heating to 
 170° or with alcoholic KCN it gives di-oyauo- 
 stilbene. With an excess of KCN di-cyano-di- 
 benzyl is also formed. On boiling with alcoholic 
 KOHit gives stilbene-di-carboxylic acid (Beimer, 
 B. 14, 1797). 
 
 Hydrobromide of the Nitrile 
 CgHs.CHBr.CBrrNH. Phenyl-bromo-acetimido- 
 hromide. Formed together with the nitrile by 
 the action of bromine on benzyl cyanide at 120° ; 
 the yield being 15 p.o. Colourless crystals. 
 Bitter taste. Its vapour attacks the eyes. Y. si. 
 sol. all solvents, most easily in boiling acetic 
 acid. Decomposed by water and alcohol. — 
 HCl at 150° converts it into o-bromo-phenyl- 
 acetio acid (?) and NH3. Dilute HCl at 150° 
 converts it into NHj, mandelio acid 
 (C8H5.CH(0H).C02H), and HBr (Eeimer, B. 14, 
 1797). 
 
 a-Bromo-di-phenyl-acetic acid 
 (OeH5)20Br.C02H. From diphenyl-acetio acid 
 and Br at 150°. Converted by boiling water 
 into benzilic acid CPh2(0H).C0jH (Symons a. 
 Zincke ^. 171, 131). 
 
 Si-bromo-phenyl-acetic acid 
 C8HjBrs.CHj.OO2H. [115°]. Formed by action 
 of sunUght on mixture of 0- and^- bromo-phenyl- 
 acetic acids and Br. Purified by conversion into 
 the methyl ether, distillation and saponification 
 (Bedson, O. J. 37, 96). White needles.— AgA'. 
 
 BEOMO-PHENTL-ACEYLIC ACID v. Bbomo- 
 oiNNAMio ACID and Bbomo-atropio acid. 
 
 DI - BROMO - DI - PHENYL - AILOPHANIC 
 ACID OnH.oNjBrjOa i.e. 
 0,H4Br.NH.CO.N(C3H4Br).COsH. 
 
 Ethyl ether. [153°]. The confpound which 
 is formed from ^-bromophenyldicyanate by long 
 boiling with alcohol is probably this ether. Fine 
 white needles. Sol. alcohol and ether. By 
 continued action of alcohol it is converted into 
 y-bromo-phenyl-oarbamio ether (Dennstedt, B. 
 13, 229). 
 
 ^-BEOMO-PHENTL-AMIDO-ACETIC ACID 
 CH2(NH.C5H4Br).C02H. Bromo -phenyl - glyco- 
 coll. [98°]. Colourless crystals. V. e. sol. al- 
 cohol, ether and hot water. Forms a Hght- 
 green copper salt. Prepared by the action of 
 ohiaro-acetic acid on^-ohloroaniline. 
 
 Toi. I. 
 
 Ethyl ether ATEt: [96°]; white needles, 
 Insol. water, sol. alcohol and ether. 
 
 p-Bromoanilide 
 CH2(NH.O„H4Br).OONH(0„H,Br) : [155°-160°] ; 
 white microscopic crystals. Sublimes at about 
 145°. SI. sol. hot water, t. sol. alcohol and 
 ether (Dennstedt, B. 13, 236). 
 
 Di-bromo-di-phenyl-amido-acetio acid. 
 Nitrile OjHjBrjNH.CHPh.CN. [92°]. From 
 di-phenyl-amido-acetic acid and Br (Tiemann a. 
 Piebst, B. 15, 2032). YeUow rhombohedra (from 
 alcohol). 
 
 Tri-bromo-phenyl-amido-acetlc acid 
 CjH2Brj.NH.CH2.CO2H. Formed by adding bro- 
 mine-water to an aqueous solution of phenyl- 
 amido-acetic acid. Minute needles (from HOAo). 
 Insol. water, acids and alkalis (Schwebel, B. XX, 
 1131). 
 
 BBOMO-PHENYL-AMIDO - CHLOBO - NAPH- 
 THOQUINONE v. Chlobo - naphthoquinonb - 
 
 BBOUANILIDE. 
 
 a . BROMO - PHENYL - & - AMIDO - CBOTONIC 
 ACID CH3.C(NHPh):CBr.002H. An/il-bromo. 
 aceto-acetic acid. [138°]. Formed by bromination 
 of phenyl-/3-amido-crotonic acid (anilacetacetio 
 acid) dissolved in chloroform. Pearly plates, 
 V. sol. hot alcohol, si, sol. water, chloroform 
 and ether. By cold H2SO4 it is condensed to 
 (Py. 2:1:3) -bromo-oxy-methyl-quinoline (Enorr, 
 B. 17, 2874). 
 
 BROMO - PHENYL - AMIDO-(a)-NAFHTHO ■ 
 
 QUINONE V. (a)-NAPHTHOQUINONE-BBOMANrLn)E. 
 
 TRI - BROMO - PHENYL -AMIDO-PBOPIONI- 
 TRILE C,HjBr3NH.CHMe.0N. [130°]. From 
 phenyl-a-amido-propionitrile and Br. Needles 
 (Stephau, C. C. 1886, 470). 
 
 ^-BB0M0-PHENYL-(P^.3)-AMID0-ftTJIN0L. 
 .CH:CH 
 INE CjH4< I [146°]. Sil- 
 
 \ N:C(NH.C5H4.NOj) 
 very scales. Formed by heating {Py. 3)-chloro- 
 quinoline with ^'-bromaniline (Friedlander a. 
 Weinberg, B. 18, 1583). 
 
 DI-BROMO-DI-PHENYL-AMINE 
 HN(CeH4Br)2. [107°]. Prisms. Sol. alcohol and 
 acetic acid. The benzoyl derivative is formed 
 by bromination of benzoyl-di-phenyl-amine. 
 
 Benzoyl derivative BzN(CeH4Br)j. 
 [142°]. Colourless plates. Soluble in alcohol 
 and acetic acid (Lellmann, B. 15, 830). 
 
 letra-bromo-di-phenyl-amine NH(CjH3Brj)j. 
 [182°]. Formed by treating an alcoholic solu- 
 tion of di- phenyl -amine with Br. Needles 
 (Hofmann, A. 132, 166 ; Gnehm, B. 8, 925). 
 
 Acetyl derivative NAo^cjB.^Br^)^. [168°], 
 
 Hexa-bromo-di>phenyl-amine NH(C|iH2Br3)2, 
 [218°]. Formed, together with the preceding, 
 by adding Br to a solution of di-phenyl-amiue 
 in HOAo (G-,). Eeduoed by sodium-amalgam to 
 di-phenyl-amine. 
 
 Ooto-bromo-di-phenyl-amine NH{C5HBr4)2. 
 [c. 304°]. From di-phenyl-amine, Br, and I at 
 260°. Prisms (from CHCI3) (Gessner, B. 9, 1511). 
 
 Deca-bromo-di-phenyl-amine NH(0sBr5)j, 
 From di-phenyl-amine, Br, and I at 350°. 
 Needles (from CHCI3). Not melted at 310°. 
 
 BROMO-PHENYL-BENZENE v. Bbomo-di- 
 
 PHENYL. 
 
 Bromo-tri-phenyUbeuzene CjjHjjBr. [104°]. 
 From Br and tri-phenyl-benzene in OSj, Needles 
 (from alcohol) (Berthold a. Engler, B. 7, 1123). 
 
 BR 
 
610 
 
 BROMO-PHENYL-BENZOIO ACID. 
 
 BSOUO - PHENYL - BENZOIC ACID v. 
 
 Bbomo-diphenyl-cakboxylic aoid. 
 
 BROMO-PHENYL BENZYL OXIDE 
 0„H,Br.0.0Hj.0,H5. [69°]. From phenyl 
 benzyl oxide, Br, and HgO. Needles (Sintenis, 
 A. 161, 335). 
 
 DI-^-BEOMO-DI-PHENYL-BITJEET 
 C„H„OjBrjN, i.e. (08H4BrNH.00)2NH. Pre- 
 pared by the action of alcoholic NHj on p- 
 bromo-phenyl-dicyanate (Dennstedt, B. 18,230). 
 SI. sol. alcohol and ether, insol. water. Begins 
 to sublime at about 240°. 
 
 7-BR0M0-7-PHENYL-BTJTYRIC ACID 
 Ph.0HBr.CHj.CH2.C0^. [69°]. From y- 
 phenyl-iso-crotonic aoid and cone. HBr at 0°. 
 Crystals (from CSj) (Jayne, A. 216, 102). By 
 boiling with water or treatment with aqueous 
 NajCOj it is converted into the lactone of 7-oxy- 
 7-phenyl-butyrio acid (g. v.). 
 
 P7-I)i-bronio-7-phenyl-butyric acid 
 Ph.CHBr.CHBr.CH2.COjH. [138°]. From phenyl- 
 iso-crotonic acid in CSj by Br at 0° (Jayne, A. 
 216, 107). Crusts of small white crystals. So- 
 dium amalgam converts it into sodium 7-oxy-7- 
 phenyl-butyrate. 
 
 exo-Si-bromo-^-phenyl-isobutyric acid 
 C5H5.CHBr.OBrMe.C02H(?) [135°]. Fromphenyl- 
 methacrylic acid and Br (Conrad a. Hodgkinson, 
 A. 193, 312). 
 
 i)-BEOMO-PHENYL-GARBAMIC ACID 
 
 Methyl ether CjH^Br.NH.CO^Me. [124°]. 
 From p-bromo-phenyl cyanate and MeOH. 
 Needles (Dennstedt, B. 13, 229). 
 
 Ethyl ether C.HjBr.NH.C02Et. Bromo- 
 carbardUc ether. [81°] (B.) ; [85°] (D.). From 
 PhNH.COjEt and bromine-water (Behrend, A. 
 233, 7) or from ^J-bromo-aniline and OlCOjEt. 
 Needles (from benzoline). Boiling alcoholic 
 KOH gives KjOO, and^J-bromo-aniline. 
 
 Di-biomo-phenyl-carbamic acid. Methyl 
 ether [4:2:1] CsHsBr^.NH.COjMe. [97°]. 
 Formed by brominating methyl phenyl-carb- 
 amate (Hentsehel, J. pr. [2] 34, 423). Needles 
 (from alcohol). Warm H^SO, gives OO2 and 
 di-bromo-aniline. 
 
 Hexa-bromo-di-phenyl-carbamic ether 
 (CjHjBrjjjN.COjEt. Hexa-bromo-di-phenyl- 
 
 amine v/rethane. [184°]. Formed by bromination 
 of di-phenyl-carbamic ether dissolved in acetic 
 acid (Hager, B. 18, 2577). Long greenish-brown 
 needles. Sol. acetic acid, nearly insol. alcohol. 
 
 ^-BROMO - PHENYL - CARBAMIKE BI- 
 CHLORIDE C6H4Br.NCl:CCl. (256°). From 
 p-bromo-phenyl oarbimide and CI. Yellowish 
 liquid (Dennstedt, B. 13, 232). 
 
 DI-BROmO-DI-PHENYL-CARBINOL 
 CijHioBrjO. [163°]. Di - bromo - benzhydrol. 
 From di-phenyl-carbinol and Br. Minute needles 
 (from alcohol). Eeduced by sodium-amalgam 
 to di-phenyl-carbinol (Linnemann, A. 133, 6). 
 
 DI-BROmO-PHENYL CARBONATE 
 (C,H3Brj)jC03. [166°]. Silky needles ; formed 
 by brominating phenyl carbonate (Lowenberg, 
 C. 0. 1886, 390). 
 
 BEOMO-DIPHENYL CAEBOXYLIC ACID. 
 [4:1] 08H,Br.C,H,.C0„H [1:4]. [194°]. From 
 p- bromo -phenyl -toluene [30°] and OrO, in 
 HOAo (Carnelley a. Thomson, 0. /. 61, 88). 
 v. sol. ether, si. sol. alcohol. 
 
 Di-bromo-diphenyl carboxylic aoid 
 C„H,Brj.CO^ [4':l':l:2or3:4]. Di-bromo- 
 
 phenyl-bensoio acid. [204°]. From di-bromo- 
 ^-tolyl-benzene [115°] by oxidising with CrO, 
 in HOAo. Needle-shaped prisms (from alcohol), 
 si. sol. alcohol (Carnelley a. Thomson, 0. J. 47, 
 589). 
 
 Di-bromo-diphenyl ^-carboxylic acid 
 C^H^Br.OsHjBr.CO^H [4' : 1' : 1 : 2or3 : 4]. [232°]. 
 Formed by oxidising di- bromo -tolyl- benzene 
 [150°] (C. a. T., 0. J. 61, 90). 
 
 Di-bromo-diphenyl carboxylic acid [212°] 
 has been obtained from (3)-di-bromo-fluorene 
 ketone [197°] by potash-fusion (Hohn, B. 16, 
 1081).— BaA'j. 
 
 ^-BEOMO-PHENYL CYANATE 
 0C:N.C„H4Br [1:4]. [39°]. (226°). V. sol. ether. 
 Prepared by distilling bromo-phenyl-oarbamio 
 ether with P^O^ (Deimstedt, B. 13, 228). 
 
 ^-BEOMO-PHENYL DI-CYANATE 
 CHHgNjOaBrj. [199°]. Small plates. SI. sol. 
 ether. Prepared by the action of a small quan- 
 tity of tri-ethyl-phosphine on bromo-phenyl- 
 cyanate heated to 100°. By long boiling with 
 absolute alcohol it gives an acid of melting- 
 point [153°] and formula CuHuOsN^Brj which 
 is probably ethyl dibromo-phenyl-aUophanate 
 (Dennstedt, B. 13, 229). 
 
 BEOMO-PHENYL-CYSTEINE C„H,„BrNSOj 
 i.e. CsH,Br.S.CMe(NHj).C02H. p-Bromo-a- 
 amido-thio -lactic acid. [181°]. Formed by 
 boiling bromo-phenyl-mercapturio aoid with 
 cone. HCl. Needles (from dilute alcohol) ; v. si. 
 sol. water, v. si. sol. alcohol, v. sol. dilute HCl. 
 Boiling alkalis slowly separate jj-bromo-phenyl 
 meroaptan and form pyruvic aoid. Sodium- 
 amalgam forms NH3, lactic acid, and CgH^Br.SH. 
 Acetic anhydride on warming gives 
 
 an anhydride CeH4Br.S.CMe<^Q> [153°] 
 
 bromo-phenyl-cystoin,' but in presence of 
 benzene it forms bromo-phenyl-mercapturio acid 
 OjH4Br.S.CMe(NHAo).C02H. Potassium cyan- 
 ate forms C8H,Br.S.0Me(NH.C0.NH2)C02H. 
 
 Salts. — CuA'j. — HA'HCl (Baumann a. 
 Preusse, H. 6, 315 ; B. 18, 258). 
 
 BEOMO-o-PHENYLENE-DIAMINE 
 C„H3Br(NH2)2 [4:1:2]. [63°]. From (1,3,4)- or 
 (6,3,4)-bromo-nitro-aniline, tin, and HCl (Hiib- 
 ner, A. 210, 359 ; Wurster, B. 6, 1544; Eemmers, 
 B. 7, 347). Needles ; v. sol. water. Sodium- 
 amalgam reduces it to o-phenylene diamine. 
 
 Salts .— B"HC1.— B"H2S0,. 
 
 Di-bromo-m-phenylene-diamine 
 C5H2Br2(NH2)2. Dark brown pp. formed by 
 adding bromine-water to an aqueous solution of 
 ^-phenylene - diamine hydrochloride; may be 
 crystallised from alcohol (HoUemftnn, Z, 1865, 
 555). 
 
 BEOMO-DIPHENYLENE KETONE 
 C H 
 CiaHjBrO i.e. \ ° ' ^.CO. [104°]. From 
 
 CABr/ 
 bromo - fluorene and CrO, (Hodgkinson a. 
 Matthews, C. J. 43, 165). Dark yellow 
 needles. 
 
 Bromo - diphenylene ketone OisH^rO. 
 [122° uncor.]. Formed by distilling bromo-di- 
 phenio acid with lime. Yellow plates. V. sol. 
 benzene, ether, and hot alcohol, nearly insoL 
 water. Sublimes readily in felted needles. By 
 distillation with zinc-dust it gives fluoreua 
 (Claus a. Erier, B. 19, 3155). 
 
BROMO-PHENYL-MEROAPTAN, 
 
 611 
 
 (a)-Di-broittO-diplien7lene-ketone 
 Cj^^rjOO. [143°]. Formed by oxidation of 
 di-bromo-flnorene [166°] with OrOa dissolved in 
 aoetio acid (Holm, B. 16, 1081). Long yellow 
 needles. V. Bol. ether and benzene. 
 
 0)-Di-bromo-dip]ienylene ketone 
 C,,HeBr,CO. [198°]. From (a) - di - bromo- 
 fluorene [165°] by CrO, in slight excess and 
 HOAo (Hodgkinson a. Matthews, 0. J. 43, 165 ; 
 Hohn). Yellow -needles, sol. alcohol, ether, and 
 benzene. Potash-fusion gives rise to di-bromo- 
 diphenyl-oarboxylio acid. 
 
 Di-bromo-diphenylene-ketone CijHsBraCO. 
 [133° imcor.]. Formed by distilling di-bromo- 
 di-phenio acid with lime. Thin yellow plates 
 or long thin needles. Eeadily sublimable (Glaus 
 a. Erler, B. 19, 3156). 
 
 DI - BEOMO - DI . PHENYLENE KETONE 
 OXIDE 0„H^rA [210°-213°]. From di- 
 phenylene ketone oxide and bromine at 180° 
 (A. G. Perkin, C. J. 43, 193). Long needles 
 (from alcohol). Combines with bromine form- 
 ing an uistable addition product. 
 
 BBOMO - DIPHENYLENE - METHANE ». 
 
 BBOMO-FL0OBENE. 
 
 DI -BaOMO - PHENTLENE-(o)-NAPHTHYL- 
 ENE-OXIDE C.sHsBrjO. [284°]. YeUowish white 
 needles. SI. sol. benzene. Prepared by bromi- 
 nation of phenylene-(o)-naphthylene-oxide (Arx, 
 B. 13, 1727). 
 
 BKOMO-PHENTLENE OXIDE CsHsBrO. 
 [196°]. From phenylene oxide and Br at 100°. 
 Needles (from alcohol) (Marker, A. 124, 250). 
 
 Di-bromo-diplieuylene oxide O^^^rfi. 
 [185°]. From Br and diphenylene oxide in CSj. 
 LaminsB (from alcohol) (Hoffmeister,4. 159,211). 
 
 DI - BEOMO - DIPHENYLENE - PHENYL - 
 METHANE Oi^H.^Brj. [182°]. From Br and the 
 hydrocarbon in HOAo (Behr, B. 5, 971). 
 
 Iri-bromo-diphenylene-plienyl-methane 
 C„H„Br3[167°-171°](B.). 
 
 BEOMO-PHENYL-ETHANE v. Bhomo-eihyi,- 
 
 BENZEKE. 
 
 p. Bromo-di- phenyl -ethane Ci^H^Br i.e. 
 C^yCB^.GB.„.G^fiT [1:4]. Bromo - dibemyl. 
 S.G. 21'40. From s-di-phenyl-ethane, Br, and 
 water (Fittig a. Stelling, A. 137, 266). OU; 
 boils above 320°. 
 
 f^-Di-bromo-di-phenyl-ethaue C„H,jBr2 t.e. 
 [4:1] 06H,Br.CH2.CH2.C^^Br [1:4]. [115°]. 
 From s-di-phenyl-ethane, water, and Br (F. a. S.). 
 Needles (from alcohol). CrO, gives ^-bromo- 
 benzoic acid. 
 
 Exo-di-bromo-s-di-phenyl-ethane 
 CACHBr.OHBr.0^5. [237°] (Z.) ; [235°] (K.). 
 Stilbene dihromide. Di-bromo-dibenzyl. 
 
 Formation. — 1. From stilbene and Br (Lim- 
 prioht a. Schwanert, A. 145, 336). — 2. From di- 
 benzyl and dry Br (Marquardt, A. 151, 364).— 
 3. From bydrobenzoin and PBrj (Zincke, A, 198, 
 127). 
 
 Properties. — Silky needles. Decomposes at 
 235° (Kade, J. pr. 127, 465). V. si. sol. boiling 
 alcohol, m. sol. boiling xylene. Alcoholic KOH 
 gives 0,H5.CH:CBr.CBH5 and CsH^.C-COsHs. Con- 
 verted by benzene and ALjClj into s-tetra-phenyl- 
 ethane some tri-phenyl-methane being also 
 formed (Anschiitz, A. 235, 207). 
 
 Tri - bromo - s - di - phenyl - ethane 0„H„Br3. 
 From s-di-phenyl-ethane, water, and Br (F. a. S.). 
 
 Nacreous laminas, v. si. sol. alcohol ; deoom> 
 poses at 170°. 
 
 Tri - bromo - s - di - phenyl . ethane C, ,H,,Br,. 
 [207°-211°], From s-di-phenyl-ethane and dry 
 Br(M.). " 
 
 Tri-bromo-s-di-phenyl-ethane 
 CsH5.CBr2.CHBr.OeH5. Bromo-stilbene dibro- 
 mide. [100°]. From bromo-s-diphenyl-ethylene 
 and Br (L. a. S.). Needles (from alcohol). De- 
 composed by distillation intoHBr, PhCBr:CBr.Ph, 
 and PhOiOPh. Alcoholic KOH gives PhCiCPh. 
 
 Tri-bromo-M-di-pheayl-ethane 
 (C,H5)jOH.CBr,. [89°]. From bromal (1 mol.), 
 benzene (2 mols.) and conc.HjSOj (Goldschmiedt, 
 B. 6, 985). MonocUnio prisms (from ether). Alco- 
 holic KOH gives BLBr and di-bromo-di-phenyl- 
 ethylene. 
 
 Hexa - bromo-s-di - phenyl-ethylene 0„HsBr,. 
 From s-di-phenyl-ethane and excess of Br. 
 Hard prisms (from benzene) (F. a. S.). 
 
 BROMO-PHENYL-ETHYL-AffilNE d.Bbomo- 
 
 AmDO-PHENYL-ETHANB. 
 
 BE0M0-j4-DI-PHENYL-ETHYIENECi,H„Br 
 i.6. (C„H5),C:0HBr. [50°] (H.); [40°] (A.).(o.l70°) 
 at 11 mm. (A.) ; (above 300°) (H.). Formed by 
 warming the di-bromide of M-di-phenyl ethylene 
 (Hepp, B. 7, 1410; Anschutz, A. 235, 160). 
 Prisms ; si. sol. cold alcohol. 
 
 Bromo-s-di-phenyl-ethylene 
 C„H5.CBr:CH.O,fH5. Bromo - stilbene. [25°]. 
 From stilbene dl-bromide by distillation or treat- 
 ment with alcoholic KOH. Prisms. AgOAc 
 gives PhC(OAc):CHPh (Limpricht a. Schwanert, 
 ^.145,340; 155,72). 
 
 Di-bromo-M-di-phenyl-ethylene(OeH5)2C:OBr2. 
 [83°]. (above 300°). From CPhjH.CBr, and alco- 
 hoho KOH (Goldschmiedt, B. 6, 985). Needles 
 (from alcohol-ether). 
 
 Di-bromo-s-di-phenyl-ethylens 
 0sH5.CBr:CBr.CsH5. Tolane di-brotnide. [208°]. 
 Leaflets. Prepared by the action of bromine on 
 tolane. An isomeride [64°] is also formed in 
 small quantity (Limpricht a. Schwanert, A. 145, 
 348 ; Liebermaun a. Homeyer, B. 12, 1974). Con- 
 verted by benzene and Mfilg in presence of CSj 
 into s-tetra-phenyl-ethane (Anschutz, A. 235, 
 209). 
 
 BEOMO- PHENYL -GLYCOCOLL v. Bbouo- 
 
 PHENYL-AMrDO-ACEIIO ACID. 
 
 DI-BEOMO-DI-PHENYL-GUANIDINE 
 
 CiaHiiBrjNj. From di-phenyl-guanidine hydro- 
 chloride, water, and Br (Hofmann, A. 67, 148). 
 Scales (from alcohol).— B'HCl.—B'jHjPtClj. 
 
 Tri-bromo-tri-phenyl-gaanidine 
 CH.jNjBraCl i.e. {G,-Bifi]:NB.)fi:^.C,Ilfir. 
 White amorphous powder. Prepared by the 
 action of ^-bromaniline on iso-cyan-^-bromo- 
 phenyl-chloride. — ^B'HCl: white crystals, easily 
 soluble in alcohol and ether.— (B'HC^sPtCl,: 
 light yellow plates (Dennstedt, B. 13, 232). 
 
 p-BROMO-PHENYL-MEECAPTAN 
 CjHjBr.SH. [75°]. (231°). From iJ-tromo- 
 benzene sulphochloride, tin, and HCl (Hubner 
 a, Alsberg, A. 156, 327). Formed also by boiling 
 bromo-phenyl-cysteine or bromo-phenyl-mer- 
 oapturic acid with NaOHAq (Baumann a. 
 PreuBse, B. 12, 806; E. 5, 319). Lamina 
 (from alcohol) ; volatile with steam ; si. sol. 
 hot water. Cone. HjSOi at 120° forms a green 
 solution, turning blue. Sodium-amalgam forma 
 phenyl-mercaptan. Chloral forms a compound 
 
 bb2 
 
613 
 
 BROMO-PHENYL-MERCAPTAN. 
 
 [72°]. HCl passed into a mixture of ^-bromo- 
 phenyl meroaptan and benzoic aldehyde forms 
 di-^-bromo - di - phenyl - di - thio - benzaldehydate 
 CsH5.CH(S.CeH<Br)sL80°] (Baumann,B.18, 885). 
 HOI and acetone form di-bromo-di-thio-di- 
 methyl ketate {CH3),C(S.C,HjBr)2 [90°]. 
 
 M-BSOMO-PHENYL-MEECAPTUEIC ACID 
 CH.^rNSO, i.e. C,H^BrS.CMe(NHAc).C02H. 
 Acetyl - hromo -phenyl - amido - thio -lactic acid. 
 [163°]. S. 1-4 at 100°. Occurs in the urine 
 of animals which have taken bromo-benzene. 
 Formed also by treating bromo-phenyl-oysteine 
 with benzene and Ac^O (Baumann a. Preusse, B. 
 12, 806, JT. 5, 309 ; Baumann, B. 15, 1782 ; 
 Jafie, B. 12, 1092). Needles ; insol. cold water, 
 sol. hot water and alcohol. Lsevorotatory in 
 alcoholic solution, dextrorotatory in alkaline solu- 
 tion. Boiling aqueous NaOH gives ^-bromo- 
 phenyl meroaptan, NH,, HOAc, and pyruvic 
 acid. Boiling cone. HClAq or dilute H^SOj gives 
 acetic acid and bromo-phenyl-oysteme. Cone. 
 H2SO4 gives a blue solution. 
 
 Salts.— BaA'j2aq : S. 2 at 15°.— MgA'^ 9aq. 
 — NH4A': S. 3 at 15°. 
 
 BEOMO-DI-PHENYL-METHAHE C,3H„Br 
 t.«. CHPhjBr. [45°]. From di-phenyl-methane 
 (1 mol.) and Br (1 mol.) at 150° (Friedel a. 
 Balsohn, Bl. [2] 33, 339, 587). Crystals, v. e. 
 sol. benzene. Water at 100° forms di-phenyl- 
 carbinol and its anhydride. Boiling alcohol 
 forms CHPhj.OEt. Cone. NHgAq gives 
 CHPh2.NHj. 
 
 Di-bromo-4i-phenyl-methane CPh^Br^. From 
 di-phenyl-methane (1 mol.) and Br (2 mols.) at 
 150°. Liquid. Water at 150° converts it into 
 benzophenone. Decomposed on distillation 
 giving tetra-phenyl-ethylene. Sodium and water 
 form tetra-phenyl-ethane. 
 
 Bromo-tri-phenyl-metliane C,gH,5Br i.e. 
 PhaCBr. [152°]. Obtained by brominating tri- 
 phenyl-methane in sunlight or at 150° (Allen a. 
 Kollicker, .4.227, 107 ; Henderson, O. J. 51, 224 ; 
 Schwarz.B. 14, 1520). Yellow hexagonal rhom- 
 bohedra (from CSj) a : c = 1 : -784 (Hintze, Z. E. 
 9, 636). Decomposed above 200° into HBr and 
 phenylene - di - phenyl - methane. Successive 
 treatment with boiling HOAo and water forms 
 tri-phenyl-carbinol. NH3 forms PhjCNH^. 
 KOy gives PhjO.Cy. Potassium sulphocyanide 
 gives PhjC.SCN. 
 
 TRI-BROMO-DI-PHENYL-METHYL-AMINE 
 
 I). TEI-BBOMO-METHyL-m-PHENYL-AMINE. 
 
 BEOMO - PHENYL - METHYL - FUEFUEANE 
 TETEA-BEOMIDE CHjBr.O. [210°]. Bronzy 
 plates. Formed by the action of bromine on 
 
 HO— CH 
 phenyl - methyl - furfurane ^ *!!% 
 
 PhC— 0— CMe 
 (Paal, B. 17, 2760). 
 
 BEOMO - PHENYL - METHYL-PYEAZOLONE 
 
 V. BbOMO-OXY-PHENYIi-METHYL-PYBAZOIi. 
 
 7-BEOMO - y - PHENYL - DI - METHYL - SUC 
 CINIC ACID Ph.CHBr.CH(C0jH).CHMe.C02H. 
 From the lactone of y-oxy-v-phenyl-di-methyl- 
 Buccinio acid (j. v.) and cone. HBr at 0° (Fittig 
 a. Penfield, A. 216, 123). SmaU crystals (from 
 benzene). V. sol. alcohol or ether, m. sol. benz- 
 ene. Warmed with water it givea off CO^ and 
 forms plates of an acid which appears to be 
 Pb.0H:0H,CHMe.CO^ 
 
 TETEA-BEOMO-PHENYL - METHYL - THIO- 
 PHENE CiiH^r.S. [137°]. Formed by bromina- 
 tion of phenyl-methyl-thiophene. Fine needles 
 or plates. V. sol. benzene, ether, and petroleum- 
 spirit, m. sol. alcohol and acetic acid (Faal a. 
 Piischel, B. 20, 2559). 
 
 BEOMO-PHENYL-METHYL-UEETHANE v. 
 Methyl ether of Beomo-phentl-cabbamio acid. 
 
 BEOMO-FHENYL MTTSTABD OIL v. Bbomo- 
 
 PHENTIi THIO-OARBIMIDE. 
 
 DI - BEOMO - PHENYL - (;3) - NAPHTHYL - 
 AMINE 0,jH,„BijNH. [140°]. White needles. 
 Prepared by bromination of phenyl- (/3)-naph- 
 thyl-amine (StreifE, B. 13, 1858 ; A. 209, 158). 
 
 Tetra-bromo-phenyl-(0)-iiaphtIiyl-amine 
 CijHsBr^NH. [198°]. SI. sol. alcohol, ether and 
 CjHj, m. sol. CS2 and CHCI3. Prepared by fur- 
 ther bromination of the dibromo- derivative. 
 
 Tri-bromo-plienyl-(a)-iiaphtIiyl-amine 
 C.jHjBraNH. [137°]. Colourless prisms. Soluble 
 in alcohol and benzene. Prepared by bromina- 
 tion of phenyl-(o)-naphthylamiue (S.). 
 
 Tetra-bromo-plienyl- (j8) -naphthyl-amiue 
 CieHjBr^NH. [203°]. Formed by the action of 
 bromine upon an acetic acid solution of benzene- 
 azo-phenyl-(i8)-naphthyl-amine, or by bromina- 
 tion of phenyl- (S)-naphthyl-amine. Long white 
 silky needles (Zincke a. Lawson, B. 20, 1170). 
 
 BBOMO-PHENYL-OCTANE v. Bbomo-ooitl- 
 
 BENZENE. 
 
 p-BEOMO-PHENYL-OXAMIC ACID 
 C,H,Br.NH.C0.C02H. [198°]. S. -194 at 25°. 
 From di-bromo-di-phenyl-oxamide and alcohoho 
 KOH (Dyer a. Mixter, Am. 8, 355). CrystalUne 
 fibres, sol. alcohol and ether. KOHAq liberates 
 p-bromo-aniline. Salts. — EA': monochuio 
 scales. — CaA'2. — ^AgA'. — BaA'j. 
 
 Ethyl ether 'Etk'. [156°]. Fromphenyl- 
 oxamic ether and Br (Klinger, A. 184, 263). 
 
 DI-BEOMO-DI-PHEITYL-OXAMIDE 
 (CeH,Br.NH)2Cj02- [above 300°]. From Br and 
 di-phenyl-oxamide in HOAc (D. a. M.) 
 
 DI-BEOMO-DI-PHENYL OXIDE (CeH,Br)30. 
 [58°]. (above 360°). From Br and di-phenyl 
 oxide in CSj. Long plates (from alcohol) (Merz 
 a. Weith, B. 14, 191). 
 
 TEI-BEOMO-TEI-PHEITYL PHOSPHATE 
 (OsHiBrO) sPO. From tri-phenyl phosphate and 
 Br at 180°. Nacreous scales (Glutz, A. 143, 193). 
 
 jp-BEOMO-PHENYL-PHTHALIMIDE 
 .0 = 
 
 CeH/ >0 
 \r.=-- 
 
 = N.CjH,Cl 
 
 [204°]. 
 
 Fine flat 
 
 needles or scales. Sol. G^g and acetic acid, 
 less in ether. Prepared by heating ^-brom- 
 aniline with phthalic anhydride (Oabriel, B. 11, 
 2261). 
 
 BEOMO- PHENYL -PEOPANE v. Bbomo- 
 
 PEOPYIi-BENZENB. 
 
 o-BE0M0-;8-PHENYL-PE0PI0NIC ACID 
 
 li-.lJOeH.fiT.O^t.GO^.o-Bromo-hydrocinnamic 
 acid. [99°]. Scales. Formed by reduction of 
 o-bromo-cinnamic acid with HI and P (Gabriel, 
 B. 15, 2295). 
 
 m-Bromo-)3-phenyl-propionic acid 
 [3:1] O8HjBr.CjH4.OOjH. m-Bromo-hydrocvima- 
 mic acid. [75°]. Formed by reduction of m- 
 bromo-oinnamio acid with P and HL Also by 
 eliminating the NH, group from (3:4:l)-bromo- 
 amido-phenyl-propionio acid by diazotising and 
 treatment with alcohol (Gabriel, B. 15, 2294). 
 
BROMO-PHENYL-THIO-CAKBAMIC ETHEE. 
 
 613 
 
 Short thick prisms. V. sol. alcohol, ether, 
 benzene, chloroform, and CS^. 
 
 f-BTomo-i3-pheuyl-propionic acid 
 [4:1] 0^4Br.CHj.CHj.C0jH. [135°]. Prom /3. 
 phenyl-propionic acid and Br in the cold (Goring, 
 O. 0. 1877, 793, 808 ; Gabriel a. Zimmermann, 
 B. 13, 1683). Hat needles {from CS^). Oxida- 
 tion gives p-bromo-benzoio acid. 
 
 ;8-Bromo-/3-pheH7l-propionic acid 
 CsH5.CHBr.CH2.COjH. [137°]. From oinnamio 
 acid and HBr (Pittig a. Binder, B. 10, 518 ; A. 
 195, 132; Ansohutz a. Kinnioutt, B. 11, 1221). 
 Also from ;8-bromo-i3-oxy-phenyl propionic acid 
 and HBr (Glaser, A. 147, 96). Laminae. De- 
 composed by heat into HBr and cinnamic acid. 
 Boiling water forms 3-oxy-^-phenyl-propionio 
 acid. Cold NaOHAq gives styiene and CO^. 
 
 a-Bromo-a-pheuyl-propionio acid 
 CHj.CPhBr.COjjH. Bromo-hyd/ratropio acid. 
 [94°]. From atropic or atrolaotio acids and cold 
 cone. HBrAq (Fittig a. Wurster, A. 195, 145 ; 
 Merling, A. 209, 13). Tables, insol. water, sol. 
 ordinary solvents. Boiling Na^COjAq produces 
 Btrolactic acid. 
 
 j3-Bromo-a-phenyl-propionio acid 
 CHjBr.CHPh.CO2H. [94°]. Formed by heating 
 atropic acid with cone. HBrAq at 100°. Prisms, 
 insol. water. Boiling NajCOaAq produces tropic 
 acid, styrene, and a very little atropic acid. 
 Ammonia forms j3-amido-a-phenyl-propionic 
 acid [169°] (M.). 
 
 a^-Di-bromo-;3-pIieiiyl-propionic acid 
 C5H5.CHBr.CHBr.CO2H. [195°] (G.); [201°] (S.). 
 From cinnamic acid and bromine-vapour 
 (Schmidt, A. 127, 320 ; Fittig a. Binder, A. 195, 
 140). Also from a-bromo-/3-oxy-phenyl-propionio 
 acid and HBr (Glaser, A. 147, 91). Lamina 
 (from alcohol) ; v. sol. ether andalcohol, v. si. sol. 
 CSj. 
 
 Beactions. — 1. Sodium amalgam forms 
 phenyl-propionic acid.— 2. Boiling water gives 
 cinnamic acid, bromo-oxy-phenyl-propionic acid, 
 phenyl-aoetic aldehyde and ai-bromo-styrene. 
 
 3. Alcoholic KOH gives a- and )3- bromo-cin- 
 namic acids. 
 
 Salts.— NaA'.—BaA'j. 
 
 Methyl ether MeA'. [117°] (Anschutz, 
 B. 12, 538). 
 
 Ethyl ether EtA' [69°]. From cinnamic 
 ether and bromine (Perkin, jun., C. J. 45, 172). 
 
 n-Propyl ether PrA'. [23°]. 
 
 a;8-Di-bromo-o-phenyI-propionic acid 
 CHjBr.CPhBr.CO^. [116°]. From Br and atro- 
 pic acid in CSj (Fittig a. Wurster, A. 195, 145). 
 Needles (from CS2). Decomposed by boiling 
 waterinto CO2, HBr,andaoetophenone. Sodium- 
 amalgam forms o-phenyl-propionic acid and 
 oxy-phenyl-propionio acid. Excess of NaOHAq 
 gives atroglyoerio acid 0,H,„Oj (Fittig a. East, 
 A. 206, 30). 
 
 Tri-bromo-plienyl-propionic acid 
 C6H5.CHBr.CBr2.CO2H. [151°]. From bromo- 
 cinnamio acid [120°] and Br (Glaser, A. 143, 
 335 ; Stockmeier, Bn. .2, 872 ; Kinnicutt, Am. 
 
 4, 25). Small flat monocUnic needles (from 
 dilute alcohol). Boiling water gives CO2, di- 
 bromo-styrene, bromo-oinnamio acid, and di- 
 bromo-oxy-phenyl-propionio acid. _ 
 
 Xri-bromo-phenyl-propionic acid 
 CsH5.CBr2.CHBr.CO2H. [148°]. Formed by the 
 combination of the bromo-oiimamic acid [159°] 
 
 with Br. Triolinio prisms. Sol. hot benzene, 
 V. e. sol. alcohol and ether, si. sol. cold CSj. It 
 decomposes at its melting-point evolving HBr. 
 By standing for a short time with water it is 
 converted into a neutral oil ; hot water decom- 
 poses it at once (Michael a. Brown, B. 19, 1380). 
 
 Xri-bromo-a-plienyl-propiouic acid 
 CjH^rjOj. [150°]. From bromo-atropio acid 
 and Br (F. a. W.). Needles (from ligroin). 
 
 ajS-DI-BBOMO-PHENYL-PEOPIONICALDE- 
 HYDE CjH5.CHBr.CHBr.CHO. Cinnamic alde- 
 hyde dibromide. [0. 100°]. Small needles. 
 Formed by the direct combination of cinnamic 
 aldehyde and bromine. It readUy splits off HBr 
 on heating, giving bromo-oinnamio aldehyde 
 (Zincke a. Hagen, B. 17, 1814). 
 
 DI-BE0M0-J3-PHENYL-PK0PYL ALCOHOL 
 CjH.oBrjO i.e. CsHj.CHBr.CHBr.CHjOH. 
 Stycerin dibromhydrin. Styrone dibromide. 
 [74°]. From Br and oinnamyl alcohol in CHClj 
 (Grimaux, Bl. [2] 20, 120). Tables or needles 
 (from ether). Insol. water. Boiling water con- 
 verts it into CbH5.CH(0H).CH(0H).CH20H. 
 
 Acetyl derivative 
 CaH5.CHBr.CHBr.CH20Ac: [86°]; prisms. 
 
 DI - BEOMO - PHENYL - PEOPYLIDENE - 
 ANILINE C6H5.N:CH.CHBr.CHBrPh. [175°]. 
 From cinnamylene-aniline and bromine (Schiff, 
 A. 239, 384). Needles (from alcohol). 
 
 DI- BEOMO -PHENYL-PYEAZOL DIHY- 
 DEIDE CjH8Br2N2. [93°]. IH-bromo-phenyl- 
 pyrazoWne. From phenyl-pyrazoline and Br in 
 chloroform (Fischer a. Enoevenagel, A. 239, 
 199). Plates (from alcohol) ; v. si. sol. water. 
 In dilute acid solution it gives a violet 
 colour with KjCr^O,. Alcoholic KOH forms 
 C3HBBr(OEt)N2 [66°], which crystallises from 
 alcohol in pale yellow prisms. Boiling HClAq 
 gives off EtCl and forms bromo-oxy-phenyl- 
 pyrazol C9H3Br(0H)N2 [214°] ; this has acid 
 characters and forms greenish-yeUow crystals 
 (from alcohol). 
 
 DI-BEOMO-(a)-PHENYL-PYEIDINE DI- 
 CAEBOXYLIC ACID C.jHjBrjNO^. [205°]. 
 From [2:1] 0sH,(C02H).C5H3N(C02H) [3:2] and 
 bromine (Skraup a. Cobenzil, M. 4, 469). 
 Granules, v. si. sol. water, m. sol. warm alcohol. 
 
 DI-BEOMO-DI-PHENYL SULPHIDE 
 (0sHiBr)2S. [110°]. From di-phenyl sulphide 
 and Br, or from (CsH^NHjJaS by diazo- reaction. 
 Nacreous laminoe (Krafft, JB. 7, 1165). 
 
 Di-^-bromo-di-phenyl disulphide (CsHjBr)2S2. 
 [94°]. From^-bromo-phenylmercaptanby atmo- 
 spheric oxidation. Plates; not volatile with 
 steam (Hiibner a. Alsberg, A. 156, 328 ; Bau- 
 mann a. Preusse, H. 5, 320). 
 
 DI-p-BEOMO-DI-PHENYL SULPHONE 
 (CBH4Br)2S02. [172°]. From p-bromo-benzene 
 and ClSOaH (Armstrong, C. J. 24, 173) or SO, 
 (Nolting, B. 8, 594). Also from bromo-benzene, 
 benzene sulphochloride, and AljClj (Beckurts a. 
 Otto, B. 11, 2065). Needles, si. sol. hot alcohol. 
 
 p - BEOMO - PHENYL - THIO - CAEBAMIC 
 ETHEE C,H,„BrNSO i.e. CjH^Br.NH.CS.OEt. 
 Bramo-phenyl-thio-urethane. [105°]. From ^- 
 bromo-phenyl thio-oarbimide and alcohol at 
 120° (Deimstedt, B. 13, 231). Slender needles. 
 
 n-Bromo-phenyl-di-thio-carbamic ether 
 C8H4Br.NH.CS.SEt. Bromo-di-thio-carbanilie 
 ether. [89°]. From ^-bromo-phenyl-thio-carb* 
 imide and meroaptan at 140° (D.). 
 
614 
 
 BROMO-PHENYL-THIO-OAEBAMIO ETHER. 
 
 p-Bromo-phenyl-tblo-car'bimide 
 C-iHiBr.N.CS. p-Bromo-phenyl mustard oil. 
 [61°]. Prepared by heating ^-bromo-aniline 
 with CS2 in alooholio solution with a little 
 aqueous KOH ; the resulting thio-urea being dis- 
 tilled -with PjOj or heated with oono. HCl at 160° 
 (Dennsteat,B.13,230; Weith and Laudolt, B. 8, 
 716). 
 
 DI-p-BEOMO-DI-PHEWYl-DI-THIO-CINNA- 
 MIC ALDEHYBATE OaH5.C2H2.CH(S.O„H^Br)2. 
 p-Bromo-phenyl-mercaptal of cinnamic aldehyde. 
 [107°]. Formed by passing HCl gas into a mix- 
 ture of ^-bromo-phenyl mercaptan and cinna- 
 mic aldehyde (Baumann, B. 18, 885). Long 
 colourless needles. SI. sol. cold alcohol and 
 ether. 
 
 BKOMO-PHENYL-THIOeLTCOLLIC ACID 
 CsHjBrSOj i.e. C„H^Br.S.CH,.CO,H. [112°]. 
 From O8H5S.CH2.CO2H and Br in CSj (Olaesson, 
 Bl. [2] 23, 444). 
 
 DI-p-BEOMO-DI-PHENYL-DI-THIO-DI- 
 METHYL - KETATE (CH3)2:C:(SC,H,Br)2. 
 
 p-Bromo-phenyl-mercaptol of acetone. [90°]. 
 Long transparent prisms. V. sol. hot alcohol, 
 ether, and benzene. Formed by passing HCl 
 gas into a mixture of ^-bromo-phenyl-mercaptan 
 and acetone (Baumann, B. 18, 888). 
 
 ^-BROMO-PHENYL-THIO-TjaEA 
 NH2.CS.NHC,H,Br. [183°]. From bromo- 
 phenyl - thio - carbimide and alooholio NH, 
 (Dennstedt, B. 13, 231). Needles. 
 
 p-Bromo-di-phenyl-thio-urea 
 NHPh.CS.NH.CaHiBr [158°]. From bromo- 
 phenyl-thio-carbimide and aniline (D.). 
 
 Di ■ j) - bromo - di - phenyl • thio - urea 
 CS(NH.0eH4Br)2. [178°]. From ^- bromo- 
 aniline, G8„ and alcohol in presence of some 
 KOHA.q(D.; Otto, B. 2, 409). Prisms. 
 
 BBOIIO- PHENYL. THIO -'DBEXHAKE v. 
 Beomo-phenyl-thto-oaebamio ethek. 
 
 TETRA-BROMO-PHENYL-^-TOlTJIDINE 
 C.sHjBr.N. [156°]. Formed by adding a solu- 
 tion of Br in glacial HOAc to an alcoholic so- 
 lution of phenyl-^-toluidine (Bonna, A. 239, 58). 
 
 Hepta-bromo-phenyl-^-toluidine C,3HsBr,N. 
 [185°]. From phenyl-^j-toluidine and Br at 280°. 
 
 Endeca-bromo-phenyl-^-tolaidine 
 CisHjBriiN. [296°]. Formed from phenyl-^j- 
 toluidine and Br at 310°. 
 
 BEOMO-^- PHENYL -TOLTTENE 0,3H„Br. 
 [127°-131°]. From ^-phenyl-toluene and Br. 
 Small tables (from alcohol) (CarneUey a. Thom- 
 son, C. J. 47, 589). 
 
 DI-p-BEOMO-DI-PHENYL-TJEEA 
 CiaHijBrjNjO i.e. COJNH.CsHjBr)^. Di-bromo- 
 tarbanilide. From di-phenyl-thio-urea and Br 
 (Otto, B. 2, 409). Formed also by decomposition 
 of the product from COClj and diazobenzene-^- 
 bromauilide. Prepared by the action of car- 
 bonyl chloride on ^-bromaniline (Sarauw, B. 
 15, 45). White glistening plates. Sublimes at 
 225° without melting. SI. sol. alcohol and 
 benzene. 
 
 Tetra-bromo-di-phenyl-urea 
 COmH.CsH,Br2)2. Sublimes in needles (0). 
 
 BROMO-PHENYL-URETHAirE v. Bbomo- 
 
 rHENYL-CARBAMIO ETHER. 
 
 DIBEOMO-PHENYL-VALEEIC ACID 
 
 C,H3.CHBr.CHBr.CH2.CH2.COjH. [109°]. From 
 Etyryl-propionio acid and Br (Baeyer a. Jackson, 
 B. 13,12a). 
 
 BEOUO-FHLOBAPHENE v. FEI.oBAfHBtni, 
 BBOMO - PHLOBEXIO ACID v. Phlobetic 
 
 AOID. 
 
 TEI-BROMO-PHLOEOGLUCIN C5Brj(0HJs. 
 [151°]. Formed by brominating phlorogluoin 
 (Hlasiwetz, A. 96, .118 ; Herzig, If. 6, 885). 
 Long needles (containing 3aq) (from water). 
 Eeduoed by tin and HCl to phlorogluoin. Con- 
 verted by cold HNO3 (S.G. 1*4) into tri-bromo- 
 di-nitro-propionio acid (Benedikt, A. 184, 255). 
 
 Tri-acetyl derivative 0„Br3(OAo),. 
 [183°] (Herzig, M. 6, 887). 
 
 Hexa-bromo-phloroglncin dibromids 
 C8Br5(OBr)3. [118°]. The final product of the 
 bromination of phlorogluoin (Hazura a. Bene- 
 dikt, M, 6, 702). Small golden needles (from 
 CHCI3). At 190° it gives ofE Br (1 mol.). 
 Aqueous SOj reduces it to C5Br3(OH)3. Tin and 
 HCl form C3H3Cl3(OH)3. 
 
 DI - eso - BEOMO - v . FHOSFHO ■ AMIDO- 
 BENZENE STTLFHONIO ACID 
 (HO)2PO.NH.C3HjBr2.SOsH. The chloride 
 Cl2PO.NH.C3H2Br2.S0201 is formed by treating 
 di-bromo-amido-benzene sulphonic acid with 
 POI5. It is converted by alcohol into the 
 ether-chloride (EtO)2PO.NH.CBH2Brj.S02Cl 
 [c. 170°] (Laar, J.pr. [2] 20, 267). 
 
 BEOMO-PHTHAIACENE v. Phthalaoene. 
 
 i-BEOMO-PHTHALIC ACID CsH3Br(C0.,H)j 
 [1:3:4]. "[140°]. Formed, together with its iso- 
 meride, by brominating phthalio acid (Faust, A. 
 160, 62 ; Pechmann, B. 12, 2124; cf. Guareschi, 
 
 A. 222, 295, StaUard, 0. /. 49, 187). Powder, 
 V, sol. water, alcohol, and ether. 
 
 Salts. — K2A"2aq: long needles (from alco- 
 hol). — BaA"2aq: crystalline powder; si. sol, 
 water. — CuA". — AgjA" : cheesy pp., si. sol. water. 
 
 Anhydride C^B.^'Bi(GO)fi. [65°]. (300°- 
 340°). 
 
 Ethyl ether Et^A" : (295°); liquid. 
 
 c-Bromo-phthalic acidCsHsBr (COjH)^ [1:2:3]. 
 [176°] (G.) ; [174°] (M.) ; [197°] (C. a. T.). 
 
 Formation. — 1. Together with the preceding, 
 by brominating phthalio acid (Pechmann).— 
 2. By the oxidation of bromo-nitro-naphthalene 
 [122-5°] with KMnO, (Guareschi, A. 222, 292), 
 of bromo- (/3)-naphthol with KMnO, (Meldola, 
 0. J. 47, 512), of liquid bromo-ditolyl (Carnelley 
 a. Thomson, C. J. 47, 591), of di-bromo-naph- 
 thalene [130°] with CrO, in HOAo (Guareschi, 
 
 B. 19, 134), of C,„H3Bri(0H) [l:!i!:3:4:2] with 
 KMnOj (Smith, C. N. 40, 87), and of (o)-bromo- 
 naphthalene, and bromo-o-toluio acid [167°] with 
 dilute HNO3 (Eaoine, A. 239, 76). The bromo- 
 o-toluio acid may be prepared from bromo-o- 
 toluidine C3H3MeBr(NHJ [1:5:2]? by Sand- 
 meyer's method ; 70 g. of bromo-toluidine gava 
 53 g. of bromo-phthalio acid. 
 
 Properties. — White prisms (from water) ; v. 
 si. sol. chloroform, m. sol. water, alcohol, and 
 ether. With resorcin it gives a fluorescein (Nour- 
 risson, B. 20, 1016). The salt BaA" forms pearly 
 plates, b1. sol. water. 
 
 Anhydride CeH3Br(CO)30. [135°] (Mel- 
 dola) ; [132°] (G.); [125°] (Smith); [108°] (Nour- 
 risson) ; [95°] (Baoine). Needles. Heated with 
 phenol and H^SO, it forma a body (? bromo- 
 phthalide) that dissolves in alkaUa forming a 
 purple solution. 
 
 Di-bromo-phthalic acid CsH2Br2(C02H), 
 []:4:2;3]. [135°]. From di-bromo-naphthalen« 
 
BROMO-PEOPANE. 
 
 616 
 
 [6i°] and HNO,. White crystalline powder, sol. 
 boilmg water and alcohol (Guaresohi, A. 222, 
 274). On melting it changes to its anhydride. 
 
 Salt.— NajA". 
 
 Anhydride [208°]. Pearly needles (by 
 sublimation) . Heated with phenol and H^SOi it 
 forms a product (dibromophthalein) that dis- 
 solves in potash forming a purple solution. 
 
 Di-bromo-phthalio acid CJB^v^iOO^)^. 
 [206°]. Formed by oxidation of penta-bromo- 
 (o)-naphthol or of tetra-bromo-(o)-naphthoquin- 
 one by means of dilute HNO3 at 150° (Bliimlein, 
 B. 17, 2490). Colourless needles. V. e. sol. al- 
 cohol, ether, and hot water. 
 
 Salts. — A"Ag2 : small colourless plates, 
 sparingly soluble. — A''Ca : pp. — A"Ba : pp. 
 
 Anhydride CsH^Brj^c^QQ^O. [208°]. Sub- 
 limes in long colourless needles. EasUy soluble 
 in alcohol, sparingly in water and ether. Formed 
 by heating the acid. Heated with resorcin it 
 yields a di-bromo-fluoresoein. 
 
 Di-bromo-tetra-hydro-phthalic acid 
 C,H|,Br2(C02H)2. Di-bromo-tetra-hydro-henzene- 
 cU-o-ea/rboxyUc acid. Formed by the direct 
 combination of dry di-hydro-phthalic acid with 
 bromine vapour. Bhombohedra (Baeyer, B. 19, 
 1810). 
 
 Tri-bromo-phthalio acid CBHBr3(002H)2. 
 [191°]. Formed by oxidation of penta-bromo- 
 (;8)-naphthol or of tetra-bromo-(j8)-naphtho- 
 quinone with HNO3 (Flessa, B. 17, 1482). Small 
 silvery plates or needles. Nearly insoluble in 
 petroleum ether and in cold water. 
 
 S alts.— AgjA".— CaA" 2aq.— BaA" 2aq. 
 
 Anhydride CsHBr3(00)20 : [157°]; sub- 
 limes in white plates ; easily soluble in alcohol 
 and ether, nearly insoluble in cold water. 
 
 Tetra-bromo-phthalic acid OsBr4(C02H)p 
 [266°]. Formed by oxidation of tetra-bromo-o- 
 xylene by heating with dilute HNO3 and bromine 
 at 170° (Bliimlein, B. 17, 2493). Small needles 
 or colourless prisms. V. si. sol. water. With 
 resorcin it yields a tetra-bromo-fluoresceiin. 
 
 Salts.— A"Ca.—A"Ba. 
 
 Anhydride 03Br4<;^Q>0. [259°]. Formed 
 
 by heating the acid. Sublimes in colourless 
 glistening needles. SI. sol. almost all solvents. 
 V, also Bromo-tebbphthaiio acids. 
 
 BEOMO-PHTHALIDE 03H3Br<^^>0. 
 
 [sorBtj]. [100°]. Formed in small quantity, 
 
 together with bromo-o-toluic acid, by the action 
 of bromine-water on o-toluio acid (Eacine, A. 239, 
 76). Needles (from dilute alcohol); sublimes 
 readily. Insol. cold water or NajCOjAq. Gives 
 bromo-o-toluio acid [167°] on oxidation. 
 
 (a).Bromo.phthaUde G3H,<^^'>0. [86°]. 
 
 Prom phthalide and bromine at 140° (Bacine, A. 
 239, 79; B. 19, 778). Small cubes or tables 
 (from ether). May be distilled. Hygroscopic. 
 Slowly decomposed by cold, quickly by hot, 
 water, forming phthalio aldehyde - acid 
 C,H,(C02H)(CH0). Alcohol converts it into 
 CsH,(COjEt)(CHO). KMnOj oxidises it to 
 phthalic acid. Ammonia forms amido- 
 
 phthalide. C.H,<gg(^^^>0. [167°]. 
 
 Di-bromo-phthalide CoH^Br^Oj i.e. 
 
 0,H^r,<g^^>0 [l l]. [188°]. S. (94 p.o. 
 
 alcohol) -37 at 15°. From di-bromo-naphthalene, 
 Cr03 and glacial acetic acid (Guaresohi, A. 222, 
 282). Prisms or needles (from alcohol). Neutral 
 reaction. Does not reduce ammoniacal AgNOji 
 With phenol and HjSO^ gives no dye on heating. 
 
 DI-BROMO-PICENE v. Picene. 
 
 BEOMO - PICKIN V. Tki - bbomo - nitbo • 
 
 METHANE. 
 
 BBOMO-PIPER-HYDEONIC ACID v. Bbomo- 
 
 DI-OXY-PHENYL-VALEKIO AOID. 
 
 BEOMO-PIPERIC ACID Dihydride. 
 C,2H„BrOj or 
 
 CH2<^Q>C,H2Br.0H3.CH2CH:0H.CO2H. 
 
 Bromo-{P)-hydro-piperic acid. [171°]. From 
 bromine and (/3)-di-hydro-piperic acid (Fittig a. 
 Buri, A. 216, 177; Weinstein, A. 227, 42). 
 Streaky white plates (from benzene). — Salt. — 
 CaA'j. 
 
 Beactions. — 1. Not affected by boiling aque- 
 ous KOH. — 2. EMuOj oxidises it, in neutral 
 solution, to bromo-piperonylio acid [204°], 
 bromo-pipero- propionic acid {q. v.) and bromo- 
 piperonal ; henceBr is in the benzene nucleus. — 
 3. Sodium-amalgam forms piperhydronic or 
 methylene-di-oxy-phenyl-valeric acid OijHuO,. 
 
 DI-BEOMO-PIPEEINIDE v. Bbomo-tbi-oxy- 
 
 PHBNVL-VALEEIO AOID. 
 
 BROMO-PIPERONYLIC ACID v. Bbomo-di- 
 
 OXY-BENZOIO AOID. 
 
 BEOMO-PIPERO-PROPIONIC ACID v. Meth- 
 of Bbomo-di-oxy-phentl-pbo- 
 
 PIONIO AOID. 
 
 DI - BROMO - PEEHNITOSE v. Di-beomo- 
 dxjbene. 
 
 BROMO-PBOFAITE v. Pbopyi, beomide. 
 
 Di-bromo-propane OjH^r, i.e. 
 CH3.CHBr.CH2Br.(141-5°). Propylene hromide. 
 S.G. 2 1-9617 (Zander, A. 214, 175). S.V. 1189 
 (Z.) ; 118-4 (Schiff). 
 
 Formation. — 1. From propylene and Br 
 (Reynolds, A. 77, 120 ; Cahours, G. B. 31, 291 ; 
 Wurtz, A. 104, 244). — 2. From bromo-propyleue 
 and HBr. — 3. Together with trimethylene bro- 
 mide by the union of HBr with aUyl bromide 
 (Geromont,BZ. [2] 16, 113, Eeboul, BZ.[2] 17, 350). 
 4. From propyl bromide and Br (Linnemann, 
 4.161,41). 
 
 PraperfAes. — ^Liquid with sweet smell. 
 
 Beactions. — 1. Alcoholic EOH forms two 
 bromo-propylenes and, finally, allylene (Sa- 
 witsoh, C. B. 52, 399).— 2. AgOAc gives the di- 
 acetyl derivative of propylene-glycol (Wurtz, A. 
 Cfe.[3]4, 438). AgOBz gives the corresponding 
 benzoyl derivative (Friedel a. SUva, G. B. 73t, 
 1379). — 3. Converted into propylene by Zn and 
 HOAc or sodium-amalgam in alcohol (Linne- 
 mann, B. 10, 1111). — 4. Aqueous HI at 150° 
 gives isopropyl bromide. — 5. Heated to 100° 
 with AgjO and water it gives propionic aldehyde 
 but no propylene-glycol (Beilstein a. Wiegand, 
 B. 15, 1496).— 6. WaUr (20 vols.) and PbO at 
 150° gives acetone, propionic aldehyde and 
 propylene-glycol (Eltekoff, J. B. 10, 212).— 
 7. Protracted boiling with wafer gives propylene- 
 glycol (Niederist.il. 196, 349). 
 
 aa-i)i-bromo-pTopaiie CHj.CBr^.CH,. Methyl 
 hrcmaeetol. Bromacetol, Acetone bromide. (115°). 
 
616 
 
 BROMO-PKOPANE. 
 
 B.G. U 1-8476 ; i| 1-8314. M. M. 10-137 at 
 20-7° (Perkin). Formed in small quantity from 
 acetone and PBr, or FGlsBr, (Linnemann, A. 
 138, 125 ; Friedel a. Ladenburg, Z. 1868, 48). 
 Also from allylene and oono. HBr (Eeboul, C. B. 
 74, 669) ; and from o-bromo-propylene and HBr. 
 Beactions. — 1. Water at 160° gives acetone. — 
 
 2. Zu and HCl give propane (Linnemann, A. 
 161, 67).— 3. Alcoholic KOH gives a-bromo- 
 propylene OHa.CBrrCHj. 
 
 aiu-Di-bromo-propane 
 CH3.0H2.0HBr2. (o. 130°). From a.-bromo-pro- 
 pylene CHj.CHiOHBr and cone. HBr (Eeboul, 
 A. Ch. [5] 14, 467). 
 
 ai,iv2-Bl-bromo-propane CHjBr.CHj.CH^Br. 
 Trimethylem bromide. (165°). B.G. s 2-006 (Z.); 
 2 2-018 (G.) ; ^^ 1-9228 (F.). S.V. 117-8 (Z.). 
 Formed from i»,a),-di-oxy-propane and HBr 
 (Freund, M. 2, 639). 
 
 Preparation. — Allyl bromide is saturated 
 with very nearly dry HBr at —16°, sealed up 
 and left at 30° for 24 hours. The tube is 
 opened and the operation repeated as long as 
 any gas is absorbed (Geromont, A. 158, 370; 
 Bebonl, A. Gh. [6] 14, 472 ; Erlenmeyer, B. 12, 
 1354 ; A. 197, 184 ; Both, B. 14, 1351 ; Bogomo- 
 Utz, Bl. [2] 30, 23). 
 
 Beactions. — 1. Alcoholic EOH forms allyl 
 bromide or allyl ethyl oxide. — 2. Alcoholic NHj 
 forms some amorphous bases (Niederist, M. 3, 
 840).— 3. Heated to 100° with Ag^O and water 
 it gives tri-methylene-glycol thus differing from 
 the isomeric propylene bromide which gives 
 propionic aldehyde (Beilstein a. Wiegaud, JB. 15, 
 1496). — 4. AljBrj converts it into propylene 
 bromide (Gustavson, J.pr. [2] 36, 303). 
 
 aiaa-Tri-bromo-propane CHs.CHBr.CHBrj. 
 (201°). From a?- bromo - propylene and Br 
 (Beboul, A. Ch. [5] 14, 481). 
 
 tecm-Tii - bromo - propane CHj.CBr^.CHjBr. 
 (191°). S.G. a 2-35. Formed by the union of 
 bromo-propylene with Br (Eeboul, A. Ch. [5] 
 14, 481 ; 0. Kolbe, J.pr. 133, 393). 
 
 a-Tri-bromo-propane CHjBr.CHBr.CHjBr. 
 Tri-bromhydrin. [17°]. (220°). S.G. 2S 2-44. 
 
 Formation. — 1. From di-bromhydrin or 
 epibromhydrin and PBrj (Berthelot a. de Luoa, 
 A. 101, 76; Henry, A. 154, 369).— 2. From 
 allyl bromide and Br (ToUens, A. 156, 168).— 
 
 3. By bromination of isopropyl bromide (Linne- 
 mann, A. 136, 63). — 4. From allyl iodide and Br 
 (Wurtz, A. 104, 247). 
 
 Propert/les. — Prisms or liquid. 
 
 BeactiUms. — 1. Alcoholic EOH gives 
 CH-CCHjOEt. — 2. Solid KOH gives two di- 
 bromo-propylenes. — 3. AgOAc gives triaoetin 
 C3H,(OAc)3.-4. KCy gives CA(Cy)3.-5. Alco- 
 holic NHj forms di-bromo-di-allyl-amine and 
 then methyl-pyridine. 
 
 Tetra-bromo-propane CHa.CBrj.CIIBrj. 
 
 Allylene tetra-hrcmide. (225°-230°)'; (110°-130°) 
 at 10 mm. S.G. 2 2-94. From allylene and Br 
 (Oppenheim, Bl. [2] 2, 6 ; 4, 434 ; A. 132, 124). 
 Liquid, decomposed by alcoholic EOH into HBr 
 and tri-bromo-propylene (o. 193°) (Pinner, A. 
 179, 59). 
 
 Tetra-bromo-propane OHjBr.CBrj.CHjBr. 
 [195°]. From iso-allylene and Br (Hartenstein, 
 /.i)r.[a]7,317). 
 
 The following tetra-bromo-propanes have also 
 been prepared : 
 
 (a) : (251°) ; S.G. 2-64. From propylene 
 bromide and Br (Eeboul, A. Suppl. 1, 232). 
 
 (6) : [69°] ; (o. 235°). By bromiuating iso- 
 propyl bromide (Linnemann, A. 136, 64). 
 
 (c) : (226°) ; S.G. 2-47. From propylene 
 bromide and Br (Oahours, A. 76, 284). 
 
 Penta-bromo-propanes OsHjBrj. The follow- 
 ing have been described : 
 
 (a) : (255°) ; S.G. 2-60. From propylene 
 bromide and Br (Oahours, O. R. 31, 291). 
 
 (6) : [173°J. From tri-bromo-propylene and 
 Br (Pinner, A. 179, 60). 
 
 (c): CHBr2.CBr2.0HBr2. S.G. is 3-01. From 
 propargyl bromide and Br (Henry, B. 7, 761). 
 
 BKOMO-PBOPIOLIC ACID OBriO.COaH. 
 Formed by decomposing muoobromio acid with 
 baryta (Jackson a. Hill, B. 11, 1675 ; Am. 3, 
 121). Prisms (from ether). V. e. sol. water 
 (crystalHsing therefrom with aaq) ; may be par- 
 tially sublimed at 100°. Boiling water liberates 
 bromo-acetylene ; boiling baryta forms bromo- 
 acetylene and also malonic acid. The acid 
 gives with di-bromo-aorylio acid a compound 
 OsHBrO.OjBr^H^O^ [105°]. 
 
 Salts. — ^BaA'jCcaq. — AgA'. 
 
 a-BEOMO-PEOPIONIC ACID CsHsBrO^ i.e. 
 CH3.CHBr.CO2H. [25°] (W.). (206° oor.). 
 Formed by heating propionic acid (1 mol.) with 
 Br (1 mol.) for several days at 150° (Friedel a. 
 Machuca, C. B. 53, 408 ; A. 120, 286). Formed 
 also from lactic acid and HBrAq at 100° (Eekul^, 
 A. 130, 16). 
 
 Beactions. — 1. Sodium-a/malgam forms pro- 
 pionic acid. — 2. Boiling water and ZnO give 
 lactic acid. The E salt changes slowly to lactate 
 in cold aqueous solution. — 3. Alcoholic NHj 
 forms alanine. — 4. Finely divided Ag at 150° 
 gives s-di-methyl-suooinic acid. 
 
 Ethyl ether EtA'. (162°); (130°) at 160 
 mm. S.G. ii 1-40. From the acid (Bischofi, A 
 206, 319). Also from lactic ether and PBr, 
 (Henry, A. 156, 176). Preparation. — Propionio 
 acid (300 g.) is converted into the bromide by 
 adding amorphous phosphorus (31 g.) and slowly 
 running in bromine (400 g.). After the evolu- 
 tion of HBr has ceased the mixture is brominated 
 by heating to 40°-50° and slowly running in 
 more bromine (640 g.). When the whole of the 
 bromine has disappeared the bromo-propionyl 
 bromide is converted into the ethyl ether by the 
 addition of absolute alcohol. It is then treated 
 with water, washed and fractionated. The yield 
 from 300 g. of propionic acid amounts to 640 g. 
 ofboihng-pointl56°-160°{Zelinsky,B.20,2026). 
 
 Bromide CHs.CHBr.CO.Br. (155°). From 
 propionyl bromide and Br ; also from propionio 
 acid, P, and Br (Weinig, A. 242, 163). ZuMe^, 
 followed by water, gives methyl isopropyl ketone 
 and di- methyl- isopropyl -carbinol (Eashirski, 
 0. G. 1881, 278). 
 
 Imide (CH3.CHBr.C0)jNH. [148°]. Formed 
 by the action of water on the compound 
 (C3H5NBr2) of propionitrile with Br (Engler, A. 
 142, 71). Needles, m. sol. hot water. 
 
 ;8-Sromo-propionic acid CH2Br.OH2.CO2H. 
 [62°]. Small glistening plates. Formed by 
 heating hydracrylio acid with HBl at 120° 
 (Beckurts a. Otto, B. 18, 227). 
 
BKOMO-PROPYL-BENZENE. 
 
 617 
 
 o/S-Bl-broma-propionic acid 
 CHBr.OHBr.COjH. [64°]. (227°). S. 1945 
 (?19-45) at 11°; S. (ether) 304 (?3-04) at 10°. 
 
 Formation. — 1. Got by oxidising di-bromo- 
 propyl alcohol with HNOj. The yield is bad 
 (Miinder a. Tollens, B. 5, 73 ; A. 167, 222) —2. 
 Also by union of acrylic acid with Br (Caspary 
 a. Tollens, A. 167, 256).— 3. Prom acrolein di- 
 bromida and HNOj (Linnemann a. Penl, B. 
 8, 1097).— 4. By the action of HBr upon a- 
 bromo-aorylio and ao-di-bromo-propionio acids 
 (PhUippi a. Tollens, A. 171, 333). 
 
 Properties. — Monoclinic crystals (Haushofer, 
 J. 1881, 687 ; Zepharovich, J. 1878, 693). It 
 crystallises in two forms : tables [64°] and 
 prisnu [61°] ; the latter slowly change into the 
 former. The salts readily split off bromide, 
 forming ;8-bromo-aorylic acid. 
 
 BeacUons. — 1. Converted into acrylic acid by 
 KI and water, or by Zn and HjSO, (v. iiotta, A. 
 192, 102; 0. a. I.).— 2. Water at 120° gives 
 bromo-oxy-propionic acid (Melikoff,J".iJ. 13,227). 
 
 Salts.— AgA'.-NH,A'.—KA'.— CaA'j2aq.— 
 SrA'j6aq. 
 
 Methyl ether MeA'. (205-8° cor.) (Weger, 
 A. 221, 84). 
 
 Ethyl ether EtA'. (214-6° cor.). 
 
 Allyl ether O3H5A'. (215°-220°). 
 
 Propyl ether PrA'. (233° cor.). 
 
 aa-Di-bromo-propionic acid CHj.OBr^.COjE. 
 [65°] (P. a. M.) ; [61°] (P. a. T.). (c. 224°). From 
 a-bromo-propionio acid and Br (Friedel a. 
 Machuca, O. B. 64, 220 ; Philippi a. Tollens, B. 
 6, 516). Trimetric tables. 
 
 Beactions. — 1. Zn and H^SO, reduce it to 
 propionic acid. — 2. Alcoholic KOHgivesa-bromo- 
 acrylio acid. — 3. Ag^O forms pyruvic acid. — 4. 
 Finely divided silver in benzene gives di-methyl- 
 maleic anhydride. —5. The salts are more stable 
 than those of the preceding acid ; but the silver 
 salt warmed with water changes to pyruvic acid 
 (Beckurts a. Otto, B. 18, 235). 
 
 Salts. — NH^A' ^aq. — NaA'. — KA'aq. — 
 BaA'o 9aq.— CaA'j 2aq.— SrA'j 6aq. 
 
 Methyl ether MeA'. (0. 177°). S.G. 2 1-904. 
 
 Ethyl ether EtA'. (191°). S.G. ^ 1-754. 
 
 Propyl ether^xM. (0. 202°). S.G. 2 1-684. 
 
 Is ohutyl ether VtCa^kl. (0. 216°). S.G. 
 s 1-578. 
 
 aajS-Tii-bromo-proplonic acid 
 CH,Br.CBrj.COjH. [96°]. 
 
 Poi-maiion. — 1. By oxidation of acrolein 
 bromide (Linnemann a. Penl, B. 8, 1097). — 
 2. From o-bromo-acrylic acid and Br (Mauthner 
 a. Suida, M. 2, 99 ; Michael a. Norton, Am. 2, 17). 
 
 Properties.- Monoclinic prisms: aib:c = 
 1-83:1: -Sie ; /3 = 66° ; m. sol. water, v. sol. alco- 
 hol and ether. On heating the Ba salt CHjiCBrj 
 is formed. Alcoholic KOH gives oj8-di-bromo- 
 acrylic acid. 
 
 Salt.— BaA'jKaq: needles. 
 
 o/3/3-Tri-bromo-propionic acid 
 CHBr2.CHBr.COjH. [118°]. Prepared by heat- 
 ing a/3-di-bromo-acrylio acid for eight hours with 
 cone. HBrAq (Hill a. Andrews, Am. 4, 180 ; P. 
 Am. A. 17, 133). Bectangular plates, v. sol. hot 
 water, ether, and alcohol,— AgA' : small rhombic 
 
 plates.— CaA'j 2aq. ., „.rr^ „r> tt • 
 
 Tetra-bromo-propiomo acid CjHBri.CO^tl i.e. 
 CHBr,.CBrj.C02H. [120°]. Prepared by ttie 
 combination of ojS-di-bromo-acrylic acid with Br. 
 
 Triolinio prisms : t. e. sol. alcohol and ether. 
 The Ba salt is decomposed by boiling water with 
 formation of tri-bromo-ethylene. Alcoholic KOH 
 gives tri-bromo-acrylic acid. 
 
 Salts. — AgA'. — KA' 2aq. — BaA'^ ^aq. — 
 CaA'2 aq (Mauthner a. Suida, M. 2, 107 ; Hill a. 
 Mabery, P. Am. A. 17, 140 ; Am. 4, 266 ; 5, 251). 
 
 aj8-DI-BE0M0-PE0PI0NIC ALDEHYDE 
 CHjBr.CHBr.CHO. Acrolein dibromide. (0. 82°) 
 at 5 mm. (Grimaux a. Adam, Bl. [2] 36, 136). 
 From acrolein and Br (Aronstein, A. Suppl. 
 3, 185 ; Henry, B. 7, 1112 ; Linnemann a. Penl, 
 B. 8, 1097). Pungent oil. Eeduces Fehling'a 
 solution. Beadily polymerises, becoming crystal- 
 line [84°] in presence of HCl. HNO3 oxidises it 
 to di- and tri-bromo-propionio acids. 
 
 Tri-bromo-propionic aldehyde. A liquid com- 
 bination of this body with propyl alcohol 
 0Br3.CH(0H)(0Pr) appears to be formed on 
 treating propyl alcohol with Br (Hardy, G. B. 
 79, 806). 
 
 7 - BBOKO - n - PEOPYL - ACETO -ACETIC 
 ETHER OH2Br.CHj.CH2.CH(OO.CH3).C02Et. 
 Liquid. Insol. water, sol. alcohol and ether. 
 Heavier than water. 
 
 Preparation. — 6 grms. of sodium are dis- 
 solved in 60 grms. of absolute alcohol and added 
 to 32 grms. of aceto-aoetic ether. The sodio- 
 aceto-acetic ether is then added to 80 grms. of 
 tri-methylene bromide and heated on the water- 
 bath for half an hour ; the yield is 75 p.c. of 
 the theoretical. 
 
 BeacUons. — ^By boiling with dilute acids it 
 yields acetyl-butyl bromide and finally acetyl- 
 butyl alcohol CH3.CO.CH2.CH2.CH2.CH2OH. 
 Alcoholic NH3 eliminates HBr forming so-called 
 ' tri-methylene-aceto-acetic ether ' (Lipp, B. 18, 
 3277. V. also pp. 24 and 40 supra). 
 
 jS-BEOMO-PEOPYL ALCOHOL CsH,BrO i.e. 
 CH.^T.CH.pC'B.20'E..Brovihydrin of tri-methyleiie 
 glycol. (98°-112°) at 185 mm. S.G. ^2 1-537. 
 S. 17 at 15°. From tri-methylene glycol (s-di- 
 oxy-propane) and HBr (Friihling, M. 3, 697). 
 
 iD-Bromo-isopropyl alcohol 
 CH3.0H(OH).CH3Br (?). Bromhydrin of Propyl- 
 ene glycol. (145°-148°). From propylene oxide 
 and HBr (Markownikoff, Z. 1870, 423). 
 
 o/S-Di-bromo-propyl-alcohol 
 CHjBr.CHBr.CH^OH. Dibromide of allyl 
 alcohol. (219°) (Weger, A. 221, 83). V. p. 184. 
 
 Methylderivative CHjBr.CHBr.CH,OMe 
 (185°) (Henry, B. 5, 455). 
 
 Ethyl derivative CHjBr.OHBr.CHaOEt 
 (194°). 
 
 s-Di-bromo-isopropyl alcohol 
 CHjBr.CH(0H).CH2Br. Glycerin di-hromhydrin. 
 (219°). S.G. iS 2-1. From glycerin and PBrj 
 (Berthelot a. de Luca, A. Ch. [3] 48, 313; 
 Eeboul, A. Ch. [3] 60, 32). Also from glycerin 
 and Br (Barth, A. 124, 349). V. also Glycekin. 
 
 DI-BEOMO-PEOPYL-AMINE 03H,BrjN i.e 
 CH2Br.CHBr.CH2.NH2. From allylamine hydro- 
 chloride and Br. Oil. Salts.— B'HCl; needles. 
 — B'^jPtCI, (Henry, B. 8, 399). 
 
 BEOMO - PEOPYL - BENZENE v. Bkomo- 
 
 OUMENE. 
 
 Di-bromo-^ - di - propyl - benzene O^'S^r^i^. 
 [48°]. From di-propyl-benzene and Br (H, 
 Korner, A. 216, 227). Needles or rectangular 
 tables (from alcohol). 
 
618 
 
 BROMO-PKOPYL-BENZOIO AOID. 
 
 BBOMO-FROFYI-BSKZOIC ACID v. Bbomo- 
 
 CCMINia ACID. 
 
 BI-SBOUO-FBOFTL BOEATE 
 B(O.CH2.0HBr.CHjBr)3. Sexabromide 0/ All¥l 
 BORATE {q.v.). Oil. 
 
 BROMO-FBOFYL BBOMIDE v. Di-bbomo- 
 
 PEOPANE. 
 
 TETRA-BEOHO-DI-FEOFYI-CARBINOL v. 
 
 reira-BKOMO-HEPTYL-ALOOHOL. 
 
 BROMO - FEOPYLENE CsH^Br i.e. 
 CH,.CH:CHBr. (60°). S.G. 24 1.43. Formed, 
 together with CHj-CBriCHj, by heating propylene 
 bromide with alcoholic KOH (Eeboul, A. Oh. [5] 
 14, 479). One of the products obtained by boiling 
 p/S-di-bromo-butyrio acid with aqueous NaiCOj. 
 HBr reunites with it forming chiefly propylene 
 bromide, but the combination is very much 
 slower than with its isomeride (48°). Alooholio 
 KOH gives allylene. Br forms CHj.CHBr.CHBrj 
 (201°). 
 
 o - Bromo - propylene 0H3.CBr;CH:2. (48°). 
 S.G. a 1-39. Formed as above (Eeynolds, A. 77, 
 122). Also by the action of alcoholic KOH 
 on CH3.CBr2.CH3 (Eeboul); and by union 
 of HBr with allylene (Eeboul, 0. B. 74, 669). 
 Oil. Eeadily combines with HBr forming 
 CH3.CBrj.CH3. Br forms CHj.CBr^.CHjBr (191°). 
 Mercuric acetate in HOAcat 100° forms acetone. 
 
 Bromo-propylene CH2Br.CH:CHj v. Ailtl 
 
 BROMIDE p. 135. 
 
 Di . bromo - propylene CjH^Brj i.e. 
 CHj:CBr.CH2Br. (140°-143°). {a).Epi-dihrom- 
 hydrin. From CHjBr.CHBr.CHjBr and solid 
 KOH (Henry, A. 154, 371 ; B. 14, 404) or sodium 
 in ether (ToUens, A. 156, 168). Converted by 
 water at 130° into bromo-allyl alcohol. 
 
 Di-bromo-propylene CHBKCH.CH^Br. (152°). 
 S.G. ii 2-06. Formed, together with the pre- 
 ceding and propargyl bromide, from s-tri-bromo- 
 propane and KOH (Eeboul, A. Suppl. 1, 230 ; 
 Henry, B. 5, 186, 452). Alcoholic AgNO, forms 
 CHBr:CH.CHjNOa; AgOAc and potassium sul- 
 phooyanide also form iS-bromo-allyl salts. 
 
 Si-bromo-propylene CH3.CBr:CHBr. Allylene 
 di-bromide. (132°). S.G. 2 2-08. From allylene 
 and Br (Oppenheim, Bl. [2] 2, 6; 4, 434; A. 
 132, 126). Also from CHj.CHBr.CHBrj and 
 AgOAc at 120° (Linnemann, A. 136, 56). 
 
 Tri - bromo - propylene CHa.CBriCBrj (?). 
 (184°) (0.); (c. 193°) (P.). From allylene tetra- 
 bromide and alcoholic EOAc (0.) or aqueous 
 NaOH (Pinner, A. 179, 59). 
 
 Tri . bromo - propylene CHjBr.CBriCHBr. 
 S.G. i- 2'53. Propargyl inbromide. From 
 propargyl bromide and Br. Non-volatile oil 
 (Henry, B. 7, 761). 
 
 Fenta-bromo-propylene CaHBrj. From allyl 
 bromide, Br, and I at 210°. Non-volatile oil 
 (Merz a. Weith, B. 11, 2243). 
 
 BEOMO-PEOFYIENE-GLYCOL v. Glycebin. 
 
 BROmO-PEOPYLENE-rEEA C^HrBrNjO i.e. 
 
 C0<;^^>C3H,Br (?). [120°J. Formed by 
 
 warming an aqueous solution of di-bromo-propyl- 
 urea (Andreasch, M. 5, 40). Silky needles ; si. 
 Bol. cold water.— B'HOl: [148°].— B'HBr: [158°]. 
 — B'jH^PtCl,. 
 
 DI-BROmO-FROFYL-MALONIC ACID 
 C^H^Br^O, i.e. (COjH)2CH.CHj.0HBr.0HjBr. 
 [121°]. From allyl-malonio acid and Br in CSj 
 (Hjelt, A. 216, 58 ; B. 15, 624). Needles in stars 
 
 (from ether). V. e. sol. ether, m. sol. water. 
 Boiled with baryta, it forms di-oxy-propyl- 
 malonate of barium {q. v.). 
 
 BROMO ■ PROPYL - PHENOL v. Bbouo- 
 cumenol. 
 
 BROMO-PROPYl-THIOPHENE 
 C,SH2(0sH,)Br. (189°). Colourless oil. Formed 
 by bromination of w-propyl-thiophene (Buffi, S. 
 20, 1741). 
 
 Di-bromo-propyl-thiophene C4SH(0aH,)Br2. 
 (248°). Oil. Formed by bromination of propyl- 
 thiophene with 2 mols. of bromine. By further 
 bromination it is converted into tetra-bromo- 
 thiophene (Euffi, B. 20, 1741). 
 
 DI-BROMO-PEOPYL-TJEEA OjHsBrjNjO i.e. 
 NH2.00.NH.CH2.CHBr.CHjBr. [109°]. From 
 allyl-urea and Br (Andreasch, M. 5, 38). Needles 
 or leaflets, si. sol. cold water. Decomposed by 
 heating with water into the isomeric hydro- 
 bromide of bromo-propylene-urea (j. v.). 
 
 BROMO-PYRIDIHE C.NH^Br [3]. (174°i.V.). 
 S.G. f 1-645. 
 
 Formation. — 1. By brominating pyridine 
 (Hofmann, B. 12, 990).— 2. By the action of 
 bromoform upon an alooholio solution of pyrrol 
 and NaOEt or upon potassium pyrrol in ether 
 (Ciamician a. Silber, B. 18, 721 ; Ciamician a. 
 Dennstedt, Q. 12, 211 ; B. 15, 1173 ; Danesi, O. 
 12, 150). 
 
 Properties. — Alkaline liquid, si. sol. water. 
 Eeduced to pyridine by zinc and HCl. 
 
 Salts.— B'jH2PtCl52aq: yellow monoelinia 
 crystals, a:b:c = 1-207:1:1-188. fi = 107° 7'.— 
 B'HCl. 
 
 Di-bromo-pyridine C-NHsBr, [2:6]. [111°]. 
 (222°). 
 
 Formation. — 1. From pyridine and Br (Hof- 
 mann, B. 12, 988). — 2. Together with pyridine 
 and mouo-bromo-pyridine by the action of bro- 
 mine onacetyl-piperidine (Hofmann, B. 16, 587 ; 
 cf. Sohotten, B. 15, 421). — 3. From tropidine 
 hydrobromide and bromine at 170° (Ladenburg, 
 A. 217, 148), di-bromo-methyl-pyridine being 
 first formed, and ethylene bromide being the 
 other product. — 4. Formed by heating the tri- 
 carboxylic acid [206°]. 
 
 Properties. — Long flat pearly needles, insol. 
 cold water, si. sol. cold alcohol. Very weak 
 base (difference from bromo-pyridine). 
 
 Salt. — B'aHjCljPtClj: golden yellow needles 
 (Pfeiffer, B. 20, 1349). 
 
 Methylo chloride CsNHjBr^MeCl. Formed 
 by heating di-bromo-apophyUin (g. v.) with HCl 
 (Anderson, A. 94, 358 ; Hofmann, B. 14, 1498 ; 
 v. Geriohten, A. 210, 99). Moist AgaO liberates 
 an alkaUne hydroxide. — ^B'jMe^PtOl,. 
 
 Di-bromo-pyridine OsNHjBrj. [165°]. Formed 
 by adding bromine to a boiling aqueous solution 
 of pyridine-sulphonic acid. Long white needles. 
 Begins to sublime at about 80°. Sol. water, 
 alcohol, ether and benzene. — B'jHjCljPtCli 2aq : 
 large orange needles, si. sol. water (Fischer a. 
 Eeimerschmid, B. 16, 1184; cf. Kiinigs, B. 
 17, 589). 
 
 DI-BBOMO-PYBIDINE-BETAINE 
 
 CsNHjBrj^^^Q 2^C0. Anhydride of di- bromo- 
 
 oxy-pyridyl-acetic add. Formed by heating di- 
 bromo-pyridine with ohloro- acetic acid.— 
 BHOl: colourless needles.— BjHjOljPtOl,: large 
 soluble brown prisms (Gerichten, B. 15, 1253). 
 
BROMO-PYROMUCIO ACID. 
 
 619 
 
 BROMO-PTEIDINE DI-CARBOXYLIC ACID 
 
 V. Bbomo-apophyllenio acid. 
 
 Bromo-pyridine-di-caTbozylia acid 
 C,NHjBr(COjH),. [165°]. Formed, together 
 with oxalyl-authranilio acid, by oxidation of 
 {i»2/)-broino-quinoline with KMnO^. Crystals. 
 V. sol. water, alcohol, ether, &o. It evolves OO2 
 at its melting-point, yielding bromo-pyridine- 
 mono-oarboxylio acid (bromo-niootinio acid) 
 [183°] (Glaus a. CoUischonn, B. 19, 2767). 
 
 Di-bromo-pyridine-tri-carboxylio acid 
 CjNBrj(C0jH)3 [2:6:1:3:5]. [206° anhydrous]. 
 Obtained by oxidation of di-bromo-s-tri-methyl- 
 pyridine [81°] with KMnO^. Plat plates (con- 
 taining 4aq). V. sol. hot water, si. sol. alcohol, 
 nearly insol. ether. FeSO, gives a red coloura- 
 tion. Heated to 165° it gives a sublimate of di- 
 bromo-pyridine [111?]. 
 
 Salts. — AgA"'aq : crystalline powder. — 
 KHjA'''^ 6aq : glistening colourless needles, sol. 
 hot water. — CujA'''^ ^aq : microorystalline blue 
 powder (Pfeiffer, B. 20, 1347). 
 
 a - BEOMO -o- PYEIDYL - (Py. 2) - PROPIONIC 
 ACID OsHsBrNOj i.e. CsH^N.CBrMe.CO^H. 
 From the corresponding oxy- acid and PBrj in 
 
 ^Salt.— (OsHjBrNOJHAuBr, (Hardy a. Cal- 
 mels, Bl. [2] 48, 232). 
 
 DI-BEOMO-PYBOCATECHIN 0,H2Brj(0H)2. 
 
 Di-methyl-ether Oa'Kfii^iOyi-B)^. [93°]. 
 Prepared by bromination of the di-methyl-ether 
 of pyrocatechin (Tiemann a.Eoppe.B. 14, 2018). 
 Formed also by the action of Br on veratric acid. 
 Colourless prisms. Sol. alcohol, ether and 
 benzene. 
 
 Tri-bromo-pyrocatechin C5HBrs(0H)2. 
 
 Mono-methyl-ether CjHBr3(0Me)(0H). 
 Tri-bromo-gtiaiacol [102°]. White felted needles. 
 Formed by bromination of guaiacol (Tiemann a. 
 Koppe, B. 14, 2017). 
 
 Tetra-bromo-pyrocateohin CeH4Br4(OH)2 
 [1:2:3:4:5:6]. [193°]. Formed by bromination of 
 pyrooateohm in chloroform solution. Colour- 
 less prisms (from acetic acid) or long fine 
 needles (from alcohol). On oxidation it yields 
 tetra-bromo-o-quinone Cfirfi^. Bromine-water 
 at 80° forms C.eHjBr.oO [139°] (Zinoke, B. 20, 
 1777; cf. Stenhouse, 0. J. 27, 586; 28, 6; 
 Hlasiwetz, A. 142, 251). 
 
 TETKA-BROMO-PYEOCOLL 0,„H5;Br402N2. 
 Formed by heating pyrocoll with bromine at 
 100°- Small yellow needles. Insol. alcohol, 
 ether, chloroform and toluene, almost insol. 
 acetic acid. By boiling with KOH it yields di- 
 bromo-pyrrol-carboxylic acid (Ciamician a. Sil- 
 ber, B. 16, 2388). 
 
 TRI-BROffiO-PYROGALLOL OsHaBrsOs i.e. 
 OaBrs(OH)3. Tri-bromo-pyrogalUc acid. From 
 tannin, glacial acetic acid and bromine at 100° 
 (Stenhouse, O. J. 27, 586 ; 28, 7; Webster, 0. J. 
 45, 207). From pyrogallol and Br (Hlasiwetz, 
 A. 142, 250). Flat needles, sol. hot water. Bro- 
 mine - water converts it into ' xanthogaUol ' 
 C,,H.Br,.08 [122°] whence alkalis form 
 C" H,Br„0, [130°] (S.). „ „ „ „ 
 
 ^-BROMO-PYROMirCIC ACID CsHjBrOs. 
 Bramo-furfurane cwrhoxyUo acid [129°]. S. 
 1-26 at 20°. From either di-bromo-pyromucio 
 acid [168°], or [192°] by reduction with zinc- 
 dust and anunonia (HiU a. Sanger, A. 232, 58). 
 On adding HOI the acid separates in matted 
 
 needles. Silky needles (from water, separating 
 at first as an oil). Sol. chloroform and benzene, 
 si. sol. light petroleum or CSj. Dry Br forma 
 di-bromo-pyromucio acid [166°]. Dilute H2SO4 
 gives bromo-fumario acid [177°]. 
 
 Salts.— BaA'jaq. S. 2-18 at 20°.— CaA'^Saq. 
 S. 1-77 at 20".— AgA'.— NaA'.— KA'. 
 
 Ethyl ether EtA' [29°] (235° i.V.). 
 
 4mide.— OsHjBrOaNHj. [156°]. Silky needles 
 (from water). 
 
 (S)-Bromo-pyromucic acid CsHaBrOj. [184°]. 
 S. -22 at 16°. 
 
 Formation. — 1. By the action of alcoholic 
 KOH on the dibromide of pyromucic acid 
 (Sehifi a. Tassinari, B. 11, 842 ; Q. 8, 297). 
 An isomeride [155°] said to be formed at the 
 same time has not been observed by others. 
 The dibromide of pyromucic ether when saponi- 
 fied also produces di-bromo-pyromuoic acid 
 (Canzoneri a. Oliveri, Q. 14, 172). — 2. From 
 pyromucic acid (20 g.) and Br (36 g.) at 100°, the 
 yield being 50 p.o. of the theoretical (Hill a. 
 Sanger, A. 232, 46 ; B. 16, 1130). 
 
 Properties. — Pearly leaflets (from water) ; si. 
 sol. cold water, cold benzene, and CHOlj, ; m. 
 sol. alcohol and ether. Aqueous bromine forms 
 fumaric, and the two di-bromo-succinic acids, 
 and di-bromo-fiirfnrane tetrabromide OiH^Br^O 
 [111°]. Dilute HNO3 produces maleic acid. 
 
 Salt 3.— KA'.— NaA'.— AgA'.— BaA'j 4aq (H. 
 a. S.) : pearly plates. S. (of BaAy 3-47 at 18°. 
 — BaA'2 2Jaq (C. a. O.). — CaA'jSaq: clumps of 
 prisms. S. (of CaAy 1-07 at 20°. 
 
 Ethyl ether EtA'. [17°]. (235° i. V.). 
 
 Amide C5H2Br02(NH2) : [145°]; needles 
 (from water). 
 
 Tetrabromide G^J&ifia '• [173°]; needles 
 (from HOAc). 
 
 Di-bromo-pyromuclc acids. Pyromucic acid 
 combines with bromine forming a tetrabromide 
 which when boiled with alcoholic NaOH forms 
 a mixture of two di-bromo-pyromucio acids (Py 
 and ;35), (S)-bromo-pyromucie acid and a tri- 
 bromopyromucic acid (the latter from tetra- 
 bromide of (S)-bromopyromuoio acid present in 
 the crude bromide). The calcium salt of the 
 (;8S) acid is ppd. from dilute (1 in 30) solutions 
 of the mixed acids by NH3 and CaCLj. Of the 
 remaining acids, the (S) acid is present in very 
 small quantity, while the tri-bromo- acid is very 
 sparingly soluble in hot water (HiU a. Sanger, A. 
 232, 67 ; B. 17, 1759; cf. TSnnies, B. 11, 1085; 
 12, 1202; Canzoneri a. Oliveri, &. 14, 177). 
 
 Constitution.— {HiiX a. Sanger, A. 232, 97). 
 Baeyer has proposed for pyromucic acid 
 
 HG = 0— COjH HC-C-COjH 
 
 (I) I >0 (II) II |>0 
 
 HC = CH HC-CH 
 
 (IH) HO- 0— COjH 
 IX>0 
 HO— CH 
 
 The two di-bromo-pyromucio acids would then be 
 BrC = C— COaH BrC— C— COjH 
 
 lla) I >0 (Ua) II |>0 
 
 ^ ' " " CH HO-CBr 
 
 BrC-C-COaH 
 
 BrC = 
 
620 
 
 BHOMO-PniOMUCIC ACID, 
 
 BrC = C-CO.,H 
 (K) I >0 
 
 HC = CBr 
 
 HO-0-COsH 
 
 (lit) y |>o 
 
 BrC— CBr 
 
 BrC— C-COjH 
 (int) IX >o 
 
 HC— CBr 
 
 inasmuch as they are formed from the tetra- 
 bromide 
 
 HCBr— CBr.COjH 
 
 I >o 
 
 HCBr— CHBr 
 by removing 2HBr. One of these ao.ids pro- 
 duces, on oxidation with HNO3, di-bromo- 
 maleic acid, the other gives mono-bromo-maleio 
 acid. Neither of the di-bromo-pyromucio 
 acids derived from (11) could produce di- 
 bromo-maleic acid, hence that formula is dis- 
 proved. Tonnula (III) is unusual in form. 
 Assuming formula (I) (iSy) -di-bromo-pyromucio 
 acid is represented by (la) while its (j8S)-isome- 
 ride is (lb), and (S)-bromo-pyromucio acid is 
 CH = C-COjH 
 
 I >0 , since on oxidation it gives 
 
 CH = CBr 
 
 maleio acid, while (/3)-bromo-pyromuoic acid is 
 CH = C— CO,,H 
 
 I >0 since it may be got by reducing 
 
 CBr = CH 
 
 either of the di-bromo-pyromucio acids. It 
 wiU be noticed that in the preceding argument 
 it has been assumed that the bromo-pyromucic 
 acids are similar in constitution to pyromucic 
 acid itself. 
 
 (37)-di-bromo-pyromuoic acid CsHJBrjOs 
 [192°]. S. -21 at 20°. From the tetrabromide 
 of pyromucic acid and alcoholic NaOH (see 
 above). Short prisms grouped concentrically 
 (from benzene) or bulky feathery crystals (from 
 water). Sol. alcohol or ether, m. sol. chloro- 
 form, si. sol. CSj, boiling water or light petro- 
 leum (HiU a. Sanger, A. 232, 82). 
 
 B,eaci/UMS. — 1. Dry iromiim forma tri-bromo- 
 pyromucic acid. — 2. Bromine-va;pour passed into 
 an aqueous solution of the acid forms tetra- 
 bromo-furfurane, Cfixfi, [65°] and a little of a 
 body CjH2Br202,[89°] (di-bromo-maleio aldehyde) . 
 3. Dilute HNO3 on warming gives mucobromio 
 and di-bromo-maleic acids. — 4. Ziiic-dust and 
 NH3 from bromo-pyromucic acid [129°]. 
 
 Salts.— AgA'.—NaA'2aq.—K4.'.—BaA'23aq. 
 S. -35 at 20°.— CaA'jSaq. S. 1-17 at 20°. 
 
 Ethyl effeer.— EtA'. [68°]. M. sol. alcohol. 
 
 Amide CsHBr^O^NHj. [196°]. Slender 
 needles (from dilute alcohol). Insol. CS, 0^ 
 light petroleum. SI. sol. boilmg water. 
 
 (;8S)-di-bromo-pyromiicic acid CaHjBrjOj 
 [168°]. S. -28 at 20°. From pyromucic acid 
 and bromine at 100° (HiU a. Sanger, A. 232,73). 
 Also from the tetrabromide of pyromucic acid 
 and alcoholic NaOH (see above). Small prisms, 
 often in twins (from water). Very soluble in 
 alcohol, ether, and boiling chloroform, less in 
 benzene, sparingly in CS2 or Ught petroleum. 
 
 BeacHons. — 1. Aqueous bromine in the cold 
 forms bromo-maleyl bromide. — 2. DUute HNO, 
 forms bromo-fumaric acid, bromo-maleic acid 
 probably being an intermediate product of the 
 reaction. 
 
 Salt s.— BaA'j aq. S. -10 at 16°.— CaA'j 3aq. 
 B. -30 at 17°.-AgA'.— NaA' 2aq.— KA', 
 
 Ethyl ether EtA'. [58*]. (271° i.V. with 
 decomposition). V. sol. ether, chloroform, benz- 
 ene, and boUing alcohol, m. sol. cold alcohol or CS^. 
 
 Bromide.— CjHBrA-Br. [46°]. (c. 154°) at 
 24 mm. One of the products of the action of 
 bromine upon pyromucic acid. 
 
 Amide C^HBrjOaNH, [176°]. SUky needles. 
 
 Tri-bromo-pyromucic acid CjHBrjOj. [219°]. 
 S. -072 at 19". From the tetrabromide of (5)- 
 bromo-pyromuoio acid and aloohoUo NaOH (HUl 
 a. Sanger, A. 232, 91). Some tri-bromo-fur- 
 fnrane is also formed. Small needles united in 
 clumps. V. sol. alcohol and ether, si. sol. chlo- 
 roform or benzene, nearly insol. CSj, light petro- 
 leum or cold water. 
 
 Beactions. — 1. Water and bromine formtetra- 
 bromo-furfurane [64°], thus: CsHBrsOa-HBr^ 
 = C4Br,0 + C02 + HBr.— 2. Dilute HNO3 forms 
 di-bromo-maleic acid. 
 
 Salts.— BaA'23aq. S. (of BaA'J -20 at 
 20°.— CaA'2 4aq. S. (of CaAy -56 at 20°.— AgA '. 
 — NaA' aq.^ — KA' aq. 
 
 Ethyl ether EtA'. [104°]. Bectangular 
 prisms (from alcohol). 
 
 Amide C5Br302NH2. [223°]. Slender needles. 
 Almost insol. CSj, light petroleum or water, 
 m. sol. ether, chloroform or benzene, v. sol. 
 alcohol. 
 
 Ito-BROMO-PYKOTABTAEIC ACID 
 OsHrBrO, i.e. CHjBr.0H(C02H).0Hj.C0.,H. 
 Bromo^methyl-sv/xima acid. [137°]. (c. 250°). 
 From itaconio acid and cone. H3rAq at 0° (Beer, 
 A. 216, 79 ; cf. Fittig, A. 188, 73 ; Swarts, Z. 
 1866, 722). MonocUnio crystals, v. sol. hot 
 water. Boiling Na^COaAq gives itaconic and 
 itamalic acids ; boiling water produces paraconio 
 acid. 
 
 Ethyl ether Et^A". (270°-275°). 
 
 Ciira - bromo - pyrotartaric acid CsHjBrOj. 
 [148°]. From oitraconic anhydride and cone. 
 HBrAq at 0°. Also from mesaconic acid and 
 fuming H3rAq at 140° (P.). MonocUnio crystals. 
 Decomposed by heating alone or with Na^COaAq 
 into methacrylio acid, CO2, and HBr. The silver 
 salt on heating with water at 130° gives off 
 allylene CHiCCHj (Bourgoin, Bl. [2] 28, 459). 
 
 Sromo - pjrrotartaric acid OsH^BrO, [204°]. 
 White prisms. Formed together with bromo- 
 crotonic acid by the action of Br on propane- 
 tricarboxylio acid CH3.CH(C0jH).CH(C0jH), 
 (2. V.) (Bischofi a. Guthzeit, B. 14, 616). 
 
 Ito-di-bromo-pyrotartaric acid CsHsBr^O,. 
 From itaconic acid, Br, and water (Kekul6, A. 
 Swppl. 1, 339). Crystals, v. sol. water, alcohol, 
 and ether. 
 
 Beacttons. — 1. Sodium-amalgam reduces it 
 to pyrotartario acid. — 2. Moist Ag20 forms di- 
 oxy - pyrotartario acid. — 3. BoilLig aqueous 
 NajCOj forms aconic acid. 
 
 Anhydride CsH^BrjOj. [50°]. Formedby 
 adding Br to a solution of itaconio acid in 
 chloroform (Petri, B. 14, 1637). 
 
 Ciira-di-bromo-pyrotartaric acid 
 COjH.OBr2.CHMe.CO2H. [150°]. S. 183 at 13°. 
 Prom citraconic acid and Br (Kekul6, A. Suppl. 
 2, 86 ; Krusemark, A. 206,1). Groups of needles ; 
 V. e. sol. water, alcohol, and ether. Heated with 
 water or aqueous Na2C0, it yields propionio 
 aldehyde, bromo-propionic aldehyde, bromo- 
 methacryUo acid, and HBr. — CaA". 
 
 Anhydride CjHjBrjOa. From citraconio 
 
TRI-BROMO-PyRUVTJRINE. 
 
 631 
 
 anhydride and Br ; formed also by heating the 
 following acid with water. 
 
 ilfesa-di-bromo-pyrotartaric acid 
 CO2H.CHBr.OBrMe.COjH. [194°] and [204°]. 
 S. 31"5 at 13°. From mesaoonio aeid and Br on 
 warming (KekuU, A. Suppl. 2, 102 ; Fittig, 
 A. 188, 86 J 206, 1). Nodules. Heated with 
 NajCOjAq it gives propionic aldehyde, two 
 bromo-methacrylio aoids, COj, and HBr. Heated 
 with water it _ gives propionic aldehyde and 
 bromo-oitraconio anhydride. 
 
 Di-bromo-pyrotartaric acid [102'']. Formed 
 by brominating pyrotartaric acid (Eeboul a. 
 Bourgoin, Bl. [2] 27, 348). 
 
 Di-bromo-pyrotartaric acid [128°]. From 
 propane tri-carboxylio acid and Br (Bischoff a. 
 Emmert, B. 15, 1107). 
 
 Tri-bromo-pyrotartaric acid CjHsBrjOj. 
 
 From pyrotartaric acid, Br, and water at 120° 
 (Lagermark, Z. 1870, 299). Hexagonal prisms; 
 sublimes above 240°. — AgjA". 
 
 TfiTBA-BBOKO-FYBOTBITAIlIG ACID 
 CiHjBr^Oa. Telra-bromo-uvic acid. [162°]. 
 Obtained by exposing powdered dry pyrotritaric 
 acid to the vapour of dry bromine at the ordinary 
 temperature. Large colourless crystals. V. sol. 
 alcohol, ether, acetone, acetic acid, chloroform, 
 benzene, and CSj, insol. water and petroleum- 
 ether. The bromine is removed by alkalis and 
 by aniline. By sodium-amalgam in slightly 
 acid solution it is reduced back to pyrotritaric 
 acid. By the action of an excess of bromine at 
 100° it yields penta-bromo-pyrotritaric acid. 
 
 Tetra - bromide CjE^BrjOj : [180°]. 
 Formed by dissolving tetra-bromo-pyrotritario 
 acid in an excess of dry bromine. Small prisms ; 
 V. sol. acetic acid, si. sol. benzene, chloroform, 
 and CSj, insol. water and ligroin. Decomposed 
 by alkalis. Eeduced to pyrotritaric acid by 
 sodium amalgam (Dietrich a. Paal, B. 20, 1078). 
 
 Penta-bromo-pyrotritaric acid 
 C^n^rfiiCOfi). [c. 197°]. Obtained by heat- 
 ing the tetra-bromo-derivative with excess of 
 bromine at 100°. White glistening crystals. 
 V. sol. ordinary solvents except water and ligroin 
 (Dietrich a. Paal, B. 20, 1082). 
 
 TBI - BEOMO - PYRBOL - (o) - CARBOXYLIC 
 ACID C4KHBrs(C02H). Tri-bromo-{a)-carbo- 
 pyrrolic acid. Long colourless needles. V. sol. 
 alcohol, ether, acetone, si. sol. hot water, insol. 
 petroleum-ether. The methyl ether is formed 
 by bromination of the methyl ether of pyrrol- (a) - 
 carboxylie acid. 
 
 Methyl ether A'Me: [210°]. Longslender 
 needles, v. sol. ether and hot alcohol, si. sol. 
 benzene and petroleum-ether, insol. water (Gia- 
 mician a. Silber, B. 17, 1153). 
 
 Di-bromo-pyrrol di-carboxylic acid. Methy I 
 ea«r 0,NHBr2(C0,Me)2. [222°]. From di- 
 methyl pyrrol di-carboxylate and Br (Ciamician 
 a. Silber, G. 17, 269). Long white needles ; 
 insol. water, sol. ether and hot alcohol. Con- 
 verted by cold fuming HNOj into CiH^BrNO, 
 
 To 171°] 
 ■ BEOMO-PYEEYL METHYL KETONE 
 
 CHj.CO.CiHjBrNH. Pseudo - acetyl - brmno - 
 pyrrol. [108°]. Long colourless needles; ob- 
 tained by brommation of pyrryl methyl ketone 
 (Ciamician a. Dennstedt, B. 16, 2354). 
 
 Di-bromo-pyrryl methyl ketone 
 CHa.CO.CiHBrjNH. [144°], white needles. 
 
 Formed by bromination of pyrryl methyl ke- 
 tone. 
 
 Tri-bromo-pyrryl methyl ketone CjHjBrjON. 
 [179°]. White silky needles. Sol. hot alcohol, 
 ether, and aqueous alkalis, insol. water. Formed 
 by the action of bromine upon pyrryl methyl 
 ketone in aqueous solution (Ciamician a. Silber, 
 B. 18, 1765). 
 
 Penta-bromo-pyrryl methyl ketone 
 CsH^BrjOH. [200°]. Small white needles. 
 Formed by bromination of the tri-bromo-deriva- 
 tive dissolved in acetic acid (0. a. S., B. 18, 
 1765) or of pyrryl methyl ketone (C. a. D.). 
 
 BEOMO-PYETIVIC ACID CsHjBrO, i.e. 
 CHjjBr.CO.COjH. From pyruvic acid, Br, and 
 water at 100° (Wichelhaus, B. 1, 265). Syrup. 
 Di-bromo-pyruvio acid CHBrj.CO.COjH. 
 [91°] (W.); [93°] (C). From pyruvic acid 
 (15g.), water (lOg.), and Br (45g.) at 100° (Bot- 
 tinger, B. 14, 1236 ; cf. Grimaux, Bl. [2] 21, 
 £31 ; Clermont, Bl. [2] 19, 103 ; Wislioenus, A. 
 148, 208). Monoclinic efdorescent tables (con- 
 taining 2aq) ; sol. water and ether. Baryta con- 
 verts it into tartronic acid. Benzene and oonc. 
 K^&O, form CHBr2.C(OH)Ph.C02H (Bottinger, 
 B. 14, 1235). — Di-bromo-pyruvio acid (1 mol.), 
 urea (1 mol.) and oonc. HjSO, form di-bromo- 
 pyruvureide C^H^Br^N^Oj, whence bromine- 
 water forms tri-bromo-pyruvurin OjBrjNjOjHj, 
 a body which is decomposed by cold ammonia 
 into bromoform and ammonic oxalurate. Am- 
 monia converts di-bromo-pyruvureide into di- 
 bromo-pyruvuramide C4H5Br2N302 which is de- 
 composed by boiling baryta-water into N!^, 
 urea, HBr, tartronic acid, and amido-uracil 
 CiHsNaOj (E. Fischer, A. 239, 185). 
 
 Tri - bromo - pyruvic acid CBrj.CO.COjH. 
 [90°], [104°, hydrated]. Formed, together with 
 the preceding, by brominating pyruvic acid 
 (Grimaux, Bl. [2] 21, 390). Also from lactic acid 
 and Br. LaminsB resembling naphthalene (con- 
 taining 2aq) ; si. sol. cold water. Decomposed 
 by boiling water into bromoform and oxalic 
 acid. 
 
 Ethyl ether EW. [97°]. Formed by add- 
 ing Br to a solution of lactic acid in ether (Kli- 
 menko, /. B. 8, 125 ; Wislicenus, A. 143, 10). 
 
 DI-BEOMO-PYETIVTJEAMIDE G,B.JiiJirfi^. 
 Di-hromo-pyvuramide. [170°-180°]. _ Prom di- 
 bromo-pyruvureide and cone. NHjAq in the cold 
 (Fischer, A. 239, 191). Slender needles (from 
 alcohol). V. sol. warm water, but slowly decom- 
 posed by boiling water. Decomposed by boiling 
 baryta-water into NH„ urea, HBr and tartronic 
 acid, another portion forming amido-uracil. 
 
 DI-BEOmO-P^EUVTJEEiDE C^HjEr^N^Oj. 
 Di-bromo -pyvureide. From di-bromo-pyruvic 
 acid {q. v.), urea, and oonc. H^SO, (Fischer, A. 
 239, 188). Granular crystals (from HOAc), v. si. 
 sol. alcohol, water, and aoids ; sol. dilute alkalis. 
 Decomposed by boiling alkalis. Decomposed by 
 heat above 280°. Its ammonium and guanidine 
 salts are si. sol. water. 
 
 TEI-BEOMO-PYEUVTIRIL ANHYDRIDE 
 CsHjBrjNiOj. Tri-bromo-anhydro-pyvuril. 
 [180°]. Formed by heating tri-bromo-pyruvio 
 acid and urea at 100° (Grimaux, A. Ch. [5] 
 11, 373). Light needles (from water). 
 
 TRI - BROMO - PYRU VTJRINE CtlL^'Bi^'S^O, 
 i.e. CBr,.C0.C0.NH.C0.NH2. JJreUe of tri- 
 bromo-pyruvic acid, Tri-bramo-pyvwrine. [247°] 
 
622 
 
 TRI-BROMO-PYRUVURINE. 
 
 From di-bromo-pyrUYureide and excess of bro- 
 mine-water at 100° or HNOg (S.G. 1-4) (Fischer, 
 A. 239, 189). Glittering plates, m. sol. boiling 
 water and alcohol, t. b1. boI. ether. Decomposed 
 even by cold alkalis into bromoform and ammo- 
 uium oxalurate. 
 
 (B. 2)-BE0M0 - CITJINOIINE 0,H„-BrN i.e. 
 CjH3Br(C3HsN). Bem-bromo-quinoUne. (278""). 
 Liquid. Volatile with steam. Prepared by 
 heating ^'-bromo-aniline with glycerin, nitro- 
 benzene and H^SO, ; the yield is 80 p.c. 
 
 Salts. — B'HCl: small white needles. — 
 (B'HC^jPtClj : microscopic needles (La Coste, 
 B. -15,558). 
 
 Bromo-quinoline CjHjBrN. (270°). Yellowish 
 oil. Prepared by bromination ol quinoline. 
 Perhaps identical with the preceding. 
 
 Salts. — B'HCl: monoolinic prisms. 
 (B'HGl)2PtCl, : fine orange-red needles. 
 
 Methylo-iodide CaHsBrNMel. By the 
 action of Ag^O on an aqueous solution of the 
 iodide, a strongly alkaline solution of the hydrate 
 is produced (CsHoBrNMeOH); this is transformed 
 on standing or warming, by splitting off H^O, 
 into the much more stable methylo-oxide. 
 
 Methylo-oxide (C„H,BrNMe)20. [147°]. 
 This is also formed by the action of KOH on the 
 iodide. Odourless needles. Soluble in hot alco- 
 hol, sparingly in cold, very slightly soluble in 
 water and ether. Combines with acids very 
 slowly (La Coste, B. 14, 915 ; 15, 188). 
 
 /OBr:OH 
 
 (Py. 1 or 2)-Bromo-qmnoIiiie OS. A I 
 
 \n : CH 
 >OH:CBr 
 or CsH,^ I , (274°unoor.). Formed, to- 
 
 \N:CH 
 gether with propyl bromide, propylene bromide, 
 quinoline hydrobromide, (fee, by heating the 
 propylo-bromide of quinoline-di-bromide to 
 170°-190°. Prepared by heating to 180° the 
 hydrobromide of quinoline - di - bromide : 
 CsH,Br2N,HBr = CsHeBrN,HBr + HBr; the quino- 
 line-di-bromide is formed by the action of bro- 
 mine on an ethereal solution of quinoline. Oil of 
 aromatic smell resembling quinoline. On oxida- 
 tion with KMnO, it yields oxaloxyl-anthranilic 
 acid C5H,(COj,H).NH.CO.C02H and bromo-pyri- 
 dine-di-carboxylic acid C5H^rN(C02H)2. 
 
 Salts. — B'HCl : needles or tables ; sublimes 
 without melting. — B'HBr : foursided tables or 
 prisms; sublimes at c. 190° without melting; 
 sol. alcohol, si. sol. cold water. — B'HNOj": 
 [180° uncor.]; small concentric prisms. — 
 B'jH^SO/ : [183° uncor.] ; small needles ; dis- 
 sociated by water. — B'jHjCrjO, : [145°] ; sparingly 
 soluble flat yellow prisms (from hot water). — 
 B'jHjCljPtClj : small orange-yellow needles. — 
 B'jAgNOj : [173°] ; needles (Glaus a. Col- 
 lischonn, B. 19, 2763). 
 
 (B.l:4)-])i-bromo-4uiuoline 
 
 CH-CBr^^'^»^- [^^^°^' («)--Di-6»"o»to-2Mi?4oZirae. 
 
 FormaiAon. — l.By bromination of quinoline by 
 heating the hydrochloride with bromine at 180° 
 (La Coste, B. 14, 917 ; 15, 191).— 2. By heating 
 di-bromo-aniline [1:4:5] with a mixture of glyce- 
 rine, nitrobenzene and HjSO. (Hetzger, B. 17, 
 186). 
 
 Properties. — ^Distils without decomposition. 
 Volatile with steam. Long white needles. Almost 
 
 insol. water, v. sol. alcohol, ether, benzene end 
 aqueous acids. 
 
 Salts. — B'HCl: small needles.— 
 B'jHjCljPtOl, : fine yellow needles.— B'jHjCrjO, : 
 orange-red miorocrystalline powder, decomposed 
 by water into the base and CrOj. The picrate 
 forms long yellow needles, decomposed by water. 
 
 Methylo-iodide B'Mel: Slender red 
 needles. Sol. hot water, insol. ether and cold 
 alcohol. 
 
 Methylo-oxide B'^MeJO. Formed by the 
 action of NaOH on the iodide. Microscopic 
 needles. 
 
 (B. 2, 4)-Di-bromo-quinoIine 0sH2Brj(0sHjN). 
 [101°]. Slender colourless needles. Volatilises 
 undecomposed. Formed by heating di-bromo- 
 aniUne with glycerin, nitrobenzene and HjSO,. 
 (B'HC^^PtCl, (La Coste, B. 15, 559). 
 
 Di-bromo-qninoline (probably B. 2 : Py. 1) 
 C„H5Br2N. [124° uncor.] Formed by the action 
 of bromine (2 mols.) upon quinoline-(S. 2)- sul- 
 phonio acid (1 mol.) in cold aqueous solution. 
 Long colourless needles (from ether). Subli- 
 mable. It is oxidised by KMn04 to bromo- 
 pyridine-di-carboxylio acid [165°] (Claus a. 
 Kuttner, B. 19, 2884). 
 
 Di-bromo-qninoline tetrahydride CjHjBrjN. 
 [66° uncor.]. Formed by reduction of tetra- 
 bromo-quinoline with sodium amalgam. Colour- 
 less tables. Volatile with steam. Sol. alcohol 
 and ether, insol. water. 
 
 Salts.— B'HCl: [75°], acioular crystals.— 
 (B'HC^jPtClj 2aq : yeUow crystalline powder. — 
 B'HNOs: [189°]: prisms. — B'H^SOi : white 
 plates, decomposes at 246° uncor. — B'H^OjOj! 
 colourless tables, decomposes at 171° uncor. 
 (Claus a. Istel, B. 15, 822). 
 
 Tri-bromo-quinoline CgHjBrsN. [170° uncor.]. 
 Formed by the action of bromine (3 mols.) upon 
 an aqueous solution of quinoline-(B. 2)-sul- 
 phonic acid (1 mol.) at 100°. Long silky 
 needles. SI. sol. cold ether (Glaus a. Kuttner, 
 B. 19, 2885). 
 
 Tri-bromo-quinoline CgH^BraN. [175°]. From 
 quinoline and Br (Lubavin, A. 155, 318). Silky 
 needles ; v. sol. hot alcohol. Possibly identical 
 with the preceding. 
 
 Tri-bromo-quinoline CgHjBrjN. [198° unoor.]. 
 Formed by the action of bromine upon an aque- 
 ous solution of quinoline- (B. 4)-sulphonic acid 
 at 100°. White felted silky needles. V. sol. 
 ether and hot alcohol. Sublimable (Claus a. 
 Kuttner, B. 19, 2882). 
 
 Tetra- bromo-quinoline CjHjBrjN [119° 
 uncor.]. Long colourless needles or thick 
 prisms. Insoluble in water. Formed by bro- 
 mination of quinoline in CSj (Claus a. Istel, B. 
 15, 820). 
 
 Hexa-bromo-qulnoline CjHBrjN. [90°]. From 
 pyridine (2, 3)-di-carboxylic acid, Br, and water 
 (Weidel, A. 173, 95). Needles (from alcohol). 
 Beduced to quinoline by sodium amalgam. 
 
 (B. 4)-BE0M:0-ftTIXN0LINE {B. 1)-CAE. 
 BOXYLIC ACID CsH5BrN(C02H). [275°]. From 
 bromo-amido-benzoio acid 0|jHjBr(NH2).C0jH 
 [1:2:4] (lOg.), glycerin (22-5g.), o-nitro-phenol 
 (6g.), and H2SO, (20g.) by heating for 5 hours at 
 160° (Lelhnann a. Alt, A. 237, 318). White 
 powder, v. si. sol. water and ether, si. sol. hot 
 alcohol. Salt.— (HA')2H2PtClj4aq. 
 
BROMO-EESOROIN. 
 
 623 
 
 (aj-BROMO-ftUINOUNE-SUlPHONIC ACID 
 
 C^s(Br)N(S03H). S. -08 at 22°; -9 at 100°. 
 Short thin needles. SI. sol. alcohol. Formed 
 together with the /S-acid by sulphonatingbromo- 
 quinoline. 
 
 Salts. — ^A'jMniaq : small yellow needles. — 
 A'Ag: spangles or needles.— A'K : short prisms, 
 S. 1-37 at 17°.— A'NH/ : felted needles.— A'^Ba : 
 nearly insoluble crystalline pp.— A'jMg lOaq : 
 colourless plates.— A'^Zn 4aq : thin colourless 
 needles (La Coste, B. 15, 1910). 
 
 (/3)-Bromo-ciuinoline-saIp}ionic acid 
 CgHsN{Br)(SOsH). S. -15 at 22°; 2-75 ai 100°. 
 Short thick needles (containing aq). Formed 
 together with the (o)-aoid by sulphonation of 
 bromo-quinoline. 
 
 Salts.— A'K IJaq: large tables, S. 17-25 
 at 22°. — ^A'Ag : colourless needles. — A'jBa 2aq : 
 sparingly soluble needles. — A'jMg 9aq : small 
 needles. — Af^Zn^aqi six-sidedtables. — ^A'^Mn 6aq: 
 colourless tables (La Coste, B. 15, 1915). 
 
 BROMO-QTJINONE CeHaBrO^. [56°]. Formed 
 by oxidising bromo-hydroquinone with FejCl, 
 (Sarauw, A. 209, 106). Groups of needles, v. sol. 
 alcohol, ether, and benzene, si. sol. hot water. 
 Ammonia gives a green colouration, turning 
 black on warming. 
 
 Di-bromo-quinone C^'B^'Brfip [188°]. Formed 
 by oxidation of di-bromo-hydroquinone (S. ; 
 Benedikt, M. 1, 346). Small golden crystals, 
 insol. water, sol. alcohol, ether, and benzene. 
 Boiling KOHAq gives di-bromo-di-oxy-quinone 
 (dibromanilic acid). 
 
 Di-bromo-quinone OeH^Br^Oj. [76°]. 
 
 Formation. — Di - bromo -p - diazo - phenol, 
 
 OsHjBrj^JT is converted by a boiling solution 
 
 of calcium chloride into di-bromo-hydroquinone, 
 CsHjBr2(OH)2. This solution is mixed with 
 FejGlg and distilled, when the quinone passes 
 over. The yield is small. 
 
 Properties. — Long, extremely slender needles, 
 sol. in alcohol, ether, CHCls, CS^, benzene, and 
 alkalis. Pungent. May be sublimed (Bohmer, 
 /.or. 132, 465). 
 
 Di-bromo-quinone CsH^BrA- [122°]. From 
 tri-bromo-phenol and fuming HNO, at 0° (Levy 
 a. Schultz, A. 210, 158). Yellow lamina (from 
 dUute alcohol). 
 
 Di-bromo-quinone? [88°]. From quercite 
 and HBrAq at 160° (Erunier,^. Ch. [5] 15, 67). 
 Three di-bromo-quinones are indicated by theory. 
 
 Tri-bromo-quinone CfiBtfi^ [147°]. Formed 
 by oxidising tri-bromo-hydroquinone in dilute 
 alcoholic solution (Sarauw, A. 209, 120). Golden 
 leaflets (from alcohol) ; sol. alcohol, ether, and 
 benzene. Alkalis give a green colouration, 
 followed by separation of red prisms. Boiling 
 cone. NaOH gives di-bromo-di-oxy-quinone and 
 tri-bromo-hydroquinone. A tri-bromo-quinone 
 [108°] is got by heating quercite with HBr (P.). 
 A tri-bromo-quinone is also formed by reduction 
 of tetra-bromo-quinone (Stenhouse, A. Suppl. 
 8, 20 ; c/. Herrmann, B. 10, 110). 
 
 Tetra-bromo-quinone O^xfip Bromanil. 
 
 Formatim.—l. By treating phenol with Br 
 and I (Stenhouse, C. J. 23, 10).— 2, By boihng 
 picric acid with Br and water (Stenhouse, .4. 91, 
 307).— 3. Prom quinone and Br (Sarauw, B. 12, 
 680, A. 209, 126).— 4. Aproduot of the action of Br 
 
 and water on benzoic acid (Hiibner, A. 143, 255), 
 and on proteids (Hlasiwetz a. Habermann, A, 
 159, 320).— 6. From tri-bromo-phenol and HNO, 
 (Losanitsch, B. 15, 474).— 6. From di-oxy-di- 
 hydro-terephthalic (succinylo-suocinic) acid and 
 Br (Herrmann, A. 211, 341).— 7. From (1,3,5,4)- 
 bromo-di-nitro-phenol by heating with Br (Ling, 
 a. J. 51, 147). 
 
 Properties. — Golden laminse (from HOAc) ; 
 sublimes as sulphur-yellow crystals. Insol. 
 water, m. sol. boiling alcohol, si. sol. ether. 
 HIAq reduces it to tetra-bromo-hydroquinone. 
 Potash forms a greenish-black solution turning 
 purple. 
 
 Tetra-bromo-or<fe)-quinone CjBr^O^ 
 [1:2:3:4:5:6]. [151°]. Obtained by oxidation of 
 tetra-bromo-pyrocatechin in acetic acid solution 
 with HNO3. It can also be prepared directly 
 from pyrocateohin by adding bromine (10 to 
 12 pts.) to a boiling solution of the latter (1 pt.) 
 in acetic acid (20 pts.). Dark-red thick prisms, 
 tables, or transparent plates. Y. sol. alcohol, 
 ether, acetic acid, and benzene, si. sol. petroleum 
 spirit. It is a powerful oxidising agent, being 
 readily reduced to tetra-bromo-pyrocatechin. 
 With aniline it gives a compound which crystal- 
 lises in bluish-black glistening plates or thick 
 needles [173°] (Zincke, B. 20, 1776). 
 
 DI-BKOMO-aUINON£-GHLORIMIDE 
 
 /NCI r .T 
 C,H2Br2<'] [2:6:*]. [80°] Long yellow 
 
 prisms. Prepared by adding a solution of 
 chloride of lime to an acidified solution of di- 
 bromo-amido-phenol [2:6:4:1] (Mohlau, B, 16, 
 2845). 
 
 DI-BBOMO.ClTTIIfONE-FH£NOI.-imiD£ 
 w /CjHj.OH 
 ^ *^0eHjBr2.0 [4:2:6:1]. 
 
 FormaUon. — 1. By adding di-bromo-quinone 
 chlorimide to an alkaline solution of phenol. — 
 2. By oxidising an alkaline solution of di-bromo- 
 amido-phenol [2:6:4:1] and phenol with K^CrjO,. 
 
 Properties. — Dark red prisms with metallic 
 reflection. Sol. alcohol, ether and acetic acid 
 with a magenta-red colour ; insol. water. 
 
 BeacOons. — On heating with HCl it is split 
 up into quinone and di-bromo-amido-phenol. 
 On reduction it yields di-bromo-di-oxy-di-phenyl- 
 
 amine HN<(,«jj^^^_oh_ 
 
 Sodium salt C,2HBBr20N(0Na) : long blue 
 prisms with golden-green reflection. Soluble in 
 water and alcohol with a blue colour. Heated 
 with an excess of aqueous NaOH the blue colour 
 changes to red, but reappears on cooUng (Mohlau, 
 B. 16, 2845). 
 
 BBOMO-BESOECIN CjH,Br(OH)j. [91°]. 
 Formed by boiling bromo-di-oxy-benzoic acid 
 with water for some hours (Zehenter, M. 8, 293). 
 Groups of needles ; v. sol. water and ether, m. 
 sol. alcohol. FejCle colours the aqueous solu- 
 tion bluish-violet, a red pp. being subsequently 
 formed. Heated with water, EjGOs, and SnOl, 
 it gives resorcin and di-oxy-benzoio acid. 
 
 Bromo-resorcin. Di-propyl derivative 
 CsHsBr(0Pr)2. [71°]. Formed by brominating 
 di-propyl-resoroin (Kariof, B. 13, 1679). Colour- 
 less silky needles ; may be sublimed. V. sol. 
 alcohol and HOAc ; b1. sol. water. 
 
624 
 
 BKOMO-RESORCIN. 
 
 Di-bromo-resorein CjHjBrjfOH),. [93°]. 
 Formed, together with 'di-bromo-mono-resor- 
 oin phtbalein,' by heating tetra-bromo-fluo- 
 rescein (eosin) -with dilute NaOHAq at 140° 
 (Baeyer, A. 183, 57; Hofmann, B, 8, 64). 
 Formed also by boiling di-bromo-(l,3,2)-di-oxy- 
 benzoio acid with water (Zehenter, M. 2, 478 ; 
 8, 293). Needles (from water); m. sol. hot 
 water, v. e. sol. alcohol and ether. Pe^Cla gives 
 a transient violet colour. 
 
 Di-methyl ether G^^tJiOM.&)2. [141°]. 
 Slender needles. Insol. water, sol. alcohol 
 and ether. Prepared by bromination of the 
 dimethyl-ether of resoroin (Tiemann a. Parri- 
 sius, B. 13, 2365 ; cf. Honig, B. 11, 1041). 
 
 Di-bromo-resorcin G^S.fir^(0^).i. [112°]. 
 From Br and resorcin in CS2 (Zehenter, M. 8, 
 293). Colourless needles (containing aq) (from 
 water) ; m. sol. hot water. Fe^Clj gives a blue 
 colour followed by a dark pp. 
 
 Tri-bromo-resoroin 08HBr3(OH)2. [104°] 
 (Typke, B. 10, 1578). From resorcin, Br, and 
 water (Hlasiwetz a. Earth, A. 130, 357), or Br, 
 and HOAo (Benedikt, M. 4, 227). Formed also 
 by heating penta-bromo-resoroin with aldehyde 
 or formic acid (Claassen, B. 11, 1439). Small 
 needles ; si. sol. water, v. sol. alcohol. 
 
 Mono-acetyl derivative 
 CsHBr3(0H)(0Ac). [114°]. From mono-acetyl- 
 resoroin and Br (C.) ; sol. hot water. 
 
 Di-aceiyl derivative C8HBr3(OAc)j. 
 [108°]., From penta-bromo-resoroin and AcjO. 
 Sol. hot water. 
 
 Mono-methyl ether OsHBr3(OH)(OMe). 
 [104°]. From mono-methyl-resorcin and Br. 
 Slender white needles ; sol. alcohol and ether, 
 insol. water (Tiemann a.Parrisius, B. 13, 2864). 
 
 Tetra-bromo-resorcin C|iBr,(0H)2. [163°]. 
 (C.) ; [167°] (B.). Formed by treating penta- 
 bromo - resoroin with H^SO, (Claassen, B. 11, 
 1440; Benedikt, M. 1, 366). SmaU needles 
 (from alcohol). 
 
 Di - acetyl derivative CjBrj(0Ac)2. 
 [169°] ; V. sol. hot water. 
 
 Penta - bromo - resorcin C8Br^(0H) (OBr) ? 
 [114°]. Formed by adding an aqueous solution 
 of resorcin to a cooled mixture of Br and water 
 (Stenhouse, A. 163, 184). Dimetric crystals, 
 a:c = '6076:1. V. si. sol. water. Alcoholic 
 AgNOj pps. more than two-thirds of its Br. At 
 160° it splits up into bromine and tri-bromo- 
 resoquinone C^HBrjOj (Liebermann a. Dittler, 
 B. 5, 1090 ; A. 169, 256). Converted into tri- 
 bromo-resorcin by cone. HI, HjS, SnClj, warm 
 alcohol, aldehyde, or formic acid (Benedikt, AT. 
 1,351; Claassen, B. 11, 1433). Boiling Ac^O 
 gives di - acetyl - tri - bromo - resorcin. Aniline 
 forms tri-bromo-aniline and tri-bromo-resoroin ; 
 phenol acts similarly (Benedikt, B. 11, 2168). 
 Boiling dilute KOH produces bromoform. 
 
 Hexa-bromo-resorcin CeBr4(OBr)2? [136°]. 
 S.G. 'i5 3-188. Prepared by heating tetra-bromo- 
 resorcinol with excess of bromine. Monoclinic 
 crystals: a:6:c = •983:1:1-687; 3 = 85°36'. Decom- 
 posed by alcohol forming tetra-bromo-resorcin 
 (Benedikt, M. 1, 365). 
 
 TEI-BROMO-RESOftTJINONE OjHBrjOj or 
 CaHjEr^Oi. Formed by heating penta-bromo- 
 resorcin at 160° (Liebermann a. Dittler, B. 5, 
 1090). Orange needles ; insol. water, v. sol. 
 alcohol and ether. At 230° it gives off Br 
 
 leaving amorphous OtJB^ifli. Eeduced by 
 Sn and HCl to tetra-bromo-tetra-oxy-diphenyl 
 (Benedikt, M. 1, 350; B. 11, 2170). 
 
 01 ■ BBOMO ■ BESOBCIX - FHTHALEIN 80> 
 called CnBJSic^O,i.e. C0j,H.0eHj.CO.CsHBr2(OH)j 
 Di-bromo-di-oxy-benzoyl-benzoic acid. [220°]. 
 Formed, together with di-bromo-resorcin, by 
 heating tetra-bromo-fluorescein with dilute 
 NaOHAq (Baeyer, A. 183, 56). Plates, v. si. 
 sol. water. 
 
 BBOMO-BETENE v. Betenb. 
 
 BBOMO-BICmELAIDIG ACID C^HajBrO,. 
 From the dibromide of ricinelaidic acid and 
 alcoholic KOH. Oil. Alcoholic KOH forms an 
 acid [71°] (Ukioh, Z. 1867, 549). 
 
 BBOMO • BICINOLEIC ACID G„H,3BrO,. 
 From rioinoleic acid by successive treatment with 
 Br and alcohoHo KOH (Ulrich, Z. 1867, 546). 
 Oil; converted by alcoholic KOH into ricin- 
 stearolic acid C,8H320s. 
 
 Bi-bromo-ricinoleic acid OisHjjBrjOa. From 
 ricinstearolic acid and Br. OU. 
 
 BBOMO-BOSANILINE v. Bosahilike. 
 
 TETBA-BBOMO-BOSOLIC ACID CjoH.jBr^O,. 
 From Br and rosolic acid in HOAo (Graebe a. 
 Caro, A. 179, 201). Lustrous green plates, insol. 
 water. Its alkaline solutions are violet. — A"Agj: 
 dark violet pp. 
 
 Ethyl ether &."lEt^: [110°-115°], soluble 
 in alcohol, ether, and benzene, insoluble in water 
 (Ackermann, B. 17, 1627). 
 
 BEOMO-ROSOCnJINOHE CjH.BriOj i.«, 
 CjHjBrj— 
 
 I I (?). Bed and steel-blue crystals. 
 
 CsHjBrj— O 
 
 Prepared by the oxidation of tetra-bromo-phenol- 
 phthalein (5 pts.) dissolved in H2SO4 (250 pts.) 
 with a mixture of HNO3 (5 pts.) and HjSO, 
 (50 pts.). 
 
 Bromo-rosohydroquinone CuHjBrjOj i.e. 
 
 (?). Tetra-bromo-di-oxy-diphenyl, 
 CsH2Br2.0H 
 
 [264°]. Sublimable. Prepared by the reduc- 
 tion of the corresponding quinone (Baeyer a. 
 Schraube, B. 11, 1301). 
 
 BBOMO-SALICYLIG ACID v. Buomo-o-oxT' 
 
 BENZOIC ACID. 
 
 BROMO-SAIICYLIC ALDEHYDE v. Bii0M0< 
 
 O-OXY-EENZOIC ALDEHYDE. 
 
 BEOMO-STEABIC ACID C.sHjsBrOj. [41°]. 
 S.G. 52 1-0653. From stearic acid (7 pts.), 
 bromine (4 pts.), and water at 135° (Oudemans, 
 J.pr. 89, 195). Crystalline mass, insol. water, 
 V. sol. alcohol and ether. The silver salt heated 
 with water forms stearidic acid CuHsjOj. 
 
 Di-bromo-stearic acid CuHsjBr^O^. From 
 oleic acid and Br (Overbeck, A. 140, 42). Oil. 
 Alcoholic KOH forms bromo-olei'c and stearolio 
 acids. Moist AgjO gives oxy-ole'ic acid C|6H3,0, 
 and di-oxy-stearic acid C,sH3j04. 
 
 Di-bromo-stearic acid CigHj^BrjOa. [27°]. 
 From elaidic acid and Br. Beduced to elaidio 
 acid by sodium amalgam. 
 
 Tri-bromo-stearic acid CuHsaBrjOj. From 
 bromo-oleio acid and Br. Oil. 
 
 Tetra-bromo-stearic acid C,8H32Br402. [70°] 
 From stearolio acid and Br. Laminsa (from 
 alcohol). 
 
 BBOmO-STILBENE v. Bromo-di fhentit 
 
 ETHTliBNB. 
 
BROMO-SUCOINIC ACID. 
 
 635 
 
 BROMO-STRYCHNINE v. Stbyohninh. 
 
 oj-BEOMO - STYRENE CeH^Br i.e. 
 
 C5H5.CH:CHBr. Bromo-phenyl-ethylene. Formed 
 by boiling styrene dibromide with alcoholic 
 KQH or by heating it with water at 190° (Glaser, 
 
 A. 154, 168; Badziszewski, B. 6, 493). Heavy 
 pungent oil ; decomposed by distillation. Con- 
 verted by heating with water into phenyl-aoetio 
 aldehyde (Erlenmeyer, B. 14, 323). 
 
 a . Bromo - styrene 0,H..CBr:CH,. r?"!. 
 (220° i.V.). 
 
 Formation. — 1. From styrene dibromide and 
 alcoholic KOAo at 160° (Zincke, A. 216, 290).— 
 2. By boiling a)3-di-bromo-phenyl-propiouio acid 
 with water (Barisch, J. pr. [2] 20, 179 ; Fittig 
 a. Binder, A. 195, 141). — 3. From bromo-oxy- 
 phenyl-propionio acid and water at 200° (G.). 
 
 Projperties. — Oil, with pleasant odour of 
 hyacinths. Maybe distilled. Does not readily 
 give up its Br. Converted into aoetophenone by 
 heating with water at 180° (Friedel a. Balsohn, 
 Bl. [2] 32, 614). 
 
 _ Di-bromo-Btyrene C^U^'Bt^. (254°). From 
 tri-ea;o-bromo-3-phenyl-propionio acid and water 
 at 100° (Kinnicutt a. Palmer, Am. 5, 384). Oil. 
 
 Tri-bromo-styrene CsHsBrj. From the pre- 
 ceding and Br. Oil (K. a. P.). 
 
 BEOMO-STYBENE DIBROMIDE v. Di-bkomo- 
 
 ETH YIi-BENZENE . 
 
 BEOMO - STJBEEIC ACID CsH„Br(C02H)2. 
 [103°]. Prepared, together with di -bromo - 
 suberic acid, by the action of bromine and 
 phosphorus on suberic acid. Crystalline 
 powder. Sol. alcohol and ether. By alcohoHo 
 KOH it gives suberconic acid (Ganttner a. 
 HeU, B. 15, 142). 
 
 Di - bromo - suberic acid CjH,(,Br2(C02H)2 
 [173°]. Formed by bromination of w-suberic 
 acid. Glistening needles. V. sol. alcohol, ether, 
 and hot water, v. si. sol. benzene, chloroform, 
 ligroin, and cold water. By heating with alco- 
 holic KOH it gives di-ethoxy-suberio acid to- 
 gether with a small quantity of subercolio acid 
 C8H,(C02H)2 (Hell a. Eempel, B. 18, 813). 
 
 BBOUO - SUCCINIC ACID C^HsBrOi i.e. 
 OOjH.OH2.CHBr.CO2H. [160°]. S. 19-2 at 
 15-5°. 
 
 Formation. — 1. By heating succinic acid 
 (5g.) with Br (2J c.c.) and water (40 c.c.) at 120° 
 (KekuU, A. 117, 125 ; Carius, A. 129, 6 ; Hell, 
 
 B. 14, 892).— 2. From succinic acid (5 g.), Br 
 (2J CO.) and chloroform (5 c.c.) at 160° (Orlow- 
 sky, J. B. 9, 277). — 3. From succinic ether and 
 Br (Schacherl, 5. 14, 637).— 4. By the action of 
 HBr on fumaric, tartaric, malic, and racemio 
 acids (Kekul6, A. 130, 21 ; Fittig, A. 188, 88 ; 
 Anscaiitz a. Bennert, B. 15, 643).— 5. By de- 
 composing its bromide with water (Volhard, 
 A. 242, 153). 
 
 Properties. — Small prisms, v. sol. water. Its 
 silver salt rapidly decomposes. Moist AgjO gives 
 malic acid. Sodium-amalgam produces succinic 
 acid. Boiling water slowly forms fumaric acid. 
 
 Anhydride C.HsBrO,. [81°]. (137°) at 
 11 mm. From the acid and AoCl at 100° (A. a. 
 p.). Decomposed by heat into HBr and maleio 
 anhydride. 
 
 Methyl ether Me^A". (c. 134°) at 30mm. 
 
 Ethyl ether M^k". (226°). Inflames the 
 pkin. Cold aqueous or alcpholio NH, convert 
 
 Vos. I. 
 
 it into fumaramide. Aqueous NH, at 110° 
 gives asparagine (Korner a. Menozzi, 0. 17, 171). 
 
 Bromide 02H3Br(C02Br)2. Formed by 
 adding Br (1100 g.) gradually to a mixture of 
 succinic anhydride (300 g.) and amorphous P 
 (36 g.) (Volhard, A. 242, 151). 
 
 s-Di-bromo-sucoinic acid 
 CO^H.CHBr.CHBr.COjH. S. 2-04 at 100°. 
 
 Formation. — 1. By heating succinic acid 
 (12 g.) with Br (11 0.0.) and water (12 c.c.) at 180° 
 (Kekul6, A. 117, 123 ; Suppl. 1, 131 ; Bourgoin, 
 Bl. [2] 19, 148).— 2. Prom fumaric acid and Br 
 (K.; Baeyer, B. 18, 676). 
 
 Properties. — Opaque prisms, si. Bol. cold 
 water, v. sol. alcohol and ether. 
 
 Beactions. — 1. Sodium amalgam reduces it 
 to succinic acid. — 2. Boiling water converts the 
 sodium salt into hydro-sodio bromo-malate, the 
 Ba salt into hydro-baric bromo-maleate and 
 barium racemate, the silver salt into inactive 
 tartaric acid, and the acid itself into HBr and 
 bromo-maleic acid. — 3. Water at 140° gives iso- 
 bromo-maleio acid. — 4. NH3 gives bromo-amido- 
 Buocinic acid. — 5. Seduction in acid solution 
 gives fumaric acid (OssipofE, Bl. [2] 34, 346). — 
 6. Heating with thio-urea gives fumaric acid 
 (Nencki a. Sieber, J.pr. [2] 25, 79). 
 
 Salts. — (NHJjA". — Na^A" 4aq.— Ag^A".— 
 CaA" 2aq. 
 
 Mono-methyl ether MeHA": decomposes 
 about 245°.— NaMeA"4aq (Claus, B. 15, 1844). 
 
 Mono-ethyl ether EtHA" [275°].— 
 KEtA" IJaq.— NaEtA" 2aq.— AgEtA" IJaq (C). 
 
 Methyl ether Me^A". [62°]. Mono-sym- 
 metrical crystals. Prepared by the action of 
 bromine on methyl f umarate. 
 
 Ethyl ether Et^A". [58°]. (E.; A.); [68°] 
 (Lehrfeld, B. 14, 1820). Ehombic crystals. 
 Prepared by the action of bromine on ethyl 
 fumarate. On heating to 170° it decomposes 
 into bromo-maleic ether and HBr (Ansohiitz, 
 B. 12, 2281). Aniline converts it into 
 02H2(NPhH)2(COjEt)2 [145°] (Lopatine, C. B. 
 105, 230). 
 
 Methyl-ethyl ether MeEtA" [63°] (C). 
 
 Chloride OiH^Br^OjClj [63°]. From Br 
 and sucoinyl chloride or fumaryl chloride 
 (Perkin a.Duppa, C. J. 13, 102 ; K.). 
 
 Amic acid COjH.CjHjBrj.CO.NH,. Un- 
 stable crystals (0. ; Michael a. Wing, Am. 6, 
 421). 
 
 Anilide(1) 
 NHPh.CO.OHBr.CHBr.CO.NHPh. From the 
 anilide of fumaric acid and bromine (Ansohiitz 
 a. Wirtz, A. 289, 138; Am. 9, 240). White 
 powder, does not melt below 300°. 
 
 Phenyl-imide ^^^^{Gfiiy.Cin^'Br^. [159°]. 
 From the phenyl-imide of maleic acid (maleanil) 
 in chloroform by adding Br (A. a. W.). 
 
 Iso- (or a2Zo-)di-bromo-Buccinic acid 
 
 ^CHBr— C(OH), 
 >0 
 CHBr— CO 
 {of. Ansohiitz, A. 239, 181). [160°]. 
 
 Formation, — 1. From maleic acid and Br 
 (KekuU, A. Suppl. 2, 89).— 2. Together with its 
 isomeride, by heating bromo-maleic anhydride 
 with HBr, or succinic acid with water and Br at 
 140° (Franchimont, B. 6, 199 ; Bourgoin, B. 6. 
 624).— 3. From (S)-bromo-pyromucio acid, Br. 
 ^nd water (Hill a. Sanger, 4.232, 53). 
 
 S 8 
 
 COoH.CH2.CBr2.COjH or < 
 
636 
 
 BROMO-SUOOINIO ACID. 
 
 Preparation. — By dissolving its anhydride 
 in water (Piotet, B. 13, 1670). 
 
 Properties. — Large crystals ; more soluble in 
 water than its isomeride. At 180° it gives oS 
 HBr, bromo-fumario acid being formed. 
 
 BeacUons. — 1. Boiling water converts the 
 acid and its Ba salt into bromo-maleie acid, but 
 the Ag salt into raoemie acid. — 2. Moist Ag20 
 gives pyruvic acid (BeOstein a. Wiegand, -B. 15, 
 1499). — 3. Sodium amalgam produces suocinio 
 acid. 
 
 The Di-methyl ether Af'Me^ and the 
 Di-ethyl-ether A"Et2are oily liquids, insol. 
 water (Piotet, B. 13, 1670). 
 
 Anhydride O^fit^-Cp, [32°]. Prepared 
 by heating maleio anhydride with bromine at 
 100° (Pictet, B. 13, 1669). Colourless tables. Has 
 a great affinity for water, with which it forms 
 iso-dibromo-succinic acid. On heating to 100° it 
 evolves HBr forming bromo-maleio anhydride. 
 
 Tri-bromo-sncciuic acid 
 C02H.0Brj,.CHBr.C0JH. [187°]. From bromo- 
 maleio or bromo-fumario acid and Br (Petri, A. 
 195, 69). Deliquescent needles ; boiling water 
 converts it into di-bromo-acrylic acid. 
 BSOMO-SULFHI-BENZCIC ACID 
 C«H3Br(S02H){COjH) [4: 2 or 3:1]. [238°-245°]. 
 Prom CsH3Br(S02Cl)COjH by treatment with 
 alcohol and zinc-dust (0. Bottinger, A. 191, 24). — 
 BaA".— BaHjA''^ 2aq.— CaHjA"j 8aq. 
 
 BBOMO-SirLFHI-BENZOIC ALDEHYDE 
 OeH3Br(SO,H)CHO. [131°]. One of the pro- 
 ducts got by reducing, by zinc-dust and alcohol, 
 the mixture of chlorides got by acting on 
 O.H,Br(SOsNa)(CO,Na) by PCI5. It is formed 
 from OeHjBr(S0801)(COCl) present in the mix- 
 ture. Salt. — ^BaA'jSaq. 
 
 BBOHO-SULFHO-BENZOIC ACID 
 CeH3Br(S03H)(C02H) [2: 3 or 5 :1]. From the 
 corresponding bromo-toluene sulphonio acid by 
 chromic mixture (Eetschy, A. 169, 45). — 
 KHA"iaq.— BaA"2aq.— PbA"2aq. 
 
 Bromo-sulpho-benzoio acid 
 CsH3Br(S03H)(C0jH) [1:3:5]. From m-bromo- 
 benzoic acid and SO, (Hubner a. Upmann, Z. 
 [2] 6, 295 ; Eoeters van Lennen, Z. [2] 7, 67 ; 
 Bottinger, B. 7, 1779). Delicate deliquescent 
 needles. Potash-fusion converts it into s-di- 
 oxy-benzoio acid. 
 
 Salts .— NaHA". — Ag^A". — CaA" IJaq— 
 BaA" 2 jaq.— BaHA", aq.— CuA". 
 
 Bromo-sulpho-benzoic acid 
 0,H3Br(S03H)(C0iH) [4:2:1]. From bromo- 
 toluene o-sulphonic acid by chromic mixture 
 (Weiss, A. 169, 26).— KHA".— CaA".— BaA" : 
 v. Bol. water. 
 
 Imide C6H3Br<^^Qi';>NH. Bromo-bemoio 
 
 sulphmide. [217°]. From (4, 1, 2)- bromo- 
 toluene sulphamide and KMnOj. Also from the 
 acid E salt by successive treatment with PCI, 
 and NHj (Bemsen a. Bayley, Am. 8, 229). Long 
 needles (from water) ; v. sol. alcohol and hot 
 water, j. si. sol. HClAq. Sublimes at 200°. Its 
 taste is extremely sweet at first and then 
 extremely bitter. — Ba(0,H3BrNS03)2 7iaq. — 
 Ca(C,H3BrNS03)j7iaq. — AgOjHaBrNSOj. — 
 CjHsJOjHsBrNSOa): [199°]; formed by succes- 
 sive treatment with PCI, and alcohol. 
 
 Bromo-sulpho-benzoic acid 
 C«H,Br(SO.H)(COjH) [4:3:1]. Formed by oxi- 
 
 dation of the corresponding bromo-toluene 
 sulphonio acid (Hasselbarth, A. 169, 12).—' 
 KHA" aq.— BaA"4aq.— PbA" 2aq. 
 
 Bromo-sulpho-benzoic acid 
 CeH3Br(S03H)(C02H) [4: 2 or 3 :1]. Probably 
 identical with the preceding. From ^-bromo- 
 benzoio acid and fuming H,S04 heated for 8 
 hours at 130° (Bottinger, A. 191, 13). Matted 
 needles, v. sol. water. 
 
 Salts.— NaHA"2aq.—Ag2A"3aq.—BaA"3aq. 
 — BaHjA"j 4aq.— CuA" 3aq.— PbA" 7aq. 
 
 Chloride CeH3Br(S02Cl)C0^. [197°] (with 
 decomposition). Needles (from ether).' M. sol. 
 cold ether, which separates it from another 
 chloride. 
 
 Acid ether 0eH3Br(SOsEt)(C02H). [84°]. 
 From the chloride and alcohol. 
 
 Amic acid CeH3Br(S0jNH2)C0jH. [230°]. 
 — BaA'2 12aq. 
 
 Amic acid C„HsBr(S03H)C0NH,. [262°]. 
 Amic ether C3H3Br(S03Et)(C0NH2) [128°], 
 Bromo-di-snlpho-benzoic acid 
 CsH2Br(SO3H)2C0jH. From p-bromo-toluene 
 diaulphonic acid and boiling fuming HNO3 
 (Eomatzki, A. 221, 196). — K3A"'aq.— 
 Ba3A"'2l2aq. 
 
 Chloride. [151°]. Trimetrio tables from 
 ether). 
 
 Amide. [above260°]. Small prisms in stars. 
 BEOMO - SULPHO - PHENYL - PEOPIONIC 
 ACID CsHsBrSOs i.e. 
 
 [4:3:1] C,H3Br(S03H).CHj.CH2.COjH. Prepared 
 by the action of fuming sulphuric acid on p- 
 bromo- phenyl -propionic acid (Goring, 0. G. 
 1877, 793, 808). Non-deUquescent rhombic 
 plates (containing 2Jaq). a:h:c = 1-3013:1:0-7831. 
 Salts. — NaHA"3aq. — BaA"2aq.— 
 H2BaA"2 8aq; triclinic crystals: a:b:c = 
 0-4941 : 1 : 0-5046 ; o = 68° 36' ; ;3 = 98° 22' ; 
 7 = 83° 38'. — CaA"3aq. — CaHjA"j8aq: 
 monoclinio crystals: a :6:c = 0-7062:1:0-9774; 
 /3 = 86°45'. 
 
 DI-BBOMO-SULPHO-PYEOMUCIC ACID 
 CBr = 0— COjH 
 
 I >0 . Di-bromc-sulpho-furfuraiie- 
 
 CBr = 0— SO3H 
 
 carboxylic acid. Formed by sulphonation of 
 di-bromo-pyromucio acid [192°] with fuming 
 H2SO4. By the action of bromine upon its 
 barium salt, di-bromo-maleio acid is formed. 
 By zinc-dust and aqueous NH, it is de- 
 brominated, yielding sulpho - pyromucio acid. 
 A"Ba 5aq : easily soluble long fine needles (Hill 
 a. Palmer, B. 18, 2096). 
 
 BBOnO-STTLFHYDEO-BEITZOIC ACID 
 C,H,Br(SH)C02H(?) [256°] (U.) ; [243°] (L.). 
 From the chloride of sulphonated jra-bromo- 
 benzoio acid by tin and HCl (Upmann, Z. 
 1870, 295 ; Van Lennen, Z. 1871, 67). Needles, 
 insol. water. Beduced by sodium-amalgam to 
 CeH4(SH)C02H. Iodine converts its Na salt 
 into an acid [130°]. 
 
 Salts .— ZnA'j.— PbA'j.— BaA'j. 
 Bromo-snlphy^o-benzoic acid 
 CsH3Br(SH)C0jH. [194°]. From the chloride 
 of (1, 3, 5)-bromo-sulpho-benzoio acid by tin 
 and HCl (Frerichs, B. 7, 795). Laminte. — 
 PbA'2 3aq. 
 
 BEOKO-TEBEFHTHALIC ACID 
 C.H^r(CO,H), |:2:1;4]. [306° cor.]. Needles 
 
DI-BKOMO-THIOPHENE-SULPHONIO ACID, 
 
 627 
 
 eontaining aq (Pis.) or anhydrous (Fil.). Pre- 
 pared by oxidation of bromo-toluio acid with 
 KMnO, (Ksohli, B. 12, 619), by oxidation of 
 bromo-oymene (Pileti, <?. 16, 286), or of p- 
 phenyl-toluene [129°] (Carnelley a. Thomson, 
 C. J. 51, 88). It gives a sublimate (7 anhydride) 
 [245°]. ^ •' ' 
 
 Salts.— KjA": needles.— AgjA" aq. White 
 insoluble floooulent pp.— A"C!u : light blue pp. 
 
 Chloride OsHsBrfCOCl)^. (305° cor.). 
 
 Amide C^n^BiiCO^H-K,)^. [270°]: insolu- 
 ble needles. 
 
 Methyl ether C8H3Br(C0.0Et)2. [42°] 
 (Fis.); [52°] (Pil.), "(above 300°). Needles. 
 
 Di-bromo-terephthalio acid OgEJir,^{GOJB.), 
 [6:8:4:1]. Formed by oxidation of di-bromo-ji- 
 toluio acid [195°] with KMnOi (Schultz, B. 18, 
 1762) or of di-bromo-oymene with dilute HNO3 
 (Clans a. Winmiel, B. 13, 902). Lamina (from 
 HOAc) ; does not melt below 320°. 
 
 Salts. — A''0a4aq: easily soluble micro- 
 scopic needles. — A"Ba 2aq and A"Ba 5aq : 
 microscopic needles. 
 
 Ethyl ether A"Et2. [121°]. (0. 335°). 
 Pearly plates. 
 
 o-Di-bromo-terephthalic acid. 
 
 Hexa -hydride OJSfii^iCO^Ta), [2:3:1:4]. 
 Di-o- bromo - ^aiai - hydro - benzene - di-p • car- 
 hoxylic acid. Formed by direct combination of 
 tetra-hydro-terephthalic acid with Br in the cold. 
 Granular crystals (containing aq). Nearly insol. 
 cold water, sparingly in hot. By Ag^O it is con- 
 verted into an acid (probably 05H8(OH)2(COi,H)2) 
 which by treatment with bromine yields tetra- 
 bromo-pyiocatechiu (Baeyer, B. 19, 1808). 
 
 DI - BROMO . TETEADECANE OuH^aBr^. 
 Tetradecylene bromide. [0°]. Colourless liquid. 
 Formed by addition of Br to tetradecylene 
 (Krafit, B. 17, 1372). 
 
 HEXA-BEOMO-DITHlfiHYL | * ' . [255° 
 C^BrjS 
 uncor.]. Formed by heating an acetic acid 
 solution of dithienyl with an excess of bromine 
 (Nahnsen, B. 17, 2198). Small needles. V. sol. 
 hot benzene, v. si. sol. cold benzene and hot 
 alcohol. 
 
 l'BI-<»-BK0MO-DI-THllNYI-ETHANE 
 CBr3.CH(C4H3S)2. [102°]. Obtained by adding 
 H2SO4 to a mixture of thiophene and bromal 
 dissolved in aoetio acid. Small pyramids. V. 
 Bol. ether, CSj, and hot alcohol. With ieatin 
 and HjSOi it gives a violet-red colour (Peter, B. 
 17, 1344). 
 
 DI-ai-BHOMO-DI-THlilNYL-ETHYIENE 
 CBrj:C(C4H,S)j. Formed by boiling tri-bromo- 
 di thiSnyl-ethane with aloohoUo KOH, or better 
 KCN (Peter, B. 17, 1344). Colourless oil. 
 Volatile with steam. Gives a violet-red colour 
 with isatin and H^SOj. 
 
 BEOMO-THIENTL methyl KETONE 
 G4SH2Br.CO.CHj. Bromo-acetotMenone. [94°]. 
 Formed by the action of acetyl chloride upon 
 mono- or di-bromo-thiophene in presence of 
 AljOlj. Stout colourless needles. Sol. hot 
 alcohol, less in cold. Very volatile with steam. 
 By alkaUne KMnOi it is oxidised to bromo-thio- 
 phene-oarboxylio acid [140°]. 
 
 Phenyl hydrazide 
 C,SHjBr.C(N2HPh).CH3: [122°]; tables; si. 
 sol. alcohol (GatteraianB a, Bomer, B. 19, 689). 
 
 BEOMO-THIO-CRESOL v. Buomo-tolyl meb- 
 
 OAPTAN. 
 
 DI-BEOMO-THIOHYDANTOIKCsHjONjSBrj. 
 Formed by the action of bromine on a solution 
 of thiohydantoin in aqueous HCl (Mulder, B. 
 8, 1263 ; Kramps, B. 13, 789). Colourless crys- 
 tals. Insol. cold water, sol. alcohol and ether. 
 Decomposed by hot water. 
 
 BEOMO - THIO - OXY - BENZOIC ACID v. 
 Beomo-sulphtdeo-benzoio acid. 
 
 (a) . BEOMO - THIOPHENE C^SHsBr. ')3'. 
 Bromo-thiophene. (150°). S.G. §| 1-652. Col- 
 ourless liquid. Formed by bromination of thio- 
 phene (Meyer, B. 16, 1472). Isolated from the 
 crude di-bromo-thiophene obtained by fractional 
 bromination of benzene that contains thiophene. 
 By BtBr and Na it is converted into ' ;8 '-ethyl- 
 thiophene (Schleicher, B. 18, 3015). 
 
 Di-bromo-thiophene C^SE^Brj. (211° cor.). 
 S.G. If 2-147. Colourless oil. Formed by 
 dropping bromine into thiophene cooled with 
 water. Prepared by fractional bromination of 
 benzene that contains thiophene. With isatia 
 and H2SO4 it gives a deep-blue colour (Meyer, B. 
 16, 1469 ; Meyer a. Stadler, B. 18, 1488). 
 
 Tri-bromo-thiophene C^SHBrj. [29°]. (260° 
 cor.). Formed by further bromination of di- 
 bromothiophene. Long white glistening crystals. 
 V. sol. hot alcohol and ether, si. sol. cold alcohol. 
 Gives the indopheniue reaction. By sulphona- 
 tion and debromination it yields thiophene-(;3). 
 sulphonic acid (Rosenberg, B. 18, 177B). 
 
 Tetra-bromo-thiopheue O^SBr^. [112°]. (326° 
 cor.). Long white needles. Formed by further 
 bromination of di-bromo-thiophene (Meyer a. 
 Kreis, B. 16, 2172). 
 
 BEOMO-THIOPHENE-CAEBOXYLIC ACID 
 C4SH2Br(C02H). [140°]. Formed by oxidation 
 of bromo-thienyl methyl ketone with alkaline 
 KMnOj. Colourless glistening needles (from 
 water). Sublimes in pearly spikes. M. sol. hot 
 water, nearly insol. cold water (Gattermann a. 
 Eomer, B. 19, 690). 
 
 Di-broma-thiopliene-(a)-carboxylic acid 
 CjSHBrj.COjH. Di - bromo - thiophenic acid. 
 [222°]. Obtained by bromination of (a)-thio- 
 phene-carboxylic acid (g^.v.). White monoclinio 
 needles. Sublimes on heating. V. sol. alcohol 
 and ether, si. sol. hot water, insol. cold water. 
 Sparingly volatile with steam. Isatin and H^SO, 
 yield a dirty -green colouration quickly becoming 
 brown. A solution of the ammonium salt gives 
 white pps. with AgN03, Pb(0Ac)2, HgNOj, and 
 SnClj; yellow pp. with Fe^Cls; and greenish- 
 white pp. with CUSO4. 
 
 Salts. — A'Ag: white curdy pp. becoming 
 crystalline. — A'K : easily soluble crystals. — 
 A'jBa 3|aq : white needles, v. sol. hot water, si. 
 sol. cold. 
 
 Chloride CjSHBr^.COCl : (250°-270°) ; 
 riIkv 1166Q.I6S 
 
 Amide C4SHBr2.C0NH2 : [167°] ; fine white 
 felted needles ; v. sol. alcohol and ether, spar- 
 ingly in hot water. 
 
 Methyl ether CiSHBrj.COjMe : [80°J; 
 white needles (Peter, B. 18, 543 ; Bonz, B. 18, 
 2308). 
 
 DI-BEOMO-THIOPHENE-SUIPHONIC ACID 
 CiHBrjS.SOjH. Formed by sulphonating di- 
 bromo-thiophene. By sodium-amalgam it ig 
 
 8 S 2 
 
DI-BKOMO-THIOPHENE-SULPHONIO AOID, 
 
 reduced to thiophene-'/S'-sulphonio acid. — 
 PbA'j 5 |aq : small crystals, sol. hot water. 
 
 Chloride O^HBr^S-SO^Cl : [33°]. 
 
 Amide C,HBr2S.S0j,NHj : [147°]; felted 
 needles ; sparingly soluble in water (Langer, B. 
 17, 1566 ; 18, 553 ; Eosenberg, B. 18, 3030). 
 
 Si-bromo-tlilopliene-di-salplionic acid 
 C4SBr2(S03H)j. Obtained by boiling tbe anhy- 
 dride with alkalis. It very readily splits off 
 HjO with conversion into the anhydride. 
 
 Salts. — Na,A"3aq: very soluble silky 
 needles.— (NHJji" aq.—PbA" : plates, sol. hot 
 water. — ^BaA" aq : sparingly soluble white glis- 
 tening spikes. 
 
 Anhydride O^SBr^^gQ^^O : white glis- 
 tening plates, V. Bol. alcohol and benzene, insol. 
 ■water and ligroin. Obtained by the action of 
 fuming sulphuric acid (4 vols.) on di-bromo- 
 thiophene (1 vol.). 
 
 Chloride C,SBr2{S02Cl)2: [220°]; glisten- 
 ing white needles ; sol. ether. 
 
 Amide 04SBr2(SOjNH2)2 : [o. 270°] ; crystal- 
 line powder; nearly insol. water (Langer, B. 17, 
 1569 ; 18, 554 ; Eosenberg, B. 18, 8080). 
 
 Tri-bromo-thiophene-sulphonic acid 
 CjSBr3(S03H). Formed together with the anhy- 
 dride by sulphonation of tri-bromo-thiophene 
 [29°]. — BaA'2 aq : sparingly soluble white warty 
 crystals. 
 
 Anhydride {CjSBra.SOj)^© : [116°]; vola- 
 tile with steam ; white solid ; v. sol. alcohol and 
 ether, v. si. sol. water. 
 
 Chloride C4SBr3(S02Cl) : [126°]; needles. 
 
 Amide C4SBr8(S02NH2) : needles (from 
 water) (Eosenberg, B. 18, 1774, 3028). 
 
 SI-BBOKO-THIOFHEinC ACID v. Di-bbomo- 
 
 THIOPHENE-OAEEOXYLIC ACID. 
 
 BROMO - THIO - PHENOL v. Bkomo-phentl 
 
 MEECAPTAN. 
 
 TETEA-BEOMO-THIOPHTHENE CsS^Br, i.e. 
 yCBr.CBr 
 
 S< I 
 >C = C . [172°]. Formed by bromination 
 
 \CBr:CBr 
 of thiophthene. Long white needles (from 
 benzene). V. sol. hot benzene, si. sol. alcohol 
 (Biedermann a. Jaoobsen, B. 19, 2447). 
 
 BEOMO - THIOTOLENE v. Beomo-methyl- 
 
 imOPHENB. 
 
 BEOMO-THIOXENE v. Beomo-di-methyl- 
 
 THIOPHENB. 
 
 TO-BEOMO-THYMOHYDEOftTJINONE 
 
 OeHMePrBr(OH)j [1:4:5:3:6]. [53°]. Formed by 
 the action of cone. HBr upon thymoquinone at a 
 low temperature. Colourlessneedles (Sohniter,B. 
 20, 1318). Formed also by reduction of the 
 corresponding quinone with SO^ (Mazzara a. 
 Discalzo, O. 16, 195). Changes spontaneously 
 to a substance melting at 87° 7m. a. D.). 
 
 Di-acetyl derivative CBHMePrBr(0Ac)2. 
 [91°]. From thymoi^ilinone and AcBr (Schulz, 
 B. 15, 657). 
 
 Di-bromo-thymo-hydroqamone 
 
 Di-acetyl derivative 05MePrBr2(OAc)j, 
 [122°]. From di-acetyl bromo-tbymo-hydro- 
 quinone and Br (S.). 
 
 BEOMO-THYMOLS and their ethyl derivatives 
 appear to have been obtained by Paterno a. 
 Qan^oueii, Q, 10, 233, Aimstrong a. Tborpe, 
 
 Brit, Assoc. Reports, 1875, 112; and Lallemand, 
 A. Ch. [3] 49, 148. 
 
 BEOUO-IHYMOL SVLFHONIC ACID 
 CioHisBrSO, i.e. CeHMePrBr(0H)(S03H). From 
 potassium thymol (a)-sulphonio acid and Br. — 
 KA'4aq.— BaA'2 (Bngelhardt a. Latschinoff, Z, 
 1871, 261). 
 
 TO-BEOMO-THYMOftUINONE C,HMePrBrO, 
 [1:4:5:3:6]. [48°] (M. a. D.) ; [45°] (S.). Formed 
 by oxidation of the corresponding bromo-thymo- 
 hydroquinone with FejClj. Glistening yellow 
 plates (Schniter, B. 20, 1318). From bromo- 
 amido-thymol and nitrous acid (Mazzara a. 
 Discalzo, G, 16, 195). A crystalline bromo- 
 thymoquinone was got by Carstanjen (J.jpr. [2] 
 3, 55) in brominating thymoquinone. Andresen 
 (J.pr. [2] 23, 184) obtained a liquid isomeride 
 by brominating thymoquinone ohloro-imide. 
 
 Di-bromo-thymo-quinone OjBrjMePrOj. 
 [74°]. The ethereal extract from the product 
 of the action of HBr on thymo-quinone-ohloro- 
 imide (g. v.) is evaporated and the residue dis- 
 tilled with steam (Andresen, J.pr. [2] 28, 184). 
 From thymoquinone and Br (C). Lemon- 
 yellow plates (by adding water to the alcoholic 
 solution). 
 
 o-BROMO-TOITrENE 0,H,Br i.e. CeH.MeBr 
 [1:2]. (182°). S.G. if- 1-2031. S.V. 141-95 
 (Schiff, B. 19, 564). 
 
 Formation. — 1. Together with p - bromo- 
 toluene, by brominating cold toluene, in the 
 dark, in daylight, or with addition of iodine 
 (Hiibner a. Wallach, Z. [2] 5, 22, 138, 499 ; A. 
 154,293; Dmochowsky, B. 5, 333; KekuU, .4. 
 187, 192 ; Beilstein, A. 143, 869 ; Cannizzaro, A. 
 141, 198; Glinzer a. Fittig, A. 183, 47; 136, 301 ; 
 Fittig, A. 147, 39 ; Eosenstiehl a. Nikiforoff, Z. 
 [2] 5, 685 ; Hiibner a. Eetschy, Z. [2] 7, 618 ; 
 Lauth a. Grimaux, Bl. 1866, i, 847 ; 1867, i, 108; 
 Kbrner, O. 4 ; Hiibner a. Jannasoh, A. 170, 117 ; 
 Louguinine, B. 4, 614 ; Eeyman, Bl. [2] 26, 588 ; 
 Schramm, B. 18, 607). — 2. From o-toluidine by 
 the diazo- reaction (Wroblewsky, A. 168, 171 ; 
 Jackson, Am. 1, 98). — 3. Together with naph- 
 thalene, by the action of (o)-bromo-naphthalene 
 on toluene in presence of Al^Cl, (Boux, Bl. [2] 
 45, 520). 
 
 Properties. — Oil. 
 
 BeacUons. — 1. Converted by dilute HNO, 
 into o-bromo-benzoic acid (Zincke, B. 7, 1502).— 
 2. Sodium has no action at 15°. — 3. Sodium 
 and Mel form o-xylene.^-4. The copper-zinc 
 couple has no action (Gladstone a. Tribe, 0. /. 
 47, 448). 
 
 TO-Bromo-toluene CjHjMeBr [1:3]. (184°). 
 S.G. IS 1-401 (W.). 
 
 Formation 1. From C6H,MeBr(NH2) [1:3:4] 
 
 by the diazo- reaction (Wroblewsky, Z. [2] «*, 
 609 ; A. 168, 155 ; Grete, A. 177, 231).— 2. 
 From the same bromo-p-toluidine by successive 
 conversion into C5H2(NOj)MeBr(NHj) [5:1:3:4], 
 C5H,(N02)MeBr [5:1:8], CeH,(NH2)Me [5:1], and 
 C„H,BrMe [5:1] (Wroblewsky, A. 192, 206). 
 
 Prcyperties. — ^Liquid, even at —20°. Oxidised 
 by chromic mixture to m-bromo-benzoic acid. 
 
 p-Bromo-toluene OsHiMeBr [1:4]. [28-5°]. 
 (185° i. V.) (Hiibner a. Post, A. 169, 6). S.G. 
 V 1-411 (KekuW, A. 137, 192). 
 
 Formation. — ^Together with o-bromo-toluene 
 (j. V.) by brominating toluene. 
 
 Properties. — Trimetrio cryatali. 
 
BROMO-TOLUENE SULPHONIC ACID. 
 
 629 
 
 Reactions. — 1. OrO, forms ^-bromo-benzoio 
 acid. — 2. Sodium even at 15° forma ditolyl 
 (Zinoke, B. 4, 396 ; Louguinine, B. 4, 514).— 
 3. Sodium and Mel gives p-xylene.— 4. The 
 copper-sine couple has no action (Gr. a. T.). — 
 5. Taken internally, it is excreted as ^-bromo- 
 benzoio and p-bromo-hippurio acids (Preusse, H. 
 5, 63).— 6. CrOjClj forms CeH.Br.CHrO.CrOCl)^ 
 (Etard, A. Ch. [5] 22, 241). 
 
 u-Bromo-toluene v. Benzyl bbomide. 
 
 Di-bromo-toluene OsHsMeBrj [1:2:8]. [28°]. 
 From OeH2(CHs){NH2)Brj [86°] by displacing 
 NHj by H (Nevile a. Winther, O. J. 37, 484). 
 Gives on ojudation with HNOj di-bromo-benzoic 
 acid [146°-148°]. On nitration it gives a mono- 
 nitro- derivative [57°] which reduces to an 
 amido- compound [SS'^. 
 
 Di-bromo-toluene OsHsMeBrj [1:2:4]. From 
 di-bromo-/»-toluidine [75°] by eliminating NHj. 
 Also from C8H,(CH3)(NH2)Br [1:2:4] by diazo- 
 perbromide reaction. Oil. On nitration gives 
 di-bromo-nitro-toluene [80°]. On oxidation with 
 HNO3 gives di-bromo-benzoic acid [169°]. 
 
 Di-bromo-toluene CsHjMeBr^ p.:2:5]. (236°). 
 S.G. — 1"813. Formed by brominating toluene 
 (Wroblewsky, Z. [2] 6, 289). From acetyl-o- 
 toluidine by brominating, saponifying, and dis- 
 placing NH2 by Br by the diazo- reaction (N. a. 
 W.). Also from aoetyl-?re-toluidine in the same 
 way. Thus CeH3(CHa)(NHj)Br [1:2:5] and 
 CBH3(CHj)Br(NH2) [1:2:5] give the same 
 CaH3(CH3)Br2. Oil. On nitration it gives a 
 nitro- compound [88°], which reduces to an 
 amido- compoimd [85°]. Oxidised by dilute 
 HNO3, it gives di-bromo-benzoic acid [149°- 
 153°] ; this diatUled with lime gives a soHd, 
 [86°], probably p-di-bromo-benzene. 
 
 Di-bromo-toluene CeH3MeBr2 [1:2:6]. (246°). 
 S.G. ^ 1-812. From di-bromo-m-toluidine [35°] 
 (Wr. ; N. a. W.) or from di-bromo-^-toluidine 
 [88°] by diazo- reaction. Oil. On nitration it 
 gives two nitro- compounds, [161°], and [0. 80°]. 
 On oxidation it gives di-bromo-benzoio acid 
 [150°-167°]. 
 
 Di-bromo-toluene CsHaMeBrj [1:3:4]. (241°). 
 S.G. is 1-812. Formed in brominating toluene 
 containing iodine in sunlight (Jannasch, A. 176, 
 286). Also from bromo-^-toluidine by the diazo- 
 perbromide reaction (N. a. W. ; Wr.). OU. Gives 
 a nitro- derivative, [87°], reducing to an amido- 
 derivative [98°]. By oxidation with CrO, it gives 
 di-bromo-benzoio acid [233°]. 
 
 Di-bromo-toluene GsH3MeBr2 [1:3:5]. [39°]. 
 (246°). From CeH2(CH,)(NH,)Brj [73°] and its 
 isomeride [46°] (N. a. W. ; Wr.). WithHNO, it 
 gives two di-nitro- compounds, [158°] and [105°]. 
 On oxidation with CrO, it gives di-bromo-benzoio 
 acid [208°-210°]. 
 
 Di-bromo-toluene 0,H3MeBrj. [108°]. The 
 existence of this body, said to be formed in bro- 
 minating toluene (Fittig, A. 147, 39), is called in 
 question by Nevile and Winther. 
 
 Other Di-bromo-toluenes are described as 
 Bbnzylidbne bromide and Bbomo-bbnzxii bro- 
 
 UIDB. 
 
 Tri-bromo-toluene C^H^MeBrs [1:2:3:4]. [44°]. 
 From CsH(CH3)(NH2)Br3, [97°], by nitrous gas 
 (Nevile a. Winther, 0. J. 37, 447). On mtration 
 it gives a nitro- compound [107°]. 
 
 Tri-bromo-toluene CAMeBr, [1:2:3:5]. [58°]. 
 From di-bromo-o-tolnidine [46°] by diazo- 
 
 perbromide reaction (N. a. W.). Long flat 
 needles. 
 
 Tri-bromo-toluene C„H2MeBr3 [1:2:5:6]. [59°]. 
 From [1:3:2:5:6] C.H(0H3)(NH2)Br, [94°] by 
 nitrous gas. On nitration it gives a nitro- com^ 
 pound [91°]. 
 
 Tri-bromo-toluene OsHjMeBrj [1:2:4:6]. [66°]. 
 (290°). From tri-bromo-m-toluidine [101°] by 
 nitrous gas (N. a. W.; Wroblewsky, A. 168, 
 194). On nitration it gives a di-nitro- compound 
 [c. 220°]. 
 
 Tri-bromo-toluene CsH^MeBrj [1:3:4:5]. [89°]. 
 From di-bromo-p-toluidine by diazo-perbromide 
 reaction (N. a. W.). 
 
 Tri-bromo-toluene C5H2MeBr3 [1:3:4:6].[112°]. 
 From di-bromo-m-toluidine [75°] and from di- 
 bromo-toluidine [85°] by diazo-perbromide re- 
 action (N. a. W.). 
 
 Tri-bromo-toluene ? [150']. Formed by heat- 
 ing potassium tri-bromo-phenol with KOAo 
 (Pfankuch, J.pr. [2] 6, 108). 
 
 Tetra-bromo-tolueue C^HMeBr, [1:2:3:4:6]. 
 [105°-108°]. From tetra-bromo-m-toluidlne 
 [224°] by alcohol and nitrous gas. Also from 
 tri-bromo-m-toluidine [100°] by diazo-perbro- 
 mide reaction (Nevile a. Winther, C. J. 37, 
 449). Fuming HNO3 forms the nitro- compound 
 [216°]. 
 
 Tetra-bromo-toluene CjHMeBrj [1:3:4:5:6]. 
 [111°]. From tri-bromo-m-toluidine [96°], by 
 diazo-perbromide reaction (N. a. W.). Its nitro- 
 compound melts at [212°]. 
 
 Tetra-bromo-toluene CeHMeBri [1:2:8:5:6], 
 [117°]. From tri-bromo-m-toluidine [94°] by 
 diazo-perbromide reaction. Its nitro- derivative 
 melts at [213°]. 
 
 Penta-bromo-toluene CjMeBrs. [285°]. From 
 tetra-bromo-m-toluidine by diazo-perbromide 
 reaction (Nevile a. Winther, O. J. 37, 450). 
 From toluene, AljBrj, and Br at 0° (Gustavson, 
 Bl. [2] 28, 347; B. 10, 971). Long needles 
 (from benzene). 
 
 o-BKOMO-TOLUENE STJIPHONIC ACID 
 C,H,BrS03 i.e. CeH3MeBr(S03H) [1:2:5?]. From 
 o-bromo-toluene by sulphonation (Hiibner a. 
 Post, A. 169, 31 ; cf. Dmochowsky, B. 5, 833). 
 Also from brominated (1, 4, 3)-jj-toluidine sul- 
 phonio acid by displacement of NHj by H 
 (Pechmann, A. 173, 212). Eeduced by sodium- 
 amalgam to toluene m-sulphonic acid. 
 
 Salts.— EA' ^aq.— NaA' ^aq.— BaA'j 2aq.— 
 BaA'j SJaq. S. (of BaAy -35 at 14°.— PbA'j 2aq. 
 S. (of PbA'2) -52 at 18°.— PbA'2 3aq. 
 
 Chloride C,H3MeBr(S0,Cl). [53°]. 
 
 Amide C3H3MeBr(S0jNH:2). [134°]. 
 
 o-Bromo-tolnene snlphonic acid 
 CBH3MeBr(S03H) [1:2:5]. From o-toluidine by 
 sulphonating and displacing NH^ by Br (Pagelf 
 A. 176, 294 ; Nevile a. Winther, B. 18, 1943 ; 
 cf. Gerver, A. 169, 384). Eeduced by sodium- 
 amalgam to toluene m-sulphonic acid. 
 
 Salts .— KA' aq.— CaA'2 aq.— BaA'^ ^aq. S.. 
 l-2at25°(P.).— BaA'„2|aq.— BaA'j9aq. S. 8-9 
 at 17-5° (G.).-PbA'22aq.— CuA'jSaq. 
 
 Chloride [58°] (P.); [56°] (N. a. W.). 
 
 Amide [c. 135°] (P.) ; [147°] (N. a. W.).. 
 This acid is probably identical with the preceding. . 
 
 o-Bromo-tolnene sulphonic acid 
 C3H3MeBr(S03H) [1:2:4]. From o-toluidine p. 
 sulphonic acid by the diazo- reaction (Hayduck,, 
 
630 
 
 BROMO-TOLUENE SULPHONIC AOID. 
 
 A. 172, 206).— KA' : nodules of minute needles. — 
 BaA'2 2aq.— PbA'2 2|aq. 
 
 Chloride C^B.^M.eBt(%O^Gl). [54=]. 
 
 Amide G^^M.6Bx{m^^B.^). [151°]. 
 
 Bromo-toluene sulphouic acid 
 CeHaMeBrSOaH [1:3:5]. Prom bromo-o-toluidine 
 Bulphonio acid or from bromo-^-toluidine aul- 
 phonio acid by displacement of NHj by H. 
 Potasb-fusion gives oroin (Nevile a. Winther, B. 
 13, 1944 ; C. J. 41, 420). 
 
 Chloride CHjMeBr.SO^Cl. [52°]. 
 
 Amide OaHjMeBr.SO^NH^. [139°]. 
 
 m-Bromo-tolueue snlphonic acid 
 C|jH3MeBr(S03H). Pormed by sulpbonating m- 
 bromo-toluene (Grete, B. 7, 795; 8, 565; A. 
 177, 238).— BaA'j aq.— SrA'j aq.— CaA'j 2aq.— 
 MgA'2 6aq. — CuA'2 4aq. — PbA'^ 3aq. Accortog 
 to Wroblewsky (A. 168, 166 ; Z. [2] 7, 6) three 
 bromo-toluene sulphonio acids are formed by 
 Bulphouating m- bromo-toluene, the Ba salts 
 being BaA'^aq. S. -528, BaA'^ 3aq. S. 1-452, 
 and BaA'j 2iaq. S. 5-248 at 19°; Grete, how- 
 ever, could only obtain the acid just described, 
 
 Bromo-toluene o-sulphonic acid 
 C^H3MeBr(S03H). From (1, 4, 2)-toluidine sul- 
 phonic acid by bromination and elimination of 
 NH^ (Weckwarth, A. 172, 196).— NaA' Jaq.— 
 KA'aq.— BaA'22|aq.— SrA'22iaq.— PbA'23|aq.— 
 CuA'j^aq. 
 
 Chloride CjH3MeBr(S02Cl) : crystalline at 
 -20°. 
 
 Amide G^S.^U.e'ST:{^O^B^: [0. 164°]; 
 needles. 
 
 Bromo-toluene sulphonic acid 
 C5H3MeBr(S03H). Prom toluene by sulphona- 
 tion, nitration, reduction, and displacement of 
 NH2 by Br (Weckwarth, A. 172, 193 ; Hayduck, 
 A. 177, 57).— BaA'^aq. 
 
 Chloride. Oil, slowly solidifying. 
 
 Amide. Does not melt below 230°. 
 
 p-Bromo-toluene m-snlphonic acid 
 C3H,MeBr(S03H) [1:4:3]. [0. 108°]. From p- 
 toluidine m-sulphonio acid by exchange of NH2 
 for Br. Formed also in sulphonating ^-bromo- 
 toluene (E. Eiohter, A. 230, 319; Post a. 
 Betschy, A. 169, 7 ; v. Peohmann, A. 173, 208 ; 
 Nevile a. Winther, G. J. 37, 631). Lamina 
 (containing aq). — BaA'j7aq. — SrA'2 7aq. — 
 PbA'j 3aq. 
 
 Chloride C3H3MeBr(S02Cl). [61°]. 
 
 Amide C8H3MeBr(SO.,NHj). [152°]. 
 
 ^-Bromo-toluene sulphouic acid 
 C,H3MeBr(S03H) [1:4:2]. The chief product of 
 the sulphonation of j)-bromo-toluene (Hubner, 
 A. 169,6; Z. [2] 7,618). Formed also from 
 p-toluidine o-sulphonic acid by exchange of NHj 
 for Br (Jenssen, A. 172, 237). Eeduced by 
 sodium-amalgam to toluene o-sulphonic acid. — 
 NaA'^aq. — CaA'2 4aq.— BaA'^aq. S. '53 at 8°. — 
 SrA'2 aq.— PbA'2 3aq.— CuA'2 7aq. 
 
 Chloride C^HjMeBriSO^Cl). [35°]. 
 
 Amide C,H3MeBr(S02NH2). [167°]. 
 
 p-Bromo-toluene exo-sulphouic acid 
 C^HjBr.OHjSOsH [1:4]. p-Bromo-benzyl sul- 
 phonic acid. Prom ^-bromo-benzyl bromide 
 and K2SO3 (Jackson a. Hartshorn, Am. 5, 264). 
 Also from 0„H4(NH2).CH2S03H by diazo- reac- 
 tion (Mohr, A. 221, 222).— KA'. S. 6-2 at 18°. 
 — CaA'j.— BaA'jllaq.- BaA'^aq. S. (of BaA'^) 
 67 at 18°.— PbA'2. S. 2 at 18°. 
 
 Chloride. [107°] (M.) ; [115°] (J. a. H.). 
 
 Bromo-toluene disulphonic acid 
 C3HjMeBr(S03H)j [1:2:3:5]. From 
 C5H2Me(NH2)(SOaH)2 by diazo- reaction (Limp- 
 richt, B. 18, 2177; Hasse, A. 230, 294).— 
 K2A"4aq.— BaA"liaq. 
 
 Chloride [90°]. 
 
 Amide [238°]. 
 
 ^-Bromo-toluene disulphonic acid 
 C5H2BrMe(S0sH)2. From jp-bromo-toluene, 
 HjSOj and SO3 (Eornatzki, A. 221, 192). Cauli- 
 flower-like deliquescent crystals. Boiled for 
 sixteen hours with oono. nitric acid it forma 
 sulphuric acid C,H2Br(C02H)(S03H)2, with 
 C,H(N02)Br2MeS03H, and OsH2(N02)Me(S03H)2. 
 
 Salts.— EjA" aq.— BaA" 5aq.— PbA" 2aq. 
 
 Chloride. [99°]. Trimetrio plates (from 
 ether). 
 
 Amide C,H2MeBr(S02KH2)2. [above 260°]. 
 
 Bromo-toluene disulphonic acid 
 C,H2MeBr(S03H)2 [1:4:3::!;]. Prepared from 
 OsB[,Me(NH2){S03H)2 by diazo- reaction (Limp- 
 richt, B. 18, 2179 ; E. Eichter, A. 230, 324).— 
 BaA" 6aq.— KjA" aq. 
 
 Chloride CeH2MeBr(S02Cl)2. [129°-133°]. 
 
 Amide CeH2MeBr(S02NH2)2. [above 240°]. 
 
 Di-bromo-toluene snlphonic acid 
 CBH2MeBr2(S03H). From o-bromo-toluene m- 
 sulphonic acid by nitration, and displacement 
 of NO2 by Br (Sohafer, A. 174, 365).— NaA' 2aq.— 
 BaA'2 2|aq. 
 
 Tri-hromo-toluene sulphonic acid 
 CjHMeBr3(S03H). Prom o-toluidinep-sulphonio 
 acid by bromination and exchange of NH2 for Br 
 (Hayduck, A. 174, 354).— KA'.— BaA'2 l^aq. 
 The chloride is a syrup, the amide an amor- 
 phous powder. 
 
 BB0MO-(a)-TOLTTIC ACID v. BBOMo-PHENyi- 
 
 AOEIIO ACm. 
 
 ^-Bromo-0-toluic acid C8H3MeBr(C02H) 
 [1:4:2]. [118° uncor.]. Fine white needles. 
 Formed by oxidation of bromo-o-ethyl-toluene 
 with dilute HNO3 (1-1) at 200° (Glaus a. Pieszcek, 
 B. 19, 3088). 
 
 Bromo-toluic acid OsH^MeBr.COjH [l:aor4:2]. 
 [167°]. Prom o-toluio acid and bromine in the 
 cold (Jacobsen a. Wierss, B, 16, 1959 ; Eacine, 
 
 A. 239, 74). Needles ; volatile with steam. 
 On oxidation it gives bromo-phthalic acid [157°]. 
 
 Salt. — BaA'jSaq. 
 
 Methyl ether MeA.'. [46°]. 
 
 Bromo -o-toluio acid OsHjMeBrOOaH 
 [l:4or5:2]. [176°]. Glistening needles. V.sl. 
 sol. hot water. Formed by oxidation of bromo-o- 
 xyleue with dilute HNO3.— CaA'j 2aq (Jacobsen, 
 
 B. 17, 2375). This acid is perhaps identical 
 with the following. 
 
 Bromo-o-toluic acid CsH3MeBr(C02H) [1:5:2]. 
 [187°]. Formed by saponification of the nitrile. 
 Sublimes in needles. V. sol. alcohol, v. si. sol. 
 water. By alkaline KMnO, it is oxidised to 
 bromo-phthalic acid [168°] (Nourrisson, B. 20, 
 1016). 
 
 Amide 03H3MeBr(CONH2) : [182°]; pearly 
 plates (from alcohol) ; sublimes in needles. 
 
 Nitrile CeH3MeBr(CN) [1:5:2]. [70°]. 
 Formed from bromo-o-toluidine by diazotisation 
 and treatment with cuprous cyanide. Long 
 needles. Easily volatile with steam. 
 
 Bromo-m-toluio acid CgH,MeBr(CO.H) 
 [1:4:3]. [153°]. 
 
BEOMO-TOLUIDINE. 
 
 681 
 
 Formation. — 1. Prom bromo-isocymene, 
 OeHaMePrBr [1:3:4] by treatment with dilute 
 HNO3 (Kelbe a. Czarnomski, A. 235, 296).— 
 2. Together with the following acid, bybromina- 
 ting ni-toluio acid in the cold (Jacobsen, B. 
 14, 2351). — 3. From bromo-nitro-toluene [45°] 
 by treatment with KCN and alcohol at 220°, and 
 saponification of the resulting nitrile (Kiohter, 
 £.5,425). ^ 
 
 Properties.— Slender needles; si. sol. cold 
 HOAo. Oxidation gives (4, 1, 3)-bromo-iso- 
 phthalio acid. 
 
 Bromo-w-toluio acid OAMeBrCO„H [1:6:31. 
 [209° cor.]. 2 L J 
 
 Formation. — 1. By oxidation of bromo-m- 
 xylene (Fittig, A. 147, 32; Jacobsen, B. 
 14, 2352). — 2. Together with the preceding by 
 brominating m-toluio acid (J.). — 3. By oxidising 
 the corresponding bromo-m-isooymene (Kelbe, 
 B. 15, 41). — 4. From the corresponding amido- 
 toluio acid by exchange of NH^ for Br (Remsen 
 a. Kuhara, Am. 3, 431). 
 
 Properties. — Crystalline powder, sol. hot 
 alcohol, insol. water. — OaA'j 3aq. — BaA.'^ 4aq. — 
 AgA'. 
 
 Ethyl ether BtA'. [c. -5°]; (270°-275°). 
 
 Bromo-2»-toluic acidCjHjMeBrfCOjH) [1:2:4]. 
 [204°]. 
 
 Formation. — 1. By the oxidation of bromo- 
 cymene OsHjMePrBr [1:4:2] (Landolph, B. 5, 
 268), bromo-^-xylene (Jannasch a. Dieckmann, 
 A. 171, 83), bromo-^-ethyl-tolueue (Bemsen a. 
 Morse, Am. 1, 138). — 2. By brominating jp-toluio 
 acid in the cold (Bruckner, B. 9, 407). 
 
 Properties. — Thin needles or laminae (from 
 water) ; m. sol. hot water. 
 
 Salts.— BaA'24aq.—CaA'23|aq CaA'^Saq. 
 
 Bromo-p-toluicacid C5H3.MeBr(C02H) [1:3:4]. 
 [196°]. Formed by oxidising bromo-p-cymene 
 CjHsMePrBr [1:4:8] (Kelbe a. Kosohnitzky, B. 
 19,1731). 
 
 Di-bromo-m-toluic acid C,H2MeBr2(COjH). 
 [186°]. Formed by oxidising crude di-bromo- 
 xylene with CrO, (Fittig, Ahrens, a. Mattheides, 
 A. 147, 36). Minute needles (from alcohol). — 
 BaA'j 9aq.— AgA'. 
 
 Di-bromo-^-toluic acid CjH^MeBr^.COjH 
 [4:6:3:1]. [195°]. Needles (from alcohol). V. si. 
 Bol. hot water. Formed by oxidation of di- 
 bromo-i)-xylene CeB^iCB.,)^!! [1:4:3:6] ia acetic 
 acid solution with CrOg. By further oxidation 
 with KMnO, it gives di-bromo-terephthalic acid 
 C,HjBrj(COjH)j [6:3:4:1]. 
 
 Salt 8.— CaA'j 4aq : S. 1 at 20°.— BaA'^ 2aq. 
 
 Ethyl ether A'Et: [49°]; (c. 310°); long 
 needles (Schultz, B. 18, 1762). 
 
 BEaMO-o-TOLUIDINE C5H3Me(NH2)Br 
 
 [1:2:3]. Formed by reducing bromo-nitro-tolu- 
 ene, itself got by the diazo- reaction frombromo- 
 nitro-toluidine [88°]. OU. Gives with bromine- 
 water di-bromo-o-toluidine, C|iH2(CH3)(NHj)Br2, 
 [47°]. Heated with oonc. HOI at 160° it forms 
 the above di-bromo-toluidine and a crystalline 
 bromo-toluidine [55°] (Nevile a. Winther, C. J. 
 87, 630). 
 
 Bromo - toluidine C5H3Me(NH2)Br [1:2:4]. 
 [32°]. (c. 255°). Formed by reducing the corre- 
 sponding bromo-nitro-toluene, [45°] (Hubner a. 
 Wallaoh, A. 154, 298 ; Komer, Z. 1869, 636 ; 
 Hubner a. Eoos, B. 6, 799; Wroblewsky, A. 168, 
 177; Hejnemann,Z. [2] 6, 402; A. 158, 340; 
 
 Nevile a. Winther, 0. J. 37, 442). Laminse. — 
 B'HOl: six-sided trimetrio tables, S. '827 al 
 11-5°.— B'2H2S04. 
 
 Bromo-o-tolnidine CsHsMe(NH2)Br [1:2:5]. 
 [58°]. Formed by brominating acetyl-o-tolu- 
 idine (Wroblewsky, A. 168, 162 ; Z. [2] 7, 135). 
 Also from bromo-nitro-toluene [55°] by tin and 
 HCl (Grete, B. 8, 565 ; A. 177, 249). lUiombo- 
 hedra (from alcohol). Its constitution is known 
 because it gives the same di-bromo-toluene (j. v.) 
 as bromo-m-toluidine. By displacement of NH, 
 by H it yields m-bromo-toluene. — B'^HjSO,. — 
 B'jHjSO.liaq.— B'HCL — B'HNOai [183°]; S. 
 4-92 at 17°. 
 
 Acetyl derivative 08H3Me(NHAc)Br. 
 [157°]. 
 
 Bromo-toluidine OsH3Me(NH2)Br [1:3:4]. 
 [32°] (N. a. W.) ; [67°] (Wr.) ; [75°] (H. a. E.). 
 By reducing the corresponding bromo-nitro- 
 toluene (q.v.) (Nevile a. Winther, O. /. 37, 442 ; 
 Wroblewsky, A. 168, 177 ; Hubner a. Eoos, B. 
 6, 800). 
 
 Acetyl derivative CaH3Me(NHAo)Br. 
 [114°] (N. a. W.). 
 
 Bromo - toluidine CaH3Me(NH2)Br [1:3:5]. 
 [36°]. (0. 258°). S.G. 12 1-1442. Formed by 
 reducing bromo-nitro-toluene, [81°]. Crystal- 
 lises with difficulty (N. a. W. ; Wroblewsky, A. 
 192, 203). Eeduced by sodium-amalgam to m- 
 toluidine.- B'HCl.— B'HNO,. S. 2-6 at 13°.— 
 B 2H2SO4. 
 
 Acetyl derivative C8H3Me(NHAc)Br. 
 [168°]. 
 
 Bromo-m-toluidlne CjH3Me(NH2)Br [1:3:6] 
 [78°]. (240°). Formed by brominating acetyl- 
 m-toluidine and boiling the product with alco- 
 hoUc potash (N. a. W.). Formed also by re- 
 ducing (l,2,5)-CeH3(CH3)Br(N02). It gives the 
 same di-bromo-toluene (j. v.) as bromo-o-tolu- 
 idiue. — B'HNOj: prisms. 
 
 Bromo-toluidine CsH3Me(NH2)Br. From 0- 
 bromo-toluene by nitration and reduction (Hub- 
 ner a. Eoos, B. 6, 801). Oil.— "B'HCl: S. 3-1 
 atl6-5°.— "B'HNOj: 1-25 at 19°. Perhaps iden- 
 tical with the preceding. 
 
 Bromo-^-toluidine C3H3Me(NH2)Br [1:4:3]. 
 [26°] (Claus a. Steinberg, B. 16, 914). (240°). 
 S.G.-- 1"S0. From aoetyl-^i-toluidine by bromi- 
 nation and saponification (Wroblewsky, A. 168, 
 153). Elimination of NHj gives m-bromo- 
 toluene.— B'HNO, : [182°] ; S. 2-533 at 19°.— 
 B'H,SO, aq.— B'H2C204. 
 
 Acetyl derivative CsH3Me(NHAc)Br. 
 [117-5°]. 
 
 Bromo-p-toluidine CsH3Me(NH2)Br [1:4:2]. 
 [26°]. Formed by reducing the corresponding 
 bromo-nitro-toluene (Nevile a. Winther, C. J. 
 39, 85).— B'HBr.— B'HCl (Wallaoh, A. 235, 255). 
 
 Di-bromo-o-toluidine CsH2(CH3) (NH2)Br2 
 [l:2or6:3:5]. [46°] (N. a. W.); [50°] (Wroblewsky, 
 A. 168, 187 ; Z. [2] 7, 210). From o-toluidine 
 and bromine (Nevile a. Winther, C. J. 37, 436). 
 Forms unstable compounds with strong acids. 
 
 Bi - bromo - toluidine CsH2(CH3)(NH2)Brj 
 [l:x:3:4]. [98°] (N. a. W.) ; [85°] (Wr.). By re- 
 ducing the corresponding nitro- compound 
 (Nevile a. Winther, C. J. 37, 439 ; Wroblewsky, 
 A. 168, 184). Does not combine with acids. 
 
 Di - bromo - m - toluidine C8H2Me(NH2)Br, 
 [1:5:3:4]. [59°]. Formed by reducing the corre- 
 
BROMO-TOLUIDINE. 
 
 sponding di-bromo-nitro-toluene (Nevile a. Win- 
 ther, O.J. 37,447). 
 
 Acetyl derivative C5H2(CH,)(NHAc)Br2. 
 [163°]. 
 
 Oi - 'bromo - m - toluidine CeH2Me(HH2)Br2 
 [1:3:2:5]. [73°], From the corresponding di- 
 bromo-nitro-toluene [70°] by reduction. V. sol. 
 alcohol (Nevile a. Winther, C. J. 37, 448). 
 
 Acetyl derivative C5H2(CHs)(NHAc)Br2. 
 [145°]. 
 
 Di - bromo -m - toluidine CsH2Me(NH2)Br2 
 [1:3:4:6]. [75°]. Formatim.—l. Aoetyl-TO-tolu- 
 idine is brominated. The product is boiled 
 with alcoholic KOH and then distilled with 
 dilute acid. This retains bromo-toluidine. By 
 fractionally distilling the rest with steam, two 
 di-bromo-TO-toluidines [75°] and [35°], and one 
 tri - bromo - toluidine [101°] may be isolated 
 (Nevile a. Winther, O. J. 37, 440).— 2. By bro- 
 minating the acetyl derivative of bromo-tolu- 
 idine [32°], and removing acetyl by heating with 
 HjSOi (2 vols.) and water (1 vol.). 
 
 Acetyl derivative CjH2(OHs)(NHAo)Br2. 
 [168°]. 
 
 Di . bromo - m - toluidine CjH2Me(NH2)Br2 
 [1:3:2:6]. [35°]. Prepared as above. 
 
 Di - bromo - m - toluidine C8H2Me(NH2)Br2 
 [1:3:5:6]. [86°]. Prepared by reducing di-bromo- 
 nitro-toluene [105°] (Nevile a. Winther, 0. J. 37, 
 434). Formed also by heating the acetyl deriva- 
 tive with equal volumes of HjSOj and water. — 
 B'HCl. 
 
 Acetyl derivative 051X2(0113) (NHAc)Br2. 
 [205°]. Formed by aoetylation of the base ; 
 also from Br and bromo-acetyl-toluidine [168°]. 
 
 Di - bromo -p - toluidine 05H2Me(NH2)Br2 
 [1:4:3:5]. [73°] (N. a. W.); [76°] (Wroblewsky). 
 From ^-toluidine and bromine (Wroblewsky, A. 
 168, 188; Nevile a. Winther, C. J. 37, 436). 
 From ^-toluidine »t-sulphonic acid and Br 
 (Peohmann, A. ITS, 216). Converted by NjOa 
 into di-bromo-toluene [39°]. 
 
 Di - bromo - p - toluidine OsH2Me(NH2)Br2 
 [1:4:2:5]. [85°] . Formed by reducing the cor- 
 responding nitro- compound [87°] (Nevile a. 
 Winther, C. J. 37, 445 ; Wroblewsky, A. 168, 
 185). Yields tri-bromo-toluene [111°]. 
 
 Di-bromo-p-toluidine C8H2Me(NH2)Br2 
 [1:4:2:6]. [88°]. Formed by reduction of the 
 corresponding nitro- compound [57°] . 
 
 Di-bromo-toluidine CBH„Me(NHj)Brj . 
 [l:4or6:2:3]. [53°]. From the corresponding 
 di-bromo-nitro-toluene [57°] (N. a. W.). 
 
 Tri - bromo - - toluidine C8HMe(NH2)Br3. 
 [106°]. Described by Gerver (A. 169, 379) as 
 formed by brominating o-toluidine. Nevile a. 
 Winther (0. J. 37, 438) say that no such body 
 is so formed. 
 
 Tri - bromo - m - toluidine C„HMe(NH2)Br3 
 [1:3:2:5:6]. [94°]. From the acetyl derivative by 
 boiling with alcohohc potash. 
 
 Acetyl derivative CjH(CH,)(NHAo)Brs. 
 [181°]. From C,H2(0H3)(NHAc)i3r2 [1:3:2:5] 
 [144°] and Br (Nevile a. Winther, C. J. 37, 
 448). 
 
 Tri - bromo - m - toluidine OoHMe(NH2)Br3 
 [1:5:2:3:4]. [96°]. From its acetyl derivative by 
 alcoholic EOH (N. a. W.). 
 
 Acetyl derivative OoH(OH3)(NHAo)Br3 
 [1:5:3:4:2]. [173°]. Formed by brominating 
 C,Hj(CH3)(NHAo)Br^ 
 
 Tri - bromo - m - toluidine CBHMe(NHj)Bra 
 [1:5:2:4:6]. [101°] (N. a. W.); [97°] (Wr.). Formed 
 by brominating di-bromo-m-toluidine (Nevile a. 
 Winther, O. J. 37, 448 ; Wroblewsky, A. 168', 195). 
 
 Tri - bromo -p - toluidine OjHMe(NH„)Br, 
 [1:4:2:3:5]. [83°]. From the hydro-chloride of 
 C3H3(CH3)Br(NH2) [1:2:4] and bromine-water 
 (N. a. W.). Needles (from alcohol). 
 
 Tri - bromo - p - toluidine OBHMe(Nnj)Brj 
 [1:4:5:6:2]. [118°],. Formed by reducing the 
 corresponding nitro- compound [106°] by iron 
 and acetic acid (Nevile a. Winther, 0. J. 39, 85). 
 
 Tri-bromo-toluidine CsHMe(NH.)Brs. [113°]. 
 From ^-toluidine wi-sulphonio acid and Bt 
 (Peohmann, A. 173, 217). 
 
 Tri-bromo-toluidinfi 03HMe(NH2)Brs. [82°], 
 From o-bromo-toluene m-sulphonio acid by 
 nitration, reduction and bromination (Schafer, 
 4.174,362; B. 7, 1855). 
 
 Tri-bromo-toluidine C5HMe(NH2)Br3. [72°]. 
 From 5)-bromo-toluene o-sulphonio acid by 
 similar treatment (S.). 
 
 Tetra-bromo-m-toluidine OjMe(NH2)Br4 
 
 [1:3:2:4:5:6]. [224°]. From bromo-m-toluidine, 
 [37°], aqueous HOI, and bromine (Nevile a. Win- 
 ther, 0. J. 37, 449). White needles (from alco- 
 hol). 
 
 Tetra-bromo-jp-tolnidine CjMe(NH2)Br4 
 
 [1:4:2:3:5:6]. [227°]. From CeH2Me(NH2)Br2 
 [1:4:2:6] dissolved in dilute HCl and treated 
 with bromine-water (Nevile a. Winther, C. J. 
 39, 85). Also from p-nitro-toluene, F6Br2, and 
 Br at 90° (Scheufelen, A. 231, 179). 
 
 BBOHO-TOLUIDINE SULFHOITIC ACID v. 
 BrOMO-AMIDO-TOIiUENE sulphonio Acn). 
 
 DI-BKOMO-TOLUftUINONE O^BMeBtfl^ 
 [85°]. Formed together with the tri-bromo-deri- 
 vative by the action of bromine on tolu-quinone, 
 and separated from it by crystallisation from 
 dilute acetic acid in which it is the more solu- 
 ble. Yellow needles ; m. sol. water and alcohol 
 (Oanzoneri a. G. Spica, 0. 12, 472). 
 
 Tri - bromo - toluquiuone CjMeBrsOj 
 [1:3:4:6:2:5]. [235°]. 
 
 Formation. — 1. From toluquinone and Br. — 
 
 2. From tri-bromo-hydrotoluquinone and FOjOlj, 
 
 3. In small quantities, by heating cresol with 
 HjSOi, MuOj, and KBr (0. a. S.). 
 
 Properties. — Pale yellow lamina ; insol. 
 water, si. sol. alcohol. Aniline forms black 
 crystalline C3MeBr(NPhH)202. Aqueous KOH 
 forms CeMeBr2(0H)02 [197°] (Spica a. Magna- 
 nimi, Q. 13, 312). 
 
 BEOMO - op - DITOLYL 
 [4 : 3or2 : 1] 0eH3MeBr.0,H,Me [1:2]. [95° cor.]. 
 Prom di-tolyl and Br (Oarnelley a. Thomson, 
 O. J. 47, 590). Purified by crystallisation from 
 alcohol, from which an oily isomeride first sepa- 
 rates. Oxidation gives bromo-terephthalio acid 
 [309° cor.]. 
 
 Bromo-o^-ditolyl [4:1] OjHjMe.O^HjMeBr 
 [l:2:3or6]. Oil; prepared as above. Oxida- 
 tion gives bromo-diphenic acid [208°] and c- 
 bromo-phthalio acid [197°]. 
 
 Di-bromo-ditolyl Ci^^g&u_ [152°]. From Br 
 and ditolyl in CSj (Oarnelley a. Thomson, O. J. 
 47, 691). Long hair-like needles; less soluble 
 in alcohol than the preceding compound. OrO, 
 in MOAc gives 0,jH3Br202 [166°] and CuHsBrjO, 
 (?) [198°], neither of which compounds dissolves 
 in KOHAq. 
 
BROMO-UMBELLIFEEON. 
 
 633 
 
 BBOMO - TOLTL - AMIDO - CHIORO - NAPH- 
 IHOQTTIN'OIfE v. Chloeo-naphthoquinonb-bro- 
 
 MO-TOLCIDB. 
 
 DI - BBOMO - o - TOLYL - AMIDO - PEOPIO- 
 
 inTRILECjH2MeBr2.CHMe.CN. [105°]. From 
 o-tolyl-amido-propionitrUa and Br (Stephan, 
 O. C. 1886, 470). ^ 
 
 Di-bromo-2)-tolyl-amido-propionitril8 
 
 C,HjMeBr,.CHMe.CN. [117°]. (S.). 
 
 TETBA-BEOMO-DI-TOLTL-AMINE 
 (O.H2MeBr,)jNH. [162°]. Prom Br and di- 
 tolyl-nitrosamine in alcohol (Lehne, B. 13, 1544). 
 Small needles. 
 
 BKOMO-p-TOLYI-BENZENE C,3H„Br i.e. 
 [4:1] CjH^Br.CsHiMe [1:4]. Bromo-phewyl-tolu- 
 ene. [0. 30°]. A product of the bromination of 
 2J - tolyl - benzene. Oxidation gives bromo- 
 diphenyl-carboxylio acid [194°] and ^-bromo- 
 benzoio acid (CarneUey a. Thomson, C. J. 51, 
 88), 
 
 Bromo-p-tolyl-benzene CjHs.CjHaMeBr 
 [l:2or3:4]. [129°]. From tolyl-benzene in CS^ 
 by Br (CarneUey a. Thomson, G. J. 47, 586; 51, 
 87). Pearly plates, si. sol. hot alcohol, v. e. 
 sol. benzene. Oxidises to bromo-terephthaUc 
 acid [306° cor.]. 
 
 Bi-broma-p-tolyl-benzene 
 [4:1] CeH^Br.OsHjBrMe [l:2or3:4]. [115°]. From 
 p-tolyl-benzene in CS2 and Br (CarneUey a. 
 Thomson, O. J. 51, 89). Oxidation gives di- 
 bromo-diphenyl-carboxylio acid [204°] and p- 
 bromo-benzoic acid. 
 
 Di-bromo-tolyl-benzene 
 [4:1] CsHjBr.CeHjBrMe [l:3or2:4]. [150°]. 
 Formed, together with the isomeride [115°] in 
 brominating ^-tolyl-benzene. Oxidation gives 
 di-bromo-diphenyl-oarboxyUo acid [232°] and p- 
 bromo-benzoic acid. 
 
 BSOMO-TOLYLEKE-m-DIAMIKE 
 CsHj(CH,)(NH2)2(Br) [l:2:4:a;]. [104°]. Colour- 
 less plates. Sol. alcohol, ether, and CS^. Pre- 
 pared by bromination of the di-benzoyl-derivative 
 of (l:2:4)-tolylene-diamine and subsequent sapo- 
 nification. 
 
 Di-benzoyl-derivative [214°]. White 
 needles (Buhemann, B. 14, 2658). 
 
 Bromo-tolylene diamine CsH2(CH3)(NH2)2Br. 
 [107°]. Formed by reducing bromo-di-nitro- 
 toluene [104°] (Grete, A. 177, 262).— B"2HCl.— 
 B"2HNOs.— B"H2S04.— B"H2C204. This body 
 is perhaps identical with the preceding. 
 
 Bromo-tolylene-o-diamine 
 CeHj(CHj)(NH2)2Br [1:2:3:4]. [59°]. Obtained 
 by nitration and reduction of ^J-bromo-o-toluid- 
 ine (Hubner a. Sohupphaus, B. 17, 775). SmaU 
 colourless needles. V. sol. water, alcohol, and 
 benzene. 
 
 Salts. — B'HCl: very soluble colourless 
 needles. — ^B'^HjSOi : colourless tables. 
 
 Anhydro-formyl derivative v. Meth- 
 
 ENTL-BEOMO-TOLTLENE-O-DIAMIKE. 
 
 BEOMO-TOLYL-ETHANE v. Beomo-eihtl- 
 
 TOLUENB. 
 
 o-BBOMO-a-m-TOLYI-ETHYLENE 
 C,H,.0Br:CH2. Formed by boiling m-tolyl-di- 
 bromo-ethane CjHj.CHBr.CHjBr with alcoholic 
 KOH. Very unstable body : begins to blacken 
 even at 100° (MuUer, B. 20, 1216). 
 
 o>-Bromo-a-m-tolyl-ethylene C,H,.CH:CHBr. 
 m-Methyl-bronw-styrene. (242°). OU. Formed 
 by adding bromine to a warm solution of sodium 
 
 m-tolyl-aorylate (methyl-oinnamate) (Miiller, 3, 
 20, 1216). 
 
 BEOMO-TOLYI MERC APTAN CjHaMeBr.SH. 
 [0. 7°]. (c.245°). Fromp-bromo-tolueae sulpho- 
 ohloride, tin, and HCl (Hubner a. WaUach, Z. 
 [2] 5, 500). 
 
 Bromo-tolyl mercaptan CjHjMeBr.SH. (246°). 
 From o-bromo-toluene m-sulphoohloride [53°] 
 by Zn and H2S04 (Hubner, A. 169, 41). Oil. 
 
 DI-BE0M0-DI-T0LYL-METHANEC,aH„Br2. 
 [115°]. From the hydrocarbon and Br (Weiler, 
 B. 7, 1181). 
 
 BBOmO-p-TOIYL-^-METHYIi-IMESATIN v. 
 
 P-Meihyl-isatin-bbomo-^-toltjidb. 
 
 TETEA-BROMO-^-TOIYL-(S)-NAPHTHYL. 
 AMINE C„H„Br,N. [169°]. Formed by bromina- 
 tion of ^-tolyl-(/3)-naphthyl-amiue (Friedlander, 
 B. 16, 2080). White silky needles. Sol. alcohol 
 and ether. 
 
 EROMO - DI - o - TOLYL - PROPIONIC ACID 
 C,H3MeBr.C(CeH,Me)Me.C02H. [144°]. Colour- 
 less crystals. Sol. alcohol, ether, &c. Formed 
 by bromination of di-tt-tolyl-propionic acid 
 (Haiss, B. 15, 1478). 
 
 a/3-DI-BROMO-m-TOLYL.PROPIONIC ACID 
 C,„H,„Br202*.e. [3:1] C,H^Me.CHBr.CHBr.C02H. 
 [167°]. From m-methyl-cinnamio acid and Br 
 (MuUer, B. 20, 1215). 
 
 DI - BROMO - DI - TOLYL - DI - SULPHIDE 
 (C,H3MeBr)2S2. [78°]. From o-bromo-tolyl 
 mercaptan and dUute HNO3 (Hubner a. Post, A, 
 169, 42). 
 
 BROMO-UMBELLIFERON 
 
 ^ ... /CH:CBr 
 
 Methyl ether U l\ 0^,{0^e)<C I . 
 -■ \0 . CO 
 
 [154°]. Formed by the action of bromine upon 
 a solution of umbeUiferou-methyl ether in CS2. 
 Long white needles; m. sol. hot alcohol and 
 ether, si. sol. cold alcohol and ether, insol. water ; 
 its dilute alcoholic solution has a green fluor- 
 escence. By alcoholic KOH it is converted into 
 methoxy-coumarilic acid 
 .CH:C.C02H. 
 C,H3(0Me)< / 
 \0 
 
 .CH:0Br 
 
 Ethyl ether 0.H3(0Et)< I : [116°] 
 
 \o.co 
 
 silvery tables ; sol. boUing alcohol and ether, si. 
 sol. cold alcohol ; its dilute alcoholic solution 
 has a violet fluorescence. Analogous to the 
 methyl-ether in its formation and properties 
 (WiU a. Beck, B. 19, 1782). 
 Di-bromo-umbelliferon 
 ,CH:CBr 
 / I (?). 
 
 C3H2Br(OH)< I 
 
 \o_co 
 
 Methyl ether C3H2Br(0Me) 
 
 /" 
 
 .CH:CBr 
 
 I 
 
 \o— CO 
 
 [251°] ; formed by bromination of umbelliferon- 
 methyl-ether dissolved in acetic acid ; white 
 glistening needles ; si. sol. alcohol. 
 
 XH:CBr 
 Ethyl ether C3H2Br(0Et)< | : 
 
 \o_co 
 
 [216°] ; formed by bromination of umbeUiferon- 
 ethyl-ether in acetic acid (WiU a. Beck, B. 
 19, 1786). 
 
634 
 
 BROMO-UMBELLIFERON. 
 
 Trl-bromo-umTielliferon OjHaBraOj. [194°]. 
 From umbelliferon and bromine-water (Posen, 
 B. 14, 2746; Mossmer, A. 119, 261). The 
 alcoholio solution shows greenish-yellow fluor- 
 escence. 
 
 BROMO-UVITIC ACID CsHsBr(CH3){C02H)j 
 [a/:l:3:5]. Prepared by oxidising bromo-a>,»2-di- 
 oxy-mesitylene with KMnOi (Oolson, A. Oh. [6] 
 6, 102). White crystals, carbonises at 285° 
 without melting. Sol. alcohol. — Na^A" : tables. 
 
 o-BEOMO-ji-VAlEEIC ACID OsHjBrOj i.e. 
 CsHj.OHBr.COjH. Formed by bromination of 
 valeric acid (propyl-aoetic acid) (Juslin, B. 17, 
 2504). 
 
 Ethyl ether A'Et: (191°); S.G. ^{ = 
 1'226 ; colourless fluid. 
 
 7-Bromo-n-valeric acid 
 CH3.CHBr.CH2.CH2.COjH. From allyl-acetic 
 acid and cone. HBrAq at 0° (Messerschmidt, A. 
 208, 94). Boiling water or cold Na^COsAq con- 
 vert it into the lactone of 7-oxy-valerio acid 
 
 a-Bromo-isovaleric acid 
 (CHs)2CH.CHBr.C02H (chiefly). [40°]. (230°). 
 i?rom ordinary valeric acid and Br (Cahours, A. 
 Suppl. 2, 74 ; Borodine, A. 119, 121 ; Fittig a. 
 Clark, A. 139, 199 ; Ley a. Popofl, A. 174, 63 ; 
 Schmidt, A. 193, 104). Formed also by the 
 action of water on its bromide which is formed 
 by treating isovaleric acid with Br and P (Vol- 
 hard, ^. 242, 163). Oil. 
 
 Ethyl ether EtA'. (186°). Is best puri- 
 fied by distillation with steam, the liquid is 
 collected as soon as the oily drops sink under 
 water (Lov6n, J. pr. [2] 33, 112). 
 
 Bromo-valerio acid CMeEtBr.COjH or, possi- 
 bly, CH3.CHBr.CHMe.CO2H Bromo- methyl- 
 ethyl-acetic acid. Bromo-hydro-tiglic acid. [66°]. 
 From tiglio and angelic acids with cone. HBrAq 
 at 0° (Fittig a. Pagenstecher, A. 195, 108, 128 ; 
 cf. p. 267). Monoclinic tables (from CS2) ; insol. 
 cold water. Boiling water forms tiglic acid and 
 some pseudo-butylene (s-di- methyl -ethylene). 
 NajCOjAq produces chiefly pseudo - butylene. 
 Sodium - amalgam forms methyl - ethyl - acetic 
 acid. 
 
 Bromo - valeric acid CjHgBrO, i.e. 
 CMeEtBr.COjH? From methyl - ethyl - acetic 
 acid and Br at 160° (Booking, A. 204, 23). 
 Liquid. Should be identical with the preceding. 
 
 Ethyl ether MA.'. (185°). S.G. V 1'2275. 
 Decomposed by boiling NajCOjAq into o-methyl- 
 B-oxy-butyrio ether CMeEt(OH).OOjH. 
 
 •yS-Di-bromo-Ti-valeric acid 
 CH2Br.CHBr.CH2.CH2.CO2H. [58°]. From 
 allyl-acetic acid and Br in CS2 (Messerschmidt, 
 A. 208, 100). Thin lamina. Converted by 
 sodium-amalgam into allyl-acetic acid. Boiling 
 water forms the lactone of bromo-oxy-valeric 
 acid, and finally C^HgOj. 
 
 Di.bromo-valeric acid CMe2Br.CHBr.CO2H. 
 [106°]. Solidifies at 70°. From CMe2:CH.C02H 
 and bromine (Ustinofl, J.pr. [2] 34, 483). 
 
 Di-bromo-valeric acid 
 CH,.0HBr.CBrMe.C02H. [86°]. From tiglic 
 acid and Br (Schmidt a. Berendes, A. 191, 119); 
 also from angelic acid and Br (JaflS, A. 135, 
 293; Pagenstecher, A. 195, 123). Triolinic 
 crystals (from CSj) ; insol. cold water. Con- 
 verted by distillation or by sodium-amalgam 
 
 into tiglio acid (Demarpay, B. 8, 830). Boiling 
 water decomposes its salts forming bromo-buti- 
 nene (87°).— KA' : insol. oono. KOHAq. 
 
 Ethyl ether EtA'. (185°). (J.). 
 
 DI-BKOMO-VALEKIC ALDEHYDE O.B.^Br.fl 
 i.e. CH3.CHBr.CBrMe.CHO. From tiglio alde- 
 hyde and Br (Lieben a. Zeisel, M. 7, 55). 
 
 BBOMO-VAIiEBO-LACIOlIE v. Bbomo-ost- 
 
 VAIiBBIO ACID. 
 
 BKOMO-VAIERYIENE C^HjBr. (125°- 
 130°). From valerylene dibromide and aloo- 
 hoUc KOH (Eeboul, A. 135, 372). Forms a yel- 
 low pp. of C3H5OU with ammoniacal cuprous 
 chloride. 
 
 BROMO-VANILLIC ACID v. Methyl deriva- 
 tive of Bbomo-di-oxy-benzoio Aom. 
 
 BKOMO-VEBATBIC ACID v. Methyl deriva- 
 tive of BROMO-m-OXT-BENZOIO ACID. 
 
 BBOMO -VINYL ACETATE O^HsBrOj i.e. 
 CHBr:OH.OAo. From acetylene di-bromide and 
 KOAc at 160° for 2 days (Sabanejeff, A. 216, 
 272). Crystals. Explode when quickly heated. 
 Forms with bromine a compound OjHjBrjOj, 
 which solidifies at 0°. 
 
 cu-BKOMO-i). VINYL -PHENOL. Methyl 
 ether C,H,(OMe).CH:CHBr. [55°]. From the 
 di-methyl-ether of o;8-di-bromo-^-oxy-phenyl- 
 propionio acid CeH,(OMe).CHBr.0HBr.0O2M8 
 by boiling with aqueous KOH (30 p.c). Plates, 
 of pleasant smell and taste (Eigel, B. 20, 
 2537). 
 
 eso-Bromo-o-vinyl-phenol 
 CsH3(OH)Br.CH:CH2. Bromo-oxy-styrene. (265°). 
 Formed by distilliiig di-bromo-ethyl-phenol, 
 C6H3(OH)Br.CjH4Br obtained by brominating 
 o-ethyl-phenol (Suida a. Plohn, M. 1, 180). 
 Liquid, gl. sol. water. Gives a leddish-brown 
 pp. with Fe2Cl3. 
 
 Di-bromo-o-vinyl-phenol. Methyl ether 
 Cja.JBTfi i.e. CjH3(0Me)Br.02H2Br. From the 
 methyl derivative of tri-bromo-oxy-phenyl-pro- 
 pionio acid C3H3(0Me)Br.CHBr.CHBr.C02H and 
 Na2C03Aq (Perkin, 0. J. 39, 418). Oil ; slightly 
 volatile with steam. 
 
 BEOMO-VINYL-PIPERIDINE 
 C5H,„N(02H2Br). Piper-ethyl-alkine-bromide. 
 Formed by heating the hydrobromide of piper- 
 ethyl-alkine (oxethyl-piperidine) with 1 mol. of 
 bromine at 100°-120°. On reduction with 
 sodium-amalgam it yields ethyl - piperidine. — 
 BTEBr : thin colourless prisms, sol. water, v. 
 si. sol. cold alcohol.— B'HCL—B'jHjCLjPtClt.— 
 B'HCl,AuCl,. (Ladenburg, B. 17, 154). 
 
 BROUO-o- XYLENE GgHsBr i.e. 
 CeH3(CH3)2Br [1:2:4]. [0°]. (214° i.V.). Mol. 
 w. 185°. S.G. If 1-37. Formed by the action 
 of bromine in presence of iodine upon o-xylene 
 in the cold and in the dark (Jacobsen, B, 17, 
 2372 ; Schramm, B. 18, 1278). 
 
 a; -Bromo -o-xylene CeH,(0H3).CH2Br. o- 
 xylyl bromide. [21°]. (217°) at 742 mm. S.G.^ 
 1-381. Colourless liquid. Prepared by the action 
 of bromine- vapour upon boiling o-xylene ; or in 
 the cold upon o-xylene exposed to direct sun- 
 shine (Eadziszewski a.-Wispek, B. 15, 1747 ; 18, 
 1281; Schramm, B. 18 1278; Colson, A. Ch. 
 [6] 6, 115). 
 
 Bromo-m-xylene 03H3(0H3)2Br [1:3:4]. (206°), 
 Formed by the action of bromine upon cold m- 
 xylene in the dark (Fittig, A. 147, 31 ; Schramm, 
 B. 18, 1277). Mel and Ha give ij^-cumene. 
 
BROMO-XYLENE-STJLPHONIO ACID. 
 
 fi35 
 
 (3) -Bromo-w- xylene CjHjMe.Br [1:3:2]. 
 (o. 206°). Liquid at - 10°. Obtained by adding 
 a HCl solution of bromine to a solution of 
 sodium »i- xylene -(/3).sulphonate, which is 
 prepared by debrominating di-bromo-OT-xylene 
 sulphonio acid CsHMei,Br2(S03H) [1:3:4:6:2] 
 with zino-dust and aqueous ammonia. By 
 methyl iodide and sodium it gives hemimelli- 
 thene C^HaMea [1:2:3] (Jaoobsen a. Deike, B. 
 20, 903). 
 
 Bromo-xylene CH^Me^Br [1:3:5]. (204°). 
 S.G. ^ 1-362. Oil. From C^HjMe.fNH^) 
 [1:3:4] vid CeH,Mo,HHAc, C.H^rMe.NHAo and 
 C.H2BrMe2(NH2) (Wroblewsky, A. 192, 215 : B. 
 9, 495). 
 
 <o-Bromo-m-xyleneC8Hj(CH3).CH.,Br.m-ZyZ^2 
 bromide. (215°) at 735 mm. (E. a. W'.) ; (c. 218°) 
 (C). S.G. S3 1.371. Colourless liquid, with 
 pungent vapour. Prepared by the action of the 
 vapour of bromine on boiling m-xylene, or from 
 Br (1 mol.) and cold m-xylene exposed to direct 
 sunlight (Eadziszewski a. Wispek, B. 15, 1745 ; 
 18, 1282 ; Schramm, B. 18, 1277 ; Colson, A. Ch. 
 [6] 6, 117). 
 
 Bromo-2)-xylene C„H3Br(CHj2 [2:1:4]. [10°]. 
 (206° i.V.). Formed by the action of bromine 
 upon cold ^-xylene in the dark (Fittig a. 
 Jannasch, A. 151, 283 ; 171, 82 ; B. 17, 2709 ; 
 Jacobsen, B. 18, 356 ; Schramm, B. 18, 1276). 
 Large plates. 
 
 ai-Bromo-p-xylene C„H^(CH3).CH2Br. p-Xylyl 
 brcmide. [36°]. (219°) at 740 mm. Long 
 colourless needles. Sol. ether and chloro- 
 form. Pungent smell. Prepared by the action 
 of bromine -vapour on boiling p--x.ylene, or of Br 
 (1 mol.) upon cold ^-xylene exposed to direct 
 sunshine (Badziszewski a. Wispek, B. 15, 1748 ; 
 B. 18, 1279 ; Schramm, B. 18, 1277). 
 
 Di-bromo-o-xylene OsH.,(CH3)jBr2 [1:2:3:4?]. 
 [7°]. (277°). S.G. if 1-7842. Liquid at ordinary 
 temperatures. Formed together with the iso- 
 meride [88°] by the action of bromine (2 mols.) 
 in presence of iodine upon o-xylene (1 mol.) in 
 the cold (Jaoobsen, B. 17, 2376). 
 
 Di-bromo-o-xylene C6H„(CHs)2Brj [1:2:4:5]. 
 [88°]. (278°). Large trimetrio plates, or long 
 needles. V. sol. hot alcohol ; v. si. sol. alcohol 
 at 0°. Formed as above (Jaoobsen, B. 17, 
 2376). 
 
 o-Dl-M-bromo-xylene C„Hj(CHj.Br)2 [1:2]. 
 o-XylyUm bromide. [95°]. S.G. e 1-934. 
 S. (ether) 20. S.H. (15°-40°) -183. Splendid large 
 trimetrio crystals. Prepared by heating o-xylene 
 with bromine (2 mols.) at 130°-155°. Also by 
 the action of Br (2 mols.) in the cold upon o- 
 xylene (1 mol.) exposed to direct sunshine. Tri- 
 metrio crystals ; a:6:c = -8581 : 1 : -5014; v. sol, 
 ether and chloroform. By boiling with a solu- 
 tion of Na^COs for 3 hours it yields phthalyl- 
 alcohol (Baeyer a. Perkin, B. 17, 123 ; Badzis- 
 zewski a. Wispek, B. 18, 1281; Schramm, B. 
 18, 1278 ; Colson, A. Ch. [6] 6, 105; 0. B. 104, 
 428 ; Perkin, jun., C. J. 53, 5). 
 
 Di-bromo-m-xylene O^HoiCHJ^Brj. [72°]. 
 (256°). From m-xylene and Br (Fittig, A. 147, 
 
 ^^'Di-^bromo-m-xylene C,H,(CH,),Br,. (252°). 
 [liquid. From brominated m-xylidine by the 
 diazo- reaction (Wroblewsky, A. 192, 216). 
 
 i.i,ai,-Di-bromo-m-xylene CeHj(CHjBr)2 [1:3]. 
 Xyl^Um dibr(mide. [77°]. S.G. « 1-734 ; sa 
 
 (liquid) 1-615. S. (ligroin) 83. S.H. (15°-40'^) 
 -184. Formed by the action of bromine (2 mols.) 
 in the cold upon m-xylene exposed to direct sun- 
 shine ; also by adding Br (2 mols.) to m-xylene at 
 130°-180' (Schramm, B. 18, 1277 ; Badziszewski 
 a. Wispek, B. 18, 1282 ; Colson, A. Oh. [6] 6, 
 109, C. E. 104, 428 ; Kipping, O. J. 53, 26). 
 Prismatic needles (from CHCI5). Attacks the 
 eyes. Converted by alcohol or boiling water 
 into C|iH,,(CH20H)2. Alkaline permanganate 
 forms isophthaUo acid. 
 
 Di-bromo-p-xylene C„H„(CH3),Br2 [1:4:2:5]. 
 [76°]. (261°). From p-xylene," Br, and L 
 A small quantity of a liquid isomeride, 
 08H2(CH3)jBr2 [1:4:2:6] (?) is formed at the same 
 time. Large triclinio crystals, plates, or flat 
 needles (Jacobsen, B. 18, 358 ; Fittig, Airens a. 
 Mattheides, A. 147, 26 ; Jannasch, B. 10, 
 1357). 
 
 iu,£ii2-Bi-bromo-p-xylene GgRt{CH.^t)2 [1:4]. 
 jp-Xylylene bromide. [144°]. (0. 245°). S. 
 (ether) 2-65 at 20°. S.H. (15°-40°) -180. 
 Formed by the action of bromine (2 mols.) in 
 the cold upon ^-xylene exposed to direct sun- 
 shine ; or by the action of bromine-vapour on 
 boihng ^-xylene (Grimaux, Z. 1870, 394; 
 Schramm, B. 18, 1277 ; Badziszewski a. Wis- 
 pek, B. 15, 1744 ; 18, 1279 ; Low, A. 231, 362 ; 
 B. 18, 2072 ; Colson, 0. B. 104, 428 ; A. Ch. 
 [6] 6, 119 ; Kipping, C. X 53, 34). Plates ; sol. 
 CHCI3. Boiled with water (20 pts.) and lead 
 nitrate (1 pt.) it forms terephthalic aldehyde and 
 some terephthalic acid and ^-aldehyde-benzoio 
 acid. Fuming HNO3 acts similarly. Alcohol 
 converts it into CjHj(CHiOH)2 ; the rate of thia 
 saponification is less than with the 0-, and still 
 less than with the m-isomeride. 
 
 eKo-Tri-bromo-p-xylene 
 CeH,(CHBrj)(CH2Br). [106°]. Formed from 
 p-xylene and impure bromine-vapour (Low, A. 
 231, 363). BoUing water gives ai-oxy-toluio 
 aldehyde. 
 
 Tetra-bromo-o-xylene Cs(CH3)2Br<. [262°] 
 (J.) ; [255°] (B.). (376°). From o-xylene and 
 Br (Jaoobsen, B. 17, 2378) in presence of ALBrj 
 (Blumlein, B. 17, 2492). Long glistening 
 needles. V. si. sol. hot alcohol; v. sol. hot 
 benzene. 
 
 Tetra-bromo-j)-xylene Ca(CH3)2Br4. [253°]. 
 (355°). From ^-xylene and Br (Jacobsen, B. 18, 
 359). 
 
 BEOMO-o-XYLENE-SirLPHONIC ACID 
 C5H3(CH,),(Br)(S03H) [1:2:4:5]. Formed by 
 sulphonation of bromo-o-xylene. Crystals (con- 
 taining aq). Very soluble in water, sparingly in 
 cold dilute H^SO,. 
 
 Salts.— NaA'lJaq: long fine needles, v. 
 sol. hot water.— KA' aq.— BaA'j 3aq : long thick 
 prisms, sol. hot water. 
 
 Amide C,H,(CH3)2(Br)(SO,NH,) : [213°]; 
 long fine needles, v. si. sol. water, si. sol. cold 
 alcohol (Jaoobsen, B. 17, 2373). 
 
 Bromo-o-xylene-snlphonic acid 
 CjH2(CH8)^r(S03H). Formed by the action of 
 bromine upon an aqueous solution of o-xylene- 
 sulphonio acid.— BaA'^ 4aq : sparingly soluble 
 
 Amide CsH^MejBr.SOjNH, : [187°]; thick 
 needles ; y. sol. hot alcohol (Kelbe a. Stein, B. 
 19, 2137). 
 
636 
 
 BROMO-XYLENE-SULPHONIC AOID. 
 
 BrQino-m-zyleue sulphouic acid 
 0sHj(CH3)jBr(S0sH) [1:3:2:4]. From di-bromo- 
 m-xyiene sulphamide by sodium-amalgam 
 (Jaoobsen a. Weinberg, B. 11, 1535). 
 
 Amide OsHjMejBrSOjNHj. [161° oor.]. 
 
 Bromo-m-xylene snlphonic acid 
 C8HjMe2Br(S03H) [1:3:6:4]. From 
 CsH3Me2(S03H) [1:3:4] by Br or from CeHaMe^Br 
 [1:3:6] by fuming H^SO^ (Weinberg, B. 11, 1062). 
 From CBH2Me2(NH2)(SOsH) by diazo- reaction 
 (Sartig, A. 230, 335 ; Nolting a. Kohn, B. 19, 
 139; Limprioht.B. 18, 2188). Slender needles, 
 V. e. sol. water. 
 
 Salts. — BaA'2 aq. — Na A' aq. — ZnA'2 9aq. — 
 CuA'2 7aq. 
 
 Chloride [61°] : large prisms. 
 
 Amide [194°] : small trimetrio prisms. 
 
 Bromo-p-zylene sulphonic acid 
 CjHjMeaBr.SOsH [1:4:2:5]. Formed by heating 
 
 diazo-^-xylene-sulphonio acid C5H2Me2<^gf| ^ 
 
 [1:4:2:5] mth strong HBr. — BaA'2 2aq; small 
 white plates. 
 
 Chloride: [78°]; small white prisms. 
 
 Amide: [201°]; small white plates, v. sol. 
 alcohol and ether, si. sol. water, benzene, and 
 chloroform (Nolting a. Kohn, B. 19, 141). 
 
 Bromo-2>-xylene-salphauic acid 
 C5H2(CH,)j(Br)(S03H) [l:4:2:a;]. Pearly plates 
 or flat needles. Formed by sulphonation of 
 bromo-^-xylene. 
 
 Salt s. — NaA' aq : long thin prisms, trimetrio 
 plates, or six-sided plates. — ^BaA'j : small prisms 
 or thin six-sided plates. 
 
 Amide O.H2(CH,)2(Br)(S02NH2). [206°], 
 flat prisms, v. sol. hot alcohol (Jacobsen, B. 17, 
 2378). This acid is perhaps identical with the 
 preceding. 
 
 Si-bromo-m- xylene salphouic acid 
 C5H(CH3)2Br2(S03H) [1:3:4:6:2]. From di-bromo- 
 m-xylene [72°] and fuming HjSO, (Jacobsen a. 
 Weinberg, B. 11, 1534). Leaflets, si. sol. cold 
 water. Beduced by sodium-amalgam to (1,3,2)- 
 m-xylene sulphonio acid. 
 
 Salts. — BaA'j. — NaA'2aq: leaflets. 
 
 Chloride [107°] : rhombic leaflets. 
 
 Amide [220°] : slender needles. 
 
 BROMO-m-XYLENOL CeH2(CH3)2Br(0H) 
 [l:3:a!:4]. From Br and wi-xylenol in HOAo. 
 Liquid (Jacobsen, B. 11, 24). 
 
 Bromo-;p-xyIenol C3H2(CH3)2Br(OH) [l:4:a;:2]. 
 [87°]. From 2)-xylenol and Br (Jacobsen, B. 11, 
 27). 
 
 Di - bromo - m - xylene! CaH(CH3)2Br2(0H) 
 [1:3:?:?:4] [73°] (J.). 
 
 6.,i»2 Di-bromo-^-xylenol C3H3(CH2Br)2(OH) 
 [1:4:2]. [74°]. S. (alcohol) 200. From p- 
 xylenol and Br at 160° (Adam, Bl. [2] 41, 288). 
 Needles; insol. water, but decomposed on boiling 
 with it, HBr coming off. 
 
 Tri - bromo - - xylenol C„(CH3)j,Br3.0H 
 
 [1:2:4:5:6:8]. [184°]. Fine needles. Formed 
 by bromination of o-xylenol CjH3(CH3)2.0H 
 [1:2:3] (Thol, B. 18, 2562). 
 
 Tri - bromo - o - xylenol C3(0H3)2Brs(0H) 
 [1:2:3:5:6:4]. [169°]. From (1, 2, 4)-o-xylenol. 
 Felted needles (Jacobsen, B. 11, 28). 
 
 Tri - bromo - m - xylenol C,(CH3)2Br3(0H) 
 [1:3:2:5:6:4]. [179°]. From (l,3,4)-m-xylenol 
 (J.). Long needles. 
 
 Tri - bromo - m - xylenol C„(CH3)2Br3.0H 
 [1:3:2:4:6:5]. [166°]. Fine white needles. From 
 m-xylenol C3H3(CH3)2.0H [1:3:5] (Nolting a. 
 Forel, B. 18, 2679 ; cf. Thol, B. 18, 362). 
 
 Tri-bromo-p-xylenol Cs(CH3)2Br3(0H). [175°]. 
 Golden yellow needles (Jacobsen, B. 11, 26). 
 
 BROMO - m - XYLIDINE OBH,„BrN i.e. 
 C3H2(CH3)2Br(NH2) [1:3:5:4]. [97°]. From 
 acetyl-TO-xylidine by bromination and saponifi- 
 cation. Minute needles (from dilute alcohol). 
 Converted by the diazo- reaction into s-bromo ■ 
 xylene (Genz, B. 3, 225; Wroblewsky, A. 192, 
 215). 
 
 Di - bromo - - xylidine C5H(0H3)»Br2.NHj 
 [1:2:4:5:3]. [103°]. Obtained by reduction of 
 the oorr'esponding nitro- compound with iron and 
 acetic acid. Colourless needles. V. sol. alcohol 
 ether, and acetic acid. Does not form salts. By 
 sodium-amalgam it is debromiuated (Ihol, B. 
 18, 2562). 
 
 Di-bromo-m-xylidine C5H(CH3)jBr2(NH2). 
 From acetyl-m-xyhdine by brominating and 
 saponifying (Genz, B. 3, 225). Needles (from 
 alcohol). 
 
 Di-bromo-ji-xylidine C5HMe2Br2(NH2) 
 
 [l:4:5:a;:2]. [65°]. Formed by acidifying an alka- 
 line solution of (1 mol. of) p-xylidine-sulphonio 
 aoidC,H2Me2(NH2)(S03H) [1:4:2:5] and (2 mols. 
 of) bromine. Also formed by bromination of p- 
 xylidine (Nolting a. Kohn, B. 19, 142). 
 
 BROMO-m-XYLIDINE-SULPHONIC ACID 
 C,HMe2(Br)(NH2)(S03H) [1:3:5?:4:6]. Small 
 white needles. Sol. hot, v. si. sol. cold water, 
 insol. alcohol. Formed by bromination of m- 
 xylidine-sulphonio acid OjH2Me2(NH2)(S03H) 
 [1:3:4:6] (Nolting a. Kohn, B. 19, 140). 
 
 Bromo-p-xylidine-sulphonic acid 
 C3HMe2Br(NH2)(S03H) [l:4:a;:6:2]. Small white 
 plates. Nearly insoluble in cold water. Formed 
 by bromination of p-xylidine-sulphonio acid 
 C3H2Me2(NH2)(S03H) [1:4:6:2].— A'K (Nolting a. 
 Kohn, B. 19, 143). 
 
 DI-BROMO-m-XYLOaUINONE C3Br2Me202 
 [1:3:4:6:2:5]. [174°]. From mesitol, C5H2Me3(0H) 
 and Br in water (Jacobsen, A. 195, 271). Golden 
 lamin£B (from alcohol), insol. water and 
 Na2C03Aq, decomposed by KOHAq. 
 
 Di - bromo - p - xyloqninone CjBr2Me203 
 
 [1:4:5:2:3:6]. [184°]. Formed by the action of 
 bromine upon p-xyloquinone under water. Thin 
 golden plates. Insol. water and cold alcohol ; 
 sol. ether and benzene (Garstanjen, J.pr. [2] 23, 
 434). 
 
 BRONZE V. Copper, alloys of. 
 
 BRTTCINE C23H23N204 4aq. [105°, hydrated]; 
 [178°, anhydrous] (Claus, B. 14, 773); [151°] 
 (Blyth). S. -12 at 15° ; -2 at 100°. [o]d= -85° (in 
 alcohol); -110° to -127° (in CHCI3) (Oude- 
 mans, A. 166, 69). 
 
 Occwrrerace.— Together with strychnine in 
 nux vomica (the seeds of Strychnos mix vomica), 
 in the bean of St. Ignatius (the seed of Strychnos 
 IgnatU), in the wood of Strychnos colubrina, in 
 upas tiente, extracted from the bark of S. Uenle, 
 and in the bark of Strychnos nux vomica {False 
 Atigustura bark) (Pelletier a. Caventou, A. Ch. 
 [2] 12, 118 ; 26, 53 ; Pelletier a. Dumas, A. Ch. 
 [2] 24, 176 ; Corriol, J. Ph. 11, 495 ; Liebig, A. 
 Ch. [2] 47, 172 ; A. 26, 50 ; Eegnault, A. Ch. 
 [2] 68, 113). Bruciue, free from strychnine, 
 
BRUCINE. 
 
 es7 
 
 occurs in the bark of StrycJmos Ligustrina 
 (Bidara Laut) (Greenish, Ph. [3] 9, 1013). 
 
 Prejaaration. — Nux vomica seeds (56 lbs.) are 
 powdered and exhausted with alcohol, to which 
 one-sixth part of water has been added. The 
 alcohol is boiled ofi and the residue treated with 
 water (40 lbs.) containing H.SO^ (-12 lbs.). The 
 filtrate is neutralised with NajCOj. The pp. is 
 collected after a few hours, dissolved in chloro- 
 form, and the solution shaken with very dilute 
 H2SO4 which dissolves bruoine. The solution is 
 placed under a bell jar together with a beaker 
 containing ammonia so that neutralisation 
 proceeds very slowly. The crystalline pp. is 
 extracted with dilute alcohol, which dissolves 
 brucine, and the solution allowed to evaporate. 
 The bruoine, containing strychnine, is dissolved 
 in dilute H^SO,, and the faintly alkaline solution 
 mixed with KI. The brucine hydriodide that is 
 ppd. is crystallised several times from alcohol. It 
 is then shaken with aqueous NajCOj and chloro- 
 form, the chloroform is then shaken with dilute 
 acid and the base pp. with ammonia (W. A. 
 Shenstone, 0. J. 39, 453). 
 
 Properties. — Monoclinio efflorescent prisms 
 (from dilute alcohol) ; v. sol. alcohol, chloroform, 
 and essential oils, insol. ether and fatty oils. 
 Feebly alkaline to litmus or phenol-phthalein 
 (Plugge, Ar. Ph. [3] 25,45)., It is Isevorotatory, 
 the extent of rotation depending upon the 
 nature of the solvents and the concentration of 
 the solution. In presence of free acids [a]-o varies 
 from -29° to -36-5° (Tykociner, E. T. G. 1, 
 144). Commercial brucine usually contains 
 strychnine, but the colour which strychnine 
 gives with oxidising agents is masked by the 
 presence of brucine. The strychnine may, how- 
 ever, be detected by adding dilute HNO3 and then 
 extracting the strychnine with chloroform in 
 presence of excess of KOH (Shenstone, Ph. [3] 
 8, 445 ; Hanriot, O. B. 97, 267). Bruoine is 
 aflected by heating with acids, alkalis, or even 
 water, and hence much is lost by the usual 
 method of preparation, but the products being 
 usually amorphous, the unaltered brucine is 
 easily separated in a pure state. 
 
 Colour tests.— V. p. 124. The most charac- 
 teristic is the red colour with nitric acid, which, 
 after warming, is turned violet by excess of 
 ammonium sulphide {v. also Cotton, Z. [2] 5, 
 728 ; J. Ph. [4] 10, 18 ; Luck, Z. [2] 6, 275 ; 
 Le Linde, C. N. 37, 98 ; Fluckiger, Fr. 15, 342 ; 
 Hager, Fr. 11, 201 ; Dragendorff, Fr. 18, 108 ; 
 Pandis, G. G. 1872, 440; Struve, Fr. 12, 164; 
 Buckingham, Ph. [3] 3, 884). 
 
 Beactimis.—l. Brucine (60 g.) heated with 
 alcohol (600 0.0.) and NaOH (30 g.) at 100° for 
 12 hours forms a solution which, after neutrah- 
 sation with CO^, filtration and evaporation, 
 leaves a varnish containing some crystals. The 
 crystals (7g.) separated from the varnish by 
 washing with water and purified by solution in 
 very little dilute HCl and ppn. by NH, are 
 thrown down as microscopic crystals of 
 C,,H,.N,0, (21 g.). This gives a yellow colour 
 with HNO3 : a pp. with bromine, and on boiling 
 a magenta colour. An ammoniacal solution 
 turns purple in air and finally green (Shen- 
 Btone).-2. HNO3 (S.G. 1-2 Jo 1-4 forms a red 
 solution, producing 'cacothehne L.2,±l22«4U„ 
 oxalic acid, and methyl nitrite (Strecker, A. 91, 
 
 76 ; Hanssen, B. 20, 451). KjCrA and HjSO, 
 oxidise caootheline to 0,sH„N204, which is alsc 
 formed by the oxidation of bruoine. — 3. Bruoine 
 (1 mol.) heated with HCl at 140° gives off MeCl 
 (between 1 and 2 mols.). Brucine is therefore 
 possibly C2,H2„(OMe)jN20,j, strychnine being 
 Cj,Hj,(OH)„NA (Shenstone, C. J. 43, 101 ; c/. 
 Hanssen, B. 17, 2266). — 4. Yields on distillation 
 with potasii, several pyridine bases. Amongst 
 others (i8)-di-methyl-pyridine and (/3)-tri-methyl- 
 pyridine, quinoline tetrahydride, together with 
 probably a di-methyl-pyridine (Oeohsner de 
 Coninok, A. Ch. [5] 27, 507 ; 0. B. 99, 1077 ; Bl. 
 [2] 42, 100).— 5. Distilled m vacuo with zinc- 
 dust it yields carbazol (Loebisch a. Schoop, M. 
 7, 613).— 6. Alkaline KMnO, gives oft about 
 half the nitrogen in the free state (Wanklyu a. 
 Chapman, O. J. 21, 161).— 7. ICl forms a light 
 floceulent pp. in solutions of salts of bruoine 
 (Dittmar). 
 
 Salts. — B'HCl: crystalline tufts, m. sol, 
 water. — B'HClHgClj: long needles (from alco- 
 hol).— B'jHjPtClj : yellow pp.— B'HI aq : rect. 
 angular laminae or very short prisms ; m. sol, 
 hot water. — B'HIj! brown violet needles (Jor- 
 gensen, A. Ch. [4] 11, 114 ; J.pr. [2] 3, 160).— 
 B'jHjI, : unstable orange needles.— ^B'HNOj 2aq : 
 four-sided prisms ; less soluble in water than 
 strychnine nitrate. — B'2H2SO,7aq: long needles, 
 V. sol. water, si. sol. alcohol. — B'^H^S^Os 5aq ; 
 S. 1 at 15° (How, N. Ed. P. J. [new] 98).— 
 B'jHjSeeaq: [125°]; insoluble yellow needles, 
 formed by atmospheric oxidation of an alcoholio 
 solution containing H^S (Schmidt, A. 180, 296 ; 
 B. 8, 1267 ; 10, 838, 1288). — B'sH^Si^. — 
 B'jHjPOiffiaq (Anderson, P. M. [3] 33, 163).— 
 B'4H,!PeCys2aq: hygroscopic needles, m. sol. 
 hot water (Brandis, A. 66, 266).— B'4H,FeCys4aq. 
 — B'HjFeCys : white powder (Hoist a. Beckurts, 
 Ar. Ph. [3] 25, 313). — B'sHaFeCy, 6aq. — 
 B'sHjCoCys lOaq (Lee, Am. S. [2] 2, 44).— 
 B'jHjNiCy^ (L.).— B'HCyS : scales, sol. water.— 
 Periodate: needles (Bodeker, A. 71, 64; 
 Langlois,^. Cfc.[3]34,278).— Nitroprusside: 
 S.-15 at 15° (Davy, P7t. [3] 11,756).— Acetate: 
 crystalline, but gummy if impure (Shenstone). — 
 Dextro- tart rates : B'^C^HjOj 5Jaq, — 
 B'2C,HeOs8aq,— B'CjHjOs.- LsBvo-tartrates: 
 B'oC-HsOs 14aq,— B'CjH^Os 5aq (Pasteur, A. Ch. 
 [3]" 38, 472),— B'C,H5(SbO)Oe (Stenhouse, A. 
 129, 26). , . 
 
 Methylo-iodide B'MelSaq: lammsB 
 (from water) ; resinified by boiling KOH (Stahl- 
 schmidt, P. 108, 513). — B'Mel,. — B'Mel^. — 
 Methylo-hromide'&'UeBTi'i^&<i.—Methylo- 
 chloride B'MeC15aq: v. sol. water and alco- 
 hol. — B'^McPtClj. — B'HAuCl,. — Methylo- 
 sulphate B'^Me^SO, 8aq : radiate crystalhna 
 mass, V. so\.v!&ter.—B'Ue^S0t2a.q,.— Methylo. 
 nitrate B'MeN032aq. The physiological ac- 
 tion of these salts has been studied by Crum 
 Brown (T. E. 25). 
 
 Ethylo-iodide E'EtlJaq: not decom- 
 posed by KOH but converted by moist Ag^O into 
 a very soluble alkaline hydroxide :— B'Etlj.— 
 B'Etljaq. — Ethylo - platino - chloride 
 B'sBtoPtCls. Silky needles (Gunning, J. pr.67, 46). 
 
 Br omo-ethylo -bromide B'CjH,Brj 3aq : 
 from brucine and ethylene bromide at 100°; 
 forms furcate groups of nacreous laminss (from 
 water). AgNOj pps. half the ?r. Moist Ag,0 
 
638 
 
 BRUCINE. 
 
 lorms the vinylo -hydroxide B'CjHsOH 
 which IB strongly alkaline ; two of its salts 
 are B'j(02H3Cl)2PtCl4 and B'CjHjSO^HSaq.— 
 Bromo-ethylo-platinochloride 
 B'j(CjH,Br)2PtCls (So^ad, A. 118, 207). 
 
 Allylo-iodide B'CjHJ aq. — B'CjHJ,.— 
 B'CjHjIjaq. — Allylo - ^latino - chloride 
 B'sfCsHsCy^PtClj. — Isoamylo - chloride 
 B'CsHiiClaq.— B'2(CsH„)2PtCls.— Isoamylo- 
 iodides B'CbHuIs.— B'C^Hi.Is. 
 
 Bromo-brucine CjsHjsBrNjO,. Formed by 
 adding an alcoholic solution of Br to an aqueous 
 solution of brucine sulphate. Small needles 
 (Laurent, A. Ch. [3] 24, 314 ; c/. Beckurts, S. 
 
 18, 1238). 
 
 Nitro-bruoine 0^^s{NO.^)0^^ii^. Formed by 
 nitration of brucine-methylo-iodide suspended 
 in absolute alcohol. Large red trimetric crys- 
 tals. Carbonises at about 240° without melting ; 
 sol. water. Salts,— B'HNOa: glistening yellow 
 needles, v. sol. water, si. sol. alcohol and ether. — 
 B'jHjCljPtCL : fine yellow needles (Hanssen, B. 
 
 19, 620). 
 
 Amidq - brneine CjaHjjfNHJO^Na. Formed 
 by reduction of nitro-brueine with tin and HCl. 
 V. sol. water. Not isolated. FezClj produces 
 a green colouration changing to brown. Very 
 dilute KjCrjO, produces a fugitive blue-violet 
 colour. Strong HNOs gives a yellow solution 
 which is turned red by SnClj.— B"'H3Cl3 : 
 colourless prisms.— B"'jH5Cl8Pt3Cl,2'< : yellow 
 amorphous pp. JHanssen, B. 19, 523). 
 
 Sinitro-brucine C23H2,(N02)20iNj. Prepared 
 by the action of HNO3 on an alcoholic solu- 
 tion of brucine. Eed amorphous powder. V. 
 sol. water, si. sol. alcohol, insol. ether. — 
 (B'HCl)2PtCl,: yeUow pp. (Glaus a. Bohre, B. 
 14, 765). 
 
 BBYONIIT CjsHgoOig. An amorphous bitter 
 substance in the root of the red-berried bryony 
 {Bryonia dicfCca) from which it may be extracted 
 by boiling water. It appears to be resolved by 
 dilute H^SOjinto glucose and two amorphous 
 bodies, bryoretin C2,H3jO, sol. ether, and 
 hydro - bryoretin C2,H„0j insol. ether 
 (Brandes a. Firnhaber, Brandes' Ar, Ph.S, 356; 
 Walz, C. C. 1859, 5). 
 
 BTJCHU. The leaves of several species of 
 Bwrosma growing at the Cape contain a volatile 
 oil and a crystalline substance [85°] (Fliiekiger, 
 Ph. [3] 4, 689 ; Jones, Ph. [3] 9, 673). 
 
 BTIBETTE v. Analysis, p. 248. 
 
 BTJTALANINE v. Amido-butteic acid. 
 
 n-BTTTANE C,H,„i.6. CH3.CHj.CH2.CH3. Di- 
 ethyl. Methyl-propyl. Butyl-hydride. Mol. w. 
 58. (1°) (Butlerow, Z. 1867, 363). S.G.2-60. 
 V.D. 2-11 (calo. 2-01) (Eonalds, C. J. 18, 54 ; 
 Pelouze a. Cahours. A. Ch. [4] 1, 5). S. (gas 
 in alcohol) 18 at 14°. Occurs in petroleum 
 (E.). Formed by the action of Zn on EtI at 
 150° (Frankland, A. 11, 221; Schoyen, A. 130, 
 233). Also, together with butylene, by heating 
 butyl alcohol with ZnCl^ (Wurtz, A. 93, 112). 
 Prepared by the action of sodium-amalgam on 
 EtI (Lowig, X 1860, 397). 
 
 Iso-butane (CHa)aCH. Trimethyl-methane, 
 Secondary butane. (-17°). H.F. p. 42,450. 
 H.F. V. 40,180 (Th.). Prepared by slowly pour- 
 ing tert-hntyl iodide into water containing zinc, 
 the equation being 2(CH3)3CI + HjO + Zn^ 
 - 2(CH,) jCfl + ZnO + Znl,. Also from iso-butyl 
 
 iodide and Mfil^ at 120° (Eohnlein, B. 16, 562). 
 Colourless gas. Chlorine converts it into 
 (CH3)3C.C1 (Butlerow, A. 144, 10). Br at 100° 
 forms di-bromo-butane (Carius, A. 126, 195). 
 Excess of Br at 300° forms 02Br4(Merz a.Weith, 
 B. 11, 2244). 
 
 BTJTAIfE CABBOXYLIC ACID v. Buitkio 
 
 ACID. 
 
 Butane dl-carboxylic add v. Pboftl-malonio 
 
 ACID, IsO-PEOPHi-MALONIO ACID, MbTHTL ETHYIi- 
 MALONIOAOrD,ExHTIi-SnOCINICAOID,tWoDl-METHTIi- 
 SDCCINIO ACIDS, AdIPIC ACID, o-MeTHYL-OLUTABIO 
 
 ACID, and iS-Mbthyl-glutabio aoid. 
 
 Butane awai- tricarboxylic acid C,H,gOe i.e. 
 MeCH2CH(C02H)CH(C0iH)j. Ethyl - ethenyl - 
 tri-ca/rboxyUc acid. [119°]. Got by saponifying 
 the ether with alcoholic potash (Polko, A. 242, 
 115). White rhombic crystals. V. e. sol. water, 
 alcohol, ether, acetone, v. sol. chloroform. — 
 Salts. — A"'^a3, insol. water and alcohol. — 
 A"'Ag3liaq, si. sol. water. — A^^CaHj, insol. al- 
 cohol, V. sol. water.— A"'CaH2Jaq. — A^Oa,, 
 hygroscopic. — A^ZnaOaq, v. e. sol. water, insol. 
 alcohol.— A"'2Srs6aq. 
 
 Ethyl ether MeOH3CH(COjEt)CH(C03Et)3. 
 (276°). (189° at 60 mm.). S.G.i^ 1-065. Formed 
 by acting on sodium malonic ether with a-bromo- 
 butyrio ether in alcoholic solution (P.). 
 
 Butane aa/S-tri-carbozylic acid 
 CH3.CH(C03H).C(C02H)3.CH3. Butenyl-tri- 
 carboxyUo acid. [157°]. V. sol. water, alcohol 
 and ether. On warming it yields s-di-methyl- 
 succinic anhydride [87°] (BischofE a. Bach, 
 A. 234, 54). Salts.— Ba3A"V—Ca3A"'j. 
 
 Ethyl ether EtjA'". (0. 190°) at 50-60 
 mm. ; (273°-275°) at ordinary pressure. Liquid. . 
 Formed by the action of o-bromo - propionic 
 ether upon sodio-methyl-malonio ether. By 
 boiling with HCl it is converted into s-di-methyl- 
 sucoinic aoid [189°] (Leuckart, B. 18, 2346). 
 
 Iso-butane tri-carbozylic acid 
 Me.C(C03H)CH(C02H)j. [120°]. Prepared by 
 saponifying the ether with alcoholic potash 
 (Bamstein, A. 242, 128). Needle-shaped crys- 
 tals (from water). V. e. sol. water, alcohol, 
 ether, acetone, v. si. sol. chloroform, benzene, 
 petroleum ether, carbon disulphide. Decom- 
 posed by boiling with water, giving oft COj. 
 Salts. — K3A"'2aq. Quadratic prisms : v. e. sol. 
 water, insol. alcohol. — Ca3A"'j9aq: m. sol. water. 
 — CaA"'2 2aq : v. e. sol. water. — Sr3A"'2 7aq. 
 
 Ethyl ether EtjA'". (181°-185°) at 30-40 
 mm.; (279°-281°) at ordinary pressure (L.); 
 (273°) (B.). S.Ot. ^ 1-064. Liquid. Formed 
 by the action of o-bromo-isobutyric ether upon 
 Eodio-malonic ether. By boHiug with HCl it is 
 converted into M-di-methyl-succinic acid [139°] 
 (Leuckart, B. 18, 2350 ; Barnstein, A. 242, 126). 
 
 Butane aia)77-tetra-carboxylie ether 0,5H„„0, 
 i.e. (C02H)2.CH.CH2.CH2.CH(COjH)j. (275°-280°) 
 at 225 mm. Formed, together with trimethylene 
 dicarboxylic acid, by the action of ethylene 
 bromide on sodium malonic ether (Perkin, jun., 
 0. J. 51, 17 ; B. 19, 2038). The yield is very 
 small. The corresponding acid splits up when 
 heated into CO, and adipic acid. By treatment 
 with sodium ethylate it gives a di-sodio-deriva- 
 tive which by the action of bromine yields tetra- 
 
 CHj.0(C02Et)j 
 methylene-tetra-carboxylic ether | | 
 
 CH,.0{C03Et), 
 
BUTENYL-TOLYLENE-DIAMINE. 
 
 689 
 
 lBO>butane tetia-carboxylio ether 
 (C02Bt)jOH.CHM6.CH(CO,Et)j. (o. 211°) at 
 20 mm. A by-produot in the preparation of 
 ethylidene-malonio ether from aldehyde and 
 malonio ether ; it is formed by the addition of 
 malonio ether to ethylidene-malonio ether 
 0H3.CH:C(C02Et)j (Komnenos, A. 218, 158; 
 Claisen, J.pr. [2] 35, 414). The corresponding 
 acid is split up by distillation into COj and 0- 
 methyl-glutaricacidC02H.CH2.CHMe.0H2,C02H. 
 
 Butane aaj8;3-tetra-carbozylic ether 
 {CO^t)fiUe.CMe{CO^M)^.Di.methyl-acetylene- 
 tetra-carboxylio ether. S.G. ^| l-il4. From 
 sodio-methyl-malonio ether by the action of 
 iodine or of chloro-methyl-malonio ether. From 
 Bodio-ethane tetra-carboxylio ether and Mel 
 (BisohofE a. Bach, B. 18, 1202 ; A. 234, 70). 
 
 Bntane tetra-carbozylio ether 
 CH(002H)j.C(C2H5)(C0jEt)j. Ethyl-acetylene- 
 tetra-carhoxylic acid. Thick colourless oil; 
 formed by the action of ohloro-malonio ether on 
 Eodio-ethyl-malonio ether (BischofC a. Bach, B. 
 17, 2785). 
 
 Butane hexa-carbozyllo ether 
 C02Et.CH2.C(C0jEt)2.C(C02Et)2.CH;,.C0jEt. 
 [57°]. Six-sided tables. From sodium ethane tri- 
 carboxylic ether (C02Et)jCNa.CH:2.C02Et by the 
 action of iodine or of (OO^EtjjCCl.OHa.COjEt 
 (Bischoff, B. 16, 1046; 17, 2786). 
 
 ISO-BTJTAWE STIIPHINIC ACID 
 (CH3)2CH.CH2.S02H. From iso-butane sulpho- 
 ohloride by zinc-dust (Pauly, B. 10, 942). 
 Liquid. Beduoed by nascent hydrogen to iso- 
 bniyl meroaptan. — ZnA'^. Plates (from alcohol). 
 
 w-BTJTANE SULPHONIC ACID CiHgSOjH. 
 Formed by the action of HNO3 on Ji-butyl mer- 
 captan (Grabowsky, A. 175, 344). Thick syrup, 
 V. sol. water and alcohol, m. sol. ether. — AgA' : 
 plates. — PbA'2 : plates, si. sol. alcohol. — 
 PbA'2,2Pb(0H)2 : crystalline powder, si. sol. 
 water. — BaA'j aq ; plates. — CaA'2, 2aq. — NaA' : 
 plates. 
 
 Iso-butane sulphonlc acid 
 (CH3)2CH.CH2.S03H. Fromiso-butyl mercaptan 
 and HNOs (MyUus, B. 5, 978). Syrup. Its 
 salts are v. sol. water.— AgA' : scales. — BaA'2 : 
 needles. 
 
 Chloride CASOjCl (190°) (Pauly, B. 10, 
 942). 
 
 ISO-BTJTENYL ACETATE CH2:CMe.CH20Ao 
 (120°) (Scheschukoff, /. R. 16, 502). 
 
 BUTENYL ALCOHOL O^HjO i.e. 
 CH3.CH:0H.0H20H, (117°). A product of the 
 action of iron and acetic acid upon orotonio 
 and tri-chloro- butyric aldehydes (Lieben a. 
 Zeisel, M. 1, 825). HI gives CH3.CH2.CHI.CH3. 
 
 Isobutenyl alcohol CH2:CMe.CH20H. (113°). 
 S.G. - -8695. Formed by boiling isobutenyl 
 chloride with very dilute KfiO, (Scheschukoff, 
 J. B. 16, 499). Dilute H2SO4 changes it to iso- 
 butvrio aldehyde. HI forms ierf-butyl iodide. 
 
 Sthyl ether CH2:CMe.CH2.0Et (78°-85°). 
 From isobutenyl chloride and KOEt. 
 
 Sec-isobutenyl alcohol CMe2:CH.0H. 
 
 Methyl ether CMejiCH.O.Me. Meth7jl 
 isocrotyl oxide. (70°-74°). From bromo-iso- 
 butylene and NaOMe at 140°. Dilute H2SO, at 
 140° gives HOMe and isobutyno aldehyde (Elte- 
 koft B. 10, 705 ; J. B. 9, 163). 
 
 Ethyl ether CMe2:CH.0Et. (9f)- Simi- 
 larly prepared (E. ; S. ; Butlerow, Z. 1870, 624). 
 
 BTJTENYL-TEI-AMINE 0H(CH2NH2)3. 
 (above 150°). From the nitrile of methane tri- 
 oarboxylio acid CH(0N)3, tin, and HCl. — 
 B'23H2PtCl, (Fairlie, C. J. 16, 362). 
 
 BUIENYL-BENZENE v. Phenyi-butylenb. 
 
 BTJTENYL CHLORIDE v. Ohloro-butylbne. 
 
 (o).BTrTENYL.CUMENE C^H^^rC^H,. Iso- 
 propyl-butenyl- benzene. (243°), S.G. -8875. 
 Obtained from bromo - oumyl - valeric acid 
 CsHjPr.CH2.CBrEt.CO2H and NajCOjAq (Perkin, 
 C. J. 32, 662). Forms a dibromide [77°]. 
 
 (3)-Butenyl-cumene CeH^Pr.CjH,. (235°). 
 S.G. i^ -889. Ouminio aldehyde (10 g.), sodio 
 isobutyrate (5 g.) and isobutyrio anhydride 
 (15 g.) are heated together. The oUy product is 
 distilled with water and then over solid KOH 
 and Na (Perkin, C. J. 35, 141). It forms a 
 liquid dibromide. 
 
 BUTENYL-GLTCERIN v. Tki-oxy-buianb. 
 
 DI-BUTENYL-KETONE v. Di-AiiLYL-ACBTONB 
 (p. 134). 
 
 o-BUTENYL-PHENOL. 
 
 Methyl ether 
 [2:1] MeO.C,H,.CH:CH.CH2.CH3. (233°). S.G. if 
 •9817 ; |g -9740. From the methyl derivative of 
 oxy-phenyl-angelic acid by successive treatment 
 with HI and NajCOjAq (Perkin, 0. J. 33, 213), 
 Oil. Combines with bromine. Forms a red 
 solid with HjSOi. 
 
 p - Butenyl - phenol. Methyl ether 
 
 [4:1] MeO.CsHj.C.H,. [17°]. (243°). S.G. S2 
 ■973. Prepared like the preceding (Perkin, C /. 
 32, 671). 
 
 - Iso ■ bntenyl - phenol C,„H,20 i.e. 
 C4H,.C„H,.0H. (223°-225°). S.G. isa l-Qiy. 
 Salicylic aldehyde (30 g.) sodio isobutyrate 
 (22 g.) and isobutyrio anhydride (45 g.) are 
 heated together for 4 hours. Water is added to 
 the product, and the oily butenyl-phenyl isobu- 
 tyrate saponified by alcoholic KOH. The alco- 
 hol is boiled oS, dilute HCl is added and the oil 
 which separates is distilled (Perkin, C. J. 35, 
 142). Properties. — Oil, with smoky and cedar- 
 like odour. Sol. potash but insol. NH3. With 
 salicylic aldehyde and cone. HjSO, it forms a 
 purple solution. 
 
 ^ - Iso - butenyl - phenol Ci„H,20 i.e. 
 C<H,.CjH,.OH. (230°-285°). From ^-oxy-ben- 
 zoio aldehyde, sodic isobutyrate and butyric 
 anhydride. Yield small (Perkin, C. J. 35, 145). 
 An oil which solidifies in a freezing mixture. 
 
 Methyl ether C,H,.C,H,.OMe. [9°]. 
 (237°). From anisic aldehyde (20 g.), sodic iso- 
 butyrate (15 g.) and isobutyrio anhydride (30 g.) 
 by boiling at 180°. The product is distilled 
 with steam and the oil dried over K2CO3. Cooled 
 by ice and HCl it solidifies. On oxidation it 
 yields anisic and acetic acid. 
 
 a, - BUTENYL - STYRENE C5H5.CH:CH.C4H, 
 (245°-248°). Phenyl-hexineme. Ciunamic alde- 
 hyde (10 g.), sodium isobutyrate (15 g.) and iso- 
 butyrio anhydride (10 g.) are heated together for 
 two hours. CO2 comes ofE, and the residue is 
 distilled with steam, washed with NH3, dried 
 and rectified over Na (Perkin, O. /. 35, 141). 
 
 Properties.— Lighter than water. Eapidly 
 oxidises in air, becoming a resin. It combines 
 with bromine. 
 
 Iso-EUTENYL-TOLYLENE-o-LIAMINE 
 
 0,.H„N, i* C,H,<Y>C.O,H,. [158°]. 
 
640 
 
 BUTENYL-TOLYLENE-DIAMINE, 
 
 Formed, together with a small quantity of tolu- 
 
 butyraldehydine OjEj^^^i^glQ'^', by shaking 
 
 a cold acetic acid solution of tolylene-o- 
 diamine (1 mol.) with an aqueous or alcoholic 
 solution of butyric aldehyde (2 mols.)- Small 
 colourless needles. V. sol. alcohol and ether, 
 si. sol. water. Very bitter taste (Hinsberg, B. 
 20, 1589). 
 
 BUTINENE C<H, i.e. 0H/.CH.CH:CH2. 
 Erythrene. Vinyl - ethylene. Pyrrolylene. 
 Occurs in the liquid got by compressing coal-gas 
 (Caventou, B. 6, 70; Grimaux a. Cloez, 0. B. 
 104, 118). Formed also (?) by passing fusel oil 
 through a red-hot tube (Caventou, A. 127, 93). 
 Obtained by boiling erythrite with cone, formic 
 ncid (5 pts.) (Henninger, B. 6, 70) ; and by 
 the action of KOH on di-methyl-pyrrolidine 
 methylo-iodide (Ciamician a. Magnaghi, B. 19, 
 569). A gas. It forms a tetrabromide [119°] . 
 Pyrrolylene and the butinene from erythrite 
 form also a second tetrabromide [40°] so that 
 they are probably mixtures of two butinenes. 
 
 Butinene CHs.CHj.CiCH. Ethyl-acetylene 
 Crotonylene. (18°). From methyl ethyl ketone 
 by successive treatment with alcoholic KOH and 
 PCI5 fBruylants,B. 8, 412). Gives a white pp. in 
 ammoniacal AgNOj and a yellow pp. in am- 
 moniacal cuprous chloride. Mercuric chloride 
 solution gives a pp. of (0.,Hj)2(HgOHgCl2)3 
 (Kutscherofi, B. 17, 24), whence HOI produces 
 methyl ethyl ketone. The same butinene 
 appears to be formed when a mixture of 
 acetylene and ethylene is passed through a 
 red hot tube. It forms a tetrabromide [113°] 
 (Berthelot, A. Ch. [4] 9, 406; Prunier, Bl. 
 20, 72; A. Ch. [5] 17, 17; 0. B. 76, 1410). 
 
 Butinene CH3.C:C.CH3(?). Crotonylene. 
 (18°). From crude butylene bromide and alco- 
 holic KOH (Caventou, A. 127, 347). From aj3- 
 di-bromo-butane and alcoholic KOH (Almedin- 
 gen, /. B. 13, 392). Also formed by distilling 
 barium acetate with S (Ptankuch, J. pr. [2] 
 6, 110). HjSOi (3 mols.) diluted with water 
 (1 mol.) converts it into hexa-methyl-benzene. 
 
 Butinene CiHj. Caoutchin. [-10°]. (15°). 
 S.G. =? -65. Formed by the dry distillation of 
 caoutchouc (g^.v.) (Bouohardat, A. 27, 33). 
 
 BUTINENE GLYCOL v. Di-oxt-butylene. 
 
 BVTONENE-AMIDO- PHENYL MEBCAF- 
 TAN O.sH.jN^S^ i.e. 
 
 C«H,<|>C.CH,.CH2.C<^>C,H,. [137°]. 
 
 From amido-phenyl-o-meroaptan and succin- 
 amide (Hofmann, B. 13, 1231). Needles (from 
 alcohol).— B'HAuCl,. 
 
 BUTYL DERIVATIVES of hydroxyHc com- 
 pounds are described under the compounds of 
 which they are the ethers. 
 
 DI-BUTYL V. OoTAME. 
 
 BUTYL ACETATE CsH.A i.e. C,Ha.OAc. 
 (124-5°). S.G. g -9016. C.B. (0°-10°) -00113. 
 S.V. 150-6 (Gartenmeister, A. 233, 259). From 
 butyl iodide and AgOAo (Lieben a. Bossi, A. 
 158, 170 ; Linnemann, A. 161, 193 ; Pribram a. 
 Handl, M. 2, 693). 
 
 Isobutyl acetate (0Hs)2CH.CHj.0Ac. V.D. 
 4-073 (calo. 4-017). (116-3°) (Blsasser, A. 
 218, 326); (117° cor.) (Perkin, C. J. 45,495; 
 (112-8°) (B. Schiff, A. 220, 109). S.G. ? -8921 
 (B.); if -8774; II -8688 (P.). O.E. (0°-10°) 
 
 -001137 (B.). M.M. 6-623 at 10°. S.V. 150-10 
 (B.) ; 152-5 (S.). Formed from isobutyl iodide 
 and AgOAc, or by distUling potassium isobutyl 
 sulphate with KOAo (Wurtz, A. 90, 121). 
 
 S«c-Butyl acetate CH3.CH2.CH(0Ac).CH,. 
 (112°). S.G. 2 -892. From sec-butyl iodide and 
 AgOAo (De Luynes, J. 1864, 501 ; Lieben, A. 
 150, 112). 
 
 Tertiary Butyl acetate (CH3)3C.OAc. (93°- 
 96°). From the iodide and AgOAo. Eeadily 
 saponified by baryta- water (Butlerow, A. 144, 7). 
 
 ISO-BUTYL-ACETIC ACID v. Hexoio acid. 
 
 ISOBUTYL-ACETO-ACETIC ETHEB v. p. 24. 
 
 BUTYL-ACBIDINE 0„H„N i.e. 
 
 CjHX I > CjH,. From valeric acid (30 g.), di- 
 
 \n 
 
 phenylamine (30 g.) and ZnClj (50 g.) heated 
 gradually for 20 hours up to 220° (Bernthsen a. 
 J. Traube, A. 224, 41 ; B. 17, 1508). 
 
 Salts.— B'HCl [191°]: yellow columns, t. 
 sol. water or alcohol, very dilute solutions show 
 bluefluoresoenoe. Insol. ether.— B'HNOj [139°].— 
 B'H2Cr04 [c. 100°]. 
 
 Dihydride C,3H,„N(04HJ. [98°-100°]. Got 
 by reducing the hydrochloride with zinc-dust. 
 White plates (from alcohol). 
 
 BUTYLACTIC ACID v. Oxy-butykio acid. 
 
 BUTYLAL V. BnTTBio aldehyde. 
 
 BUTYL ALCOHOL C,H,„0. Mol. w. 74. The 
 four butyl alcohols indicated by theory are 
 known. 
 
 m-Butyl-alcohol CH3.OH2.CH3.CH3OH. (117° 
 cor.). S.G. a -8233 (Zander, A. 224, 79) ; f -8096 
 (Bruhl,4.203, 16). S.8-3. C.B. (0°-10°) -00087 
 (Z.). fji^ 1-4040. S.V. 101-6 (Schiff, A. 220, 
 101). Bo5 35-45 (B.). Critical point 287° 
 (Paulewsky, B. 16, 2634). 
 
 Occurrence. — In the heavy oils from brandy. 
 It is completely absent from the products of the 
 fermentation of sugar with elliptical yeast 
 (Claudon a. Morin, O. B. 104, 1187). 
 
 Formation. — l.Frombutyrylchloride.butyrio 
 acid and sodium-amalgam (Saytzeff, J. pr. [2] 
 3, 76). — 2. By the fermentation of glycerin by 
 a Schizomycetes or by certain Bacteria i'n pre- 
 sence of CaCO, and ammonium tartrate ; n- 
 butyrio acid and a little alcohol are formed at 
 the same time (Fitz, B. 9, 1348; Vigna, B. 16, 
 1438).— 3. A product of the reduction of butenyl 
 alcohol (Lieben a. Zeisel, M. 1, 825). 
 
 Preparation. — From butyric aldehyde, 
 water, and sodium-amalgam (Lieben a. Bossi, 
 C. B. 68, 1561 ; 78, 1561 ; 4. 151, 121 ; 158, 137 ; 
 165, 145 ; C. J. 24, 516 ; Linnemann, A. 161, 179). 
 
 Properties. — ^Liquid. Separated by OaClj 
 from aqueous solution. On oxidation it produces 
 butyric acid. Fused ZuClj forms the two n- 
 butylenes (Le Bel a. Greene, C. B. 89, 413). 
 
 Combination. — (C4Hi„0)3CaCl2 (Heindl, M. 
 2, 200). 
 
 Iso-butyl alcohol (CH3)jCH.CHjOH. (106-6°- 
 106-8°) at 763-2 mm. (E. Schiff, A. 220, 102) 
 (108°) (Linnemann, A. 160, 238). S.G. f -8062 
 (Bruhl) ; Jf -8069 ; |j -8009 (P.). S. 9-5 at 18°. 
 S.V. 101-63. H.F. p. 71,150. H.F. v. 68,580 
 (Th.). A13 1-4007. Boo 35-41. M.M. 4-936 at 
 17-7°. 
 
 Occii/rrence. — In fusel oil from beet or pota- 
 toes and other sources (Wurtz, A. Ch. [3] 43, 
 129 ; A. 85, 197 ; 93, 107 } 0. B. 35, 810). 
 
BUTYLAMINE. 
 
 641 
 
 Inobutyl angelate and isobutyrate occur in Roman 
 oil of chamomile (Eobig, A. 195, 96). 
 
 Formation. — 1. Isobutylene combines with 
 ClOH forming (0H3)2:CC1.CH„0H, which is re- 
 duced by sodium amalgam and water (Butlerow, 
 
 A. 144, 24). — 2. Isobutyl alcohol is produced by 
 the action of Bacillus butylicus upon sugar, 
 glycerin, &c., even in presence of 8 p.o. alcohol 
 (Ordonneau, C. B. 102, 219 ; Claudon a. Morin, 
 O. B. 104, 1187). 
 
 Properties.— Liquid ; smelling like fusel oil ; 
 separated from its aqueous solution by CaCla. 
 The rate of etherification has been studied by 
 Mensohutkin {A. Ch. [5] 23, 14). 
 
 Beactions. — 1. CrO, produces isobutyric, 
 acetic and carbonic acids, and acetone (Kramer, 
 
 B. 7, 252 ; Schmidt, B. 7, 1361).— 2. Distilled 
 over zinc - d/ust splits up into isobutylene 
 and H2O (Jahn, B. 13, 989).— 3. Dropped 
 upon fused ZuClu it forms isobutylene and 
 CH3.CH:CH.CH3 (Le Bel a. Greene, Am. 2, 23). 
 4. Heated with ammoniacal ZnCl^ at 260°-280° 
 it yields a mixture of mono-, di- and tri- isobutyl- 
 amine (the latter in smaller quantity), the yield 
 of mixed bases amounting to 50 to 70 p.o. of 
 the alcohol used (Merz a. GasiorowsM, B. 17, 
 623). 
 
 Combinations. — (C4H,jO)3CaCl2 (Heindl, M. 
 2, 208). 
 
 Metallic derivatives. — KOO4H9. — 
 Na004H,(C4H,„0)3 (De Forcrand, O. B. 104, 
 169).— A12(0C4H;,),. [140^. S.G. 4 -9825 (Glad- 
 stone a. Tribe, 0. J. 39, 6). From Al (4 g.), 
 iodine (2 g.) and isobutyl alcohol 40 c.c. at 100°. 
 The yield is good (16 g.). Once fused it remains 
 long fluid at 70°. 
 
 Secondary butyl alcohol 
 CH3.CH2.C(CH3)H.OH. Methyl-ethyl-carbinol. 
 Butylene hydrate. (99°) at 740 mm. S.G. a 
 •827 (Lieben, A. 150, 114). 
 
 Formation. — 1. From n-butylamine by 
 nitrous acid ; at the same, time some w-butyl 
 alcohol is also formed (Linnemann a. Zotta, A. 
 162, 3 ; Meyer, B. 10, 130).— 2. By treating 
 the compound of HCIO with isobutylene, 
 CH3.CHC1.0H(0H).CH3, with sodium amalgam 
 (Lieben, A. 151, 121).— 3. By the action of zinc 
 ethide on glyoolio iodhydrin (Butlerow a. Osso- 
 kin A. 145, 263).— 4. Symmetrical dichloro-di- 
 ethyl oxide, (CH3.0H01)2O is converted by ZnEt^ 
 into (CH,.CHEt)20, a butyl ether which, on 
 treatment with HI at 130° gives secondary butyl 
 iodide (Lieben, A. 141, 236 ; Kessel,4. 175, 44). 
 5 Zinc ethide forms a orystallme compound 
 with aldehyde, CH3.CHEt(0ZnEt), which is de- 
 composed by water into secondary butyl alcohol, 
 ethane, and Zn(OH),. (Wagner, /. B. 8, 37; 4. 
 181 261).— 6. From formic ether by treatmg 
 with a mixture of ZnEt^ and ZnMe^ and deoom- 
 posin" the product with water (KanonnikofE a. 
 
 Saytzeff, A. 175, 374). , , , . .,.^ , , 
 
 Prepara«iore.—Secondary butyl iodide [q.v.) 
 
 is treated vrith silver acetate and the Product 
 
 saponified by potash (De Luynes, A. 128, 3d0 ; 
 
 132 274) 
 
 Properties. -Li(imd. with strong odour, ppd. 
 from aqueous solution by KjCO,. 
 
 Be^cPhns.-!. Oxidises to methyl-ethyl- 
 ketone and acetic acid (Saytzeff, Z. \ff)--- 
 " The pure alcohol is unaltered when heated &t 
 240°-250° during 8 to 16 hours in a sealed tube. 
 
 Vol.. I. 
 
 but the presence of a trace of HCl, HBr, 01 
 
 especially HI, is sufficient to split it up, forming 
 pseudobutylene. The reaction commences at 
 220° and is complete in 5 or 6 hours (Bougaieff 
 a. Wolkoff, Bl. [2] 45, 249). 
 
 Tertiary butyl alcohol (CH3)30.0H. Tri- 
 methyl-carbinol. [25°]. (83° cor.). S.G. 21-779 
 (Lmnemann); so .779 (Butlerow); =J -786; 
 =5" -780 (Briihl); if -7836; p -7761 (Peilcin). 
 M.M. 5-122 at 24-3°- ^,9 1-3924. B 00 35-53. Cri- 
 tical point 235° (Pawlewski, B. 16, 2634). 
 
 Formation. — 1. Zinc methide (2 mols.) and 
 acetyl chloride (1 mol.) mixed at 0°, form, 
 after some hours, a crystalline compound, 
 CH3.CMe(0ZnMe)Me, which is decomposed by 
 water into tertiary butyl alcohol, Zn(0H)2 and 
 CH, (Butlerow, A. 144, 1 ; Wagner a. Saytzeff, 
 A. 175, 361 ; Pawloff, A. 188, 118).- 2. Together 
 with isobutyl alcohol by treating isobutyl iodide 
 with acetic acid and Ag^O (Linnemann, A. 162, 
 12 ; Butlerow, A. 168, 143).— 3. From isobutyl- 
 amine and HNOj. — 4. From isobutyl cyanate 
 and EOH (Linnemann, A. 162, 12). — 5. From 
 tertiary butyl iodide (q.v.) and water, even in the 
 cold (Dobbin, 0. /. 37, 238).— 6. A mixture of 
 iso- and tert- butyl chlorides is got by heating 
 isobutyl alcohol with HCl; when heated with 
 water (6 vols.) at 100° the chloride of ieri-butyl 
 alcohol is the only one converted into its alcohol 
 (Freund, J.pr. [2] 12, 25). 
 
 Preparation. — ^Liquid isobutylene is sealed 
 np with twice its volume of a mixture of equal 
 parts of water and sulphuric acid, and the con- 
 tents are left till homogeneous and then distilled 
 (Butlerow, Z. [2] 6,237 ; A. 180, 246). 
 
 Properties. — Trimetrio prisms. Forms a 
 hydrate (C4Hi„0)2H20 which boils at 80° (But- 
 lerow). 
 
 Beacikms. — 1. CrOa mixture gives acetone 
 together with acetic, carbonic and a little iso- 
 butyric acid (Butlerow, Z. 1871,485).— 2. Heatr 
 ing with anhydrous HjCjO, produces butylene 
 (Cahours a. Demarpay, C. B. 86, 991).— 3. When 
 taken internally it is excreted in the urine as 
 butyl-glycuronic acid C,|,H,gO, (Thierfelder a, 
 Mering, S. 9, 514) which is decomposed by 
 boiling dilute HCl into ieri-butyl alcohol and 
 glyouronic acid. 
 
 DI-ISOBTTTYL ALDEHYDATE v. p. 105. 
 
 ISO-BTTTYL ALDEHYDE v. Isoeutykio alde- 
 hyde. 
 
 ISO-BTTTYL-ALDOXIM v. Isobuitbio aide- 
 
 HYDE. 
 
 ISO-BUTYL- AMID 0- ISO-BTJTYL - BENZEKE 
 C,H,.NH.CsH,.C4H,. (260°-270°). From anihne 
 hydrochloride (10 g.) and iso - butyl alcohol 
 (13 g.) at 230° (Studer, A. 211, 240 ; B. 14, 
 1473). Oil. Does not give the carbamine reac- 
 
 Nitroso -derivative S.G. ** "gOl- Solidi. 
 fies on keeping. 
 
 Acetyl-derivative. [74°]. (above 300°), 
 Needles (from benzoline). 
 
 BTITYL-AMIDO-TOLTIENE v. Methyl-buiyj> 
 
 PHENYL-AMINE. . „ „„ „„ 
 
 n-BTTTYLAMINE C^H^NHj %.e. Pr.CH^.NHj, 
 Mol. w. 73. (76°). S.G. 2-755, a.«- -733. 
 
 Formation.— 1. From butyl cyanate and 
 KOHAq (Lieben a. Eossi, A. 158, 172 ; Meyer, 
 B. 10, 131). — 2. From butyronitrile by reduction 
 
C42 
 
 BUTYL AMINE. 
 
 (Linnemann a. Zotta, A. 162, 3). — 3. From 
 nitrobutane, Sn and HOI (Ziiblm, B. 10, 2083). 
 
 Properties.— Misaihle with water; dissolves 
 Ireslily ppd. Cu(0H)2 and Ag^O. Beduoes alka- 
 line solutions of copper, silver, and mercury. 
 Nitrous acid converts it into sec-butyl alcohol. — 
 Platino-ohloride (B'.HC^jPtOl^ : yellow 
 crystalline plates, m. sol. cold water. 
 
 Primary isobntyl-amine Pr.CHj.NHj. (68°) 
 (E. Sohiff, JB. 19, 565). S.G.i2-736. S.V. 106-16 
 (S.). H.F. p. 38,460. H.F. v. 35,560 (Th.). 
 
 Formation. — 1. By distilling potassium iso- 
 butyl sulphate with potassium cyanate and treat- 
 ing the product with KOH (Wurtz, A. 98, 124 ; 
 Linnemann, A. 162, 23).— 2. By heating iso- 
 butyl bromide with alcoholic NH3 and separating 
 the mono-, di-, and tri- butylamines by oxalic 
 ether (Eeimer, B. 3, 756; Hughes a. Eijmer, B. 
 7, 511 ; Malbot, C. E. 104, 63, 228). On heating 
 isobutyl chloride with ammonia (molecular pro- 
 portions) in isobutyl alcoholic solution or in 
 aqueous solution very nearly similar results 
 are obtained ; namely one part of mono-butyl- 
 amine, four of di-, and five parts of tri-butyl- 
 amines (M.). — 3. Formed, together with di- and 
 tri- isobutylamine, by heating isobutyl-alcohol 
 with ammoniaeal ZnClj at 260°-280° ; the yield 
 of mixed bases amounts to 50-70 p.c. of the 
 alcohol used (Merz a. Gasiorowski, B. 17, 623). 
 4. By reducing nitro-isobutane (Demole, A. 
 175, 142). — 5. A mixture of equal mols. of valer- 
 amide (ordinary) and bromine is run into an 
 excess of a 10 p.c. solution of KOH at 60° ; the 
 yield is 90 p.c. (Hofmanu, B. 15, 769). 
 
 Salts.— B'HCl. [160°]. S. 133 at 15°.— 
 (B'HC^jPtCl, : microscopic rhombic tablets. — 
 B'HAuCli. — Sulphate : cauliflower-like groups 
 of needles, not deliquescent. 
 
 Secondary butyl-amiue 
 CH8.CH2.CH(NH,).CH5. (63°). From dilute 
 H2SO4 and s«c-butyl thio-carbimide (from vola- 
 tile oil of scurvy-grass) (Eeyman, B. 7, 1289). 
 Also from the iodide or cyanate (Hofmann, B. 
 7, 513).— B'^HjPtCl,. 
 
 Tertiary butyl-amiue Me3CNH2 (46° cor.). 
 S.G. 2 -7155 ; ^ -7004. C.E. (0°-7-8°) -0014. 
 Formed together with isobutylamine by the 
 successive action of silver cyanate and aqueous 
 KOH on isobutyl iodide. Colourless ammoniaeal 
 liquid, attacks indiarubber and cork. Misoible 
 with water, but separated by KjCO, or KOH 
 from its solution (Brauner, A. 192, 72 ; cf. 
 Linnemann, A. 162, 19 ; Hofmann, B. 7, 513). 
 
 Salts.— B'HCl melts at [270°-280°] and 
 boils soon after. On solidifying it increases 
 greatly in bulk. — (B'HCl) uPtClj. Large mono- 
 clinic prisms (from alcohol). — B'HI. — B'HNOj. 
 Sulphate: six-sided prisms, not deliquescent. 
 
 Di- TO- butyl- amine (Pr.CHj)2NH. (160°). 
 Formed, together with Ji-butylamine, by treating 
 butyl cyanate with KOH (Lieben a. Eossi, A. 
 158, 175). Converted by nitrous acid into 
 primary and secondary w-butyl alcohols and 
 Ji-butylene (Meyer, B. 10, 130).— B'^H^PtClj. 
 Nitroso- derivative (C4H,)2N.NO. (236°cor.). 
 
 Dl-iso-butyl-amine (Pr.CH2)2NH. (137°). 
 Formed, together with mono- and tri- iso-butyl- 
 amine, by heating iso-butyl alcohol with am- 
 moniaeal ZnClj at 260°-280°. The secondary 
 amine is isolated from the mixture of bases 
 (which amounts to 60-70 p.c. of the alcohol 
 
 used) by means of its nitrosamine (Merz a, 
 Gasiorowski, B. 17, 623). Prepared by heating 
 iso-butyl iodide or bromide with alcoholic NH, 
 to 150° (Ladenburg, B. 12, 948). Butyl iodide 
 (1 mol.) in the cold acts upon di-isobutylamine 
 (1 mol.) forming di-isobutylamine hydrochloride 
 and free tri-iso-butylamine (M.). 
 
 Salts.— B'HCl: plates or scales. S. 62-5 at 
 15° ; S. (ether) -07 at 15°; S. (alcohol) -06 at 14° 
 (Malbot, O. B. 104, 366). — B'^H^PtClj. — 
 B'HClAuClj. Yellow tables, sparingly soluble 
 in cold water. 
 
 Nitroso- derivative N(N0)(C^Hs,)2. [0°]. 
 (213°-216°). Oil. Prepared by the action of 
 KNO2 on a solution of di-isobutylamine hydro- 
 chloride. 
 
 Tertiary di - butyl-amine (C^HJjNH i.e. 
 (CMe3).jNH. From tertiary butyl iodide and 
 tertiary butylamine at 50°. But above 70° iso- 
 butylene is given off : 04H,NH2 + CjH„I = 
 C4H8-|-C,H5NH,,HI (Eudnew, Bl. [2] 33, 299). 
 
 Salt.— B'HI. Very soluble in water and 
 alcohol. Converted by potash, or even boiling 
 water, into tertiary butylamine. 
 
 Tri-n-butyl-amine (CiH,)3N. Mol. w. 185. 
 (c. 213° cor.). S.G. 2 -791 ; n -778. From n- 
 butyl iodide and NH, (Lieben a. Eossi, A. 165, 
 115).— B'jH^PtClj. 
 
 n-Butylo -iodide {Cfi^^l: plates (Lie- 
 ben a. Eossi, A. 165, 113). 
 
 Tri - isobutyl - amine (PrCH2)3N. (185°). 
 S.G. 11 -785 (Sachtleben, B. 11, 733). Formed, 
 together with mono- and di- iso-butylamine, by 
 heating isobutyl alcohol with ammoniaeal ZnClj 
 at 260°-280°. The tertiary amine is isolated 
 from the mixture of bases (yield 50-70 p.c. 
 of the alcohol) by means of its sparingly soluble 
 ferrocyanide (Merz a. Gasiorowski, B. 17, 623). 
 Also from di-iso-butylamine and isobutyl bro- 
 mide. Also from isobutyl iodide (1 mol.) and 
 NHjAq (1 mol.) at 160° (Malbot, G.R. 105, 575). 
 Does not mix with water. With isobutyl bro- 
 mide it gives off butylene and forms tri-iso- 
 butylamine hydrobromide (Eeimer, B. 3, 757); 
 Isobutyl iodide (1 mol.) at 180° forms hydriod- 
 ides of di- and tri-isobutylamine and butylene 
 (M.). Isobutyl chloride (1 mol.) at 170° gives 
 pure di-isobutylamine hydrochloride and butyl- 
 ene. 
 
 Salts.— B',HC1, B',HN03 and B'j,HjS04 are 
 extremely soluble. — (B'HC^jPtOl, orange plates, 
 sol. hot water. — B'HClAuClj : amorphous, insol. 
 water. 
 
 Tert - BUTYL - tert - AMYL - AMINE 
 (CiHg)(C5H„)NH. The iodide of this base ia 
 formed by the slow action of tertiary amyl 
 iodide on tertiary butylamine in the cold. It is 
 very unstable, being decomposed by solution in 
 water (?) (Eudneff, Bl. [2] 33, 297). 
 
 n - BUTYL - ANILINE 0,„H,5N i.e. 
 
 C„H5.NHC,H„. (235° at 720°). Colourless oily 
 fluid. Easily volatile with steam. 
 
 Salts. — ^B'HCl: very soluble white needles. 
 — B'HNOjX : easily soluble.— B'jHjSOi'" : easily 
 soluble fine white needles. 
 
 Acetyl derivative C5H5.N(04H5)Ao ; 
 (274°) at 718 mm., colourless fluid. 
 
 Nitrosamine C5H5.N(C4Hb)NO ; yello\! 
 fluid ; easily soluble in alcohol and ether, in- 
 soluble in water (Kahn, B. 18, 3365). 
 
BUTYL-BENZOIO ACID, 
 
 613 
 
 laobutyl-aniline Fr.CHj.NHPh. (242°) (G.) ; 
 (226°) (N.). S.G. 14 -926 (G.)- STom isobutyl 
 bromide and aniline (Gianetti, O. 12, 268). — 
 B'HCl.— B'HBr.— B'HI. 
 
 Acetyl derivative (267°) (Nolting, J. 
 1883, 703). 
 
 p-Nitroso- derivative 
 
 >NH.CH,I'r 
 [4:1] OsH,(NO).NHCH2?r or C^H/ I >0 
 
 \n 
 
 [94°]. From isobutyl-aniline, HCl, and NaNOj 
 (W acker, A. 243, 297). Steel-blue crystals, v. sol. 
 alcohol, si. sol. water. Beaotions. — 1. Beduction 
 gives isobutyl-phenylene diamine.— 2. The chlor- 
 ide boiled with aqueous NaOH gives " iso-butyl- 
 amine and p-nitroso-phenol. — 3. HOI and NaNOj 
 give a nitrosamiue C8H^(N0).N(N0).CH,?r 
 crystallising in bright green plates, v. sol. 
 alcohol and ether, insol. water. 
 
 Di-isobutyl-aniline (PrCHJ^NPh. (o. 248°). 
 From aniline and isobutyl bromide (Studer, A. 
 211, 235). 
 
 DI-BUTYIi-ANILINE-AZYIINE v. Di-butyl- 
 amido- bemene-i.zo-di- butyl-aniline. 
 
 BUTYL-ANISOL v. Methyl ether of Butyi.- 
 
 PHENOL. 
 
 ISO - BTJTYI - ANTHRACENE CisHi, i.e. 
 
 C,H,< 
 
 /' 
 
 ■C(0,H,). 
 
 \ 
 
 C,H, [57°]. 
 
 Fluorescent 
 
 needles. Prepared by the action of zinc-dust, 
 isobutyl bromide and NaOH on anthraquinone 
 (Liebermann a. Tobias, B. 14, 802; A. 212, 
 107). The picric acid compound forms 
 long brownish-red needles. 
 
 I>i-hydrideC^,<^^^^0^,. From 
 
 isobutyl-oxauthranol, HI, and P (L.). Oil ; oxi- 
 dised by CrOj in HOAo to isobutyl-oxanthranol 
 and finally to anthraquinone. 
 
 BTJTYL-ANTHEANOL-DIHYDEIDE 
 
 06H4<cH(0,H,)>^=^*- ^'^°'^- •^™"' ^'°-''^^^' 
 quinone, aqueous NaOH and zino-dust, boiled 
 for some time and then iso-butyl bromide added 
 (Liebermann, A. 212, 103). 
 
 ISO-BUTYL-ANTHRANYL CHLORIDE 
 
 OeH4<coi^l^>C6H4. [78°]. Tables. Pre- 
 pared by the action of PClj on isobutyl-oxanthra- 
 nol (Liebermann a. Walder, B. 14, 463). 
 
 TO-BTJTYI-BENZENE CoH,, i.e. C A.CH^Pr. 
 Phenyl-butarie. (180°). S.G. is -862. From 
 OT-propyl bromide, benzyl chloride, and Na 
 (Eadziszewski, B. 9, 260). Also from n-butyl 
 bromide, bromo-benzene, and Na (Balbiano, B. 
 
 10, 296). . , u • • 
 
 Bromination.—'By the action of bromine in 
 the dark, or in presence of iodine, the product 
 is probably a mixture of o- and p- bromo-butyl- 
 benzene. By the action of bromine in direct suri- 
 shine, the substitution takes place in the 7-po|i- 
 tion of the side-chain giving CjHs.CHBr.CjH, 
 
 or CA.CBr,.C3H,. « t^! V'°T°;>''T°/i nno 
 vative is further brominated m the dark at 100 
 the second Br atom probably enters the ^-posi- 
 tion, the product being identical with the butyl- 
 ene-benzene-dibromide [70°] of Badziszewski 
 
 <'lKTfi-BVaE CA.OH^r (167°). 
 S.d. 2 -880 (G.) ; -858 (B.). V.D. 4-72 (G.). 
 
 Formation. — 1. From isobutyl bromide, 
 bromo-benzene and Na (Bless, B. B, 779; 
 Wreden a. Zuatowioz, B. 9, 1606). — 2. From 
 benzyl chloride, isopropyl iodide, and Na (Kohler 
 a. Aronheim, B. 8, 509). — 3. By the action of 
 50 g. iso-butyl chloride on 150 g. benzene ia 
 presence of about 50 g. AljCl, (Gossin, Bl. [2] 
 41, 446). — 4. By heating benzene with isobutyl 
 alcohol and ZuCl^ (Goldschmidt, B. 15, 1066). 
 5. By distilling m- or p- isobutyl-benzoic acid 
 with lime (Eelbe a. Pfeiffer, B. 19, 1728). 
 
 Properties. — Colourless liquid ; CrOj oxidises 
 it to benzoic acid. Passed over red-hot PbO it 
 forms naphthalene. 
 
 /S«o-butyl-benzene CH3.CH2.CH(CeH5).CH,. 
 (171°). S.G. 12 -873. From C5H5.CHBr.CH3 
 and ZnEt., (Kadziszewsky, B. 9, 261). 
 
 (a)-«-B'TJTYL-BENZENE SITLPHONIC ACID 
 CsH.,(CH2Pr)S03H. Formed by sulphonating 
 M-butyl-benzene (Balbiano, O. 7, 343). — BaA'^: 
 small laminas, si. sol. cold water. — ZiiA'2 7aq. — 
 PbA'2 aq. — Mn A'2 6aq. 
 
 (/3)-»j-Eutyl-benzene sulphonic acid, Formed 
 at the same time as the preceding (B.). — 
 BaA'2 2aq : nodules, more soluble than the Ba 
 salt of the (a)-aoid. — PbA'22aq. 
 
 Jso-Butyl-benzene-sulphonic acid 
 CeHj(C4H<,).S03H. Formed by sulphonation of 
 isobutyl-benzene.— A'2Ba2aq : glistening plates. 
 — A'K aq : plates. 
 
 Amide C,H,(CA).S02NH2: [137°] ; glisten- 
 ing needles (Kelbe a. Pfeiffer, B. 19, 1728). 
 
 BTTTYL BENZOATE v. p. 470. 
 
 BTJTYI BENZIMIDO-ETHEE v. p. 479. 
 
 m-ISO-BTITYL-BENZOIC ACID 
 C„H^(C,H3)C0jH [1:3]. [127°]. Long stout 
 needles. Formed by oxidation of m-isobutyl- 
 toluene with dilute HNO3. By further oxida- 
 tion with dilute HNO3 at 170°-200° isophthalic 
 acid is formed. Gives anitro- derivative [140°]. — 
 AgA' : white pp. 
 
 Amide 05H,(CA).C0NHj: [130°] ; hair-fine 
 needles from water (Kelbe a. Pfeiffer, B. 19, 
 1725). 
 
 Tj-Isobntyl-benzolc acid CjH4(C4H3).C02H 
 
 [1:4]. [164°]. . 
 
 Formation. — 1. By oxidation of p-isobutyl- 
 toluene with dUute HNO3. By further oxidation 
 with dilute HNO, terephthalic acid is formed 
 (Kelbe a. Pfeiffer, B. 19, 1725).— 2. By saponifica- 
 tion of its nitrUe (Pahl, B. 17, 1237). 
 
 Properties.— Monoelinio crystals ; gives a 
 nitro- derivative [161°]. 
 
 Salts. — AgA': white flocculent pp.— 
 BaA'z^aq: plates, sol. hot water. — CaA'jisaq: 
 si. sol. cold water. 
 
 Amide C.H,(C,H3).CONH2: [171°]; long 
 hair-fine needles (from water). 
 
 Methyl ether MeA': (247°); oil. 
 
 Nitrile C,H^(C,H,).CN. (249°) (G. a. M.) ; 
 (244°) (K.); (238°) (P.). V.D. 5-47 (obs.) (K.) ; 
 5-35 (obs.) (P.). Colourless oil. Formation.— 
 1. By distilling the formyl derivative of isobutyl- 
 phenyl-amine with zino-dust ; the yield is about 
 12 p.c. (Gasiorowski a. Merz, B. 18, 1009).— 2. 
 Bv heating p-isobutyl- phenyl -thio-carbinude 
 with copper powder at 200° (Pahl, B. 17, 1236). 
 3. Formed by heating tri-isobutylphenyl-phos- 
 phate with dry ECN (Kreysler, B. 18, 1707). 
 
 ISO-BTJXYI-BENZOYl-ACETIC ETHEE v. p. 
 
 482. „ 
 
 T T 2 
 
644 
 
 BUTYL BORATE. 
 
 ISO-BUTYL BORATE B(0CjH„)3. (212°). 
 Formed by heating Bfl, -with isobutyl alcohol 
 for 8 hours at 170°. Burns with green flame. 
 Insol. water and slowly decomposed by it 
 (Couneler, J. pr. [2] 18, 382). Not acted upon 
 by ammonia. 
 
 TO-BUTYL BROMIDE C^H^r i.e. 
 CH3.CH2.CH2.CHjBr. (100° cor.). S.G. 2 1-305; 
 =-2 1-299. Prom m-butyl alcohol, Br, and P 
 (Lieben a. Eossi, A. 158, 161). With Br at 
 150° it gives OjHsBrj (167°) (Linnemann, A. 
 161, 199). With bromine containing iodine 
 at 250° it reacts thus: C4H„Br + 8Br2 = 
 2C,Br, + 9HBr (Merz a. Weith, B. 11, 2244). 
 
 Isobutyl bromide ?r.CH2.Br. (92°) (L.); 
 (91°) at 758 mm. (Sohifi, B. 19, 563). S.G. H 
 1-2722; p 1-2598 (Perkin, C. J. 45, 457). S.V. 
 110-39. M.M. 8-003 at 16° (P.). From the alco- 
 hol and HI or P and I (Pierre a. Puohot, J. -Ph. 
 [4] 13, 9 ; Wurtz, A. 93, 114 ; Chapman a. Smith, 
 C. J. 22, 153). At 220° it partially changes to 
 tertiary butyl bromide (Eltekoff, B. 8, 1244). 
 
 Tertiary butyl bromide CMe^I. (72°). 
 S.G. ^ 1-215 ; if 1-2020 ; |f 1-1892. V.D. 4-7 
 (obs.). M.M. 8-238 at 18°. From isobutylene 
 and HBr (Boozeboom, B. 14, 2396). From 
 tri-methyl carbinol and PBrj (Eeboul, C. B. 93, 
 69). 
 
 Beaclions. — 1. Eeadily decomposes into HBr 
 and isobutylene. This occurs when it is treated 
 with AgjO, with KHO, with NEt^, or with Zn 
 and water (Butlerow, Z. 1867, 362).— 2. With 
 ZnO it forms tri-isobutylene, C^^'H.2^. — 3. With 
 water, even in the cold, it forms tertiary butyl 
 alcohol. 
 
 EUTYL BUTYRATE v. Butyric aoid. 
 
 ISO-BUTYL CARBAMINE CiH,NG. (c. 116°). 
 B.G. 4 -787. Preparation and properties like 
 those of ethyl oarbamine. Less readily attacked 
 by HCl than ethyl oarbamine (Gautier, A. 152, 
 221 ; Bl. [2] 11, 211 ; Z. [2] 5, 445). 
 
 n ■ BUTYL CARBONATE (PrCH^.^COa. 
 (207° cor.) at 740 mm. S.G. " -941 (Lieben a. 
 Eossi, A. 165, 112). 
 
 Isobutyl carbonate (Pr.CH2)2CO,. (190° 
 eor.). S.G. — -919. From isobutyl iodide and 
 AgjCO, (De Clermont, A. Gh. [3] 44, 336). From 
 isobutyl alcohol and CyCl (Hiimann, A. Ch. [3] 
 44, 3401. From sodium isobutylate and chloro- 
 picrin (Eoese, ^.205, 253; c/. Wurtz, 4. 93, 119). 
 
 Isobutyl-orthooarbonate (PrCH20)4C. (245° 
 cor.). S.G. a -900. The chief product of the 
 action of ohloropicrin on sodium isobutylate 
 (Ecese, A. 205, 253). 
 
 BUTYL-CHLORAL v. Tei-okloko-butybio 
 
 ALDEHTEE. 
 
 TC-BUTYL CHLORIDE C^HjCl i.e. 
 CH3.CH,.CHj.CH2Cl. Mol. w. 92-5. (78° cor.). 
 S.G. 2 -907 ; ii -897 (Linnemann, A. 161, 197). 
 S.V. 114-3 (Eamsay). From w-butyl alcohol and 
 HCl (L.; cf. Lieben a. Eossi, A. 158, 161). 
 From m-butane and chlorine (Schoyen, A. 130, 
 235). 
 
 Isobutyl chloride (CH3)2CH.CH201. (69°). 
 e.G. iS. -880 (Lmuemann) ; if -8886 ; |f -8739 
 (Perkin, C. J. 45, 4S5). M.M. 6-144 at 21°. 
 H.F. p. 45,370. H.F. v. 43,050 {Th.). S.V. 
 114-26 (E. Schiff, B. 19, 562). From isobutyl 
 alcohol and HOI or POlj (Wurtz, A. 93, 113 ; 
 Pierre a. Puchot, 0. iJ. 72, 832). 
 
 Tertiary butyl chloride (CH3)sC.Cl, (SI"*. 
 S.G. If -8471 ; || -8368. M.M. 6-257 at 15°. 
 
 Formation.— 1. By action of chlorine on 
 (CH3)3CH (Butlerow, J". 1884, 497).— 2. By heat- 
 ing isobutylene, (CH3)2C:CH2, with cone. HCl at 
 100° (Salessky, A. 165, 92 ; B. 5, 480 ; Le Bel, 
 Bl. [2] 28, 462 ; Puohot, A. Ch. [5] 28, 549).— 
 
 3. Prom tri-methyl-carbinol and AcCl or PCI5. — 
 
 4. Prom isobutyl iodide and ICl (Linnemann, 
 
 A. 162, 18). 
 
 Properties. — With water (5 vols.) at 100° it 
 is readily converted into tertiary butyl alcohol 
 (Butlerow, A. 144, 33). It partakes, therefore, 
 somewhat of the character of an acid chloride. 
 
 BUTYL-CHLORO- v. Chloko-euttl-. 
 
 BUTYL-CmCHONIC ACID v. Butyl-quino- 
 
 LINE-CAEBOXYLIO ACID. 
 
 BUTYL-CRESOL v. Mbthyl-eutyl-phenol. 
 ISO-BUTYL CYANATE ^r.CH^.N.CO. (110°). 
 From isobutyl iodide and silver oy anate (Brauner, 
 
 B. 12, 1877). 
 
 Tertiary butyl cyanate (CH3)3C.N.CO. (86° 
 cor.). S.G. a -8676. The chief product of the 
 action of isobutyl iodide on silver cyanate (B.) 
 
 BUTYL CYANIDE v. Vaieeonitbile. 
 
 n-BUTYLENE C^H, i.e. CH3.CH3.CH:CHj. 
 Vinyl-ethane. Ethyl- ethylene. Mol. w. 56. 
 (c — 4°). Occurs in the oils deposited from 
 compressed coal-gas (Colson, Bl. [2] 48, 52; 
 
 C. B. 104, 1286). 
 
 Formation. — 1. By boiling w-butyl iodide with 
 alcoholic KOH (Grabowsky a. Saytzeff, A. 179, 
 325 ; Lieben a. Eossi, A. 158, 164).— 2. From 
 bromo-ethylene and ZnEt^ (Chapman, O. /. 
 20, 28 ; Wurtz, Z. [2] 5, 407).— 3. Together with 
 secondary butyl alcohol by the action of HNOj 
 on n-butyl-amine (Meyer, B. 10, 136). 
 
 Properties. — Gas. Forms with Br a dibro- 
 mide (167°). HI forms CH3.CH2.CHI.CH3. 
 
 ^--Butylene CHj.CHtCH.CHj. {P)-ButyUne. 
 s-Di-methyl-ethylene. (1°). 
 
 Occurrence. — In the oils from compressed 
 coal-gas (Colson, C. B. 104, 1286). 
 
 Formation. — 1. From secondary butyl iodide 
 and alcoholic KOH, AgjO and water, or AgOAo 
 (De Luynes, A. 129, 200 ; 182, 275 ; Lieben, A. 
 150, 108 ; 151, 121).— 2. Together with isobu- 
 tylene by distilling 51- or iso- butyl alcohol with 
 ZnClj (Nevoid, Bl. 24, 122 ; Le Bel a. Greene, 
 Are. 2, 23 ; Bl. [2] 29, 306).— 3. By heating 
 secondary butyl alcohol. — 4. From Mel, allyl 
 iodide, and Na, small quantities of the two 
 other butylenes being also formed (Wurtz, Bl. 
 [2] 8, 265; Grosheintz, Bl. [2] 29, 201).— 5. 
 H2SO4 acting on isobutyl alcohol forms (1 vol. of) 
 CH3.CH:CH.CH, and (2 vols, of) (CH3)3C:CH3 
 (Eonovaloff, Bl. [2] 34, 333 ; of. Puchot, A. Ch. 
 [5] 28, 508).— 6. By boiling isobutyl iodide with 
 PbO (Eltekoff, Bl. [2] 84, 347). 
 
 Properties. — Gas. Br gives C^HjBrj (156°- 
 159°). HI gives CH3.CH.,.CHI.CH3. 
 
 Isobutylene (CH3)2C:CH2. u-Di-mcthyl-ethyl- 
 ene. (-6°). S.G. =j-* -637 (Puchot). H.F. p. 
 10,660. H.F.V. 8920 {Th.}. V.D. 1-93 (oalo. 
 1-94). Occurs in the oils obtained by compress- 
 ing oil-gas (Faraday, T. 1825, 440) or coal-gas 
 (Colson, Bl. [2] 48, 52 ; cf. Prunier, Bl. [2] 19, 
 109). 
 
 Formation. — 1. By electrolysis of potassium 
 
DUTYLIDENE-AMIDO-BENZOIC ACID. 
 
 643 
 
 ralarate (Kolbe, A. 69, 269).— 2. From see- or 
 tert- butyl alcohol and H^SO^ or ZnCL (Wurtz, 
 A. 93, 107 ; Eonovalofl, Bl. [2] 34, 333 ; Ler- 
 montoff, A. 196, 117; Puchot, A. Ch. [5] 28, 
 508 ; 0. B. 85, 757 ; Sohesohukoff, Bl. [2] 45, 
 181 ; cf. Nevoid, Bl. [2] 24, 122).— 3. Together 
 with ethylene and propylene by passing fusel 
 oil through a red-hot tube (Wurtz, A. 104, 249 ; 
 Butlerow, A. 145, 277).— 4. From iso- or tert- 
 butyl iodide and alcoholic KOH (De Luynes, 
 C. B. 56, 1175 ; A. Oh. [4] 2, 385 ; Butlerow, A. 
 144, 19 ; Z. [2] 6, 236).— 5. By heating di- 
 methyl-acrylic acid to 210°-220' during 25-30 
 hours (Gorboff a. Eesslef, Bl. [2] 41, 392). 
 
 Preparation.— Isohutjl iodide is run into 
 boiUng alcoholic KOH and the gas collected. 
 
 Properties. — Gas, si. sol. water, v. sol. alco- 
 hol, V. e. sol. ether and HOAc. 
 
 Beactions. — 1. Cone. HCl at 100° forms tert- 
 butyl chloride. — 2. Cone. HI aq absorbs it, form- 
 ing tert-butyl iodide and tri-methyl carbinol 
 (Seheschukoff, Bl. [2] 46, 823).-3. Cone. H^SO, 
 3 pts.) mixed with water (1 part) absorbs it, 
 and on diluting with water and distilling tert- 
 bntyl alcohol is got. H^SOj (5 pts.) mixed with 
 less water (1 pt.) forms much dodecylene. — 
 4. Br in CS^ forms C^HsBrj (148°) and C^H-Br, 
 (173°-183°) at 235 mm. (Nevoid, C. B. 83, 65 ; 
 Norton a.WiUiams, Am. 9, 88).— 5. HCIO forms 
 a chloro-butyl alcohol (137°) (Butlerow, A. 144, 
 1; Z. [2] 6, 236; Henry, Bi. [2] 26, 23).-6. 
 CrOj gives acetone, oxalic acid, acetic acid, &o. 
 (Zeidler, A. 197, 251).— 7. CI forms isobutenyl 
 chlorides CjH,Cl (Seheschukoff, J. B. 16, 488). 
 
 Combinations. — (CjHg)2Al2Cl5. From ethylene, 
 Al,Cle, and HCl (Gustavson, /. B. 16, 97).— 
 (CjHj)2Al2Bre : oU. S.G. s 2-1. V. p. 147. 
 
 BTJTYLENE ALGOHOI. v. Di-oxt-butane. 
 
 BTJTYLENE DIAMINE C^H.^Nj 
 t.e.0,H,(NHj)2(?). (above 140°). From ethylene 
 cyanide, tin, and HCl (Fairley, C. J. 17, 362 ; 
 could not be obtained by Ladenburg, B. 16, 1150, 
 or Lellmann a. Wiirthner, A. 228, 229).— 
 B'jHjPtCls. 
 
 BTJTYLENE BROUIDE v. Di-bromo-bctane. 
 
 BUXYLENE TBI-OAEBOXYLIC ACID 
 CH3.CH:C(COjH).CH(COjH)2. Ethylidene- 
 
 ethenyl-tri-carboxylic acid. [185°]. Formed by 
 the action of o-chloro-crotonio ether upon sodio- 
 malonic ether, and saponification of the product 
 (Hjelt, B. 17, 2833). V. sol. water, m. sol. 
 ether.— A"'Ag3 : flocculent pp.— A^jCaa" and 
 A."'^a,3 *: easily soluble powders. 
 
 Mono-ethyl ether A"'H2Et3aq: [70°]: 
 large triolinic crystals, a:6:c = -9111:1: "7553. — 
 A"'H2Etaq [145°]. 
 
 Tri-ethyl ether EtjA'". (286°). 
 
 BUTYLENE GLYCOL v. Di-ont-BUTANE. 
 
 BUTYLENE GLYCOL CHLOEHYDBIN i). 
 
 CHLOEO-BniTL AIiOOHOIi. 
 
 BTTTYLENE GUANAMINE OjH.jNs. [173°]. 
 Formed by heating guanidine isovalerate at 225°. 
 Trimetrio needles, m. sol. cold water. Converted 
 by cone. H^SO, into butylene guanamide 
 OH„N,0,, whence HNO3 forms oyanuric acid 
 (Bandrowski, B. 9, 240).-B'H01.-B'AgNO,.- 
 BjHjSO^. 
 
 BUTYLENE HYDRATE v. Sco-Bctyii alcohoIi, 
 
 BUTYLENE NITBITE (?) O.B^^fi^. From 
 
 isobntylene and cone. HNO, (Haitinger, ilf . 2, 287). 
 
 Butylene nitrite (?). [96°]. Formed by boil- 
 ing petroleum of Tiflis with HNO, (Beilstein a. 
 Kurbatoff, B. 14, 1621). 
 
 IS0-BUTYLENE0XIDEC„H„Oi.«.O<;^?|^2'v>, 
 
 (52°). S.G. 2 -8311. From isobutylene with & no- 
 cessive treatment with HGIO and KOH (Eltekoff, 
 Bl. [2] 40, 23; J. B. 14, 368). Water, at ordinary 
 temperatures, unites with it, forming di-oxy- 
 butane. 
 
 s-Butylene oxide 0<^™g>. (57°). S.G. « 
 
 •8344. Formed similarly from 0H3.CH:CH.CH3 
 (E.). Water at 100° forms di - oxy - butane 
 CH,.CH(OH) .CH(OH) .CH3. 
 
 BUTYL ENNYL KETONE OhH^sO (?) or 
 CjH5.CO.CjH8(C5H„). Amyl valerone. (209°). 
 S.G. 12 -845. From CO on sodium amylate, 
 NaOCjH,,, at 160° (Geuther a. Frohlich, A. 202, 
 301). Liquid, does not combine with NaHSOj. 
 
 BUTYL ETHEB v. Butyl oxide. 
 
 BUTYL-FOEMIC ACID v. Vaiebio acid. 
 
 BUTYL-GLYCEBIC ACID v. Di-oxy-buttkio 
 Acro. 
 
 BUTYL-GLYCIDIC ACID v. Di-oxy-buiteio 
 
 ACID. 
 
 BUTYL GLYCOL v. Di-oxy-butane. 
 
 BUTYL-GLYOXALINE C,H3(CjHs)N2. Gly- 
 oxal-amyline. [121°]. (274°). Flat needles. 
 SI. sol. water. Prepared by the action of valeric 
 aldehyde-ammonia on glyoxal (Badziszewski, B. 
 16, 747; 17, 1291). Br forms C^H.^Br^N^ [158°] 
 and 0,H,Br3N3 [217°]. 
 
 Salts.— B'HCl [136°]. — BTIBr [100°].— 
 B'B.fifit [196°].— B'^H^PtCl,. 
 
 ISO-BUTYL DIGUANIDE C^H.^N, i.«. 
 C2HjN5(C4Hj). The sulphate of the copper 
 derivative Cu(0sHnN5)2H2S04 is formed by the 
 action of aqueous GuSOj and isobutylamina 
 on dicyandiamide at 100° (Smolka, M. 4, 815). 
 Alkaline syrup, absorbing COj from the air. 
 
 Salts. -B'jHjSO.liaq. S. 26-3 at 16°. 
 Colourless transparent leaflets. — ^B'H^SOj l^aq. 
 —B'HCl. [216°]. S. 40 at 16°. — B'2HC1. 
 [194°]. Deliquescent.— B'jHjPtCljaq : golden 
 four-sided tables.— B'^HjCrO^ aq.— B'^HAOj. 
 
 Metallic derivatives Cu(C|jH„Ns)j : 
 silky red needles, si. sol. water, sol. dilute acids. 
 -Cu(C,H„N5),2HN03. — Cu(CeH„N5),H,Cl, aq. 
 — CulCjHuNsJjHjSO, : carmine-red grains. S. 
 •26 at 18°.— Cu(C,H,A)2H2SO,aq: pale red 
 grains.— Cu(0sH,jN5)jH2S04 3aq : light rose-red 
 crystals. 
 
 jj- BUTYL -HEPTYL- OXIDE CiHj.O.CjH.s. 
 (205-7°). S.G. g -8023. S.V. 27t3. C.E. (0°-10°) 
 -00097 (Dobriner, A. 243, 8). 
 
 BUTYL-HYDEO-ANTHEANOL v. Bdtyl- 
 
 ANTHKANOL DIHYSaiDE. 
 
 ISO-BUTYL HYPOPHOSPHATE {C,Ii^)tFfis- 
 S.G. is 1-125. From isobutyl iodide and 
 AgiPjO, at 140° (Sanger, /. 232, 12). Oil. De- 
 composed by hot water. 
 
 Iso-butyl-hypophosphate of barium 
 (C,H5)BaHP305 5aq. Needles. 
 
 BUTYLIDENE-ACETO -ACETIC ETHEE v. 
 
 p. 24. 
 
 ISO-BUTYLIDENE-AMIDO-BENZOIC ACID 
 
 C„H,3N0j i.e. Pr.CH:N.CeH,C03H. [145°-150°]. 
 From amido-benzoio acid and iso-butyric alde- 
 hyde (Schiff, A. 210, 114). Slender needles, 
 decomposed by cold dilute alkalis. 
 
646 
 
 TRI-ISO-BUTYLIDENE DI-AMINE. 
 
 TEI-ISO-BTITYLIDENE DI-AMINE v. Hydro- 
 butyramide under Ibobutteic ai/Dehtde. 
 
 ISO-BTJTYLIDENE CHLORIDE v. Di-chloko- 
 
 ISOBnTANE. 
 
 ISO - BUTYLIDENE - ETHYLENE - ANILINE 
 
 V. Dl - PHENYL -ISOPKOPYL - METAPYBAZOL - lETBA- 
 HYDRIDE. 
 
 TC- BUTYL IODIDES CH3.CH2.CH,.CH2.I. 
 Mol. w. 184. (131° cor.). S.G. "£ 1-617 
 (Bruhl) ; § 1-6476. S.V. 128-2. C.E. (0°-10°) 
 •00098 (Dobriner, A. 243, 26). ju^s 1-510. Ea, 
 54-47. From n-butyl alcohol and HI (Linne- 
 mann, A. 161, 196). ICI3 at 250° acts on it 
 thus : CtB.,1 + IIICI3 = 2O2CI5 + 9HC1 + 12IC1 
 (Krafft, B. 10, 805). 
 
 Secondary w-butyl iodide CHj.CHj.CHI.CH,. 
 (118°). S.G. % 1-626 ; f 1-592 ; %° 1-679 
 (Lieben) ; » 1-632 ; 22 1-600 (Luynes). V.D. 
 6-6 at 20° (obs.). Formation.—l. By distilling 
 erythrite with HI (De Luynes, A. 125, 252; Bl. 
 2, 3). — 2. From ethyl-ohloro-ethylio ether 
 CH2Cl.CEtH.0.Et and HI at 140° (Lieben, 
 A. 150, 87). — 3. From w-butylene and HI 
 (Wurtz, A. 152, 23). 
 
 Isobutyl iodide (CH3)2CH.CHjI. (120°). 
 S.G. "," 1-606 (Briihl) ; if 1-6139, || 1-6007 (Perkin, 
 C. J. 45, 462). 11^ 1-506. E „, 54-41. S.V. 
 128-28 (Schiff, B. 19, 564). C.E. (0°-20°) -0110 
 (Brauner, A. 192, 69). M.M. 12-199 at 19-4°. 
 From isobutyl alcohol and HI. Distils con- 
 stantly with 21 pts. water at 96° (Pierre a. Puchot, 
 C.B. 74, 224). Treated with AgNCS gives a pro- 
 duct, (CH3)2CH.CH2NCS, which on saponifica- 
 tion yields isobutylamine and, in greater quan- 
 tity, tertiary butylamiue (B.). Heated with lead 
 oxide it yields pseudo-butylene besides iso-butyl- 
 eue (Eltekoff, Bl. [2] 34, 347). 
 
 Tertiary butyl iodide Me3CI. (100°). S.G. s 
 1-571. Formation. — From tertiary butyl alcohol 
 and HL 
 
 Preparation. — By passing isobutylene (c[.v.) 
 into fuming HI, cooled with ice and weU shaken 
 (Markownikoff, Z. [2] 6, 29). 
 
 Beactions. — 1. If the iodide (20 g.) be shaken 
 with water (30 g.) for two days it dissolves, being 
 converted into the alcohol : Me3CI + H20 = 
 Me3C.0H + HI (Dobbin, C. J. 37, 237).— 2. With 
 dry ZnO it forms tri-isobutylene. — 3. With 
 sodium it forms isobutylene, tri-isobutylene, and 
 hydrogen, with small quantities of a hydrocarbon 
 not absorbable by H2SO4 (Dobbin).— 4. Moist 
 AgjO, Zn and water, and AgOAc, form iso- 
 butylene (Butlerow, Z. [2] 6, 237).— 5. With 
 MeOH at 100°-110° it gives Mel and trimethyl 
 carbinol (Bauer, A. 220, 163).— 6. With MeOAo 
 at 110° it form a isobutylene, HO Ac and Mel. 
 
 DI-BDTYL-KETINE v. Di-methyl-di-butyl- 
 
 PYEAZINE. 
 
 DI-ISOBDTYL KETONE CsHuO i.e. 
 C4Hg.C0.C^Hp. Valerone. Mol. w. 142. (182°). 
 S.G. ^ -833. Formed, in small quantity, by 
 distilling calcium valerate (6 pts.) with CaO 
 (1 pt.) (Lowig, P. 42, 412 ; Ebersbach, A. 106, 
 268 ; Schmidt, B. 5, 600). Does not combine 
 with NaHSOa. 
 
 DI-IS0B1TTYL-EET0NE-S1TLFH0NIC ACID 
 C4H8(HS03)— CO— 0,H3(HS03). The sodium 
 salt is formed by leaving phorone in contact with 
 a saturated solution of NaHSOj for 2 or 3 weeks. 
 It forms colourless prisms (A''Na22^aq) : soluble 
 in water and alcohol (Pinner, B. 15, 593). 
 
 BTTTYLLACTIC ACID v. Oxy-bdtyeio aoid. 
 BUTYL-LUTIDINE v. Di-methyl-boiyl-pyri 
 
 DINE. 
 
 TC-BUTYL-MALONIC ACID C^Hi^O, i.e. 
 CjHi,.CH(C02H)2. [101°]. Prepared by saponi- 
 fication of the nitrile C4Hj.CH(CN).C02Et 
 obtained by the action of KCN on chloro- 
 hexoic-ether. Thick prismatic crystals. V. sol. 
 water, alcohol, and ether. It gives a reddish- 
 violet colouration on warming with H^SO.,. At 
 about 150° CO2 is evolved and it is converted 
 into caproio aoid. 
 
 Salts.— A"Ba: whiteplates. S.2-98at24°. 
 — A"Pb : very sparingly soluble white glistening 
 plates. S. -Oil at 20°.— A"Cuaq: blue glisten- 
 ing plates. S. -086 at 22°.— A"Agj : white pp. 
 S. -119 at 23° (Hell a. Lumpp, B. 17, 2217). 
 
 Isobutyl-malonic acid ?rCH2.CH(C02H)2. 
 [107°]. From its ether (Hjelt, J. 1882, 875). 
 
 Ethyl ether Et^A". (225°). S.G. 15-983. 
 From sodium malonic ether and isobutyl iodide. 
 
 n-BUTYL MEBCAPTAN C^HsSH. Mol. w. 
 90. (98°). S.G. g -858 ; « -843 (Saytzeff a. 
 Grabowsky, A. 171, 251; 175, 851). HNO, 
 gives butane sulphonic acid. 
 
 Isobutyl meroaptan (88°). S.G. 12 -848 
 (Humann, A. 95, 256) ; f -8357 (Nasini, Q. 13, 
 301). V.D. 3-10 (obs.). Eoo 27-47 (N.). Formed 
 by distilling K(0,H5)S04 with aqueous KHS.— 
 KSC^Hj. — Hg(C4H9S)2 : pearly scales.— 
 Pb(C4H5S)2 : yellow crystalline pp. 
 
 Secondary batyl mercaptan (85°). S.G. 
 IZ -830. From sec-butyl iodide and KHS.— 
 CjH^SAq.— (C4HjS)2Hg [189°] (Eeymann, B. 7, 
 1287). 
 
 TETRA - ISOBUTYL - METHYLENE - DI- 
 AMINE C^HjjNj i.e. N(C4H3)2.CH2N{0,Hs)2. 
 (245°-255°). From ' trioxymethylene ' (formio 
 paraldehyde) and di-isobutylamine (Ehrenberg, 
 /. pr. [2] 36, 117).— B"H,PtClB [198°]. Forma 
 with CS2 a compound C^HjsNjCS^ [54°]. 
 
 BUTYL - MUSTARD OIL v. Butyl thio- 
 
 OAEBIMIDE. 
 
 ISO-BUTYL-NAPHTHALENE C„H,3 i.e. 
 CioBi,{GJS.,). (280°). Prepared together with 
 (o-a) and (a-;8)-dinaphthyl by heating naphthal- 
 ene and isobutyl chloride in presence of alumi- 
 nium chloride. Colourless oil, very slightly 
 volatile in steam. Picric aoid compound; 
 [96°] aggregates of golden needles (Wegscheider, 
 M. 5, 236). 
 
 ISO-BUTYL NITRATE CANO,. (123°). 
 S.G. 2 1-038. From AgNOs, urea, and isobutyl 
 iodide (Wurtz, A. 93, 120 ; Chapman a. Smith, 
 Z. 1869, 433). 
 
 ISO-BUTYL NITRITE (CH3)20H.CH2O.NO. 
 (67°). S.G. 2-894. H.F.p. 47,800. H.P.V. 
 44,900 (Th.) (Chapman a. Smith, Z. 1869, 433 ; 
 Pribram a. Handl, M. 2, 658 ; Bertoni a. TrufiS, 
 G. 14, 23). 
 
 Tertiary butyl nitrite (CH3)3C.ONO. (63°) 
 (B.) ; (76°-78°) (T.). S.G. « -8914 (B.). Formed 
 together with a little of the isomeric nitrobutana 
 (110°-130°) by distilling tertiary butyl iodide 
 with silver nitrite (Tscherniak, A. 180, 155 ; S. 
 7, 962). Prepared by distilling tertiary butyl 
 alcohol (1 mol.) with glyceryl tri-nitrite (1 mol.) 
 (Bertoni, (?. 15, 357). 
 
 BUTYL-PSEUDO-NITEOLE v. Niteoso-otibo- 
 
 BOIANE. 
 
DI-p-ISO-BUT YL-DI-PHENYL-UREA . 
 
 647 
 
 BUTYL-NITEOLIC ACID v. Nitkoso-nitko- 
 
 BDTANE. 
 
 TO-BUTYL-OCTYt-OXIDE C,H,.O.C.H,,. 
 (225-7°). S.G. § -8069. S.V. 295-7. C.E. (0°-10°) 
 •00097 (Dobriner, A. 243, 9). 
 
 ISO-BTJXYI OXALATE v. Oxalic acid. 
 
 ISO-BTJTYL-OXAMIC ACID 
 PrCH2.NH.C0.C0,H. From oxalic ether (1 
 mol.) and dry isobatylamine (1 mol.) at 160° 
 (Malbot, O. B. 104, 229).— CaA'j. 
 
 Di-isobutyl-ozamic acid 
 (PrCHJ,N.C0.C02H. Similarly prepared from 
 di-iso-butylamine (M.). 
 
 DI-IS0-BrTYl-0XAMIDE(?rCH2NH)2CA- 
 
 [167°]. Prom oxalic ether (1 mol.) and iso- 
 butylamine (2 mols.). Acute plates, insol. boiling 
 water ; may be sublimed (Malbot, 0. B. 104, 228). 
 
 DI-BUTYL OXIDE {OJS.,)fi. Mol. w. 130. 
 (141°). S.&. 2 -784 (Lieben a. Eossi, A. 165, 
 110) ; g -7865. S.V. 197-3. C.E. (0°-10°) -00109 
 (Dobriner, A. 243, 8). 
 
 Di-isobutyl oxide (100°-104°). From iso- 
 butyl iodide and KOO^H,, or AgjO (Wurtz, A. 
 93, 117). 
 
 Di-sec-butyl oxide (121°). S.G. ^ -756. 
 From aldehyde hydrochloride and ZnEtj (Kessel, 
 4.175,56; 5.7,291). 
 
 ^-ISO - BUTYL - PHENOL C^.C^H^OH. 
 [99°]. (231°) (S.) ; (237°) (L.). 1. From amido- 
 iso-butyl-benzene by the diazo- reaction (Studer, 
 A. 211, 242; B. 14, 1474, 2187).— 2. From 
 phenol (100 g.), isobutyl alcohol (80 g.) and 
 ZnClj (240 g.) (Liebmann, B. 14, 1842 ; 15, 150, 
 1991 ; Dobrzycki, J. pr. [2] 36, 390). Needles 
 (from alcohol). Volatile with steam. V. sol. 
 alkalis. Gives a pp. with bromine-water, but 
 no colour with Fe^Cls. Is antiseptic. PCI5 
 gives ehloro-iso-butyl-benzene, which on oxida- 
 tion gives ^-chloro-benzoic acid. Gives a di- 
 nitro- derivative [93°]. Fused with P2O5 it gives 
 phenol and isobutylene. Ammonia and ZnClj 
 give C,H,.C„H,NHj (Lloyd, B. 20, 1254). 
 
 Methyl ether C^Ha.C„H^OMe. (215-5°). 
 S.G. ^ -937. 
 
 Ethyl ether O^H,.C,H,OEt. (235°) (S.); 
 (242°) (L.). 
 
 Benzoyl derivative CjHj.CjHjOBz. 
 [83°] (S.); [80°] (Kreysler, B. 18, 1717); 
 (335°) ; (344°) (K.). White plates (from alcohol). 
 
 Acetyl derivative OjHs.OsHjOAc. (245°). 
 g (} El -999 
 
 ' isO-BUTYL-PHENOL SULPHONIC ACID 
 C.H„.C.Hs(0H).S03H. From isobutyl phenol 
 and H-SO, (Liebmann, B. 15, 1990).— BaA'^ 2aq. 
 
 ISO-BTJTYL-PHENYL -AMINE v. Amido- 
 
 PHENYIi-BtJTANE. 
 
 Di-isobutyl-di-phenyl-amine 
 (aH,.C4Hs)2NH. (290°-315°). Thick oil. 
 Formed together vrith C,H,(C4H„).NH2 by heating 
 oxy-phenyl-isobutane C^-B.,(Cfi,).OB. [1:4] with 
 ammoniac»l ZnBr^ (or ZnCl^) and NH,Br (or 
 NH^Ol) at 320°-330°; the yi aid is 20-25 p.c— 
 B'uHjOljPtCl, : yellow needles. 
 
 Acetyl derivative (OjHj.CiHgjjNAo : 
 [75°] • glistening white plates ; si. sol. water, 
 V sol.' alcohol and benzene (Lloyd, B. 20, 1255). 
 
 DI-ISO-BUTYL-DI-PHENYL CYANAMIDE 
 C„H,,N,i.e. 0(NC,H^.OH,Pr),. Carbo-di-phen- 
 isohutyl-imide. [189°]. Formed by boilmg a 
 solution of di-isobutyl-di-phenyl-thio-urea m 
 benzene with PbO (Pahl, B. 17, 1242). Colour- 
 
 less crystals. Sol. hot benzene, si. sol. ether. 
 By warm dilute alcohol it is converted into di- 
 isobutyl-di-phenyl-urea. With amines it com- 
 bines to form guanidines. Heated with CS^ at 
 170° it yields isobutyl-phenyl-thio-carbimide. 
 
 ISO-BTJTYL-PHEN YLENE-DIAMINE 
 CsH4(NH2)(NHCH2?r). [39°]. Formed by the 
 reduction of ^-nitroso-iso-butylaniline (Wacker, 
 
 A. 243, 299). Plates (from ether) ; can be dis- 
 tilled. Its chloride forms white plates; v. soL 
 water, si. sol. alcohol, insol. ether. 
 
 DI-p-ISO-BUTYL-DI-PHENYL-GUANIDINE 
 HN:C(NH.C|jHj.C4H5)2. Di-phenisobutyl-gicanid- 
 ine. [173°]. Formed by heating an alcoholic 
 solution of di-2)-isobutyl-di-phenyl-thiourea with 
 NH3 and lead oxide (Pahl, B. 17, 1240). Corour- 
 less plates. V. sol. alcohol and benzene. — 
 B'jHjCljPtCl, : yellow crystalline pp. 
 
 Tri-p-iso-butyl-tri-phenyl-guanidine 
 C4H,.C.H,.N:C(NH.CeH,.0,H„),. Tri-pheniso- 
 huhjl-guanidine. [164°]. Obtained by digesting 
 an alcoholic solution of di-^J-isobutyl-di-phenyl- 
 thiourea with ^-isobutylphenyl-amine and lead 
 oxide (P.). SmaU white needles. V. sol. benzene 
 and hot alcohol.— B'jH^CljPtCl,: yellow needles. 
 
 ISO.BTrTYL-PHENYL-(S)-NAPHTHYL-THIO- 
 UKEA C,„H,.NH.CS.NH.C,H,.C4H,. Pheniso- 
 butyl-{$)-napMhyl-thiuurea. [152°]. Prepared 
 by warming an alcoholic solution of (/8)-naphthyl- 
 thio-carbimide and isobutylphenyl-amine (Main- 
 zer, B. 16, 2026). White plates. Sol. boiUng 
 alcohol. By phosphoric acid it is split up into 
 isobutylphenyl - thio - carbimide, (|8) - naphthyl - 
 thio-carbimide, isobutylphenyl-amine, and (j8). 
 naphthylamine. 
 
 ISO-BUTYLPHENYI - PHENYL - THIOTTEEA 
 
 v. PhENYL-ISOBUTYIiPHENYL-THIOUEEA. 
 
 Tfil-ISO-BUTYLPHENYL-PHOSPHATE 
 
 P0(0CsHj.CjHs)3. (above 400°). Obtained by 
 heating isobutyl-phenol with POCI3 ; the yield is 
 90 p.c. of the theoretical (Kreysler, B. 18, 1700). 
 Thick liquid. V. sol. ether, benzene, and warm 
 alcohol, si. sol. petroleum-ether. 
 
 TETEA.-ISO-BUTYLPHENYL SILICATE 
 Si(OC„Hj.CjHj)j. (c. 380°). Obtained by heating 
 isobutyl-phenol with SiCl, ; the yield is 70 p.o. 
 of the theoretical (Hertkorn, B. 18, 1692). Thick 
 colourless oil. V. sol. benzene, chloroform, 
 CSj, etc. 
 
 ^-ISO-BUTYL-PHENYL-THIOCABBIMIDE 
 SC:N.CjHj(C4H8). Phenisobutyl - musta/rd ■ oil. 
 [42°]. (277°). Formed by heating di-^-isobutyl- 
 di-phenyl-thiourea with phosphoric acid (Pahl, 
 
 B. 17, 1235). Long white needles. V. sol. alcohol 
 and ether. 
 
 DI-jp-ISO-BTTTYL-DI-PHENYL-THIOUREA 
 SC(NH.CsHj.C4Hg)2. Di-phenisohutyl-thiourea. 
 [193°]. Formed by cohobating an alcoholic solu- 
 tion of ^-isobutylphenyl-amine with CSj (Pahl, 
 B. 17, 1235). Fine white needles. Sol. ether 
 and benzene, si. sol. alcohol, insol. water. 
 
 DI-jp-ISO-BTTTYL-DI-PHENYL-UKEA 
 0C(NH.C,Hi.C4Hb)j. Di - phenisobutyl - urea. 
 [284°]. 
 
 Formation.— 1. By the action of carbonyl 
 chloride on p-isobutylphenyl-amine dissolved in 
 benzene. — 2. By cohobating an alcoholic solution 
 of the thiourea with mercuric oxide (Pahl, B. 
 17,1240). Colourless needles. Sol. hot alcohol, 
 insol. water. 
 
B18 
 
 BUTYL-PHOSPHINE. 
 
 ISO. BUTYL -PHOSPHINE C^H^PH^. (62°). 
 Prepared, together -with the following, from iso- 
 butyl iodide, ZnO, and PH J at 100° (Hofmann, 
 B. 6, 296). Eesembles ethyl-phosphine in pre- 
 paration and properties. 
 
 DUsobutyl phosphine (CjH„)2PH. (153°). 
 
 Tri-isobutyl phosphine (CjHsJjP. (215°). 
 From the preceding and isobutyl iodide. 
 
 Tetra-isobutyl-phosphonium iodide 
 (C4H„)jPI. Crystalline. 
 
 ISO-BUTYL-PHOSPHINIC ACID C,H„P0,H2 
 [100°]. Paraffin-like soUd (Hofmann, B. 6, 304). 
 — ^A'Ag. Amorphous pp. 
 
 Si - isobutyl - phosphinic acid (CjHg)2F02H. 
 Oil A'Ag. Amorphous. 
 
 ISOBUTYL PHOSPHITE. Bichloride. 
 C^H„0.PCl2. (155°). S.G. a i-igi. a by- 
 product in the conversion of isobutyl alcohol 
 into isobutyl chloride by PCI, (Menschutkin, A. 
 139, 347). 
 
 DI-ISO-BUTYL-PINACONE C.iHsA »-e- 
 Pr.CH,.CHj.CMe(OH).CMe(OH).CHj.CH:j.Pr. i>i- 
 oxy-tetra-decame. Tetra-decylene glycol. [30°]. 
 (268°). A product of the action of Na upon 
 methyl iso-amyl ketone (Eohn, A. 190, 305: 
 Purdie, C. J. 39, 468). Needles, insol. water. 
 
 BUTYL-METAPYSAZOLONE v. Di-oxY- 
 
 BCITIi-UEIAPYBAZOL. 
 
 {Py. 3)-IS0-BnTYL - ftiriNOLINE Ci^H.^N 
 .OH:CH 
 i.e.Cs'B.X I (271°). Colourless oily 
 
 \n = C{C.H,) 
 liqmd. Formed by distilling its (Py. l)-car- 
 boxylic acid with lime (Doebner, B. 20, 280 ; A. 
 242, 282). 
 
 Picric acid compound B'.CgHjKjO,. 
 
 [161°]. Lemon-yellow plates (from alcohol). — 
 
 (B'HC^jPtCl,. Orange-red needles (from water). 
 
 (Py. 3)-IS0-BTrTYL-airiN0LINE— (Pu. 1)— 
 
 CAKBOXYIIC AGIO 
 
 .C(CO.^):CH 
 C.^isNOj i.e. CsH,<^ | . Isobutyl- 
 
 ^N- 
 
 zC(C,H,) 
 
 einchonic acid. [186°]. Formed by the action of 
 isoTalerio aldehyde upon pyruvic acid and 
 aniline. White satiny plates (containing l^aq) 
 (Doebner, B. 20, 279 ; A. 242, 280).— B'HClaq : 
 plates.— B'jHjPtCls.- AgA'. 
 
 ISO-BUTYL SILICATE (PrCH2),Si04. (c. 258°). 
 S.G. 1^ -953. From SiCl, and isobutyl alcohol 
 (Pahours, 0. B. 77, 1408). Slowly decomposed 
 by water. 
 
 BUTYL SULPHATES 
 
 rt-Butyl-aalphnric acid Pr.CHj.SO^H. 
 
 Salt. — BaA'jaq: crystalline plates. S.G. ^ 
 1-778 (Lieben a. Bossi, A. 165, 116 ; Clarke, B. 
 11, 1506). 
 
 Isobutyl sulphuric acid Pr.CH2.SO4H. From 
 the alcohol and H^SO, (Wurtz, C. B. 35, 310).— 
 KA' : laminss (from alcohol). 
 
 Chloride C^Hg.O.SOjCl. From isobutyl 
 alcohol and SOjCLj (Behrend, J. pr. [2] 15, 34). 
 Liquid. 
 
 Ji-BUTYL SULPHIDE (C4H„)jS. Mol. w. 
 146. (182°). S.G. 8 -852 ; « -889 (Saytzeff, A. 
 171, 253). From butyl iodide and E^S. 
 
 Isobutyl sulphide (Pr.CHJ^S. (171° i. V.). 
 B.G. ifi -836. Formed by distilling isobutyl sul- 
 phate with cono. aqueous KHS (Beokmann, 
 ■J.jM-. [2]17,446). 
 
 Secondary butyl sulphide (CMeElH) S 
 (165°). S.G. sa -832. Combines with Mel (Bey. 
 mann, B. 7, 1288). 
 
 Isobutyl disulphide (CH2Pr),S2. (220°) 
 (Spring a. Legros, B. 15, 1938). 
 
 ISO-BUTYL SULPHOCYANIDE CH^Pr.S.CN. 
 (175°) (Beimer, B. 3, 757). 
 
 TC-BUTYL SULPHONE (C^HJ^SO^. [44°]. 
 From fuming HNO3 and (CjH3)2S (Grabowsky, 
 A. 175, 348). 
 
 Di-isobutyl sulphoue (C^HJ^SOj. [17°]. 
 (265° i. v.). S.G. 12 1-006. Di-isobutyl sulph- 
 oxide (100 pts.) is dissolved in water (1000 pts.) 
 and oxidised by EMnOj (63 pts.) dissolved in 
 water (1900 pts.). Excess of permanganate de- 
 stroyed by sodio formiate and the sulphone 
 extracted by ether. The yield is quantitative 
 (Beckmann, J.pr. [2] 17, 448). 
 
 Properties. — White plates. Not affected by 
 reducing agents 
 
 ji-BUTYL SULPHOXIDE (C4H,)2SO. [32°]. 
 From HNO, (S.G. 1-3) and (C.HJ^S (Grabow- 
 sky, A. 175, 348). 
 
 Di-isobutyl sulphoxide (C^HJ^SO. [69°]. 
 From di-isobutyl sulphide (1 pt.) and (2 pts. of) 
 HNO3 (S.G. 1-4) in the cold. Extracted with 
 ether after neutralisation. The yield is quanti- 
 tative (Beckmann, /.jpr. [2] 17, 446). 
 
 Properties. — Yellow needles. Soluble in 2 
 parts of cold water, but separates as an oil oit 
 warming. Beadily reduced to di-iso-butyl sul- 
 phide. 
 
 BUTYL SULPHUEIC ACID v. Buiyi, snii- 
 
 PHATE. 
 
 DI-ISO-BUTYL-THETINE 
 C02H.CH2.S(C4H<,)2(OH). The hydrobromide 
 is a syrup formed by the action of isobutyl sul- 
 phide on bromo-acetic acid at 100°. Lead con- 
 verts it into crystalline CjoH^jSOjSPbBrj and 
 C,„H2„SOj3PbBrj (Letts, Pr. E. 28, 588). 
 
 n-BUTYL THIO-CAEBIMIDE CH^Pr.N.CS. 
 Mol. w. 115. (167°). Formed by boiling w- 
 butylamine with CSj and alcohol. Evaporating 
 the alcohol and heating theresidue with aqueous 
 HgClj (Hofmann, B. 7, 508). NH3 gives butyl- 
 thio-urea [79°]. 
 
 Isobutyl thio-carbimide CH^fr.N.CS. (162°). 
 S.G. a -937. SimUarly prepared. (H.). NHj 
 gives isobutyl-thio-urea [94°]. 
 
 Secondary isobutyl thio-carbimide 
 CHMeEt.N.CS. (160°). S.G. 12.944. Similarly 
 prepared. It is the essential constituent of the oil 
 of scurvy-grass or spoon-wort (from Cochlearia 
 officinalis) (Hofmann, Z. [2] 5, 400 ; B. 2, 102). 
 NH3 gives butyl-thio-urea [135°]. 
 
 Tertiary butyl thio-carbimide CMe.,.N.CS. 
 [11°]. (140°). S.G.S4 -900 (Eudneff,J-.'iJ. 11, 
 179 ; B. 12, 1023). 
 
 BUTYL THIO-CAEBONIC ACID v. Thio- 
 
 CABBONIO ACID. 
 
 M-BUTYL-THIOPHENE C,SH,(C4H5) (181°). 
 S.G. 12 -957. Colourless oU. Formed by the 
 action of sodium on a mixture of iodothiophene 
 and butyl bromide (Meyer a. Ereis, B. 17, 1561). 
 
 BUTYL-THIO-UEEAS. The preparation and 
 properties of these bodies are analogous to those 
 of the corresponding ethyl thio-ureas (j. v.). 
 
 TO -Butyl thio - urea OH2Pr.NH.OS.NHj. 
 [79°]. From butyl thio-carbimide and NH, 
 (Hofmann, B. 7, 512). 
 
 Isobutyl thio-urea [94°] (H.). 
 
BUTYRIC ACID. 
 
 C4» 
 
 Sec-butyl thio-urea [133°] (H.). 
 
 Tert - butyl thio - urea CMej.NH.CS.NHj. 
 1165°] (Eudnefl, Bl. [2] 33, 300). Prisms, sol. 
 alcohol. 
 
 Di-<«r<. butyl thio-urea SC{NHCMes)a. 
 [162°]. Prom tert-butyl-amine, CSj, and alco- 
 hol. Formed also by the action of tert-butyl 
 thiooarbimide on tert-butyl-amine (EudnefE Bl. 
 [2] 33, 300). 
 
 TO-ISO-BTrTYL-TOLTJENE C,H,(CH,)(C4H,) 
 [1:3]. (187=) (K. a.B.) ; (194°) (R.) ; (185°) (E.). 
 Methyl • isobutyl - benzene. Colourless liquid. 
 Occurs in oil of resin (Kelbe a. Baur, B. 16, 
 619, 2559; Eenard, A. Oh. [6] 1, 250). Pre- 
 pared by the action of isobutyl bromide on 
 toluene in presence of Al^Br^ (K. a. B.). Formed 
 by diazotising methyl -isobutyl -phenyl -amine 
 and treating the diazo- salt with an excess of 
 SnClj (Effront, B. 11. 2329). On oxidation with 
 HNOj it first gives ?w-iso-butyl-benzoio acid and 
 finally isophthalio acid (Kelbe a. Pfeiffer, B. 
 19, 1723). 
 
 p-{Iso ?) - Butyl - toluene CsH,(0H3) (C^H,) 
 [1:4]. (178°). Occurs in oil of resin. HNO, 
 oxidises it to p-toluic acid (Kelbe a. Baur, B. 
 16, 2562). 
 
 ^-Isobntyl-toluene (c. 195°) 7 Formed by 
 heating toluene with isobutyl alcohol and 
 ZnCOj (Gcldschmidt, B. 15, 1067). Formed, 
 together with the m-isomeride, by the action 
 of isobutyl bromide on toluene in presence of 
 AljBr, (Kelbe a. Pfeiffer, B. 19, 1725). HNO, 
 oxidises it to jj-isobutyl-benzoio acid. 
 
 m-lSO-BUTYL-TOLTI£NE-SUL PHONIC ACID 
 CsH3(CH3)(CA)(SO,H) [1:3:!C]. [76°]. Small 
 hygroscopic plates. Formed by sulphonation of 
 wi-iso-butyl-toluene. 
 
 Salts. — KA'aq: large soluble pearly plates. 
 — NaA'aq: needles. — CuA'j4aq: large blue 
 soluble plates. — BaA'^aq: small plates, si. sol. 
 cold water and alcohol.— PbA'j 3aq : pearly plates. 
 
 Amide : [75°], small plates, soluble in water 
 (Kelbe a. Baur, B. 16, S560). 
 
 p-(Iso ?)-Bntyl-toluene-salphonic acid 
 C8H,(CH3)(0,H,)(S03H) [l:4:x]. Obtained by 
 sulphonation of p-isobutyl-toluene. 
 
 Salts. ~ KA'l|aq: small easily soluble 
 plates.— NaA'2aq. — BaA'jaq: small sparingly 
 soluble plates.— CuA'jCtaq : easily soluble blue 
 crystals. — PbA'2 3aq : small plates, sol. hot 
 
 Amide : [113°], large pearly plates, si. sol. 
 hot water (Kelbe a. Baur, B. 16, 2563). 
 
 ISO-BTTTYL-o-TOUJIC ACID 
 O.H3(CH3)(C.H,)CO,H [1:3:6]. [140°]. Formed 
 by saponification of its nitrile (Effront, B. 17, 
 2334). White needles. V. sol. alcohol and 
 ether, si. sol. hot water, insol. cold water.— 
 A'As : colourless plates, v. sol. hot water. 
 
 Nitrile C,H3(CH,)(CA)CN [1:3:6]. [60°]. 
 (248°). Formation.— 1. By distilhng the formyl 
 derivative of methyl-isobutyl-phenyl-amme with 
 zinc-dust.— 2. By heating isobutyl-tolyl-thio- 
 oarbimide with copper powder (B.). Long 
 white needles. V. sol. alcohol and ether, si. 
 sol. hot petroleum-ether, insol. water. 
 
 Iso-btttyl-toluic acid 0„H(CH3)(0,H,)C0,H 
 rl-5-61 ri32°l . Formed by saponification of its 
 nitrile (Effront, B. 17, 2343). White silvery 
 plates. V. sol. alcohol and ether, si. sol. hot 
 water.— A'Ag : colourless plates, sol. hot water. 
 
 Niirile O.H,/CH3)(0,,H„)CN [1:5:6]. (243°). 
 
 Formation.-—!. By distilling the formyl 
 derivative of methyl-isobutyl-phenyl-amine with 
 zino-dust. — 2. By heating isobutyl-tolyl-thio- 
 carbimide with copper-powder (Effront, B. 17, 
 2343). Colourless oil, solidifies on freezing to 
 a white crystalline mass. V. sol. alcohol and 
 ether. 
 
 ISOBUTYL-TOLTJIDINE v. MEiHTL-isoBnTm- 
 
 PHENYL-AMINE. 
 
 BUTYL-TOLYL-AMINE v. Metbvl-butyl- 
 
 PHENYL-AMINE. 
 
 ISO-BUTyL-TOLYI,-THIOCARBIMIDE 
 
 C„H3(CHJ(C^HJ.NCS [1:3:6]. [46°]. (275°-280°). 
 Formed by the action of phosphoric acid on di- 
 isobutyl-di-tolyl-thiourea (Effront, B. 17, 2336). 
 Long white needles. V. sol. alcohol and ether. 
 
 Iso-butyl-tolyl-thio-carbimide 
 CeH3(CH3)(C,H,)NCS [1:5:6]. [44°]. (267°). 
 Formed by heating di-isobutyl-di-tolyl-thiourea 
 with phosphouic acid (Effront, B. 17, 2345). 
 White crystalline soUd. V. sol. alcohol and 
 
 Di-ISOBUTYL-DI-TOIYX-THIOUEEA 
 
 S0(NH.C„H,(CH3)(C,HJ[6:1:3])2 [184°]. 
 Formed by digesting methyl-isobutyl-phenyl- 
 amine with CSj in aloohoUo solution (Effront, 
 B. 17, 2335). Long thin silky needles. V. sol. 
 ether, si. sol. alcohol. 
 
 Di-isobutyl-di-tolyl-thiourea 
 
 SC(NH.C.H3(CH3)(C,HJ[6:1:5]),. [175°]. 
 
 White needles. Sol. hot alcohol. Formed by 
 
 digesting methyl-isobutyl-phenyl-amine with an 
 
 alcoholic solution of CSj (Effront, B. 17, 2344). 
 
 ISO-BTJTYL-TTREA. Valeryl derivative 
 NH(C^Ns).C0.NH(C0.C4H,). [102°]. Flat needles. 
 Sol. alcohol and ether, si. sol. water. Formed 
 by the action of KOH on a mixture of (2 mols. of) 
 valeramide (isopropyl-aoetamide) and (1 mol. of) 
 bromine (Hofmann, B. 15, 758). 
 
 iBo-feri-di-butyl-urea 
 CMe3.NH.C0.NH.CH2Pr. [163°]. From tert- 
 butyl cyauate and isobutylamine (Brauner, B. 
 12, 1875). 
 
 Di-ier«-butyl-urea (Gile;SB)SiO. [242°]. 
 From ieri-butyl cyanate and tert-butylamine (B.). 
 
 ISO-BUTYI-XANTHAMIDE v. THro-OARUONio 
 
 EIHEBS. 
 
 BTJTYBAL v. Buiybio aidehyde. 
 
 BTJTYEAMIDE v. Amide of Bdtykio acid. 
 
 Di-isobutyramide (C3H,.CO)2NH. [174°]. 
 Formed by the action of ammonia on isobutyryl 
 chloride (Hofmann, B. 15, 981). Long needles. 
 Sublimable. Sol. alcohol. On distillation it 
 splits up into isobutyric acid and isobutyro- 
 nitrile. 
 
 w-BUTYBIC ACID C^HjO^ i.e. 
 CH3.CH,.CHj.C0.H. Mol. w. 88. [o.-3°]. 
 (162° cor.). S.G. ^J "9594 (Briihl) ; g -976 (Zander) ; 
 IS -9670 ;M -9588 (Perkin,C./.45). C.E. (0°-10°) 
 •00104 (Z.). M.M. 4-472 at 18-8° (P.). Me 1-4025. 
 E rr, 35-50. S.V. 107-85 (B. Sohiff, A. 220, 105) ; 
 108-3 (Z.). S.H. -440 at 0° (Schiff, A. 234, 300). 
 
 Occurrence. — 1. Butter contains 2 p.c. of 
 glyceryl butyrate (Chevreul, A. Ch. [2] 23, 23). 
 Eancid butter contains free ji-butyrio acid (Grun- 
 zweig, A. 162, 193).— 2. In crude wood vinegar.— 
 
 3. In perspiration (Sohotten, J. 1852, 704).— 
 
 4. In muscular juice (Soberer, A. 69, 196)--- 
 
 5. In the contents of the large intestine.— 6. As 
 hexyl butyrate in oil got from fruit of Heracleum 
 
650 
 
 BUTYRIO ACID. 
 
 •tRum. — 7. The fruit of Pastinaca sativa 
 contains ootyl butyrate. — 8. In cheese (e.g. of 
 Limbnrg) (Iljenko, A. 63, 268). 
 
 A great many vegetable and animal juices 
 and oils contain butyric acid, but in most cases 
 it has not been determined whether the acid is 
 n- or iso- butyric acid (Gorup-Besanez, A. 69, 369 ; 
 Klinger, A. 106, 18 ; Kramer, Ar. Ph. [2] 54, 9 ; 
 Wagner, J. pr. 46, 155 ; Soberer, A. 69, 196 ; 
 Bebling, Ar. Ph. [2] 92, 83 ; 93, 800). 
 
 Formation. — 1. A product of the fermentation 
 of sugar, starch, milk, fibrin, and most kinds of 
 vegetable and animal matter (Pelouze a. G61is, 
 A. Oh. [3] 10, 436; Leroh, A. 49, 216 ; Bonaparte, 
 O. -R. 21, 1070 ; Erdmann a. Marohand, J. pr. 29, 
 468; Wurtz, A. 52, 291; Soharling, A. 49, 313; 
 Schubert, J. pr. 33, 256 ; Sullivan, J. 1858, 280 ; 
 Eitthausen, Z. [2J 4, 314). — 2. By fermentation of 
 calcium lactate : 2C3HSO3 = CiHgOj + 200^ + 2H2. 
 3. Along with w-butyl alcohol by the fermentation 
 of glycerin through a Sohizomyoetes in presence 
 of CaOOa (Fitz, B. 9, 1348).— 4. By the action of 
 CrOj on albuminoids (Guckelberger, A. 64, 68). — 
 5. By the action of HNO3 on fats (Eedtenbacher, 
 A. 59, 49) and on Chinese wax (Buokton, C. 3. 
 
 10, 166).— 6. By oxidation of ooniine (Blyth, A. 
 70, 89). — 7. By the aceto-acetic ether synthesis 
 (Franklanda. Duppa, A. 138, 218) n. Aceto-aoetio 
 ETHEB. — 8. By passing CO over a mixture of NaOEt 
 and NaOAoat 200° : CjHjNaO + C^HaNaO^ + CO = 
 CHNaO^ + CjHjNaOj (Frohlich, A. 202, 306). 
 
 Preparaiioji. ^ Sugar (6 kilos.), water (26 
 litres), and tartaric acid (30 g.) are left for some 
 days, after which there is added putrid cheese 
 
 i250 g.), sour skimmed milk (8 kilos.), and chalk 
 3 kilos.). The mixture is kept at 30° to 35° with 
 occasional stirring. Calcium lactate is first 
 formed, and this is afterwards decomposed with 
 evolution of hydrogen (i>. 'Formation 2) ; at the 
 end of six weeks the evolution of gas ceases and 
 the whole is now converted into calcic butyrate 
 (Bensch, A. 61, 177, c/. Grillone, A. 165, 127; 
 Lieben a. Bossi, A. 158, 146 ; and Fitz, B. 
 
 11, 52). Crude butyric acid may be purified by 
 etherifioation, followed by saponification of the 
 butyric ether (121°) (Bauuoff, B. 19, 2552). 
 
 Properties. — Liquid, miscible with water, of 
 powerful unpleasant smeU. Separated from 
 aqueous solution by CaClj. Its barium salt is 
 more soluble in alcohol than those of formic, 
 acetic, or propionic acids. Its calcium salt is 
 ppd. by boiling a solution saturated in the cold. 
 
 Beactions. — 1. Boiled with HNO3 it gives 
 succinic acid (Dessaignes ; Brlenmeyer, A. 180, 
 207).— 2. With CrOj it gives CO^ and acetic acid 
 (Grunzweig a. Hecht, B. 11, 1053).— 8. With 
 MnOj and dilute H^SO, it gives propyl butyrate 
 (Veiel, A. 148, 164). — 4. The silver salt decom- 
 poses on dry distillation according to the equation : 
 
 403H,.C02Ag = 3C3H,.C02H + CO^ + C + 4Ag 
 (Iwig a. Hecht, B. 19, 240).— 5. Distillation over 
 ziue-dust at 850° gives di-propyl ketone, propyl- 
 ene, CO, H, and other products (Jahn, B. 13, 
 2115). 
 
 Salts.-NaA'.— KA'. S. 125 at 15°. Very 
 deliquescent. — MgA' 5aq. Very soluble plates. — 
 CaA'2. S. 20 at 0° ; 18 at 22° ; 15 at 60° ; 16-2 
 at 100° (Chancel a. Parmentier, 0. B. 104, 474; 
 Hecht, A. 213, 69). Trimetrio needles.— 
 CaA'j aq. S. 19-6 at 22°.— (CaA',) ^(CiH.Oj) 5aq. 
 CaA':0a0L(C4HjOj),.— CaCl8(C,H30j)j 2aq (Lie- 
 
 ben, M. 1, 926).— SrA'j. S. 40 at 22°.— 
 BaA'2 4aq. S. 40 at 14°. S. (alcohol) 11-7. 
 Trimetric. — BaA'^ 2aq. — BaA'jCjHgO^ (Mixter, 
 Am. 8, 343). — ^BaA'22CaA'2. Eegnlar octahedra 
 (Fitz, B. 13, 1314). ZnA'2 2aq. S. 11 at 16°. 
 Monoolinic prisms. Gives pp. of basic salt on boil- 
 ing.— PbA'^ : oil.— PbA'2 2PbO. — PbA'j2CaA'j : 
 cubes. — CuA'j 2aq. Monoclinio. — CuA'j aq. 
 Triclinic (Alth, A. 91, 176).— CuA'j 2Cu(AsOj)j 
 (Wohler, A. 94, 44).— AgA'. S. -843 at 4-6°. 
 Needles or monoolinic prisms. 
 
 Methyl ether (102°). S.G. g -9194 (Gar- 
 tenmeister, A. 233, 249) ; 2 -9194 (Elsasser, A. 
 218, 314) ; 4 -948 (Kahlbaum, B. 12, 344) ; ^ 
 ■8962 (Briihl) ; if -9037 ; §f -8945 (Perkin, C. J. 
 45, 483). M.M. 5-387 at 16-4° (P.). S.V. 126-35 
 (E.Sohifl,A220,332). m/3 1-3936 (Briihl). Ea, 
 43-11 (B.). O.E. (0°-10°) -001156 (E.). 
 
 Fthyl ether.— Mol.w.lie. (121°cor.). V.D. 
 3-99 (for 4-00) (S.). S.G. g -9004 (Gartenmeister) ; 
 I -8996 (E.) ; la -898 (Linnemann a. Zotta, A. 
 
 161, 178) ; \° -8892 (B.) ; if -8849 ; || -8762 (P.). 
 M.M. 6-477 at 16-1° (P.). S.V. 150-23 (S.). 
 11.^ 1-4007. Eoc, 50-33 (B.). C.E. (0°-10°) 
 •001162 (E.). Smells Uke pine-apples, in which 
 it occurs as well as in other fruits. 
 
 Allyl ether (140°) (Cahours a. Hofmann, 
 2^.1857, 555; A. 102, 296); (145°) (Berthelot 
 a. De Luca, A. 100, 360). 
 
 Propyl ether (148° cor.). S.G. s -8930 
 (E.) ; 14 1-879 (Linnemann, A. 161, S3). S.V. 
 173-85 (S.). C.E. (0°-10°) -001077 (E.). 
 
 Iso-propyl ether. (128°). S.G. 2 -879; 
 IS -865 (Silva, A. 153, 135). 
 
 n-Butyl ether (165° Cor.). S.G. § -8878 
 (G.) ; 12 -876 (Linnemann, 4. 161, 195) ; 2 -889 ; 
 22 -872 (Lieben a. Eossi, A. 158, 170). S.V. 
 197-8 (G.). C.E. (0°-10°) -00105 (G.). 
 
 Iso-butyl ether (ISr.) (S.) ; 157° (B.). 
 S.G. 2 -8818 (E.) ; 2 -880 ; 12 -866 (Griinzweig, A. 
 
 162, 207). S.V. 197-66 (S.) ; 200-53 (E.). C.E. 
 (0°-10°) -001093 (E.). Velocity of bromination : 
 Urech, B. 13, 1693. 
 
 n-Amyl ether {18i-8°). S.G. g -8832. C.E. 
 (0°-10°) -00099. S.V. 222-3 (Ga.). 
 
 Iso-amyl ether. (176°) (Delffs, A. 92, 
 278) ; (178-6°) (E.). S.G. 2 -8828 (E.). S.V. 
 221-52 (B.). C.E. (0°-10°) -001014 (B.). 
 
 Sexyl ether. (205°). S.G. g -8825. C.E. 
 (0°-10°) -00096. S.V. 246-4 (Ga.). From Bera- 
 cleum (Franohimont a. Zinoke, A. 168, 198). 
 
 Heptyl ether (225°). S.G. g -8827. C.E. 
 (0°-10°) -00093. S.V. 270-2 (Gartenmeister). 
 
 Octyl ether. (245°) (E.) ; (242°) (G.). 
 S.G. 2 -8794. C.E. (0°-10°) -00091. S.V. 295-6 
 (G.). From Pastinaca sativa (Eenesse, A. 166, 
 80). 
 
 Cetyl ether. [20°]. (0. 265°) at 200 
 m.m. S.G. 22 -856 (DoUfus, A. 131, 285). 
 
 Ethylene ether v. Glycoii. 
 
 Ethylidene ether v. Di-butyryl ortho- 
 Aldehyde p. 106. 
 
 Glyceryl ether v. Glyoeein. 
 
 Amide CsHj.CONHj. [115°]. (216°). 
 Prepared by heating ammonium butyrate under 
 pressure at 230° ; the yield is 75 p.o. (Chancel, 
 
 A. 52, 294 ; Buckton a. Hofmann, C. J. 9, 241 ; 
 
 B. 16, 982).-Hg(0,H,NO)j. 
 
 Anilide GsB.,.C0.1iiB.{CgB.;). [92°]. Pearly 
 plates (from dilute alcohol). Sol. ether. Formed 
 by heating butyramide, butyric anhydride, oi 
 
BUTYRIC ACID. 
 
 651 
 
 chloride with aniline (Gerhardt, A. Oh. [31 37, 
 329 ; Kelbe, B. 16, 1200). 
 ,.yj^^°'^^^^ CsHj.COCl. Mol. w. 106-5. 
 aOP). S.G.Y 1-0277. /.^ 1-4178. B«, 41-43 
 (Bruhl, A. 203, 19). From butyric acid (96pts.) 
 and PCI, (100 pts.) (Buroker, A. Oh. [5] 26,468 ; 
 Linnemann, A. 161, 179). Converted by sodium- 
 amalgam into dibutyryl (OjH,0)j. Al^Cl^ forms 
 crystalline C,JB.,fi^ [107°] ' butyro - butyryl - 
 butyric anhydride." NaOH forms C,Ji,.NaO, 
 (Combes, C. B. 104, 853). 
 
 Bromide C^H,O.Br. (128°) (Berthelot, /. 
 1857,344). V / V 
 
 Iodide CtB.,0.1 (147°) (Oahours, A. 104, 
 
 Anhydride (CjH,0)jO. (192°). S.G. ia -978. 
 V.D. 5-38 (obs.). From sodium butyrate (4 pts.) 
 and POCl, (2 pts.) or BzCl (2ipts.) (Gerhardt, 
 A. 87, 155). Also from butyryl chloride and 
 butyric acid (Linnemann, A. 161, 179). Heated 
 vrith sodium butyrate at 180° it forms di-propyl- 
 ketone (Perkin, O. J. 49, 325). 
 
 Peroxide (04H,0)20j. From butyric an- 
 hydride and BzA- Oil (Brodie, Pr. 12, 655). 
 
 NitrileC^.ClS. Propyl cyanide. Mol.w. 
 69. (119°). S.G.ia-795. Formed by distilling 
 the amide or ammonium butyrate with PjOj 
 (Dumas, A. 64, 334 ; Henke, A. 106, 272). 
 
 Isobutyric acid {CB.,)J0B..GOjs.. Mol. w. 
 88. (153° cor.). S.G. if -9539 ; if -9457 (Perkin, 
 O. J. 45, 487) ; f "9490 (Bruhl) ; g -9651 (Zander). 
 C.E. (0°-10°) -00110 (Z.). S. 20 at 20°. M.M. 
 4-479 at 17-8° (P.). S.V. 108-57 (E. Schiff, A. 
 220, 105). Ms 1-3979. B.^ 35-48 (B.). S.H. 
 -485 at 0° (Schiff, A. 234, 300). Heat of solution 
 973. Heat of neutralisation in dilute solution 
 13989 (Gal a. Werner, Bl. [2] 46, 801). Valour- 
 pressure : Richardson (C. J. 49, 766). 
 
 Occurrence. — 1. In St. John's bread, the fruit 
 of Oeratonia siligua (Griinzweig, A. 158, 117 ; 
 162, 193). — 2. In the root of Arnica montana 
 (Sigel, .4. 170, 345).— 3. Asanether(isobutylio?) 
 in Eoman oil of chamomile (Kopp, A. 195, 85 ; 
 Kiibig, A. 195, 96). — 4. In human excrement 
 (Brieger, B. 10, 1029). 
 
 Formation. — 1. From iso-propyl cyanide and 
 potash (Markownikoff, A. 138, 361).— 2. By 
 saponifying di-methyl-aceto-acetio ether (Prank- 
 land a. Duppa, A. 138, 337). — 3. Aqueous calcium 
 butyrate which had been heated and cooled in a 
 sealed tube 30 or 40 times in 10 years was 
 found to have changed to the extent of 10 p.c. 
 into calcium isobutyrate (Erlenmeyer, A. 181, 
 126). — 4. By the oxidation of pyroterebic acid 
 (WilHams, B. 6, 1094). 
 
 Preparation.— "Zj adding K^CrjO, (4 pts.) to 
 a cold mixture of isobutyl alcohol (3 pts.), HjSOj 
 (51 pts.) and water (15 pts.). Isobutyl isobutyrate 
 separates. It is distilled with moist potash, and 
 the potassium salt is distilled with strong HjSOj 
 (Pierre a. Puchot, A. Oh. [4] 28, 366). 
 
 P?-c5n«riJes.— Unpleasant smelling liquid. 
 
 Beactims.—'i.. Oxidised by CrOj mixture at 
 140° to COj, acetone (Popoff, Z. 1871, 4) and 
 acetic acid (Erlenmeyer, Z. [2] 7, 57).— 2. Oxi- 
 dised by KMnO, in alkaline solution, to fl-oxy- 
 isobutyric acid, (CH3),C(0H).C0,H, according 
 to Richard Meyer's rule that when the group CH 
 is united to three carbon atoms it may be oxi- 
 dised to C.OH.— 3. Calcic isobutyrate on distil- 
 lation gives di-isopropyl-ketone, with smaller 
 
 quantities of methyl tert-hvAyl ketone, iso- 
 butyric aldehyde, and isobutyric acid (Barbaglia 
 a. Gucci, O. 11, 84). 
 
 Salts . — More soluble than those of M-butyrio 
 acid. — CaA'2 aq : small plates. S. (of CaA'j) 20 
 at 0'; 28 at 80°; 25 at 100°.— CaA'^ 5aq : long, 
 monoclinic prisms (Chancel a. Parmentier, O. B. 
 104, 477).— SrA'jSaq. S. 44 at 17° (hydra- 
 ted) (Griinzweig). — BaA'a^aq. Monoclinic — 
 BaA'„HA' [74°] (Mixter, Am. 8, 346).— 
 BaA'^a(C,H30j2aq.— ZnA'jaq. S. (hydrated). 
 17 at 20°.— PbA'2. S. 9 at 16°. Trimetrio 
 plates. Melts under hot water. — AgA'. S. -93 
 at 16°. Plates. 
 
 Methyl ether. (92°). S.G. i -9112 
 (Elsasser, A. 218, 332). C.E. (0°-10°) -001223 
 (E.). S.V. 126-5. H,F. p. 109,660. H.F. v. 
 116,760 (Th.). 
 
 Ethyl ether. (110°). S.G. § -8904 (E.) ; 
 If -8758 ; If -8670 (Perkin, 0. J. 45, 487). M.M, 
 6-479 at 21-8° (P.). C.E. (0°-10°) -001156 (E.). 
 S.V. 148-86 (E.) ; 150-68 (Schiff, A. 220, 333). 
 
 Propyl ether. (135°). S.G. £ -8843 (E.). 
 C.E. (0°-10°) -001039 (E.). S.V. 173-7 (B.) ;' 
 174-2 (S.). 
 
 Iso-propyl ether (120°). S.G. 2 -879 
 (Pribram a. Handl, M. 2, 691). 
 
 Iso-butyl ether. (146-6°) (E.) ; (149°). 
 (S.). S.G. s -8750 (E.). C.E. (0°-10°) -000994 
 (E.). S.V. 198-2 (S.) ; 196-0 (E.). 
 
 Is o- amy I ether. (169°) (E.). S.G. 2-8760. 
 C.E. (0°-10°) -001031. S.V. 223-04. 
 
 Benzyl ether v. p. 493. 
 
 Amide [129°]. (c. 218°). Prepared by 
 heating ammonium isobutyrate at 230° under 
 pressure ; the yield is 90 p.c. (Hofmann, B. 15^ 
 982 ; cf. Letts, B. 5, 672 ; Miinoh, A. 180, 340 ; 
 
 and J)i-tSO-BUTTRAMII)E). 
 
 Bromo- amide CgHi.CO.NHBr. [92°]. 
 Prepared by the action of bromine and EOH on 
 isobutyramide (Hofmann, B. 15, 755). Larga 
 colourless needles, sol. ether, si. sol. water. De- 
 composed by caustic alkahs into propylamine, 
 HBr, and COj, but by carbonated alkaUs the reac- 
 tion stops half way with production of propyl 
 cyanate. 
 
 Iso-propyl -amide PrCO.NHPr. [102°]. 
 (210°). Formed by the action of acetyl chloride- 
 on di-isopropyl acetoxim (Meyer and Warring- 
 ton, O. J. 51, 685). Also by the action of iso-. 
 butyryl chloride on isopropylamine. Colour- 
 less transparent needles v. sol. alcohol and 
 ether, m. sol. water. Sublimes at ordinary tem- 
 peratures and distils without decomposition. 
 Is decomposed by prolonged boihng wi.,h alco- 
 holic potash into isobutyric acid and isopro- 
 pylamine. 
 
 Anilide CjHj.CO.NHOeHs. [103°]. From, 
 isobutyric acid and aniline (Norton, Avi. 7, 116). 
 Prisms. 
 
 p-Bromo-anilide CaHj.CO.NH.CsHjBr 
 [1:4]. [128°]. From the preceding and Br (N.).. 
 
 Chloride C^Hj.CO.Cl. (92°) (Markowni- 
 koff, Z. 1866, 501). S.G. =5° 1-0174 (Briihl, A. 
 203, 20). M,9 1-4135. Eo, 41-41 (B.). ZnMe^ 
 (1 mol.) followed by water converts isobutyryl 
 chloride into a ketone C,„H,80 (190°). S.G. 2 
 •870 (Pawlow, A. 188, 139). ZnMe^ (2 mola.) 
 followed by water forms tertiary butyl alco- 
 hol and sometimes a ketone OijH^jO (218°). 
 S.G. 2 -864. 
 
4)5a 
 
 BUTYEIC ACID. 
 
 Bromide (117°). 
 
 Anhydride (G,-E,0)fi. (182°). S.G. l| 
 •9574 (MarkovmUroff, Z. 1866, 501 ; Tonnies a. 
 ■Staub, B. 17, 850). 
 
 Nitrile (CH3)2CH.CN. (108°). From iso- 
 propyl iodide, EON, and alconol (Markownikoff, 
 Bl. 1866, 53). From isobutyric acid and potas- 
 sium sulphooyanide (Letts, B. 5, 669). 
 
 n-BUTYEIC ALDEHYDE O^HjO i.e. 
 -CH3.CHj.OH2.CHO. (74°). Mol. w. 72. S.G. 
 w -8170 (Briihl). /ig 1-3893. E(„ 32-93. S. 3-7. 
 iGot by distilling calcium butyrate with calcium 
 formate (Linnemann, .4. 161, 186 ; Lipp, A. 
 211, 855). From casein by oxidation with HjSO^ 
 and MnOj (Guckelberger, A. 64, 39). 
 
 Beaction. — Aqueous NaOH and NaOAc 
 -form oily 0„H,jO (173°). It is probably 
 Pr.CH2.CH:CEt.CH0 as it reacts with phenyl- 
 iydrazine and combines with bromine (Baupen- 
 •Btrauch, M. 8, 108). 
 
 Ammonia compound 
 <(CH3)jCH.OH(OH)(NHj)3iaq. [31°]. Trimetrio 
 pyramids. V. si. sol. water, v. sol. alcohol, m. 
 •sol. ether. Deliquesce above 4°, giving oH water. 
 
 Bisulphite compound CjHgONaHSOj 
 .(Juslin, B. 17, 2505 ; Kahn, B. 18, 3364). 
 
 Bulyraldines. Dibutyraldine CgH,,NO and 
 tetra-butyraldine OuHj^NOj ate formed by the 
 protracted action of alcoholic ammonia on 
 butyric aldehyde (SchifE, A. 157, 352). Butyral- 
 -dine, on distillation, gives para-coniine C«H,5N. 
 
 Butyral CAO (?) (95°). S.G. s^ -821. A 
 product of distillation of calcic butyrate (Chancel, 
 A. Gh. [3] 12, 146; Limpricht, A. 90, 111; 
 -98, 241). Beduces AgjO. Does not combine 
 -with NH3. Combines with NaHSOj. 
 
 Beactions. — 1. Air or Ag,0 forms butyric 
 .acid.— 2. Chlorine forms 0,H,C10 (141°) and 
 KJ^H^CljO (200°).— 8. PCI5 forms G^Efil (c. 100°). 
 
 Isobutyric aldehyde (CH3)jCH.CH0. (64°). 
 S.G. if -7972 ; |f -7879 (Perkin, C. J. 45, 476) ; 
 ^,° -7938 (Briihl, A. 208, 18). S. 11 at 20°. 
 p.g 1-8777. Boo 32-89. H.F.p. 61,340. H.F.v. 
 ^9,810. M.M. 4-321 at 19-3°. 
 
 Formation. — 1. From isobutyl alcohol by 
 •chromic mixture (Pfeiffer, B. 5, 699 ; Michael- 
 son, A. 138, 182; Pierre a. Puchot, 0. B. 
 70, 484).— 2. By heating iso-butylene bromide, 
 .(CHs)2CHBr.CHBr, with water (20 vols.) at 160° 
 .(Linnemann a. Zotta, A. 162, 86).— 3. By dis- 
 tilling calcium isobutyrate (Popoff, B, 6, 1255 ; 
 Barbaglia a. Gucci, B. 13, 1572).— 4. By dis- 
 iilling calcium isobutyrate with calcium formate 
 ■(Linnemann a. Zotta, A. 162, 7).— 5. By distil- 
 ling colophony (Tilden, B. 13, 1604). 
 
 Prepa/ratum. — A mixture of cone, aqueous 
 KjCrjO, with an equal volume of H^SO, is 
 *lowly run into a flask containing iso-butyl 
 alcohol (100 g.) and water (200 g.) until the 
 Jayer of alcohol has disappeared. The product 
 is distilled. The yield is 55 p.c. of the theo- 
 retical (W. H. Perkin, jun., O. J. 43, 91 ; cf. 
 Tossek, M. 4, 660). 
 
 Properties. — Pungent liquid. Forms a com- 
 I)ound with NaHSOa from which it is separated 
 'by potash without change. 
 
 Beactions. — 1. By the action of potash (4 g.) 
 an alcohol (140 g.) upon the aldehyde (50 g.) the 
 ifo'lowing bodies may be obtained; isobutyric 
 -aei.l, an acid Cy^jd, (245°-255°) and an alde- 
 favile C.sHjjOp— 2. If more potash (8 g.) and a 
 
 higher temperature be used, the neutral products 
 are : C,^Ji„ C,eR,fi,^, G^„B.,fi„ O^^KJ), and 
 C^aHjgOs (W. H. Perkin, jun., O. J. 43, 101).— 8. 
 Aqueous potash forms an acid CgHuOj [75°-80°], 
 a crystalline body CgHjgOj [90°], and di-oxy- 
 octane (Fossek, M. 8, 622).— 4. PCI5 gives ohloro- 
 isobutylene Me,C:CHCl (68°) and di-chloro-iso- 
 butane (104°) MejCH.CHClj (Oeoonomides, C. B. 
 92, 884). — 5. H2S and aqueous ammonia form 
 isobutyraldineC.jHaNSz (Pfeiffer, B. 5, 700). 
 
 6. CS2 and cone. NHgAq give NH2.CS.SN(CiHg), 
 [91°]. Prisms, insol. water, v. sol. alcohol. — 
 
 7. Alcohol and HCl followed by NaOEt form 
 di -ethyl -ortho -isobutyric aldehyde 
 CMe2CH.CH(0Et)j (185°). S.G. is -996, V.D. 
 143-5, and, when some water is also present, a 
 compound C,„H,„0 (223°) (Oeconomides, Bl. [2] 
 86,210; C.S.92,886).— 8. Gives with ammojMa 
 a crystalline compound (C4H8),NgHgO (Lipp, A. 
 205, 1; 211, 344; B. 13, 906; 14, 1746). 
 
 7C3H,CHO + 6NH3 = 6B.fi + (C3H,CH),NgHgO. 
 When the product, ' oxy-hepta-iso-butyUdene- 
 amine ' [32°], is heated, it first splits up into 
 2NH3, CjHgO and 2(C,Ha)3N2. The latter is 
 hydro-butyramide, an oil, nearly insoluble in 
 water, v. sol. alcohol or ether. If quickly heated 
 it distils at 154°, but if heated slowly it splits 
 up into NH3 and CgHisN. Hydro-butyramide 
 or tri-isobutylidene-diamine is not affected by 
 boiling EOH, but dilute HCl splits it up int() 
 butyric aldehyde and NH3. It is, therefore, 
 CjHg:N.C<Hg.N:CiHB. Dry HCN added to its 
 ethereal solution forms the dihydrochloride of 
 (Cy.C,Hg.NH)2C4Hg a body that is decomposed 
 by water into isobutyric aldehyde and amido- 
 valero-nitrile. When hydro-butyramide is slowly 
 heated it does not, like hydro-benzamide, change 
 into an isomeride, but splits up, giving CgH^N. 
 This compound, ' iso-butenyl-butylidene-amine,' 
 is a liquid (145°-147°) at 715 mm., nearly 
 insoluble in water, miscible with alcohol or 
 ether. It is not affected by aqueous EOH, 
 but acids split it up into isobutyric aldehyde 
 and KH3. It would thus appear to be 
 (CH3)2CH.CH:N.CH:0(CHs)2. It combines with 
 Br, forming CgHuNBr^, a body that, when kept 
 for a long time, and then treated with water, 
 gives NHjBr, isobutyric aldehyde and bromo-iao- 
 butyrio aldehyde, or rather a polymeride of the 
 latter [129°]. If CgH.sNBrj be at once treated 
 with water, the unstable liquid bromo-butyrio 
 aldehyde is probably formed (Lipp.). 
 
 Oxim CsH5.CH:N(0H). [139°]. Colourless 
 liquid. Sol. water. Formed by the action of an 
 aqueous solution of hydroxylamine on isobutyric 
 aldehyde (Petraczek, B. 15, 2784). 
 
 Description of condensation products, ob- 
 tained as above (W. H. Perkin, jun., C. J. 43, 90). 
 
 Acid CijHjjOs (245°-255°). Brownish oU. 
 Beduces ammoniacal Ag^O. 
 
 Compound C.^H^A (154°_157°). CKl. 
 Ethereal odour. Beduces ammoniacal Ag^O. 
 Combines slowly with NaHSOg. Decomposes on 
 prolonged heating. Is probably Urech's CgHuO 
 (B. 12, 191). With Na and wet ether, it is re- 
 duced to O.jHjgOj (170°-175°), an alcohol (?) 
 which does not combine with NaHSOj. 
 
 Compound Cjai^fi^ (228°-225°). Oil 
 Smells of camphor. Very slowly combines with 
 NaHSOj, forming needles. Beduces ammoniacal 
 AgjO. V.D. 167 (Theory 342). With AojO it 
 
BUXmE. 
 
 C6» 
 
 forms CjoH„AoO, (240°-242°). oa, which with 
 Ao^O at 200° gives C,,H3^oA (248'-252°). 
 
 r22°o°) irSfa."^ ^°= ^ '^'^ °^«^«°^ 
 
 (airi°ri2°9 (TVeo"?f3ir°"'''°^- °"- ''■''• 
 
 ^m?P,°"??^^^'»^<«Os (227°-229°) at 100 
 mm. ihiok oil. Decomposed when heated under 
 atmospheric pressure. 
 
 Di-isobutyric di-aldehyde CsH.^O,. (138°) at 
 18 mm. V.D. 5-2 (oalc. 5-0). This polymeride 
 of isobutyno aldehyde is obtained, together with 
 octenoic aldehyde (?) CjHuO (150°) by heating 
 isobutyric aldehyde with cone, aqueous NaOAc at 
 150° (Fossek, M. 2, 622). It is an oU, sol. alco- 
 hol and ether, forming a crystalline compound 
 with NaHSOj. 
 
 Iso-butyrio paraldehyde (0,H.O),. [60°1. 
 (195°). V.D. (H = l) 104-8. Prom iso-butyr- 
 aldehyde by H,SO„ HCl, PC1„ 01, Br, or I (Bar- 
 baglia, B. 5, 1052 ; 6, 1064 ; G. 16, 430 ; Dem- 
 tsohenko, B. 6, 1176). Needles (from water or by 
 sublimation). Difficultly attacked by oxidising 
 agents (Ureoh, B. 12, 1749). Does not combine 
 with NaHSOa or react with NH3. At 150° it par- 
 tially changes to ordinary isobutyric aldehyde. 
 
 Iso-butyric poly-aldehyde (G^B^O)^. S.G.si 
 •969. Prepared by leaving isobutyric aldehyde 
 in contact with dry NajCO,. Thick liquid. SI. 
 sol. water. Decomposed on distillation, with 
 separation of water and formation of isobutyric 
 aldehyde and condensation products (Urech, B. 
 12, 191, 1744 ; 13, 483, 590). 
 
 BTJTYEIN V. Glycerin. 
 
 BUTYEO-CHLOEAL v. Tm-chloeo-butyeio 
 
 ALDEHYDE. 
 
 BTJrYRO-CGXrMAEIC ACID v. Oxy-phenyl- 
 
 PEKTENOIC ACro. 
 
 BTJTYEO-CEEATININE v. Methyl-amido- 
 
 BniYBIC ACID. 
 
 BTJTYEO-FUEONIC ACID 0,n,fi^ i.e. 
 COjH.CH:GH.CO.CH2.CH2.CH2.CH2.C02H (?). 
 [142°]. Prepared by treating furfurvalerio acid 
 with bromine-water and subsequent action of 
 silver oxide. White crystals. Sol. water and 
 alcohol, si. sol. ether. By HI and P it is reduced 
 to azelaic acid (Toennies, B. 12, 1200). 
 
 BUTYEO-IACTONE v. 7-Oxy-buiyeio acid. 
 
 BTJTYEOLIC ACID v. Tetbolio acid. 
 
 BUIYEONE V. Dl-PKOPYL-KBTONE. 
 
 BUTYEOHITEILE v. Nitrile of Butybio acid. 
 
 BTITYEO-PINACONE CnHjoOj i.e. 
 CPrj(0H).CPr2(0H). Di-oxy-tetradeeane. [68°]. 
 (260°). From di-propyl-ketone, water, and Na 
 (Kurtz, A. 161, 215). Crystals, smelling of 
 camphor, si. sol. water. 
 
 BTTTYEO-THIENONE v, THiiJNYii peopyl 
 
 KETONE. 
 
 DI-BOTYEYL OeH^Oj i.e. Pr.CO.CO.Pr. 
 
 Di-propyl di-Jcetone. (245°-260°). From butyryl 
 chloride and sodium-amalgam or zinc (Freund, 
 A. 118, 35). Yellow oil. Boiled -with potash it 
 forms butyrate of potassium and a liquid C,HnO 
 which does not unite with NH3 or NaHSOj. 
 
 Mono-oxim C3H,.C0.G(N0H).CsH, : thick 
 oil; can be distilled in small quantity without 
 decomposition. A di-oxim has not been obtained 
 (Miinehmeyer, B. 19, 1846). 
 
 BUTYEYL-ACETOPHENONE 
 C-H..CO.CH2.CO.C3H,. Benzoyl-meihyl-propyl- 
 Utone. (174° at 24 mm.). S.Q. 1-061 at 15°, 
 
 Colourless oil. Formed from acetophenone and 
 butyric ether by EtONa (Beyer a. Claisen, B, 
 20, 2181). 
 
 Isobutyryl-acetophenone 
 CjH5.CO.CH2.OO.C3H,. Benzoyl-methyl-iso- 
 
 propyl-ketone. (170° at 26 mm.). Colourless 
 liquid. Formed from acetophenone and iso- 
 butyric ether by EtONa (Beyer a. Claisen, B, 
 20, 2181). 
 
 BTJTYEYI-AMIDO-BENZOIC ACID 
 PrC0.NH.0„H,.002H. [209°]. From n-butyii© 
 ether (20 c.c.) and Mt-amido-benzoic acid (10 g.) 
 at 180° in sealed tubes (Pellizzari, A. 232, 148). 
 Sol. water and alcohol. 
 
 BUTYEYL BROMIDE v. Butybio acid. 
 BUTYEYL CHLORIDE v. Butybio acid. 
 BUTYEYL CYANAMIDE v. Cyanamide. 
 n-BTJTYEYL CYANIDE C^H^NO i.e. 
 PrCO.CN. (133°-137°). From AgCN and PrCOCT 
 (E. Moritz, C. J. 39, 16). 
 
 ra-Di-butyryl di-cyanide (PrC0)2(CN)2 
 (c. 234°). By-product in preparation of above. 
 Iso-bntyryl cyanide Pr.CO.CN. (117°-120°). 
 From PrCO.Cl (40 g.) and AgCN (50 g.). Bad 
 yield (E. Moritz, C. J. 39, 13). The greater 
 part of the product is di-iso-butyryl di-cyanide 
 (226°-228°). S.G. -96. 
 
 BUTYEYL IODIDE v. Butybio acid. 
 BUTYEYL-MALOHIC ETHEE 
 C3H,,C0.CH(C0.,Et)2. (247°-252°). Formed by the 
 action of butyryl chloride upon sodio-malonio 
 ether. By nitrous acid it is converted into iso- 
 nitroso-butyryl-acetic ether (Lang, B. 20, 1326). 
 BUTYEYL PEROXIDE v. Butybio acid. 
 BUTYEYL-PEOPYL-UEEA v. Butyryl deri- 
 vafive of Pbopyl-ueea. 
 
 BUTYEYL SULPHOCYANIDE (180°). From 
 butyryl chloride and lead sulphoeyanide. Decom- 
 poses when boiled (Miquel, A. Ch. [5] 11, 295). 
 BUTYEYL-UEEA v. Ueea. 
 BUXElNE. An alkaloid extracted by dilute 
 oxalic acid from the bark of the box-tree Buxus 
 senvpervirens. Yellowish-white crystalline sub- 
 stance, sol. alcohol and ether, si. sol. water. 
 HNO3 gives a greenish-yellow colouration turn- 
 ing brick-red. H2SO4 gives a blood-red colour. 
 Chromic acid mixture gives an orange pp. 
 (Alessandri, (?. 12, 96). It is perhaps identical 
 with buxine. Barbaglia finds four alkaloids in 
 the leaves and twigs of the box : buxine, para- 
 buxine, buxidine, and buxinidine (Q. 13, 249 ; 
 B. 17, 2655). 
 
 BUXINE C,8H2jNOs(?). An alkaloid extracted 
 by dilute oxalic acid from the leaves of the box 
 tree. White crystalline substance, sol. alcohol 
 and ether, si. sol. water. HNOj gives a purple- 
 red colouration. H3SO4 gives a brick-red colour. 
 Chromic aoid mixture gives a canary-yellow pp. 
 (Alessandri, 0. 12, 96 ; Barbaglia, B. 4, 757 ; 
 Faur6, /. Ph. 16, 428 ; Couerbe, /. Ph. 1854, 51). 
 According to Walz {J. 1860, 548) buxine is 
 identical with bebeerine {q. v.). 
 
 Parabuxine Cs^H^NjO (?) An alkaloid oc- 
 curring in both leaves and bark of the box 
 tree. It is a reddish-purple amorphous resin, 
 sol. water and alcohol, insol. ether. HNO., 
 gives a permanent greenish-yellow colouration. 
 H2SO4 gives a greenish-yellow colour becoming 
 dark. Chromic acid mixture gives no pp. — 
 B"HjSO,.— B"2HC1.— B"HjPtClj (Pavesi a. Eo. 
 tondi, O, 4, 192 ; Alessandri). 
 
«54 
 
 OAOAO. 
 
 c 
 
 CACAO V. Theobbouinb. 
 
 CACODYL V. p. 318. 
 
 CACOSTBYCHNINE O^iHajNiO,,. A product 
 of the action of HNO3 on strychnine (3. v.). 
 Golden needles (from dilute HNO3) or hexagonal 
 plates (from cone. HClAqj. SI. sol. most 
 menstrua, sol. alkalis, forming red solutions. — 
 B'jHjPtCls (Glaus a. Glassner, B. 14, 773). 
 
 CACOXHELINE C2(,H22Nj05. A product of 
 the action of HNOj on brucine {q.v.). Orange 
 lamina3 (containing aq). Weak base ; sol. 
 alkalis, v. si. sol. hot water, insol. alcohol and 
 ether.— B'BaO 7aq.—B'2H2PtCl5 (Streoker, A. 
 91, 76; a. B. 39, 52 ; Bosengarteu, A. 65, 111 ; 
 Claus a. Eohre, B. 14, 765). 
 
 CADAVERIC ALKALOIDS v. PioMAiNES. 
 
 CADET'S EDMIITG LIQUID v. p. 318. 
 
 CADMIUM. Cd. At. w. 111-7. Mol. w.- 
 111-7 ; gaseous molecule is monatomio. [820°] 
 (Person, A. Ch. [3] 27, 250 ; Eudberg, P. 71, 
 460; V. Biemsdyk, O. N. 20, 32). (763°-772°) 
 /Carnelley a. WiUiams, O. J. 33, 284). S.G. 
 (molten) 8"65, (hammered) 8'8 (Stromeyer, S. 
 22, 362; Schroder, P. 106, 226; 107, 113; 
 Matthiessen, P. 110, 21, cfec). V.D. 55-8 
 <Deville a. Troost, C. B. 52, 920). S.H. (0°-100°) 
 ■0548 (Bunsen, P. 141, 1), -0567 (Regnault, 
 A. Ch. [3] 26, 268). C.E. (linear, 0°-100°) 
 •003323 ; (cubical for 1°) -000094 (Kopp, A. 81, 
 32; Matthiessen, P. 130, 50; Fizeau, 0. B. 
 68, 1125). T.C. (Ag = 100) 20-06 (Lorenz, W. 
 13, 422). B.C. (Hg at 0= = 1) at 0°, 13-46 ; at 
 100°, 9-5 (Lorenz, W. 13, 422 a. 582). Heat of 
 fusion 13,660 (Person, P. 76, 426). S.V.S. abt. 
 12-8. Emission-spectrum characterised by lines 
 3609-6, 3465-4, 2747-7, 2572-2, 2313-6, 2288-9 
 (Hartley, T. 1884. 63). 
 
 Cd was discovered by Stromeyer in 1817 in 
 a specimen of zinc carbonate {S. 21, 297 ; 22, 
 362 ; V. also Hermann, G. A. 59, 95). The 
 name ca&mium was derived from cadmia fossilis 
 by which name zinc ore was then known. 
 
 Occurrence. — With Zn in various native sul- 
 phides, carbonates, and silicates, especially in 
 the Silesian zinc ores [v. Damour, J", pr. 13, 
 354; Stadler, J. pr. 91, 359; Blum, /. 1858. 
 734 ; Bunsen, A. 183, 108). CdS occurs nearly 
 pure as Oreenockite at Bishopton in Eeufrew- 
 shire. 
 
 Formation. — In the distillation of crude zinc 
 oxide with charcoal ; the greater part of the Cd 
 distils over before the Zn. 
 
 Preparation. — ZuO containing CdO, or 
 metallic Zn containing Cd, is dissolved in dilute 
 HjSOjAq or HClAq ; the warm solution is satura- 
 ted with HjS ; the CdS thoroughly washed and 
 dissolved in cone. HClAq ; most of the free HCl 
 is removed by warming, the solution is diluted 
 and filtered, and an excess of (NHJ^COj is added; 
 the pp. of CdCOj is well washed, dried, and 
 strongly heated ; the CdO thus produced is 
 mixed with ^ of its weight of pure powdered 
 charcoal and heated in a retort of hard-glass or 
 porcelain when pure Cd distils over (Stromeyer, 
 8. 22, 362). 
 
 Properties. — White with slight blue tinge; 
 very lustrous ; soft, but harder than zinc ; very 
 
 malleable, ductile, and flexible ; more tenaoicas 
 than tin ; crystallises easily in monometrio 
 forms, chiefly the octahedron {v. Kammerer, B. 
 7, 1724 ; also G. Eose, P. 85, 293). Vapour w 
 yellow. Cd does not decompose water even at 
 100°; but if Cd vapour and steam are passed 
 through a hot tube the steam is decomposed 
 (Eegnault, A. Ch. 62, 351). Cd oxidises slowly 
 on the surface by exposure to air ; when heated 
 in air it burns to CdO. The atomic weight of 
 Cd has been determined (1) by finding the V.D. 
 of, and by analysing, CdBrj (Meyer, B. 12, 1292 ; 
 Dumas, A. Ch. [8] 55, 158 ; Huntington, P. Am. A. 
 17, 28) ; analyses of CdOjOi (Lenssen, X pr. 
 79, 281) ; reduction of CdSO^ to CdS (v. Hauer, 
 C. C. 1857. 897) ; analyses of CdO (Stromeyer, 
 S. 22, 366) ; (2) by determining the S.H. of Cd 
 (Bunsen, P. 141, 1; Eegnault, A. Ch. [3] 26, 
 268); (3) 'by comparing, as regards crystalline 
 form and general reactions, salts of Cd with salts 
 of Zn, Be, Mg, and Hg. In the gaseous mole- 
 cule CdBr2 (this is the only compound of Cd 
 whose V.D. has been determined) the atom of 
 Cd is divalent. The gaseous molecule of Cd is 
 monatomio. Cd is a distinctly metallic element ; 
 it acts on HClAq, H2S04Aq, &c., evolving H and 
 forming salts of the form CdX^ where X, = Cl^, 
 Br^, SO4, CO3, &c. ; many of these salts combine 
 with the similar salts of the more positive 
 metals (K, Ca, Mg, &c.) to form double salts ; 
 but few basic salts of Cd are known, the most 
 marked are derived from such weak acids as 
 H^CrO^, H3BO3, &c. No compound of Cd 
 exhibits any acidic functions. CdOjH, acts to- 
 wards acids as a salt-forming hydroxide ; its 
 heat of neutralisation by H2S04Aq is about the 
 same as that of the corresponding hydroxide of 
 Mn, Ni, Co, Fe, or Zn, [CdO^H^Aq, H^SO'Aq] = 
 23,824 (d. Th. 1, 389 a. 436). CdO^H;, is de- 
 hydrated by heat ; the oxide CdO is not converted 
 to CdOjH^ by direct addition of H^O. Cadmium 
 is closely related to Zn, it is less positive than 
 that metal ; it is also related to Mg on one hand 
 and to Hg on the other {y. MAONESinii group oi? 
 elements). 
 
 Beactions. — 1. Heated in air, or 0, CdO ia 
 produced. — 2. Heated nearly to redness in 
 bromine, CdBrj is formed. — 3. Aqueous solu- 
 tions of hydrochloric, sulphuric, or nitric, acids 
 are decomposed by Cd with formation of chloride, 
 sulphate, or nitrate of the metal. — 4. Heated 
 with SOjAq to 200° CdS is formed (Geittner, 
 A. 129, 354) ; possibly sulphite and thiosulphate 
 are first formed (v. Schweitzer, 0. N. 23, 293 ; 
 Fordos a. G61is, A. 50, 260). 
 
 Combinations. — Most compounds of Cd are 
 formed from the oxide or other salt. Cd com- 
 bines directly with the elements 0, 01, Br, I, P, 
 S, Se, Te, and with many metals {v. Caduium, 
 OXIDE or, &o., and Cadmium, alloys or). 
 
 Detection and Estvmation. — Formation of 
 the yellow sulphide, CdS, insoluble in dilute 
 HClAq and also in solution, of ammonium sul- 
 phide, characterises Cd salts. Cd is usually 
 estimated by ppn. as CdC03 (by KjCOjAq), the 
 pp. is strongly heated, and the CdO is weighed. 
 Separation from other metals may be effected! 
 
CADMIUM. 
 
 655 
 
 by repeated ppn. by H,S, and solution of CdS 
 m oono. HOlAq. Cd may be ppd. as oxalate ; 
 on this fact is founded a volumetric method of 
 estimation. 
 
 Cadmium, Alloys of. Usually prepared 
 by melting the metals together. Several are cha- 
 racterised by low melting-points. An amalgam 
 ■with_ Hg is formed at ordinary temperatures : 
 by dissolving Cd in warm Hg, and pressing, a 
 crystalline amalgam, having the composition 
 HgjCdj, and S.G. 12-62, is formed; by com- 
 pletely saturating Hg with Cd, octahedral 
 crystals of Hg^Cd, melting at 75°, are produced 
 (Gaugain, G. B. 42, 430 ; Eegnauld, O. B. 51, 
 779 ; Crookewitt, J. pr. 102, 65 a. 129 ; Kopp, 
 A. 40, 186). Easily fusible alloys with Bi 
 agreeing in composition with the formulae BiCdj, 
 BiCdj, and BiCd, are known (Matthiessen, P. 
 110, 21). Various alloys of Cd with (1) Bi and 
 Pb, (2) Bi, Pb and Sn, (3) Bi and Sn, are also 
 known ( [1] Wood, D. P. J. 164, 108 ; v. Hauer, 
 J. pr. 94, 436 : [2] Lipowitz, D. P. J. 158, 376 : 
 i;3] Wood, I.C.). AUoys with Pb (Wood, C. N. 6, 
 185) ; Na (Sonnensohein, /. pr. 67, 169) ; Tl, and 
 with Tl and Bi (Carstanjen, J. pr. 102, 65 a. 129) ; 
 and Sn (Eudberg, J. 1847, 71), have been de- 
 scribed. An arsenide, AsCdj, is said to be 
 obtained as a faintly red-coloured alloy, S.G. 
 6-26, by reducing the arsenate by KCN (Desoamps, 
 C. B. 86, 1022 a. 1065). 
 
 Cadmium, Arsenates of. Cd3(AsOj)2-3H20, 
 and Cd5H2(As04)2.4H20 ; v. aksenaies, under 
 Aesbnic, aoeos of. 
 
 Cadmium, Arsenide of. CdjAs v. Cadmium, 
 Alloys of. 
 
 Cadmium, Bromide of. CdBrj, Mol. w. 271-2. 
 [570°] (Carnelley, 0. J. 38, 278). (806°-812°) 
 (CameUey a. Williams, C. J. 37, 126). S.G. ?g 
 4-794 (Clarke, Am. 5. No. 4). H.P. [Cd.Br^ = 
 75 ,200 ; [Od,Br',Aq] = 75,640 (Thomsen) . 
 
 PreparaUon. — ^By heating Cd to redness in 
 Br vapour ; or by dissolving CdCOa in HBrAq 
 and subliming. 
 
 Properties and BeacUons. — ^White, crystal- 
 line, non-hygroscopic, solid; soluble in water, 
 ether, and alcohol; decomposed by HNO.,Aq 
 (Bodeker a. Gieseoke, J. 1860. 17 ; Croft, P. M. 
 [8] 21, 355 ; Berthemot, A. Ch. 44, 387 ; Eam- 
 melsberg, A 44, 267)._ , ^ . „. , 
 
 Oombinatians.—DiBBobredi m H^O, and 
 evaporated, yields long white needles of 
 CdBr,.4H20; these are dehydrated at 200° 
 [CdBr^4H20] = 7,780 (Thomsen). CdBr^Aq 
 and KBrAq mixed and evaporated yield 
 2CdBrj.2KBr.H.,0, and on further evaporation 
 CdBro.4KBr. The double salts 
 
 2CdBrj.2NaBr.5H2O, and CdBrj.BaBr2.4H,0, 
 have also been obtained (v. Hauer, J. pr. 64, 
 477 • 69, 121. Croft, J. pr. 68, 399). CdBr^ 
 absorbs NH3 to form CdBr2.4NH3 ; all NH3 is 
 removed by heat. Cone. CdBr^Aq saturated 
 v.ith NH„ and evaporated, gives crystals of 
 CdBrj.2NH, (Croft, P. M. [3] 21, 355; Bam- 
 melsberg, A. 44, 267). 
 
 Cadmium, Chloride of. CdClj. Mol. w. un- 
 known: probably as represented by formula 
 OdC™ [S'n (O'melley, 0. J. 33, 279) (861° 
 954°) (Parnelley a. Williams, 0. J. 35, 564). 
 S G.55 3-655 (Clarke, Am. 5, No. 4). S. (20°) 
 140 i '(100°) 160 (Kremers, P. 103, 57 ; IW, 133 ; 
 
 105, 860). H.F. [Cd,CP] = 98,240; [Cd,CP,A(]] 
 = 96,250 (Thomsen). 
 
 Preparation. — By dissolving Cd in EClA.q 
 and heating to low redness the crystals of 
 CdCl2.2H20 which separate on evaporation. 
 
 Properties and BeacUons. — Pearly, lustrous 
 plates; white powder after exposure to air for 
 some time. S. (20°-100°) abt. 140 (Kremers, P. 
 103, 57 ; 104, 133). Insoluble in cone. HClAq, 
 
 Combinations. — 1. With water to form 
 efflorescent prisms of CdCl2.2H20; [CdCP,2H'0j 
 = 2,250 (Thomsen) ; best obtained by dissolving 
 Cd, CdO, or CdCO, in HClAq, evaporating, and 
 crystallising. — 2. With hydrochloric acid and 
 water to form CdCl2.2HCl.7H2O : obtained by 
 passing HCl into CdOl2Aq; easily decomposed in 
 air with evolution of HOI ; [CdCP,2HCl,7H''0] = 
 40,200 (Berthelot, O. B. 91, 1024).— 3. With 
 ammonia, to form CdClj.ONHs and CdCl2.2NH.5. 
 CdCl2.6NH3 is obtained by passing NH, over 
 CdClj, or by passing HCl into CdCljAq containing 
 excess of NH3 until the NH3 is partly neutral- 
 ised. Loses 4NH3 by exposure to air, leaving 
 CdCl2.2NH3; this compound is also produced by 
 exposing to air a solution of CdOL in excess of 
 warm NHjAq (Croft, P. M. [3] 21, 55 ; Schiller, 
 A. 87, 34; v. Hauer, J. pr. 64, 477; v. also 
 Andr6, C. B. 104, 908).— 4. With various metallic 
 chlorides to form double salts. These salts have 
 been prepared chiefly by Croft (P. M. [3] 21, 55), 
 and V. Hauer {J. pr. 68, 432 ; 64, 477 ; 66, 176 ; 
 69, 121) ; their crystalline forms, and the thermal 
 conductivities of some of them, have been de- 
 termined by Grailich (J. 1858. 182), and v. Lang 
 (P. 185, 29). These double compounds are ob- 
 tained by evaporating mixed solutions of the 
 two chlorides ; the chief are : — 
 
 2CdCl2.2NH4Cl.H2O ; 
 
 CdCl2.4NH,Cl; 
 2CdCl2.2KCl.H2O; 
 
 CdCl2.4KCl ; 
 
 OdOlj.2NaCl.3H2O ; 
 
 CdCl2.BaCl2.4H2O ; 
 2CdCl2.BaCl2.5H2O ; 
 2GdCl2.SrCl2.7H2O ; 
 20dCl2.CaCl2.7H,0; 
 
 CdCl2.2CaCl2.12H20 ; 
 
 CdCl2.2MgCl2.12H20 ; 
 
 CdCl2.MCl2.12H20 
 when M = Co, Fe, Mg, Mn, or Ni ; 
 
 CdCl2.CuCl2.4H2O. 
 
 5. With the hydrochlorides of many organic 
 bases to form double salts; e.g. with toluidine 
 4(C,H,N.HCl).3CdCl2.2H20 (Williams, 0. O. 
 1856. 47 ; Galletly, 0. C. 1856. 606). 
 
 Cadmium, Cyanide of. Cd(CN)2. Prepared 
 by evaporating KCNAq with CdCl2Aq {v. 
 
 CIANIDES). 
 
 Cadmium, Fluoride of. CdPj. Mol. w. un- 
 known; probably as represented by formula. 
 [520°] (Carnelley, C. J. 33, 280). S.G.'f 5-994 
 (Clarke, Am. 5, No. 4). Hard, white, crystalline 
 mass; by evaporating solution of CdO in 
 HFAq; not easily soluble in water; much 
 more soluble in HPAq (Berzelius, P. 1, 26). 
 By dissolving CdO and oxide of Sn, Zr, or 
 Mo in HPAq, and evaporating, the double com- 
 pounds CdF2-SnP2-6H20, 2CdF2.ZrF,.6H20, and 
 CdF2.2ZrF,.6H20, were obtained by Marignao 
 {Ann. M. [5] 15, 221 ; A. Ch. [3] 60, 257) ; and 
 the double compound CdP2.MoOjP2.6H2O by 
 Delafontaine {J. 1867. 236). 
 
 Cadmium, Hydrated oxide of, CdO.H,0 V. 
 next article. 
 
650 
 
 CADMIUM. 
 
 Gadminm, Hydroxide of, CdO^H,. A white, 
 amorphous solid, obtained by adding KOHAq 
 to a dilute aqueous solution of a Cd salt, wash- 
 ing with warm water, and drying at 100°-200° 
 (Sohaffner, A. 51, 168). According to Nickl^s 
 (J. Ph. [3] 12, 406) GdOjHj is obtained in crys- 
 tals by keeping Cd in contact with Fe in 
 NHjAq. De Schulten (C. B. 102, 72) describes 
 the formation of hexagonal crystals of OdO^Hj, 
 S.G-. 1^° 4-79, by dissolving 10 grams Cdl^ in 150 
 c.c. HjO mixed with 360 grams KOH contain- 
 ing 13 p.c. HjO, heating till all is dissolved, and 
 cooling. Thomseu gives the thermal value 
 [Cd,0,H'^0] = 65,680 ; and the following values 
 lor the heat of neutralisation of solid CdOjHj 
 (Th. 3, 285) : 
 
 Q [M.QAq] M = Cd02Hj. 
 
 H^SO. 24,200 
 
 H^N^O, 20,620 
 
 HAO. 20,360 
 
 HjClj 20,290 
 
 HjBrj 21,560 
 
 HJj 24,210 
 
 The quantity of heat produced with the three 
 haloid acids increases as the atomic weight of 
 the halogen increases ; in this respect CdOjHj 
 is analogous to the corresponding compounds of 
 Hg and V\>, and differs from those of Ba, Ca, Sr, 
 and Mg. CdO^Hj loses H^O at 300° (H. Kose, 
 P. 20, 152) ; CdO is not hydrated by contact with 
 H2O ; according to the thermal values given by 
 Thomson (Th. 3, 285 ; and P. 143, 354 a. 497) the 
 reaction CdO + H^O = CdO^Hj would require the 
 expenditure of about 10,000 units of heat. 
 
 Cadmium, Iodide of. Cdl^. Mol. w. un- 
 known, but probably as represented by the 
 formula. [404°] (CarneUey, G. J. 33, 278). 
 (708°-719°, with decomposition) (CarneUey a. 
 
 '- 5-644, and 
 
 Williams, O. J. 37, 126). S.G. 
 4-626 (v. Preparation a. Properties). H.F. 
 [Cd,I^ = 48,830; [Cd,F,Aq] = 47,870 (Thomsen). 
 ■Vi=V<, (1 -h -000087480, t not greater than 40° 
 (Fizeau, C. B. 64, 314). S. (20°) 92-6; (60°) 
 107-6 ; (100°) 133-3 (Kremers, P. 103, 57 ; 104, 
 133 ; 111, 60). 
 
 Preparation and Properties. — 1. By heating 
 together Cd and I, in the ratio Cd:!^, in absence 
 of air. — 2. By digesting together Cd and I under 
 water (Stromeyer, S. 22, 362). — 3. By evapora- 
 ting a solution of 20 parts KI and 15 parts CdSOj 
 to dryness, dissolving in alcohol, and crystaUi- 
 sing (Vogel, N. B. P. 12, 893).— 4. By dissolving 
 CdCOj in HIAq, decolourising by addition of 
 clippings of Cd, and crystallising (Clarke, Am. 
 5, No. 4). — 5. By dissolving Cd in HIAq, evapo- 
 rating, and crystallising (Clarke, l.c.). Accord- 
 ing to Clarke (I.e.) Cdlj exists in two forms ; the 
 normal salt is white, is unchanged by heating 
 to 250°, and has S.G. 5-644 ; the other salt is 
 brownish, loses weight even at 40°, and has 
 S.G. 4-626. The conditions under which the 
 less stable salt is formed have not yet been 
 exactly determined ; Clarke obtained it twice, 
 by the action of HIAq on Cd and on CdCOj. 
 The S.G. of the less stable salt increases by 
 heating to 50° for some time. If the formula- 
 weight Cdlj is divided by the S.G., the results 
 are, for the stabler salt 64-8, and for the less 
 stable salt 79-2; now S.V.S. of Cd-l-S.V.S. of 
 L,-64-3 (Clarke, Z.C.). 
 
 Combinations. — 1. With ammonia to form 
 Cdl2.6NH3 and Cdl2.2NH3 ; obtained as the 
 corresponding CdCl^ compounds (q. v.) : both are 
 decomposed by H^O with ppn. of CdOjHj (Eam- 
 melsberg, P. 48, 153). — 2. With some metallia 
 iodides to form double salts ; Croft (/. pr. 68, 
 399) described CdI2.2KI.2H2O (aqueous solution 
 of this salt pps. most of the organic bases 
 from plants; Marm6, 2^. B. P. 16, 306); 
 
 Cdl2.2NH,I.2H20 ; CdI2.2NaI.6H2O ; 
 CdI2.BaI2.5H2O; and CdI2.SrI2.8H2O. Clarke 
 {Am. 5, No. 4) obtained Cdl2.3Hgl2 as gold- 
 coloured plates. 
 
 Cadmium, Oxide of. CdO. Mol. w. unknown. 
 S.G (amorphous) 6-95, (crystalline) 8-11 (Stro- 
 meyer, S. 22, 362; Werther, J. pr. 55, 118; 
 Schiiler, A. 87, 34 ; Sidot, 0. B. 69, 201 ; Fol- 
 lenius, J'r. 13, 279). H.F. [Cd,0] = 75,500 (cal- 
 culated from data given by Thomsen, Th. 3, 
 285 ; P. 143, 354 a. 497). 
 
 Preparation.^Ae a dark-brown, amorphous, 
 infusible, powder, by burning Cd in air or ; 
 or by strongly heating Cd02H2, or CdCOj. As 
 black-brown very small octahedra (or other 
 forms of the monometric system), by strongly 
 heating Cd.2NOs, or CdSO^ (Werther, i.e. ; Schti- 
 ler, l.c. ; Herapath, B. J. 3, 109). 
 
 Properties dc. — Eedueed to Cd by heating 
 with C. At red heat CI forms CdGlj. 
 Readily combines with CO2 forming CdCO.,. 
 Dissolves in aqueous acid with production of 
 Cd salts. Thomsen (P. 143, 354 a. 497) gives 
 the thermal values, [CdO,mSO'Aq] = 14,240 
 for crystalline CdO, and 14,510 for amorphous 
 CdO. 
 
 Marchaud (P. 38, 145) supposed that a 
 lower oxide than CdO was formed when CdCjOi 
 was heated ; but Vogel's experiments (/. 1855. 
 390) seem to prove that the substance was a 
 mixture, in varying proportions, of CdO and 
 Cd. 
 
 By the action of H202Aq (about 3 p.c. H^Oj) 
 on moist Cd02H2, Haas (B. 17, 2249) obtained 
 an oxide of Cd containing more than CdO. 
 Analyses gave results agreeing fairly with the 
 formula CdjO^, in one case with Cd,0,. These 
 results were confirmed by Bailey (G. J. 49, 484) 
 who obtained CdjOj by the action of HjOjAq on 
 CdSO^Aq followed by addition of NHaAq. The 
 pp. obtained by these methods may have been 
 a mixture, or possibly a loose compound, of 
 CdO and Cd02 {v. Haas, l.o. 2255). 
 
 Cadmium, Phosphides of. Cd and P are said 
 to combine when heated together to form a 
 grey, slightly metal-like, mass, which burns in 
 air to phosphates, and dissolves in HClAq with 
 evolution of PH3 (Stromeyer, S. 22, 362). 
 According to B. Eenault [G. B. .76, 283) when 
 P vapour is passed over hot Cd, two phosphides 
 are formed, CdjPj and CdjP. Oppenheim (B. 5, 
 979) describes CdjPj as a grey, metal-like, crys- 
 talline substance, produced by heating CdO 
 with KOHAq and P, and heating in H. 
 
 Cadmium, Salts of. Compounds obtained by 
 replacing the H of acids by Cd. The Cd salts 
 form one series CdX^, when X2 = Cl2, (NOjjj, 
 (0103)2, SOj, CO3, HPO3, &o. The V.D. of one 
 salt, CdBrj, has been determined ; from this 
 result, and from the similarities between the 
 salts of Cd and Zn, it is probable that the 
 gaseous molecules of the haloid Cd salts are 
 
O^SIUM. 
 
 667 
 
 oorreotly represented by the formula CdXj where 
 X = S', 01, Br, or I. The greater number of the 
 salts of Od are soluble in water ; the aqueous 
 solutions redden blue litmus paper; they are 
 poisonous. The haloid salts are not decom- 
 posed by heat ; salts of volatilisable acids give 
 CdO when strongly heated. Many Od salts are 
 isomorphous with corresponding salts of Zn ; 
 some, especially more complex double salts, are 
 isomorphous with corresponding salts of Mg, 
 Ni, Oo, and Zn. A great many double salts 
 containing OdXjIX = Cl.Br.I) are known; but 
 few basic salts of Od have been prepared. The 
 principal Od salts are borate; bromate ; car- 
 bonates; chlorate, perchlorate; ch/romate; 
 cyanates, &o. ; iodate, periodate ; molyhdate ; 
 nitrates, nibrites; phosphates, phosphite; sele- 
 nates, selenite ; su^hates, sulphite, &c. ; tung- 
 state ; vanadate : v. Borates, Carbonates, &o. 
 
 Gadmium, Selenide of. OdSe. Golden yellow, 
 metal-like, crystalline, mass; by heating Cd in 
 Se vapour; S.G. 8-79 (Stromeyer, S. 22,362). 
 The same body is said to be formed as a dark- 
 brown pp. by passing H2Se into solution of a 
 Cd salt (Vigier, Bl. 1861. 5 ; Eenault, C. B. 76, 
 283). 
 
 Cadmium, Silicofluoride of. OdSiFg. Long, 
 columnar, deliquescent crystals, obtained by 
 action of H^SiFsAq on CdO (Berzelius, P. 
 1, 26). 
 
 Cadmium, Sulphide of. CdS. Occurs native 
 in hexagonal prisms (a:c = 1"31257) as Qreen- 
 ocTtite. Obtained as an amorphous yellow solid, 
 by repeatedly heating to dull redness CdS04 in 
 HjS (v. Hauer, J. pr. 72, 338) ; by passing H^S 
 into a slightly acid solution of a Od salt ; by 
 heating Od with SO^Aq (Geitner, A. 87, 34; 
 Fordos a. G61is, A. 50, 260 ; Schweitzer, O. N. 
 23, 293). Obtained also in crystalline form by 
 fusing the amorphous CdS with KjCOj and S 
 (Schiller, A. 87, 34) ; by heating OdGl^ in H^S ; 
 or by melting together CdSO,, CaPj, and BaS 
 (Troost a. DeviUe, O. B. 52, 920). OdS is also 
 produced in crystals, but in small quantity, by 
 passing S vapour over strongly heated CdO, or 
 Cd (Follenius, Fr. 13, 411; Sidot, 0. B. 62, 
 999). Crystalline CdS is non-volatile at any 
 temperature ; it dissolves easily in boiling cone. 
 HClAq, or dilute H^SO^Aq (FoUenius, I.e.; 
 Hofmann, A. 115, 286) ; S.G. 4-5, when melted 
 4-6. Schiff {A. 115, 74) described CdS^ as a 
 yellow powder obtained by the action of KjSjAq 
 on a neutral Cd salt in solution ; according to 
 Follenius {Fr. 13, 411) this yellow solid is a 
 mixture of CdS and S. 
 
 Cadmium, Snlphocyanide of. 0d(0NS)2. Ob- 
 tained by action of HCNSAq on CdCOs; v. 
 stiLPHOCTANiDES, Under Cyanides. 
 
 Cadmium, Telluride of. CdTe. Black crys- 
 tals, S.G. 6-20, by heating Cd with Te, and 
 subliming the product in H (Margottet, C. B. 
 85, 1142). M. M. P. M. 
 
 CASMIUU ETHIDE OdEtj. Obtained in 
 impure condition from EtI and Cd. Takes fire 
 in air (Wanklyn, 0. J. 9, 193 ; Sonnenschein, 
 J. pr. 67, 169). 
 
 CMSIVTH. Cs. At. w. 132-7. [26°-27°] 
 (Setterberg, A. 211, 100). S.G. is." 1-88 (Setter- 
 berg, Z.c). S.V.S. 70-7. Discovered by Bunsen 
 and Kirchoff as chloride in the water of a 
 mineral spring at Diirkheim (P. 113, 342). 
 
 Vol. L 
 
 Name given because element characterised by 
 two sky-blue (ccesius) lines in the spectrum. 
 
 Occurrence.— l\ever free. Salts very widely 
 distributed, but in very small quantities, along 
 with Eb, chiefly as chloride and oxide ; in many 
 minerals and mineral waters, in sea water and 
 sea weed, in residues from saltpetre refining, 
 in ash of tobacco, tea, coffee, and oak wood, &o, 
 (v. especially Laspeyres, A. 134, 349 ; 138, 326 : 
 also Smith, Am. S. [2J 49, 335 ; Erdmann, J. pr, 
 86, 377 ; Grandeau, G. B. 53, 1100 ; Lonstadt, 
 a. N. 22, 25 a. 44). The rare mineral Pollux, 
 from Elba, according to analyses by Pisani, 
 contains 34 p.c. Cs oxide combined with sUioa, 
 and is free from Eb {A. 132, 31). 
 
 Preparation. —1. The mother liquor, obtained 
 by repeatedly evaporating the water of the mine- 
 ral spring at Nanheim, and separating from the 
 crystals which form, contains nearly J p.o. CsCl. 
 Fe, Al, and the alkaline earth metals, are 
 removed in the usual way ; the liquid is evapo- 
 rated, and heated to volatilise ammonium salts 
 added in the preceding processes ; the residue is 
 dissolved in water and the Cs and Eb are ppd. 
 as double chlorides of Cs, or Eb, and Pt, by 
 addition of PtCl^Aq. The pp. is boiled in 
 a very Utile water, and allowed to settle, the 
 water is poured off while stiU hot ; this process 
 is repeated about 20 times, when the pp. will 
 be quite free from E^PtClj and wUl consist of 
 CSjPtCls mixed with Eb^pPtOlj. The pp. is now 
 reduced in H, CsCl and EbCl are dissolved out 
 in boiling H^O (Bottger, J. pr. 91, 126). The 
 mixed chlorides are converted into sulphates, 
 these are dissolved in H^O, BaOAq is added, 
 BaSO, is removed by filtration, and the filtrate 
 is evaporated to dryness in a silver dish after 
 addition of (NHJ^CO,; the residue is dried, 
 dissolved in water, BaCOj removed by filtration, 
 and twice as much H2.C,H40e is added as is 
 required to neutralise the solution of Cs^OO, and 
 Eb^CO, ; the liquid is evaporated at 100° and 
 crystallised; the pp. consists of CsH.C^HjO, 
 mixed with EbH-C^HjO,,. As the latter salt 
 requires 8 times as much HjO as the former for 
 solution, the two salts may be completely 
 separated by fractional precipitation ; this pro- 
 cess is continued until the crystals of Oa 
 tartrate do not show a trace of Eb in the 
 spectroscope (Bunsen, P. 119, 1 ; Allen, P. M. 
 [4] 25, 189). By heating the tartrate, and 
 dissolving the residue in !l^SO,Aq, and crystal- 
 lising, CS2SO4 may be prepared ; this is dissolved 
 in HjO, decomposed by BaOAq, and the solution is 
 filtered andevaporated to dryness in a silver dish, 
 when CsOH is obtained. The CsOH is dissolved 
 in absolute alcohol, and dry HON is passed into 
 this solution : CsCN is thus obtained as a white 
 solid (Setterberg, A. 211, 100). A mixture of 4 
 parts OsCN and 1 part Ba(CN)2 is heated just to 
 melting in a porcelain crucible, and an electric 
 current from 2 or 3 Bunsen cells is passed into 
 the molten mass, in the manner described by 
 Bunsen (P. 155, 633). The contents of the 
 crucible are then warmed under petroleum when 
 the metallic Cs melts into globules (Setterberg, 
 A. 211, 100).— 2. The mixed chlorides of Cs and 
 Eb, obtained as in 1, are converted into sul- 
 phates, and then into alums by adding 
 Al23SOjAq and evaporating. Eb alum is 4 
 times more soluble than Cs alum ; Cs alum 
 
 U U 
 
668 
 
 C^SIUxM. 
 
 may be obtained quite free from Eb by a few 
 orystallisations. The Cs alum is dissolved in 
 hot HjO, and ppd. by NHjAq, the liquid is filtered 
 from AI2O3, evaporated to dryness in a Pt dish 
 and strongly heated to remove (NHJ2SO4; the 
 residue is dissolved in HjO, and BaCljAq is 
 added so long as a pp. of BaSO, forms ; the pp. 
 is filtered off, NHjAq and {NHj)2C03Aq are 
 added to the filtrate, the liquid is kept warm 
 for some time, and is then filtered from any 
 BaCOj which has formed; the filtrate is eva- 
 porated to dryness, and heated to fusion ; 
 solution in H^O, treatment with NHjAq and 
 (NHJjCOs, evaporation, and fusion are repeated ; 
 finally CsCl is obtained by dissolving the fused 
 mass in H^O, and crystallising (Godeffroy, 
 A. 181, 176; Eedtenbacher, /. ■pr. 95, 148). 
 This is converted into CsjSO, and then into 
 CsOH which is treated as described in 1. — 
 3. LepidoUte (a silicate of Al), from Hebron, in 
 Maine, U.S.A., contains about '4 p.o. Cs oxide 
 and -2 p.o. Bb oxide. The powdered mineral is 
 well mixed with 2 parts freshly slaked OaO, 
 and very strongly heated for some time; the 
 mass is powdered, half its weight of cone. 
 HjSOjAq is added, followed by water; the 
 whole is boiled, filtered, and evaporated to 
 dryness; the residue is dissolved in water, 
 filtered from OaSO, and evaporated until the 
 aluma of E, Cs, and Bb crystallise out. About 
 4 kilos, of the crude mixed alums was prepared 
 by Setterberg (A. 211, 100), and dissolved in hot 
 water, so that the solution had S.G. = 20° 
 Beaum6; this was cooled slowly to 45°, when 
 the Cs and Bb alums were deposited, as they 
 are insoluble in cold cone, potash alum solu- 
 tion. The alums were dissolved in a little hot 
 water and again cooled, and then solution and 
 crystallisation was continued until the crystals 
 were free from potash. Cs alum is 4 times less 
 soluble in H^G than Bb alum, and is insoluble 
 in a saturated solution of the latter ; the mixed 
 alums were dissolved in a little hot water, and 
 allowed to cool, when Cs alum separated with 
 a little Bb alum ; this process was repeated 
 until pure Cs alum was obtained. The alum 
 was dissolved in hot water, enough BaOAq 
 added to ppt. AljO, and aU the HjSO^, the 
 solution was filtered off and evaporated to 
 dryness : the CsOH thus obtained was dissolved 
 in absolute alcohol, and CsCN was prepared ; 
 the CsCN was then electrolysed as described 
 in 1. fPor other processes for preparing pure 
 salts of Cs V. Godeffroy, B. 7, 241 ; Cossa, B. 
 11, 812 ; Stolba, D. P. J. 197, 336 ; 198, 225 ; 
 Bharples, Am. Ch. 3, 453. Por an account of 
 attempts to prepare the metal by various 
 methods similar to those used for preparing Bb, 
 V. Smith, Am. Ch. 6, 106.) 
 
 Properties. — Silver white, soft, ductile, metal; 
 oxidises rapidly with production of heat and 
 light in air ; decomposes H^O at ordinary 
 temperature with inflammation of H produced. 
 Melts 26°-27° ; S.G. at 15° 1-88 (Setterberg, A. 
 211, 100). Spectrum characterised by two lines 
 in the blue, Cs„ = 4560, Cs/9 = 4597 ; -00005 mgm. 
 Cs may be detected by the spectroscope ; -003 
 CsCl may be detected in presence of 300-400 
 parts of KCl or NaCl; -001 CsOl in presence of 
 1500 LiCl (Bunsen, l.c.). The atomic weight of 
 Cs has been determined (1) by determination 
 
 of V.D. of CsCI, and analyses of the same salt; 
 by Bunsen (P. 113, 353 ; 119, 4), by Johnson 
 a. Allen {Am. S. 35, 94), and by Godeffroy 
 {A. 181, 185) ; (2) by comparing the reactions 
 of Cs compounds with compounds of Li, E, Na, 
 and Bb. One gaseous compound of Cs has been 
 obtained; the S.H. of the metal has not been 
 determined. Cs is positive to all other elements 
 (v. AlkaijI metals). 
 
 Combinations. — No compounds of Cs have as 
 yet been prepared directly from the metal. When 
 cone. CsClAq is electrolysed with Pt as the + , 
 and Hg as the — electrode, an amalgam of Cs 
 and Hg is formed, and solidifies to a white 
 crystalline mass ; the Cs in this amalgam very 
 quickly oxidises to CsOH. 
 
 Detection and Estimation.— Moet of the 
 salts of Cs are easily soluble in water. Cs salts 
 may be detected by the comparative insolubility 
 in HjO of CSjPtClj (v. Preparation, No. 1), and 
 by the spectroscope. There is no satisfactory 
 method for separating and estimating Cs salts ; 
 the pp. by PtCl, contains Eb^PtClj and a little 
 EjPtOl,; by repeating the ppn. the pp. may be 
 obtained almost free from EjPtCl,; the pp. is 
 then reduced in H, the CsGl and BbCl dis- 
 solved out, the liquid evaporated and the residue 
 weighed ; the CI is then estimated and the 
 quantity of CsCl is calculated. 
 
 Caesium chloride CsCl. Mol. w. 168'07 
 (Scott, Pr. E. 1888). For preparation v. C^sinu, 
 Preparation, No. 2. Small, white, cubes ; not 
 deUquesoent when pure ; partially decomposed 
 by melting in air, residue is alkaline. Melts at 
 low red heat, and volatilises at a higher tempera- 
 ture. Easily soluble in HjO and alcohol. CsCl 
 forms several, double compounds, insoluble in 
 cone. HClAq, with other metallic chlorides; they 
 are obtained by adding OsCl in cone. HClAq to a 
 solution of the other chloride also in cone. 
 HClAq. The following are known : 2CsCl.CdCl2, 
 2CsCl.HgCl^, 2CsCl.ZnClj, 2CsCI.CuClj, 
 2CsCl.MnCl2, 2CsCl.NiCl„ 2CsCl.PdCl„ 
 
 eCsCLFe^Olj, 6CsCl.BiCl3, ftCsCLSbCl,, 
 CsCLAuCls, 2CsCl.PtCl4 (Stolba, D. P. J. 198, 
 225 ; Godeffroy, B. 7, 375 ; 8, 9) ; 2CsCl.PtCl„ 
 S. (0°) -024, (100°) -377. When molten CsCl is 
 electrolysed in an atmosphere free from 0, a 
 small blue mass is obtained which is dissolved 
 by H2O with evolution of H ; probably this is 
 due to formation of a subohloride. 
 
 Caesium cyanide CsCN. Prepared by the 
 action of dry HON on CsOH dissolved in 
 absolute alcohol ; v. Cyanidbs. 
 
 Caesium hydroxide CsOH. Mol. w. unknown. 
 Prepared (as described under Ca:sinM, Pre- 
 pwration, No. 1) by decomposing CsuSOjAq by 
 BaOAq, filtering off BaSOj, and evaporating to 
 dryness in a silver dish. Grey -white solid, melt- 
 ing below redness ; undecomposed by heat; deli- 
 quesces in air, with production of much heat, to 
 form strongly alkaline CsOHAq. 
 
 Caesium oxide. An oxide of Cs baa not yet 
 been prepared. 
 
 Caesium, Salts of. Compounds obtained by 
 replacing H of acids by Cs. CsOHAq acts as a 
 very strong base. The salts belong to one 
 
 series CsX where X = C1, NO,, ^' 22s &o.; 
 
 the formulffl are established from the vapour 
 
CAFFEINE. 
 
 density of CsOl, (Soott, Pr. E. 1888), and 
 also by comparing the salts with those of the 
 other alkali metals. The salts of Cs are very 
 similar to those of Eh ; they are well marked, 
 stable, compounds ; no basic salts are known ; 
 so far as investigation has gone the Cs salts 
 show a marked tendency to form double salts. 
 Most of the salts of Ca are soluble in water; 
 the solutions are ppd. by PtCljAq (yellow), by 
 HyC,H,OsAq (white), by HClO^Aq (white), and 
 by sUicotungstio acid (white). The chief salts 
 are carbonates, nitrate, selenates, silicotungstate, 
 sulphates, tartrate (v. Oabbonates, &o.). 
 
 M. M. P. M. 
 
 CAFFElC ACID C,nfi^ i.e. 
 [4:3:1] CeH3(0H).,.CH:CH.C02H. Di-oxy-cin- 
 namic acid. Di-oxy-phenyl-acrylic acid. 
 
 Formation. — 1. By boiling caffetannic acid 
 with aqueous KOH (Hlasiwetz, A. 142, 221).— 
 2. From its acetyl derivative. — 3. Powdered 
 cuprea bark is extracted with ether followed by 
 alcohol.; the residue is boiled with aqueous 
 KOH, H2SO4 is added, and the liquid filtered 
 while hot. The filtrate, when cold, is exhausted 
 with ether, and the ethereal solution, after de- 
 colourising with animal charcoal, is set aside to 
 crystallise (G.Korner,P;i. [3] 13, 246).— 4. From 
 hemlock (in which it is combined with con- 
 hydrine?) (Hofmann, B. 17, 1922). 
 
 ProperUes. — Yellow monoclinio tables (con- 
 taining ^aq), v. e. sol. alcohol. The aqueous 
 solution is turned green by Fefil^, on adding 
 TXafiO, it then changes to blue and violet. It 
 does not reduce Fehling's solution but reduces 
 warm ammoniacal AgNO,. Its solution 10 
 KOHAq turns brown in air. 
 
 BeacUons. — 1. Dry distillaticm gives pyro- 
 cateohin. — 2. Potash fusion forms protooate- 
 chuio acid. — 3. Sodiwm amalgam reduces it to 
 di-oxy-phenyl-propionic acid. 
 
 Salt s.— CaA'j 3aq.— SrA'j 4aq.— BaA'^ 4aq. 
 Ba3(C,H50Jj 9aq.— Pb3(CgH5O02 2aq. 
 
 Mono-methyl derivative v. Ferulio 
 
 40ID. 
 
 Di-methyl derivative 
 C6H3(OMe)2.CH:CH.COjH. [180°]. Formed by 
 saponifying the ether or by heating caffeic or 
 ferulio acid with Mel and KOH. White needles. 
 Sol. alcohol and ether, nearly insol. water. On 
 oxidation with KMnO^ it produces veratrio acid. 
 Methyl ether A'Me. [64°]. Prisms. Pre- 
 pared by methylation of isoferulic acid (Tie- 
 mann a. Will, B. 11, 651; 14, 959). 
 
 Methylene ether 
 
 CH,<Q>C^3.CH:CH.C02H. [232°]. Formed 
 
 by boiling piperonal CHA^ObHs-CHO with 
 NaOAo and Ao^O (Lorenz, B. 13, 757). Minute 
 crystals (from dilute alcohol). Cone. HaSO, 
 forms a brick-red solution. — AgA'. 
 
 Acetyl-methyl derivative v. Acehii- 
 
 FEBULIO AOID. 
 
 Di-acetyl derivative 
 CA(0Ae)2CH:CH.C02H. [191°]. From caffeic 
 acid and AOjO or by heating protooatechuio alde- 
 hyde (2 pts.) with NaOAc (2 pts.) and Ac^O 
 (6 pts.). Slender needles. V. si. sol. water, v. 
 sol. alcohol and ether (Tiemann a. Nagai, B. 
 11, 659). 
 
 Hydro-cafEeic acid v. Di-oxs-phbnyii-pbo- 
 
 PIONIO ACID. 
 
 659 
 
 CAFFElDINE C,B.^^fl. Formed, together 
 with methylamine, COj, and NHj, by boiling caf- 
 feine with cone, baryta-water (Streoker, A. 123, 
 860 ; 157, 1 ; 0. B. 52, 1269 ; Schmidt, B. 14, 
 816; Schultzen, ^. 1867, 616). Alkaline liquid. 
 Sol. water, alcohol, and chloroform, si. sol. ether. 
 Long boiling with baryta-water gives methyl- 
 amido-acetic acid, formic acid, CO^, and NH,. 
 Chromic acid oxidises it to di-methyl-oxamide, 
 methylamine, CO^, andNHj, (Maly a. Andreasoh, 
 M. 4, 381). EtI forms C,H„EtN,0. 
 
 Salt s.— B'HCl.— B'^jPtCls 4aq. 
 
 CAFFElDINE CABBOXYLIC ACID 
 CjHijN^Oj. Prepared by the gradual solution of 
 caSeine in dilute KaOHAq; this solution is 
 neutralised with HOAo and the copper salt ppd. 
 with Cu(OAo)2 (Maly a. Andreasoh, M. 4, 369). 
 Very soluble crystalline mass ; its aqueous solu- 
 tion on boiling gives off CO^and leaves caffeidine. 
 
 Salt s.— KA' : golden syrup.— HgA'22HgCl, ; 
 bulkypp. — CuA'j: minute crystalUnegranules. — 
 CaA'^.- ZuAV— CdAV— MgA',. 
 
 CAFFEINE CjH.oN^Oj. Theine. [230-5°]. 
 S.G. iS 1-23. S. 1-35 at 16°; 45-6 at 65° (Com- 
 maille, 0. B. 81, 817). S. (alcohol) -61 at 16° ; 
 3-12 at 78°. S. (ether) -044 at 16°. S. (CSJ -06 
 at 16°. S. (chloroform) 13 at 16°. 
 
 Occurrence. — 1. In coffee berries and leave! 
 (Eunge, MateriaUen zur Phytologie, 1820; Sten- 
 house, P. M. [4] 7, 21 ; Pfaff a. Liebig, A. 1, 17). 
 Coffee berries contain from 1 to 1'28 p.c. caffeine ; 
 roasted coffee about 1'3 p.c. (Paul a. Cownley, 
 Ph. [3] 17, 565 ; cf. Stenhouse a. Campbell, C. J. 
 9, 33 ; A. 89, 246).— 2. In tea leaves (Oudry, 
 Mag. Pharm. 19, 49 ; Jobst, A. 25, 63 ; Mulder, 
 1>. 43, 160). Tea contains 2 to 4 p.c— 3. In 
 guarana, the dried pulp of Paulinia sorbilis 
 (Martins, A. 36, 93). Guarana contains about 
 5 p.c. of caffeine.^4. In Mat6 or Paraguay tea 
 the leaves and twigs of Ilex Paraguayensis (Sten- 
 house, P. M. [3] 23, 426).— 5. In the seeds of 
 the Kola tree {Cola acuminata) of West Central 
 Africa, to the amount of 2-13 p.c. of the dried 
 seed (Attfield, Ph. [2] 6, 457).- 6. Present to a 
 email extent in cocoa (E. Schmidt, A. 217, 306). 
 
 Formaticm. — By heating silver theobromine 
 with Mel for 20 hours at 160° : caffeine is thus 
 shown to be methyl-theobromine (Streoker, A. 
 118, 151 ; E. Schmidt, A. 217, 282). 
 
 Preparation. — 1. Tea or coffee is exhausted 
 with boiling water ; tannin is ppd. by lead sub- 
 acetate ; the filtrate is freed from lead by HjS 
 and evaporated to crystallisation (P^ligot, A. Ch. 
 [3] 11, 129).— 2. Eaw ground coffee (5 pts.) is 
 mixed with moist lime (2 pts.) and extracted 
 with alcohc'l, chloroform, or benzene, from which 
 the caffeine crystallises on evaporation (Vers- 
 mann, Ar. Ph. [2] 68, 148; Vogel, C. C. 
 1858, 367 ; Payen, A. Ch. [3] 26, 108 ; Paul a. 
 Cownley, Ph. [3] 17, 565).— 3. Tea or coffee is 
 boiled with water and either the whole, or else 
 the filtrate, is evaporated to a syrup, mixed with 
 slaked lime and extracted with chloroform 
 (Aubert, Pflilger's Archiv, 5, o89 ; Cazeneuve a. 
 Caillol, Bl [2] 27, 199).— 4. By sublimation 
 from tea (Heiynsius, 7. pr. 49, 317). — 5. A de- 
 coction of tea is evaporated with PbO to a syrup, 
 KJCO3 is added, and caffeine extracted by alcohol 
 (Grosschoff, /. 1866, 470). 
 
 ProperUes. — Mass of slender silky needles 
 (containing aq) ; begins to sublime at 79° 
 
 nD2 
 
660 
 
 caffeTne. 
 
 (Blyth). SI. Bol. cold water and alcohol, v. si. 
 8ol. ether. The oiystals from alcohol and ether 
 are anhydrous. Weak base; the salts being 
 decomposed by water; does not aSect red 
 litmus. Tastes bitter. Produces tetanus and 
 rigor in the voluntary niusoles of frogs (Aubert ; 
 Brunton a. Cash, Pr. 42, 238). In men it in- 
 creases the heart's action, excites the nervous 
 system, and diminishes metabolism (?) (Leh- 
 mann, A. 87, 205). Caffeine gives a yellow pp. 
 with phosphomolybdio acid. 
 
 Estimation.— The various methods of pre- 
 paration may also be used for estimation 
 (Stenhonse, A. 102, 126; Lieventhal, C. G. 
 1872, 631; Weyriok. Fr. 12, 104; P^ligot, Bep. 
 Pharm. 82, 340 ; Ciaus, J. 1863, 708, Zoller, /. 
 1871, 818 ; Mulder, J. pr. 15, 280 ; Oommaille, 
 Bl. [2] 25, 261; Paul a. Cownley, Ph. [3] 
 17, 565). 
 
 Colour Test. — Evaporate with chlorine- water 
 on platinum-foil. A yellowish residue is left, 
 which on further heating becomes red, and is 
 turned purple by ammonia (Schwarzenbach, J. 
 1861, 871; 1865, 780). Xanthine, theobromine 
 and uric acid also give this test. Cafieine 
 evaporated with cone. HNO3 gives a yellow 
 residue (amalic acid) which is also turned purple 
 (murexide) by ammonia (Boohleder, A. 69, 120). 
 
 Eeactiohs. — 1. Gaseous chlorine or HCl and 
 KCIO3 give in the first place di-methyl-alloxan 
 and methyl-urea (E. Fischer, A. 215, 257): 
 C,H,<,N,02 + O2 + 2H2O = CeH,N A + C^H^N^O. 
 Fart of the di-methyl-alloxan becomes amalio 
 acid. Chloro-caffeiLne,methy1amine, and cyano- 
 gen chloride are also formed, and, if the reaction 
 is prolonged, di-methyl-parabanio acid (choles- 
 trophane). Bromine and water at 100° act 
 similarly (Maly a. Hinterberger, M. 3, 85).— 2. 
 Cold HNO3 attacks it slowly, giving off COj 
 (1 vol.) and NjO (about 2 vols.) (Franchimont, 
 B. T. C. 6, 223).— 3. Hot dilute HNO3 gives di- 
 methyl-parabanio acid (Stenhouse, A. 45, 366 ; 
 46, 227; Eochleder, A. 69, 120; 71, 1).— 3. 
 Chromic acid gives di methyl-parabanio acid, 
 NH3, methylamine, and COj (Maly a. Hinter- 
 berger, M. 2, 87). — 4. Boihng baryta water ST^litB 
 up caffeine into caSeidine and CO, ; the caffei- 
 dine then breaks up into CO,, NH3, methylamine, 
 formic acid, and methyl-amido-acetio acid 
 (sarcosine) (Eosengarten a. Strecker, A. 157, 1). 
 5. With cone. HCl at 250° it forms ammonia, 
 methylamine, sarcosine, formic acid and CO, 
 (B. Schmidt, A. 217, 270). The volume of NH3 
 is to that of NMeH, as 1:2. Below 200°, HCl 
 has no action. Hence there are three NMe 
 groups in caffeine, CjHijN^O, + 6H,0 = 
 2C0, -I- 2NMeH, + NH3 + CH,0, + CjHjNO,. 
 
 Salts.— (E. Schmidt, A. 217, 282; Herzog, 
 A. 26, 344; 29, 171 ; Biedermann, Ar. Ph. [3] 
 21, 175 ; Tilden, 0. J. 18, 99 ; 19, 145.) 
 B'HCl. — ^B'HCl 2aq : monoclinio ; decomposed 
 by moist air into HCl and caffeine. — B'2HC1. — 
 B'4HC1.— B'^jPtCl, (at 100°).-B'HAuCl4 2aq: 
 glittering plates.— B'HBr 2aq.— B'HI.— B'2HI. 
 — B'Hl, liaq (Tilden). — B'HCICU; : [175°] ; 
 yellow needles converted by NH3 into a greenish- 
 black pp. (Tilden, Z. 1866, 350 ; Ostermayer, B. 
 18,2298).— B'HNOjaq.—B'H^SO^.-B'HjSO^aq. 
 
 Formate B'HjCO,.- Acetate B'2HOAo.— 
 ButyrateB'C.H80j.— IsovalerateB'CsHioOj. 
 — Citrate: prepared by adding a solution of 
 
 citric acid (1 pt.) in alcohol (7^ pts.) tc one of 
 caffeine (Ipt.) in chloroform (14ipts.) and evapo- 
 rating. Semi-crystalline powder, decomposed 
 by most solvents (Lloyd, Ph. [3] 11, 760). 
 According to Tanret (/. Ph. [6] 5, 591) the last 
 five salts are merely mixtures. — Oaffeate 
 B'CjHjOj 2aq (Hlasiwetz, A. 142, 226). 
 
 Combinations. — B'HgCl, (Nicholson, A. 62, 
 78; Hinterberger, A. 82, 316).— B'HgOyj (Kohl 
 a. Swoboda, A. 83, 841).— B'AgNO,. 
 
 Methylo - chloride B'MeCl aq. At 
 200° it splits up into MeCl and caffeine. — 
 (B'MeCy^PtCli. Sparingly soluble. 
 
 Methylo-iodide B'Melaq (Tilden, J. pr. 
 94, 874; E. Schmidt, A 217, 286; E. Schmitt 
 a. E. Schilling, A. 228, 141). From caffeine and 
 Mel at 130°. At 100° it loses aq, at 190° it 
 splits up into caffeine and Mel. TricUnio: 
 a:6:n = -6962:l:-4161; a = 91°24'; /3 = 74°; y = 88°. 
 — B'Mel3. 
 
 Methylo-hydroxideB'MeOBAq [91°], and 
 B'MeOH [138°]. From the methyloiodide and 
 Ag,0 (Schmitt a. SchiUing, A. 228, 143). 
 Crystals. V. sol. water, alcohol, and chloroform. 
 V. si. sol. ether or light petroleum. Its solutions 
 are neutral. It is not poisonous. Heated at 
 200° in the dry state it gives off methylamine 
 while caffeine is also formed. HCl or dilute 
 H^SO, convert only part of it into the corre- 
 sponding salt, the rest gives methylamine, 
 formic acid and dimethyldialuric acid, the 
 latter being converted by atmospheric oxygen 
 into amalic acid. When HCl is used, caffeine 
 methyloehloiide is one of the products. With 
 water at 200° it gives sarcosine, methylamine, 
 formic acid, and CO,. Chromic acid forms cho- 
 lestrophane, methylamine, formic acid and CO,. 
 
 Ethylo-triiodide B'Etl,. From caffeine 
 and Btl at 130° (Tilden, O. J. 18, 99 ; 19, 145).— 
 B',Et,PtCl5. 
 
 Chloro-caffeine CgHaClN^O,. [188°]. Formed 
 by passing chlorine into dry caffeine in dry CHCl,. 
 Crystallised from water. V. si. sol. cold water 
 and ether, v. sol. strong acids but ppd. by water. 
 Bednced to caffeine by zinc-dust and HCl 
 (Fischer, A. 215, 262; 221, 836). 
 
 Bromo-caffeine v. p. 561. 
 
 Amido-caffeme C8Hj(NH,)N40,. [above 360°]. 
 From bromo-caf!feine (2 pts.) and alcoholic NH, 
 (20 pts.) by heating for 7 hours at 130° (Fischer, 
 A. 215, 265). Slender needles ; may be distilled. 
 V. si. sol. water and alcohol ; sol. cone. HOAo ; 
 sol. cone. HClAq, but reppd. by water, being 
 apparently less basic than caffeine. 
 
 Oxy-caffeine 08H5(0H)N,02- [o- 345°]- Frpm 
 ethoxy-caffeine by heating with dilute HCl 
 (Fischer, A. 215, 268). Mass of white needles 
 (from water). V. si. sol. alcohol, ether, or cold 
 water. Sol. cone. HCl but reppd. by water. 
 Oxy-caffeine is an acid. — NaA' 3aq. Needles. — 
 BaA', 3aq. Beactions. — 1. The silver salt with 
 EtI at 100° gives ethoxy-caffeine.— 2. PClj in 
 POCI3 gives chloro-caffeine. — 3. CI at a high 
 temperature gives di-methyl-alloxan. — 4. CI gas 
 at 0° in a solution of oxy-caffeine in HCl gives 
 apo- and hypo-oaffeine. — 5. Dry bromine forms 
 an addition compound CgHB(0H)N40,Br,(?) as a 
 red mass, decomposed by water or alcohol, the 
 latter giving diethoxy-oxy-caffeine dihydride. 
 
 Ethoxy - caffeine CgH,(0Et)N,02. [140°]. 
 From bromo-caffeine and alcoholic KOH (Fig. 
 
CAFFEINE. 
 
 661 
 
 oher, A. 215, 266}. White needles (from water). 
 SI. sol. cold alcohol or ether, v. e. sol. hot alco- 
 hol. Melts in boiling water, partly dissolving. 
 Sol. dilute HCl and reppd. by KOH. 
 
 Di-methoxy-oxy-caffeine dihydride 
 C^sNA(OMe)jOH. [179°]. Prepared by the 
 action of methyl alcohol on oxy-oaffeine bromide. 
 Colourless crystals. Sol. water and alcohol. 
 By HCl it is decomposed into methyl alcohol, 
 methylamine and apo-caffeine (Fischer, B. 14, 
 642). V.I 
 
 Di-ethoxy-oxy-caffe'ine dihydride 
 C^5(OEt)2(OH)N^Oj Di-ethyl derivative of tn- 
 oxy-caffeine dihydride. [195°-205°]. From oxy- 
 oaffeine, Br, and alcohol, as above. Warmed 
 with HCl it gives alcohol, methylamine, apo- 
 oafleiine, and hypo-caffeine. Fuming HI or HI 
 gas passed into chloroform solution reduces it 
 to oxy-caffeine. With phosphorm oxychloride 
 it forms a crystalline substance that appears to 
 be CsH,N,02(0H)(0Et)Cl. This body is recon- 
 verted by alcohol into diethoxy-oxy-caffeine di- 
 hydride, but it is decomposed by water, one of 
 the products being di-methyl-alloxan, although 
 this is not formed from ^ethoxy-oxy-cafieine 
 dihydride by water or acids (Fischer a. Eeese, A. 
 S21, 387). 
 
 AUo-caffeine CsHaNsOs. [198°]. A by-pro- 
 duct obtained in the preparation of the preced- 
 ing body from oxy-oaffeine, bromine and alco- 
 hol, especially when the latter is wet (92 p.c). 
 Sandy powder. V. si. sol. water, si. sol. boiling 
 alcohol. Decomposed by boiling HCl (Fischer, 
 A. 215, 276). 
 
 Apo-caffeine C,H,Nj05. [148°]. 
 
 formation. — 1. From di-ethoxy-oxy-oaffeine 
 dihydride (5 g.) by evaporating with (20 g.) di- 
 lute (20 p.c.) HCl at 100° (Fischer, A. 215, 277) ; 
 the equation is: CaHa(OH)N<Oj(OEt)j+2H20 
 = 0,H,Ns05-HMeNHj + 2HOEt.— 2. From oxy- 
 caffeine and aqueous 01 at —10°. — 3. From 
 caffeine, HCl and KCIO, (Maly a. Andreasch, M. 
 3, 100). 
 
 Properties. — Monoclinio crystals (from 
 water). o:6:c = -8025:1: -6976. V. sol. hot water, 
 alcohol or chloroform, si. sol. cold water, benz- 
 ene or CSj. Boiling water decomposes it into 
 COj, hypo-caffeine and caff uric acid (j. v.). 
 
 Hypo-caffeine CsH^NsOa. [182°]. 
 
 Formaticm. — 1. Formed along with_ apo- 
 caffeine by warming the di-ethyl derivative of 
 tri-oxy-oafteine dihydride with hydrochloric 
 acid, thus: 0,H,(0H)NA(0Et)2 -i- 2H,0 = 
 OjE^NaOs + 2H0Et + NHjMe -i- CO^. — 2. From 
 oxy-oaffeine, HCl and CI (Fischer, A. 215, 288). 
 
 Properties. — Crystallised from water. V. 
 sol. hot water or alcohol, si. sol. cold water. 
 May be distilled with but sUght decomposition. 
 Ba(C.H,N,03)AH,N30,: v. sol. water. 
 
 Beactions. — Not affected by boiling fuming 
 HNO3, chlorine- or bromine-water, K^Cr^O, and 
 dilute HoSO,, HMnO„ cone. HCl, fuming HI, 
 Sn and HCl, Ac^O or POCI3 and PCI5. Water at 
 150° completely destroys it. Boiled with baryta 
 it gives oaffolin (g. v.). 
 
 Caffolin CsH,N,Oj. [194°-196°]. Formed by 
 boiling hypo-caffeine with lead sub - acetate 
 (Fischer, A. 215, 292). Slender needles (from 
 alcohol) or long prisms (from warm water). 
 V. e. sol. warm water. SI. sol. alcohol. Does 
 not combine with acids. It is but a feeble 
 
 acid, for its barium compound is decomposed by 
 COj. Boiled with AgjO, it forms a crystalline 
 silver compound. 
 
 Beactions. — 1. Cone. HCl at 100° splits it up 
 into CO2, NH3, NMeHj &o.— 2. Cone. HI forms 
 methyl-urea.— 3. KjFeCyj gives methyl-oxamio 
 acid and methyl-urea: CsHjN302 + + H20 = 
 MeNH.CO.CO.;a-(-MeNH.00.NH2. — 4. KMnO. 
 and EOH give di-methyl-oxamide and ammonia 
 according to the reaction: OsHgNjOj-l-O-HHjO 
 = MeNH.CO.CO.NHMe + CO^ + NH,.— 0. Potas- 
 sium bichromate and H^SOfgive cholestrophane : 
 C5H3N3O2-1-O = CsHaN.Oj + NH,. — 6. Nitrous 
 acid completely destroys it. — 7. Boiled with 
 ACjO it forms the acetyl derivative of acecaffin 
 OaH.oAoNaO,. 
 
 Aeecaffin CsHiiNaOj. [110°-112°]. From its 
 acetyl derivative by evaporating with fuming 
 HCl at 100° and decomposing the resulting 
 hydrochloride by Ag^O (Fischer, A. 215, 800). 
 Trimetric crystals (from benzene). a:b:c = 
 ■6707:1:1'2445. May be distilled undeoomposed. 
 V. e. sol. water and alcohol. 
 
 Acetyl derivative 
 CeHioAcNaOj. [106°-107°]. From caffolin by 
 boiling with Ao^O as long as COj comes off 
 (12 hours). Monoclinie tables (from chloroform 
 mixed wdth ether). 
 
 Caffuric acid CjHsNsO,. [210°-220°]. From 
 apo-caffeine by boiling water (Fischer, A. 215, 
 280). C,H,N,03 + HjO = CjH,N30,H-C02. Trans- 
 parent tables (from alcohol). V. sol. water, si, 
 sol. cold alcohol, chloroform or ether. Feeble 
 acid, its barium salt being decomposed by COj. 
 
 Salt. — AgA'. Tables, si. sol. water. 
 
 Beactions. — 1. Not affected by chlorine- or 
 bromine-water, — 2. HI converts it into hydro- 
 caffurio acid. — 3. Warmed with lead sub-acetate 
 it gives mesoxalic aeid, methyl-urea and methyl- 
 amine.— 4. Hot KOH gives off NH^Me. 
 
 Hydro-caffurio aeid OSH5N3O3. [240°-248°]. 
 From caffuric acid, fuming HI and PH^I 
 (Fischer, A. 215, 285). Colourless prisms (from 
 water). V. sol. hot water, si. sol. cold water. 
 
 Beactions. — 1. Gives no pp. when boiled with 
 lead sub-acetate (unlike caffuric acid). — 2. Gives 
 with ammoniacal AgNOj a mirror in the cold. — 
 4. Chlorine-water oxidises it to caffuric acid. — 
 3. Hot KOH gives off methylamine. — 5. Warmed 
 with baryta it forms methylamine and methyl- 
 hydantoin carboxylio acid, the latter splitting up 
 into CO2 and methyl-hydautoin. 
 
 Methyl-caffuric acid C,H„N30j. [167°]. From 
 allocafleine by boiling with water (Schmidt a. 
 Schilling, A. 228, 172). Needles (from water). 
 y. sol. water, alcohol, and chloroform. Basio 
 lead acetate converts it into mesoxalio acid, 
 methylamine and dimethyl urea. 
 
 Amalic acid v. p. 149. 
 
 Constitution of Caffeine. — Medious {A. 175, 
 MeN-CO 
 
 250) proposed the formula CO C— NMe 
 
 I II >CH 
 MeN— C— N 
 while Emil Fischer [A. 215, 314) proposed 
 Me.N-CH 
 
 I II 
 
 COO.NCH, . Both formulas readily re- 
 I I >co 
 Me.N— 0-N 
 
662 
 
 CAFFEINE. 
 
 present the formation by oxidation of di-methyl- 
 alloxan and methyl urea. According to Fischer's 
 formula the derivatives of caffeine would be re- 
 presented as follows • Oxy-caffe'ine would be 
 vNMe— C(OH) = C - NMe 
 1/^ I 
 
 CO 
 
 ^NMe 
 
 I >C0. Ethoxy-oxy- 
 
 -C = N 
 
 caffeine dihydride would be 
 
 .NMe— C(OH)(OBt)— C(OEt).NMe 
 C0<^ 
 
 \NMe 
 
 =N 
 
 >C0. Apo- 
 
 co< 
 
 oaffeine would be 
 
 >0 C(CO,H)— NMe 
 
 )< \ >C0. 
 
 \NMe — N 
 
 Caffurio acid would be 
 
 HO.C(CO.H)— NMe 
 < >C0 
 
 HNMe— 0-=^=N 
 Hydro-caffuric acid might be written : 
 HC(CO,H)— NMe 
 \ >C0. 
 
 HMeN— N 
 
 Methyl-hydantom earboxylic acid would be 
 HC(CO»H) . NMe 
 I >C0; 
 
 CO NH 
 
 HjCNMe 
 whence methyl-hydantoin | >C0. 
 CO.NH 
 Hypo-oafleme may be 
 0— OH— NMe 
 CO^ \ >C0, so that apo-caffe'ine 
 
 \NMe— = N 
 would be its earboxylic acid. Caffolin may then be 
 HO.CH.NMe 
 
 I >C0 ; but the formation of oholestro- 
 HNMeC = N 
 
 .00 — NMe 
 K I from it is in that case 
 
 '^NMe— CO 
 somewhat anomalous. 
 Strecker'fl cafteiidine (from caffeine by alkalis) 
 
 MeHN.OH=C-NMe 
 would be I >C0 , which by 
 
 MeHNC = N 
 boiling alkalis gives OO2, NHj, 2NMeH2, formic 
 acid and sarcosine. 
 
 MeN— CH 
 
 phane C0<^ 
 
 Theobromine will be 
 
 CO 
 
 NMe , 
 
 I I >co 
 
 HN-C=N 
 HN— OH 
 
 . I II 
 not CO C — NMe as is shown by the 
 I J >C0 
 MeN— = N 
 formation of hypo-ethyl-theobromine. 
 
 Somewhat similar formula are arrived at if 
 we start from the formula of Medicus. Inasmuch 
 as oaffeinmethylo-hydroxide differs from cafieine 
 in giving no NH, but only NMeHj in its decom- 
 positions, we must assume that it has the formula 
 MeN— CO 
 
 CO O— NMe V 
 
 I II >CH 
 
 M«N— 0— NMe(OH)'^ 
 
 MeN— CH 
 
 I II 
 or CO C— NMe- 
 
 CO 
 
 MeN— C— NMe(OH)'' 
 Its decomposition-product, di-methyl-dialurio 
 acid, should, according to Maly a. Hinterberger 
 {M. 3, 85), be represented by the formula 
 MeN— CO 
 
 CO CH(OH), which agrees better with the for- 
 
 MeN— CO 
 
 mula of Medicus. On the otherhand, the frequent 
 occurrence of methyl-urea as well as s-di-methyl 
 urea amongthedecomposition-products of caffeine 
 and its derivatives accords best with Fischer's 
 formula (Schmidt a. Schilling, A. 228, 174). 
 
 CAFFEOL CjH.oOj. (196°). Given off (to 
 the extent of -05 p.o.) on roasting coffee together 
 with oaHeine ('18 p.o.), palmitic acid, acetic 
 acid, COj, and traces pyrrol, methylamine, and 
 hydroquinone. It is extracted by ether from 
 the liquid distillate (Bernheimer, M. 1, 459). 
 Liquid, smelling like coffee, si. sol. hot water, 
 V. e. sol. alcohol and ether; v. si. sol. cone. 
 KOHAq. FezCl, colours its alcoholic solution 
 red. Potash-fusion gives salicylic acid. It is 
 perhaps a methyl derivative of o-oxy-benzyl 
 alcohol. 
 
 CAFFETANNIC ACID CisHijOj. Occurs in 
 coffee berries to the amount of 3 to 6 p.o. as Ca 
 and Mg salt, and perhaps also as a double salt 
 of K and caffeine (Pfaff, (1830) Soher. 61, 487 ; 
 Eochleder, A. 59, 300 ; 63, 193 ; 66, 35 ; 82, 
 196; Liebich, A. 71, 57; Payen, A. Ch. [3] 
 26, 108). Prepared by mixing an alcoholic in- 
 fusion of coffee with water ; filtering from ppd. 
 fatty matter ; boiling the filtrate, and ppg. as 
 lead salt by Pb(0Ac)2. Colourless mammellated 
 crystalline groups, v. sol. water, m. sol. alcohol ; 
 has an astringent taste ; strongly reddens lit- 
 mus. FejCl,, colours its solutions green. It 
 does not ppt. ferrous salts, tartar-emetic, or 
 gelatin, but it ppts. quinine and oinohonine. 
 It reduces AgNOjAq, forming a mirror. Its 
 salts turn green in air. Potash-fusion gives 
 protocatechnic acid. Boiling cone. KOHAq 
 splits it up into caffeic acid and a sugar (Hlasi- 
 wetz, A. 142, 220). 
 
 Salts. — BaA'2 (at 100°): amorphous, v. 
 sol. water; addition of baryta forms a yellow 
 pp.-PbC„H„Os.-Pb3(C,5H,50,)2.-Pb2C„H„0. 
 (at 100°). 
 
 Viridio acid. An acid formed by the at- 
 mospheric oxidation of an ammoniacal solution 
 of cafietanuic acid. According to Bochleder the 
 green colour of coffee berries is due to calcium 
 viridate. It is ppd. by Pb(0Ac)2. Amorphous 
 brown mass, v. sol. water. Cone. HjSO, forms 
 a crimson solution whence water gives a floccu- 
 lent blue pp. The aqueous solutions are turned 
 green by alkalis, and give a bluish-green pp. 
 with baryta-water (c/. Vlaanderen a, Mulder, J, 
 1858, 261). 
 
 CAFFOLIIT V. Caiteine. 
 
 CAFFUBIC ACID ». Cafpeinb. 
 
 CAIL-CEDRIN. a bitter, neutral, resinous 
 substance present to a minute extent in the 
 bark of the OaU-cedra (Caventou, /. Ph. [3] 
 16, S55; 33,123). 
 
OALOIUM. 
 
 663 
 
 CAlNClN C„H„0„. 
 
 ~ ., - „- Cdiyicie acid. S. -14. 
 h ound m Caluoa root (from Chiococca anguif-uga 
 aniracemosa) {Prangois, PeUetier, a. Caventou, 
 J. Ph- 16, 465; Liebig, A. Ch. [2] 47, 185; 
 Koclileder a. Hlasiwetz, A. 76, 338 ; KooUeder, 
 J. W-S5, 275). The root ia exhausted with 
 alcohol and the cainom ppd. either by tYiillf of 
 Ume or Pb(OAo)j. Crystalline flakes, tasteless 
 at first, afterwards very bitter ; v. si. sol. water 
 and ether, v. sol. aloohol; reddens litmus. 
 Boiling alcoholic HOI splits it up into a sugar 
 (CsHijOj) and crystalline oainoetin O^^^fl,. 
 Cainoetin is resolved by potash-fusion into 
 butyric acid and cainoigenin CnH^^O^ which 
 is possibly related to sesoigenin. Caincin in 
 dilute alcoholio solution is converted by sodium- 
 amalgam into crystalline CssHjsOis whence 
 fuming HCl forms gelatinous G^sS^fi^. 
 
 CAJEPUT, OIL OF. A Ught green oil pre- 
 pared in India by distilling the leaves of Mela- 
 leuca leucodendron with water. Its chief con- 
 stituent is oineol 0,„H,gO (g. v.), which is also 
 called oajeputol. Pfii converts it into ter- 
 penes {g[.v.) which when so obtained may be 
 called oajeputenes (Schmidt, O. J. 14, 63; 
 Wright a. Lambert, G. J. 27,619; Histed, Ph. 
 [3] 2, 804; Blanchet, A. 7, 161; Gladstone, 
 C. J. 49, 621). 
 
 CALAMUS HOOT. According to Geuther 
 (A. 240, 92) the aoorin prepared by Thoms 
 (p. 60) from Acorus calamus is not a definite 
 substance, but is aepara,ted by alkalis into a 
 neutral amorphous brown mass (Ci„H„NO, ?) 
 and ail acid (0„H,80a ?). Calamus root after 
 extraction with water still contains a combined 
 acid (CuHijO^ ?) which may be extracted by 
 adding HCl and shaking with ether. When the 
 root is distilled with steam, methyl alcohol 
 and a mixture of terpenes (g. v.) and a compound 
 C|„H,jO{?) is obtained (G. ; Sohuedermann, A. 
 41, 374 ; Kurbatow, B. 6, 1210 ; Gladstone, C. J. 
 17, 1). 
 
 CAICIUM. Ca. At.w.39-91. Mol.w. unknown. 
 Melts at red heat. S.G. 1-57 (Matthiessen, A. 
 93, 27). S.H. (0=-100°) -1686 (Bunsen, P. 141, 
 1). S.V.S. abt. 25. E.C. (Hg at 0" = 1)12-5 
 (Matthiessen, P. M. [4] 12, 199; 13, 81). Chief 
 lines in emission-spectrum, 6121*2, 5587*6, 
 4226*8, 3968, 3932*8. 
 
 Occvm'ence. — Never free. Very widely dis- 
 tributed, and often in large quantities, as 
 silicate, phosphate, sulphate, carbonate, flu- 
 oride, &a. Most natural waters contain Ca 
 salts; phosphate and carbonate of Ca are 
 found in plants and animals. Ca salts occur 
 in the sun, fixed stars, and meteorites. Calcium 
 carbonate and burnt lime have been known 
 from very ancient times. In 1722 Pr. Hoff- 
 mann showed that lime is a distinct earth ; 
 Black (1756) was the first to make a quantita- 
 tive examination of limestone and burnt lime. 
 In 1808 Davy obtained calcium (impure) by the 
 electrolysis of lime. 
 
 Formation. — 1. Dry Calj is heated with Na 
 in an iron crucible with an air-tight cover 
 (Lifis-Bodart a. Jobin, A. Ch. [3] 64, 363; 
 Dumas, C. B. 47, 575 ; Sonstadt, C. N. 9, 140).— 
 2. Dry fused CaOl, (300 parts), Na (100 parts), 
 and pure distilled granulated Zu (400 parts), 
 aie heated in a crucible with loosely fitting lid, 
 as high s temperature being maintained as is 
 
 possible without volatilisation of much Zn ; an 
 alloy of Ca and Zn is thus produced (Zn,2Ca 
 according to v. Eath, P. 136, 434). This alloy 
 is heated in a crucible of gas coke until the 
 Zn is all distilled off (Caron, G. B. 48, 450 ; 
 50, 547). — 3. A boiling cone, solution of CaClj 
 is electrolysed, using an amalgamated Pt wire as 
 negative electrode (Bunsen, A. 92, 248). 
 
 Pre;paration. — ^A mixture of dry OaClu and 
 SrCLj, in the ratio 2CaCl2:SrCl2, mixed with a 
 little NH^Ol, is melted in an open crucible ; the 
 current from 3 or 4 Bunsen cells is passed 
 through the molten mass, the positive electrode 
 being a stick of carbon, and the negative an 
 iron wire as thick as a knitting needle, drawn 
 out to a fine point. The point of the iron wire 
 is kept just under the surface of the molten 
 mass for a minute or so at a time ; the Ca 
 separates in small lumps (Matthiessen, A. 93, 
 277; 94, 108). Prey obtained lumps of Ca 
 weighing from 2^ to 4 grams (A. 183, 367) ; he 
 passed the negative electrode through the stem 
 of a tobacco pipe with the bowl dipping under 
 the molten mass in the crucible ; H was then 
 passed into the pipe ; when the pipe and bowl 
 were filled with this gas, the H was stopped, 
 and the current was started ; the Ca rose into 
 the bowl of the pipe, and being in contact with 
 H remained quite unoxidised. 
 
 Properties. — ^Lustrous, clear yellowish-white, 
 very ductile, but brittle when hammered out, 
 malleable ; about as hard as calcspar. Prey 
 (A. 183, 367) says it is brittle and caimot be 
 hammered oat or drawn into wire. Melts at full 
 red heat, and then bums with yellow fiame and 
 production of much heat and light ; [Ca, 0] = 
 180,930 (Th. 3, 251). Does not oxidise in dry 
 air ; but in ordinary air is quickly covered with 
 CaO. Not volatilised at temperature of inflam- 
 mation (Caron, 0. B. 48, 440). Decomposes 
 cold HjO rapidly; 
 
 [Ca, Aq] = [Ca, 0^ H^ Aq] - 2[H^ 0] = 80,900 
 {Th. 3, 251). As no compound of Ca has been 
 gasified, the value to be given to the atomic 
 weight of the metal is decided partly by the 
 S.H. and partly by purely chemical considera- 
 tions. The mass of Ca that combines with 
 15*96 (i.e. with 1 atom) is 39*91, hence the 
 simplest formula for the oxide is CaO 
 (Ca = 39*91) ; the same mass sf Ca combines 
 with 2 X 35*37 CI, 2 x 79*75 Br, &c. ; the simplest 
 formulae for the chloride and bromide are there- 
 fore CaClj and CaBr, respectively (Ca = 39*91). 
 These formulsa are in keeping with the reac- 
 tions of the compounds, hence they are adopted. 
 The chief compounds of Ca by analyses ot 
 which the value Ca = 39*91 has been found are : 
 (1) CaClj (Berzelius, G. A. 57, 451 ; Dumas, 
 A. Ch. [3] 55, 190) ; (2) CaCO, converted into 
 CaO (Dumas, C. B. 14, 537; Erdmann a. 
 Marchand, J. pr. 26, 472). Ca is a strongly 
 positive metal, forming well-marked and stable 
 salts by replacing the H of acids. Salts of Ca 
 derived from ahnost every acid are known ; 
 several of these form doable salts; very few 
 basic salts are known. CaOgHj is an alkaline 
 hydroxide ; CaO combines with HjO with pro- 
 duction of much heat; CaO^H, is dehydrated 
 to GaO at a high temperature. [CaO, E'O] 
 " 16,640 (Th. 3, 251). The heat of neutralisation 
 of CaOjHjAq is the same aa that ot EOHAq, 
 
664 
 
 CALCIUM. 
 
 NaOHAq, and BaOjHjAq, viz. 31,150 for 
 HjSO^Aq and 27,640 for HjCljAq. Ca com- 
 bines with the halogens with production of 
 heat; [Ca,X^ = 169,820 when X = C1; 140,850 
 when X = Br ; 107,250 when X=I {Th. 3, 251). 
 
 BeacUons and ComUnaUmis. — 1. With water 
 forms CaOAq andH.— 2. With acids forms salts, 
 usually evolving H ; cone. HNOjAq only acts at 
 high temperatures. — 3. Combines directly, when 
 heated, with many non-metals; especially CI, 
 Br, I, 0, S, P {v. Calcium chloeidb, &c.). — 
 4. Forms alloys with several metals, by heating 
 the metala together. Alloys with Al, Sb, Pb, 
 Hg, Na, and Zn have been described (Caron, 
 0. B. 48, 440; 50, 547; Wohler, A. 188, 253). 
 Calcium is usually estimated either as carbonate 
 or sulphate ; or volumetrioally, by KjMn^OgAq, 
 after ppn. as CaC^O, and decomposition of thi« 
 salt by H^SOjAq. 
 
 Calcium, Alloys of, v. Oaioium ; Combina- 
 tions, No. 4. 
 
 Calcium, Arsenates of. CaHAsOj and 
 Ca3(As04)j : V. AESENATES, Under Arsenic, 
 Acms OF. 
 
 Calcium, Arsenites of. Ca3(AsOs)2; Ca(As02)2; 
 and CajAsjOs: v. abbeoties, under Absenio, 
 
 ACmS OE. 
 
 Calcium, Bromide of. CaBrj. Mol. w. 
 unknown, as compound has not been gasified. 
 r676''-680°] (CameUey, 0. J. 29, 497 ; 38, 279). 
 S.G. 3-32 (Kopp, A. 93, 129). S. (0°) 125; 
 (20°) 141 ; (40°) 212 ; (60°) 277 ; (105°) 313 
 (Kremers, P. 103, 65). H.F. [Ca,Br'^ = 140,850 ; 
 [CaBr^Aq] = 165,360 (Thomsen). 
 
 Formation.— CaBi^ is formed by dissolving 
 CaO or CaCOj in HBrAq, evaporating, and 
 crystallising ; or by decomposing FeuBr^Aq by 
 CaOAq. 
 
 Preparatdon.—!. 12| parts Br and 1 part 
 amorphous P are allowed to react in presence 
 of HjO ; the solution is neutralised by CaCO, 
 or CaOjHj, filtered from Ca3.2POj, evaporated, 
 and crystaUised (Klein, A. 128, 237).— 2. 20 
 parts S are dissolved in 240 parts Br, and the 
 liquid is poured into thin milk of lime, contain- 
 ing 140 parts CaO ; CaSO^ is ppd. by alcohol, 
 the solution is filtered off, evaporated, and 
 crystaUised (Faust, Ar. Ph. [2] 131, 216). 
 
 Properties.— yfhite, lustrous, deliquescent, 
 needles : very soluble in HjO and alcohol. 
 Absorbs NH, forming CaBrj.6NH3 (Eammels- 
 berg, P. 55, 239). CaBr^Aq boiled with CaO^Hj, 
 and filtered, on cooling yields crystals of 
 CaBrj.3Ca0.15HjO. 
 
 Combinations. — With water to form 
 CaBrj-eHjO. [CaBrSeH^O] = 25,600 ; 
 [CaBr^6H20,Aq]= -1090 (Th. 3, 251). 
 
 Calcium Bromide, hydrated, v. Galoiuu, 
 BBOMiDE OF, Combmatious. 
 
 Calcium, Chloride of. CaClj. Mol. w. un- 
 known, as compound has not been gasified. 
 [719°-723°] (CameUey, O. J. 29, 497). S.G. a° 
 2-205 (Schifl, A. 108, 23). S.H. (23°_99°) -1642 
 (Eegnault, A. Ch. [3] 1, 129). S. (0°) 49'6; 
 (10°) 60 ; (20°) 74 ; (30°) 93 ; (35°) 104 ; (40° 
 110 ; (50°) 120 ; (60°) 129 ; (70°) 136 ; (80°) 
 142; (90°) 147; (95°) 151; (99°) 154 
 (Mulder, J. 1866. 66). H.F. [Ca,01'G = 169,820 ; 
 [Ca,CP,Aq] = 187,230 (Thomsen). 
 
 Formation. — In making NH, by the action 
 
 of CaOaHj on NH^ClAq; also as a by-prodaot 
 in many chemical manufactures. 
 
 Preparation. — 1. Pure CaCOj is dissolved in 
 pure HClAq ; the solution is evaporated to dry- 
 ness and heated to about 200°. — 2. Ordinary 
 marble or chalk is dissolved in HClAq, CI is led 
 into the acid liquid until all Fe and Mn salts are 
 completely oxidised. Milk of lime is added to 
 alkaline reaction, the whole is digested, the 
 liquid is filtered from Ume and ppd., oxides of 
 Mg, Fe, and Mn, neutralised by HClAq, and 
 evaporated as in 1. 
 
 Properties and Beactions. — A white, porous, 
 very deliquescent, solid : after melting and 
 cooling it is distinctly orystaUine. Absorbs 
 moisture rapidly : hence is much used for drying 
 gases, &c. ; if the CaCla to be used must be free 
 from CaO, e.g. for drying CO^, it should be placed 
 for some time in a stream of CO^ and then of 
 dry air at the ordinary temperature. CaCl^ is 
 very soluble in water and alcohol, much less 
 soluble in HClAq. It is partly decomposed by 
 heating in air {v. Weber, B. 15, 2316), more com- 
 pletely by heating in 0, with production of CaO. 
 Heated vrith KGIO3 or KCIO4, part of it is changed 
 to CaO (Sohulze, J. pr. [2] 21, 407). CaCljAq 
 is used as a bath for maintaining temperatures 
 above 100°; 60 parts CaClj in 100 parts H^O 
 forms a solution boiling at 112° ; 100 CaClj in 
 100 water, B.P. 128° ; 200 CaCl^ in 100 H2O, 
 B.P. 158° ; and 325 CaCl^ in 100 H^O, B.P. 180° 
 (Magnus, P. 112, 408; Wiillner, P. 110, 564; 
 Legraud, A. 17, 34). 
 
 Combinations. — 1. With water to form 
 hexagonal crystals of CaCl2.6H20 [CaCl^ 6ff 0] 
 = 21,750 (Th. 3, 251) ; best prepared by evapora- 
 ting a solution of CaCO,, or CaO, in HClAq and 
 crystaUising. CaCl2.6H20 melts at 28° (Tilden, 
 C. J. 45, 268) ; heated to 200°, or placed in 
 vacuo, the hydrate CaC1^.2Hj0 remains. 
 This hydrate is also produced, according to 
 Ditto (O. B. 92, 242), by saturating HClAq 
 with CaCl^ at 12' and cooling. Hamerl 
 (Sits. W. (2nd part) 72, 667) says that 
 CaCl2.4H20 is formed by repeatedly melting and 
 cooling CaCl2.6H20. According to Dibbits 
 [Ar. N. 13, 478) CaClj.eH^O loses 4H2O in a 
 current of dry air, and 6H2O in dry air at 80°. 
 S.G. ifio of CaCl2.6H20, 1-612 (Kopp, A. 93, 
 129). S.H. of CaClj.6H20 (-20° to 2°) -345, 
 (4°-28°) -647 ; melted (34°-59°) -5601, (34°-99°) 
 -552, (100°-127°) -519 (Person, O. B. 23, 162). 
 C.E. (cubical) for solid CaClj.eHjO; Vi=V<> 
 (1-1- -000 645 K--000 053 77i'=-H-000 001 906 t') 
 for interval ll°-26° (Kopp, A. 93, 129). H.F. 
 [Ca, CIS 6H^0] = 191, 980 ; CaClj.eH^O dissolves 
 in water with disappearance of much heat 
 [CaCP.6ffO,Aq] = -4,340 (Thomsen). This 
 salt mixed with snow produces great lowering of 
 temperature ; for use as a freezing mixture the 
 salt is best prepared by boiling a cone, solution 
 untU temperature rises above 129°, then allowing 
 to cool, shaking weU as the solid forms. 
 CaClj.6H20 is thus obtained as a fine dry 
 powder; 4 parts are mixed with 3 parts dry 
 snow. Hamerl (Site. W. (2nd part) 78, 59) 
 observed —54-9° by mixing this salt with dry 
 snow, both - cooled under 0°, in the ratio 
 CaCl,.6H20: 8-45 H^O (as snow). CaClj.eH^O; 
 S (0°) 72-8 ; (13-8°) 80-9 ; (24-5°) 89-5 ; (29-5°) 100 
 (Hamerl, Site. W. (2nd part) 72, 287).— 2. With 
 
CALCIUM, 
 
 eea 
 
 ammonia toima CaOlj.SNH,; dissociated by heat 
 intoCaClj andNHj; NH, also removed bydis- 
 solymg in HjO and passing in a current of air 
 (Weber, B. 15, 2316). Isambert (0. B. 66, 1259) 
 dssonbes OaClj-iNH, and OaOl,.aNH, ; he gives 
 these thermal values iECaCl^, 2NH»] = 14,000 ; 
 KOaOT, 4NH»] = 12,200 ; i[CaCl^ 8NH>] = 11,000 
 (O. B. 86, 968).— 3. With alcohol to form 
 Oa01j.20jH80 ; decomposed by ELjO (Chodnew, 
 A. 71, 241 ; Johnson, J. pr. 62, 264). Forms 
 combinations also with acetone (Hlasiwetz, 
 A. 76, 294).— 4. With lime to form 
 GaCLj.3Ca0.15H20; prepared by boiling GaCljAq 
 with CaO^Hj, filtering whUe hot, and allowing to 
 cool; decomposed by H^O or C^HjO (Beesley, 
 Ph. 9, 568 ; Eose, S. 29, 155 ; BoUey, D. P. J. 
 153, 202 ; Grimshaw, C. N. 30, 280).— 5. With 
 pUtinous chloride to form CaOl2.PtOl2.8H2O; 
 M.P. = 100° (Nilson, J.pr. [2] 15, 260). 
 
 Calcium chloride, hydrated, v. Caloium, 
 OHLOBiDE OF ; Combinations, No. 1. 
 
 Calcium, Cyanide of. Ca(CN)2. Said to be 
 obtained by heating Ca ferrooyanide and dis- 
 solving out with water (Schulz, /, pr. 68, 257). 
 0. Cyanides. 
 
 Calcium, Fluoride of. CaPj. Mol. w. un- 
 known, as compound has not been gasified, 
 [abt. 902°] (CarneUey, O. /. 33, 280). S.a.-5S^° 
 3-15-3'18 (Schroder, Dichtigkeitsmessungen 
 (Heidelberg, 1873) ; Kengott, Sitz. W. 10, 295). 
 S.H. (21°-50°) -209 (Kopp, T. 155, 71) ; (15°-99°) 
 •2154 (Begnault, 4, Ch. [3] 1, 129). Index of 
 refraction at 21° for line B = 1-432; line D = 
 1-4389; Une P = 1-43709 ; line G = 1-43982 ; 
 line H= 1-44204 (Stefan, Site. W. 63 (2nd part), 
 239). S. (15°) -0004 (Wilson, J. 1850. 278). 
 [CaH''0^2HFl = 66,600 (Quntz, O. B. 97, 1483, 
 1558 ; 98, 816). 
 
 Occurrence. — ^As Fluorspar, in octahedra, 
 cubes, and other forms of the monometrio system ; 
 fairly widely distributed in many rocks ; in 
 small quantities in many mineral waters, plant> 
 ash, bones (Lassaigne, S. 52, 141), enamel of 
 teeth, &o. 
 
 Pr^araUon. — 1. As a gelatinous mass, by 
 decomposing an aqueous solution of a Ca salt by 
 that of a fluoride. — 2. As a granular powder by 
 digesting freshly* ppd. CaOO, with HPAq. — 3. 
 In small octahedra by digesting the gelatinous 
 pp. obtained in 1 vrith dilute HClAq for 10 hours 
 at 240° {a&naimont, A. Ch. [8] 32, 129 ; Scheerer 
 a. Drechsel, J.pr. [2] 7, 63). 
 
 Properties and Beactions, — Transparent, 
 colourless crystals, melting without decom- 
 position at about 900°. Forms easily fusible 
 mass vrith BaSOj, SrSOf, and many other 
 insoluble compounds; hence much used as a 
 flux. Soluble in aqueous solutions of KH, salts 
 (Bose, P. 79, 112). Not decomposed by fusion 
 with KOH or NaOH,bnt partially by fusion with 
 excess of alkali carbonates. Decomposed, to 
 CaO and HF, by heating to redness in steam ; 
 also decomposed by hot H2S04Aq, but only very 
 partially by boiling HClAq or HNO,Aq. Said 
 to be partly decomposed byAlj.SSO^Aq (Friedel, 
 Bl. [2] 21, 241). 
 
 Combinations. — With hydrofluoric acid and 
 water to form CaFj.2HF.6HjO ; produced in 
 email crystals by evaporating a solution of CaO 
 iu large excess oi HFAq ; decomposed to CaF, 
 
 and HFAq by hot water (Fremy, A. Ch. [3] 47, 
 35). 
 
 Calcium, Hydrate of, CaOjHj, «, Oaloium, 
 
 HYDBOXIDE OV. 
 
 Calcium, Hydrosulphide of, #. Caioidm 
 
 SULPHYDEATB. 
 
 Calcium, Hydroxide of, CaO^H^. (Slaked 
 Kme.) Mol. w. unknown : compound is decom- 
 posed by heat. S.G. 2-078 (Filhol, A. Oh. [3] 
 21,415). S.G. f (crystalline) 2-236 (Lamy, 
 A. Oh. [5] 14, 145). S. (15°) -13 ; (54°) -103 ; 
 (100°) -08 (Dalton, New System, 2, 831) : S. (18°) 
 -13 ; (100°) -07 (Bineau, O. B. 41, 509, v. also 
 Lamy, O. B. 86, 333). H.F. [Ca,0,H'=0] = 
 146,470 ; [CaO.H'G] = 15,540 (Th. 3, 251). 
 
 Preparation. — 1. By adding to 1 part H2O 
 3-1 parts CaO. — 2. By allowing Ca to oxidise in 
 moist air. -3. By adding KOHAq, or NaOHAq, 
 to a oono. aqueous solution of a Ca salt, collecting 
 pp., washing well, and drying at 100'^. Gay- 
 Lussac [A. Oh. 1, 334) obtained CaO^H^ in 
 small six-sided plates by evaporating an aqueous 
 solution over HjSO, m vacuo. 
 
 Properties and Beactions. — ^A white, com- 
 pact mass ; slightly soluble in cold, less soluble 
 in hot, water [CaO-ff,Aq] =2,290 {Th. 3, 251). 
 Strongly alkalinereaction. CaOjHjAq neutralises 
 acids with production of same quantity of heat 
 as when 2NaOHAq, or 2K0HAq is used, viz. 
 about 31,000 for H2S0iAq, and about 27,900 for 
 2H01Aq (Thomsen) ; also pps. many heavy 
 metals as oxides or hydroxides, and saponifies 
 fats. Moist OaHjOj absorbs CO2, forming CaCO, 
 and H2O. CaHjOjAq forms insoluble salts when 
 neutralised by HjSiOjAq, HjBOaAq, H3P0jAq, 
 &c. ; pps. are also formed by adding animal 
 char, sand, &:o. CaHjOj is soluble in solutions 
 of cane sugar ; on adding alcohol pps. are 
 obtained, said to have the compositions 
 Ca0.0,2H220„,H20; 2Ca0.C,2H220„ ; 
 SCaO.CijHjjO,, ; and eCaO.CijHjjO,, 
 (Pelouze, J. 1864. 672 ; Bowin a. Loisean, A. Ch. 
 [4] 6, 203 ; P6Ugot, A. Ch. [3] 54, 383 ; D4on, 
 Bl. [2] 17, 155 ; Berthelot, A. Oh. [8] 46, 173). 
 CaH202 is much more soluble in glycerin than 
 in water. At a bright red heat CaH202 is decom- 
 posed to CaO + HjO. For reaction between CI 
 and CaHjOj v. Bleaching Powder under hypo- 
 CELOBiTES, under Chlobine, oxyacids of. 
 
 Calcium, Iodide of. Calj. Mol. w. unknown, 
 as compound has not been gasified. [631°] 
 (CarneUey, O. J. 33, 279). S. (0°) 192 ; (20°) 
 204 ; (40°) 228 ; (43°) 286 ; (92°) 435 (Kremers, 
 P. 103, 65). H. F. [Ca, P] = 107,250; 
 [Ca, P, Aq] = 134,940 {Th. 3, 251). 
 
 Formation. — By the action of HIAq on 
 Ca02H2; or of I on CaS suspended in water 
 (Liis-Bodart a. Jobin, A. Ch. [3] 54, 863). 
 
 Preparation. — To 1 part amorphous P and 
 40 parts HjO, 20 parts I are slowly added i the 
 whole is digested at 100° ; the colourless liquid 
 is neutralised by milk of lime, and evapotraed 
 in an atmosphere free from CO, (Liebig, A, 
 121, 222 ; Wagner, 0. O. 1862. 143). 
 
 Properties and Beactioyis. — White, deliques- 
 cent mass ; very soluble in water and alcohol ; 
 nndecomposed when melted out of contact with 
 air: melted in air gives CaO and I. Cone. 
 CaljAq dissolves I; on evaporation m vacua 
 crystals of a periodide are said to be obtained. 
 
666 
 
 CALOIUM. 
 
 Absorbs 6NH, (Isambert, 0. A. 66, 1259). Fonns 
 an easily decomposed double compound with 
 Agl; CaI2.2AgI.6H2O (Simpson, Pr. 27, 120) 
 Calcium hydroxyhydrosulphide v. post under 
 
 OAtOIUM SULFHTDBATE. 
 
 Calcium, Oxides of. Two oxides are known ; 
 CaO a strongly basic compound, and CaO^ which 
 acts as a peroxide. CaO^ cannot be formed by 
 the action of on CaO (comp. BaOj). 
 
 I. Calcium monoxide. CaO (Lime, hwrnt 
 lime). Mol. w. unknown, as compound has not 
 been gasified. S.G. 3-15 (Schroder, P. Jubelbd. 
 452); S.G. (crystalline, uy heating Ca2NOs) 3-251 
 (Brugelmann, W. 2,466; 4, 277). S. variable 
 according to state of aggregation of the GaO &o. 
 Lamy (A. Ch. [5] 14, 145) gives the following 
 numbers representing grams of CaO in 1000 
 grams of solution ; CaO being made (1) by 
 heating Ca2N03, (2) by heating CaCOa, (3) by 
 heating OaOjH^: — 
 
 Temp. (1) (2) (3) 
 
 0" 1-862 1-381 1-430 
 
 10 1-811 1-842 1-384 
 
 15 1-277 1-299 1-348 
 
 30 1-142 1-162 1-195 
 
 45 0-996 1-005 1-033 
 
 60 0-844 0-868 0-885 
 
 100 0-562 0-576 0-584 
 
 H. F. [Ca, 0] = 130,930 ; [Ca, 0, Aq] = 149,260 
 {Th. 3, 251). 
 
 Preparation. — ^Pure marble, or Iceland spar, 
 is strongly heated in a crucible with a hole in 
 the bottom to allow escape of COj ; or a piece of 
 charcoal is placed in the crucible beneath the 
 marble, CO is thus formed and sweeps out the 
 CO2 with it. CaCO, is not completely decom- 
 posed when heated in an atmosphere of CO, ; 
 V. CALCIUM OABBONATE, Under Carbonates. 
 Sestini (Fr. 4, 51) strongly heats powdered 
 marble with sugar, washes with H^O, dissolves 
 in HNOjAq, pps. CaCOg by (NHJ^ COjAq, and 
 strongly heats the dried pp. By strongly heating 
 Ca2N0„ in quantities of about 15-20 grams at 
 a time, in a porcelain flask, Brugelmann (W. 
 2, 466 ; 4, 277) obtained cubical crystals of CaO ; 
 semitransparent, harder than the amorphous 
 form, and less easily acted on by HjO and CO^. 
 Properties and Reactions. — White, amor- 
 phous (or crystalline v. supra), powder : does not 
 fuse at full white heat. Strongly basic ; reacts 
 vrith most acids to form salts. CaO is decom- 
 posed by heating to whiteness with K ; heated 
 in CI, CaClj is formed. CaS is produced by 
 heating with S, and OaS and CaCO, by heating 
 in CSj. CaO does not combine with O (v. Conroy, 
 0. /. [2] 11, 809). 
 
 Combinations. — With ca/rbon dioxide to form 
 CaCOj (but dry CaO does not react with CO2 : 
 Scheibler, B. 19, 1973) ; combination begins at 
 about 400° {v. Birnbaum a. Mahn, B. 12, 1547); 
 [CaO, 00^ = 42,520 {Th. 3, 251). Heated with 
 silica or silicates, silicates of Ca are formed, 
 which in contact with water set to a hard com- 
 pact mass (hydraulic mortars). With water, 
 CaOjHj is formed with production of much heat 
 [CaO, H»0] = 15,540 (Thomsen) ; the lime is 
 said to be slaked. , 
 
 II. Calcium dioxide, CaOj {Calcium per- 
 ' ' ■ Mol. w. unknown. Prepared by adding 
 
 pure HjOjAq to excess of CaOAq, or by adding 
 excess of CaOAq to Na^^jAq containing gome 
 
 HNOjAq ; collecting pp., washing well with cold 
 water, and heating the CaOj.SH^O thus produced 
 in a current of dry air free from CO2 to 100° — 
 120°. Forms a snow-white crystalline powder ; 
 does not melt at red heat, but gives oS and 
 forms CaO. The hydrate CaOjj.SH^O is slightly 
 soluble in HjO, in contact with H^O it slowly 
 decomposes to CaO^HjAq and H; soluble in 
 NHjClAq, but not in NHjAq ; dissolves easily in 
 dilute acids, even in H.O^HjOjAq, without 
 evolution of 0. It forms prismatic dimetrio 
 crystals, isomorphous with Ba02.8H20 and 
 Sr02.8H20 (Sehone) (Th^nard, A. Ch. [2] 8, 300; 
 Conroy, C. J. [2] 11, 808; Sehone, B. 6, 1172). 
 
 Calcium oxide, hydrated, 0a02H2, v. Cal- 
 cium, HTDBOXIDE OP. 
 
 Calcium, Oxybromide of, CaBr2.3Ca0.15HjO 
 V. Caloium, bromide op ; Properties. 
 
 Calcium, Oxychloride of, CaOl2.3Ca0.15H20, 
 V. Calcium, chloride oe ; Combinations, No. 4. 
 
 Calcium, Oxysulphides of, v. Calcium poly- 
 SULPHIDBS ; under Calcium, sulphides op. 
 
 Calcium, Phosphide of. When Ca and P are 
 heated under rock oil, and the unacted-on P is 
 dissolved out by CS^, a black powder remains 
 which is acted on by B.fi and acids with pro- 
 duction of PH3 ; this black powder is said by 
 Vigier to be Ca phosphide (Bl. 1861. 5). By 
 strongly heating CaO in P vapour, a brown, 
 amorphous mass is obtained ; when heated vrith 
 cone. HOlAq, non-inflammable PH3 is evolved, 
 but with dilute HClAq the gas evolved takes 
 fire. Probably in the first case liquid PH2 is 
 formed and at once decomposed to gaseous PH, 
 and solid PjH ; in the second case the decomposi- 
 tion of PH2 proceeds more slowly, so that some 
 is carried into the air with the PH3 and causes 
 the combustion (Thfiuard, A. Ch. [3] 14, 12). 
 The brown substance got by heating CaO in 
 P vapour is said to be a mixture of CaP and 
 Ca2P20, (Th^nard, l.c.) : this brown substance is 
 described by ThSnard as a very hard solid ; un- 
 changed in dry air ; deliquescent in moist air ; 
 burns when heated in air ; acted on by water 
 free from air gives CaOAq and PH^, PH, decom- 
 poses to PHj and P2H, and the P2H is decom- 
 posed by the CaOAq to Ca(H2P02)2Aq and H. 
 
 Calcium, Salts of. Compounds obtained by 
 replaciag H of acids by Ca. These salts form 
 one series CaXj where X2=Cl2, (NOj)^, SO^, 
 CO3, f PO4, (fee. They are generally formed by 
 the action of CaO or Ca02H2 on the acids in 
 aqueous solution, or by the decomposition of 
 salts of the heavier metals by CaOjH^Aq. As 
 none of the Ca salts has been gasified, the 
 f ormulse are based partly on similarities between 
 these salts and those of analogous metals which 
 form gasifiable compounds, chiefly Zn, Cd, and 
 Hg, and partly on the fact that the general 
 formula CaX2 is the simplest that can be given, 
 provided the atomic weight of Ca is about 40 
 (this has been established by analyses of CaClj, 
 CaCOj &o. and by determinations of the S.H. of 
 the metal; v. Calcium). Salts of Ca derived 
 from a great many acids are known ; they are 
 well marked stable bodies ; many form double 
 salts ; few basic salts are known. Most of the 
 Ca salts are soluble in water ; the more insoluble 
 are the arsenite, carbonate, fluoride, oxalate, 
 phosphate, sulphate, and sulphite. With the 
 exception of CaF, all the salts are more or leas 
 
CALLUTANNIO AOID. 
 
 607 
 
 soluble in dilute acids. The Ca salts of non- 
 volatile acids are generally undecomposed by 
 heat. Ca salts derived from a great many acids 
 are known {v. Borates, Carbonates, Phosphates, 
 Bdmhates, (fee, &o.). 
 
 Calcium, Selenide of. CaSe. Mol. w. un- 
 known. White solid, rapidly changing in air, 
 prepared by heating CaSeOj to dull redness in 
 H; [Ca,Se] = 78,000 (Pabre, C. B. 102, 1469). 
 
 Calcium, Seleniocyanide of. {? CaSe2(CN)2). 
 Probably exists. Data very meagre (Crookes, 
 J. j»r. 53, 161). 
 
 Calcium, Sulphides of. One calcium sul- 
 phide, CaS, is known as a solid; solutions 
 which most probably contain CaS, and CaSj, 
 respectively, have been prepared. The sulphides 
 of Ca are decidedly less basic than those of 
 Ba, e.g. they do not react with the sulphides of 
 the negative metals As and Sb to form thiQ> 
 salts. 
 
 I. Calcium monosulphide. CaS. Mol. w. 
 nnknown. H.F. solid, from solid materials: 
 [Ca,S] = 92,000 (Sabatier, A. Ch. [5] 22, 598). 
 
 Preparation. — 1. HjS is passed over CaOjH^ 
 kept at about 60°; the sole products are CaS 
 and H^O. If the reacting bodies are perfectly 
 dry the change does not occur (Veley, O. J. 
 47, 478). — 2. By gently heating crystals of 
 CaSjHlj.eHjO (j.^.y in H^S; the product con- 
 tains some CaOjHj (Divers a. Shimidzu, C. J. 
 45, 270). Schone's method, heating CaCO, in a 
 mixture of COj and H^S (P. 112, 193) is said 
 by Divers to yield a mixture of CaS and CaO 
 in the ratio llCaS:5CaO (C. J. 45, 282). 
 
 Properties and Reactions. — A white amor- 
 phous solid; soluble in water with gradual 
 decomposition, giving H^S, and solution of 
 Ca.SH.OH {g.v.) which then slowly decom- 
 poses in air forming CaSjOgAci and CaS^Aq 
 (Divers a. Shimidzu, Z.C.). The impure OaS 
 produced by heating CaO with CSj, or CaSO, 
 with C, is not soluble in, although it is partially 
 decomposed by, water. Perfectly dry CaS does 
 not absorb CS^ ; but in presence of HjO a basic 
 calcium thiocarbonate, 2OaO2Hj.CaCS3.10H2O, 
 is produced (Veley, C. J. 47, 486). Sabatier 
 (A. Ch. [5] 22, 698) gives the thermal value 
 [Oa,S] = 92,000 ; [CaS, Aq] = 6,010 (? pure mate- 
 rials). 
 
 II. CAiiOiuM EOLYSULPHiDES. When CaS 
 (prepared by heating CaO in CS2 and CO^ and 
 therefore containing some CaO) is boiled with 
 S and HjO, it dissolves, forming an orange-red 
 liquid ; the quantity of S which goes into solu- 
 tion corresponds with that required to form 
 CaS, and CaSj ; if more S is used it is deposited 
 on cooling the liquid ; if less S than S3 to CaS 
 is used, some of the CaS remains undissolved. 
 Both solutions are decomposed on concentration 
 with ppn. of Ca02H2 and S, and evolution of 
 HjS (v. Soh5ne, P. 117, 58). Warm CaS^H^Aq 
 dissolves S very readily, forming a solution of 
 CaSs and evolving H^S ; this solution is com- 
 pletely decomposed (if cold and dilute) by HjS 
 forming CaSjHjAq with ppn. of S (Divers a. 
 Shimidzu, C. /. 45, 270). ,,.,,. 
 
 CaSjAq is decomposed m contact witb an:. 
 By boiling 3 parts CaO, 1 part S, and 20 parts 
 ILO for some time, and allowing to stand for 
 Mveral days, orange-red needles are obtained of 
 8C80.CaS,.12HjO (Herschel, N. Ed. P.J. 1, 8; 
 
 SchSne, P. 117, 58), 2CaO.CaS:,. 10 or 11 H^O 
 according to Geuther {A. 224, 178). If CaS 
 (prepared by action of CSj and CO^ on CaO) ia 
 boiled with much water and filtered hot, CaSO, 
 is said to separate out and then yellow needles 
 of 5CaO.CaS5.20H2O (H. Bose, P. 55, 483), 
 or 4CaO.CaS,.18HjO (Schone, P. 117, 58), or 
 SCaO.CaSj, 14 or 15 H2O (Geuther, A. 224, 
 178). These oxysulphides are easily decomposed. 
 
 Calcium, Sulphocyanide of. Ca(GNS)2. By 
 saturating HCNSAq with CaCOj, v. sulpho 
 CYANIDES, under Cyanides. 
 
 Calcium Sulphydrate {or hydrosulpMde); and 
 
 Calcium hydroxy-sulphydrate (or hydroxy- 
 hydrosulphide). CaSjH^.eH^O, and 
 Ca.SH.OH.3H2O. By passing HjS into a 
 solution of CaO containing solid CaHjOj, 
 CaS2H2.6H20 is formed : 1 part CaO is added to 
 3-4 parts warm water ; when cold, HjS is passed 
 into the semi-solid substance until all has dis- 
 solved ; more CaO is added, little by little, the 
 whole being surrounded by ice, and HjS is 
 passed in until a little CaO remains un- 
 dissolved ; the liquid is quickly decanted into a 
 tube kept in ice ; the crystals which separate 
 are drained and a current of dry HjS is swept 
 over them at 0°. Air must be excluded during 
 the entire operation (Divers a. Shimidzu, C J. 
 45, 270 ; Veley, 0. J. 47, 478). CaS2H2.6H20 
 forms colourless prismatic crystals, which melt 
 in their water of crystallisation, giving oft HjS 
 and forming Ca.SH.OHAq and CaOjHj. At 
 about 15°-18°, HjS is evolved even in an atmo- 
 sphere of EjS. CaS2H2.6H20 is very soluble in 
 water and alcohol. CaSjHjAq is slowly oxidised 
 in contact with air, giving a little CaS203Aq and 
 CaSsAq. Thomsen (Th. 3, 251) gives the thermal 
 value [Ca,S^H^Aq] = 115,250. 
 
 iJe/erewces.— Pelouze, G. B. 62, 108; H. 
 Bose, P. 55, 433 ; Berzelius, S. 34, 12 ; P. 6, 442 ; 
 Bottger, A. 29, 79 ; 33, 344. 
 
 When a stream of H is passed through 
 an ice-cold solution of CaS2H2, crystals of 
 Ca.SH.OH.3H2O are formed, and HjS is evolved. 
 The same compound is formed by the combi- 
 nation of HjO with CaS, as in the interior of 
 heaps of soda-waste ; and by the mutual action 
 of Ca02H2 and H2S, as in the purification of coal 
 gas. Calcium hydroxysulphydrate crystallises 
 in colourless four-sided prisma ; it is soluble in 
 water with decomposition into CaS2H2Aq and 
 CaOjHj; insoluble in, but slowly decomposed 
 by, alcohol (CaS2H2 goes into solution and 
 CaOjHj remains ; Divers a. Shimidzu, O. J. 45, 
 270). It absorbs CSj forming a basic thiocar- 
 bonate 2CaO2H2.CaCS3.10H2O ; it is the active 
 agent for absorbing CS2 in gas-purification 
 (Veley, C. J. 47, 478). M. M. P. M. 
 
 CAILXTTANNIC ACID CuH^Oa. Occurs in 
 Calluna vulgaris, the common Ling. The green 
 parts are extracted with alcohol, water is added, 
 and from the filtrate the lead salt is ppd. by 
 Pb(OAo)j. Amber-coloured mass. Its solution 
 in alkalis rapidly absorbs oxygen from the air. 
 Beduces AgNOjAq. 'FejOl^ gives a green colour. 
 Dyes mordanted wool sulphur - yellow. — 
 
 Salts. — (PbC„H,20,)2(PbO)3aq(?)— 
 
 (PbC„H,20,),(PbO),2aq(?)- 
 
 Sn(C„H,20j2(Sn02)»2aq(?). 
 
 Boiling dilate mineral acids convert callutannio 
 
 acid into calluxanthin ChH^O,, a yellow floocu- 
 
368 
 
 OALLUTANNIO ACID. 
 
 lent pp., si. sol. cold water, t. sol. hot water 
 and alcohol. Its alkaline solntions rapidly ab- 
 Borb oxygen from the air (Bochleder, A. 84, 354). 
 
 CAIUTTS V. Calamus. 
 
 CALOMEL. Merourous chloride (HgOl). V. 
 Mebouby, chlobibes of. 
 
 CALOPHYLLTJM EESIN ChHisO,. [105°]. 
 S.Q-. 1'12. A resin from Calajghyllvm calabaot 
 longifoUwm of South America. Said to give 
 butyric acid on oxidation (Levy, C. B. 18, 242). 
 
 GALOBIMEIEB. Instrument for measuring 
 quantities of heat. V. Physioal methods, Sect. 
 
 IHEBMAIi. 
 
 CALYCIN CisHijOs [240° unoor.]. Occurs 
 in a yellow lichen, OaVycmm chrysocephalMm, 
 from which it is extracted by boiling ligroin 
 (Hesse, JB. 13, 1816). Sublimable. Yellow needles 
 or prisms. S. sol. cold petroleum spirit, petro- 
 leum ether, ether, alcohol, and acetic acid, more 
 easily in the hot solvents. By strong aqueous 
 KOH it is split up into oxalic and phenyl-acetio 
 acids. Carbonated alkalis give salts of calycic 
 acid. 
 
 CAMELLIN CssHmOij. A glucoside occurring 
 in the seeds of CamelUa jajponica (Katzujama, 
 Ar. Ph. [3] 13, 334). Extracted by alcohol, and 
 ppd. by lead acetate. White powder with bitter 
 taste, insol. water. Somewhat resembles digi- 
 talin. 
 
 CAMPHANIC ACID C,oH„04 i.e. 
 
 OsH,3(C02H)^ I . Oxy-camphoric anhydride. 
 
 \00 
 From bromo-oamphoric anhydride, the product 
 of the action of bromine on camphoric anhy- 
 dride, by treatment with water (Wreden, A. 103, 
 330 ; Woringer, A. 227, 3). From oampholic 
 acid and bromine (Kachler,4. 162, 264). Formed 
 also as a by-product in the preparation of cam- 
 phoric acid by oxidation of camphor with HNO3 
 (Eoser, B. 18, 3112). According to Fittig (A. 
 172, 151) it is a lactouic acid, formed vi4 
 
 C,H,3Br<^°>0 and C,H,3(OH)(C02H),. 
 
 ProperUes. — Feathery crystals or prisms 
 (from water). Monoclinic, a:b:c = l-2723:l:l-522. 
 i8 = 66°34'. 
 
 Salt.— BaA'2 3|aq 
 
 Beactkm. — 1. On distillation camphanic acid 
 
 /° 
 
 gives CO2, campholactoue OsH,a I ,andlauro- 
 
 \co 
 
 nolio acid CsHiaCOjH.— 2. Kfitfi, and HjSO, 
 oxidise it to camphoronio acid CgHi^O^ (Bredt, 
 B. 18, 2989). 
 
 CAMPHENE V. Tebpenes. 
 
 CAMFHEN'OL v. Boeneol and Cineol. 
 
 CAMPHENYL-p-TOLYL-AMIDlNE 
 0,H,sC(NHj):NC,H, [115°]. Fine white glisten- 
 ing needles (from ligroin). Formed by heating 
 eampholenonitrile CbHijON with ^-toluidine 
 hydrochloride at 250° (Goldschmidt a. Koreff, 
 B. 18, 1633). 
 
 CAMPHIC ACID C.oH.jOj. S. -14 at 19°. 
 [o]d = 15°45' (in alcoholic solution). Formed to- 
 gether with camphoric acid by passing air 
 through a boiling solution of sodium camphor, 
 CiuHi^NaO in xylene. Thick mass, v. sol. alco- 
 hol and ether. EHnOt oxidises it to camphoric 
 acid. The calcium salt distilled with calcium 
 formate gives camphor and camphreue C,H„0 
 
 (0. 233°) (Montgolfier, A. Gh. [S] 14, 70; C. B. 
 88, 916). 
 
 GAMPHILENE v. Tebfenbb. 
 
 OAMPHIMIDE CioHijN or C8H„<^ ||\nH (?) 
 
 Formed together with dicamphoriUmide by dis- 
 tilling the hydrochloride of amido-camphor (v. 
 Camphok) with steam (Schiff, B. 18, 1405). 
 
 CAMPHINE V. Tbepenes. 
 
 CAIIFHO-CAIIBOXYLIC ACID v. Campiiob 
 
 CAEBOXYLIO ACID. 
 
 (a)-CAMPH0GLYCUE,0NIC ACID C.A^O,. 
 [130°]. S. 5. [o]d=-33°. Occurs, together 
 with uramido-camphoglycuronio acid in the 
 urine of dogs that have taken camphor (Schmie- 
 deberg a. Meyer, H. 3, 422). Small thin lamiu89 
 (containing aq) ; v. e. sol. alcohol and hot 
 water, insol. ether. Boiling dilute HOI splits it 
 up into glycuronic acid CgS.,fi, and crystalline 
 campherol CioHuOj [198°]. HNO3 oxidises 
 it to camphoric acid. — BaA". — BaA"2aq. — 
 AgHA"a;aq. 
 
 (j3)-CampIioglycuronio acid CibHjjOj. An 
 amorphous modification of the preceding, 
 formed by warming it with baryta. — AgHA" 3aq : 
 crystals, more soluble than the Ag salt of the 
 (a) acid. 
 
 GAIIPHOL a name for Bobneoi, (q.v.). 
 .CO 
 
 CAMPHOLACTONE CsH,,< | . [50°]. 
 \ O 
 (230°-235°). From camphanic acid by distilla- 
 tion, together with lauronolio acid (Woringer, 
 A. 227, 10). Slender needles (from water). 
 Has a pungent odour of camphor. Like other 
 lactones, its solution becomes cloudy when 
 gently heated, but the oily drops afterwards 
 dissolve up again. Volatile with steam. KjCO, 
 separates it from its aqueous solution. When 
 boiled with baryta the salt of the corresponding 
 oxy- acid, C8H„(0H)C02H, is formed. 
 
 CAMPHOLENE CgH,, (136°). V.D. 4-35. 
 Prepared by the action of dehydrating agents on 
 camphoUc acid (Delalande, A. 38, 340) and by 
 distilling potassium oampholate with soda-lime 
 (Kachler, A. 162, 266). Probably identical with 
 the hydrocarbon got by distilling the calcium 
 salt of campholenio acid (Goldschmidt, B. 
 20, 483). The name campholene has also 
 been given to CjH,, (c. 123°) obtained by the 
 action of dehydrating agents on camphoric acid 
 and its amides (Ballo, B. 12, 324). 
 
 CAMPHOLENIC ACID O.oH.jOj i.e. 
 CjHis.CO^H or CaH,3(C0jH):CHj. Oxy-caniphor. 
 (c. 260°). Colourless oil. Formed by saponi- 
 fication of its nitrile which is obtained by heat- 
 ing camphoroxim with acetyl chloride. Formed 
 also by treating an alcoholic solution of ^B)-di- 
 bromo-camphor with sodium-amalgam (Gold- 
 schmidt a. Ziirrer, B. 17, 2069; Kachler a. 
 Spitzer, B. 17, 2400 ; M. 3, 216 ; 4, 643). Tlie 
 Ca salt on dry distillation yields Oji^e, possibly 
 campholene (Goldschmidt, B. 20, 483). Oxi- 
 dising agents give oxy-camphoronic acid. At 
 250° the NH, salt gives the amide [127°].— 
 NH^A'.— BaA'j4aq. 
 
 Amide CjHij.CONHj. Isoeamphoroxim 
 [125°]. Glistening plates ; sol. alcohol, ether, 
 and cone, acids. Formed by heating the nitrile 
 with alcoholic KOH, or by heating the ammo- 
 
CAMPHOR. 
 
 681! 
 
 ■T^^o °* *^ ^°^^ *o 250°. By distillation 
 SSr &,?, '' yields the nitrile (Nageli, B. 17, 
 805 ; Goldsohmidt a. Ziirrer, B. 17, 2069). 
 1 i'*':^'*— C»H,3.0N. (216°). Formdtim.- 
 1. iJy heating camphoroxim with AoCl which 
 removes H,0.-2. By distilling campholenamide 
 (isooamphoroxiin) with P,S,. Beacti(ms.—l. By 
 heating with alcoholic KOH it is converted into 
 campholenamide. By long boiling with aloo- 
 holio KOH it yields oampholenio acid.— 2. By 
 heatmg with hydroxylamvm it gives an amid- 
 oxim 0,„H,gNjO which crystallises in white 
 plates melting at [101°].— 3. Eeduced in alco- 
 holic solution by Zn and HCl to the amine 
 CsHij.CHj.NHj (Goldsohmidt a. Ziirrer, B. 
 17, 2069; Goldsohmidt a. Eoreff, B. 18, 
 1634). — 4. Successive treatment with sodium 
 amalgam and HCl yields CigHj^NaClj, the hydro- 
 chloride of camphyl-di-phenyl-hydrazinamine 
 C,H„(CHjNHj)NjHjPh. [157°] (Balbiano, 
 Gf. 17, 155). 
 
 Nitro - campholenic acid C,„H,5(NOj)02. 
 Nitro-oxy- camphor. [164°] (Z.) ; [170°] 
 (K. a. S.). Formed by nitration of campholenic 
 acid (Zurrer, B. 18, 2228 ; Kaohler a. Spitzer, 
 M. 4, 643; B. 15, 2336; Swarts, B. 15, 2135). 
 Monoolinic pyramids, a:6:c = *76:l:-43 ; $ = 
 89° 18". Sol. hot alcohol and ether. Eeduced by 
 tin and HCl to amido-campholeuic acid whose 
 hydrochloride crystallises in lamina [250°]. 
 
 CAMPHOLIC ACID C,„H„Oj. Mol. w. 170. 
 [95°] (K.) ; [106°] (M.). [a]j = 50° (in alcohol). 
 
 Formation. — 1. By passing camphor-vapour 
 over nearly red-hot potash-lime (Delalande, A. 
 Ch. [3] 1, 120). — 2. By adding potassium in 
 small pieces to a solution of camphor (1 pt.) in 
 boiling petroleum (3 pts.) at 130° (Malin, A. 
 145, 201). — 3. By boiling camphor with alco- 
 hoUo KOH (Kachler, A. 162, 259). — 4. By 
 heating camphor with Na at 280° (Montgolfier, 
 A. Ch. [5] 14, 99). 
 
 Properties. — Monoclinic prisms (from dilute 
 alcohol) or nodular groups of lamince (from 
 ether-aleohol). V. si. sol. water ; volatile with 
 steam. 
 
 Beactions. — 1. HNO3 gives first camphoric 
 and then camphoronic acids. — 2. Moist Br 
 gives at first camphoric acid, then bromo- 
 camphoric anhydride, and lastly oxy-camphoric 
 anhydride CjjH^Oj. — 3. PjOj gives oampholene ; 
 red-hot soda-lime acts similarly. 
 
 Salts. — KA.'2aq: laminae. — CaA'^aq. — 
 AgA'. 
 
 Chloride (224°) (Kachler, A. 162, 265). 
 
 CAMPHOR C,„H„0. Mol. w. 152. [175°]. 
 (204°). S.G. i2 .992. S. -1. S. (alcohol of 
 S.G. -806) 120. V.D. 5-82. Ka, 73-11 (m 
 a 32-3 p.o. benzene solution) (Kanonnikoff). 
 [a]D = 55-4— "1372 2 (where 2 = no. of grms. of 
 alcohol in 100 grms. of solution). 
 
 Occurs in the wood and bark of Laurus 
 camphora, from which it is extracted by distil- 
 lation with steam followed by sublimation. 
 Varieties of camphor occur also in several essen- 
 tial oils (v. infra). Camphor may be recovered 
 "from its bromo- derivative by the action of 
 nascent H or of alcoholic KOH (Schiff, B. 13, 
 1407; 14, 1377). Camphor is also formed by 
 distilling calcium camphate with calcium for- 
 mate and by oxidising dextro- and levo- rota- 
 
 tory borneols (Montgolfier, C. B. 88, 915 ; A. Ch. 
 [5] 14, 20). 
 
 Properties. — Hexagonal prisms, terminated 
 by hexagonal pyramids (Descloizeaux, A. Ch. 
 [3] 56, 219; Cazeneuve a. Morel, C. B. 101, 
 438). Tough, vrith peculiar odour; sublimes 
 at ordinary temperatures. Small pieces rotate 
 upon pure water. V. si. sol. water, v. sol. 
 ordinary solvents. Camphor is dextro-rotatory, 
 the rotation varying greatly with the nature 
 and strength of the solvent (Arndtsen, A. Ch. 
 [3] 54, 403; Landolt, A. 189, 334). Its re- 
 fractive power is that of a saturated compound 
 (Gladstone, O. J. 49, 621). 
 
 Beactions. — 1. Camphor (5 kilos.) gives, 
 when oxidised by HNOj, (1-7 kilos, of) pure cam- 
 phoric acid insol. cold water, and (1-8 kilos, of) 
 crude camphoronic acid. Besides camphoronic 
 acid the soluble portion contains (-1 kilo, of) 
 dinitroheptoic acid, and (-2 kilo, of) acids 
 CsHijOo (hydro -oxy camphoronic acid), OoHuO,, 
 OjHijOs (?) [145°], and another acid, A very 
 small quantity (2 g.) of mesooamphorio acid, 
 OioHjeOj, is also got. This forms woolly needles, 
 soluble in cold water [120°].— 2. By oxidation 
 with CrOa it gives camphoronic acid CsH^Os 
 and hydro-oxy-camphoronio CsHnGj but not 
 adipic acid (Kaohler, B. 13, 487 ; cf. Ballo, B. 
 12, 1597). Alkaline KMnOi gi^es camphoric 
 acid (Grosser, B. 14, 2507).— 3. The chief pro- 
 ducts of the dry distillation of camphor with 
 ZnClj (2 pts.) are m-methyl-isopropyl-benzene 
 (m-oymene) and (l:2:4)-di-methyl-ethyl-benzene 
 (laureue), together with smaller quantities of 
 (1:2:3:5) - tetra - methyl - benzene (isodurene), 
 carvaerol, camphorone, and various other bodies 
 (Armstrong a. Miller, B. 16, 2255) such as CH„ 
 benzene, toluene, xylene, and i/z-cumene (Fittig, 
 A. 145, 129 ; Kommier, Bl. 12, 383 ; Lippmann 
 a. Longuinine, Z. [2] 5,413; Montgolfier, 4. Ch. 
 [5] 14, 87).— 4. By the action of iodine it yields 
 a hydrocarbon C,„H2|„ carvaerol, (l:2:4)-di- 
 methyl-ethyl-beuzene, (1:2:3:5) -tetra -methyl - 
 benzene, and traces of ordinary cymene (A. a. 
 M. ; cf. Armstrong a. EaskeU, B. 11, 151 ; Bay- 
 man a. Preis, B. 13, 346). — 5. By treatment 
 with P2O5 ordinary cymene is formed, which is 
 also the chief product of the action of PjSj but 
 accompanied in the latter case by small quan- 
 tities of m-methyl-isopropyl-benzene and tetra- 
 methyl-benzene (Delalande, A. Ch. [3] 1, 368 ; 
 Armstrong a. Miller, B. 16, 2255).— 6. By dis- 
 tillation over red-hot zinc-dust a mixture is 
 formed of toluene, ^-xylene, cymene, and a little 
 benzene (Schrotter, B. 13, 1621).— 7. Cone. 
 HjSOi forms camphrene or oamphorphorone 
 C„H„0 (Chautard, C. B. 44, 66 ; Sohwauert, A. 
 123, 298).— 8. Boiling alcoholic KOH forms 
 oampholio acid and borneol (Berthelot, A. Ch. 
 [3] 66, 94 ; Bl. [2] 17, 390 ; Montgolfier, Bl. [2] 
 18, 114 ; 25, 13 ; Wheeler, A. 146, 84; Kachler, 
 A. 162, 268). CamphoUc acid is also formed by 
 passing camphor-vapour over heated soda lime. 
 9. CI has no action, but in presence of alcohol 
 or PCI3 chlorination ensues (Claus, J. pr. 25, 
 257).— 10. HCIO forms chloro-camphor.— 11. Br 
 forms CjoHijOBrj which readily splits up into 
 HBr and bromo-camphor. — 12. 101 at 250° 
 forms CCl,, CjCl,, and CeCV— 13. PCI5 forms 
 C,||H,jClj. — 14. Camphor absorbs HCl (Binoau, 
 A. Ch. [3] 24, 328). Aqueous HCl at 170" 
 
670 
 
 CAMPHOR. 
 
 Bplita it up into HjO and oymene (Alexejefi, 
 J. B. 12, 187). — 15. Camphor absorbs SOj, 
 becoming liquid. — 16. It also absorbs NOj. — 
 17. Cone. HIAq at 200° forma 0,„H,a (163°), 
 CgH,, (135°-140°), and C,„Hj„ (170°-175°) 
 (Weyl,\Z. [2] 4, 496; B. 1, 96).— 18. Sodmm- 
 amalgam has no action. — 19. Na acting at 90° 
 on a solution of camphor in toluene forms 
 sodium-camphor and sodium borneol (Baubigny, 
 Z. [2] 2, 408 ; 4, 298) (c/. p. 672).— 20. COj gas 
 passed into the product of the action of Na on 
 camphor in toluene forms the carboxylio acids 
 of camphor and of borneol (Baubigny, Z. [2] 4, 
 482, 647). Air passed into the same mixture 
 forms camphoric acid (Montgolfier, A. Ch. [5] 
 14, 75). — 21. Camphor does not combine with 
 NaHSOj (Fittig a. ToUens, A. 129, 371).— 
 22. AcCl has no action.— 23. Converted in the 
 animal economy (of a dog) into camphoglycu- 
 ronic acid (g. v). — 24. Melted camphor absorbs 
 BF3 forming C,(,H,jOBF3 [70°] ; when this is 
 heated for 24 hours there is formed cymene and 
 its polymerides, CjHjj, C,H,2, and other hydro- 
 carbons (Landolph, C. B. 86, 539).— 25. Chloral 
 hySrate forms an unstable molecular compound 
 with camphor. It is a viscous liquid, sol. alco- 
 hol and CHCI3, insol. water (Cazeneuve a. Im- 
 bert, Bl. [2] 34, 209 ; Zeidler, J. 1878, 645).— 
 26. By heating with ammoivium formate 
 at 220°-240° it yields formyl-bornylamine 
 
 .CH, 
 CsHiX 1 (Leuchart a. Bach, B. 20, 
 
 \CH.NHCHO 
 104). — 27. It does not react with phenyl-cyanate 
 (L. a. B.). — 28. Hydroxylamine forms an oxim, 
 V. Camphoboxim. 
 
 Phenyl-hydrazide CuHietNjHPh. (233°) 
 at 10 mm. From camphor and phenyl-hydra- 
 zine. OU. Split up by dilute HCl into cam- 
 phor and phenyl-hydrazine, and by dry HCl 
 into aniline and the nitrHe of campholenio 
 acid (Balbiano, G. 16, 132). 
 
 Constitution. — The action of hydroxylamine 
 on camphor coupled with the fact that camphor 
 does not combine with NaHSOj indicates that 
 it is a ketone. The ready formation of benzene 
 derivatives indicates a six-carbon ring. Its opti- 
 cal properties are those of a saturated compound, 
 V. also Tekpenes. 
 
 The two following formula amongst others 
 have been proposed for camphor : 
 CH,.C(C,H,).CH, 
 
 I I I (Schiff, A. 226, 249 ; Kanon- 
 
 CHj.C(0H3).C0 
 
 nikofi, J.pr. [2] 32. 511; cf. KekuU, B. 6, 931); 
 CH2.CH2.CH . CH2 
 
 I I I (Armstrong a. Miller, B. 
 
 CH3.CH.CH2.CMe.CO 
 16, 2255). V. also TbepenEs. 
 
 Chloro - camphor C,„H,5C10. [95°]. From 
 camphor and cone. HClOAq (Wheeler, 4m. 8. [2] 
 45, 48; A. 146, 81). Crystalline powder (from 
 alcohol) ; at 200° it gives off HCl. Decomposed 
 by alcoholic AgNOj. 
 
 (a).Chloro.camplior C,„H,5C10. [84°]. (C); 
 [93°] (B.).(246°).[b]j = 90°. Formed by passing dry 
 CI into a solution of camphor (760g.) in absolute 
 alcohol (230g.) (Cazeneuve, C. B. 94, 1530 ; Bl. 
 [2] 38, 9 ; 44, 161). Formed also by heating 
 chloro-camphor carboxylio acid (Schiff a. Puliti, 
 B. 16, 887 ; Balbiano, G. 17, 96). Hard, brittle. 
 
 monoclinic needles; smelling like camphor; vola- 
 tile with steam. Not decomposed by alcoholio 
 AgNO,. Sodium-amalgam reduces it to cam- 
 phor; the copper-zinc couple, and hot soda- 
 lime, act similarly. Alcoholio EOH at 180° 
 gives borneol. Phenyl - hydrazine forma 
 C,„H,5(N2HPh)(N2H2Ph) [56°] (B.). 
 
 (;8)-ChIoro-eamphorC,„H,sC10. [100°]. (246°). 
 [o]j = 57°. Deposited from the mother-liquor 
 after the preceding has separated (Cazeneuve, 
 C. B. 95, 1368 ; Bl. [2] 39, 116). Soft, minute, 
 needles, more soluble than the preceding ; mis- 
 cible vrith boiling alcohol. Not decomposed by 
 alcoholic AgNOj, but converted by boiling alco- 
 holic KOH into the preceding body. Phenyl- 
 hydrazine produces the same compound [66°] aa 
 with the preceding (B.). 
 
 (a)-Di-cliloro-camphor C,„H„Cl20. [96°]. S.G. 
 4-2. [o]j = 57-3° (in alcohol or chloroform). 
 Formed by passing dry chlorine for several hours 
 into camphor dissolved in absolute alcohol at 
 80°-90°. The product is ppd. by water and 
 crystallised from alcohol (Cazeneuve, C. B. 94, 
 730, 1058 ; Bl. [2] 37, 454). Trimetrio prisma 
 (from alcohol); a:6:c = l-8358:l:l-4820 ; si. sol. 
 cold, V. sol. hot, alcohol ; almost insol. water 
 but rotates upon it. Above 150° it blackens, 
 giving off HCl. Insol. HOAc (difference from 
 camphor). It forms a liquid combination with 
 aldehyde. 
 
 (e)-Di-cliloro-camphor C,„H„CLjO. [77°]. [a],- 
 = 57-4° (in alcohol) ; 606° (in CHCI3). Ppd. by 
 adding water to the mother-liquor from which 
 the preceding has crystallised (Cazeneuve, C. B. 
 94, 1360 ; Bl [2] 38, 8). CrystaUises from al- 
 cohol with difficulty; v. e. sol. alcohol, ether, 
 and chloroform; liquefied by chloral-hydrate 
 (difference from the preceding). 
 
 Tri-ehloro-camphor CioHijOlaO. [54°]. [o], 
 = 64° (in alcohol). Formed by saturating chloro- 
 camphor with chlorine at 100° (Cazeneuve, 0. B. 
 99, 609). Minute crystals, insol. water, sol. 
 other menstrua. Gives off HOI when heated. 
 
 Bromo-camphor C,(,H,5BrO. [76°]. (274°). 
 S.G. 1-44 Eoo 88-5 (in a 7-37 p.o. alcoholio 
 solution) (Kanonnikoff, J. pr. [2] 32, 504). 
 [o]d = 139°. Formed by heating camphor di- 
 bromide at 100° (Perkin, O. J. 18, 92 ; Maisch, 
 0. C. 1873, 437). Monoclinio prisms (from 
 alcohol); m. sol. alcohol, v. sol. CHCI3 and 
 benzene ; may be sublimed (Montgolfier, Bl. [2] 
 23, 253). 
 
 Beactions. — 1. Sodium-amalgam reduces it, 
 in alcoholic solution, to camphor; alcoholio 
 KOH also gives camphor. Sodium added to 
 its solution in toluene gives sodium camphor 
 (E. Schiff, B. 13, 1407).— 2. PCI, has no action 
 even at 100° (Schiff, B. 14, 1378; Kachler 
 a. Spitzer, M. 3, 205).— 3. Heating with ZnClj 
 at 160° gives a mixture of ^J-xylene hexahydride 
 and a phenol C,|,H„0 apparently identical with 
 the carvaorol obtained by the action of I on 
 camphor (E. Schiff, B. 13, 1407).— 4. Nitric acid 
 forms bromo-nitro-oamphor and camphoric acid 
 (Armstrong, B. 12, 1358 ; E. Schiff a. Maissen, 
 G. 10, 317). — 5. Phenyl - hydrazine forms 
 C,„H,5(N2PhH)(NjPhH2), [56°] (Balbiano, Q. 
 17, 95, 155). 
 
 (a)-Di.bromo-oaniphor d^H^BrjO. [115°]. 
 Formed, together with the preceding, by heating 
 bromo-eamphor (1 mol.) with Br (2 mols.) for 11 
 
OAIilPHOE, 
 
 671 
 
 hours at 130° (K. a. S.; c/. Swarts, Z. [2] 2, 205; 
 B. 15, 1622). Formed also by heating (6)-di- 
 bromo-oamphor with gaseous HBr at 130° 
 (Swarts. B. 15, 2185). Trimetrio crystals; 
 a:6:o = -95:l:-52; si. sol. alcohol, ether, and 
 petroleum. Less volatile with steam than the 
 preceding. 
 
 Beactuyns. — 1. Sodium-amalgam gives cam- 
 phor and campholenic acid.— 2. Couo. HNO. 
 gives di-bromo-nitro-camphor [130°]. 
 
 (e)-Di-bromo-camphor 0,„H„BrjO. [61°]. 
 Formed, together with its isomeride, by the 
 aetion of Br (1 mol.) on bromo-camphor (1 mol.) 
 for 7 hours at 120° (Kachler a. Spitzer, M. 3, 
 208; Zepharovioh, M. 3, 281; cf. E. SohifE, O. 
 11, 178; Montgolfier, Bi. [2] 28,253). Trimetrio 
 crystals, o:6:c = 2-0685:l:l-5778 (Cazeneuve a. 
 Morel, Bl. [2] 44, 161) = l-944:l:l-558 (K. a. S.). 
 V. sol. alcohol, ether, and petroleum. 
 
 Beactkms. — 1. Alcoholic KOH, or sodium- 
 amalgam, reduces it to bromo-camphor, and 
 finally to camphor. — 2. Sodium and CO^ form 
 camphor carboxylio acid. — 3. Cone. HNO3 gives 
 camphoric, and hydro-oxy-camphoric, acids, to- 
 gether witii bromo-di-nitro-methane (Kachler 
 a. Spitzer, M. 4, 554). 
 
 (a)-Chlora-bromo-camphor 0,„H„ClBrO. 
 
 [98^. [o]j=78°. Formed by heating ohloro- 
 oamphor [84°] with bromine in sealed tubes for 
 5 hours at 100°. White needles. Insol. water, 
 sol. hot alcohol, ether, and CHGl, (Cazeneuve, 
 Bl. [2] 44, 115 ; 0. B. 100, 802). 
 
 (;3)-0hloro-bromo-camphor G,oH„ClBrO. 
 [51'5°]. [o]j = 51°. Prepared by heating chloro- 
 oamphor (1 mol.) with bromine (2 mols.) in 
 sealed tubes for one hour at 100° C. Hard, 
 trimetrio crystals, a:6:o = l'9144:l:l'5395. Insol. 
 water, v. sol. alcohol, v. sol. ether, CHCI3, CgHj 
 and CS2 (Cazeneuve, Bl. [2] 44, 115; C. B. 
 100, 859). Decomposed by boiling AgOAcAq 
 (difference from preceding). 
 
 lodo-camphor C,„H,5lO. [44°]. Formed, to- 
 gether with NaCy and Nal, by the action of ICy 
 on sodimn-borneol dissolved in benzene (HaUer, 
 G. B. 87, 695). Monoelinio crystals, insol. 
 water, sol. alcohol. Decomposes at about 150°. 
 
 Nitro-camphor C,„H,5N03 [83°]. Prepared 
 by the action of alcoholic KOH on bromo-nitro- 
 camphor (Schift, B. 13, 1402 ; Q. 10, 330 ; 11, 
 21). Dissolves in aqueous alkalis. Gives a red 
 colouration with FcjClj. HNO^ gives a nitroso- 
 compound. On oxidation with HNO3 it gives 
 camphoric acid. By reduction it gives amido- 
 camphor. Bromine forms C3„H43N3Br20„ 1 
 [95°]. 01 forms similarly 03„H43N3Cl20i, ? 
 [110°]. Steam-distillation gives camphoric acid 
 and anhydride and NH3. This substance is 
 probably a mixture of the two following. 
 
 (o)-Nitro-camphor C,„H„(N02)0. [101°]. 
 [o]j (19-978 p.o. in benzene) -98°; (3-33 p.o. 
 in alcohol) —7-5°. Formed, together with its 
 (;3)-isomeride, by the action of Zn, Cu, Fe, or 
 alkalis on either chloro-nitro-camphor dissolved 
 in alcohol. Best prepared by using the copper- 
 zinc couple. The resulting zinc-salt of nitro- 
 camphor is decomposed by HCl. The (a)- 
 compound is the less soluble in cold alcohol 
 (Cazeneuve, C. B. 103, 275 ; 104, 1522 ; Bl. [2] 
 47, 920). Trimetrio prisms. Decomposes at 
 160°. LsBVorotatory. Its rotation varies with 
 concentration of the solution. It forms a com- 
 
 pound with benzene. It reddens litmus, and 
 decomposes carbonates. Fe^Cl^ colours its alco 
 holio solution blood-red. 
 
 (i8)-Nitro-camphor 0,„H„(N02)0. [98°]. 
 [o]j (3-33 p.o. in benzene) -75°; (3-83 p.o. in 
 alcohol) + 7"5°. Prepared as above. Soft, fern- 
 like, crystals (from alcohol). Insol. water, sol. 
 other menstrua. Less stable than the (a). 
 isomeride. Fe^Clj colours its solutions red. 
 Its salts are more soluble than those of the 
 (a)- compound. — NaA'. — ZnA'j : sol. water. 
 
 (a) - Chloro - nitre - camphor C,„HnCl(N0.J0. 
 [95°]. [o]j=-6-2°. Fromchloro-camphor[93°] 
 (1 pt.) and fuming HNO3 (4 pts.). Large trime- 
 trio prisms (from alcohol); a:6;c = 2-022:l:l'475 
 (the author does not say whether these numbers 
 belong to this or to the following body). Insol. 
 water, m. sol. cold alcohol. Decomposes above 
 100°. Beduoed by nascent hydrogen to nitro- 
 camphor (Cazeneuve, G. B. 96, 589 ; Bl. [2] 39, 
 503). 
 
 (/3) - Chloro - nitro - camphor C,„H,4C1(N02)0. 
 [98°]. [o]j = 10-5° (in alcohol). Occurs in the 
 mother-liquor from which the preceding has 
 separated. Soft crystals, v. sol. cold alcohol. 
 Beduction gives nitro-camphor. Less stable 
 than the (o) -isomeride, for alkalis remove CI 
 forming nitro-camphor even in the cold. Not 
 decomposed by alcoholic AgNOj (Cazeneuve, 
 C. B. 98, 306; Bl. [2] 41, 285; 44, 161; 47, 
 926). 
 
 (o) - Bromo - nitro - camphor 0,|,H,4BrN03. 
 [105°]. [o]j = -27°. Prepared by nitration of 
 bromo-camphor. Trimetrio crystals, a:b:o = 
 2-0854:l:l-5423. Nearly insol. cold alcohol. 
 By the action of alcoholic KOH or nascent H 
 it gives nitro-camphor (Schiff, Q. 10, 324 ; B. 
 13, 1402 ; 14, 1377). 
 
 Li-bromo-nitro-camphor C,|,H,5Brj(N02)0. 
 [130°]. From (a)-di-bromo-camphor by nitra- 
 tion (Kachler a. Spitzer, M. 4, 554). Trimetrio 
 prisms or needles, a:b:c = 1"76:1:1"49. Eeduced 
 by tin and HOAo to amido-camphor. 
 
 Amido-camphor 0,„H„NO. (247°). Waxy 
 solid. Strong base of alkaline reaction. Pre- 
 pared by reduction of nitro - camphor with 
 sodium-amalgam in alkaline solution. It reduces 
 Fehling's solution, AgNO,, and HgClj. With 
 HNOj it produces oxy-camphor (Schifi, B. 13, 
 1404). On distillation of the hydrochloride 
 of amido-camphor with steam, 'dicamphyl- 
 amine ' 02oH3,N02 passes over and ' camph- 
 imide' CigHi^N remains in the retort. Dicam- 
 phylamine [160°] crystallises in needles, 
 insol. acids, volatile with steam. Camph- 
 imide forms crystalline flakes, soluble in acids ; 
 nitrous acid converts its hydrochloride into 
 'diazo-camphor ' CioHnNjG [74°] which may be 
 reduced by Zn and HOAo to amido-camphor. 
 Diazo-camphor is converted by heat into ' de- 
 hydro-camphor ' C,„H„0 [160°] (R. Schiff, 
 a. 10, 362; 11, 171; B. 14, 1375). 
 
 Oxy-camphor (?) C,„'B.,fi^ [155°]. Prepared 
 by the action of HNO2 on amido-camphor 
 (Schiff, B. 13, 1404). Colourless crystals. Vola- 
 tile with steam. 
 
 Wheeler's ohloro-camphor (3. «.) gave with 
 alcoholic KOH an ' oxy-camphor ' [137°]. 
 
 The acetyl derivative [69°] of an ' oxy- 
 camphor ' [249°] is formed by ozidtsing acetyl- 
 boraeoli 
 
672 
 
 CAMPHOR. 
 
 _ An ' oxy -camphor ' [61°] is formed by oxi- 
 dising oamphene («, Terpbnbs) (Eachler a. 
 Bpitzer, A. 200, 358). 
 
 V. also Oampholknio acid. 
 
 ' mtro-ozy-camphor,' v. Niibo-oampholbnio 
 
 ACID. 
 
 Cyano-camphor v. Nitrile of Oamphob oae- 
 
 BOXTLIO AOID. 
 
 Ethyl-camphor O.oH.^EtO. (228°). S.O. 
 ^ -946. [o]j = 161°. From sodiura-oamphor 
 and EtI (Baubigny, Z. [2] 4, 481). Oil. 
 
 Isoamyl-camphor 0,„H,5(0jH„)0. (278° cor.). 
 [a]j = 59"4°. From sodium-camphor and isoamyl 
 iodide (B.). 
 
 ' Nitrohexolc acid' CsH„(N0j)02 i.e. 
 Me.CH(N02).CMej.C0jH(?) [115°]. Fromdinitro- 
 heptoic acid and sodium-amalgam (Kullhem, A. 
 167, 45; Kachler, A. 191, 157). Eectangular 
 four-sided columns (from water). Monoclinio; 
 6:c = 1: -6115 ; iS = 83° 30'. After several fusions 
 it melts at 111'5°. Quickly heated, it explodes. 
 
 Reactions. — 1. Dissolved in a little aqueous 
 KOH, mixed with KNOj and dilute H^SO, a fine 
 blue colour is formed. This colour is taken up 
 by ether; hence the body is probably akin to 
 pseudo-nitroles. — 2. Sn and HCl produce methyl- 
 isopropyl ketone, hydroxylamine, and COj. — 3. 
 Baryta in sealed tubes at 95° does not decom- 
 pose it, but forms the basic salt CsHjBaNOj. 
 
 Dinitrohezoic acid 0sH,„(NO2)jO2? i.e. 
 MeC(NjO,).OM:e2.C02H(?) [215°]. Got by 
 EuUhem by treating the residues in the pre- 
 paration of camphoric acid with strong HNO3 
 (A. 163, 281; Kachler, A. 191, 155). Mono- 
 clinic plates ; a:6:c = -5735:1: -6024; j3 = 70°42'. 
 M. sol. cold water, v. sol. hot water. Explodes 
 when rapidly heated. Its ammonium salt 
 gives with cupric acetate a bluish pp. sol. excess 
 of the acetate (difference from camphoric acid). 
 The free acid does not pp. oupric or lead acetate. 
 The neutral salts give a flocculent pp. with lead 
 acetate. 
 
 Salt. — BaA'jSaq. Needles. 
 
 Beactions. — 1. Eeduced in alcoholic solution 
 by sodium amalgam, to mononitroheptoic acid. 
 2. Beduced by Sn and HGl to methyl iso-propyl 
 ketone and hydroxylamine. — 3. Potash and 
 haryta heated with the aqueous acid in sealed 
 tubes produce both nitro-heptoic acid and 
 methyl isopropyl ketone. 
 
 Hydro-oxycamphorouic acid OjH„08. [164-5°] 
 (Kachler, A. 191, 148). Needles. Sol. cold 
 water. Tribasio acid. Gives no pp. with BaClj 
 or CaClj and NHj, even on boiling (difference 
 from camphoronio acid). Cupric acetate gives 
 no pp. until boiled when a bluish-green cupric 
 salt is ppd. Lead acetate gives a white pp. 
 soluble in excess. AgNOj gives a white pp. 
 soluble in hot water. 
 
 Salt s.— NHjHjA'".— CaHA'" 2aq.— CajA'",. 
 -Ba3A"V-Cu3A».-Ag3A"'. 
 
 ISOMEEIDES OF OAMPHOB. 
 
 leevorotatory camphor C|„H,„0. [172° cor.] 
 (R.); [175°] (0.). (204°). S.G. ia -9853 (0.). 
 [o]j=-47° (C); -42° (H.). Occurs together 
 with a terpene in the ethereal oil obtained from 
 the leaves of fever-few, Matricaria Parthenium 
 (Chautard, G. B. 37, 166). Apparently formed 
 also by oxidising the laavorotatory terpene ob- 
 tained by treating with alcoholic KOH the pro- 
 
 duct of the action of HCI on Imvorotatory oil 
 of terpentine (Biban, Bl. 24, 19). Obtained also 
 by oxidising the borneols of madder, valerian, 
 Ngai, and Bang-Phien (Haller, G. B. 103, 64 ; 
 104 ,66). HNO3 gives Isevorotatory oamphorio 
 acid [o]j=— 46°. The corresponding bromo- 
 oamphor is also Isevorotatory, [o]i = — 128°. 
 
 Inactive camphor C,„H,jO. [173°]. Got by 
 oxidising inactive borneol (q. v.) with cold HNO, 
 and then adding water (Armstrong a. Tilden, 
 G. J. 35, 752). Also by oxidising inactive 
 camphene with H2SO4 and K^Cr^O,. Heated 
 with HNO, it forms a oamphorio acid, [203°] 
 and giving when heated alone an anhydride, 
 [223°]. 
 
 Inactive camphor Vrcym Oil of Sage. 0,pH,jO. 
 [174"']. (205° uncor.). When oil of sage is dis- 
 tilled, the fraction 205°-208° deposits this 
 camphor. It apparently only differs from ordi- 
 nary camphor in being inactive, for:— 1. PCI5 
 gives an oil which ia converted by water into a 
 wax-like solid, [80°] whence Na forms a white 
 solid.— 2. Boiled with HNO, (2:1) it forms in- 
 active camphoric acid [186°]. — 3. Dissolved in 
 toluene and treated with Na and CO2 it forms 
 inactive borneol, [200°].— 4. Distilled with P^Sj 
 it forms cymene (M. M. P. Muir, G.J. 37, 685). 
 
 'Eaoemio' camphor OjoHsjOj (?). [179°]. 
 This name is given to the product of the oxi- 
 dation of a mixture of equivalent quantities of 
 Isavo- and dextro- rotatory borneol, and in 
 therefore inactive by compensation, as racemio 
 acid is (Haller, G. B. 105, 66). It gives a bromo- 
 derivative [51°] and a camphoric acid [205°]. 
 The 'racemic' camphor, bromo-camphor, and 
 camphoric acid were also prepared by mixture 
 and found to be identical with the above. They 
 differ in solubility as well as in melting-point 
 from the active compounds. The borneol of 
 amber, and consequently the camphor derived 
 therefrom, appear to be a mixture of dextro- 
 and IsBvo-rotatory varieties in unequal propor- 
 tions. 
 
 Camphors, or bodies resembling camphor, 
 have been found in many essential oils, e.g. oils 
 of alant (p. 94), absinthe (p. 2), chamomile, 
 eucalyptus, lavender, nutmeg, rosemary, &o. 
 When a camphor is converted into borneol, the 
 rotatory power of the resulting borneol varies 
 with each operation, but the camphor regene- 
 rated by oxidising the borneol has in each case 
 the rotatory power of the original camphor 
 (Montgolfler). According to HaUer (C. B. 105, 
 228) this may be explained by supposing that 
 the resulting borneol is always a mixture of 
 a stable borneol rotating in the same direction 
 as the original camphor and of an unstable 
 borneol rotating in the opposite direction. 
 
 CAMPHOB-CARBOXYLIC ACID C„H,eOs. 
 [129°]. Formed as a by-product in the pre- 
 paration of borneol from camphor by the action 
 of Na on a solution of camphor in toluene, 
 the product being treated with COj. It is 
 produced by the union of 00^ with sodium, 
 camphor (Baubigny, Z. [2] 4, 481, 647 ; A. Gh. 
 [4] 19, 221; Kachler a. Spitzer, B. 13, 1412; 
 M. 2, 233). Long colourtess monoclinic pyra- 
 mids. Sol. water. Decomposes below 100° 
 into CO2 and camphor. 
 
 Reactions. — 1. Boiling AoCl forms C^Ji^^O, 
 [196°], crystallising in needles. — 2, P,Oj, acting 
 
OAMPHORIO ACID. 
 
 673 
 
 on its solution in CHClj, forms C.^.H^Os [265°]. 
 3. PCI, forms OjjHjaCl, [45°] which separates 
 from ether-aloohol in triclinio crystals a:b:c = 
 1: -804 : -47. 
 
 Salts .— NaA.'.— BaAV— PbAV 
 
 Ethyl ether EtA' : (276= unoor.) ; S.G. 
 IS. 1-052 ; colourless fluid (Eoser, B. 18, 3113). 
 
 Nitrile 0,|,H,5CyO. Cyano-camphor. [128°]. 
 (250°). Pormed by passing cyanogen into a 
 mixture of camphor and sodium-camphor dis- 
 solved in hot toluene; extracted by shaking 
 with aqueous NaOH and ppg. by HOAo. Beet- 
 angular prisms (from ether) ; sol. alcohol, ether, 
 and HOAc. Contains an atom of hydrogen 
 displaceable by Na or E, forming unstable salts. 
 Cone. HOI at 100° converts it into camphor 
 carboxylio acid. Oxidising agents give HCyand 
 camphoric acid. Alcoholic NaOH slowly con- 
 verts it into the ether of camphor carboxylio 
 acid (Haller, C. B. 87, 843 ; 93, 72 ; 102, 1477). 
 
 Chloro-camphor carboxylio acid CiiHijClOj. 
 Formed by passing CI into a solution of sodium 
 camphor, carboxylate (Sohiff a. Puliti, B. 16, 
 887). Floeeulent pp. ; decomposes on fusion 
 into CO2 and chloro-camphor. 
 
 Bromo-oamphor carboxylio acid OnHisBrOj. 
 [110°]. From camphor carboxylio acid and Br 
 (Silva, B. 6, 1092). Both the acid and its salts 
 readily decompose into COj and bromo-oam- 
 phor. — ^BaA'2. — AgA'. 
 
 Oxy - camphor carboxylio acid C,,H,sO,- 
 [160°]. [a]D = 59°. Pormed by boiling the 
 nitrile of camphor carboxylio acid with aqueous 
 KOH jailer, C. B. 87, 929). Nodules (from 
 ether).— CaA" 6aq.— BaA" 6aq. 
 
 CAKFHOB DIOHLORIDE C.^HibCIj. [165°]. 
 Prepared by the' action of PCI5 on camphor in the 
 cold : C,„H„0 + PCI5 = POGI3 -1- C,„H,eCl2 (Spitzer, 
 B. 11, 363, 1819 ; M. 1, 319). Formed also 
 by chlorinating bornyl chloride (Kachler a. 
 Spitzer, A. 200, 361). Feathery trimetric needles ; 
 d:6:c = •917:1:1-686. Easily soluble in alcohol 
 and ether. Easily splits off HCl. 
 
 CAMFHOBIC ACID C,„H,sOi i.e. 
 CHj— OPr— OOjH 
 C,H„(COjH), or I I (Schifi) 
 
 • '" ' OH,— CMe-CO^H 
 
 or Pr.CH(C0jH).CH2.CH:CMe.C0.,H (W. Eoser, 
 
 A. 220, 278). Mol. w. 200. [186°]. S.G. 1-19. 
 S. -625 at 12°. E 00 83-14 (in a 1 p.c. aqueous 
 solution) (Kanonnikoff, J. jor. [2] 31, 849). 
 [o]n = 46°. Pormed by boiling camphor or cam- 
 pholio acid with cone. HNO, (Kosegarten (1785) ; 
 Laurent, A. Oh. 63, 207 j Malaguti, A. Ch. 64, 
 151- A. 22, 50; Wreden, A. 163, 323; V. Meyer, 
 
 B. 3', 116 ; Kachler, 4. 162, 262). It is best to use 
 the mixture of camphor and borneol obtained by 
 the action of Na on camphor (Maissen, (?. 10, 
 280). Formed also by the oxidation of chloro- 
 or bromo- camphor with alkaline permanganate 
 (Balbiano, (?. 17, 240). Monoolinio crystals; 
 the rotation in alkaline solution has been 
 studied by Thomsen (J. pr. [2] 85, 157). The 
 refractive power indicates a double union, which 
 does not agree with Sohiff's formula. 
 
 Beactions.—l. Seat splits it up into water 
 and an anhydride— 2. Water at 180° changes it 
 into meso-camphorio acid— 3. Fuming HCl at 
 200° forms C,H„ and OeH,, (Wreden, A 187, 
 ^g9\ _4. Cone. HIAq at 200° gives xylene tetra- 
 
 yoji. I, 
 
 hydride and hexahydtide (W.). — 5. By the action 
 of ZnClj xylene tetrahydride CjHu is produced ; 
 
 C,H„(C02H)2 = 0,H,4 -^ CO2 -H CO -I- H^O. 
 The same hydrocarbon is produced by the action 
 of ZnClj on ammonium camphoramic acid : 
 
 0,oH„02(NH2) (ONH J + ZnOlj + B.fi = 
 2NH<Cl-i-ZnO-fCO-HCOj-H05H„ (Ballo, B. 12, 
 324). — 6. The ammonium salt distilled with 
 PjOs gives a terpene CjoH,, (Ballo, A. 197, 322). 
 7. Cone. HjSO, forms CO and ' sulphocam- 
 phorio acid.' — 8. Cone. HNO3 gives campho- 
 ronic acid. — 9. Potash-fusion gives pimelic acid 
 Pr.CH(C02H).CHj.C02H and an acid OioH,jO, 
 (Hlasiwetz a. Grabowsky, A. 145, 205).-— 
 10. Distillation with soda-lime gives camphoric 
 anhydride and phorone C9H14O (Meyer, B. 3, 
 117). Distillation of oamphorates gives similar 
 
 Salts.— (Kemper, Ar. Ph. [2] 110, 106; 
 117, 23). NH^HA"a;aq.— (NHJjA".— LijA".- 
 Na^".— KjA": deliquescent.— MgA" 7^aq. S.40 
 at 20°.— MgA" 12aq.— MgA" 13|aq.— CaH^'V— 
 CaA" 4laq. — CaA" 7aq. — OaaHjA", 8aq. — 
 BaHjA'j 2aq.— BaA" aq : needles and feathers 
 (Kingzett, G. J. 45, 93).— BaA"4iaq.— ZnA".— 
 PbA".— CuA".— Ag,A". 
 
 Ethyl -ammonium salt (NH3Et)jA"; 
 small needles (from alcohol). Converted by 
 PCI5 into camphoric di-ethyl-imidine. 
 
 Mono-methyl ether MeHA". [68°]. 
 [a]j = 51-4°. Trimetric prisms (from ether); 
 gives camphoric anhydride when distilled. V. 
 si. sol. water (Loir, A. Ch. [3] 38, 488). 
 
 Mono-ethyl ether EtHA". S.G. ?21« 1-095. 
 
 Syrup. 
 
 Di-ethyl ether Et^A". (286°). S.G.isi-029. 
 Formed, together with camphoric anhydride, by 
 the distillation of the mono-ethyl ether (Mala- 
 guti, A. Ch. [2] 64, 152 ; 70, 360 ; Meyer, B. 
 3, 118). Liquid. Chlorine produces a tetra- 
 ohloro- derivative (O^HjOyjA". S.G. ii 1-386. 
 
 Chloride O.oHiAClz- Heavy oil, decom- 
 posing at 200° (Moitessier, A. 120, 252). 
 
 Anhydride C,^^fir [217°]- (above 270°). 
 
 S.G. ^ 1-194. [o]b 7-7° (in benzene). 
 
 Formed by heating camphoric acid or its salts 
 (Bouillon-Lagrange, A. Ch. 28, 153 ; Laurent, 
 A. Ch. 68, 207; Malaguti, A. Oh. 64, 151; 
 Blumenau, A. 67, 119 ; Monoyer, J. Ph. [3] 45, 
 177). Pormed also from camphoric acid by the 
 action of (1 mol. of) PCI5 (Gerhardt a. Chiozza, 
 A. 87, 294), of cone. HjSO,, of Ac^O, or of AcCl 
 (Anschiitz, B. 10, 1881). Long trimetric prisms 
 (from alcohol) (Montgolfier, A. Ch. [5] 14, 5). 
 V. si. sol. water, v. sol. alcohol, v. e. sol. ether. 
 Slowly converted by boiling water into cam- 
 phoric acid. The statement of Brodie {Pr, 9, 
 361; 12, 655) that barium peroxide formed 
 camphoric peroxide has been denied by Kingzett 
 (C. /. 45, 98). 
 
 Amide CjH„(C0NH2)j. Amorphous mass 
 (Moitessier, A. 120, 253). 
 
 Imide C,H„:CA:NH. [180°] (in sealed 
 tubes, Ballo, A. 197, 332). Formed by heating 
 ammonium camphoramate at 160° (Laurent, 
 Cornet. cUm. 1845, 147 ; A. 60, 327). Lamina. 
 May be distilled. 
 
 Ethylimide 0,H„:0j0,:NEt. [50°]. 
 (275°). Colourless crystals. Prepared by dis- 
 
674 
 
 CAMPHORIC ACID. 
 
 tilling ethylamine eamphorate (Wallaoh a. 
 Kamenski, B. 14, 164 ; A. 214, 248). 
 
 Allyl-imide C.n^-.CfiiiNO,^^. [49°]. 
 Formed by heating oamphorio acid with allyl 
 thiooarbimide. Insol. water, sol. alcohol and 
 ether. 
 
 Phenyl-imide CsHniCjO^rNPh. [116°]. 
 Formed, together with phenyl-oamphoramio 
 acid, by warming camphoric anhydride with 
 aniline (Oerhardt a. Laurent, A. 68, 3S). 
 Needles (from ether) ; insol. cold water. 
 
 Di-ethyl-imiao-imidine OjjH^iNjO i.e. 
 >0=NC,H5 
 0,H„< >N02H. (286°). S.(J. iS 1-018. 
 
 ^0 = 
 Liquid ; y. si. sol. water. Fps. salts of Cn and 
 Fe. Prepared by the action of POI5 on ethyl. 
 amine-camphorate or by the action of ethyl- 
 
 /CCl, 
 amme on the chloride (OgHX >NEt) obtained 
 
 \co 
 
 from PCI, and camphorio-ethyl-imide. By HCl 
 at 200° it is decomposed into ethylamine and 
 camphorio-ethyl-imide. Salts. — B'HCl: deli- 
 quescent crystals. — B'HI: sparingly soluble 
 needles.— (B'HOlj^PtCl,. Its ethylo-iodide 
 B'Etl : [245°] ; forms long colourless prisms 
 (Wallach a. Eamenski, B. 14, 162; A. 214, 
 242). 
 
 Nitrile CjH„(CN)2. Formed, in small 
 quantity, together with hydrocarbons OgHu and 
 CjgHgj by distilling ammonium camphoramate 
 with PjOj (Ballo, A. 197, 334). CrystalUne; 
 insol. water. 
 
 Camphoramio acid C8H„(CONH2)(C02H). 
 So-called 'amido-camphoric acid.' The ammo- 
 nium salt is formed by the action of NH3 on 
 an alcoholic solution of camphoric anhydride 
 (Laurent, Gompt. cMin. 1845, 147 ; A. 60, 326). 
 Trimetrio crystals ; m. sol. hot water, v. sol. 
 alcohol.— NHjA'aq. [100°]. When heated with 
 dry ZnCL, it gives xylene tetrahydride and a ter- 
 pene (Ballo, B. 12, 324).— PbA'j.— AgA'. 
 
 Fhenyl-camphoramic acid 
 0,H„(CONPhH) (COjH). Formed by boiUng the 
 phenyl-imide of camphoric acid with alcoholic 
 NHg, or camphoric anhydride with aniline. 
 Needles (from alcohol) ; v. si. sol. boiling water. 
 — AgA' pCiaurent a. Gerhardt, A. 68, 36). 
 
 Bromo-camphoTic anhydride 
 CO 
 0|,H,jBr^QQ^O. From camphoric anhydride 
 
 (10 g.) and Br (15 g.) at 130° (Woringer, A. 227, 
 3) ; an additive compound CijHuOjBrj appears 
 to be first formed (Wreden, A. 163, 330). Tri- 
 metrio crystals (from chloroform). a:li:c = 
 •8866:1: -6766. NHj gives the imide of oxy- 
 oamphorio acid, 
 
 (aj-Oxy-camphorio acid 0,„H,s05. Formed, 
 together virith pimelic acid, by fusing camphor 
 with KOH (Hlasiwetz a. Grabowski, A. 145, 212). 
 Thick liquid ; the salts are amorphous. 
 
 (J3)-Oxy-campIiorio acid C,|,H,jO, 
 
 Anhydride CuHnOji.e. 
 CjH„(OH):OA:P(?) Cam^hamc acid. [201°]. 
 Formed by boiling bromo-camphoric anhydride 
 with water (Kachler, A. 162, 264). Monoolinio 
 prisms (containing aq or 2aq) (Griinling, 2.227, 
 4). Sublimes at 110°. Decomposed on distil- 
 lation giving COj, lauronolio acid CjHuOj, and 
 • canipho-lastone ' C,H„Or Water at 180° 
 
 splits it up into COj and CsH,, (119°).— 
 Ba(0,„H,30,), liaq.-Cd(C,.H,30,)j 3aq. 
 
 Ethyl ether BtO,„H,A- [63']- F'^o'» 
 bromo-camphoric anhydride and alcohol at 150°. 
 Prisms. 
 
 Imide CjoH.sNO, i.e. CsH„(0H):C.,02:NH (?) 
 [208°]. Anndo - camphoric anhydride. From 
 bromo-camphoric anhydride and cone. NHjAq 
 at 150° (Wreden, A. 163, 339). Long needles 
 (from alcohol). Sublimes at 150°. Converted 
 by nitrous acid into the anhydride. 
 
 Oxy-camphoramic acid CuH^NO, i.i. 
 C8H,3(OH)(CONH2)(C02H). ' Amido-camphoria 
 acid.' [160°]. Formed by boiling the imide of 
 oxy-camphoric acid with dilute KOH (Wreden, 
 A. 163, 340). Prisms containing aq (from alco- 
 hol). On fusion it is converted into the parent 
 imide. Converted into oxy-camphoric anhy- 
 dride by HNOj, by cone. HClAq, or by H2SO4.— 
 CaA'2 2aq. 
 
 ' Sulpho - camphoric acid' so - called, 
 0|,H,„SOj. [160°-165°]. SulphocamphyUe 
 acid. Formed, together vrith CO, by heating 
 oamphorio acid or anhydride with cone. HjSO, 
 (Walter, A. Ch. [3] 9, 177 ; Kachler, A. 169, 
 179). Triolinio prisms (containing 2aq) ; 
 ffi:6:c = -8515:1: -7590; o=82°39'; 3=121° 10'; 
 7= 111° 36' (Zepharovich, Sits. B. 73, 7). V. e. 
 sol. water, alcohol, and ether. HNO, (S.G. 
 1-25) converts it into C^Hj^SO,. Potash-fusion 
 gives OjHijOj [148°], insol. cold water, but sepa- 
 rating from alcohol in monoolinic crystals. 
 
 Salts. — (NHj2A"aq. — KjA". — CaA", — 
 BaA". — PbH2A"j4aq: trimetrio. — PbA". — 
 BaCuA"j.— Ag^A". 
 
 ISOSIEIIIDES OF OAMPHOEIO AOID. 
 
 Lsevo - rotatory camphoric acid OigEigO^. 
 [186°], [a]j = - 46-3° (in alcohol). Formed by 
 the oxidation of Isevo - rotatory ([o]j = — 38°) 
 borneol, or the corresponding camphor, by heat- 
 ing for several hours with a large excess of 
 HNO3 (S.G. 1-27) (Ohautard, C. B. 37, 166; 
 Haller, C. B. 103, 64). Besembles camphoric 
 acid in all respects except that its rotation 
 though equal is opposite. 
 
 Inactive camphoric acid (C,jH,50Jj. [204°], 
 S. 1; S. (alcohol) 33 _; S. (ether) 28 (C). 
 Formed by heating inactive camphor with HNO, 
 at 100°, or by mixing equal weights of dextro- 
 and Isevo-camphorio acids (Chautard, O. B. 56, 
 698; Armstrong a. Tilden, C. J. 35, 757- 
 Haller, G. B. 105, 66), Less soluble than its 
 isomerides. 
 
 Diethyl ether Et^A". (270°-275°). S.G, 
 15 1-03 (0.). 
 
 Anhydride (0,„H,A)2- [223°] (A. a. T.), 
 S. (chloroform) 25 ; S. (ether) 4 ; S. (alcohol) 1-5 
 (0.). Formed by heating the acid. 
 
 An inactive camphoric acid [186°] was ob- 
 tained by Muir (0, J. 37, 685) by oxidising the 
 camphor of oil of sage. 
 
 Ueso-camphoric acid CigHisO,. [113°], 
 
 Formation. — 1. Formed by heating dextro- 
 camphoric acid (S g.) with (20 c.c.) fuming HCl 
 at 140° for 30 hours (Wreden, Z. [2] 7, 419 ; A. 
 163, 328 ; B. 6, 565).— 2. By heating dextro- 
 camphorio acid (5 g.) with HI (30 c.c, of S.G, 
 1"6) at 160°. — 8. By heating camphoric acid 
 with water at 200° (Jungfleisch, B. 6, 268, 680), 
 4, Together with ' sulphocamphorio acid ' by tha 
 
CAJIPHOROXIM. 
 
 675 
 
 action of H„SOj on camphor. Ooeurs also in 
 small quantity in the preparation of camphorio 
 acid from camphor and HNO. (Kaohler, A, 169, 
 179 ; 191, 146). 
 
 Prqperiies.— Crystalline, but separates from 
 alcohol and ether as an oil. More soluble than 
 ordinary camphoric acid. Cone. HjSO, converts 
 it on warming into ' sulphocamphorio acid.' 
 When heated it gives the anhydride of ordinary 
 camphoric acid. Boiling dilute HOI changes it 
 into inactive camphorio acid. 
 
 CAMPHOEILE O.^HijOj. [222°]. Occurs to- 
 gether with galangin and alpinin in the galanga 
 root (Alj^nia officmarum). Flat yellow needles 
 (containing aq), sublimable. Sol. hot alcohol, 
 ether, and acetic acid, si. sol. chloroform and 
 benzene, insol. water. Dissolves in alkalis. On 
 oxidation with dilute HNO3 it produces anisio 
 and oxalic acids. 
 
 Salts. — A"Pb: yellow amorphous pp. — 
 A'TbjO. — A"Ba 2aq : orange pp. 
 
 Di-acetyl derivative C,5H,„Oi(OAo)2. 
 [189°]. Colourless crystals. Insol. water. 81. 
 sol. alcohol. 
 
 Di-benzoyl derivative C|jHi|,04(0Bz)2. 
 [186°]. Pine white needles. Scarcely sol. alcohol, 
 insol. water. 
 
 Di-bromo-derivative CijHuBrjOj. [225°]. 
 Yellow needles. SI. sol. alcohol (Jahns, B. 14, 
 2385). 
 
 CAUFHOB-IMIDO-ACmiC ETHER 
 
 C,.HaN04i.e. C(P„<^°>N.CH2.C0,Et. [86°]. 
 
 Formed by adding a solution of CHjCl.COjEt to 
 a solution of sodio-camphorimide in absolute 
 alcohol. Large transparent crystals (from alco- 
 hol), sol. ether (Haller a. Arth, C. B. 105, 
 281). 
 
 CAMFHOB OIL. An oil obtained, together 
 with camphor, by distilling the wood of Laurits 
 camphora with water. It consists chiefly of 
 ' camphorogenol ' but contains also several 
 terpenes {q. v.). 
 
 Camphorogenol C.oHisOj or C,„H,b02 or 
 C,„H„Oaq(?) S.G. 22 .9794. [a]j = 29-6°. An 
 oil, V. e. sol. alcohol and ether. HNOj acts upon 
 it forming a small quantity of camphor. CrOj 
 acts similarly. Excess of cone. HNO, gives 
 camphoric acid [185°], [a]j = 40'3°. AcjOhasno 
 action. Sodium reduces it, in alcoholic solution, 
 to bomeol, [198°], (212°), [aJj = 22-9°. With 
 ZnOlj it yields cymene (Yoshida, C. J. 47, 785 ; 
 Oishi, C. N. 50, 275 ; Wallach, A. 227, 296 ; 
 Lallemand, A. Oh. [3] 57, 404). 
 
 CAMPHOB-PHORONE v. Phobone. 
 
 CAMPHORONIC ACID C,H„Oj. Mol. w. 
 218. [137°] Formed by oxidising campholic 
 or camphanic acids (Bredt, JB. 18, 2989). 
 
 Preparation. — From camphor and HNO3. 
 Present in the mother liquor from which oam- 
 phoronic acid has separated. Obtained by means 
 of the barium salt (Kachler) and purified by de- 
 composing this with HOI, extracting with ether, 
 boiling off the ether, dissolving in water, 
 neutralising with lime and boiling. The pure 
 calcium salt then separates (Bredt, A. 226, 251 ; 
 c/. Kaohler, B. 7, 1728 ; A. 159, 286 ; 162, 262 ; 
 Kachler a. Spitzer, M. 6, 173). 
 
 Properties, — Crystallineaggregates of needles, 
 V. e. sol. water, alcohol, and wet ether, si. sol. 
 pure ether. Produces on distillation COj, iso- 
 
 butyrio acid and the anhydride CjEj^Oj [135°] 
 which forms trimetric crystals, a:5:c = "96:l: -82 i 
 Bol. water, alcohol and ether. This anhydride 
 forms with NH3 the compound CjHiiNHJO, 
 [0. 128°], V. sol. water. 
 
 Reactions. — 1. AoOl gives CjHuOs and then 
 the anhydride OigHjjOs [176°] ; crystals, insol. 
 cold alcohol and ether ; reconverted into oam- 
 phoronic acid by boiling alkalis. — 2. Br at 130' 
 gives oxy-camphoronic acid. — 3. Potash-fusion 
 gives isobatyric acid. — 4. Aqua-regia forms two 
 acids C„H,20|i. — 5. KMnO, gives HOAo and an 
 acid CgHi^Oi (Kachler, M. 5, 415). -6. The Ca 
 salt distilled with lime gives a ketone C.H,jO. 
 
 Salts .— NH^H^A'" : [128°]. — (NHJ^HA'" : 
 [148°].— K^HA'" aq.— CajA'"^ 12aq.— BaHA"'aq : 
 m.sol.water.— BasA'''^ : insol. water.— BasA"'j 6aq. 
 — BasA"'jslOaq.— ZnHA'": v. e. sol. water.— 
 CdHA"'6aq. — Pb,A"'2 4aq. — Cu3A"'j2aq. — 
 CuHA"'2iaq.— CujA",.— AgjA'".— AgjHA"'aq. 
 
 Mono-ethyl ei/ier.- Theanhydride(302°) 
 (or anhydrides liquid and solid [67°], Hjelt, 
 B. 13, 797) CaHiiEtOs of this ether is formed 
 together with alcohol by distilling the di-ethyl 
 ether. 
 
 Di-ethyl ether EtjHA'". From the acid, 
 alcohol, and HCl. 
 
 Tri-ethyl ether EtaA'". (302°). From 
 AgjA'" and Btl. Liquid. 
 
 Chloride OsH„OCl. [131°]. Needles, si. 
 sol. water, sol. alcohol and ether. 
 
 Mono-amio acid C5H„(CONH2)(C02H)2. 
 
 Anhydride CaHuNO^. [212°]. Fromliquid 
 mono-ethyl camphoronate and alcoholic NH, 
 (Hjelt, B. 13, 798). By the same treatment the 
 solid ethyl camphoronate gives a compound 
 C|,H,jN204 (? di-amic acid) crystallising with 
 HOEt. It melts at [145°], and is converted by 
 boiling HClAq into camphoronic acid. 
 
 Di-amic acid OgHisNjOj i.e. 
 C,H„(CONH2)2(COi,H). [0. 160°]. Prom di- 
 ethyl camphoronate and NH3 at 120° (H.). 
 HOlAq converts it into a compound CpHuNO, 
 [212°]. 
 
 Constitution. — Camphoronic acid appears to 
 contain 3 oarboxyls: CbH„(C02H)3, as shown 
 by the salts and ethers. AcCl gives no acetyl 
 derivative. The formation of an anhydride by 
 distilling the ether does not prove it to be lac- 
 tonic. Potash-fusion produces iso-butyric acid, 
 hence it contains isopropyl. Since it does not 
 split off CO2 on distillation, the carboxyls must 
 be attached to different carbon atoms. Hence 
 it is iso-propyl-tri-carballylio acid, 
 
 CHj(C02H).CPr(C02H).CHrCOjH or 
 CH2(C02H).CH(C0jH).CHPr.002H. 
 
 Oxy - camphoronic acid OsHjjOe. [0. 210°]. 
 Formed by heating camphoronic acid OjHuO, 
 (1 mol.) with Br (1 mol.) for two hours at 130° 
 (Kaohler, A. 159, 296). Monoclinic crystals 
 (containing aq),a:6:c = l-4918:l:-9808 ; j8 = 86° 50'. 
 According to Zepharovioh (J. 1877, 641) they 
 are dimorphous. V. sol. water, alcohol, and 
 ether ; may be distilled. 
 
 Salts . — KHA" aq : crystals.— KjA" : gummy. 
 — ^BaA"aq: pearly plates. — Pb3(08H5O8)j2aq.— 
 Ag^A". 
 
 Hydro-ozy-camphoronlc acid v. Camfhok. 
 
 CAMPHOROXIM C,„H„N0 i.e. 0,„H,e:N.OH. 
 [115°]. (c. 250°). Formed by the action of 
 hydroxylamine on camphor (Nageli, B. 16, 498), 
 
 SX2 
 
676 
 
 CAMPHOROXIM. 
 
 liong needles. Smells like camphor and rotates 
 on water. Sol. .alcohol, ether, acids and alkalis. 
 Beactions. — 1. Hydroxylamine is not split ofE 
 by heating with aqueous HCl even at 120°. — 2. 
 By heating with acetyl chloride it loses HjO 
 yielding the nitrile of oampholenio acid C|„H]5N 
 (Goldsohmidt a. Ziirrer, B. 17, 2069).— 3. Is re- 
 duced in alcoholic solution by metallic sodium 
 
 to bornylamine C,H,4C I . The oxim- 
 
 \CH.NH2. 
 anhydride is reduced to the isomeric oamphyl- 
 amine (Leuchart a. Bach, B. 20, 111). 
 
 Hydrochloride C,„H,5N0H,HC1 : white 
 powder, si. sol. water, v. sol. alcohol and acids. 
 
 Sodium salt. — C,||H,8N(0Na) : white pow- 
 der, V. sol. hot water and hot alcohol. 
 
 Ethyl ether 0,oH,^N(OBt) : (209°); mobile 
 liquid. 
 
 Anhydride C,„H,5N: (217°), liquid; formed 
 by heating camphoroxim with acetyl chloride. 
 Is the nitrile of Oampholenio acid (a. v.) (Nageli, 
 B. 16, 2981). 
 
 Isocamphor-ozim is the amide of Oampho- 
 lenio ACID (g. v.). 
 
 GAKPHO-TEBFENE v. Terpbnes. 
 
 CAMPHBENE v. Phobone. 
 
 CAMPHKESIC ACID or CAMPHEETIC ACID 
 so called by Sohwanert (A.. 128, 77) has been 
 shown by Kachler (A. 191, 143) to be a mixture 
 of camphoric and camphoronic acids. 
 
 CAMPHYIAMIBTE 0,„H,gN possibly 
 0,H,3(CH2NH2):CHj (195°). Prepared by adding 
 metallic sodium to an alcoholic solution of 
 campholenio nitrile (camphor-oxim-anhydride). 
 Colourless liquid. VolatUe with steam. Readily 
 absorbs 00^ from the air and solidifies to a 
 crystalline carbonate. Primary base. 
 
 Salts.— B'jH^CljPtCli: glistening golden 
 plates, nearly insol. water. — B'HClHgClj: 
 colourless orthorhombic plates ; sol. hot water. — 
 B'CjHjOjJaq: [194°], colourless orthorhombic 
 glistening crystals, v. sol. hot water. — 
 B'jH2S04aq: long rhombic prisms, m. sol. cold 
 water. — ^B'^H^OrjO, : orange-red plates. — The 
 picrate forms fine yellow needles, [190°-194°]. 
 
 Benzoyl derivative C,„H,8NBz: [77°], 
 colourless prisms (Goldschmidt a. Sohulhof, B. 
 18,3297; 19,708; 20,483). 
 
 Isomeride v. BonNYiyAMiNE. 
 
 CAMPHYE-PHENYL-THIO-UEEA 
 SC(NH0eH5)(NHC,„H„). [118°]. Formed by 
 combination of phenyl-thiocarbimide and cam- 
 phylamine. Short colourless prisms. V. sol. 
 alcohol and benzene, si. sol. ether, v. sol. ligroin 
 (Goldsohmidt a. Schulhof, B. 19, 712). 
 
 CAMFHYL ■ DI ■ THIO ■ GABBAMIC ACID 
 C,„Hi,.NH.OS.SH. The camphylaraine 
 salt, 0,„H„.NH.CS.SNH3(C,„H„), is formed by 
 mixing camphylamine with CS^. White 
 powder, [110°-116°], sol. benzene. The sodium 
 salt OjjHjj.NHiOS.SNa forms white glistening 
 plates, sol. cold, decomposed by hot, water 
 (Goldschmidt, B. 19, 712). 
 
 CANADA BALSAM. Exudes from incisions 
 in the bark of Abies balsamea. Transparent 
 thick liquid with refractive index (1'532) nearly 
 the same as that of crown glass. Dextro- 
 rotatory. Steam-distiUation separates a Isbvo- 
 rotatory terpene (167°), which forms a crystal- 
 line compound with BCl (Donastre, ^. Ph. 
 
 8, 572 ; Caillot, J. Ph. 16, 436 ; Wirzen, Disser- 
 tation, Helsingifors, 1849). 
 
 CANADOL. A term applied by Vohl (D. P. J. 
 172, 319) to that portion of the volatile hydro- 
 carbons of Canadian and Pennsylvanian petro- 
 leum which boils at 60° and has a S.G. -65 to 
 ■70. It is also called petroleum-ether or ligroin. 
 It consists chiefly of w-hexane. 
 
 CANAITQA OIL. Alan-gilan. From Can- 
 anga odorata. Neutral oil (170°-290°). It con- 
 tains benzoyl and acetyl derivatives, a compound 
 that unites with NaHSOj, and probably a phenol 
 (Miickiger, Ph. [3] 11, 934). 
 
 CANAEIUM. The fixed oil of Canarimn 
 comnvwne contains 61 p.c. olein and 49 p.o. 
 stearin and myristin (Oudemans, J. pr. 99, 407). 
 
 CANAiJBA WAX v. Oabnauba wax. 
 
 CANE STTGAE v. Suoab. 
 
 CANNABIS INDICA. Indian hemp when 
 distilled with steam yields an essential oil 
 C.^H,, (257°); V.D. 7-1 ; S.G. g -93; [a]„ = 
 - 10-81 at 25-5° (in chloroform). The oil resini- 
 fies on exposure (Valenta, G. 10, 479 ; 11, 196 ; 
 cf. Martius, O. G. 1856, 225 ; Personne, J. Ph. [3] 
 31, 46). HNO, (S.G. 1-32 to 1-42) acting on the 
 resinous extract of Indian hemp forms 'oxy- 
 cannabene ' OjoHjuN^D, (Bolas a. Francis, G. J. 
 22, 417; C. N. 24, 77). This separates from 
 methylated spirit in flat yellow prisms [176°], 
 insol. water, si. sol. alcohol. Indian hemp, and its 
 alcoholic extract, contain a poisonous resin (T. 
 a. H. Smith, Ph. 6, 127, 171 ; Martius). Hay 
 (Ph. [3] 13, 998) has extracted a crystalline 
 alkaloid ' tetano-cannabine ' which produces 
 tetanus in frogs. The fixed oil from hemp-seed 
 (Garmabis sativa) is probably a fatty oil, though 
 Lefort (O. B. 35, 734) gives it the formula 
 OiiHjjOj and describes CnH^gCl^O, and 
 CiiHji^rjOj as products of substitution. 
 
 CANNON-METAL v. Copper, alloys of. 
 
 CANTHAEENE CsH.j i.«. 0,H.(CH3), [1:2]. 
 (134°). o-Zylene-di-hydnde. 
 
 Formation. — 1. By heating canthario acid 
 with fused KOH. — 2. By heating canthario acid 
 or cantharidin with water at 300°, COj being 
 split ofi. — 3. In a pure state by boiling with 
 cone, aqueous EOH, the product G,gH,20,l2, 
 obtained together with canthario acid by the 
 action of HI upon canthartdine (Piccard, B. 12, 
 577 ; 19, 1404). 
 
 Properties. — Liquid, smelling like turpentine 
 and camphor. Absorbs oxygen with avidity. 
 Dilute HNO3 oxidises it to o-toluic and phthalio 
 
 CANTHAEIC ACID Ci^B.,fi, i.e. 
 (08H„0)CO.C02H. [278° cor.]. S. 85 at 15° ; 
 8-5 at 100°. Prepared by heating 1 pt. of can- 
 tharidine with 4 pts. of HI (1-96 S.G.) for 2.L 
 hours at 100°. Trimetric crystals (from water) ; 
 V. e. sol. alcohol, v. si. sol. ether. Distilled with 
 lime it gives oantharene, a little xylene, butyric 
 acid, and di-methyl-benzoic acid. It is an 
 o-ketonic acid, for on heating with di-methyl- 
 aniline and ZnCI, it evolves 00, and yields a 
 condensation product O25H32ON2; the latter is 
 converted into a green colouring-matter by 
 MnOj, into a violet colouring-matter by chloranil 
 or arsenic acid. —A'Ag: white pp. — KA': slender 
 needles. — PbA'j a;aq. 
 
 Methyl ether A'Me: (210°-220°) at 60 
 mm. ; colourless lii^uid. 
 
OAOUTCHOUO. 
 
 677 
 
 Ethyt ether AT&t (o. 300°). 
 
 Oxim C,oH,A(NOH) : [ITS'-ISO"] ; 
 colourless four-sided plates (Piooard, B. 10, 
 1504 ; 11, 2121 ; Homolta, B. 19, 1086). 
 
 CANTHAMDIC ACID C,<,H„05 i.e. 
 (C8H,aOj).CO.C02H. The alkaline salts are 
 formed by heating oantharidin with aqueous 
 alkalis. When a cold solution of the salts is 
 treated with acids, the free oantharidio acid 
 appears to be formed, but on warming the 
 solution it loses H^O and oantharidin is pre- 
 cipitated. With hydroxylamine it gives an 
 oxim, from the salts of which aoids Uberate 
 the oxim of cantharidine. — ^AgjA" aq. — Ag„ A" 2aq. 
 (NH JjA."aq.— KjA" aq. - CdA" a(i.—K^G\iA."^ 2aq. 
 
 Di-meihyl ether M'Me^: [91°]; large flat 
 glistening prisms ; sol. alcohol, ether, and hot 
 water, si. sol. cold water (Homolka, B. 19, 1082 ; 
 DragendorfE a. Masing, Z. 1867, 464; Masing, 
 J. 1872,841). 
 
 CANTHABIDIN C^^,fi^. Lactme of can- 
 tharidic acid. [218° cor.]. S. -02 at 15° ; -29 
 at 100°; S. (alcohol) 2-1 at 78° ; -13 at 15° ; S. 
 (benzene) 8-38 at 80° ; -51 at 15° (Eennard) ; 
 S. (ether) -11 at 18°; S. (CSj) -06 at 18°; S. 
 (CHCy 1-2 at 18° (Bluhm). 
 
 Occv/rrenoe. — In Spanish flies {Lytta vesi- 
 eatoria) and many other insects (Thierry, A. 15, 
 315; J. Ph. 21,44; Bobiquet, A. Ch. 76, 302; 
 Gossmann, A. 86, 317 ; Pocklington, Ph. [8] 3, 
 681 ; Begnault, A. Ch. [2] 68, 159 ; Warner, 
 Am. J. Ph. 28, 193 ; Ferrer, J. 1860, 697 ; 
 Mortreux, J. Ph. [3] 46, 33 ; Fumouze, J. Ph. 
 [4] 6, 161; Bluhm, Z. [2] 1, 675; Dragendorff, 
 Z. [2] 8, 187, 464 ; 4, 308 ; Eennard, C. G. 
 1872, 568; Wolff, Ar. Ph. [3] 10, 22 ; Picoard, 
 . B. 10, 1504). 
 
 Preparation. — 1. Powdered cantharides are 
 extracted with chloroform or ether, the solvent 
 is evaporated and the residue freed from fat 
 by washing with GS^. — 2. Cantharides are 
 mixed with water and MgO, dried, treated with 
 dilute H2SO4 and then shaken with ether. 
 
 Properties. — Trimetrio plates. Blisters the 
 skin. Sublimes readily at 85° (Blyth). 
 
 Reactions. — 1. HI forms oantharic acid. — 
 2. By distillation with P^Sj it gives o-xylene 
 (Piocard, B. 12, 580).— 3. By heating with 
 alkalis it is converted into salts of cantharidic 
 acid Oi|H,«0„ from whose hot solutions oantha- 
 ridin is re-precipitated on the addition of acids. 
 
 Oxim C,„H,A(NOH): [166°]; splendid 
 long glisteaing prisms; v. e. sol. alcohol and 
 ether, v. sol. hot water, si. sol. cold. By cone. 
 HCl at 150° it is split up into its constitu- 
 ents. — CiDHiaOsfNOAg) : four-sided prisms. — 
 C,(,H,203(NOMe) : [134°] ; large colourless prisma ; 
 y. e. sol. alcohol and ether, v. sol. hot, si. sol. 
 cold, water (Homolka, B. 19, 1082). 
 
 Compound CjgHi^Ogl,. ' Oantharidin iodide ' 
 is formed as a by-product (5-8 p.c.) in the 
 preparation of oantharic acid by the action of 
 HI (1-96 S.G.) upon oantharidin at 85°. Crys- 
 talline solid. V. sol. benzene and chloroform, si. 
 sol. alcohol, insol. water. On boiling with cone. 
 EOH it is converted into pure cantharene 
 (o-xylene-di-hydrlde) C.H,(0Hs)2 (Piccard, B. 19, 
 1404). 
 
 CAOUICHOnC. India rubber. This sub- 
 stance is obtained from the milky sap of 
 
 various trees belonging to several natural orders. 
 The sap, which is obtained by making an in- 
 cision in the bark of the tree, is a white creamy 
 liquid with a sp. gr. 1-012. 
 
 The caoutchouc exists in the sap in the form 
 of minute globules, and is consolidated in various 
 ways, often by heating over a smoky fire which 
 produces the brown colour of the commercial 
 article. 
 
 Caoutchouc is colourless when pure, it is 
 a bad conductor of heat and a non-conductor of 
 electricity. S.G. about -925. At ordinary tem- 
 peratures it is soft, flexible, and very elastic, 
 but at about 10° it begins to lose its elasticity, 
 and at 0° beoomeshard and rigid. When heated 
 it loses its elasticity and becomes soft, slowly 
 resuming its original properties when cooled ; if 
 heated to 150°-200° it melts, and after this it 
 remains semi-liquid and sticky on cooling. It 
 burns readily with a smoky flame, leaving little 
 or no ash. 
 
 Exposure to air in the absence of light pro- 
 duces little effect on caoutchouc, but light and 
 air together cause it to lose its elasticity and 
 become glutinous, due to the absorption of 
 oxygen (Spiller, C. /. 18, 44; Miller, ibid. p. 
 273). 
 
 Caoutchouc is insoluble in water, but when 
 immersed in it becomes white and increases in 
 bulk, absorbing about 25 p.c. of its weight of 
 water, which is given up again on exposure to 
 air. Alcohol acts upon it in a similar way. 
 
 Dilute acids do not affect it, but it is attacked 
 by strong nitric or sulphuric acid. Chlorine 
 renders it hard and brittle. Alkalis produce 
 Uttle effect. 
 
 Ether, benzene, mineral oil, sulphide of 
 carbon, chloroform, oil of turpentine, oil of 
 caoutchouc, and many essential and fixed oils, 
 act upon caoutchouc, causing it to swell greatly 
 and become gelatinous and soft. The action of 
 these solvents appears to be to dissolve one 
 constituent part of the caoutchouc, leaving the 
 less soluble part in a disintegrated condition. 
 
 According to Payen, sulphide of carbon with 
 about 5 p.c. of absolute alcohol is the best 
 solvent. 
 
 Caoutchouc is composed of carbon and hy- 
 drogen. The proportions vary in different 
 analyses 0. 86-1 - 90-6 p.c. ; H. 10 - 12 -8 p.c. It 
 appears to consist chiefly of two hydrocarbons, 
 which can be partly separated by the prolonged 
 action of a solvent, but the proportion of these 
 constituents obtained varies according to the 
 solvent employed. The more soluble part is 
 soft and ductile, while the less soluble is tena- 
 cious and elastic. 
 
 When caoutchouc is subjected to dry dis- 
 tillation an oil consisting of a mixture ol 
 various hydrocarbons is obtained. This ia 
 called oil of caoutchouc. 
 
 Among the constituents of this oil are iso- 
 prene CgH, (37°-38°) S.G. -682; caoutohene 
 C,„H,s (17i°) S.G. -842, and heveene (315°) 
 S.G. -921 (Himly, A. Ch. 27, 41; Gregory, ibid. 
 16, 61 ; G. Williams, Pr. 10, 517 ; Bouchardat, 
 J. Ph. 1837, 454 ; Bl. 24, 108 ; 0. B. 89, 361). 
 
 When isoprene is acted on by strong hydrio 
 chloride a mixture of the mono- and di- hydro- 
 chlorides, together with a solid substance, ia 
 obtained. This latter is identical in its proper* 
 
6V8 
 
 CAOUTCHOUC. 
 
 ties with oaoutohouo (Bouohardat, 0. B. 89, 
 1117). 
 
 Valcanised caontchouc. — ^When caoutchouc 
 is heated to about 115° in contact with sulphur, 
 it absorbs some of the latter and becomes vul- 
 canised. The introduction of the sulphur can 
 be attained in many ways, immersion in a 
 mixture of carbon disulphide and chloride of 
 sulphur, or in a solution of polysulphide of 
 calcium, &c. 
 
 About 2 p.o. of sulphur appears to enter 
 into combination with the caoutchouc. If more 
 than this quantity is introduced the excess 
 remains mixed with the rubber and can be 
 dissolved out by the ordinary solvents of sulphur, 
 while the combined sulphur cannot be so ex- 
 tracted. An excess of sulphur renders the 
 caoutchouc less durable. Vulcanised caoutchouc 
 does not lose its elasticity at a low temperature 
 and does not soften so easily with heat as ordi- 
 nary rubber. It is less affected by solvents than 
 pure caoutchouc. 
 
 The ordinary vulcanised rubber, besides con- 
 taining an excess of sulphur, is often adulterated 
 with 40-60 p.o. of mineral matter. 
 
 Ebonite. — When caoutchouc is heated with 
 half its weight of sulphur, with or without the 
 addition of some mineral matter, a hard darksub- 
 stance which can be polished is obtained. This 
 is much used for insulating purposes, but accord- 
 ing to Wright (Am. S. [3] 4, 29) it becomes 
 hygroscopic when exposed to the action of ozone 
 owing to the formation of HjSO,. Eboniteis little 
 affected by the solvents of caoutchouc. 
 
 0. J. W. 
 
 CAPILLARITY v. Peysioaii ueihoss, Sect. 
 
 MISOELLANBOUS. 
 
 C AFSAMIDE the Amide of Deooio Aoto (q.v.). 
 The name has also been applied to the amides 
 of OoToio ACID (q.v.) and Hexoio acid (g.w.). 
 
 CAPRAMIDOXIM v. Hexamidoxim. 
 
 CAPRIC ACID v. Deooio acid. 
 
 CAPRIC ALDEHYDE v. Deooio aldehvdh. 
 
 CAPRILAMIDE v. Armde of Ooioio aoib. 
 
 CAPRILIC ACID V. Ocioio acid. 
 
 CAPRILONE V. Dl-HEPTYL-KETONE. 
 
 CAFRILOXITRILE v. Nitrile of Ooioio acid. 
 
 CAPRINONE V. Dl-ENKYL-KETONE. 
 
 CAPRO-AMIDE v. AmAde of Hbxoio aoid. 
 CAPRO-ANILIDE v. AniUde of Hexoio aoid. 
 CAPROIC ACID V. Hexoio acid. 
 CAPROIG ALDEHYDE v. Hexoio aldehyde. 
 CAPRO-LACTONE v. Lactone of Oxy-hexoio 
 acid. 
 
 caprone v. dl-amyl-ketonb. 
 
 CAPRONITRILE v. Nitrile of Hexoio aoid. 
 
 CAPROYL=Hexoyl. 
 
 CAPROYL AMIDE v. Amide of Hexoio acid. 
 
 CAPROYL CHLORIDE v. Chloride of Hexoio 
 
 ACID. 
 
 CAPRYL ALCOHOL v. Octyl aioohol. 
 CAPRYL-AMIDE v. Amide of OoTOio aoid. 
 CAPRYLAMINE v. Ooiyiamine. 
 CAPRYL CHLORIDE v. Chloride of Deooio 
 
 aoid ; also OOTYL CHLOBIDE. 
 
 CAPRYL-BENZEWE v. OotyIi-benzeke. 
 CAPRYLENE v. Ootylene. 
 CAPRYLEHE HYDRATE v. Ootyi. aioohol. 
 CAPRYLIC ACID v. OoTOio acid. 
 CAPRYLIC ALCOHOL v. Octyl alcohol. 
 CAPBYLIC ALDEHYDE v. Ooioio aldehyde. 
 
 CAPRYLIDENE v. OoiiSESE. 
 
 Caprylidene tetrabromide v. Tbtra-bboMO- 
 
 OCTANE. 
 
 CAFRYLONE v. Di-hepiyl-eetoke. 
 
 CAPRYLONITRILE v. Nitrile of Ooioio acid. 
 
 CAPRYL-PHENYL-AMINE v. jb-Amido- 
 phenyl octane, p. 178. 
 
 CAPSAICIN CHi^O^. [59°]. 
 
 Prepa/ration. — Powdered cayenne pepper 
 (Ga;psicwm fasttgial/wm) is extracted with ether, 
 the extract is evaporated, dissolved in hot alco- 
 holic KOH, diluted with water, ppd. by BaOl^, 
 and the dried pp. treated with ether. On 
 evaporating the extract, an oily red liquid re- 
 mains, which is dissolved in dilute potash, and 
 ppd. by addition of ammonium chloride. 
 
 PropertAes. — Colourless prismatic crystals, 
 insol. water, sol. alcohol. Begins to volatilise 
 at 100°. Powerful irritant. The pungent taste 
 is removed by heating with potassium bichro- 
 mate and dilute sulphuric acid. BaCl^ and 
 CaOlj in alcoholic solution give a pp. sol. ether ; 
 AgNOj a pp. sol. ammonia; FojCla a red pp. 
 when warmed (Thresh, Ph. [3] 7, 21, 259, 478). 
 
 CAPSICINE. An alkaloid which may be 
 extracted by benzene from the fruit of Ca/psicum 
 fastigiatum. The benzene is evaporated, and 
 the residue dissolved in ether, from which the 
 alkaloid is obtained by shaking with dilute 
 HjSO, (Thresh, Ph. [8] 6, 941). Needles ; insol. 
 water, v. sol. alcohol and ether ; may be sub- 
 limed. Volatile with steam. It is not pun- 
 gent. The hydrochloride crystallises in 
 cubes and tetrahedra, the sulphate in prisms. 
 
 CAPSUL^SCIC ACID 0,3H,A- An aoid 
 obtained from the husks of the horse-chestnut 
 (Roehleder, Z. 1867, 83). Crystals; may be 
 sublimed. FcjCl, turns its solution greenish- 
 blue. 
 
 CABAGHEEN MOSS. Irish pearl moss. A 
 gelatinous seaweed {Chondrus crisptis). Swells 
 up in cold water, almost entirely dissolves in hot 
 water. Ppd. by Pb(0Ae)2. Appears to be 
 chiefly composed of a carbohydrate, which ia 
 insol. Sohweizer's solution, and not turned blue 
 by HjSOi and I (Schmidt, A. 51, 56 ; Pluokiger 
 a. Obermayer, N. B. P. 1868, 350). Caragheen 
 moss gives galactose when boiled with dilute 
 H^SOi (Haedicke, Bauer, a. ToUens, A. 238, 
 302). 
 
 CABAJ1TRA. A red dye, probably identical 
 with chica red. Insol. water, sol. alcohol and 
 dilute alkalis, reppd. by acids (Virey, /. Ph. 
 1844, 151). 
 
 CARAMEL. A black substance obtained by 
 heating cane-sugar at c. 200°. It is said to be 
 a mixture of caramelan CijHjgOg, caramelen 
 CsjHjjOjs, and caramelin C,jH,„|j05,. They all 
 reduce Fehling's solution. Dilute (84 p.c.) alco- 
 hol extracts caramelan, cold water then dissolves 
 caramelen, leaving caramelin. Caramelan is 
 a colourless, brittle, deliquescent resin. — 
 CijBaHi.OeBaO.— C,2PbH„0„-— OiifPbH^OgPbO. 
 Caramelen is a mahogany-coloured solid. — 
 CssH^BaOa.— CasH^PbOsr Caramelin is a 
 glittering black solid, sol. boiling water.— 
 C,eH„^a0„. — 0,,H,„„Ba05,BaO.-0,,H,ooPbOn 
 (G61is, A. Ch. [8] 62, 352). Caramelan and 
 caramelen are crystalloids, caramelin is a 
 colloid. The formulae and purity of these 
 bodies are, of course, very doubtful ; other 
 
.CARBAMIC ACID. 
 
 m 
 
 observers have arrived at somewhat different 
 results, indeed the nature of the resulting pro- 
 ducts depends upon the temperature used in 
 preparing them (P61igot, A. Oh. [2] 67, 172; 
 Volokel, A. 85, 59 ; Maumen6, G. B. 39, 422 ; 
 Graham, O. J. 15, 258 ; Thomson a. Sherlock, 
 C. N. 25, 242, 282). 
 
 CARAWAY OIL. Oil of caraway contains 
 aterpene (q.v.) 0,(,H„ identical with citrene, and 
 carvol (2. v.) C,„HnO. 
 
 CARB-ACETO-ACETIC ETHER is mesitene- 
 lactone carhoxyUa add, p. 20. 
 
 CARBACETOXYLIC ACID C^HjO,. A syrupy 
 acid, said to be formed by the action of moist 
 Ag^O on j8-ohloro-propionio acid and on aa-di- 
 ahloro-propionio ether. Eeduoed by sodium- 
 amalgam to glyceric acid, and by HI to pyru- 
 vic acid (Wichelhaus, A. 143, 7; 144, 351; 
 Klimenko, B. B, 468; 5, 477; 7, 1406; cf. 
 Beckurts a. Otto, B. 10, 2039). 
 
 TRI-CARBALLYLIC ACID C^B.fie i-e- 
 C02H.CH(CH2.C0jH)2. s-Propane tri-carboxt/lio 
 acid. Mol. w. 176. [158°]. S. 40-5 at 14°. 
 
 Formation. — 1. In the preparation of sugar 
 from beet-root (Lippmann, B. 11, 707; 12,1649; 
 Weyer, C. J. 38, 864).— 2. By the saponification 
 of its nitrile which is prepared by the action of 
 KCy on s-tri-bromo- propane in alcohol (M. 
 Simpson, Pr. 12, 236 ; 14, 77 ; C. J. 18, 331).— 
 3. By reducing aconitio acid or its ether with 
 sodium-amalgam (Dessaignes, O. B. 55, 510 ; 
 Wichelhaus, A. 132, 61; Hlasiwetz, Z. 1864, 
 734).— 4. By the action of potash on the product 
 of the action of KCy on /3-chloro-isocrotonio 
 ether (obtained from aceto-acetic ether and 
 PCy (Glaus a. Lischke, B. 14, 1089).— 5. In 
 the same -way from a-chloro-orotonio ether or 
 from di - chloro - propylene (epidiohlorhydrin) 
 (Glaus, B. 5, 358; 9, 223; A. 170, 131; 191, 
 63). — 6. Appears to be formed by the action 
 of HGl and KGIO3 on gallic acid (Schreder, A. 
 177, 292). — 7. Acetyl-succinic ether is con- 
 verted by Na into acetyl-tri-carballylic ether 
 CH,00.G(GH2.G02Et)j.G02Et whence alcoholic 
 EOH or baryta-water produce tri-carballyUo acid 
 (Miehle, A. 190, 322).— 8. By the oxidation of 
 di-allyl-acetio acid by dilute HNO3 (Wolff, A. 
 201, 53). — 9. By boiling citraoonio acid with zinc 
 and HCl (Behrmann a. Hofmann, B. 17, 
 2692).— 10. Prom propane tetra-carboxylio acid 
 (GOjH.OH^jG(CO^)j by heat (Bischoff, A. 214, 
 66). 
 
 Properties. — Hard short trunetric prisms 
 (from water) ; v. sol. water and alcohol, si. sol. 
 ether. The ammonium salt gives with BaClj 
 or CaClj no pp., even on adding NH3. Pb(0Ac)2 
 Rives a white pp. PejGls gives a red pp. 
 
 Salts. — Na,HA"' 2aq(?) — KH,A"'. — 
 Ca3A"'j 4aq.— BaHA"'.-BasA"'j 6aq.— PbsA'''^— 
 CujA-'V-AgaA'". 
 
 Tri-ethyl ether Bt.k.'" (0. 300°). 
 
 Tri-isoamylether{C^'Ej,)sA."'{a,hoveS60°). 
 
 CARBAMIC ACID GH3NO2 i.e. NH^.CO^H. 
 Amido-forrmo acid. Amide of carbonic acid. 
 Not known in the free state. The ammonium 
 salt is formed by the union of dry or moist 
 CO, (1 vol.) with gaseous NH3 (2 vols.) (J. Davy, 
 N. Md. P. J. 16, 345 ; Eose, P. 46, 352 ; A. 30, 
 47). Formed also by sublimation of neutral 
 ammonium carbonate, and therefore occurs in 
 commercial ammonium carbonate. Formed also 
 
 by oxidising glyooooU, leucine, tyrosine, and 
 albumen, with alkaline KMnO, (Drechsel, J pr, 
 [2] 12, 417 ; cf. Hofmeister, J. pr. [2] 14, 173). 
 It may be conveniently prepared by digesting 
 commercial ammonium carbonate with saturated 
 aqueous NH, for 30 or 40 hours at 20°-25'' 
 (Divers, C. J. 23, 215; cf. Kolbe a. Basaroff, 
 0. /. 21, 194). 
 
 Beactions. — 1. Acids decompose carbamates 
 with formation of GO2 and NHj. — 2. Boiling 
 water converts carbamates into carbonates. — 
 3. Strongly heating converts the Na salt into 
 sodium cyanate and H^O (Drechsel, J.pr. [2] 16, 
 199). 
 
 Salts. — The carbamates are soluble in water 
 (difference from most carbonates). — NH^A' {v. 
 supra). Deliquescent plates. Its aqueous solu- 
 tion quickly changes to carbonate, but it is stable 
 in presence of excess of NH3 in the cold. At 60° 
 it is completely split up into COj and NHs (Nau- 
 mann, A. 160, 1 ; JB. 18, 1157 ; Horstmann, A. 
 187, 48 ; Erckmann, B. 18, 1154). In a sealed 
 tube at 140° it forms urea. — NaA'caq : formed 
 by adding NaOEt to an alcoholic solution of the 
 ammonium salt ; prisms. — KA' : deliquescent. 
 — OaA'j aq : ppd. by adding lime and alcohol to 
 a solution of NH^Af at 0° ; crystalline powder, 
 sol. water, the solution quickly deposits CaCOj. 
 When strongly heated it leaves calcium cyan- 
 amide. — SrA'2. — ^BaA'j. 
 
 Chloride OC(NH,)G]. [c. 50°]. (62°). Pre- 
 pared by passing a stream of dry COGlj into 
 NH4CI heated to about 400°. Long broad 
 needles. Strong odour. On keeping it slowly 
 changes into cyamelide with evolution of HCl. 
 By water it is decomposed into NH^Cl and CO^. 
 On vaporisation it probably dissociates into 
 cyanic acid and HCl, which again recombine 
 on cooling. By CaO it is converted into cyania 
 acid. With aromatic hydrocarbons in presencl 
 of AI2CI3 it gives amides of aromatic acida 
 (Gattermann a. Schmidt, B. 20, 858). 
 
 Carbamic ethers. Urethanes. 
 
 Prepa/ration. — 1. Prom chloro-formio ethers 
 and NH3. — 2. From cyanic acid and alcohols. — 
 3. From cyanogen chloride and alcohols. — 4. By 
 heating alcohols with urea nitrate. 
 
 Properties. — Solid substances, si. sol. water, 
 T. sol. alcohol and ether ; may be distilled. 
 
 Beactions. — 1. Heating with NH3 gives urea. 
 2. FqOj gives cyanates. — 3. Alcoholic EOH acts 
 upon carbamic ethers of the fatty series accord- 
 ing to the equation: NH,.G02C„Hj„+, -1- KOH 
 = KN.C0 + C„Ha,„0H + H2O (Arth, Bl. [2] 45, 
 702 ; A. Ch. [6] 8, 428). Bornyl and menthyl 
 carbamates act similarly. 
 
 Methyl ether MeA'. [52°]. (177°). S. 
 217 at 110° ; S. (alcohol) 73 at 15° (Echevarria, 
 A. 79, 110). 
 
 Ethyl ether EtA'. Urethane. Mol. w. 89. 
 [c. 50°]. (c. 182°). Formed by the above 
 methods (Dumas, A. Ch. [2] 54, 233; A. 10, 
 284; Liebig a. Wohler, A. 54, 370; 58, 260; 
 Wurtz, A. 79, 286 ; C. B. 22, 503 ; Bunte, Z. 
 [2] 6, 96; A. 151, 181). Also from carbonic 
 ether and NH, (Cahours, C. B. 21, 629 ; A. 56, 
 
 Beactions. — Alcoholic potash, at the ordinary 
 temperature, gives large crystals of potassium 
 cyanate. In this ease NHj.COjK is not formed 
 as an intermediate product. A solution of 
 
680 
 
 CARBAMIO ACID. 
 
 urethane in absolute ether, treated with K 
 or Na gives the derivatives KNH.C02Et, and 
 NaNH.COjEt. Of these, the Na derivative is 
 Bufliciently stable for analysis. It is v. sol. abso- 
 lute alcohol, insol. absolute ether. With alco- 
 holic potash containing water Kfi, is obtained. 
 The body HgN.CO.OEt is obtained by mixing 
 alcoholic solutions of urethane, HgClj, and KHO 
 (Mulder, B. T. C. 6, 170). 
 
 Acetyl derivative NHAo.CO.,Bt. [78°] 
 (Conrad a. Salomon, J.pr. [2] 10, 28). 
 
 Ghloro. ethyl ether B.^S.GO^.G.'B.fil. 
 [76°]. From NH, and the chloro-ethyl ether 
 of chloroformic acid. Prisms. V. sol. water, alco- 
 hol and ether (Nemirowsky, J. pr. [2] 31, 174). 
 
 n-Propyl ether FiA'. [53°]. (195°) (Ca- 
 hours, J. 1873, 748; Eoemer, B. 6, 1102). 
 Long prisms. 
 
 Isohutyl ether C^HgA'. [55°]. (207°) 
 (Mylius, B. 5, 973 ; Humann, A. Ch. [3] 44, 
 340 ; A. 95, 372). 
 
 Isoamyl ether C^U^iA.'. [60°]. (220°) 
 (Medlook, A. 71, 106 ; Wurtz, J. Ph. [8] 20, 22). 
 
 Ociyl ether G^B.„k'. [55°]. (135°) at 25 
 mm. ; (231°) at 760 mm. On distillation it is 
 partially converted into cyanurio acid (Arth, 
 C. B. 102, 977). 
 
 Bornyl carbamate v. p. 523. 
 
 Menthyl carbamate v. Menthol. 
 
 CARBAMIDE v. Ubea. 
 
 CAEBAMIDO- v. Ueamido-. 
 
 CAEBAMINES. Carbylamines. Iso-nitriUs. 
 Compounds of the formula B.N:C. 
 
 FormaUon. — 1. By distilling primary mon- 
 amines with chloroform and alcoholic potash ; 
 
 BNHj + OHOI3 + 3K0H = 3EC1 + ENC -^ 3H2O 
 (Hofmann, A. 144, 114; 146, 107). — 2. By 
 treating an alkyl iodide (1 mol.) with silver cyan- 
 ide (2 mols.) a double salt BNCAgOy is formed ; 
 on distilling this compound with cone, aqueous 
 KCy there is formed KCyAgCy and the oarb- 
 amine passes over (Gautier, A. 146, 119 ; 149, 
 29, 155 ; 151, 239). HgOyj and ZnCy^ may also 
 be used in preparing carbamines (Calmels, Bl. 
 [2] 43, 82). — 3. In small quantity in preparing 
 nitrites by distilling potassium alkyl sulphates 
 with potassium cyanide. — 4. By cfistiUing the 
 compounds of thio-carbimides with tri-ethyl- 
 phosphine (Hofmann, B. 3, 766 ; Z. 7, 29). 
 
 Properties. — Volatile stinking poisonous oils. 
 
 Beactions. — 1. Alkalis have no action. — 2. 
 Mineral acids instantly convert them into 
 alkylamines and formic acid: ENO-i- 211^0 = 
 ENHj -I- H.CO2H. Water at 180° acts similarly. 
 3. Dry HCl forms a compound, quickly decom- 
 posed by water as in 2. — 4. Organic acids form 
 alkyl-formamides. — 5. EtI forms a compound 
 (difierence from nitriles). — 6. HgO oxidises 
 them to alkyl oyanates B.N:CO, alkyl- form- 
 amides being also formed (Gautier, A. 149, 
 811). 
 
 CABBAMINE-CYAMIDE or CABBAMINE- 
 CTANAMIDE so called is described as Amido- 
 Di-OTANio Aom. Its derivatives are described as 
 Ethyii-oabbimido-T7bea, Caebimedo-ethtl-ueea, 
 &c. 
 
 CABBANIL 1). Phenyl otanatb. 
 
 CARBAMLIC ACID v. Phentl - oaebamio 
 
 lOID. 
 
 CAEBANILIDE v. s-Di-phenyl-tjeea. 
 
 CARBANILIDO- v. Phenyl-tjeamidO-. 
 CABBAZOLE Oj^HoN i.e. 
 Mol. w. 167. [238°]. (352° cor.). "V.D. 5-86 
 
 <C:1:>N3- 
 
 (calo. 585). S. (alcohol -92 at 14° ; 388 at 78°. 
 S. (toluene) -55 at 16-5 ; 5'46 at 100° (Beohi, B. 
 12, 1978). 
 
 Occurrence. — Among the products of the dis- 
 tillation of coal tar ; hence it occurs in crude 
 anthracene (Graebe a. Glaser, B. 5, 12, 376 ; A. 
 163,343; 167,125; 174,180; 202,21; Zeidler, 
 A. 191, 297). 
 
 Formation. — 1. By passing vapour of aniline 
 or diphenylamine through a red-hot tube. — 
 2. From imido-di- phenyl sulphide (thio-di- 
 
 phenyl-amine) by boiling HN<^^«g*]>S with 
 
 freshly reduced copper for 2 or 3 hours ; the 
 yield is about 60 p.c. (Goske, B. 20, 233). 
 
 Properties. — White lamina or tables. Easily 
 sublimes. A solution in cone. H2SO4 is turned 
 green by HNO3. May be distilled over red-hot 
 zinc-dust without change. Although an imide, 
 it forms a compound with picric acid and its 
 acetyl derivative is obtained with difficulty. 
 
 Beactions. — 1. It is not affected by cone. 
 HClAq or alcoholic KOH even at 300°. Cold 
 cone. HjSOj dissolves it without change, but at 
 100° a di-sulphonio acid results. — 2. HNO, 
 forms nitro- compounds. — 3. Sodium-amalgam 
 does not reduce it in alcoholic solution, but EI 
 and P at 210° reduce it to carbazoline CjjHisN. — 
 
 4. By exhaustive chlorination with SbClj it 
 yields per - ohloro - diphenyl or per - chloro- 
 benzene according to circumstances as yet un- 
 determined (Merz a. Weith, B. 16, 2875).— 
 
 5. By heating with oxalic acid the compound 
 
 CsjHj^NjO or HO.C(OeHs<;^^ », is obtained. 
 
 It forms minute crystals which very readily yield 
 blue solutions (carbazole blue) on oxidation 
 (Suida, B. 12, 1403 ; Bamberger a. Miiller, B. 
 20, 1903). 
 
 Potassium derivative Oi^HsNE, Prom 
 carbazole and KOH at 230°. Picric acid 
 compound C„H„N C,H,(NO J3OH. [182°]. 
 Prom carbazole (1 pt.) and picric acid (If pts.) 
 in toluene. Bed prisms ; v. si. sol. cold benz- 
 ene or alcohol. Decomposed by a large quan- 
 tity of alcohol, by water, and by alkalis. 
 
 Nitrosamine CijHsN.NO. [82°]. Nitrous 
 acid in an alcoholic solution of carbazole forms 
 mono- and di-nitro-carbazole. If carbazole 
 (3 g.) be mixed with acetic acid (60 g. of S.G. 
 1-04) and ether (60 g.) be poured in, on adding 
 KNO2 the nitrosamine is dissolved in the ether 
 as fast as it is formed, and crystallises out on 
 evaporation. Long flat golden needles. Soluble 
 in ether, CSj, chloroform, glacial acetic acid 
 and benzene. It is decomposed if heated with 
 alcohol mixed with an acid, carbazole being 
 regenerated. Alcoholic KOH turns it blood-red. 
 Beducing agents regenerate carbazole. Cone. 
 HjSO^ gives a dark-green colour (Zeidler, A. 
 191, 305). 
 
 Acetyl derivative CijHbNAo. [69°]. 
 (above 360°). From carbazole and Ao^O at 
 .250°. Slender needles (from water) ; v. si. sol. 
 water, v. b. sol. alcohol. Erdmann's solution 
 does not turn it green. Its picric acid compound 
 ie orange. 
 
CARBOHYDRATES. 
 
 631 
 
 References. — Bbomo-, Chloro-, Nitho-, 
 Methyl-, and Ethyl-, oabbazom. 
 
 CARBAZOLE TETRAHYDSIDE C,2H,,N. 
 [120°]. (o. 328°). Formed, together with 
 hydrogen, by heating oarbazoline hydrochloride 
 at 300°. Crystallises from alcohol. V. e. sol. 
 alcohol, insol. water. Does not combine with 
 Boida. Eednoed by HI and P to oarbazoline. 
 The picric acid compound 
 C,2H,3NajHj(N02)30H forms brown lamina. 
 
 CABBAZOLE v-CARBOXYLIC ACID 
 CiaHsNOj i.e. 0,2HsN.C0,H. [272°]. Prom 
 potassium carbaaole and CO.^ at 270°. Micaceous 
 scales or flattened prisms with faint blue fluor- 
 escence: insol. water, si. sol. cold alcohol 
 (Ciamician a. Silber, G. 12, 272). 
 
 OARBAZOLINE C,jH,5N. Garhazole hexa- 
 hydride. [99°]. (297° i.V.). V.D. 6-13 (5-99 calc). 
 Formed by heating carbazole (3 pts.) with (12 pts. 
 of) HIAq (127°) and amorphous P (1 pt.) at 
 220°. White needles (from alcohol) ; may be 
 sublimed ; volatile with steam ; v. e. sol. alcohol 
 and ether, v. si. sol. water. HI and P at 330° 
 reduce it to diphenyl decahydride OijHj,,. Does 
 not combine with picric acid. 
 
 Salts.— B'HOl: v. e. sol. water.— B'HBr : 
 tables.- B'HI. 
 
 Acetyl derivative C,jH,jNAc. [98°]. 
 Prom oarbazoline and AojO at 110°. Needles 
 ][from alcohol). 
 
 CABBISES. Compounds of carbon with one 
 other more positive element. A carbide of iion 
 FejC probably exists in cold roUed steel ; other 
 carbides of this metal are described, but their 
 existence is doubtful. Silver is said to form 
 three carbides, A.gfi, Ag^C, and AgC. Nickel 
 takes up a small quantity of carbon when 
 strongly heated with charcoal, but no definite 
 compound has yet been prepared. We have 
 very Uttle definite information regarding this 
 class of compounds {v. iBininM, Ibon, Nickel, 
 Palladium, PLATisrnM, and Silveb). M. M. P. M. 
 
 CARBIMIDE V. Cyanic acid. 
 
 CARBIMXDO-AILYL-THIO-UREA CsHjNaS 
 
 i.«. SC<^^^'>C:NH or C3H,NH.CS.N:C:NH. 
 
 AUyl-tMo-carbamine-cyamide. Formed, as the 
 crystalline sodium salt, by mixing allyl-thio- 
 carbimide and sodium cyanamide. Decomposed 
 by acids into its constituents (Wunderlich, B. 
 19, 448). 
 
 GARBIUIS-AUIDO- BENZOIC ACID is 
 Ouanido-di-benzoic acid v. p. 157. 
 
 CARBIUISAMISO-BENZOYL v. Oxy-quin- 
 AzoLiNE and p. 155. 
 
 CARBIMIDO-CTANAUIBE v.Auido-dicyanic 
 ACID, p. 163. 
 
 CARBIMIDO-ETHYL-THIO.TTREA O.HjNaS 
 
 i.e. SC<^2*>^=^^ "'■ EtHN.CS.N:C:NH. 
 Eihyl-thio-carbamine-cyamide. Formed, as the 
 crystalline sodium salt, by mixing ethyl-thio- 
 carbimide and sodium cyanamide. Decomposed 
 by acids into its couttituents (Wunderlich, B. 
 
 19, 448). 
 
 CARBIMIDO-ETHYL-UREA CjHjNjO i.e. 
 
 0C<^2>C:NH or EtHN.CO.N:C:NH. JEthyl- 
 
 earbamine-cyarmde. Formed, as the crystalline 
 Bodium salt, by mixing ethyl cyanate and 
 sodium cyanamide. Decomposed into its con- 
 
 stituents by acids. Forma a green orystalliua 
 copper compound (Wunderlich, B. 19, 448). 
 CAEBIMIDO-METHYL-THIO-TJREA 
 
 C3H3N3S i.e. SO<™^>0:NH or 
 
 MeHN.CS.N:C:NH. Methyl-thio-carbamim-cy 
 amide. Formed, as the crystalline sodimn salt, 
 by mixing methyl-thiooarbimide and sodium 
 cyanamide. Decomposed by acids into its con- 
 stituents (Wunderlich, B. 19, 448). 
 CAKBIMIDO-PHENYL-XHIO-UEEA 
 
 C,H,N3S i.e. SC<^^>C:NH or 
 
 PhNH.CS.N:C:NH. Phemyl-thio-carbamine- 
 cyamide. Formed, as the crystalline sodium 
 salt, by mixing phenyl -thiocarbimide and sodium 
 cyanamide. Decomposed by acids into its con- 
 stituents (Wunderlich, B. 19, 448). 
 
 DI-CAEBIN-TETRA-CARBOXYLIC ACID v. 
 Eihylenb-tetba-oarboxylio acid. 
 
 CARBINOL. A name given by Kolbe to 
 methyl alcohol, but used only in describing 
 alcohols derived therefrom by displacement of 
 hydrogen of its methyl by one or more alkyls. 
 Cf. Alcohols. 
 
 CARBINYL. The corresponding term for 
 the alcohol radicles of the alkyl-carbinols j 
 thus, MCjC may be called tri-methyl-carbinyl. 
 
 CARBO-ACETO-ACEXIC ETHER v. p. 20. 
 
 CARBO-ALIYI-PHENYL-AMIDE v. Phbhyl- 
 
 ALLYL-CTANAMIDE . 
 
 CARBO-DI-BUTYL-DI-PHENYL-imiDE v. 
 
 Dl-BDTYL-DI-PHENYL-OYANAMIDE. 
 
 CARBO-ISO-BUTYRALDINE CjHjNjSj i.e. 
 (NHj)CS.S.N(C,Hs)j. [91°]. From iso-butyralde- 
 hyde, CSj, and aqueous NHj. Prisms, insol. 
 water, sol. alcohol (Pfeiffer, B. 5, 701). 
 
 CARBO-CAFRO-LACIONIC ACID v. Lactone 
 
 of OXY-PEOPYL-SUOCINIC ACID. 
 
 Di-oarbo-capro-lactonic acid v. Lactone of 
 
 OXY-PENTANE TEI-CAEBOXYLIO ACID. 
 
 CARBOCINCHOMERONIC ACID is Fybidine 
 
 TEI-OABBOXYLIO ACID. 
 
 CARBO-GLTJCONIC ACID 0,H„Os. An 
 amorphous acid whose NH, salt is obtained by 
 treating glucose or cane-sugar with aqueous 
 HON (Schiitzenberger, Bl. [2] 36, 144). 
 
 CARBO-DI-GLYCOLLIC ETHER v. Glycollio 
 ACID. 
 
 CARBOHOMOPYRROLIC ACID v. Methyl- 
 
 PYKKOL-CAKBOXYLIO ACID. 
 
 CARBOHYDRATES. A term applied to com- 
 pounds which may be represented by the formula 
 Ox(H20)y where x is 5, 6, or 12, and y is 5, 6 or 
 11, and to compounds derived from several such 
 molecules by abstraction of water. They are 
 non - volatile solids, and the non - saccharine 
 members of the group may be converted by 
 boiling dilute acids into a sugar, usually glucose 
 (dextrose). They contain hydroxyl. On oxida- 
 tion they frequently give rise to oxalic, raoemic, 
 saccharic, and mucio acids. Most of them are 
 optically active. Cellulose is insoluble in water ; 
 the gums dissolve, or at least swell up, in water, 
 but are ppd. by alcohol. Sugars are soluble in 
 water, are not reppd. by alcohol, and have a 
 sweet taste. lodme turns starch blue, and 
 affects cellulose in the same way after it has 
 been treated with a dehydrating agent. The 
 carbohydrates vary also in their behaviour to- 
 wards alkaline copper solutions, and as regards 
 
683 
 
 CARBOHYDRATES. 
 
 fermentation by yeast. They are described in 
 the articles Ababio acid, Cellulose, Dexibin, 
 
 81ABCH, SUQAB, ETC. 
 
 GABBOIiIC ACID v. Phenol. 
 CABBO-MESYL v. Methyl-oxikdolb. 
 CAKBO-DI-NAPHTHYL-IMIDE v. Di-naph- 
 
 THyL-CYANAMIDE. 
 
 CARBON GROUP OF ELEMENTS.— Car6o« 
 and Silicon. Of these elements, carbon occurs 
 in the free state in the forms of diamond, graphite, 
 and amorphous carbon ; silicon is not known as 
 such in nature, but combined mth oxygen it is 
 one of the most widely-distributed elements. 
 Diamond was regarded by Newton as a com- 
 bustible body because of its great refractive power : 
 in 1694 the Florentine academicians succeeded 
 in burning small pieces of diamond ; and in the 
 early years of this century Davy proved it to 
 be pure carbon. In early times graphite was 
 thought to be very similar to lead ; hence the 
 
 n&me plumbago ; for a time it was confused witb 
 molybdenum-glance, but in 1799 Scheele proved 
 it to be closely related to coal in its composition. 
 It is only in somewhat recent times that approxi- 
 mately pure graphite has been obtained. Char- 
 coal is the commonest form of impure amorphous 
 carbon ; this modification of carbon can be ob- 
 tained approximately pure only with consider- 
 able difficulty. 
 
 After the earths had been proved to be 
 metallic oxides in 1807, it was generally sup- 
 posed that the common earth-like body silica 
 would also be found to contain oxygen and a 
 metal. In 1823 Berzelius decomposed silica 
 and obtained the non-metal silicon, in the form 
 of a brown amorphous powder. A good many 
 years later Deville prepared crystallised silicon 
 in two f orms,one more or less resembling diamond, 
 and the other, graphite. The leading properties 
 of the two elements are as follows : — 
 
 Cabboit. 
 
 SlLICOir. 
 
 1197 
 
 28 
 
 Atomic weights 
 
 Many compounds of each element have been gasified. Molecular weights unknown: 
 (?) probably greater than C^ and Si^. 
 
 Does not melt at any temperature 1,100°-1,300° (uncertain). 
 
 hitherto attained. 
 Diamond 3'6 ; graphite 2-25 ; amor- Graphitoidal 2-2-2-5 (doubtful). 
 
 phous l-5-i"9. 
 0-46 (at about 1000°). 0-203 (at about 250°) 
 
 The specific heat of either element increases rapidly as temperature increases from — 50° : the 
 rate of this increase is, however, very small after about 500° for carbon and about 150° for 
 silicon. The specific heats of diamond and graphite vary considerably at temperatures below 
 about 600°, but from this point upwards the values are practically identical. 
 
 Ato mic weight 
 
 4-6 
 
 Specific gravities 
 (approximate) 
 Specific heats 
 
 Spec. grav. _ 
 (approximate) 
 
 11-2 
 
 Meats o^ formation of various compounds (Thomsen, Berthelot, &o.), 
 (Generally from amorphous Carbon or Silicon.) 
 
 24,800 
 
 167,600 (product liquid) 
 
 219,200 
 
 40,000 
 
 8,100 
 Heats of neutraUsation of agueous solutions of CO, and SiO^ (Thomsen). 
 
 [M,H'] . . . 
 
 21,750 
 
 [M,C1*] . . . 
 
 21,000 
 
 ^m ■ ■ . 
 
 96,960 
 
 -26,000 
 
 Change of amor- 
 
 
 phous M to crys- 
 
 8,000 
 
 talline M 
 
 
 n [CO^Aq, wNaOHAq] 
 
 1 11.000 difl-q 150 
 
 2 20,160 <l>fi--».lSO 
 
 [SiO^Aq, n NaOHAq] 
 3,240 
 4,315 
 4,730 
 5,230 
 5,410 
 
 Silicic acid shows no constant neutralisation-point. The quantity of heat produced ia ft 
 hyperbolic function of the quantity of soda added, and approaches a probable maximum of 
 6,300 gram-units for one formula-weight of SiO, (v. Silicates). 
 
 Physical properties 
 
 Diamond : hardest known substance -, 
 crystallises in regular forms, octa- 
 hedral predominating; bad con- 
 ductor of electricity; refractive in- 
 dex large (/tD = 2-430) ; lustre very 
 marked ; usually colourless and 
 transparent, but sometimes green, 
 brown, or yellow, 
 
 Adamantine; very hard, scratches 
 glass ; darkiron-grey colour, reddish 
 by refiected light ; crystallises in 
 foniis derived from a rhombic octa- 
 hedron, 
 
 Qraphitoidal : softer than adamantine 
 but scratches glass ; may be pul- 
 verised; metal-like lustre, leaden- 
 
OAEBON GEOUP OF ELEMENTS. 
 TabiiB— confc 
 
 ess 
 
 GABBOir. 
 
 SlUCON. 
 
 Oeewrence and 
 
 OhtimcalproperUes. 
 
 OrapMtei oiystaUisea in hexagonal 
 foims; good oonduotor of eleo- 
 trioity ; tough and difficult to pul- 
 verise; grey, metal-like appear- 
 ance. 
 
 Amorphous: black powder; very 
 porous, absorbs large quantities of 
 gases and of many colouring mat- 
 ters from solutions. 
 
 The three forms occur in nature, but 
 neither graphite nor amorphous 
 pure ; constituent element of all 
 animal and vegetable matter ; car- 
 bonates very widely distributed; 
 graphite prepared by dissolving 
 amorphous in molten iron, or by 
 decomposing by heat the CN com- 
 pounds in the mother liquor of 
 soda manufacture, &c. : approxi- 
 mately pure amorphous, prepared 
 by washing sugar-charcoal in acid, 
 alkaU, and water, and strongly 
 heating in chlorine; or by de- 
 composing CO2 by Na, &c. 
 
 AUotropy marked. Diamond heated 
 by powerful battery in absence of 
 oxygen gets grey-black and coke- 
 like but does not volatilise ; heated 
 in air combustion begins at 950°- 
 1000°. Graphite not affected at 
 any temperature in absence of 
 oxygen ; oxidised by repeated 
 treatment with KCIO3 and HNO3 
 to graphitic acid C^^fi^ (or O5), 
 a yellow solid, si. sol. water, act- 
 ing towards alkaline bases like a 
 feeble acid. Amorphous burns 
 easily in air ; combines with H at 
 a very high temperature to form 
 CjHj ; also combines directly with 
 S to form CS2, with to form CO 
 and CO2, and under special con- 
 ditions with N to form C^^; com- 
 pounds with halogens formed in- 
 directly; combines directly with 
 Ir, Pe, Ni, Pd, Pt, Ag, and perhaps 
 some other metals. Carbon a 
 negative element ; does not form 
 salts by replacing H of acids ; CO^ 
 an anhydride; an aqueous solution 
 of CO2 probably contains the di- 
 basic acid H2CO3, salts of this 
 acid well marked; H2CS3 prepared. 
 Atom of is tetravaJent ; C atoms 
 tend to combine with each other ; 
 vast number of compounds pro- 
 duced by addition of other atoms 
 to groups of C atoms. 
 
 grey colour ; crystallises in leaflets 
 composed of ootahedra ; good con- 
 ductor of electricity. 
 Amorphous: brown powder; heated 
 out of contact with air to high tem- 
 perature it contracts and becomes 
 crystalline ; bad conductor of elec- 
 tricity; dissolves in molten Al or 
 Zn and crystallises out on cooUng. 
 
 Very widely distributed as silicates 
 of Ca, Mg, Pe, Al, &c. ; amorphous 
 obtained by action of K on hot 
 SiClj, SiP,, orKjSiPj; graphitoidal 
 obtained by melting Al with K2Si03 
 and cryolite, or by decomposing 
 SiClj at a high temperature by Na ; 
 adamantine obtained by melting 
 Zn with KjSiPg and Na. 
 
 AUotropy marked. Amorphous Si 
 burns easUyinair to SiO^; graphi- 
 toidal does not oxidisewhen heated; 
 adamantine not even at a white 
 heat in oxygen ; adamantine Si 
 oxidised at red heat in CO2 (giving 
 CO + SiOa), also by strongly heating 
 with KjCOs or NaaCO, (giving 
 CO + Si02 + C), but not changed by 
 molten KHSO,, or by heating with 
 KNO3 if temp, at which that salt 
 decomposes is not reached. Amor- 
 phous Si soluble in HPAq giving 
 HjSiPsAq and hydrogen, also in 
 strong hot potash ley giving 
 KjSiOsAq and hydrogen ; adaman- 
 tine Si insoluble in HPAq and hot 
 alkaU solutions. Si does not di- 
 rectly combine with H, SiH, pro- 
 duced by action of HClAq on com- 
 pound of Si and Mg; combines 
 with S at high temperature to form 
 SiSj; with to form SiOj; with CI, 
 Br, or I, to form SiCl,, SiBrj, or 
 Sil,; and with N at white heat to 
 form Si2N3; combines directly with 
 Al, Cu, Pe, Mg, Mn, Ni, Pt, and 
 perhaps some other metals. SiO, 
 an anhydride ; probable existence 
 of several silicic acids ; SiO(OH), 
 probably present in solution ob- 
 tained by neutralising K2Si03Aq by 
 HCIAqand dialysing; this solution 
 very readily gelatinises. Atom of 
 Si is tetravalent, and, to some ex- 
 tent at least, atoms of Si tend to 
 combine together and form groups 
 which combine with other atoms, 
 forming molecules similar to those 
 of the organic compounds. 
 
684 
 
 CARBON QUOtSV OP ELEMENTS. 
 
 General formula and characters of compounds. 
 
 MO, MOj, MSj, (SiO unknown, ?CS and 
 C2S3) ; MO3H2 (neither known except (?) in 
 aqueous solution, v. Cakbon and Shioon), CSjHj; 
 MH,; 0„Hj,„^.„ C„H2„, C„Ha,_j, C„H2„_|„ 
 Ac, &o., and a vast number of derivatives; 
 MX, (X = 01, Br, I, or in case of Si also =P), 
 MjX,(X = Cl, Br, or I where M = Si, X = 01 or 
 nr where M = C), O^Cl,, C^Br,, &o.; SiPeH,; 
 CH3CI, CHjCl„ CHCI3, SiHCl3, SiHIj, &o. ; C^N^, 
 CNH and salts, CsN^eH, and salts, CjNsFeHa 
 and salts, OsNjNOFeHj and salts, (fee, &o. ; 
 SijN, &a. The compounds of C and Si exhibit 
 considerable differences in their properties ; CO 
 and COjare gases, SiOj is a very fixed solid; CSj 
 is a liquid, SiS^ a soUd ; CCl, is not acted on by 
 water, SiClj is at once decomposed into SiOj 
 and HCl ; Si readily forms a fluoride and also a 
 double fluoride with hydrogen, no corresponding 
 compounds of C are known ; CH4 is a stable 
 gas, SiH, is oxidised by mere contact with air 
 and is easily decomposed by heat (at 400°) ; Si 
 (amorphous) dissolves in potash evolving hydro- 
 gen and forming a silicate, carbon is unacted on 
 by alkalis. Both elements form many com- 
 pounds with H and (alcohols, ethers, acids 
 &c.), the composition of which is similar, in 
 some oases the properties of the Si compounds 
 closely resemble those of C, e.g. C(C2H,)3H 
 and Si(C2H,)3H, C(C2H5)30H and Si(C,H,)36H ; 
 but in other cases the properties of the two 
 classes of compounds differ much, e.g. CH3.CO2H 
 and C2H5.CO2H are liquids soluble in water, 
 but CHa.SiOjH and C^Hs.SiOjH are amor- 
 phous solids insoluble in water. Many sili- 
 cates and carbonates are isomorphous. SUi- 
 cates, except those of the alkali metals, are 
 insoluble in water, and most of them are with 
 difBoulty decomposed by acids; the normal 
 carbonates of the alkali metals are solu- 
 ble in water, other normal carbonates are in- 
 soluble; aqueous solutions of acid carbonates 
 are generally easily decomposed by heat yielding 
 either normal or basic carbonates ; the normal 
 carbonates of the alkali metals are not decom- 
 posed by heat alone, other normal carbonates 
 are decomposed into metaUio oxide and COj. 
 
 Group IV. of the elements, as the elements 
 are classified by the application of the periodic 
 law, contains the following : — 
 
 
 
 
 Series 
 
 
 
 Even 
 
 2 
 
 4 
 
 6 8 
 
 10 
 
 12 
 
 
 C 
 
 Ti 
 
 Zr Ce 
 
 — 
 
 Th 
 
 Odd 
 
 3 
 
 5 
 
 7 9 
 
 11 
 
 
 
 Si 
 
 Ge 
 
 Sn - 
 
 Pb 
 
 
 The metals titanium, zirconium, and germa- 
 nium show considerable analogies with tin ; 
 cerium and thorium are usually classed toge- 
 ther among the rarer earth-metals, and lead is 
 generally considered apart from other metals : 
 nevertheless there are well-marked analogies 
 between all the elements which comprise Group 
 [V. of the periodic system. Titanium is an 
 amorphous body closely resembling amorphous 
 silicon; it forms the compounds Til?,, TiCl., 
 TiBr„ Til„ TijClj, TiO^ (probably TiO(OH) and 
 Ti(0H)4), TijOj. TiaN,, &o. ; titanates are known 
 (MjTi03), many of them isomorphous with sili- 
 cates and carbonates. Ti is more metallic than 
 
 C or Si, it forms a sulphate 11(804)2, an^ °*^** 
 salts wherein the hydrogen of acids is replaced 
 by titanium. Zirconium again is more decidedly 
 metallic than titanium ; it forms a series ol 
 well-marked salts Zr(S04)2, ZriNO,, &o., &a. 
 On the other hand Zr resembles and Si in 
 that it has been obtained both as an amorphous 
 powder, and also in crystals which resemble Si 
 in their behaviour towards acids ; zirconates 
 (M2Zr03) are also known. Germanium forms 
 oxides, chlorides, and sulphides, ifec. (GeX and 
 GeX2, X = = S = CI2), resembling those of Sn ; 
 it is, however, more markedly non-metallio in 
 its chemical functions than Sn ; physically 
 Ge is decidedly metallic. Cerium forms two 
 oxides Ce203 and Ce02 ; the former dissolves in 
 acids forming a series of salts of which COaSSO, 
 is a type; CeO^ is a peroxide, it dissolves in 
 HCl with evolution of 01 and formation of CeOlj, 
 but a sulphate 06(804)2 is known corresponding, 
 to the sulphates of Ti and Zr. Ce also forms a 
 fluoride CeP,„ a double fluoride 3KP. 206^4, and 
 a chloride CejClj. Thorium again approaches 
 more closely than cerium to Zr and Ti ; it is a 
 dark-coloured amorphous powder resembling Si, 
 but more soluble in acids than Si, Zr, or Ti ; it 
 forms the compounds ThClj, ThF,, K2ThI'5, 
 ThOj, <Src. ; the sulphate is Th(S04)2, and other 
 analogous salts are known. Tin forms the 
 two oxides and chlorides SnO and SnO,, SnCl2 
 and SnCl4; the hydrates of Sn02 are feeble acids, 
 producing stannates (MaSnOJ and metastan- 
 nates (MjSn^O,,), both of which are easily de- 
 composed by dilute acids or by heat. Both 
 the stannous salts e.g. SnSO,, and the stannic 
 salts e.g. Sn(SO ,)2i are well-marked compounds. 
 Lead is decidedly metallic in its character ; it 
 forms four oxides PbO, PhjO,, Ph^Oa, and Pb02i 
 the last is a peroxide, and it may also be re- 
 garded as an anhydride inasmuch as plumbatea 
 (M2Pb03) exist, but these salts are very un- 
 stable and easily decomposed. The best-marked 
 salts of lead are derived from the oxide PbO, 
 e.g. PbCl2, Pb2N03, PbS04, &c. ; PbCl4 has not 
 been obtained pure, but this series of salts is 
 represented by the tetramethide Pb(CH3)4 which 
 is stable as a gas. The atoms of all the elements 
 of Group IV., so far as evidence has been ob- 
 tained, are tetravalent. Looking at the pro- 
 perties of these elements as a whole, it may be 
 said that carbon is to a considerable extent set 
 apart from the others, but that it is more closely 
 allied to silicon than to any other member of 
 the group ; that titanium and zirconium are 
 closely related ; and that tin and lead, while 
 showing distinct analogies with the rest of the 
 group, are yet each characterised by properties 
 which mark them off from the other elements. 
 Not much can yet be said regarding cerium and 
 thorium ; they require further study. 
 
 For more details and descriptions of the 
 various elements see the articles on these ele- 
 ments; also V. TlTANITJM OKOUP OF ELEMENTS; 
 
 also V. Cabbonates, Nitrates, Sulphates, &c. 
 In some of their physical properties carbon and 
 silicon, especially the latter, resemble boron, but 
 boron must be classed with those elements the 
 atoms of which are trivalent ; v. Bobon. 
 
 M. M. P. M. 
 CARBON 0. At. w. 11-97- Mol. w. unknown ; 
 element has not been gasifi 3d. S.G. diamond 
 
UARBON. 
 
 686 
 
 1^' 3-514 (Sohrotter, Sitz. W. 63, (and pt.) 462), 
 ji 3-518 (Baumhauer, Ar. N. 8, 1). S.G. 
 graphite 2-11 to 2-26 (Eenngott, Brodie, M^ne ; 
 Situ. W. 13,469; A. 114, 7; C. B. 64,104). 
 S.G. amorphous charcoal 1-45 to 1-7 (v. Vio- 
 lette, A. Gh. [3] 39, 291). S.G. hard gas-ooke 
 2-356 (Marchand a. Meyer). S.H. about -5 at 
 1000° (v. infra). C.E. (diamond, linear at 40°) 
 •00000118; (diamond, cub. at 49°) -00000354; 
 (graphite, linear at 40°) -00000786; (Fizeau, 
 C. B. 62, 1133 ; 68, 1125). mb = 2-46, fi^ = 2-479, 
 for diamond (Schrauf, P. 112, 588). E.G. gra- 
 phite, -082 (Hg at 0° = 1) [varies much for dif- 
 ferent specimens] (Muraoka, W. 13, 307). E.G. 
 hard gas-coke, -01 (Hg at 0° = 1) (Muraoka, I.e.). 
 Crystalline form; diamond, regular octahedra 
 and forms derived therefrom ; graphite, hexago- 
 nal forms chiefly rhombohedral (Kenngott, Situ. 
 W. 18, 469) ; Nordenskiold (P. 96, 100) observed 
 monoolinio crystals in graphite from Finland. 
 H.O. [C,0'] = 96,960 for amorphous {Th. 1, 
 411) ; 93,350 for diamond, and 93,560 for graphite 
 (Fayre a. SUbermann, A. Ch. [3] 33, 414). 
 Emission-spectrum observed by passing sparks 
 through pure CO or COj is characterised by a 
 double line 6583 and 6577-5, three sharp lines 
 5150-5, 5144-2, 5133, and a band 4206 (Angstrom 
 a. Thal^n, Nov. Act. Ups. 9 [1875J). Besides 
 these, and many other less marked, lines, 
 Liveing a. Dewar describe the arc-spectrum 
 as showing the following marked lines, 3919-3, 
 2837-2, 2836-3, 2511-9, 2509-9, 22y6-5 {Pr. 30, 
 152, 494 ; 33, 403 ; 34, 123, 418). A very dif- 
 ferent spectrum — the band-spectrum — is ob- 
 served at the base of a candle or gas flame, also 
 in cyanogen burnt in O, or by passing sparks 
 through CN, CO at increased pressure, CSj, &b. ; 
 the most characteristic bands are 5633, 5164, 
 and 4736. There has been much discussion as 
 to whether this spectrum is that of C or of a 
 hydrocarbon (v. B. A. 1880. 264). Three allo- 
 tropio forms of carbon are known ; diamond, 
 graphite, and amorphous carbon. 
 
 The diamond was regarded by Newton as a 
 combustible body because of its high refractive 
 power; in 1694 diamond was burnt by the 
 Florentine Academicians ; Lavoisier found that 
 CO2 is produced when diamond is burnt, and 
 Davy showed that diamond is pure carbon. 
 Lavoisier, about 1780, recognised that carbonic 
 acid (then called fixed air) was a compound of 
 O and the element which is the essential element 
 of coal ; to this element he gave the name car- 
 bone. Graphite was long considered to be a 
 kind of lead ; Scheele, in 1799, showed it to be 
 closely related to coal ; he regarded it as a com- 
 pound of iron and carbon, but Kastner proved 
 that the iron found in graphite was only an 
 impurity, and that pure graphite is a form of 
 carbon. 
 
 Occurrence. — Carbon occurs as diamond and 
 graphite, the former is pure, the latter some- 
 times approximately pure, carbon ; many com- 
 pounds of occur in nature ; the chief are CO^ 
 in the air and all waters, mineral carbonates e.g. 
 of Ca and Mg, and compounds with H, 0, N, and 
 sometimes P and S, in all animal andvegetable 
 organisms. Diamonds are found in India, 
 Borneo, Brazil, the Cape, &c.; graphite, in 
 Op?nberland, Qftlifornia, Siberia, &o, Berthelot 
 
 (G.R. 73, 494) found graphite in a meteorite 
 which fell near Melbourne (Australia) ; and 
 Fletcher found a cubic form of graphite in a 
 meteorite from Western Australia {Mineralog. 
 Mag., Jan. 1887). Graphite is found both amor-* 
 phous and foliated. Coal, anthracite, peat, &o., 
 contain from 50 to 95 p.o. of carbon. 
 
 Formation. — Many attempts have been made 
 to form diamond ; none has been certainly suc- 
 cessful (v. Liebig, AgriauUurchemie [1840] 285 ; 
 Wilson, J. 1850. 697 ; Favre, /. 1856. 828 [from 
 CGIJ ; Despretz, C. B. 37, 369 [electric current 
 for a month from Pt to G pole] ; Simmler, P. 
 105, 466 [crystallisation from liquid CO2] ; Lion- 
 net, C. B. 63, 213 [from CSJ; Chancourtois, 
 0. G. 1856. 1037 [oxidation of hydrocarbon]; 
 Eossi, O. B. 63, 408 ; Hannay, Pr. 30, 188 a. 
 450 [action of Mg, and Li, on gaseous hydrocar- 
 bons mixed with N-containing compounds at 
 very high temperatures and pressures] ; Mars- 
 den, Pr. E. 11, 20 [by dissolving amorphous C 
 in molten Ag]). Graphite is formed: — 1. By 
 heating charcoal with molten iron, and dissolv- 
 ing out the Fe by HCl and HNOaAq.— 2. By 
 the slow decomposition of HGNAq, and boiling 
 the product with HNOsAq (Wagner, J. G. T. 
 1869. 230). — 3. By evaporating the mother 
 liquors obtained in making soda; these con- 
 tain GN compounds which are decomposed 
 at a certain concentration of the liquid with 
 formation of NH, and graphite (Pauli, D. P. J. 
 161, 129 ; Schaffner, W. J. 1869. 250).— 4. By 
 leading CO over Fe^Oa at 300°-400° (Gruner, 
 G. B. 73, 28 ; Stingl, B. 6, 392). Amorphous 
 is also formed (Berthelot, G. B. 73, 494).— -5. By 
 the decomposition of CS^ at high temperatures. 
 6. By leading CCl^ over molten pig-iron (DeviUe, 
 A. Gh. [3] 49, 72). Amorphous carbon is formed 
 in many ways : — 1. By heating wood, coal, or 
 almost any animal or vegetable matter, out of 
 contact with air, to a high temperature. — 2. By 
 the incomplete combustion of wax, tallow, oil, or 
 other combustible compounds of C and H. — 3. 
 By decomposing, at a very high temperature and 
 out of contact with air, the gaseous C compounds 
 obtained in the production of gas from coal : the 
 carbon thus obtained is very hard (v. Proper- 
 ties). 
 
 Preparation. — Pure graphite is obtained by 
 intimately mixing 14 parts of finely powdered 
 foliated graphite with 1 part KCIO3 and 2 parts 
 cone. H2S0i, heating on the water-bath so long 
 as CI comes off, washing repeatedly with hot 
 water, drying and heating to remove HjSOj : if 
 the graphite contains silica it is treated with 
 NaF and H2SO4, besides ti-eatment with KCIO3 
 and HjSO, (Brodie, T. 1860. 1 ; v. also Winckler, 
 J. pr. 98, 243 ; Stingl, B. 6, 391). 
 
 Amorphous carbon is prepared approximately 
 pure by strongly heating cane sugar in a closed 
 Pt crucible, boiling the charcoal thus produced 
 with (1) cone. HClAq, (2) KOHAq, (3) water, 
 drying, heating to full redness in a stream of 
 dry CI and allowing to cool in the same ; H is 
 removed as HCl, as GO, also traces of SiO^, 
 Fe^Oa, &o. as SiCl4, Fe^Glj, AljClj, &c. The 
 soot from semi-burnt turpentine oil, after treat- 
 ment with ether, and heating to a high 
 temperature in a closed vessel, is approximately 
 pure carbon. It seems to be impossible to obtain 
 finely divided amorphous quite free from gaaet 
 
686 
 
 CARBON. 
 
 such as H, O, or CI ; even when purified as de- 
 scribed it retains traces of CI, this may be 
 removed by strongly heating in connection with 
 a Sprengel pnmp, but on exposure to the air 
 considerable quantities of 0, CO2, &o. are 
 quickly absorbed. The absorbed gases cannot 
 be removed by heating at ordinary pressures; 
 Erdmann a. Marchand (/. pr. 23, 159) found 
 •2 p.o. H and -5 p.c. in sugar-oharooal which 
 had been heated nearly to whiteness for 3 hours. 
 According to Poroher (0. N. 44, 203) amorphous 
 C free from H, 0, and N is obtained by passing 
 CCl, vapour over hot pure Na in a hard glass 
 tube, and then heating the C obtained to a 
 little under the temperature at which burning 
 begins. A very hard kind of amorphous carbon 
 is formed by placing wood (box, ash, elder, lilac, 
 or oak), or flax, hemp, cotton, paper, or silk, in 
 a porcelain tube, driving out all air by CS2 
 vapour and then gradually heating to redness 
 for an hour (Sidot, G. B. 70, 605). The harder 
 the wood and the higher the temperature to 
 which it is heated, the harder and denser is the 
 carbon produced. Various materials consisting 
 mainly of carbon are prepared for industrial 
 use ; charcoal, by partially burning piles of 
 wood covered with turf or earth, or by the dry 
 distillation of wood ; coke, by heating coal in 
 iron retorts arranged so that the liquid and 
 gaseous products may be separated from the 
 residual carbonaceous matter; lamp black, by 
 partially burning tallow, turpentine, &o., and 
 condensing the soot on cold surfaces; animal 
 cliar (which however contains only about 10-20 
 p.c. C) by heating bones in closed vessels. 
 
 Properties.— Vnch&ngeSL by action of acids ; 
 has not been melted or vaporised. 
 
 Diamond is a colourless, transparent, very 
 refractive and dispersive, crystalline, solid ; some 
 diamonds are coloured yellow, brown, blue, or 
 black. Diamond is the hardest substance known, 
 but rather brittle ; very bad conductor of electricity 
 and heat. C.E. small, especially at low tem- 
 peratures, at — 42° = 0. Unchanged by heating 
 out of contact with air to 1300°-1400°; but 
 placed between the carbon poles of a powerful 
 battery it glows brilliantly, swells up, splits, 
 and after cooling the surface resembles coke 
 from bituminous coal (comp. Eose, P. 168, 497 ; 
 V. Schrotter, Sitz. W. [2] 63, 462; Morren, 
 C. B. 70, 990 ; Jacquelain, A. 64, 256 ; Gassiot, 
 Fh. 0. 1850. 893; Baumhauer, Ar. N. 8, 1). 
 Unchanged when heated to whiteness in water- 
 vapour (Baumhauer, l.c.). Strongly heated in a 
 stream of 0, diamond is completely burnt to 
 COj ; it may also be burnt by heating with 
 molten KNO3 ; or, very slowly, by powdering 
 finely and heating with EjCrjO,, H^SO^, and a 
 little HjO (Sogers, J. pr. 50, 411). 
 
 Graphite occurs native both crystalline 
 {foUated) and amorphous; it forms a grey, 
 metal-like, hard, opaque, solid; fair conductor 
 of electricity, tspecially after purification by 
 KCIO3, &c. (?' supra) ; fair conductor of heat; 
 is not changed by heating out of contact with 
 air ; burns in to COj at a high temperature, 
 but more slowly than diamond; burnt to OOj, 
 more easily than diamond, by molten KNOs, or 
 by KjCrjO, and H^SOjAq ; also by heating with 
 various metallic oxides. When graphite is 
 Seated with KCIO, and HNOjAq a compound pf 
 
 0, H, and is formed, called by Brodie ffraphitie 
 acid (probably OnH^Os) ; this body is not ob- 
 tained from cLiamond or amorphous carbon (i>. 
 EeacUons, No. 9). 
 
 The graphite-like form of coke which ia 
 formed in the upper parts of the retorts in which 
 coal is heated for gas -making, or is obtained by 
 passing hydrocarbon vapours through red-hot 
 porcelain or iron tubes, is an extremely hard, 
 metal-like, lustrous, sonorous solid ; S.G. 
 (2-356) nearly same as that of graphite ; it is 
 a good conductor of electricity and a fair con- 
 ductor of heat ; burns with difficulty ; it contains 
 no H, and leaves only from "2 to •$ p.c. ash 
 (Marchand a. Meyer). 
 
 Amorphous carbon (sugar-charcoal; lamp- 
 black) is a dense, black, powder ; it is ex- 
 tremely slowly acted on by any reagents, even 
 energetic oxidisers ; non-conductor of electricity. 
 The harder forms of amorphous carbon, obtained 
 by calcining hard woods at high temperatures 
 out of contact with air, somewhat resemble 
 graphite in appearance, they are more or less 
 lustrous, conduct electricity fairly well, and 
 burn slowly when heated in air or 0. Ordinary 
 amorphous C, or ordinary wood charcoal, ab- 
 sorbs large volumes of gases : Saussure (O. A. 
 47, 113) gives the following volumes absorbed 
 by 1 vol. box-charcoal at 12° and 724 mm. : 
 NH3 90, HCl 85, SOj 65, H^S 55, N^O 40, 
 CO2 35, CO 9-4, CjH, 35, 92, N 7-5, H 175. 
 Hunter (P. M. [4] 29, 116 ; 0. J. [2] 3, 285 ; 
 5, 160; 6, 186; 8, 73; 9, 76; 10, 649) gives 
 these numbers for 1 volume cocoa-nut charcoal 
 at 0° and 760 mm.: NH3 171-7, CN 107-5, 
 NO 80-3, CH,C1 76-4, (CH,),0 76-2, C^H, 74-7, 
 Nj,0 70-5, PH3 69-1, COj 67-7, CO 21-2, 17-9. 
 According to Angus Smith {Pr. 28, 322) absorp- 
 tion of gases by charcoal takes place in definite 
 volumes ; thus if the vol. of H absorbed under 
 definite conditions is 1, the vol. of = 8, CO = 6, 
 CO2 = 22, N = 4-66. Chemical reaction some- 
 times occurs between gases absorbed by char- 
 coal ; thus, HCl is produced by leading H over 
 charcoal which has absorbed CI, and SO^Cl^ by 
 leading SO^ over charcoal under the same con- 
 ditions. The absorbed gases are removed in 
 vaciio. Eecently heated porous wood char- 
 coal removes many colouring matters, e.g. 
 indigo, from solutions ; it also removes Eusel oil 
 from weak alcohol, alkaloids from aqueous 
 solutions, many metallic salts from solutions, 
 &c. ; in some cases chemical change is pro- 
 duced, e.g. CuSOjAq and AgNOjAq are reduced 
 with pps. of Cu and Ag (Monde, J. pr. 67, 
 255 ; V. also G-raham a. Hofmann, A. 83, 39 ; 
 Graham, P. 19, 139 ; Weppen, A. 55, 241 ; 59, 
 854 ; Favre, A. Ch. [5] 1, 209 ; Guthe a. Harms, 
 Ar. Ph. 69, 121 ; Stenhouse, A. 90, 186). 
 
 Specific heat of carbon. — The follow- 
 ing numbers summarise the chief determinations 
 exclusive of those of Weber : the temperature- 
 interval is about 35°-55° : — 
 
 Diamond: 443 BettendorfE a. WuUner (P. 
 133, 293) ; -147 Eegnault (A. Oh. [3] 1, 202) j 
 ■866 [20''-l,000°] Dewar (P. M. [4] 44, 461). 
 
 Oas carbon : -165 Kopp (A. 126, 362 ■, 
 Stt^lbd. 8, 1 a. 289) ; -186 B. a. W. (I.e.) ; -197 
 E. (J.C.) ; -32 [20°-l,000°] D. (I.e.). 
 
 Graphite: -174 Kopp ilc); -188 B.%Vft 
 {l.c.) ; -m S,. (U.). 
 
CAEBON. 
 
 687 
 
 Wood charcoal : •241 E. (I.e.). 
 
 In 1874 Weber made careful determinations 
 of the S.H. of the different forma of carbon at 
 different temperatures; he used (1) diamond, 
 (2) native graphite, (3) porous -wood charcoal in 
 a Blender filament strongly heated in dry CI and 
 sealed at once in a glass tube. His chief results 
 were as follows (v. P.M. [4] 49, 161 a. 276) :— 
 
 Diamond, 
 Temp. -50° +10° 85° 250° 606° 985° 
 S.H. -0635 -1128 -1765 -3026 -4408 -4529 
 
 Temp. -50° +10° 61° 201° 250° 641° 978° 
 B.H. -1138 -1604 -199 -2966 -325 -4454 -467 
 
 Wood Charcoal. 
 Temp. 0°-23° 0°-99° 0°-223° 
 S.H. -1653 -1935 -2385 
 
 These numbers show that the S.H. increases as 
 temp, increases, but that the rate of this in- 
 crease is much smaller at high than at low 
 temperatures. From 600° onwards the S.H. of 
 diamond is the same as that of graphite ; as 
 the values for wood charcoal are nearly the same 
 as those for graphite for the same temperature- 
 intervals, the conclusions may fairly be drawn 
 that at temperatures above 600° the different 
 forms of carbon have all the same S.H., and that 
 at lower temperatures there are two values for 
 the S.H., one belonging to graphite and amor- 
 phous 0, the other to diamond. 
 
 Allotropy of carbon. Carbon exhibits 
 allotropio changes in a marked way ; diamond 
 may be, superficially at any rate, changed to 
 graphite ; amorphous may also be changed to 
 graphite ; each of the three varieties is charac- 
 terised by special properties. The S.G. of each 
 is characteristic. The heats of combustion {v. 
 supra) are different. The S.H.s are not the 
 same ; but Weber's results tend to show that, 
 as regards S.H., there is but one form of C ex- 
 isting at temperatures above 600°- Amorphous 
 remained unchanged when subjected to a 
 pressure of 6,000-7,000 atmos. (Spring, A. Ch. 
 [5] 22, 170). The three forms are clearly dis- 
 tinguished, chemically, by their reactions with 
 KCIO3 and HNO3 {v. Reactions, No. 9). 
 
 Atomic weight. — Determined (1) by burn- 
 ing diamond in and weighing the CO^ produced 
 (Dumas a. Stas, A. Ch. [3] 1, 5 ; Erdmann a. 
 Marohand, J. pr. 23, 159 ; Boscoe, A. Ch. [5] 
 26, 136 ; Friedel, Bl. [2] 41, 100) ; (2) by heating 
 silver acetate and weighing the Ag (Marignac, 
 A. 59, 287) ; (B) by heating Ag salts (oxalate and 
 acetate) and weighing the Ag and COj formed 
 (Maumenfi, 4. Ch. [3] 18, 41). The mean of 
 all the (closely agreeing) results is 11-97 
 (0 = 15-96). 
 
 Chemical properties. — The atom of 
 C is tetravalent in gaseous molecules (CH„ CCI4, 
 CBr,, <feo.). The atomicity of the molecule of 
 C is unknown, as the element has not been gasi- 
 fied; certain considerations, e.g. the increase 
 in S.H. as temperature increases, and perhaps 
 the character of the spectrum, seem to indicate 
 that the molecule of is probably composed of 
 
 several atoms. 1 „. 1 1 
 
 Carbon is distinctly a non-metalUo element ; 
 it does not replace the H of acids to form salts ; 
 it forms stable, but easily g9,sified, compounds 
 
 with the halogens ; its oxides, and also the 
 sulphide CS.^, are distinctly acidic in their re- 
 actions ; it exhibits allotropy in a most decided 
 way ; the spectrum of C is very complex ; yet in 
 some of the physical properties of graphite and 
 dense amorphous carbon, this element approaches 
 the metals (v. supra). Carbon stands at the 
 beginning of Group IV. in the periodic classifica- 
 tion of the elements ; the other members of this 
 group, except Si, are more metallic than non- 
 metallic ; C shows closer relations to Si, the first 
 odd-series member of the group, than to any 
 other element in the group {v. Cakbon qkoup of 
 elements). Both elements are remarkable for 
 the great number of compounds which they 
 form with H, 0, and N. Most of the elements 
 of Group IV., except 0, form characteristic com- 
 pormds with F, or double compounds with F and 
 other elements. 
 
 Reactions. — 1. Unchanged by action at acids. 
 2. Heat, in absence of air, produces no change 
 (com/p. Properties of Diamond). — 3. When 
 strongly heated in excess of oxygen, COj is 
 formed : the combination is much retarded if 
 the C and are carefully dried (Baker, C. J. 
 47, 349). — 4. Heated with sulphuric acid and 
 potassium dichromate is slowly burnt to COj. 
 5. Oxidised to CO2 by heating with molten 
 nitrate or chlorate of potassium. — 6. Eeacts with 
 sulphur vapour at high temperatures to form 
 CSj. — 7. Combines with hydrogen to form CjHj ; 
 by passing electric sparks between C poles in 
 atmosphere of H. — 8. Combines indirectly with 
 nitrogen to form cyanogen. — 9. Graphite is oxi- 
 dised hj potassium chlorate and nitric acid to 
 graphitic acid (?C„H<05 or C,|HjOj). Brodie 
 (T. 1859. 249) heated an intimate mixture of 1 
 part purified and very finely divided graphite and 
 3 parts KClOs, with enough very cono. HNOjAq 
 to bring all into solution, at 60° for 3-4 days, 
 until yeUow vapour ceased to come off ; the 
 contents of the retort were then poured into 
 much water ; the insoluble matter was tho- 
 roughly washed by deoantation, dried on a 
 water-bath, and again oxidised by KClOj and 
 HNOjAq, as before. These operations were 
 repeated (usually 4 times) until no further 
 change was produced, and the insoluble 
 matter formed a olear-yeUow solid. Analysis of 
 this yellow solid, dried at 100°, gave the formula 
 CiiHiOj. This body— called graphitic acid by 
 Brodie — forms small, transparent, lustrous, 
 yellow plates ; it is sUghtly soluble in water ; 
 insoluble in water containing acids or salts; 
 turns blue Utmus slightly red; shaken with 
 solutions of alkaline bases it appears to form 
 insoluble salts, but the composition of these ia 
 very uncertain; when heated it burns explo- 
 sively, leaving a fine, black residue ; it is easily 
 decomposed byreduoing agents such as (NHJHS, 
 SnClj, HIAq, &o. {v. infra). Brodie supposed 
 this body to be a compound of a hypothetical 
 element which he called graphon, and to which 
 he gave the atomic weight 83 ; he formulated 
 graphitic acid as Gr^H^Oj, and regarded it as 
 the carbon analogue of a silicic acid SijHjOs 
 obtained by Wohler from graphitoidal silicon. 
 Gottschalk (J.pr. 95, 321) placed a very intimate 
 mixture of 1 part (50 grms.) purified, very finely 
 divided graphite with 3 parts KOlO, in a large 
 flask surrounded by ice-opld water, and very 
 
688 
 
 CARBON. 
 
 riowly added enough HNOaAq, S.G. 1-525, to 
 completely moisten the whole ; he then digested 
 at 50° to 60°, and then at 60° to 70°, for 25-30 
 hours; he poured off the greater part of the 
 acid and dissolved KNOj, washed with hot water 
 by decantation, dried m vacuo and then at 100° ; 
 he repeated this treatment 5 or 6 times ; finally 
 he washed the residue with HNOjAq S.G. 1-28, 
 removed the acid by pressing between paper and 
 then by washing with alcohol, washed with ether 
 to remove alcohol, pressed again, and dried on 
 the water-bath in the dark. Gottsohalk's 
 analyses lead to the formula C,,Hj05 for 
 graphitic acid ; he describes a salt, CjjH^KjOib, 
 obtained by treating with cone. KOHAq and 
 washing with cold water. 
 
 The action of KClOj and HNOj on graphite 
 has also been investigated by Stingl {B. 6, 391), 
 and by Berthelot (A. Ch. [4] 19, 899). Berthelot 
 calls the compound produced as described 
 grcupMtic oxide, he says it does not react as an 
 acid; he calls the carbon-like mass left on 
 heating graphitic oxide pyrographitic oxide; 
 the body is completely dissolved by heating with 
 KOIO3 and HNO3. The porous, amorphous, 
 insoluble body obtained by heating 1 part 
 graphitic oxide with 20 parts HIAq — S.G. 2'0 
 to 280°, Berthelot calls hydrographitic oxide ; 
 this body is not explosively decomposed by 
 heating, treated with KCIO3 and HNO3 it yields 
 graphitic oxide. There appear to be differences 
 between the graphitic acids obtained from 
 different kinds of graphite. Berthelot distin- 
 guishes the three allotropic forms of carbon by 
 their reactions with KCIO3 and cone. HNO3; 
 amorphous carbon is oxidised to brown humus- 
 like bodies, which dissolve in water; graphite 
 forms graphitic acid ; diamond is unchanged. — 
 10. Both graphite and amorphous carbon are 
 said to yield mellitio acid Cj(C02H)s by the 
 action of Ti^Unfia in KOHAq (Schulze, B. 4, 
 802). — 11. Carbon combines with many metals 
 when strongly heated with them, e.g. with Fe, 
 Ni, Co, &o. ; none of these carbides has been 
 isolated as a pure compound {v. Carbides). 
 
 Carbon, halogen compounds of. Carbon 
 does not combine directly with the halogens. 
 These compounds are represented by the formulsa 
 CX4, C2X5, and C2X4, where X = Br or CI ; when 
 X = I only CX, is known : no fluoride of C has 
 been isolated. The chlorides have been gasified 
 and V.D. of each determined ; the formula are 
 therefore molecular. The bromides decompose, 
 partially or wholly, when heated : the formulte 
 are probably molecular. The iodide is easily 
 separated by heat into C and I. The methods 
 of preparation, and reactions, of the chlorides 
 and bromides are very similar. [C,C1'] = 21,080 ; 
 [C^Cl'] = — 1,150 (at const, press. Thomson). 
 Besides these compounds, several bromochlorides 
 of carbon exist ; CBrCla ; two isomeric CjBr^Cl,, 
 CjBr^Clj, GJBifil, CjBrjClj, G^rfil. [For more 
 details of the halogen compounds of carbon v. 
 the halogen deri/oatmes of Ethane, Ethylene, 
 and Methane.] 
 
 Carbon bromides. Carbon dibromide 
 CjBrj (Tetrabromethylene). White crystals; 
 M.P. 53° ; produced by heating C^Br^, or better, 
 by reducing CjBrj with Zn and H^SOjAq ; also by 
 reacting with Br on alcohol or ether, adding 
 SOHAq to remove EBr, and distilling ; 01 by 
 
 treating C2HBr5.Br2 with alcoholic KOH (Len- 
 nox, C. J. 14, 209). Decomposed by hot Zn, 
 Cu, Fe, ZnO, CuO, &c., giving metallic bromido 
 and or COj (Lowig, A. 8, 292). 
 
 Carbon tribromide C^x^lflexdbromidt 
 Tetrabromethylene dibromide). Hard, rectan- 
 gular prisms, easily soluble in CS^, insoluble in 
 alcohol or ether ; decomposed to CjBr, and Br, 
 at 200°. Produced by brominating CjHjBrj, 
 and by heating C^HBrj with Br and H^O to 
 170°-180° (Eeboul, A. 124, 271). 
 
 Carbon tetrabromide CBr^ (Tetra- 
 bronio-methane). White lustrous tables; S.G. 
 3-42 ; M.P. 91°. B.P. 189-5° (at 760 mm.) with 
 partial decomposition. lusol. in water, very sol. 
 in alcohol, ether, or CHCI3. Partially decom- 
 posed with liberation of Br, at 200° ; with alco. 
 hoi at 100° gives HBr, CHBr,, and CH3.CHO ; 
 with alcohoUc NHj at 100° gives GS&r-j and a 
 little guanidine. Formed by the reaction between 
 (1) Br, in presence of I or SbBrj, and CHBrj or 
 CS., or CBr3(N02) ; (2) Br, in presence of I, and 
 CHCI3. Best prepared by heating 1 part CS^ 
 with 1^ parts I and 7 parts Br to 150°-160° for 
 48 hours in a closed tube, shaking contents of 
 tube with NaOHAq, distilling in steam, pressing 
 between paper, and crystallising from alcohol 
 (Bolas a. Groves, O. J. [2] 8, 161 ; 9, 773). 
 
 Cabbon Chlorides. Carbon dichloride 
 CjCl, (Tetrachlorethylene). -Golouilesa liquid; 
 ethereal odour ; S.G. at 10° 1-62 (E.), 1-612 (G.); 
 S.G. at 0° 1-6595 (B.). B.P. 122° (E.), 116-7° 
 (G.), 121° (B.). Y.D. 5-82. Easily combines 
 with CI in sunlight forming C^Ol,. Prepared by 
 reducing C^Clg; C^Cl^ is placed in a flask with 
 water and Zn, H^SOjAq is added from time to 
 time, the flask being kept cold and frequently 
 shaken ; the OjCl, is distilled over in steam, 
 dried, and fractionated (Faraday, T. 1821. 47 ; 
 Eegnault, A. Ch. 71, 377 ; Geuther, A. 107, 
 212 ; Bourgoin, Bl. 23, 344). 
 
 Carbon trichloride C^Cl, {Tetra- 
 chlorethylene dichloride. Carbon hexachloride). 
 Hard, colourless, rhombic prisms ; S.G. 2-0. 
 M.P. 187° and B.P. the same (Stadel a. Hahn, 
 B. 9, 1735). V.D. 8-15. Insol. in B-fi, sol. in 
 alcohol or ether. Easily reduced, e.g. by Zn and 
 H2S04Aq, or by alcoholic EHS, to C^Cl,; with 
 KOHAq at 200° gives KOI, HjO, and KjC^Oj. 
 Prepared by leading 01 into boiling CjH,Clj till 
 saturated, cooling by ice, pressing between 
 paper, dissolving in alcohol, ppg. by H^O, press- 
 ing, and crystallising from alcohol (Faraday, T. 
 1821. 47; Eegnault, A. Ch. 69, 165; 71, 871; 
 Liebig, A. 1, 219; Geuther, A. 60, 247; Ber- 
 thelot, A. 109, 118). 
 
 Carbon tetrachloride CCl, (Tetra- 
 chloro-methane). Colourless liquid, with ethereal 
 odour; S.G. | 1-68195; B.P. 76-74° (Thorpe, 
 O. J. 37, 199). V.D. 5-24. Prepared by leading 
 dry CI into boiling CHCl, containing a little 
 SbClj or 101, in a large flask with inverted con- 
 denser, removing excess of 01 by shaking with 
 Hg, and fractionating. Also by passing OS, 
 and 01 through a hot porcelain tube (Kolbe, A. 
 45, 41 ; 54, 146). Unchanged by KOHAq ; with 
 alcoholic KOH slowly gives KOI, KjCOb, and 
 H2O ; passed through a hot tube gives C2CI4, 
 CjCls, and C ; heated with SO, gives COClj and 
 S^OjCl,; with P,0, gives yOOl, and 0001, 
 
CARBON. 
 
 689 
 
 (Ile^nault, .1. Ch. 71, 377 ; Dumas, A. Ch. 73, 
 95). 
 
 Cahbon iodide. CI^. Dark red octahedra ; 
 S.G. ?^4-32; sol. in alcohol, ether, or CS.,. De- 
 composed by heat to C and I ; boiled with H..0 
 or dilute HIAq gives CHIj. Prepared by mixing 
 equal vols. CClj and CSj with saturated solution 
 of Aljj in CS„, then diluting with H^O out of 
 contact with air. The solution of Aljl,, is pre- 
 pared by placing the proper quantities of Al (in 
 small pieces) and I in a stoppered flask and 
 adding 3 times the quantity of CS, (Gustavson 
 
 B. 14, 1705). 
 
 Cabbon Bbomochlobides : Trichlorobromo- 
 viethane CCljBr ; two tetrachlorodibromo-ethanes 
 C^CliBr^ ; dichloroietrabromo-ethane OjCljBrj ; 
 chloropentabromo-ethane CjClBrj ; dichlorodi- 
 bromo-ethyUne C/jl^r^; chlorotribromo-ethylene 
 CfilBr, (v. these compounds under Methane, 
 Ethane, and Kthylene). 
 
 Carbon, hydrate of (?) By treating pig-iron 
 with (1) CuSOjAq, (2) Fe-^Cl^Aq containing HCl, 
 a brownish-black substance remains, contain- 
 ing, according to Schiitzenberger a. Bourgeois 
 (C. B. 80, 911) carbon and water in the ratio 
 llCiSHjO. Besides the C and H^O, the sub- 
 stance gives about 10 p.c. ash. It loses SHjO 
 at 250°. 
 
 Carbon nitride = Cyanogen (g. v.). 
 
 Carbon, oxides of. Two oxides certainly 
 exist, CO and COj; these formulie are molecular ; 
 each bears the relation of anhydride to an acid, 
 CO is formic anhydride (the acid is BljCOj), 
 CO2 is carbonic anhydride (the acid is HjCO,) 
 (v. imfra). Both oxides can be obtained by 
 direct combination of with C ; either can be 
 produced from the other, by combining with O 
 or with 0, respectively. Both are stable gases ; 
 CO is an energetic reducer ; COj in a few cases 
 acts as an oxidiser. Brodie {Pr. 21, 245) and 
 Berthelot {Bl. [2] 21, 102) have described 
 bodies, produced by the induced electric dis- 
 charge on CO, as oxides of C. Brodie noticed 
 a gradual diminution in vol. of the CO and the 
 formation of a red-brown film on the glass tube ; 
 the solid was soluble in water giving a markedly 
 acid solution ; its composition appeared to differ 
 in different experiments ; Brodie gives the for- 
 mulae C^Oa and CjO,. Berthelot got brown, 
 amorphous, humus-like bodies which dissolved 
 in water with acid reactions, gave brown pps. 
 with AgNOsAq, BaOAq, and Pb2N03Aq; at 
 300°-400° CO and COj (equal vols.) were evolved, 
 and another dark body remained, to which B. 
 gave the composition CjOj. B. also {A. Ch. [5] 
 17, 142) states that by the action of electric 
 sparks on pure CO2 a gas was produced which 
 reacted violently with Hg and oxidisable bodies. 
 
 Carbon monoxide. CO. (Carbonic oxide; 
 more properly, although rarely, carbonous oxide ; 
 formic anhydride.) Mol. w. 27'93. S.G. -9078 
 (air = l). V.D. 14. (c.-186°) (Wroblewski, 
 
 C. B. 98, 982). S.H. p. -2346. S.H. v. -16844 
 (E. Wiedemann, P. 157, 1). C.B. -003667 (Eeg- 
 nault). S. (6°) -0287; (9°) -0269; (18-5°) -02315 
 (Bunsen). S. alcohol (2°) -20356; (13°) 
 -20416; (16°) -20566; (24°) -20452 
 (Bunsen). /io = 1-000301 ; a'b = 1-000360; Mo = 
 1-000391 (Croullebois, A. Ch. [4] 20, 136). 
 [CO, 0] = 67,960 at const, press., and 67,670 at 
 const, vol.; [C,0] = 29,000, and 29,290, respec- 
 
 VCL. I. 
 
 tively (Thomsen). Does not exactly obey Boyle'a 
 
 law; IL = 1'00293 (Eeguault, Acad. 1862. 26, 
 
 229). Liquefied by cooling to — 136° at pressure 
 of 200-300 atmos. and then decreasing pressure, 
 not too quickly, to not less than 50 atmss. (Wro- 
 blewski a. Olszewski, A. Ch. [6] 1, 112 ; v. also 
 Natterer, W. A. B. 12, 199 ; and Cailletet, C. B. 
 85, 1213 a. 1217, and A. Ch. [5] 15, 132). First 
 obtained in 1776, by Lasonne, by heating C with 
 ZnO ; obtained by Priestly, in 1796, by heating 
 charcoal with iron oxide, but supposed by him 
 to be H; proved by Cruickshank not to be a 
 hydrocarbon ; true composition determined by 
 Clement and Desormes. 
 
 Occurrence. — In the gases from burning coal 
 or charcoal ; from the partial combustion or 
 putrefaction of organic matter; or from the 
 reduction of metallic oxides by charcoal, e.g. in 
 the blast-furnace (Bareswil, J. Ph. [3] 25, 172 ; 
 Bunsen, P. 46, 193 ; 50, 81). During the oxida- 
 tion of gallic and tannic acids by exposure to air 
 in alkaline solutions (Boussingault, A. Ch. [3] 
 66, 295 ; Calvert, C. B. 57, 873). In pig-iron 
 and steel according to Troost a. Hautef euille, also 
 Parry (/. 1873. 997; 1874. 1083). 
 
 Formation. — 1. By passing steam over excess 
 of red-hot C ; the product may contain about 
 28J p.c. CO, 66i p.c. H, 14J p.c. CO,,, and 
 traces of CH^ (v. Naumann a.Pistor, B. 18, 164). 
 2. By passing a slow current of CO2 over red-hot 
 C, and washing the gases through KOHAq and 
 soda-lime. — 3. By heating COj with those me- 
 tallic oxides which do not readily part with O, 
 e.g. ZnO, PbO, PejOj ; oxides which readily give 
 up yield but httle CO, as it is again oxidisedl 
 to COj. — 4. By passing CO^ over red-hot Cu, or 
 over hot Zn-dust (Noack, B. 16, 75).— 5. By 
 heating COj to 1300° (DeviUe, C. B. 59, 873).— 
 6. By electric sparks through COj (Buff a. Hof- 
 mann, A. 113, 140). — 7. By heating powdered 
 CaCOa or K^COj with one-sixth its weight of 
 powdered charcoal ; Na^SO^ heated with C alsa 
 yields CO (with NajS). — 8. In very small quanti- 
 ties (with COS) by passing CO^ and S vapour 
 through a red-hot tube (Berthelot, A. Ch. [5} 
 30, 547).— 9. By heating dry 'S..fi.fi„ or by 
 reaction between HjCjO^ or an oxalate and hot 
 cone. HjSOj.- 10. By heating H.CO^H, or a 
 formate, with cone. H^SO^. 
 
 Preparation. — 1. One pt. dry powdered 
 K4Fe(CN)5 is heated, in a capacious vessel, with 
 8-10 pts. cone. HjSO^ ; as soon as frothing 
 begins the lamp is lowered to a small flame; 
 the gas is passed through milk of lime and 
 KOHAq, to remove CO2 and the SO2 formed in 
 the process ; SO2 is evolved only in the earlier 
 stages of the reaction (Grimm a. Eamdohr, A. 
 98, 127). 15 g. KjFe(CN)e yield about 4 litres CO : 
 
 K,Fe(CN)5 + 6H2S04 + 6H2O 
 = 6C0 -t- 2X280^ + 3(NH,)2S04 -I- FeSOj (Fownes). 
 2. Dry CaC^O,, or BaC204, is mixed with about 
 ^ pt. dry CaOjHj, and the mixture is strongly 
 heated in a hard glass flask ; the gas is passed 
 through milk of lime, and is then dried : — 
 CaC204 gives CaCOa + CO ; the CaHaOj absorbs 
 any COj formed. — 3. According to Cherrier 
 (0. B. 69, 138) pure CO may be prepared by 
 passing the gases produced by heating H2C20j 
 with H2SO4 through a red-hot tube filled with 
 
690 
 
 CARBON. 
 
 cliarcoal, and then through a mixture of CaOAq 
 and KOHAq. 
 
 Properties. — A colourless, tasteless, slightly 
 odorous gas ; liquefied at low temperature and 
 great pressure {v. supra). CO is combustible 
 but a non-supporter of combustion : the tem- 
 perature of the flame of CO in air is about 
 1400° (Valerius, /. 1874. 58). Absorbed by C, 
 and by several metals, e.g. K, Ag, Au ; quickly 
 absorbed by CujClj in a little HClAq («. infra) ; 
 decomposed at very high temperature to C and 
 COj; decomposed when moist by induction- 
 sparks ; CO is an energetic reducer ; it combines 
 with moist EOH (or NaOH) to form K formate ; 
 combines directly with CI and Br in sunlight. 
 CO is extremely poisonous ; it removes from 
 the blood and combines with the hcemoglobin. 
 CO may be detected in the blood by observing 
 the absorption-spectrum ; this is almost identi- 
 cal with that of oxygenated blood, and is charac- 
 terised by two bands between D and E ; on add- 
 ing a little ammonium sulphide these bands dis- 
 appear in the case of oxygenated blood, and the 
 spectrum shows one band midway between D 
 and E ; if the blood contains CO the two bands 
 remain unchanged for several days (Vogel, B. 
 
 11, 235 ; Hoppe-Seyler, Fr. 3, 439). 
 Reactions. — 1. Electric sparks cause a partial 
 
 decomposition to CO^ and C ; if the CO^ is re- 
 moved the change proceeds (Berthelot, A. Ch. 
 [5] 80, 547). According to Berthelot {Bl. [2] 
 21, 102 I A. Ch. [5] 17, 142) CO is decomposed 
 by the induction-discharge, with production of 
 CO.^ .and (?) CjO^ and Cfi, («. arete; beginning of 
 this art.). According to Buff a. Hofmann (C /. 
 
 12, 282) the induction-spark does not decompose 
 dry pure CO. Dixon (O. /. 49, 103) found that 
 CO was decomposed (only about ^ p.c. of the 
 total gas) by sparks from a Leyden jar. — 2. Heated 
 to about 1300" CO is partially decomposed to 
 and CO2 (Deville, C. B. 59, 873).— 3. A mixture 
 of CO with oxygen is burnt to CO^ by applica- 
 tion of a flame or electric sparks. Dixon {T. 
 1884. 617) has proved that if both gases are 
 perfectly dry no chemical change occurs when a 
 spark is passed; that a mere trace of steam 
 renders the mixture explosive ; that the oxida- 
 tion of CO by takes place very slowly if only 
 a very small quantity of steam is present ; and 
 that as the quantity of steam is increased the 
 rapidity of the explosion is increased also. 
 The steam acts as a carrier of to the CO ; it 
 ia probably reduced, and the H is then again 
 oxidised : the reactions which occur are very 
 probably these (v. Dixon, C. J. 49, 94) : 
 
 ( 2C0 + 2H2O = 2CO2 -K 2H2 1 
 HB., + 0^ = 2B.fi !■ 
 
 Or (Armstrong, O. J. 49, 112) the changes may 
 be represented by the formulsa, before explosion 
 O.H2q.C0; after explosion OH^.OCO. Small 
 quantities of gases other than H^O were tried 
 {H,S, C,Hj, B.fiO„ NH„ C^H.^, HCl ; SO^, CS^, 
 CO2, NjO, C2N2, CCIJ ; if the gas contained H, 
 explosion occurred; if the gas did not contain 
 H the mixture did not explode. — 4. When a 
 mixture of CO and steam is heated to about 
 600°, a portion of the CO is oxidised to CO^; the 
 amount of CO oxidised depends on the con- 
 ditions («. Dixon, C. J. 49, 94: references to 
 other memoirs are given) ; if the COj is removed 
 as it is formed the whole of the CO can be 
 
 oxidised. L. Meyer's experiments (B. 19, 1099), 
 however, seem to prove that a mixture of dry 
 CO and can be exploded if a very strong 
 spark is used, and the temperature is thus made 
 very high. The gases must be under consider- 
 able pressure ; the more dilute the gaseous 
 mixture the more difficult is it to explode it.— 5. 
 When sparks from an induction-coil are passed 
 through u, mixture of CO and steam, CO2, a 
 little formic acid, and in some cases C, are 
 formed (Dixon, G. J. 49, 94).— 6. When to a 
 mixture of dry CO with hydrogen, oxygen in- 
 sufficient for complete combustion is added, and 
 the mixture is exploded by the spark, COj and 
 HjO are formed; the ratio of CO^ to S^O 
 depends on the shape of the vessel, and the 
 pressure up to a certainlimit ; above this pressure 
 — the ' critical pressure ' — the ratio C02:HjO 
 is independent of the shape of the vessel. The 
 larger the quantity of used the lower is the 
 critical pressure. So long as the volume of H 
 is more than twice that of the the ratio of 
 CO X H20:C02 X H^ remains constant, provided 
 no HjO can condense, and the pressure is above 
 the critical pressure: when the vol. of H ia 
 less than twice that of the value of the ratio 
 diminishes. The presence of an inert gas, e.g. N, 
 increases the formation of COj and diminishes 
 that of H2O, hence it lowers the value of the 
 ratio CO x H20:C02 x Hj. This ratio is called by 
 Dixon the co-efficient of affinity of the reaction 
 («. Dixon, T. 1884. 617 ; G. J. 49, 94 ; Horst- 
 mann, B. 12, 64 ; v. also Chbmicai. ohanob). — 7. 
 CO is oxidised to CO2 (1) by bichrome and sul- 
 phuric acid (Ludvig, J. 1872. 248) ; (2) by palla- 
 dium charged with hydrogen, in presence of 
 oxygen and water, H2O2 being also produced 
 (Traube, B. 15, 2325, 2854; 16, 123; Bemsen a. 
 Reiser, B. 17, 83) ; (3) by mixing with oxygen 
 and passing over platinum-black ; (4) by nitro- 
 gen dioxide [NOJ (Hasenbach, /. pr. [2] 4, 1) ; 
 (5) by heating with most metallic oxides ; (6) by 
 heating with many oxysalts, e.g. alkaline sul- 
 phates (sulphides produced). — 8. Many experi- 
 ments have been made to determine whether 
 CO is oxidised by contact with moist oxygen in 
 presence of slowly oxidising phosphorus ; the 
 balance of evidence seems to show that CO^ is 
 not produced (Eemsen (and others) Am. S. [3] 
 11, 316 ; B. 17, 83 ; Am. 6, 153 ; Leeds, B. 12, 
 1836 ; O. N. 48, 25 ; Baumann, B. 16, 2146 ; 17, 
 283). — 9. CO reacts with moist potash or soda to 
 form alkali formate (Berthelot, A. Ch. [3] 61, 
 463) ; the reaction proceeds most quickly at 
 190°-200°, and is best accomplished by leading 
 moist CO over soda-lime (Frohlich a. Geuther, 
 A. 202, 317).— 10. With ferrous oxide at 
 300°-400°, CO2 and a little C are formed (Griiner, 
 C. B. 73, 281).— 11. CO appears to react with 
 certain metallic peroxides to form carbonates, 
 but, according to Wright a. Luff (0. J. 33, 540), 
 CO2 is formed by partial reduction of the per- 
 oxide and reacts with the lower oxide to produce 
 carbonate. — 12. Many of the preceding reactions 
 exhibit CO as a reducing agent ; it also reduces 
 PdCljAq to Pd. — 13. When sodium, or potassium 
 is heated to redness in CO, alkali carbonate and 
 C are formed. 
 
 Combinations. — 1. With potassium at about 
 80° to form the explosive compound KCO 
 (Brodie, C. J. [2] 12, 269), v. PoTASsinM.— 
 
CARBON. 
 
 691 
 
 2. With chlorine or bromine in sunlight, to form 
 COClj, or COBr^ (v. Cabbon, oxychlobide, and 
 OXYBEOMIDE, op).— 3. With sulphur to form COS 
 {v. Cabbon, oxtsulphide of). — 4. 'Vfith platinio 
 chloride to form CjOjPtCl, and C.^O^PtClj 
 (Sohutzenberger, A. Ch. [4] 21, 350).— 5. CO is 
 absorbed by anhydrous HON (Bottinger, B. 10, 
 1122) ; by several metals, e.g. Fe, Ag, Au ; by 
 carbon. — 6. CO does not combine with cyano- 
 gen, nor does it react with HgfCNjj. 
 
 Estimation, — CO in a gaseous mixture is 
 absorbed by CujClj solution. Thomas (C. N. 
 37, 6) prepares the solution by filling a vessel 
 of 120 0.0. capacity J full of Ca turnings, 
 adding 6 g. crystallised CuClj and 20 c.o. oono. 
 HClA.q, and shaking until solution of the CuClj 
 is effected; he then adds 30 o.c. water and 
 shakes briskly for some time, and then adds 
 30 o.c. water. 
 
 Cabbon dioxide. CO^. (Carbonic anhydride, 
 often called carbonic acid.) Mol. w. 4B-89. S.G. 
 gas 1-53; S.G. liquid 1-057 at -34°; 1-016 at 
 -25°; -966 at -11-5°; -91 at -1-6°; -84 at 
 + 11°; -726 at +22-2° (Cailletet a. Mathias, 
 C. B. 102, 1202). S.G. solid (hammered) slightly 
 under 1-2 (Landolt,B. 17,309) [-65°] (Mitchell); 
 [-57°] (Faraday); [-78-2°] (Eegnault, 4. Ch. 
 [3] 26, 257). V.D. 22 ; 22-42 at 800° ; 21-2 at 
 1180° (Meyer a. Goldschmidt, B. 15, 1165). 
 S.H.V. -33 (equal vol. of air = l), -2169 (equal 
 weight of air=l) (Eeguault, O. B. 36, 676, &c.; 
 
 V. also Wiedemann, P. 157, 24). ^•^•^ • = 1-29 
 
 to 1-305 (Amagat, Eontgen, O. B. 71, 336 ; 77, 
 1325). C.E. -0037 (Begnault, Magnus, Joly). 
 
 — = 1-00722 (Begnault, C. B. 20, 975). 
 
 At 
 
 200° COj obeys Boyle's law (Amagat, C. B. 68, 
 1170; 73, 183). C.E. liquid CO^ very large, 
 120 vols, at -20° become 150 vols, at +30, 
 (Thilorier, A. Ch. 60, 427). Critical tempera- 
 ture =30-9° (Andrews, T. 1869. 575). Vapour- 
 pressure of liquid CO2 (Begnault) in atmospheres : 
 -25°, 17-1; -5°, 30-9; 0°, 35-4; +5°, 40-5; 
 15°, 52-2; 25°, 66; 35°, 82-2; 45°, 100-4. 
 Vapour-pressure of solid CO2 (Faraday) in atmos. : 
 -57°, 5-33; -70-5°, 2-2; -99-4°, 1-14. B.P. 
 of solid COj — i.e. temp, at which vapour-pressure 
 = 760 mm. — is much lower than the M.P. ; 
 Eegnault (and Pouillet) found -78° to -79° 
 (P. 77, 107); Thilorier, -95° to -98°; and 
 Faraday, as shown by values for vapour-pressure, 
 under —99°. By evaporation of solid COj mixed 
 with ether, temp, is c. — 100°. 
 
 S. CO2 gas (Bunsen, A. 93, 1) : 
 
 At 0° 
 
 1-7967 
 
 At 11° 
 
 1-1416 
 
 1 
 
 1-7207 
 
 12 
 
 1-1018 
 
 2 
 
 1-6481 
 
 13 
 
 10653 
 
 3 
 
 1-5787 
 
 14 
 
 1-0321 
 
 4 
 
 1-5126 
 
 15 
 
 1-0020 
 
 5 
 
 1-4497 
 
 16 
 
 0-9753 
 
 6 
 
 1-3901 
 
 17 
 
 0-9519 
 
 7 
 
 1-3339 
 
 18 
 
 0-9318 
 
 8 
 
 1-2809 
 
 19 
 
 0-9150 
 
 9 
 
 1-2311 
 
 20 
 
 0-9014 
 
 10 
 
 1-1847 
 
 
 
 Absorption-coefficient = 
 1-7967 - -0776K + -001642 it\ 
 
 S. CO2 gas in alcohol (Bunsen) : 
 
 At 
 
 3-2° 4-0442 
 
 6-8 3-7374 
 
 10-4 3-4875 
 
 At 14-2° 3-2357 
 18 30391 
 22-6 2-8277 
 
 Absorption-coefficient = 
 4-32955 - -09395« + -001 24*^ 
 
 ;«o = 1-000395, ;ui. = l'000456, /i8 = 1-000496 
 (Croullebois, A. Ch. [4] 20, 136 ; v. also Chap- 
 puis a. Eivi^re, 0. B. 103, 37). H.F.p. [C,0^ =. 
 96,960 ; [C0,0] = 67,960. H.F.v. [CC] = 
 96,960; [C0,0] = 67,670. [0,0 •,Aq] = 102,840. 
 [CO,0,Aq] = 73,840. [C0-,Aq] = 5,880. 
 
 [CO-'Aq,wNaOHAq] ; w = 1 = 11,016 ; w = 2 = 
 20,184; w = 4 = 20,592 (Thomsen). 
 
 Carbon dioxide has been known for cen- 
 turies. The identity of the gases produced 
 during fermentation and by the action of acids 
 on chalk was established by Black. Bergmann 
 recognised the same gas in the atmosphere. 
 Cavendish proved that the same gas was pro- 
 duced by burning charcoal. Lavoisier estab- 
 lished the composition of the gas. Faraday 
 liquefied, and Thilorier solidified, carbon di- 
 oxide. 
 
 Occwrrence. — In the atmosphere {v. Atmo- 
 spheke) ; in mineral waters ; issues from the 
 earth in different places ; sometimes found liquid 
 in cavities in quartz, &o. Produced by the 
 breathing of animals, by the decay of organic 
 matter, by the combustion of coal, charcoal, &o. 
 In combination as carbonate, of calcium, magne- 
 sium, &o., &o. 
 
 Formation. — 1. By burning in air or 0.— 
 2. By oxidation of most C-compounds. — 3. By 
 burning CO. — 4. By reducing many metallic 
 oxides by C. — 5. By heating together H^O and 
 CO. — 6. By the reaction between red hot C and 
 steam. — 7. By the action of steam on CaCOj at 
 red heat.^8. By heating a mixture of KfirJ), 
 with NajCOj. — 9. By heating several carbonates. 
 10. During fermentation.— 11. By reaction be- 
 tween acids and carbonates. 
 
 Preparation. — CaCOj or MgCO, in lumps is 
 treated with dilute HClAq at the ordinary tem- 
 perature ; the gas is passed through NaHCOjAq 
 (to remove HCl which may have passed over), 
 and is then dried by CaClj. Bunsen recom- 
 mends the use of &iely powdered chalk and 
 cone. HjSO,, and addition of a very little water. 
 
 Liquid carbon dioxide was obtained by 
 Faraday by decomposing (NH4)2C03 by H^SO^Aq 
 in one limb of closed glass tube bent at an 
 obtuse angle. Thilorier {A. Ch. 60, 247) decom- 
 poses NaHCOj by^ dilute HjSOiAq in an iron 
 vessel connected with an iron cylinder in which 
 the C02is liquefied byits own pressure. Natterer 
 (J. pr. 35, 169) compresses CO2 by a specially 
 constructed air-pump (v. also Gore, T. 1861. 63). 
 
 Solid carbon dioxide is obtained by allow- 
 ing the liquid to escape into a tin vessel ; part 
 of the liquid becomes gas and part is solidified 
 Landolt allows the liquid to evaporate freely 
 into conical woollen bags ; he then compresses 
 the solid COjin conical moulds of hard wood by 
 wooden pistons (B. 17, 309). 
 
 Properties. — A heavy, colourless, gas; in- 
 combustible; non-supjorter of ordinary com- 
 bustion, but strongly heated K or Na, or brightly 
 burning Mg, burns in CO^. Absorbed by water, 
 solution colours litmus wine-red and reacts as 
 
 it2 
 
692 
 
 CARBON. 
 
 a, weak acid [v. Caebonio acid). Absorbed by 
 moist alkalis and alkaline earths forming carbo- 
 nates ; rapidly absorbed by ruixture of powdered 
 KOH and hydrated Na^SOj. Poisonous, by 
 cutting off supply of 0. 
 
 Liquid carbon dioxide is a limpid, colourless, 
 refractive, liquid ; nonconductor of electricity ; 
 not changed by strong induction-sparks ; very 
 expansible by heat ; C.E.is greater than that of 
 the gas. Insol. in water which swims on the 
 surface; mixes with alcohol, ether, &o. Does 
 not dissolve S or P ; dissolves I ; no reaction 
 with Na or K (Cailletet, G. B. 75, 1271). 
 
 Solid carbon dioxide is a white, loose, snow- 
 like, solid ; when compressed by hammering in 
 wooden moulds it resembles chalk {Landolt, B. 
 17, 309). Very bad conductor of heat. Evapo- 
 rates slowly, a specimen prepared by Landolt 
 53 mm. by 71 mm. diam. took 6 hours to 
 volatilise in the air. Burns, if pressed against 
 the skin. 
 
 BeacUons. — 1. Seated to c. 1300° in porcelain 
 tube is partly changed to CO and (Deville, 
 C. B. 56, 729 ; v. also Berthelot, 0. B. 68, 
 1035). — 2. Partly decomposed hjelectric sparks; 
 a condition of equilibrium is attained when 
 change of COj into CO -I- equals that of CO 
 and into COj (Dixon a. Lowe, 0. J. 47, 571).— 
 8. Mixed with hydrogen, and heated to bright 
 redness or submitted to indiiction-s-parhs, HjO 
 and CO are formed ; if B.fi is removed the 
 whole of the CO, goes to CO (Dixon, 0. J. 49, 
 94). According to Dubrnnfaut (C. B. 74, 125) 
 COj and H passed over hot pumice give C and 
 HjO. — 4. A mixture of carbon dioxide and sul- 
 phur vwpowr passed through a red-hot tube 
 yield a Uttle COS, CO, and SO^ (Berthelot, Bl. 
 [2] 40, 362). — 5. With sulphuretted hydrogen, 
 passed through red-hot tube, forms CO, H2O and 
 S (Kohler, B.ll, 205).— 6. Decomposed by chloro- 
 phyll--paxts of plants in sunshine. — 7. Eeduoed 
 to CO by heating with carbon, iron or zinc, or 
 with cc^er which has occluded hydrogen (Tis- 
 sandier, 0. B. 74, 531 ; Sohrotter, W. A. B. 34, 
 27). — 8. Partly reduced to CO by reaction with 
 ferrous sulphate and a little water, in a closed 
 tube (Horsford, B. 6, 1390).— 9. Eeduced to C 
 by heating strongly with sodium, potassium, or 
 magnesium ; alkali carbonates strongly heated 
 ?i)ii/ipfeosj)/jorMS or 6oroTOgiveC02whichis reduced 
 to C (Tennant, Crellis A. [1793] 1, 158 ; Dragen- 
 dorfi, /. 1861.111 ; Leeds, B. 12, 1834 a. 2131).— 
 10. With moist alkalis, or alkaline earths, forms 
 carbonates. — 11. With water probably forms a 
 solution of carbonic acid, H^COj (v. Cabbonio 
 acid). — 12. Withsodium,- or potassium-amalgam 
 at e. 350° gives Na (or K) oxalate (Drechsel, A. 
 146, 141). — 13. With sodium C02Aq reacts to 
 give Na formate (Kolbe a. Sohmitt,^. 119, 251). 
 14. Decomposes moist potassium iodide at high 
 temperature giving HI (Papasogli, Q. 1881.227). 
 
 Carbon, oxybromide of. The existence of 
 a Br compound of CO analogous to COClj is 
 doubtful. A mixture of Br vapour with excess 
 of CO is slowly, but not fully, decolourised in 
 sunlight ; in contact with KOHAq this gas pro- 
 duces KBr and K^COj (Schiel, A. Suppl. 2, 311). 
 Emmerling a. Lengyel could not obtain a trace 
 of any compound of C, Br, and 0, by the re- 
 action between COS and Br at a high tempera- 
 ture (fi 2, 647). By the reaction between 
 
 H.,SOj (50 parts), Kfirfi, (20-25 parts), and 
 CHBra (5-10 parts), EmmerUng {B. 13, 874) 
 obtained a small quantity of a Hquid, which he 
 slowly distilled through Sb, to remove Br ; he 
 thus obtained a colourless heavy liquid, smell- 
 ing like COCI2. The B.P. rose from 12° to 
 30° ; analyses seemed to show that the liquid 
 was a mixture of COCl^ and C oxybromide. 
 
 Carbon, oxychloride of. COClj. {Carbonyl 
 chloride. Phosgene gas. Chloro-ca/rbo7m acid ) 
 M0I.W. 98-67. (8-2° at 756 mm.). S.G. -f (Uquid) 
 1-432; ^ 1-392 (Emmerling a. Lengyel, A. 
 Suppl. 7,101). V.D. 50-6 (E. a. L.). [0,0,01^ = 
 54,850 at constant volume ; 55,140 at constant 
 pressure (Thomsen). First prepared by J. Davy 
 in 1811 {T. 1812. 144) by the action of sunlight 
 on Cl-f CO (hence the name phosgene). 
 
 Formation. — 1. By leading CO into boiling 
 SbClj (Hofmann, A. 70, 139 ; v, also Butlerow, 
 Z. 1863. 484 ; Kraut, Gm.-K. I. 2, 386), or over 
 hot PbClj or AgCl (Gobel, J. pr. 6, 388).— 2. By 
 heating CClj with ZuO at 200° in a closed tube j 
 or by passing CCI4 and CO through pumice in a 
 tube heated to about 400°.— 3. By heating CHCI3 
 (1 part), K^Cr^O, (2^ parts), and H^SO^ (10 
 parts) at 100°, and passing the gas over Sb to 
 absorb CI (E. a. L.).— 4. By passing CI and CO 
 over Pt black at about 400° (Sohiitzenberger, Bl. 
 [2] 10, 188 ; 12, 198).— 5. By passing CI and 
 CO2 over hot C (Schiel, J.pr. 6, 388). (Eor other 
 methods v. Schutzenberger, B. 2, 218; Dewar 
 a. Cranston, C. N. 22, 174; Armstrong, B. 3, 
 730.) 
 
 Prepa/raUon. — Dry CI and dry CO are slowly 
 passed through a succession of large bottles 
 freely exposed to sunlight, then through a U- 
 tube loosely filled with pieces of Sb (to remove 
 free CI), and finally into a tube surrounded by 
 snow and salt. Each gas should pass through 
 the drying-bottles at as nearly as may be the 
 same rate. 100 litres CO give 140-150 g. COClj 
 in direct sunlight. Patemo (0. 5, 233) passes 
 the mixed gases through a tube 400 mm. long 
 filled with animal charcoal : combination occurs 
 with production of heat ; the tube must be 
 cooled by a wet cloth from time to time (v. also 
 Wilm a. Wischin, A. 147, 150). 
 
 Properties. — Colourless gas with penetrating 
 odour ; at 8° and under it is a colourless limpid 
 liquid; the gas is soluble in acetic acid, benzene, 
 and several liquid hydrocarbons. 
 
 Beactions. — 1. Water absorbs COClj with 
 formation of COjAq and HClAq. Berthelot 
 (C.iJ. 87, 591) gives the value [COCP.Aq] = 64,600. 
 2. Alcohol toTTHschlorocarbonic ether CO.Cl.OEt 
 (j. v.). — 3. Several metals decompose COClj, 
 when heated with it, to CO and metallic chloride ; 
 e.g. Sb, As, Na, Sn, Zn ; potassium forms KCl, 
 K2CO3, and C. — 4. With slightly w.oiat potassium 
 carbonate, KCl, H^O, and COj are formed. — 
 5. .ZiMC oxide produces ZnClj andCO^. — 6. Com- 
 bines with 4 vols, ammonia to form urea and 
 NH,C1 (Natanson, A. 98, 288; Fenton, C. J. 
 35, 793). 
 
 Carbon, oxysulphide of. COS. (Carbonyl 
 sulphide.) M0I.W. 59-91. V.D. 30-4. [CO,S] = 
 8,030 ; [C,0,S] = 87,030 ; [008,0=] = 131,010 
 (Thomsen). 
 
 Occurrence. — According to Thorn (A. Suppl- 
 
CAHBON. 
 
 693 
 
 6, 23G), in several mineral waters, and in vol- 
 canic gases. 
 
 Formation.—!. By passing CO and S vapour 
 through a red-hot porcelain tube (Thorn).— 
 2. By gently heating SO, with CS^ ; SO^ and S 
 also produced (Armstrong, B. 2, 712).— 3. By 
 aotion of CO, on boiling S ; or by electric sparks 
 on CO2 mixed with S vapour (Cossa, B. 1, 117 ; 
 Chevrier, C. B. 69, 136) .-4. By leading alcohol 
 and CS2 over red-hot Cu (Carnelley, 0. J. [2] 13, 
 523). For other methods v. Ladenburg, B. 1, 
 273 ; 2, 30, 53, 271 ; Dewar a. Cranston, C. N. 
 20, 174 ; Salomon, /. pr. [2] 5j 476. 
 
 Preparation.— Bj decomposing KCNS by 
 HjSG^Aq; KCNS + H^G + 2H2SO,Aq 
 
 = COS + KHSO^Aq + NH,.HSO,Aq. KCNS is 
 added to a cold mixture of 5 vols. 3^80^ with 4 
 vols. H2O as long as the whole remains liquid ; 
 if much gas comes off the vessel is cooled, if 
 very little gas is evolved the vessel is warmed 
 gently. The gas is passed through three U 
 tubes, containing (1) cotton wool charged with 
 moist HgO (to remove HCN and formic acid), 
 (2) cuttings of unvulcanised caoutchouc (to re- 
 move CS2), (3) CaClj ; the gas is then collected 
 over Hg (Thom). Bender (A. 148, 137) recom- 
 mends passing the gas through a tube surrounded 
 by snow and salt, andHofmann {B. 2, 73) through 
 wool moistened with PEt, ; the object in either 
 method being to remove CSj. 
 
 Properties. — Colourless, heavy, gas, with a 
 pleasant somewhat aromatic odour. Colours 
 moist blue litmus slightly reddish. Absorbed 
 by water ; solution sometimes contains COj and 
 iLjS. Very sol. in alcohol. 
 
 Reactions. — 1. Bums in air to CO^ and SO^. 
 2. At full red heat giyei CS^ and COj (Berthelot, 
 C. R. 87, 571).— 3. With wafer gives CO^Aq and 
 HjSAq. — 4. With potash solution gives K^SAq 
 and KjCOjAq; similar reactions with NH.,Aq, 
 CaOAq, and BaOAq. — 5. Ammonia gas, or 
 alcoholic NH3, gives C0.NH:2.SNHj(^. Berthelot, 
 A. Ch. [6] 30, 539).— 6. Solutions of salts of 
 copper, cadmium, lead, or silver give no pps., 
 but on adding NH,Aq the sulphides of the 
 metals are ppd. — 7. The gas is decomposed by 
 hot mercury, copper, silver, and iron, giving 
 sulphides ; by hot sodium, giving Na^S, NajCOj, 
 and C. 
 
 Carbon selenide. Carbon and selenion do 
 not combine directly. No definite compounds 
 have been isolated. Eathke obtained a liquid 
 which probably contained about 2 p.c. of a 
 selenide of carbon (along with CCI4), by heating 
 selenide of phosphorus with moist CClj (v. A. 
 152, 181). 
 
 Carbon, sulphides of. Carbon disulphide, 
 CSj, is a well-marked compound. A mono- 
 sulphide, CS, probably exists. According to 
 Low a sesquisulphide, C^Sj, can be obtained 
 by the action of Na amalgam on CS.^ (Z. 
 9, 173 ; 10, 20). When sodium and CS^ react 
 a red-brown solid is obtained which according 
 to Baub has the composition C-S^ (0. 0. 
 1870. 579). 
 
 Cabbon monosulphlde. CS. Mol. w. un- 
 known. S.G. 1'66. CSj was exposed to sun- 
 light for 2 months in a (J tube of special 
 construction ; the solid which had formed on 
 the walls of the tube was removed by water, 
 washed with CSj, and dried in H (Sidot, C. E. 
 
 C9, 1303 ; 74, 180 ; 81, 32). CS is a red powder ; 
 insol. in water, alcohol, turpentine, and benzene. 
 Somewhat soluble in CS^ or ether. Dissolved 
 by HNOjAq, not by HClAq or H^SO^Aq. At 
 200° gives C and S. Heated with S gives CS^. 
 CS is not produced by leading CS^ over hot 
 carbon or pumice, by heating Sb^Sj with C, by 
 reaction between CO and HjS^, by reaction 
 between CO and HjS, by reaction between 
 CHj and SO^ or S^Clj, by heating (CN)jS, 
 by heating Fe spiral in OSj, by electric sparks 
 through CS2, or by reaction between CSCL and 
 hot Cu. 
 
 Beferences. — Baudrimont, C. B. 44, 100 ; 
 Berthelot, J. 1859. 83 ; Playfair, C. J. 13, 248 ; 
 Buff a. Hofmann, A. 113,129 ; Hermann, J.pr. 
 79, 448 ; Husemann, A. 117, 229 ; Kern, G. N. 
 33, 253 ; Eathke, A. 167, 195. 
 
 Cakbon DisuiiPHiDE. CSj. (Thiocarhouio 
 anhydride. Sulphocarbon/ic acvi.) Mol. w. 
 75-93. [c. -12°] (Wartha, B. 3, 80). (46-04° at 
 760 mm.) (Thorpe, C. J. 37, 362; references in 
 this paper to other determinations). S.G. f 
 1-29215 (T.). V.D. 38. S.H. (liquid; 14°-29°) 
 •2468 (SohuUer, P. Ergzhd. 5, 116 ; v. also Him, 
 A. Ch. [4] 10, 63 and 91). S.H. p. (equal mass 
 of air = l) -1569; (equal vol. of air = l) -413 
 (Eegnault). C.E. v. Thorpe (i.e.). [C, S-] const. 
 press. = -26,010; const, vol. = -25,480 ; liquid 
 = -19,610; [CSS 0"] = 265,130 (Thomsen). 
 For table of vapour-pressures from 0° to 50° v. 
 Eamsay a. Young, O. J. 47, 653. /ia 1-6059 ; 
 /*o 1-6729 (at 13°) (Kundt, W. 4, 34). For 
 relations between volume as gas and pressure 
 V. Herwig, P. 137, 19 ; 141, 83 ; 147, 161. 
 
 Occurrence. — In crude benzole ; and in mus- 
 tard oil. First prepared, in 1796, by Lampadius, 
 by heating iron sulphide with charcoal. Com- 
 position was long uncertain. Clement a. Des- 
 ormes (A. Ch. 42, 121) regarded it as a com- 
 pound of C and S ; it was also thought to be a 
 compound of S and H, and at other times of C, 
 S, H, and N. Composition established by Vau- 
 quelin, Berzelius, and Marcet, in 1812 {v. O. A. 
 28, 427 a. 453 ; 48, 177 ; S. 9, 284 ; A. Ch. 83, 
 252). 
 
 Formation. — 1. By heating S with excess of 
 C in a porcelain tube, condensing product in 
 vessel surrounded by cold water, shaking with 
 NaOHAq, drying by CaCl,, and distilling from 
 water bath. — 2. By heating C with a metallic 
 sulphide which gives off S at a high tempera- 
 ture, e.g. CuS or Sb^S,. — 3. By heating wax, 
 sugar, resin, &c., with S. — 4. By heating (CN)jS. 
 5. By heating CClj with PjSj to 200° in a closed 
 tube. 
 
 Preparation.— Corameroial CS^ is distilled oS 
 quicklime at 60°-70°, leaving a little undistilled ; 
 the distillate is shaken in contact with powdered 
 KjMnjOg, about 5 grams to 1 litre CSj, for some 
 time (to remove H^S) ; it is then decanted and 
 shaken thoroughly vrith Hg until fresh Hg is 
 not blackened (various S compounds are thus 
 removed); the liquid is poured off and again 
 shaken vrith HgjSOjAq (abt. 25 g. salt per litre) 
 until a few drops leave no trace of badly smell- 
 ing residue when allowed to evaporate on filter 
 paper ; the CSj is poured off, allowed to stand 
 in contact with CaClj, and then distilled (from 
 a water bath) directly into the bottle in which it 
 is to be preserved. It is kept in perfect dark- 
 
694 
 
 OAKBON. 
 
 neBB (Obaoh, /.^. [2] 26, 281; for other me- 
 thods i>. Sidot, C. E. 69, 1303; Friedburg, B. 8, 
 1616 ; 9, 127 ; MiUon, J. 1868. 928 ; Cloez, 
 C. B. 69, 1356). 
 
 Properties. — Colourless, limpid, highly re- 
 fractive, liquid ; ethereal odour when quite pure ; 
 vapour even when much diluted is poisonous, it 
 stops fermentation {v. Cloez, C. B. 63, 185). 
 According to Wartha {B. 3, 80 ; 4, 180) CS^ may 
 be solidified by placing a small quantity in the 
 vessel of a Carrfi freezing machine, exhausting 
 the air, and then opening the stopcock while 
 continuing to exhaust ; in large quantities solid 
 CSj is obtained by mixing with absolute ether 
 and exhausting the air by a Carr6 machine. 
 Wartha also obtained a snow-like solid by blow- 
 ing dry air through CS2 at the ordinary tem- 
 perature; according to Ballo (B. 4, 118) this 
 body is a hydrate of CSj ; Berthelot (A. Ch. 
 [3] 46, 490) and Duclaux (C. B. 64, 1099) ob- 
 tained such a hydrate (probably 2CS2.H2O) by 
 evaporating CSj in moist air (v. also Venables, 
 Am. 5, 15). CSj vapour is very easily inflam- 
 mable, ignition-temp. = 149° (Prankland, C. N. 
 6, 3), 170° (Braun) ; with air or it forms a 
 very explosive mixture ; mixed with NO and ig- 
 nited it burns instantaneously with production 
 of white light rich in actinic rays {v. Berthelot, 
 
 A. Ch. [3] 49, 486 ; Berzelius a. Maroet, S. 9, 
 284; Frankland, C.N. 6, 3; Sell, B. 5, 733; 
 Delachanal a. Mermet, D. P. J. 214, 483). 
 Water dissolves about ^„- of its weight of CS2 
 (Sestini, G. 1871. 473) ; it is miscible in all pro- 
 portions with alcohol, ether, ethereal and fatty 
 oils, and liquid CO^ (v. Tuchsehmidt a. Pollenius, 
 
 B. 4, 583). CS2 is a solvent for fats, resins, 
 gutta percha, alkaloids, I, S, P, &a. {v. Lieber- 
 mann, B. 12, 1294; Gore, P.M. [4] 30, 414). 
 According to Sidot, CSj is slowly changed in 
 sunlight to CS and S {v. ante, Carbon monosul- 
 phide). 
 
 Reactions. — 1. Heated strongly CSj gives C 
 and S (Berthelot, Bl. [2] 11, 450 ; Buff a. Hof- 
 mann, A. 113, 129). — 2. Bums in air or to 
 CO2 and SOj. — 3. Decomposed by many metals ; 
 Fe is said to give CS at ord. temp. (Kern, C. N. 
 33, 253 ; v. also Merz a. Weith, Z. 11, 513) ; Cu 
 at 200°-250° forms CUjS, S, and C (M. a. W.) ; 
 K gives a sulphide and C; Na at 140°-150° 
 forms NajS and Na2CS3, the latter body reacts 
 with dilute HGlAq to produce H^CSj (Low, Z. 
 9, 173 ; 10, 120) ; Na amalgam according to Low 
 (l.c.) gives C2S3, according to Eaab (N. B. P. 19, 
 449) C5S2 (u. also Hermann, J. pr. 79, 448; 
 Eeiohl, G. C. 1880. 420; Guignet, Bl. 1861. 
 111). — 4. Hydrogen, when passed with CS2 over 
 heated Pt black, produces HjS and C ; nascent 
 H (Zn and HClAq) forms HjS and (?) CfLfi., (v. 
 Vernon Harcourt, C. N. 26, 267 ; Cossa, B. 1, 
 117; Girard, C. B. 43, 396; Becquerel, C. B. 
 66, 237). — 5. OWorme reacts with CSj differently 
 according to the conditions : dry CI at ord. temp, 
 gives S2CI2 and CClj ; moist CI, or MnOj and 
 HClAq, or other CI producer, forms H2SO4 
 and CSCI2 (Kolbe, A. 45, 41); CI and CSj 
 passed through a hot tube give S.^Clj and CClj 
 (K.) ; CI passed into boiling CS2 containing a 
 little I forms S2CI2, CClj, and CSCI2 (Miiller, C. J. 
 15, 41) ; the same products result by action of 
 lOI, (v. Weber, W. A. B. 1866. 348 ; Hannay, 
 
 C. N. 37, 224).— 6. Chlorides which readily give 
 
 up chlorine react similarly to CI : MoClj and 
 SbCls give CCI4 and SjClj, SbOls also producing 
 SbCljS which separates into SbCla and 8 
 (Aronheim, B. 9, 1788 ; Hofmann, A. 115, 264 ; 
 Husemann, A. 117, 229); PCI, forms CSClj 
 (Oarius, A. 113, 193), or according to Eathke 
 {Z. 13, 57) CCliand PSOl, (at 100°).— 1. Bromine 
 reacts in presence of I or SbBrj ; 2 parts CSj,, 
 14 parts Br, and 3 parts I, heated to 150° in a 
 closed tube form CBr, (Bolas a. Groves, B. 3, 
 508; V. also Berthelot, A. Ch. [3J 53, 145). 
 Hell a. Urech describe a compound CjSsBrj, 
 obtained by slow action of Br and CS2 and sub 
 sequent distiUatiou {B. 15, 273). — 8. Water, irt 
 presence of air, oxidises CSj slowly and partially 
 to COjAq and SOjAq (Berzelius) ; heated to 150°' 
 in a closed tube from 3 to 4 hours, COjAq and 
 H2SAq are formed (Sehlagdenhauffen, J. Ph. [3J 
 29, 401) ; evaporated in m/)ist air a hydrate 
 (?2CS2.H20) is said to be formed (v. Properties). 
 
 9. Warmed with sulphuric anhydride, COS, 
 SO2, and S, are produced (Armstrong, B. 2, 712). 
 
 10. Mixed with carbon dioxide and passed 
 through a hot tube, or over hot Pt black, COS is 
 produced (Winkler). — 11. Passed through a hot 
 tube with sulphuric acid, CO, S0„ H^S, and S 
 are formed (W.). — 12. Many metallic oxides 
 when heated with CSj react to form sulphides, 
 sometimes also carbonates (Sehlagdenhauffen, 
 /. Ph. [3] 29, 401 ; MuUer, P. 127, 404 ; Fremy, 
 0. 25. 35, 27). — 13. Oxidising agents, e.g. KNO, 
 or KjMujOg, generally produce CO^ and HjSOj, 
 sometimes CO2 and HjS ; As20a, ASjOj, (and 
 salts of these) produce AS2S3 \v. Sehlagden- 
 hauffen, l.c. ; Cloez a. Guignet, C. B. 46, 1110). 
 14. Boric acid and borates react at red heat 
 to form B2S3. — 15. Sulphuretted hydrogen mixed 
 with CS2 and passed over hot Cu produces CH,. 
 16. Alkalis in aqueous solution form carbon- 
 ates and thiocarbonates {v. thiooabbonates, 
 under Carbonic ACID, &c.) ; alcoholic potash ioims 
 K xanthate C2H5O.CS.SK. — 17. Ammonia 
 reacts with CS2 probably to form CS(NH2)2 and 
 (NHJ2CS3 (Laurent, A. Ch. [3] 22, 103; Zoute- 
 veen, O. C. 1870. 821) ; CS2 and NH3 passed 
 through a hot tube, or CSj heated in a closed 
 tube with alcoholic NH3, produce H^S and 
 HCNS ; alcoholic NH3 at ord. temp, forms 
 (NH,)2CS3, (NHJCNS, and CS.NH2.SNH, (Debus, 
 A. 73, 26; v. also Millon, J. Ph. [3] 38, 401; Hof- 
 mann, J. 1858. 332) ; NHjAq form (NHj)2CS3Aq 
 and NH^.CNSAq. 
 
 Combinations. — 1. With many metallic sul- 
 phides to form thiocarbonates (g. v.). — 2. With 
 various ammonia derivatives; e.g. NMej.CSj. 
 3. With zinc ethyl and methyl to form 
 ZnEtj.CSz, and ZnMOj.CSj, respectively.— 4. 
 With t/riethylphosphine to form PBtj.CSj. 
 
 Analysis. — BxA^hxa, by heating in a glass 
 tube with NajCOj and a little KNO3, and esti- 
 mating sulphates produced, as BaSO,. Carbon, 
 by burning with PbCrO, as in organic analyses. 
 
 Detection and Estimation, — Small quantities 
 of CSj may be detected by adding alcoholic 
 solution of potash, whereby K xanthate ; 
 (C2H5O.CS.SK) is formed; on now adding so- 
 lution of a copper salt a yellow pp. is pro- 
 duced (Vogel, A. 86, 369). This reaction is 
 applied to liquids, e.g. mustard oil, by distilling 
 a little in a current of air into alcoholic potash ; 
 coal-gas m.ay be tested by passing through 
 
CAP.BONATES. 
 
 695 
 
 alooholio potash. A very delicate reaction is to 
 bring tlie CS^ into contact with PEts when a 
 characteristic carmine-red compound, PEts-CSa, 
 forms ; it may be crystallised from ether. This 
 reaction may also be applied for the estimation 
 of CSj (Hofmann, B. 13, 1732). CS., is some- 
 times determined, e.g. in xanthates, by standard- 
 ised CuSOjAq (Grete, B. 9, 921) ; thiocarbonates 
 may be converted into the Pb salt (by addition 
 of _Pb acetate), and this may be decomposed by 
 boiling with water, and the CSj led into weighed 
 bulbs containing alcoholic potash (Delaohanal 
 R. Mermet, B. 8, 1192). 
 
 Carbon, sulphochlorides of. 
 
 I. Thio-cabbonyl chlobide. CSCL. Mol. w. 
 114-69. (70°). V.D. 57-5. 
 
 Formation.— 1. By reaction between CI and 
 CS^.— 2. By heating CCl^ with S.— 3. By passing 
 CCl, and H^S through a hot tube (Kolbe,4. 45, 41 ; 
 Carius, A. 113, 193; MuUer, C. J. 15, 41; 
 Gustavson, B. 3, 989). 
 
 Preparation. — To dry CS2 about -2 p.c. I is 
 added and dry CI is passed in (a reversed con- 
 denser being attached) until the volume of 
 liquid has increased by about 5. The whole is 
 boiled with water (to remove S^Clj) ; separated 
 S is removed, water is separated, the liquid is 
 distilled from the water-bath whereby CCl^ and 
 CS^ distU over ; the residue is then distilled till 
 a thermometer in the liquid reaches 175° ; the 
 distillate is fractionated, digested with water to 
 remove SjCl^, dried, and fractionated. About 
 320 g. CSCI4 {v. infra) are thus obtained from 1 
 kilo. CSj ; very finely divided silver (by reducing 
 AgCl) is then added little by little (the liquid 
 being kept cold) untU the whole of the liquid is 
 soaked into the silver ; it is then distilled, the 
 distillate is shaken with water to remove traces 
 of SjClj, dried, and fractionated (Eathke, B. 3, 
 858). The reactions are (1) 2CS2-h5Cl2 = 
 2CSC14 + S^Cl^; (2) CSCl^ + 2Ag = 2Ag01 -I- CSCl^. 
 
 Properties and Reactions. — Golden-red, lim- 
 pid, liquid ; penetrating odour, resembling that 
 of COCI2 ; fumes in air. Exposed to light and 
 then to a low temperature, large colourless 
 crystals of a polymeride, toCSCIj, separate ; 
 this body is unchanged in air ; melts at il2'5° ; 
 is volatilised in steam ; at 180° in a closed tube 
 it gives CSCI2. 
 
 II. ThionyIi PEBOHiOEiDE. CSCI4 (Eathke, 
 B. 3, 858). Prepared by action of CI on CSj 
 {v, Thionyl chlobide, Prepa/raUon). A clear, 
 golden-yellow liquid ; vapour causes free flow of 
 tears ; B.P. 146°-147°; S.G. 1-712 at 12-8°. De- 
 composed, slowly by moist air, quickly by heat- 
 ing with water to 160°, to COj, HClAq, and S. 
 Heated to 200° is decomposed to CClj, S^Clj.and 
 a little CSCl^. M. M. P. M. 
 
 CABBONATES v. Caebonic acid, Oaebonates, 
 and Thio-caebonates. 
 
 CARBON TETRA-BROMIDE v. Tetea-bkomo- 
 mbthane. 
 
 DI-CAEBON-TETRA-CABBOXYLIC ACID v. 
 Ethtlene-tetea-oaeboxtlic acid. 
 
 CARBONIC ACID, CARBONATES, AND 
 THIOCARBONATES. 
 
 Caebonic acid. A solution of CO2 in water 
 probably contains carbonic acid, HjCOj. The 
 chief reasons for this statement are as follows. 
 The mass of CO^ dissolved by water at ordinary 
 temperatures and small pressures (less than 
 
 760 mm.) varies as the pressure. But at pres- 
 sures of 2, 3, or more atmospheres, the mass of 
 CO2 dissolved is less than that calculated by the 
 law of Henry a. Dalton. Khanikoff a. Longui- 
 nine [A. Ch. [4] 11, 412) give these numbers: — 
 P = pressure in mm., a = vol. of CO, (measured 
 at 0° and 760 mm.) dissolved by 1 vol. water 
 at about 15°. 
 
 P. 
 
 a. 
 
 P. 
 
 a. 
 
 697-71 
 
 0-9441 
 
 2188-65 
 
 3-1764 
 
 809-03 
 
 1-1619 
 
 2369-02 
 
 3-4857 
 
 1289-41 
 
 1-8647 
 
 2554-0 
 
 3 7152 
 
 1469-95 
 
 2-1623 
 
 2738-33 
 
 4-0031 
 
 2002-06 
 
 2-9076 
 
 3109-51 
 
 4-5006 
 
 When the pressure is decreased to 760 mm. over 
 water saturated with CO^ at pressures greater 
 than 760 mm. most of the COj escapes, at first 
 rapidly, then slowly ; the last traces of COj can 
 be removed by placing the water in vacuo, or by 
 long-continued boiling. Magnesium reacts with 
 a solution in water of CO^ to form MgCOj and 
 H ; the quantity of H evolved is ahnost exactly 
 that calculated on the hypothesis that the re- 
 action is HjCOjAq -^ Mg = MgCO^ -1- Hj (Ballo, B. 
 15, 3003). Water holding in solution Na^COj or 
 K2CO3 dissolves considerably more CO2 than 
 pure water ; NaHCOj (or KHCO3) is produced 
 (Ballo, I.e.). Mg reacts with aqueous solutions 
 of NaHCOj or KHCO, to form MgCOj, K^ (or 
 Na2)COs, and H (Ballo, Z.c). Aqueous solu- 
 tion of CO2 turns blue litmus wine-red, the blue 
 colour returns on exposure to air ; blue litmus 
 in contact with CO2 at pressures of Ij to 2 
 atmospheres becomes vermilion-red (Malaguti, 
 A. Ch. [3] 37, 206). When CO, dissolves in 
 water, heat is produced ; [CO^Aq] = 5,880 {Th. 
 1, 260). This solution reacts thermally with 
 alkalis as a dibasic acid ; thus (Thomsen)^ 
 
 n [CO'Aq,?iNaOHAq] 
 
 1 11,016 
 
 2 20,084 
 
 The thermal value of the second formula-weight 
 of NaOH (9,068) is considerably less than that 
 of the first (11,016) ; in this respect carbonic 
 acid behaves like sulphurous, selenious, boric, 
 acid, &o. {v. AoiDS, basicity of). When moist 
 CO2 reacts -with KOH, KjCO, is obtained; 
 from this a great many carbonates may be 
 formed, the composition of which is that of 
 metallic derivatives of a dibasic acid H2CO3. 
 The aqueous solutions of carbonates are decom- 
 posed by almost all acids, not by HCNAq or 
 H2B204Aq; hence the affinity of carbonic acid 
 is small {v. Aefinity). But soluble silicates are 
 at once decomposed by COjAq, and even in- 
 soluble silicates e.g. of Ca, Al, &o. are slowly 
 decomposed by moist CO2. The sulphur ana- 
 logue of carbonic acid — H2CS3 — has been iso- 
 lated. Finally various derivatives, both of 
 C0(0H)2and CS{SH)2 are known; viz. COCL, 
 (?C0Br2), C0(NH2)2, COS, CSClj, CS.NHj.SH, 
 CS(NH2)2. 
 
 Oaebonates. Normal carbonates have the 
 composition M2CO3 or MCO,. Certain acid car- 
 bonates, MHCO3, have also been isolated ; very 
 few of these are known as definite solids, the 
 principal are when M = Na, K, NH^ (? Tl) . Some 
 insoluble normal carbonates, e.g. Ba, Mg, Fe, 
 dissolve in water saturated with CO2; at a 
 
890 
 
 CARBONATES. 
 
 pressure of 4 or 5 atmos. acid carbonates are 
 probably formed. Many ' basic ' carbonates 
 exist ; these are most simply represented by the 
 general formula a;MO{or M^Osj.j/CO^.zHjO. A 
 few double carbonates are also known, usually 
 compounds of alkali carbonates with others, e.g. 
 (NHJjC0s.MgC03 ; K2C03.NiC03.4H.,0. Several 
 ethereal carbonates are known, derived from 
 the hypothetical ortho-carbonic acid C{0H)4; 
 e.g. C(0Et)4, CfOPr)^ {v. Carbonic etheks). 
 
 Formation. — 1. By reaction between metallic 
 oxides or hydroxides and CO^ in presence of 
 water; the oxides which act as weak bases, 
 FcjOs, AI2O3, &c., do not combine with CO2 
 when dry. — 2. By ppn. from solutions of salts 
 by alkali carbonate solutions ; only the salts of 
 BaO, SrO, CaO, Ag^O, and HgO, yield normal 
 carbonates; other salts give basic carbonates 
 containing less CO^, relatively to MO, the weaker 
 is the oxide MO, and the warmer and more 
 dilute is the solution ; salts of such weak bases 
 as FejOj, AljO,, and SnO, give pps. of hydrates 
 free from CO^. — 3. By strongly heating the 
 alkali or alkaline earth salts of organic acids. — 
 4. In some cases by reaction between COjAq 
 and a metal ; e.g. Mg, Fe, Zn. 
 
 Solubility in water. — Carbonates of Na, K, 
 Rb, and Cs, are easily soluble in water ; car- 
 bonates of Li and Tl are much less soluble ; 
 other carbonates are nearly, or quite, insoluble. 
 All carbonates are soluble, to some extent, in 
 water in which CO^ has been dissolved. All, 
 except those of NHj, Bb, and Cs, are insoluble 
 in alcohol. 
 
 Reactions. — 1. All carbonates, except those 
 of the fixed alkalis, are wholly or partially de- 
 composed by heat alone ; BaCOj begins to 
 decompose only at a full white heat, SrCOj at 
 beginning white heat, and CaCO, at full red 
 heat ; AgjCO, gives up CO^ at 200°, and at 250° 
 the AgjO gives off O and leaves Ag; MnCOj 
 heated to 200°-300° in air gives MnO^ and CO^.— 
 2, Heated in steam all carbonates are decom- 
 posed to hydrates and CO2 («. Eose, P. 85, 
 99 a. 279). — 3. Carbonates are decomposed by 
 aqueous solutions of most acids at ordinary 
 temperatures with evolution of CO2; HCNAq 
 and HjBjOjAq, however, do not decompose car- 
 bonates. — 4. Solid carbonates are decomposed 
 by heating with solid boric acid, silica, potassium 
 Sichromate, and some other salts. Sulphuretted 
 hydrogen reacts with many insoluble carbonates 
 suspended in water, e.g. of Sr, Ba, Ca, Zn, Mg, Li, 
 to form sulphides and COj; the change pro- 
 ceeds the further the more water is present 
 (Naudin a. Montholon, 0. B. 83, 58).— 5. The 
 more stable carbonates when heated with carbon 
 give CO. — 6. Alkali carbonates heated in phos- 
 phorus - vapour give phosphates and C. — 
 V. Aqueous solutions of acid carbonates do not 
 usually affect the colour of litmus ; they give an 
 alkaline reaction with rosolic acid. 
 
 Detection and Estimation. — Usually detected 
 by decomposing by an acid and examining action 
 of gas evolved on CaOAq. Usually estimated 
 by decomposing weighed quantity by acid and 
 determining COj by loss. 
 
 Aluminium carbonate. Existence doubtful. 
 Pp. produced by alkaline carbonates with Al 
 salts variously formulated ss a highly hydrated 
 bssic carbonate (Muspratt, G. J. 2, 200 ; Lang- 
 
 lois, A. Ch. [3] 48, 502 ; Wallace, C. Gazette, 
 1858. 410) ; as a compound of AI^ObHs and a 
 small quantity of the carbonate employed, e.g. 
 Al2(HO). + 2NH4HC03 (Eose, P. 41, 462); 
 and as pure Al^O^Hj (Barratt, C. J. 18, 190). By 
 Wibain and Eenoul the pp. in the cold is said to 
 be 2Al203.CO.,.8H20 and to decompose about 30" 
 (C. B. 88, 1133) {v. also H. Eose, P. 91, 460 ; 
 Parkmann, Am. S. [2] 34, 324). 
 
 Ammonium carbonates. Three definite salts 
 seem to exist, the normal, the acid, and the ses- 
 qui, carbonate (Divers, C. J. [2] 8, 171). The 
 last is sometimes regarded as a compound of the 
 first and second (Devtlle, C. R. 34, 880). Divers 
 considers the compositions of the three salts to 
 be: 
 
 Normal carbonate, 2CO2.4NH3.4H2O. 
 
 Sesguiccui-bonate, 3CO2.4NH5.4H2O. 
 
 Acid carbonate, 4CO2.4NH3.4H2O. 
 Eose's hyperacid carbonate may be the fourth 
 term of this series. 
 
 I. Normal carbonate (NHJ2CO3.H2O. Pre- 
 pared (1) by adding excess of NHjAq to a warm 
 cone, solution of the commercial carbonate ; (2) 
 by warming water with the ordinary carbonate, 
 and allowing solution to cool and crystallise ; 
 after this has been done repeatedly the cold 
 mother liquor from the last crop of crystals 
 deposits normal carbonate. Large elongated 
 plates, freely soluble in water, insol. alcohol, 
 sparingly sol. NH3Aq. Decomposes in air tc 
 NHjHCOa, with evolution of NH3, and at 85° to 
 NHj, CO2, and H2O. Is converted into carbam- 
 ate by digestion in closed vessel at 20°-25°- 
 
 II. Acid carbonate T^m^.HGOs. Occurs in 
 guano-deposits (Ulex, A. 61, 44). Prepared by 
 saturating NHjAq, or solution of NH^ sesqui- 
 carbonate, with COj, and drying over HjSOj and 
 KOH. S. (0°) 11-9 ; (10°) 15-85 ; (20°) 21 ; 
 (30°) 27 (Dibbits, J. pr. [2] 10, 417). This is 
 the stable salt to which the other NHj carbon- 
 ates are converted. Large, transparent, trime- 
 tric crystals. Dimorphous, but never isomor- 
 phous with EHCO3 (Deville). Solution at 36° 
 evolves CO2 ; even at ordinary temperature un- 
 stable in solution. 
 
 in. Sesquicarbonate. 
 (NHi)2C03.2NHjHC03. By slowly heating the 
 commercial salt till melted and then cooling ; 
 or crystallises from warm solution of the same 
 salt mixed with NHjAq. Large transparent 
 crystals, losing HjO and NH3 in air and 
 giving NH^HCOj. S. (13°) 25 ; (17°) 30 ; (32°) 
 37; (41°) 40; (49°) 50 (Berzelius). Solution 
 easily decomposes with evolution of CO2. 
 
 Another carbonate — (NHjj^COj — appears to 
 exist in the mother -liquor from the preparation 
 of the sesquicarbonate (Divers). The commer- 
 cial carbonate is probably 3NH3.2CO2.H2O. It 
 generally contains 1 p.c. Hfl in excess of this 
 formula, and a little ammonia. Prepared 
 (1) by dry distillation of animal matter and 
 subsequent purification by redistillation with 
 charcoal ; (2) by heating to redness NH^Cl and 
 CUCO3 in retort with receiver. The first pro- 
 ducts are B..fl and NHj carbamate, subssquent 
 distillation produces the commercial carbonate. 
 A white, transparent, fibrous mass, with strong 
 ammoniacal smell, volatile, but not without 
 some decomposition. Solution strongly alka- 
 line. 
 
CARBONATES. 
 
 697 
 
 Barium carbonate. BaCOj. By adding 
 (NH,)jCO,Aq to BaCl^Aq or Ba(NO,).^q; or 
 Na^COsAq to BaSAq ; or (impure) by strongly 
 heating a mixture of BaSO,, obarooal, and 
 K2CO3, and extracting the K^S formed with 
 water, leaving BaCOj. S. = 0; in water satu- 
 rated with CO2 at 4 to 6 atraos. pressure S = -75. 
 The salt remains in solution at ordinary pres- 
 sure, but is completely ppd. on boiling (Wagner, 
 /. pr. 102, 233 ; J. 1867. 185). Found native as 
 Wttherite. This mineral can be obtained arti- 
 ficially from amorphous BaCOj by crystallising 
 from fused KCl and NaCl (Bourgeois, Bl. [2] 37, 
 447). A soft white poisonous powder, easily 
 soluble in solution of NHjCl, NH^NOj, or am- 
 monium succinate. Above red heat in presence 
 of C it yields BaO and CO^. Decomposed at red 
 heat by aqueous vapour especially in presence 
 of chalk. Yields BaSO, when shaken with 
 KjSOj or NajSOjAq, and is completely decom- 
 posed by boiling with NH^ClAq. 
 
 Barium acid carbonate, 2BaC03.C02, de- 
 scribed by Boussingault {A. Ch. [2] 29, 280) 
 but Bose thinks it cannot exist except in solu- 
 tion. 
 
 Beryllium carbonate. A compound of vari- 
 able composition is obtained by exposing 
 Be(H0)2 to air, ppg. beryllium salts with alka- 
 line carbonates, or boiling solution of double 
 Be-NHj carbonate. The composition of pp. by 
 last method is SBeO.COj.SHjO (Schaffgotsch). 
 Decomposed by boUing water, soluble in alkaline 
 carbonates. Xhe salt BeC03.4H20 is obtained 
 by passing COj through water containing basic 
 salt in suspension and evaporating over H^SO^ 
 in atmosphere of COj. 
 
 Beryllium ammonium carbonate. 
 2(BeC03.(NH,)jC03).Be(HO),2HjO. By dissolv- 
 ing BeO in cone. AmjC03Aq at gentle heat, then 
 boiling till solution becomes cloudy, filtering, 
 and adding cone, alcohol ; crystals are drained, 
 washed with alcohol, and dried by pressing be- 
 tween paper (Humpidge, Pr. 39, 14). By simi- 
 lar method Deville (A. Oh. [3] 44, 5) obtained 
 a salt of formula B(BeC03.(NHJ,C0,,).Be(H0)j 
 soluble in cold, and decomposed by hot, water. 
 
 Bismuth carbonate. BijOj.COj (Berzelius) 
 a white pp. obtained by dropping a solu- 
 tion of BiSNOj into an alkaline carbonate. 
 According to Lefort this pp. contains ^ H^O 
 evolved at 100°. Heated strongly yields 
 Bi20,,.3(BiO)2C03.2Bi03H3.3H20. Occurs native 
 as Bismuthite in South Carolina. 
 
 Cadmium carbonate. CdC08(?) Occurs native 
 with ZnCO,. By ppg. solution of a cadmium 
 .-alt with (NHJjCOsAq. The white pp. is said 
 to contain water, which is lost at 80°-120°, and at 
 a higher temp, to lose CO^ and leave CdO (Le- 
 fort, J. Ph. [3] 12, 78) ; Bose (P. 85, 304) says 
 pp. is nearly represented by CdC03. Moist 
 Cd(HO)j absorbs COj and at 300° loses aU its 
 water, leaving 2CdO.CdC03. 
 
 Caesium carbonate CS2CO3. S. alcohol (19°) = 
 11-1. Ill-defined hydrated deliquescent crystals 
 separate from a syrupy solution. On melting 
 these leave CS3CO3 as sandy powder. Acid 
 carbonate, CS.H.CO3, crystallises from aque- 
 ous solutions in large prisms. 
 
 Calcium carbonate. CaC03. S. (cold) = -0094 ; 
 (100°) = 1-13 (Fresenius, A. 59, 117); S. (0° in 
 water saturated with 00^) = -07, (10°) = -088 
 
 (Lassaigne, J.Chem. Med. 1848. 312; Schloo- 
 sing, C. J. [2] 10, 788). 
 
 Occurrence. — Native ; in rhombohedra (hexa- 
 gonal) as calcspar, S.G. 2-69-2-75 ; and in right 
 rhombic prisms (trimetric), S.G. 2-92-3-28, as 
 arragonite ; also abundantly as chalk, limestone, 
 &c. Formed when hydrated or anhydrous CaO 
 is exposed to moist air ; but not by action of 
 CO2 on dry CaO. 
 
 Preparation. — 1. By ppg. CaCLjAq by 
 (NHJjCOjAq. From not too dilute solutions 
 below 30°, it is ppd. entirely as calcspar ; 
 above 30° the pp. contains arragonite, in 
 gradually increasing quantity as the temp, rises, 
 until about 90° the pp. is almost entirely arra- 
 gonite. CaC03 which separates as calcspar 
 from a cold, not too dilute, solution of the acid 
 carbonate, is deposited partly in arragonitio form 
 on addition of a very little PbC03, CaSO,, or 
 SrSO, (Credner, /, /. Mineral. 1871. 288). The 
 arragonite tends to change to calcspar form if 
 left under cold solution. Can be obtained in 
 form of calcite from ppd. carbonate by crystal- 
 lising from fused NaCl and ECl (Bourgeois, Bl. 
 [2] 37, 447). 
 
 Properties and Reactions. — Tasteless, white, 
 slightly alkaline ; easily soluble, when recently 
 ppd., and to a certain extent even when it 
 becomes crystalline, in aqueous solutions of 
 (NHJ2CO3, NHjCl, NH4.N0a, and ammonium 
 succinate. These salts, therefore, prevent com- 
 plete ppn. of calcium as carbonate. At full red 
 heat is decomposed into COj and CaO. Temp. 
 of decomposition is lowered by passing air or 
 steam over the CaCOj. In closed tube fuses 
 to marble-like substance. Boiling ammonium 
 chloride solution decomposes CaCOa forming 
 CaClj and (NHJ^COj. Sulphur decomposes 
 CaC03 forming CaSOj without previous forma- 
 tion of Hj,S (Podacci, G. 1874. 177). The 
 sulphur is oxidised at expense of oxygen of 
 water (Brugnatelli a. Pelloggio, G. 1874. 536), 
 and the formation of sulphuric acid is preceded 
 by that of penta- and tetra-thionic acids 
 (BeUucci, S. 1874. 179). A salt of the formula 
 CaCl2.2CaCO3.6H2O was obtained by Pelouze 
 {Bl. [2) 3, 183). 
 
 Sydrates : above 30° CaCOj is ppd. ; below 
 30° hydrates are formed containing amounts of 
 water (10-27 p.c.) which vary with the temp, 
 and time occupied in ppn. From a solution of 
 lime in sugar-water cooled to 0°-2°, a hydrate 
 CaCOs.6H20, decomposed at 30°, is obtained; 
 while the same solution at a little higher temp, 
 yields CaCOj. 5'Rfi crystallising in rhombohedra, 
 S.G. 1'783, decomposed above 15° even in water 
 (Pelouze, Bl. [2] 3, 183). Same hydrate found 
 by Soheerer (P. 58, 382) and Rammelsberg (B. 4, 
 469). A gelatinous hydrate formed by action of 
 COj on CaO and water is described by Bondon- 
 neau (Bl. [2] 23, 100). 
 
 Acid carbonate CaIL,(C03)2 (?) is known 
 only in solution ; obtained by passing CO2 into 
 cold water containing suspended CaC03. De- 
 composed with separation of CaC03 on exposure 
 to air, or more quickly on boiling. 
 
 Basic carbonate 2CaO.C02. Obtained 
 from CaC03 at a moderate red heat. Hardens 
 by action of water, forming CaC03.Ca02H2, 
 which is also produced by exposing CaO to 
 moist air. This hydrate gives 2CaO.C02 at low 
 
ees 
 
 CARBONATES. 
 
 red heat, and at strong red heat gives off COj 
 and H^O (Fuohs, P. 27, 601). 
 
 Cerium carbonate Ce2(COj3.'JH20 by ex- 
 posing Ce^Oj to air or by ppn. A. white powder, 
 partially converted on heating strongly in air 
 into CejOj. 
 
 Chromous carbonate OrCOj. An amorphous 
 greyish-white substance, prepared by heating a 
 chromous salt with NajCO^Aq out of contact 
 with the air (Moissan, A. Ch. [5] 25, 401). 
 
 Cobalt carbonate CoCOj. By heating CoClj 
 with CaCOa to 150° in sealed tube for 18 hrs., 
 or by decomposing CoCl^ with a solution of 
 NaHCOj supersaturated with COj and heated to 
 140° in a strong vessel allowing slow escape of 
 COj. Light, rose-coloured, sandy powder; micro- 
 scopic rhombohedra ; not attacked by acids in 
 the cold (Senarmont, A. Ch. [3] 30, 129). 
 
 Hydrated carbonates and double 
 salts are formed on adding cobalt solutions to 
 alkaline carbonates. Hot or cold, not too dilute, 
 solutions yield a rose-coloured pp., which dried 
 at 100° is 2CoCOs.3Co(HO)2 (Setterberg, P. 
 19, 55 ; Winkelblech, A. 13, 148 ; Eose, ibid. 
 80, 237). Boiling water partially converts it 
 into CoA (Field, G. J. 14, 50) ; digested with 
 NaHCOs or (NH,)HC03Aq yields SCoCOs.HjO 
 (Deville, A. Ch. [3] 83, 75). Hot very dilute 
 solutions yield blue CoC032Co(HO)2aq. Heated 
 above 150° both pps. give off HjO and COj, 
 yielding COjO., (Eose). 
 
 Cobalt-potassium carbonate 
 (CoKH)(C03)2.4HjO. Eose-coloured crystals, 
 prepared by action of excess of KHCOjAq on 
 Co(N03)2 f"^ CoS04Aq. Decomposed by water 
 (Eose; Deville). Deville also obtained 
 CoK2(C03)2.4H20. 
 
 Cobalt-sodium carbonate CoNa2(COs)2.4H20. 
 Prismatic, and CoNa2(CO3)2.10H2O dark red, 
 crystals ; obtained together by the action of 
 Co2N03Aq on solution of Na sesquicarbonate 
 (Deville). 
 
 Copper carbonate. Unknown except in solu- 
 tion. Obtained by dissolving the ppd. basic 
 carbonate in CO^Aq at 4-6 atmospheres pressure 
 (Wagner, J.pr. 102, 233). 
 
 Sydrated basic carbonates. 
 CUCO3.CUO2H2 occurs native as malachite. Pre- 
 pared by ppg. a cupric salt with an alkaline 
 carbonate. The pp. at first is greenish blue, 
 and is said to contain 1 mol. H^O; left in con- 
 tact with liquid and washed it has above com- 
 position and is dark green. Heated to 200° 
 yields malachite. Boiled with water it yields 
 CO2 and CuO (H. Eose ; Field, 0. /. 14, 71). 
 Digested with (NHJ^COsAq at 48-8° it is con- 
 verted into CuC03.5CuO, a dense black powder, 
 which is also obtained by prolonged boiling 
 CuSOjAq with AmjH2(COs)3, filtering from 
 CuC03.Cu(HO)2, and adding more CuSO^ (Field). 
 Digested with Na^COa yields CuCO3.7CuO.5H2O. 
 
 The basic salt 2CuC03.Cu(HO)2 occurs 
 native as asurite in blue monoclinio crystals. 
 Boiled with water yields CuO and evolves COj. 
 With hot NaHC03 yields a blue solution which 
 after protracted boiling, deposits CuCOj.CuOjHj 
 (Field). Prepared artificially by secret process 
 (Phillips, A. Ch. [2] 7, 44). Asurite can be 
 formed from malachite at ordinary temps, by 
 addition of COj and abstraction of H^O in pre- 
 sence oi a dehydrating agent and COj at high 
 
 temp. (Weibel, J. fUr Mineral. 1873. 245)- 
 Crystallised Cu(N03)j heated with CUCO3 under 
 a pressure of 54 atmospheres yields crystalline 
 warty mass of asurite (Debray). 
 
 Double salts. Potassic-cuprio carbonate. 
 5CUO.K2O.CO2.IOH2O. A dark-blue silky mass, 
 obtained by adding Cu(N03)2 to KHCO3. 
 
 Sodic-cupric carbonate CuNa2.(C03)2.6H20. 
 By action of NaHCOj on CuCOj-CuOaHj at 
 40°-50°. Ehombio prisms. 
 
 Cuprammordum carbonate (NH3)2Cu.COj. 
 Obtained as dark-blue crystals by dissolving 
 basic carbonate of copper in k.m.fiO, and pouring 
 solution into alcohol. Water decomposes it into 
 kxafiO, and CuC03.CuO.Cu(HO)2 (Favre, Traiti 
 de Chem. par Pelouze et Fr6my). Also formed 
 when CuO or Cu is digested in NHjAq with access 
 of air. 
 
 Didymium carbonate. Di2(C03)3. A red 
 crystalline powder obtained by passing CO^ into 
 water containing suspended Di03H3. A hy- 
 drated carbonate is obtained, as a very slightly 
 rose-coloured pp., by adding an alkaline car- 
 bonate to solution of a Di salt. Loses f H2O 
 and a little COj at 100° (Marignac). 
 
 Indium carbonate. In23C03. White, gela- 
 tinous pp., soluble in (NHj)2C03Aq, and ppd. on 
 boiling ; insoluble in solution of fixed alkali 
 carbonates (Winkler, J. pr. 94, 1). 
 
 Iron carbonates. Ferric carbonate does not 
 appear to exist (Gmelin ; Sonbeiran, A. Ch. [2] 
 44, 326). Double salts oJE ferricum and alkaline 
 carbonates appear to exist in solution, as the 
 pp. of ferric hydrate obtained by cone, alka- 
 line carbonate solutions gradually redissolves, 
 whereas pure well-washed FCjOsHj does not 
 dissolve in these solutions. 
 
 Ferrous carbonate, FeC03, occurs abundantly 
 as spathic ore. Prepared by methods similar 
 to those described for C0CO3 {q. v.). It is a 
 greyish-white crystalline solid, composed ol 
 minute rhombohedra ; scarcely attacked by 
 dilute acids, nearly unchanged in dry air. It 
 is darker and less alterable the higher the 
 temperature at which it has been formed, and 
 the longer it has been heated (Senarmont, A.Ch. 
 [3] 30, 129). Spathic ironstone dissolves under 
 pressure in water saturated with COj (S. = "72), 
 and is deposited as a black amorphous pp. on 
 boiling (Wagner, J. 1867, 135). 
 
 Hydrated ferrous carbonate, FeC03.H20, 
 occurs native. Amorphous, white, earthy, little 
 altered in air, scarcely decomposed by acids at 
 ordinary temps. (Moissan, C. R. 59, 238). The 
 hydrate obtained by ppg. solution of a ferrous 
 salt with an alkaline carbonate rapidly decom- 
 poses on exposure to air. It can be obtained 
 fairly pure, as a greenish tasteless powder, by 
 ppg. ferric-free ferrous sulphate with normal 
 or acid alkaline carbonates. The salts are dis- 
 solved_ in de-aerated water, the pp. washed by 
 decantation out of contact with air, and dried 
 in CO2. If dry it is fairly permanent ; if moist 
 it gives off HjO and CO2 ; but if mixed with 
 sugar the change is less rapid. 
 
 Ferrous-hydrogen carbonate. Solution of 
 CO2 dissolves FeC03 and Fe ; the latter with 
 evolution of H. 
 
 lanthanum carbonates. La2(C03)3.8H20. 
 Found native as LcmthanAte in four-sided 
 plates or minute tables of the trimetric system. 
 
OAKBONATES. 
 
 099 
 
 The carbonate obtained by ppn. forms a white 
 gelatinous mass which changes to shining 
 crystalline scales. 2La,(COs)3.15H20 ; ppd. by 
 NajCOaAq from La^SSOjAq, and dried at 
 ordinary temperature. Micaceous scales with 
 silky lustre (Hermann, J.pr. 82, 385). 
 
 Lead carbonate. PbCO,. Occurs native in 
 trimetrio crystals as white lead ore or cerusite. 
 Has also been found on bronze objects from 
 Pompeii (Luca, 0. B. 84, 1457). Prepared by 
 ppg. Pb(N03)2Aq with excess of alkaline car- 
 bonates in the cold (Berzelius ; Lefort, J. Ph. 
 [3] 15, 26). According to Eose (A. 80, 285) 
 these pps. are all hydrooarbonates, the ratio 
 of hydrate to carbonate increasing with the 
 temp, and dilution of the solutions. Bodies of 
 the same composition are formed by direct 
 action of COj on Pb(H0)2, but differ in being 
 amorphous and opaque, instead of consisting of 
 minute transparent crystalline grains. 
 
 White lead is a hydrooarbonate present- 
 ing varieties of composition represented by 
 
 (1) 2PbC03.Pb02H2 ; (2) SPbCOs.SPbOjHj ; 
 
 (3) 3PbC03.PbO.^ (MuMer, A. 33, 242); 
 
 (4) 5PbC03.PbOjHj (Phillips, O. J. 4, 165). 
 Prepared by (1) Dutch method. Thin lead 
 sheets are placed over gallipots containing 
 weak acetic acid (2| p.c.) ; the pots are em- 
 bedded in fermenting tan at a temp, of 60°-65°. 
 The metal disappears in a few weeks. Oxide 
 of lead is first formed, and dissolved by the 
 acetic acid, forming a basic acetate, and this 
 is decomposed by the COj evolved from the tan. 
 
 (2) PbO is mixed with water and about 1 p.c. 
 of Pb acetate, and COj is passed over it. 
 Pb(N0s)2 has been used instead of acetate. 
 Nearly insol. in sat. COjAq even under pressure 
 (Wagner). The ppd. carbonate has S. = '05 in 
 sat. COjAq. 
 
 Lead - sodium, carbonate. 4PbCOs.Na2C03 
 (Berzelius, P. 47, 199). 
 
 Lead-chloro-carbonate. A compound of the 
 chloride and carbonate of lead is obtained as 
 a pp. by the action of COj under pressure on 
 PbClj (Miller, C. /. [2] 8, 37). 
 
 Lithium carbonate. LijCOj. S. (0°) = 1-539 ; 
 (50°) = 1-181; (100°) = -728 (Bevade, Bi. [2] 43, 
 123). Pound in many mineral waters. Pre- 
 pared by dissolving an excess of (NH4)2C03 in 
 cone. LiClAq, and washing resulting pp. with 
 alcohol, or by strongly heating Li acetate. 
 Not decomposed by heat. Melts at low red 
 heat, and solidifies to a vitreous mass on 
 cooling. The solution is alkaline and decom- 
 poses NH4 salts, but is decomposed by Ba(H0)2 
 and Ca(H0)2. By slow evaporation the solution 
 deposits salt in small prisms. Water saturated 
 with CO2 dissolves it more readily than pure 
 water. 
 
 Magnesium carbonate. MgC03. Occurs 
 native as magnesite, in rhombohedral crystals 
 isomorphous with calcspar ; infusible ; dissolves 
 slowly in acids. Prepared (1) By suspending in 
 water the washed pp. obtained by adding solu- 
 tion of an alkaline carbonate to solution of a Mg 
 salt (which always contains MgO^H^), passing 
 CO, through the liquid till pp. is dissolved, and 
 evaporating by heat (Eose, P. 42, 866) ; (2) By 
 heating MgSO,Aq with Na^COjAq to 160° m a 
 sealed tube ; (3) By inclosing a soluble Mg salt 
 with an alkaline-hydrogen carbonate, super- 
 
 saturated with CO2, in a strong vessel closed by 
 a cork through which the COj can slowly escape 
 (Senarmont, G. E. 28, 693) ; (4) By carefully 
 heating MgCOs.KHCOa. 4aq to 200°, and extract- 
 ing with water (Engel, Bl. [2] 44, 855). A 
 white crystalline powder, ismorphous with 
 arragonite by method (1) ; obtained in rhombo- 
 hedra by (3) ; isodimorphous with CaCOj. When 
 moist it is alkaline to litmus. CaSO^Aq par- 
 tially decomposes it, especially in presence of 
 NaClAq (Fleischer, J. pr. [2] 6, 273). Soluble 
 in cold solutions of alkaline borates, ppd. on 
 heating, but redissolved on cooling (Wittstein, 
 Ar. Ph. [3] 6, 40). Hydrates (a) MgC0a.3Hi,0. 
 Hexagonal prisms obtained by spontaneous 
 evaporation of a solution of MgCOj in excess of 
 COjAq. They lose water in dry air but retain 
 their form. (/3) MgCOj.SHjO. Transparent 
 oblique prismatic crystals obtained by exposure 
 of above solution at a low temp. Converted 
 into (o) by exposure to air &o. Boiled, they 
 yield 4Mg0O3. MgH^O^. 4aq (Fritzsche ; v. also 
 Engel, C.B. 101, 814). 
 
 Sydrocarbonates. As in the case of lead, 
 the composition of pp. formed by adding an alka- 
 line carbonate to solution of a Mg salt depends 
 on proportions, strength, and temp., of solutions. 
 A variable mixture of hydrocarbonates is known 
 as magnesia alba ; (a) 4MgC03.MgHj02. 4aq ; a 
 white granular powder (for preparation v. Eose, 
 A. 80, 234). (j8) 3MgC03.Mg(H0)2. 3aq, occurs 
 native as hydromagnesile in small white mono- 
 clinic crystals (Dana). Prepared artificially 
 (Berzelius, Fritzsche) it is a white, slightly 
 soluble powder forming alkaline solutions. 
 Dried at 100° in air it yields a (Eose). 
 (7) 3Mg0.2COj. 8aq(?) (Fritzsche, P. 37, 310). 
 Denied by Eose. 
 
 Magnesium hydrogen carbonate. Mg.H2(C03) ^ 
 (Soubeiran). Obtained by shaking up magnesia 
 alba with C02Aq. The sol. has a bitter taste 
 and alkaline reaction ; becomes turbid at 75° 
 but clears on cooling. Heated to 50°, or eva- 
 porated in vacuo, it yields hydrate a (v. supra) 
 (Berzelius ; Fritzsche). 
 
 Magnesium-ammonium carbonate. 
 Mg.(NH4)j(C03)2.4H20. Translucent rhombo- 
 hedra, from a mixture of cold MgCl^Aq, or 
 MgSOjAq, and NH4 sesquicarbonate solution. 
 
 Magnesium - potassium carbonates : (1) 
 Mg(KH). (003)2. 4aq. ^^ large crystals from cold 
 aqueous mixture of MgCl2 or Mg(N03)2 vath 
 excess of KHCO3. The crystals at 100° laecome 
 opaque, and lose water. Decomposed by water, 
 leaving a residue eMgCOj.MgHjOj. 6aq (Ber- 
 zelius) ; also obtained in oblique rhombic prisms 
 (Deville, A. Gh. 33, 75) ; (2) MgK2(C03)24aq by 
 digesting magnesia alba at 60°-70° for 12 to 15 
 hours with KHCOjAq (Deville, l.c.). 
 
 Magnesium-sodium carbonate MgNa^.(C03)2. 
 Prepared in anhydrous microscopic crystals as 
 the corresponding K salt. 
 
 On solubOity of MgC03 in COjAq under 
 pressure v. Merkel (/. 1867. 136) and Wagner 
 (J. pr. 102, 233). On solubility of MgCOj and 
 CaCOj in solutions of calcium and magnesium 
 salts, and the reactions of dolomite or gypsum 
 and magnesite in presence of water containing 
 CO2 V. Hunt (Am. S. [2] 42, 49). For reactions 
 of basic MgCOj and gypsum with CO.^Aq v. 
 Gossmann (Am. S. [2] 42, 217, 3G8). 
 
roo 
 
 CARBONATES. 
 
 Manganese carbonate. MnOO,. S. water = 
 •013 ; aqueous 00^= -028 (John). Occurs native 
 as diallogite, in rhombohedral crystals, isomor- 
 phous with caloite. Prepared by heating 
 MnCljAq in sealed tubes to 160° with NajCOaAq, 
 or to 140°-170° with CaCOj for 12 to 48 hours 
 {Senarmont, C. B. 28, 693). 2MnC03.H20 is 
 obtained by drying in vacuo the pp. formed by 
 ■alkaline carbonates with manganous salts [Om. 
 i, 214; Prior, Fr. 1869. 428). Dried in air pp. 
 ■contains MnjO,. Equivalent quantities of 
 Na^COa and MnCl^ yield 6MnCOs.2MnH202 
 (Eose, A. 80, 235). MnCOg is a fine amorphous 
 faintly rose-coloured powder. The hydrate is 
 ■Snow-white and tasteless. Anhydrous or 
 hydrated the salt is permanent at ordinary 
 temps. Heated to redness in air it yields 
 MnjOj. Strongly heated in H it yields MnO^. 
 In chlorine it gives 4MnC03-^Cl2 = 
 MnCLj + Unfit + 4C0j (Wohler). Chlorine water, 
 or calcium hypochlorite solution, converts it first 
 into MnjOj, and then into MnOj. Solutions of 
 «,mmoniacal salts dissolve it when freshly ppd. 
 
 Mercury carbonates. Mercuric carbmiate 
 unknown. Neutral or acid carbonates of K or 
 Na yield brown red pps. 2HgO.HgC03 (Setter- 
 berg, P. 19, 60). Mercuric chloride yields an 
 ■oxy chloride. 
 
 Mercurous carbonate. HgjCO,. A black or 
 jellow powder. Hg2N0sAq is mixed with slight 
 excess of Na(orK)HC03Aq ; the mixture is set 
 aside for a few days and frequently stirred, and 
 thepp. then washed quickly, and dried over HjSO, 
 in vacuo (Setterberg, Z.c). Easily loses CO2 ; 
 is converted into HgO by exposure to air ; 
 blackened by alkalis with separation of Hg 
 iGm. 6, 15). 
 
 Nickel carbonate. NiCOa. For preparation, 
 V. CoBAiiT CAKBONATE. It is a grcenish-white 
 powder in minute rhombohedra scarcely at- 
 tacked by strong acids at ordinary temperatures. 
 
 Sydrocarbonates : 
 <1) NiCOs.2NiH2Op.4H2O. Occurs native as 
 ■emerald nickel (Silliman, Am. S. [2] 6, 248; 
 ■Shepard, ibid. 250). (2) 2NiCO3.3NiH2Oj.4H2O 
 is the pp. obtained from cold NiSO,Aq and 
 Na2C0sAq, when dried at 100°. Boiled with 
 water takes up water and loses' COj. Heated 
 Above 100° in air gives off water and COj, and 
 is partly converted into Nifi, (Eose, A. 80, 
 ^37). Not altered by digestion at 60°-70° with 
 NaHCOsAq (Deville). The pps. produced by 
 ■alkaline carbonates in solutions of nickel salts 
 vary with temperature, strength, and proportions, 
 ■of solutions employed. 
 
 Nickel -potassium carbonates : 
 (1) NiK2(C03)2.4H20 ; shining apple-green micro- 
 scopic needles. (2) NiKH.(C0s)2.4H20 : light- 
 green, apparently oblique rhombic prisms. Ob- 
 tained similarly to corresponding cobalt salts 
 (Deville). 
 
 Nickel-sodium carbonate, 
 NiNa2(CO3)2.10H2O is obtained like the cobalt 
 ;salt, in small prisms (Seville). 
 
 Palladium carbonate. A light yellow pp. is 
 iormed by adding solution of an alkaline car- 
 tonate to a solution of a Pd salt. No CO2 is 
 evolved at first, but on continuing ppn. effer- 
 vescence ensues and pp. turns brown. A small 
 ■quantity of CO2 retained when dry (Berzelius). 
 
 Potassium carbonates. Two salts have been 
 obtained. 
 
 I. Normal carbonate : KjCOj. S. 95-2 at 3° j 
 111 at 12° ; 204 at 70°. The commercial salt 
 is prepared by treating the ash of plants, 
 especially of beetroot, with water, and evapora- 
 ting. The residue, containing 60-80 p.c. KfiO,, 
 is sold as ' cru^e potash.' The impurities — KCl, 
 KjSO,, and a little K silicate — are partially re- 
 moved by digesting for several days with its 
 own weight of cold water, decanting, and evapo- 
 rating quickly with constant stirring. The 
 small crystals obtained are washed with pure 
 K2C03Aq, dried, and heated to redness in metal 
 vessels ; the product is 'pearl ash,' which usually 
 contains from 2 to 3 p.o. impurities. 
 
 Pure EjCOj is prepared (1) by heating pure 
 K oxalate ; (2) by digesting powdered eream of 
 tartar with water containing a little HCl, wash- 
 ing, drying to render sOica insoluble, crystal- 
 lising from water to remove Na salts, heating in 
 a closed silver dish, digesting residue with hot 
 water, filtering, evaporating to dryness, dis- 
 solving in cold water, evaporating, and repeat- 
 ing treatment with cold water and evaporation 
 two or three times (Stas, Ohem. Prqport. 340). 
 {v. also Smith, C. N. 30, 234). 
 
 Properties and Beactions. — White solid, 
 melting at red heat (83°) (Carnelley, C. J. 33, 
 280), volatilised without change at white heat ; 
 very deliquescent ; [E2CO»,AqO = 6490 {Th. 3, 
 198). Solution strongly alkaline ; hot solution 
 deposits rhombic octahedra K2CO3.2H2O ; 
 cone, solution deposits monoelinic crystals 
 2K2CO3.3H2O, which at 100° give K2CO3.H2O 
 (Stadeler, A. 133, 371 ; Pohl, W. A. B. 41, 630). 
 Seated with aqueous napowr is partly decom- 
 posed, giving KOH ; heated with charcoal gives 
 K and CO {v. Potassium) ; heated with sulphur 
 forms K sulphide and sulphate, and CO2 (Ber- 
 thelot, Bl. [2] 40, 362) ; heated in sulphwr 
 dioxide gives KjSO, and traces of K2S (Berthelot, 
 A. Ch. [5] 30, 547). Solutions, about 1 in 
 IOH2O, partly decomposed by CaOjHj giving 
 KOHAq ; amount of change much increased by 
 boiling; reverse reaction occurs with more 
 cone, solutions. 
 
 II. Potassium-hydrogen carbonate : KHCO,. 
 S. 22-4 at 0°; 33-2 at 20°; 45-2 at 40°; 16-4 
 at 60° (Dibbits, J. pr. [2] 10, 417). Prepared 
 (1) by passing CO^ into solution of commercial 
 normal carbonate ; (2) by passing COj into 
 solution obtained by lixiviating residue from 
 heating K-H tartrate in closed vessels, and crys- 
 tallising. Properties and Beactions. — ^Large 
 transparent monoelinic crystals, KHCO3.H2O ; 
 solution has slightly alkaline reaction, and 
 gives off CO2 on gently warming (v. Dibbits, 
 J. pr. [2] 10, 417). At 200° gives KjCO, and 
 CO2. 
 
 Bnbidium carbonate Eb2COs. By ppn. of 
 Eb2S04Aq with BaOAq, adding (SB.,)fiO, to 
 filtrate, evaporating to dryness, exhausting with 
 water, and evaporating this solution, indistinct 
 crystals of Eb2C03. B.fi are obtained. Soluble 
 in alcohol, strongly alkaline. Heated, lose 
 water and leave Eb2C03, as a sandy powder, 
 which melts at a higher temperature. In air it 
 deliquesces, and yields EbHCOj, in glassy pris- 
 matic crystals ; permanent in air ; having very 
 faint alkaline reaction ; easily converted by heat 
 
UAllBONATES. 
 
 ~i)\ 
 
 Into RbjCOa (Bunsen a. Eirchofi) (melting-point, 
 837°; Camelley a. Williams, C. J. 37, 125). 
 
 Samarium carbonate Sm2(0O3)3.3H2O. 
 Needles insoluble in water. The following 
 double salts have also been prepared. Sama- 
 rium-ammonium carbonate, 
 SmNHj(C03)2.2H,,0. Samarium-potassium car- 
 bonate, SmK(C63)2.6H20 ; brilliant needles. 
 Samarium-sodvum carbonate, 
 SmNa(C03),.8H,0 ; a crystalline pp. (CWve, Bl. 
 [2] 43, 168). 
 
 Silver carbonate Ag2C03. Prepared in crys- 
 tals by adding ammonia by drops to mixed 
 solutions of AgNOa and Na^COs of definite 
 strength (Vogel, J. pr. 87, 288). As a white 
 pp., becoming yellow on washing, by adding 
 NajCOjAq to AgNOjAq. Blackens on exposure 
 to light. Is readily soluble in strong NHjAq. 
 Solution treated with absolute alcohol yields a 
 pp. containing AgjCOs and ammonia (Berzelius). 
 At 200° loses CO^ and leaves Ag^O. By ppg. 
 AgNOjAq with large excess of alkaline carbon- 
 ate and boiling, a substance, possibly a mixture, 
 is obtained which dried at 100° has formula 
 Ag2C03.2Ag20 (Eose, A. 84, 202). Ammonio- 
 sUver carbonate Ag2C03.4NH3. A grey pp. on 
 adding absolute alcohol to Ag^COa dissolved in 
 NHaAq (Keen, C. N. 31, 231). 
 
 Sodium carbonates. Three salts have been 
 isolated, besides various hydrates, and several 
 double salts. 
 
 I. Normal carbonate NajCOa- Occurs in waters 
 of several lakes and mineral waters ; is a con- 
 stant constituent of ash of sea-plants. 
 
 Formation. — 1. From NaaSOj, by heating 
 with C and CaCOj, and lixiviating with HjO 
 (Leblano's process). — 2. From cryolite, by heat- 
 ing with CaO and decomposing the Na aluminate 
 formed by COj. — 3. By reaction between NaOl 
 and (NHJjCOj in solution. 
 
 Preparation. — 1. Soda crystals are repeatedly 
 washed with cold water until all sulphates, 
 chlorides, &c. are removed; the last traces of 
 SiO^ are removed by dissolving the washed salt 
 in water, evaporating nearly to dryness, adding 
 a little (NHJjCOa, heating till quite dry, dis- 
 solving in water, filtering, evaporating, and 
 heating (Wurtz, J. 1852. 857).— 2. Soda crystals 
 are repeatedly recrystaUised, the crystals being 
 obtained as small as possible (Gay-Lussac, A. 
 12, 15) ; most of the chlorides and sulphates 
 and iron salts are thus removed. The washed 
 salt is dried, heated in a silver dish, and the 
 residue is repeatedly washed with small quan- 
 tities of cold water ; the salt is now free from 
 iron, but may contain traces of silica {v. supra) 
 (Stas). 
 
 Properties and Reactions. — White solid ; 
 melts at c. 818° (CarneUey, O. J. 33, 280), 
 giving oft a little CO^ (Jacquelain, A. Ch. [3] 32, 
 205 ; MaUard, A. Ch. [4] 28, 86 ; Scheerer, A. 
 116, 134). Heated in steam gives NaOH. De- 
 composed at high temperature by carbon, to 
 Na and CO ; by phosphorus, to C, CO, and Na 
 orthophosphate (Dragendorff, C. C. 1861. 865) ; 
 by siUcon to C, CO, and Na silicate ; by sulphur, 
 at 275°, to NajS and NajSA. a* melting-point, 
 to NajSj and Na^SO^ ; hj ferric oxide, ot ferrous 
 oxide, with evolution of CO^ (Stromeyer, A. 107, 
 866) ; by ferrous sulphide to Na and Na-Fe 
 sulphide (E. Kopp, Bl. [2] 6, 207). Solubility 
 
 in water increases from 0° to 34°; from 
 34° to 79° S. is constant: S. = 46-2 at 34° 
 (Lowel, A. Ch. [3] 33, 353 ; Poggiale, A. Ch. r3] 
 8, 468 ; TomlinsoU; C. N. 18, 2 ; Gerlaoh, Fr. 
 8, 279). Solution is accompanied with produc- 
 tion of heat ; [Na^CO', Aq] = 6,640 (Th. 3, 198). 
 
 Hydrates o/ Na^COj.— (1) NajCOa.loaO ; 
 separates from moderately cone, solutions at 
 ordinary temperatures, in clear, monoolinio crys- 
 tals ; these melt at c. 34°, leaving Na2C03.HaO 
 (Schindler, Mag. Pharm. 33, 14) ; according to 
 Thomsen (B. 11, 2042) the residue is 
 Na2C03.2H20 but this gives up another H2O in 
 the air. Crystals of Na^COj.lOHjO effloresce in 
 air ; at 12-5° they give the hydrate with SH.fi ; 
 and at 38° in vacuo, or over CaClj, the hy- 
 drate Na2C03.H;0 (Watson, P. M. 12, 130). 
 Dissolve in water with disappearance of heat 
 [Na'COM0H^O,Aq]= -16,160 {Th. 3, 198). 
 
 (2) Na2C03.15H20 (Jacquelain, A. Ch. [3] 
 32, 205). Crystallises from cone, solutions of 
 Na2C03at -20°. 
 
 (3) Na2C03.7H20 (Lowel, A. Ch. [3] 33, 
 353; Eammelsberg; Marignac, Ann. M. [5] 
 12, 55). Crystallises from hot saturated solu- 
 tions by cooling in closed vessels ; if air has en- 
 trance the lOHjO hydrate forms. Said to crys- 
 tallise in two modifications, rhombohedra and 
 rhombic tables, with difEerent solubihties. 
 
 (4) NajCOj.eH^O ; crystallises from Na^SAq 
 standing in air, also from NaClAq mixed with 
 KjCOjAq (Mitscherlich, P. 8, 441). 
 
 (5) Na2C03.5H20; crystallises at tempera- 
 tures over 33° from molten Na2CO3.10H2O (Ber- 
 zelius, P. 32, 303) ; also by the efflorescence of 
 NajCOj.lOHjO at 12 5°. 
 
 (6) Na2C03.2H20 ; melting NajCOj.lOHaO at 
 34° (Thomsen) ; [Na'CO».2H20,Aq] = 20. 
 
 (7) Na2C03.H20 ; from hot saturated solu- 
 tions of NajCOs, or from hot solutions of 
 NajCOj.lOHjO ; separates from boiling solu- 
 tions ; also produced by efflorescence of some of 
 the hydrates with more H2O (Marignac, Arm. M. 
 [5] 12, 55 ; Haidinger, P. 5, 369). 
 [Na2CO'.H20,Aq] = 2,250 (Th.). 
 
 II. Sodium-hydrogen carbonate ; NaHCO, 
 {Bicarbonate of soda). Formation. — 1. By pass- 
 ing NH3 into NaClAq, and then decomposing by 
 CO2 under pressure ; 
 
 NH3 + NaClAq -h CO^ -t H^O = 
 NaHCOj -I- NHjClAq (Ammoniasoda process). — 2. 
 By reaction between soda crystals in solution 
 and commercial NH, carbonate. — 3. By reaction 
 between COj and eiHoresced soda crystals, or a 
 mixture of 1 part crystallised and 3 parts dry 
 Na2C03. — 4. By passing CO2 into Na2C03Aq as 
 long as it is absorbed (1 part NajCO, in 2 parts 
 H2O) (L. Meyer, A. Supplbd. 2, 170 ; Berzelius, 
 P. 16, 434 ; Mohr, A. 19, 15; 29, 268). Proper- 
 ties and Reactions. — White monocHnio tables ; 
 alkaline taste ; changes moist red Htmus to blue, 
 but has no action on colour of turmeric paper. 
 In moist air readily goes to Na2C03.a;aq. When 
 heated gives off COj and HjO ; solution decom- 
 posed on boiling (Eose, P. 34, 158). S. 8-8 at 
 10° ; 14-64 at 70° (Poggiale, A. Ch. [3] 8, 468; 
 also Dibbits, J.pr. [2] 10, 417). 
 
 III. Sesguica/rhonate. Na,Hj(C03)s.3HjO 
 ( = Na2C03.2NaHC03.3H20). Occurs native; 
 S.G. 2-112. Prepared (1) by heating NaHCOj to 
 200° (Hermann, J. pr. 26, 312) ; (2) by evapa- 
 
702 
 
 CARBONATES. 
 
 rating solutions of NaHCO., in vacuo over 
 H2SO4 ; (3) by melting together the two carbon- 
 ates, in the ratio Na2CO;,.10H.p:2NaHCO3, and 
 standing in air till mass becomes crystalline, 
 when it contains crystals of the sesquicarbonate ; 
 (4) by pouring alcohol on to a mixture of 
 NajCOjAq and NaHCO,, the salt separates in 
 fine needles (Winkler, B. P. 48, 215). Mono- 
 clinic crystals ; non-eiillorescent in air, goes to 
 NajCOj at red heat ; aqueous solution in vacuo 
 over HjSOj gives Na^CO., and NaHCO, (Rose, P. 
 34, 160). S. 12-63 at 0° ; 41-59 at 100° (Poggiale). 
 Vf. Double Salts. Sodium-potassium 
 carbonates. 
 
 (1) NaKCOj.BH^O ; monoelinic crystals, 
 unchanged in dry air, effloresces in moist air ; 
 by evaporating solution of equal equivalents of 
 the constituent salts, and crystallising from 
 KjCOsAq. At 100° loses 6H2O. S. 185 at 15° 
 (Marignao, 0. B. 45, 650; Marguerite, A. 56, 
 220 ; Stolba, Bl. [2] 4, 192, 7, 241). 
 
 (2) 2Na2C03.KjC03.18HjO ; from mother- 
 liquor from which K4J"e(CN)|| has crystallised out. 
 May be crystallised from K^COjAq (Marguerite). 
 
 SoDiuM-CAiiOrnM oakbonate : 
 Na2CO3.CaCO3.5H2O ; occurs native as Oay- 
 Lussite ; obtained, in microscopic monoelinic 
 crystals, by reaction between freshly ppd. CaCOj 
 and cone. Na^COjAq at ordinary temperature. 
 When dry this compound is decomposed by 
 water (Fritzsche, /. pr. 93, 339 ; Boussingault, 
 P. 7, 97 ; H. Kose, P. 93, 606). 
 
 Strontium carbonate. SrCO,. S.G. (pp.) 
 = 3-62. S. (cold or hot) = -0003 (Bineau, C. B. 
 41, 509). S. (cold)= -005 (Fresenius) solubility 
 diminished by NH^Aq or (NHJjCOaAq. S. (10° in 
 satd. COjAq) = -12 (Lassaigne). Occurs native as 
 strontiamte. Crystals of trimetrio system, isomor- 
 phouswith arragoniteandwitherite. Prepared by 
 ppn.with an alkaline carbonate as a smooth white 
 substance ; in form of strontianite, by crystal- 
 lising amorphous carbonate from fused KCl and 
 NaCl (Bourgeois, Bl. [2] 37, 447). Heated in 
 closed vessel CO2 given off only at about white 
 heat, but in aqueous vapour SrH202 is formed 
 at a much lower temp. Alkaline sulphates in 
 solution do not decompose it at any temperature 
 (Rose, P. 95, 284). Ammonium chloride solu- 
 tion boiled with it converts it into SrCl,. 
 
 ThalUum carbonate. TI2CO3. S.G. (fused) 
 7-06 (Lamy). S. (15-5°) = 4-02 ; (60°) = 11-7; 
 (100°) = 27-21. M.P. c. 272° (Carnelley, O. J. 33, 
 275). Formed by exposure of Tl in a saturated 
 solution of TI2O to air. Prepared by allowing 
 granulated metal to oxidise in warm air, boiling 
 with water containing excess (NHJ2CO3 and 
 filtering. TI2CO3 is deposited in groups of prisms 
 (Miller, Pr. 14, 555), which are brilliant, highly 
 refractive, very heavy, anhydrous, colourless; 
 melting, undecomposed, much below redness to 
 clear liquid which solidifies to dark-grey mass, 
 and at red heat decomposes evolving COj. Taste 
 mildly caustic and metallic. Solution has alka- 
 line reaction not completely removed by super- 
 saturation with CO2 (Crookes ; Werther, /. 1864. 
 249). 
 
 Thorium carbonate. Th(C03)2.3ThH^04.2H20. 
 Alkaline carbonates throw down a basic salt 
 with evolution of COj. Moist ThH^O, absorbs CO2 
 from air. ThOj is not sol. in water containing 
 COj (Berzelius). Salt of above formula obtained 
 
 as an amorphous pp. by treating hydrate sus- 
 pended in water with COj, or by ppg. solution 
 of ThCli with an alkaline carbonate. 
 
 Tin carbonates. SnCOj.SnO ; by adding 
 solid SnCljto cone. NajCOjAq in absence of air : 
 very unstable. If (NHJjCOjAq is used, hexa- 
 gonal prisms of (NH4)20.2Sn0.3C02.3H20 are 
 said to be formed (Deville, A. Ch. [3] 35, 448). 
 
 TTraninm carbonates have not been isolated. 
 Alkaline carbonates ppt. uranous hydrate from 
 UCl,, a basic sulphate from 17(804)2, and double 
 carbonates from uranic salts. 
 
 Uranyl-ammomum carbonate. 
 (U02)C03.2(NH,)2CO,. S. = 5 at 15° ; increased 
 by (NH4)2C03. Prepared, in small yellow trans- 
 parent crystals, by digesting in (NH4)2C03Aq 
 at 60°-80° the pp. produced by NH3Aq or 
 (NH4)2C03Aq from uranic salts, filtering, and 
 allowing to cool. Decomposed slowly at ordinary, 
 more quickly at higher, temps, leaving UOj ; 
 solution boiled evolves NH, and COj, and 
 deposits yellow pp., containing uranium, of doubt- 
 ful composition (Arfredson, Pffigot ; Ebelmen, 
 A. Ch. [3] 5, 189 ; Delffs, P. 55, 229). 
 
 TJranyl-potassi/um carbonate. 
 (U02)C03.2K.2C03. S. = 7-4 at 15° ; insol. in aloo- 
 nol. Prepared, as a bright yellow crystalline 
 crust, by dissolving in KHCOjAq the pp. formed 
 from uranic salts by KjCOjAq, and evaporating. 
 At 300° evolves CO2 ; at red heat leaves mixture 
 of K uranate and carbonate. KOHAq pps. all 
 the U as K uranate, even in presence of excess 
 of K2CO3. 
 
 Uranyl-sodium carbonate. 
 (XJ02)C03.2Na2COj. Preparation and properties 
 similar to E salt. Two Ca salts, 
 
 (1) (UO2)CO3.CaCO3.10H2O; 
 (2) (U02)C03.CaC03.5H20 ; 
 occur native (Smith, A. 66, 253). 
 
 Yttrium carbonate. ¥2(003)3. NajCOsAq 
 pps. it from yttrium salts with I2H2O in the 
 cold, and 2H2O at 100°. Not easily decomposed 
 by heat ; sparingly soluble in water containing 
 CO2. Solution in (NH4)2C03Aq, if concentrated, 
 deposits a white crystalline double salt which 
 does not redissolve in (NH4)2C03Aq ; also soluble 
 in K2CO3 and Na2C03Aq (Berzelius). 
 
 Zinc carbonate. ZnCOj. Occurs as calam- 
 ine. Not obtained by precipitation. Pp. 
 formed by KHC03Aq in ZnS04Aq is 
 2ZnC03.3Zn02H2 (Berzelius). ZnCOj unaltered 
 at 200° ; slowly evolves CO2 at 300° (Rose). 
 
 Hydrocarbonates. Native hydrocar- 
 bonates are (1) zinc bloom ZnO.ZnC03.3ZnH20j 
 (Berzelius), or ZnC03.2ZnH2024aq (Smithson a. 
 Borndorff, Om. 6, 15). (2) Aia-icalcite or green 
 calamme 2ZnC03.3ZnH202, in which Zn is 
 partly replaced by Cu. (3) Buratite, a hydro- 
 carbonate containing Cu and Ca. 
 
 The pps. formed by alkaline carbonates in 
 solutions of zinc salts all appear to contain 
 water, and to vary in composition with strength, 
 temperature, and proportions, of solutions. For 
 results obtained under varying conditions, v. 
 Rose (P. 85, 107), Schindler a. Boussingault 
 (Gm. 1, 15). They all evolve CO2 and HjO at 
 200°, yielding ZnO (Rose). 
 
 Ammonio-carbonate of zinc (NH3Zn)C03. 
 Deposited in crystals from a solution of ppd. 
 zinc carbonate in cone. (NH4)2C03Aq (Favre, 
 Traitide 0/iimie, Pelouze etFr^my, 2nded. 3,47). 
 
UARBONIO ETHERS. 
 
 708 
 
 Zinc-potassium carbonate 
 8ZnC03.3Kj,C03.7H,0 (?). Crystallises from a 
 solution of ZuClj mixed with K sesquicarbonate 
 (Deville, A. Ch. [3] 32, 75). 
 
 Zinc and sodium carbonate 
 SZnCOs.SNajCOa (?). Small crystals, obtained 
 as potassium salt (Deville). 
 
 Zirconiom carbonate. Excess of alkaline 
 carbonate solution produces a pp. in solutions 
 of Zr salts, soluble in Na2(orK.)C03Aq. Com- 
 position seems to be variable (Hermann, Klap- 
 roth, Vauquelin). 
 
 Thio-cakbonio acid. H2CS3. Mol. w. un- 
 known. A dark yellow very strongly smelling 
 oil; obtained by adding cold dilute HOlAq to 
 E2CSJ or NajCSj ; very easily decomposed, by 
 heating, to CSj andH^S (Zeise, S. 41, 105 ; Ber- 
 zelius, P. 6, 450). 
 
 Thio-oarbonates. These salts have the 
 compositionMjCSa, or MCSj, when M2 = Naj &c., 
 and M = Ca &c. A few basic salts are also 
 known. The composition of the salts of the 
 alkali and alkaline earth metals has been de- 
 termined; several other thio-carbonates seem 
 to be produced in the reactions between solu- 
 tions of metaUio salts and K^CSaAq or 
 Na2CS3Aq, but the composition of very few of 
 these thio-carbonates of the heavy metals has 
 been determined. Thio-oarbonates are formed 
 by reactions between CS^ and aqueous solutions 
 of the monosulphides of the alkali and alkaline 
 earth metals, MJS and MS. By using MOHAq 
 and CSj, thio-carbonates and carbonates are 
 formed simultaneously; with MO^H^Aqand CS, 
 (M = Ca,Ba,Sr) basic thio-carbonates are formed, 
 e.g. CaCS3.2CaO2Hj.6H2O. NHjAq reacts with 
 CS2 to form (NHJ2CS., and (NHj)CNS (G61is, J. 
 1861. 340). The thio-carbonates are yellow, 
 red-yellow, brown, or black, solids ; the hydrated 
 salts are yellow. The salts of the alkali and 
 alkaline earth metals are soluble in water ; 
 those of the heavy metals are more or less solu- 
 ble in excess of M2CS3Aq (M = Na &o.). The 
 thio-carbonates are not very stable ; those of 
 the heavy metals easily decompose to metallic 
 sulphide and CSj ; cone, solutions of the alkali 
 salts change to HjS and alkali carbonates when 
 boiled, dilute solutions decompose by standing 
 in air to carbonates and S. Heated alone, most 
 of them give metaUio sulphide and CSj ; KjCS, 
 gives K2S3 and C. The thio-carbonates have 
 been chiefly investigated by Zeise {S. 41,105) ; 
 Berzelius (P. 6, 450) ; Walker (O. N. 30, 28) ; 
 Sestmi ((?. 1871. 473 ; B. 5, 327) ; G6Hs (/. Ph. 
 [3] 39, 95 ; G. S. 81, 282) ; P. Th^nard (O. B. 
 79, 673) ; Husemann {A. 123, 67) ; Mermet 
 (C. B. 81, 344). 
 
 Ammonium thiocarbonate (NHJjCSj. Pre- 
 pared by mixing a saturated alcoholic solution 
 of NH3 with ^ its vol. CS2, coohng after the 
 liquid has become brown, pouring off hquid, 
 and washing the crystals several times with 
 alcohol, then with ether, and pressing between 
 paper (Zeise). Yellow crystals, v. sol. in water, 
 insol. in alcohol or ether ; may be sublimed in 
 dry ah: by gentle warmmg ; very hygroscopic. 
 Aqueous solution heated to 90°-100° evolves 
 H2S, and NH^CNSAq remains (Gffis). 
 
 Barium thiocarbonate BaCSj. By shakmg 
 BaSAq with CSj, washing with alcohol, and 
 drying invactio. 
 
 Calcium thiocarbonate. CaCS3. By digesting 
 CaS with excess of CSj, and evaporating in vacuo. 
 Citron-yellow ; sol. in alcohol or water ; milk 
 of lime shaken with CS2 gives an orange-red pp. 
 of CaCSs.2CaO2H2.6H2O, and this at 30° gives 
 red liquid from which red crystals of 
 CaCS3.3CaO2H2.7H2O separate (Walker; Sestini). 
 
 Potassium thiocarbonate. K2CS3. When 
 KjSAq is digested with CS2 at 30° in a closed 
 vessel, or CS, is dissolved in a cone, alcoholic 
 solution of KjS, yellow deliquescent crystals 
 separate ; dried at 60°-80° these give K2CS3, a 
 red-brown solid; v. sol. in water, si. sol. in 
 alcohol. 
 
 The other thiooarbonates which have been 
 fairly well examined and analysed are those of 
 Lithium, Magnesium, Sodium, and Strontium. 
 Thiooarbonates of Bi, Cd, Cr, Co, Au, Fe, Pb, 
 Mn, Hg, Ni, Pt, Ag, Sn, Zn, seem also to be 
 formed by adding the solution of an alkali thio- 
 carbonate to a solution of a salt of each of these 
 metals. M. M. P. M. 
 
 CAKBONIC ANHYDRIDE COj v. Cabbon, 
 
 OXIDES OF, 
 
 CARBON TETRA-CHLORIDE v. supra and 
 Tetea-chloko-methane. 
 
 CARBONIC ETHERS. There are three 
 classes of carbonic ethers: viz. acid ethers 
 CO(OE)(OH), normal ethers C0(0B)2, and 
 ethers of ortho-carbonic acid C(OE)j. In these 
 formula E may be any alkyl. They are de- 
 scribed as salts of the alkyl: e.g. Ethyl cak- 
 
 BONATB, MeIHIL CARBONATE, PhENYIi CARBONATE, 
 &0. 
 
 Orthocarbonic ethers are formed by the 
 action of sodium alcoholates on chloropiorin 
 (Williamson a. Basset, A. 132, 54). They are 
 converted by ammonia into guanidine. 
 
 Normal carbonic ethers. 
 
 Formation. — 1. From alkyl iodides and 
 silver carbonate (de Clermont, A. 91, 375). — 
 2. By the action of Na, K, soUd NaOEt (J mol.) 
 or KOEt (^ mol.), upon alkyl oxalates (1 mol.) 
 (Ettling, A. 19, 17 ; Lowig a. Weidmann, A. 36, 
 301 ; Geuther, Z. 1868, 656 ; Cranston a. Ditt- 
 mar, Z. 1870, 4).— 3. By the action of alkyl 
 chloroformates upon sodium alcoholates, e.g. : 
 
 Cl.CO.OEt + NaOMe = NaCl + MeO.CO.OEt 
 (Eoese, A. 205, 240). The mixed ether prepared 
 from ethyl chloroformate and sodium methylate 
 is identical with that from methyl chloroformate 
 and sodium ethylate.— 4. From COClj and sodium 
 alcoholates. 
 
 Properties. — The boiling-points and specifio 
 gravities of the fatty carbonic ethers are aa 
 follows (Eoese, A. 205, 244):— 
 
 Ether 
 
 Boiling-point 
 
 S.G. 
 
 Me^COa 
 
 90-6° 
 
 1-065 at 17° 
 
 MeEtCOa 
 
 109-2° 
 
 1-00 at 27° 
 
 lEtfiO, 
 
 125° 
 
 -97 
 
 MePrCO, 
 
 130-8° 
 
 •98 at 27° 
 
 PrjCOs 
 
 168-2° 
 
 •95 at 17° 
 
 Me(PrCH2)C0, 
 
 143-6° 
 
 •95 at 27° 
 
 Et(PrCH2)C03 
 
 160-1° 
 
 •93 at 27° 
 
 (PrCH2)2C03 
 
 190-3' 
 
 -92 at 15° 
 
 Et(C,Hn)CO. 
 
 182-8° 
 
 •92 at 27° 
 
 (C,H„)2C0, 
 
 228-7° 
 
 •91 at 15° 
 
704 
 
 CARBONIC ETHERS. 
 
 Reacticms. — 1. Ammonia converts the ethers 
 B2CO3 into carbamio ethers, and finally into 
 nrea. — 2. PCI5 forms ohloroformio ethers. In 
 mixed ethers EE'COj the alkyl which is con- 
 verted into chloride is the smaller of the two : 
 Et(C,H„)CO, + PCI5 = EtOl + CICO AH, , + POCI3 
 The amides of the ohloroformates, which may be 
 regarded as half chloride half amide of carbonic 
 acid (carbamic chlorides), are obtained by the 
 action of COGI2 upon the hydrochlorides of 
 amines, e.g. COClj + NEtH;, = COCl(NEtH) + HCl 
 (Gattermann a. Schmidt, B. 20, 118) cf. CmoKO- 
 roBMio ACID. — 3. When an alkyl carbonate is 
 heated with an alcohol containing a heavier 
 alkyl, the heavy albyl displaces the light one (E.) . 
 
 Chloro - imido - carbonic ethers C1N:C(0B)2. 
 These are formed by leading chlorine into a 
 cooled solution of NaOH and EON in an 
 alcohol (Sandmeyer, B. 19, 862). They are 
 crystalline, and converted by dilute acids or by 
 aqueous HjS into the corresponding carbonic 
 ethers. Aqueous potassium arsenite reduces 
 them to imido-earbonie ethers {cf. Chloeo-imido- 
 
 CAEEONIO ETHEKS). 
 
 Imido-oarbonic ethers HN:C(0E)2. Prepared 
 as above, are alkaline liquids, readily decom- 
 posed by aqueous acids into NH3 and carbonic 
 ethers {cf. Imieo-caebonio ethees). 
 
 CAEBO-DI-NICOTINIC ACID v. Ptkidine 
 
 TKI-CABEOXYLIO ACID. 
 
 CARBONIC OXIDE. Name usually given to 
 CO, V. Cakbon, oxides op. 
 
 CAEBONIC - OXIDE - POTASSIUM v. po- 
 tassium salt of Hexa-oxy-benzene. 
 
 CAHBONODS OXIDE CO,^.Caebon, OXIDES OE. 
 
 CAEBON TETEA-IODIDE v. Tetea-iodo- 
 
 MEIHANE. 
 
 CAEBONPIMELIC ACID v. iso-Pentane tki- 
 caeboxylio acid. 
 
 CAEBONYL. The divalent radicle C;0. 
 When attached to two carbon atoms the product 
 is a ketone, when attached to one carbon atom 
 and to hydroxyl the compound is a carboxylio 
 acid ; when attached to one carbon atom and 
 to one hydrogen atom the product is an aldehyde. 
 Two or three carbonyls attached to CH render 
 the hydrogen displaceable by metals. Many 
 carbonyl derivatives of amido- compounds are 
 described under the amido- compounds from 
 which they are formed by the action of COCI2. 
 
 CAEBONYL - DI - ot - AMIDO- DI - BENZOIC 
 
 ACID V. Dl-PHENYL-UEEA-DI-m-CAEBOXYLIC ACID. 
 
 CAEBONYL - AMIDO - PHENOL v. Anhy- 
 dride of OXY-PHENYL-CAEBAMIO ACID. 
 
 CAEBONYL BEOMIDE v. Caebon, oxy-beo- 
 
 MIDE OE. 
 
 CAEBONYL DI -BIURET v. Bidbei. 
 
 CARBONYL-CAEBAMIC ETHER CjHjNOa 
 i.e. CO:N.CO.OEt or (C4H5N03)3. Carboxethyl 
 cyanate or cyanurate. [119°]. Formed by 
 the action of chloroformio ether on potassium 
 cyanate. If dry ether be present a second com- 
 pound C.oHisNjOs [107°] is also formed. Ehom- 
 bio plates, si. sol. cold alcohol, v. sol. CHCI3. 
 When heated with water to 100° it loses COj 
 forming cyanuric ether. Its formula should 
 therefore possibly be trebled. The compound 
 Ci,H|5N305 when distilled with water behayes 
 Biiuilarly (Wurtz a. Henniger, O. B. 100, 1419 ; 
 A. Ch. IG] 7, 132). 
 
 Com,pounds with cyanic ether 
 
 (o) C.oHjjNjOj or (C0:NC02Et){C0.NEt), 
 [107°]. Formed as above, or together with car- 
 boxy - carbamic (imido - diformio) ether [50°],. 
 (226°) when the ether is wet. Needles, whioh> 
 lose CO2 on heating, yielding cyanuric ether 
 (W. a. H.). 
 
 (6) Oi.H.jNsO, i.e. (CO.N.C02Et)2(CONEt). 
 [123°]. Formed together with imido-diformio: 
 ether when KCNO acts on an aqueous ethereal 
 solution of ohloroformic ether for a long time 
 On distilling it forms cyanuric ether (W. a. H.).. 
 
 CAEBONYL CHLORIDE v. Caebon, oxyohlo- 
 
 BIDE OE. 
 
 CAEBONYL-GTJANIDINE v. Amido-dioyanio 
 
 ACID. 
 
 CAEBONYL DI-PHENYLENE v. Diphenyl- 
 
 BNB KETONE. 
 
 CARBONYL-DI-PHENYL OXIDE v. Di- 
 
 PHENYLENE KETONE OXIDE. 
 
 CAEBONYL-PYRROLE CsHsN^O i.e. 
 °°<NCh'- Di-ietrol-urea. [63°]. (0. 288°). 
 Formed, together with di-pyrryl-ketone, by the 
 action of carbonyl chloride upon pyrrol- 
 potassium (Giamician a. Magnaghi, B. 18, 414 ;, 
 1829). Large monoclinic crystals, a:6:c' 
 = 1-1688:1: -7189. V. sol. alcohol and ether, 
 insol. water. By heating to 250° it is trans- 
 formed into a mixture of pyrroyl-pyrrol' 
 C,H,N.C0.CjH3NH and di-pyrryl - ketone 
 C0(0,H3NH)2. 
 
 CAEBONYL SULPHIDE v. Caebon, oxysul- 
 
 PHIDE OF. 
 
 CAEBONYL-UEEA v. Ueea. 
 CAEBOFEIEOCENE v. Peteooene. 
 CAEBO - DIPHENYLENE v. Diphenylenb 
 ketone. 
 
 CAEBO-DIPHENYLIMIDE v. Di-phenyl- 
 
 OTAN AMIDE. 
 
 CAEBO-TEI-PHENYL-TEIAMINE v. Dl- 
 
 phenyl-amido-benzamidine. 
 
 CAEBO-PHENYL-TOLYL-IMIDE v. Phenyl 
 
 TOLYL OTANAMIDE. 
 
 CAEBO-DI-PROPYL-DI-PHENYL-IMIDE v. 
 
 Dl-PEOPYL-DI-PHENYL-OYANAMIDE. 
 
 CARBO - PYEIDENIC ACIDS v. Pyeidine 
 
 CABBOXYLIO ACIDS. 
 
 CAEBO-PYEOTEITAEIC ACID v. Di-mbthyl- 
 
 FUEFUBANE CAEBOXYLIO ACID. 
 
 CAEBO-PYEEOLIC ACID v. Pyeeol-cae- 
 
 BOXYLIO ACID. 
 
 CAEBO-PYEROLYL-FORMIC ACID v. 
 
 Pybeyl-glyoxylio aoid. 
 
 .CH:CH 
 CAEBOSTYEIL C,H,NO i.e. CeH,< I or 
 
 \nh.co 
 
 ,CH:CH 
 ^e^i\ I • Lactam or lactim of 0- 
 
 \N= C(0H) 
 amido-cinnamic acid. (Py-i)-Oxy-guinoline. 
 [199°]. 
 
 Formation. — 1. By boiling o-amido-cinnamio 
 aoid with HClAq (Chiozza, C. B. 34, 698 ; A. 83, 
 117 ; Tiemann a. Oppermann, B. 13, 2070).— 2. 
 Obtained by reducing tri-ohloro-oxy-quinoline 
 with HI (Eotheit, J.pr. [2] 29, 300). 
 
 Preparation. — o-Nitro-oinnamic ether is 
 heated with alcoholic (NHJjS to 100° under 
 pressure, the solution is evaporated to dryness, 
 taken up with NaOH and the carbostyril ppd. 
 
CARBOXY-BENZYUMALONIC ACID. 
 
 705 
 
 by COj (Friedlander a. Ostermeyer, B. U, 
 
 Properties.— Frisms (from alcohol) ; or long 
 tliin threads (containing aq) from dilute aqueous 
 solution. May be sublimed. V. si. sol. cold, 
 V. sol. hot, water. Sol. alcohol and ether, 
 ilkaline KMnO^ oxidises it to isatin and oxal- 
 oxyl-amido-benzoic acid (carbostyrilio acid). 
 COjH.0„H,.NH.C(OH)2.CO,H [200°]. 
 
 Salts. — The K and Na salts form easily 
 soluble plates. The barium salt A'^Ba: spar- 
 ingly soluble plates. 
 
 Methyl ether : (247° uncor.). Colourless 
 liquid. Smells of oranges. 
 
 Ethyl ether: [below 0°]. (256°). Prepared 
 by the action of ethyl iodide on sodium-car- 
 bostyril, or of alcoholic KOH on ohloro-quino- 
 line. Volatile with steam. Colourless liquid. 
 Sweet smell. — B'HOl : hygroscopic crystals. 
 
 Phenyl ether: [69°]. Sublimable. Glis- 
 tening plates. Sol. ordinary solvents (Fried- 
 lander a. Ostermayer, B. 15, 335). 
 
 Beference. — Amido-oaeeostykil, Bromo-oab- 
 BOSTTKIL, &c. Hydrocarbostyril is described 
 under AMrDO-PHENYL-PROPioNio acid. Ethyl- 
 pseudo-carbostyril is described as (Py. 3, 4)-0xy- 
 
 ETHYL-QUINOliINE. 
 
 CABBOSIYBIL-CABBOXYLIC ACID v. Oxy- 
 
 QUINOLINE-OABBOXYLIO ACID. 
 
 CARBOTHIALDINE CsH^N^Sj. Crystals 
 which separate on adding CS2 to an alcoholic 
 solution of aldehyde-ammonia (Eedtenbaoher a. 
 Liebig, A. 65, 43). Also from aldehyde and 
 ammonic thio-carbamate (Mulder, A. 168, 235). 
 Insol. water. Sol. acids. 
 
 Beactions. — 1. HCl splits it up into aldehyde, 
 NH3 and CSj.— 2. KMnO, forms H^SOj, CO^, KCy, 
 and acetic acid. — 3. HGl and FcjCl, forms NH^Cl, 
 aldehyde, and NH^.CS.Sj.CS.NHj (Guareschi, 
 O. 8, 246 ; B. 11, 1383). 
 
 CARBO-TEI-THIO-HEXABKOMIDE v. Hexa- 
 
 BKOMO-DI-METHYL TRI-SULPHIDE. 
 
 C ASBO - TOLTLENE-DI - PHENYL - TETKA- 
 
 MIKE V. Dl - PHENYL -XOLYLENE- TETEA-AMIDO- 
 UEIHANE. 
 
 CARBO-DI-TOLYIi-IMIDE v. Di-tolyii-cyan- 
 
 AMIDE. 
 
 DICARBOTHIOHIC ETHER S(COjEt)j. 
 (180°). From ClCOjBt and alcoholic Na^S. 
 OU; decomposed by baryta- water or alcoholic 
 KOH into BtjS and CO., (V. Meyer, B. 2, 298). 
 
 CABBO-VALEETHIALDINE CnHjaN^Sj. 
 [109°]. (G.) ; [117°] (S.). V.D. 60. From iso- 
 valeric aldehyde (5g.), CS, (3g.) and aqueous NHj 
 (Schroder, B. 4, 469). From isovaleric alde- 
 hyde and ammonium thio-carbamate (Mulder, 
 A. 168, 237). Colourless needles (from alcohol). 
 FejOlj on warming gives the sulphooyanide re- 
 action. KMnO< forms HON, HjSO^ and valeric 
 acid. Fe.Clg and HCl form in the cold a yeUow 
 powder (SlCSNHj)^. Carbovaleraldine may there- 
 fore be dithiooarbamate of di-valerylidene am- 
 monium H2N.CS.SN(CH.CHj.CHMej)2 (Guares- 
 chi, A. 222, 310; ff. 13, 500). 
 
 CABBOVINIC ACID is Hydrogen Ethyl 
 
 OABBONATE (o. V.). 
 
 CARBOXAMIDO - BENZOIC ACID v. Di- 
 
 FHENYL-nREA DI-CARBOXYLIC ACID. 
 
 CARBOXAMIDO - CAEBIMIDAMIDO - BEN- 
 ZOIC ACID V. p. 157. 
 Vol. I. 
 
 CARBOXAMIDO - CYANAMIDO - BENZOYL 
 
 V. p. 155. 
 
 CARBOXAMIDO-HIPPURIC ACID v. p. 164. 
 CARBOXAMIDO-o-OXY-BENZOIC ACID 
 
 CijHijNjO,. A product of the action of urea on 
 amido-salioylic acid at 200° (Griess, J. pr. [2] 
 1, 235). Minute needles, v. si. sol. most sol- 
 vents. 
 
 CARBOXETHYL CYAN ATE or CYANURATE 
 V. Cabbonyl-oarbamio ethek. 
 
 CARBOXY-ACETO-GLTTTARIC ACID v. 
 Methyl propyl ketone tbi-oarboxylm acid. 
 
 ■/-CARBOXY-o-AMIDO-BENZOIC ACID v. 
 
 ISATOIO ACID. 
 
 y-Carbozy-Tii-ainido-beiizoic ether v. p. 157. 
 CARBOXY-BENZENE PHOSPHONIC ACID 
 
 C02H.CjH,.PO(OH)2. [above 300°]. Prepared 
 by the oxidation of ^-toluene phosphonic acid 
 OeH,(CH,).PO(OH)2 with KMuO,. Needles or 
 tables. V. sol. water, m. sol. aqueous HGl or 
 alcohol. On heating to 300° it decomposes, 
 giving metaphosphoric and benzoic acids. 
 
 Salts. — A'"Ag3 : slightly soluble pp. — 
 A"'H2Kaq : fine needles sol. water, si. sol. alco- 
 hol. — A"'2H5K : long prisms si. sol. water. 
 
 Chloride GJ[1,{C0C\)(P0G\). [83°]. (315°). 
 Colourless crystals. Heated with PClj it gives 
 2)-ohlorobenzoyl chloride PCI, and POCI3. 
 
 Trimethyl ether A"'Mej: thick liquid (Mi- 
 ohaelis a. Panek, B. 14, 405). 
 
 CARBOXY-BENZOYL-ACETIC ACID v. AoB- 
 tophenone di-oaeboxtlio acid, p. 37. 
 
 CARBOXY - BENZOYL - AMIDO - BENZOIC 
 ACID V. Phthaloxyl-amido-benzoio acid. 
 
 CARBOXY-BENZOYL-ETHENYL TRI-CAK- 
 BOXYLIC ACID v. Phenyl-ethyl-ketone tetba- 
 
 OARBOXYLIC AOtD. 
 
 CARBOXY -BENZOYL -PROPIONIC ACID 
 C„H,„05 i.e. C02H.C.H,.CO.CjHi.C02H. The 
 free acid is unstable, but its Na salt is 
 formed by dissolving phthalyl-propionio acid in 
 NaOHAq (Gabriel a. Michael, B. 11, 1680). 
 
 - CARBOXY - BENZYL - ACETO - ACETIC 
 ETHER 
 
 C„H,A »•«■ C02H.CeH,.CH,.CHAc.C0^t, 
 [92°]. Formed by reducing phthalyl-aceto- 
 acetic ether with zinc-dust in glacial acetic acid 
 (BQlow, A. 236, 190). Needles; v. sol. hot 
 water, alcohol, ether, and HOAo. The ammo- 
 nium salt melts at [121°]. Boiling baryta- 
 water converts it into benzyl-acetone o-car- 
 boxylic acid. 
 
 Phenyl hydrazide C^oH^NjOj. [235°]. 
 Decomposes slowly, forming alcohol and 
 
 C„H,„N.A [229°]. 
 
 o-CARBOXY-BENZYL-MALONIC ACID 
 
 'E.O.p.CgB.fiB^.CB.(COfi\. Formed by saponifj 
 ing o-carboxy-benzyl-malonio ether (WislicenuSi 
 A. 242, 37). Prisms. V. sol. hot, si. sol. cold, 
 water. Heated to 190° gives off CO., and forms 
 o-carboxy-phenyl-propionic acid [166°]. 
 
 Salt. — A"'Ag3. V. si. sol. hot water. 
 
 Di-ethyl ether 
 C02H.C„Hj.CHi.CH(C0^t)j. [86°]. S. -045 at 
 17°. Formed by reducing phthalyl maJonic 
 ether with acetic acid and zinc fWislicenus, A. 
 242, 32). Fine needles. V. e. sol. ether and hot 
 alcohol, si. sol. hot water. 
 
 Salts. — A'Ag: white needles. — A'Na: deli- 
 quescent needles. V. sol. alcohol, insol. ether. 
 
 Tri-ethyl. ether A"'Et3. (250°) at 4.5 mm. 
 
 ZZ 
 
ro6 
 
 CARBOXY-OAEBAMIO ETHER. 
 
 CAEBOXT-CARBAMIC ETHEE CaH„NOj 
 i.e. NH(C02Et)j. [50°]. (226°). 
 
 FormaHon. — 1. By the action of ohloroformic 
 ether on potaasium oyanate in the presence of 
 wet ether. A second compound Gi^K^^'Sfl, [107°] , 
 insoluble in water, is also formed, while a small 
 quantity of yellow oil [170°] is found in the 
 aqueous extract. If absolute alcohol be used 
 instead of ether, the second compound is not 
 formed. — 2. Ohloroformic ether (34 gr.) and car- 
 bamic ether (24 gr.) are heated together at 120°. 
 
 Properties. — Long prisms. It forms biuret 
 and alcohol when made with aqueous NHj. The 
 salt CjH,„NOiAg crystallises in cubes (Wurtz a. 
 Henniger, A. Ch. [6] 7, 135). 
 
 CAEBOXY-CINNAMIC ACID v. Cinnamio 
 
 i.e. OeH5.C(CO,H):CH.CO.CH(CO,H).C8H5. 
 Formed as u, by-product in the reduction of 
 pulvic acid to dihydrooornicularic acid. It was 
 not isolated, but was converted into the lactone 
 by means of acetic anhydride. 
 
 Carbozy-comicularic-lactone 
 
 00 CO^H 
 
 C,,H„0, or III. [215°]. 
 
 C,H5.C:CH.O : C.O,H, 
 Long felted needles or short prisms. In cold 
 aqueous NH, or alkaline carbonates it dissolves 
 forming salts of the formula OijHuOjM, but on 
 heating it gives salts of carboxy-oorniculario 
 acid O.sH.jOsM^ (Spiegel, B. 15, 1546). 
 
 CABBOXY-CYANAHIDO-BENZOYL V. p. 155. 
 
 DI-CAEBOXY-GLITTACONIC ACID C,H,Os. 
 Pr(ypylene tetracarboxylic acid. 
 
 Ethyl ether (CO,Et)j.0H.CH:0(0O,Et)2. 
 (270°-280°). S.G. 1-131 at 15°. Prom its sodium 
 salt by HCl. OU, soluble in alcohol or ether. 
 Boiled with HCl it gives off COj and forms 
 glutaconic acid (q. v.) and iso-aconitic ether, 
 NaOH acts similarly. Sodium derivative 
 (C0jEt)2.CNa.CH:C(C02Et)2. [260°]. From 
 malonic ether, KaOEt and chloroform (Oonrad a. 
 Guthzeit, A. 222, 251): 2(C02Et)CNa2 + CHCl3 = 
 (COjEt)2.CNa.CH:C(C02Et)j + 3NaCl. Bright 
 yellow prisms. Insol. ether, si. sol. cold water 
 or cold alcohol, v. sol. hot water or hot alco- 
 hol. Gives a violet colour with ferric chloride, 
 and pps. with metallic salts. Sodium amal- 
 gam reduces it to dicarhoxy-glutaric acid, 
 XC0^)J3R.GE^.CR(C0^B.), [167°]. When this 
 acid is heated it gives off CO^, becoming glu- 
 taric acid. 
 
 Methyl - di - carbozy - glutaconic ether. — 
 Sodium di-carboxy-glutaconic ether heated with 
 alcoholic Mel at 150° forms methyl-di-oarboxy- 
 glutaconic ether, (C02Et)2.CMe.CH:C(C02Et)2, 
 an oil, which on saponification gives rise to 
 (C02H)2CMe.CH:C(C02H)2, and this readily splits 
 off CO2, forming methyl-gVutaconic acid, 
 C02H.CHMe.CH:CH.C02H [137°]. Methyl glu- 
 taconic acid forms white crystals ; v. sol. water, 
 alcohol, or ether. 
 
 Benzyl-di-carboxy-glutaconic ether 
 (C02Et)j.C(C,H,).CH:C(C02Et)2, [78°], is formed 
 in a sinular way, using benzyl chloride. Insol. 
 water, v. sol. hot alcohol, ether, or cono. H^SO,. 
 When saponified by caustic soda it gives off OO2 
 carbonic acid and forms hemyl-glutaoon/ic acid 
 CO,H.CH(C,H,).CH:CH.CO,H, [145°]. 
 
 DI-CAEBOXY-GLTJTAEIC ACID v. Di-OAB- 
 
 BOXT-OLnTAOONIO Aoro. 
 
 CABBOXYL. Oxatyl. The monovalent acid 
 radicle COjH i.e. CO.OH. Its hydrogen is always 
 displaceable by metals, cf. Aoins. 
 
 CARBOXYLIC ACID, so-called, v. Dl-OXY- 
 
 BENZENE-W-QUINONB. 
 
 Di- hydro -carboxy lie acid v. Tbtba-oxi- 
 
 QUINONE. 
 
 Tri-hydro-carboxylic acid «. Hexa-oxy-benz- 
 
 ENE. 
 
 Ozy-carbozyllc acid v. Benzene tbi-quinone. 
 iz-CAEBOXY-OXAMIC ACW Di-ethyl ether. 
 C,H„NOs i.e. C02Et.NH.C0.C02Et. [45°]. From 
 OlCO.COjEt and oxamic ether (Saloman, J" .pr. 
 [2] 9, 292). Needles (from ether); sol. water 
 and alcohol. 
 
 o-CAEBOXY-FHENOXY-AGETIC ACID 
 CsH,(CO^).O.CH2.C02H. Carboxy-phenyl-gly- 
 colUc acid. [187°]. Formed by oxidation of 
 o-aldehydo-phenoxy-acetic acid with KMnO,. 
 White needles. Sol. alcohol, ether, and hot 
 water. — A'Ag^ : white, sparingly soluble pp. 
 
 Di-ethyl ether A"Et2: liquid. 
 
 Di. amide C,HsO(CO.NH;,)2. [158°]. Long 
 yellow needles, sparingly soluble in ether, benz- 
 ene, and hot water, v. sol. chloroform and hot 
 alcohol (Bossing, B. 17, 2995). 
 
 m-Carboxy-pheuozy-aeetic acid 
 C,Hj(COja).O.CH2.CO,H[l:3]. [206°]. Prepared 
 by oxidation of TO-aldehydo-phenoxy-acetic acid 
 with KMnO,. Needles; v. sol. alcohol, ether, 
 and acetic acid, si. sol. cold water. — A"Ag2: crys- 
 talline (ELkan, B. 19, 3044). 
 
 ^-Carbozy-pheuozy-acetic acid 
 CeH,(C02H).O.CH2.CO,H [1:4]. [278°]. Pre- 
 pared by oxidation of j)-aldehydo-phenoxy-aoetic 
 acid with EMnO,. White needles ; v. sol. alco- 
 hol, ether, and acetic acid, more sparingly in 
 benzene, chloroform, and ligroiin, si. sol. cold 
 water. 
 
 Salts. — A"Ag2: white sparingly soluble pp. 
 The Pb, Cu, and Fe salts are sparingly soluble 
 pps., the Cu and Ba salts are soluble (Elkan, B, 
 19, 8044). 
 
 o-CAEBOXY-PHEinrL-ACETIC ACID 
 C5Hj(CO^H)CH2.C02H [1:2]. JSomophthalic acid, 
 Phenyl-acetw-carboxylic acid. IsvmMc acid. 
 [174°]. Formed by saponification of benzyl- 
 eyanide-o-oarboxylic acid by boiling with dilute 
 KOH. Colourless crystals. V. sol. alcohol and 
 hot water, insol. benzene. 
 
 Salts.— A"Ag2: insoluble amorphous pp. — 
 A"Ca 2aq : sparingly soluble crystalline powder. 
 — A"Ba : easily soluble crystals (Wislicenus, B. 
 18, 173). 
 
 .CH^.CO 
 
 Anhydride CsH<^ I . [141°]; long 
 
 \co-o 
 
 prisms ; v. sol. ether and chloroform. Formed 
 by the action of acetyl chloride on the acid. 
 
 Ethyl ether A"Et2 : (292°); thick aro 
 matic oil (Gabriel, B. 20, 2499). 
 .CH2.CO 
 
 Imide C,Hj^ I di-oxy-isoquinoUne) : 
 \C0 . NH 
 [c. 233°]. Formed by dry distillation of the 
 ammonium-salt. Short colourless needles (from 
 alcohol or acetic acid). Sublimes in long crys- 
 tals. SI. sol. alcohol. Dissolves in aqueous 
 caustic alkalis. Heated with POCl, at 150°- 
 
CARBOXY-PHENYL-OXAMIO ACID. 
 
 707 
 
 170° it is converted into di-ohloro-iso-quinoline. 
 
 .CHj.CO 
 
 Methyl-imide CjHj^ I : [123°]: 
 
 \C0.NMe 
 
 (314°-318°) ; long colourless needles ; v. sol. 
 
 ordinary solvents. Dissolves in aqueous alkalis. 
 
 Obtained by dry distillation of the methylamine 
 
 salt of the acid. By Mel and methyl-alcoholic 
 
 KOH at 100° it is converted into a tri-methyl 
 
 ^CMe„.00 
 
 derivative 0^^ 
 
 /^ 
 
 I , [103°], which is 
 
 *\C0 . NMe 
 also obtained by methylatiou of the imide 
 (Gabriel, B. 19, 1654, 2354, 2363). The imide 
 and methyliimde combine with diazo-benzene in 
 alkaline solution. 
 
 Amic acid CJB.t(COJS).CB.^.COTiiB.^ (homo- 
 phthalamio acid) : [187°] ; colourless needles. 
 Formed by slowly warming benzyl-cyanide-o- 
 oarboxylic acid OeH,{C02H).CH2.CN with cone. 
 H^SOj to 70°, and pouring into water. 
 
 Amic methyl ether 
 C,H,(COjMe).CH3.CONH2 : [112°] ; crystalline 
 solid (Gabriel, B. 20, 1203). 
 
 Benzene-azo-carboxy-phenyl-acetic-imide 
 .OH— N„— C^H^ 
 
 CMi 
 
 '\ 
 
 ■CO.NH.CO 
 
 [260°]. Formed by the 
 
 action of diazo-benzene chloride upon an alka- 
 line solution of the imide of carboxy-phenyl- 
 acetic acid. Orange-yellow needles (Gabriel, B. 
 20, 1205). 
 
 CABBOXY -PHENYL - BENZ - GLYCOCYAMI- 
 DINE V. Benzoltcooyamidine. 
 
 CAEBOXY-PHENYL-GLYCOLIIC ACID v. 
 Carboxy-phenoxy-acetic acid. 
 
 C&SBOXY-FHENYL-MALONAMIC ACID. 
 
 Ethyl ether CO^EtGH^.CO.T!fS.G^E.^.CO.,B.. 
 [173°]. A product of the action of malonic 
 ether on m-amido-benzoic acid (Schiff, A. 232, 
 144 ; B. 17, 403). Silvery needles. When 
 heated it breaks up into malonic ether and 
 malonyl-di-amido-di-benzoic acid : 
 
 2C0jEt.CH;,.C0.NH.C,Hj.C0jH = 
 
 coj:t.CH;,.co2Et -i- ch2(conh.c„h,co2H)j. 
 
 o - CAEBOXY - PHENYL - METHYL - ACETIC 
 ACID 08Hj(C02H).CHMe.C02H. a-Methyl-honw- 
 o-phthalic acid. Hydratropic-o-carboxylic acid. 
 [147°]. Formed by heating the imide with fuming 
 HCl at 200°. Colourless crystalline powder. — 
 A"Ag2 : crystalline pp. 
 
 .CHMe.CO 
 
 Imide C.H,^ | 
 
 \C0 NH 
 
 Di-oxy-methyl-isoquinoline. [145°]. Formed 
 by heating o-oyauo-phenyl-methyl-aceto-nitrile 
 CsH4(CN).CHMe.CN with cone. H^SO^ at c. 130° 
 and pouring into water. Glistening prisms. 
 Can be distilled undecomposed. Dissolves in 
 aqueous alkalis. By digestion with alcoholic 
 KOH and Mel it is converted into the methyl- 
 imide of carboxy-phenyl-di-methyl-acetic acid 
 
 .CMej.CO 
 C H.< I • By POCI3 it is converted 
 
 ' \C0 . NMe 
 into (Py. 2:4:l)-di-chloro-methyl-isoquinoline, 
 whilst (Py.4:2:l)-ohloro-oxy-methyl-isoquinoline 
 is formed as a by-product (Gabriel, B. 20, 2503). 
 
 o-Carboxy-phenyl-di-methyl-acetic acid 
 C H,(COjH).CMe2.C02H. Di -methyl -Jiomo-o- 
 
 Anhydride OjHj^ 
 
 ^CO- 
 
 phthalic acid. [c. 123°]. Obtained by dissolving 
 the anhydride in boiling aqueous NaOH and 
 ppg. with HCl. On heating it is reconverted 
 into the anhydride. By distillation with soda 
 lime it gives isopropyl-benzene. — A"Ag2: crys- 
 talline pp.— A"K2aq: plates. 
 
 CMe,— 00 
 
 I . [85°]. 
 
 
 (312°) at 760 mm. Prepared by heating the 
 imide or methylimide with fuming HCl (4 pts.) 
 at 210° for 4 or 5 hrs. Flat crystals, slowly 
 dissolved by aqueous alkalis, forming salts of the 
 acid. 
 
 /CMcj— CO 
 Imide 0^3.,^ . I (di-methyl-homo- 
 
 \C0 NH 
 
 phthaUmide) : [120°] ; (318°) at 770 mm. Pre- 
 
 pared by the action of methyl iodide on a solu- 
 
 tion of the imide of oarboxy-phenyl-acetic acid 
 
 in methyl-alcoholic KOH at 100°. Flat needles. 
 
 ^CMe2.C0 
 
 Methyl-imide C^Hj^^ I (tri- 
 
 \C0— NMe 
 
 methyl-homo-phthalimide). [103°]. (295°) at 
 
 770 mm. Formed by further methylation of 
 
 the preceding imide or of the methylimide of 0- 
 
 .CH2.CO 
 oarboxy-phenyl-acetic acid C^HjC^ | 
 
 \OO.NMe 
 Long needles. Slowly sublimes at 100°. V. sol. 
 ordinary solvents, insol. alkalis (Gabriel, B. 19, 
 2363 ; 20, 1198). 
 
 CARBOXY-PHENYL-METHYL-;'.m-PYEEYL. 
 BENZOIC ACID 0„H,5NO. i.e. 
 HOi,C.C:CMe. 
 
 I >N.C,Hj.C02H [210°]. Obtained 
 
 HC:CPh/ 
 by saponification of its mono-ethyl-ether which 
 is obtained by several days' standing of an acetic 
 acid solution of acetophenone-aceto-aoetic ether 
 (1 mol.) and m-amido-benzoic acid (1 mol.). 
 Aggregates of colourless needles. Sol. ordinary 
 solvents except water. 
 
 Et02C.C:CMe. 
 Ethyl ether I >N.C,H..CO,H: 
 
 HC:CPh/ 
 [160°] ; slender yellow needles (from dilute acetic 
 acid) ; sol. alcohol, ether, &c. Its Ca, Ba, Sr, 
 and Mg salts are white granular pps. (Paal a. 
 Schneider, B. 19, 3162). 
 
 o-CAEBOXY-PHENYL-OXAMIC ACID 
 C,H,N05 i.e. CeH^(C02H).NH.CO.C02H. [210°]. 
 S. -11 at 10°. 
 
 Formation. — 1. By heating oxalic acid with 
 o-amido-benzoic acid at 120°. — 2. From carbo- 
 styril and alkaline KMnO, (Friedlander a Oster- 
 maier, B. 14, 1916 ; 15, 334).— 3. From acetyl- 
 quinoline tetrahydride and cold dilute KMnO, 
 (Hofmann a. Konigs, B. 16, 734).— 4. From 
 cynuriu or cynurenio acid and alkaline KMnO, 
 (Kretsohy, Jf. 4, 156; 5, 16).— 5. Formed by 
 oxidation of (P2/.)-bromo-quinoline with KMiiOj 
 (Claus a. CoUisohonn, B. 19, 2767). 
 
 Properties. — Silvery needles (containing aq). 
 (from water), or geodes (from ether). Decom- 
 posed by dilute acids, or by long boiling, into 
 oxalic and amido-benzoio acids. 
 
 Salts . — (NH,)2A" : minute felted needles. — 
 KHA"iaq.— BaA"aq.— BaHjA"2aq.-CaA"2iaii. 
 CuA"Cn0 4aq.— Ag^". 
 
 xz 2 
 
708 
 
 CAEBOXY-PHBNYL-OXAMIC AOID. 
 
 Mono-ethyl ether 
 C„H,(C02H).NH.C0.C0jEt. Ethyl -oxalyl- an- 
 thranilic acid. [181°]. Felted needles. Formed 
 by oxidation of indoxylio ether or indoxanthic 
 ether with CrOa (Baeyer, B. 15, 777). 
 
 »j-Carboxy-pheiiyl-oxamic acid 
 CO2H.CO.NH.O5H4.CO2H. Oxaloxyl-amido-hen- 
 zoic acid. 
 
 Formation. — 1. By boiHng an aqueous solu- 
 tion of the barium salt of oyano-oarbimido- 
 amido-benzoio acid. — 2. By heating (equal mols. 
 of) OT-amldo-benzoio acid and anhydrous oxalic 
 acid for an hour at 180° (Griess, B. 16, 336 ; 18, 
 2412). 
 
 Properties. — SmaU white plates. V. sol. hot 
 water, m. sol. alcohol, insol. ether.— BaA" 2aq. 
 
 Monp-ethyl ether 
 C02Et.CO.NH.CBHj.C02H(ethoxal-benzamicacid) 
 [225°]. Formed by boiling »ra-amido-benzoio 
 acid with oxalic ether (Schiff, A. 282, 132 ; B. 
 17, 402 ; G. 15, 534). Silky needles (from water 
 or alcohol). When heated above 225° it splits up 
 into oxalic ether and carboxy-phenyl-oxamide. 
 Amide-ether COjEt.CO.NH.CsH^.CONH^. 
 [191-5°]. Got by heating m-amido-benzamide 
 with oxaUc ether. Gives with aniline the amide- 
 auihde CO(NHPh)CO.NH.C5H4CO.NH2 [0. 310°]. 
 Anilide-ether CO^Et.CO.NH.C^Hi.CONPhH 
 [180°]. From TO-amido-benzaniUde and oxalic 
 ether. Satiny needles. 
 
 Amic acid C0(NHJC0.NH.CjH,.C02H v. 
 Phbitil-oxamidb oabboxylio acid. 
 
 CABBOXY-PHENYL-OXAMIDE v. Phenyl- 
 
 OXAMIDE CAEBOXTIiIO AOID. 
 
 CARBOXY-PHENYL-OXY-ACETIC ACID v. 
 
 Carboxt-phekoxt-acetio acid. 
 
 0-CABBOXY - PHENYL PHENYL - CASBA . 
 MATE CeH4(C02H).0.C0.NHC,H5. 
 
 Methyl ether CeHj(C02Me).0.C0.NHC,H5. 
 [238°] ; long needles ; sublimable. Formed by 
 heating methyl salicylate with phenylcyanate 
 (Snape, B. 18, 2431). 
 
 m-CABBOXY-PHEHYL-PHOSPHOEIC ACID 
 CsH4(C02H).O.PO(OH)2. [201°]. From its chlo- 
 ride and water. Scales, v. sol. water, alcohol, 
 and ether. Water at 160° decomposes it into 
 phosphoric and w-oxy-benzoic acid (Ansohutz a. 
 Moore, A. 239, 333). 
 
 Chloride G^KfilsPO^ i.e. 
 C5H,(C0Cl).0.P0.Cl2. (170°) at 12mm. S.G. =^ 
 1'548. From m-oxy-benzoic acid (1 mol.) and 
 PCI5 (li mols.). Further treatment with PCI5 
 (1 mol.) produces CjHiClsPO, (178°) at 11 mm. 
 This is probably CsH4(C0Cl).b.PCli, and is con- 
 verted by water into C6H4(C02H).O.PO(OH)2. 
 (l further quantity of PCI5 converts CjHjClsPOo 
 into C,H,Cl.CCl3. 
 
 o-CAEB0XY-;8-PHENYL.PE0PI0NIC ACID 
 H02C.CjH4.CH2.CHj,.C02H. [166°]. Formed by 
 heating o-carboxy-benzyl-malonio acid to 190° 
 (Wislioenus, A. 242, 39, cf. Gabriel a. Michael, 
 B. 10, 2204). Prisms, v. sol. hot, si. sol. cold, 
 water. 
 
 CAEBOXY-PHENYL-SEBACAMIC ACID 
 CO,H.CsH,5.CO.NH.C„H,.C02H. [193°]. From 
 its ether by saponification. Prisms. 
 
 Mono-ethyl ether 
 C02Et.C,H,e.CO.NH.C„Hj.C02H. [146°]. From 
 Bebacio ether and j»-amido-benzoic acid (Pelliz- 
 zari, A. 232, 146 ; B. 18, 215 ; G. 15, 650). 
 
 m-CAEBOXY-PHENYL-SUCCIBAMIC ACID 
 
 C2H2(C0jH)C0.NH.CsHj.C0jH. BerezflSTOSMcciJiic 
 acid. [223°]. Colourless prisms. Its ethyl- 
 ether is formed, together with di-phenyl-suooin- 
 amide di-oarboxyfio acid, by boiling amido- 
 benzoic acid with an alcoholic solution of suc- 
 cinic ether. On heating to its melting-point it 
 loses H(0 and is converted into succinyi-amido- 
 
 benzoio acid CA<;;^°>N.CsH,.C02H [283'']. 
 
 Ethyl ether 
 C2H2(0O2Et)CD.NH.C„H4.CO2H [174°] ; gUsten- 
 ing plates from water. 
 
 Amide C2H2(CONH2)CO.NH.O,H4.C02H 
 [229°]. 
 
 Anilide 0^T3i^(C01XJIPh)G0.NB..C,nt.C0.,B. 
 [252°] (PeUizzari, ^. 232,146; B. 18,214; O. 
 15, 550; Muretoff, J. B. 4, 298). 
 
 ^-Carboxy-phenyl-succinamic acid 
 [4:1] CeH,(C02H).NH.CO.CHi,.CH2.C02H. [226°]. 
 From jp-tolyl-sucoinimide and dilute aqueous 
 KMnO, (Michael, B. 10, 577). Needles, si. sol. 
 cold water and cold alcohol. Boiling cone. 
 HCLAq gives succinic and jp-amido-benzoio 
 acids. — AgHA". 
 
 o-CAEBOXY-PHENYL-STILPHUEIC ACID 
 COjH.CjHj.O.SOj.OH. SaHcyl-sulphwric acid. 
 Prepared by the action of E^S^O, on a solution 
 of salicylic acid in strong EOH. By heating 
 the K salt to 190° it gives K^SOj and salioylide. 
 — A"K2. Colourless spikes. Beadily decomposed 
 by dilute acids into salicylic acid and KHSO4 
 (Baumann, B. 11, 1914). 
 
 m-Garboxy-phenyl-sulpharic acid 
 [3:1] C0jH.CeH,.0.S02.0H. Prepared by the 
 action of K^SjO, on a solution of m-oxybenzrale 
 acid in strong KOH.— A"Kj: r220°-225° with 
 decomposition] ; needles, more stable towards 
 dilute acids than the ortho- compound ; is de- 
 composed however at 100°. 
 
 p-Carbozy-pheuyl-sulphuric acid 
 [4:1] C02H.CjH4.0.S02.0H. Prepared by the 
 action of EjSjO, on a solution of ^-oxybenzoio 
 acid in strong EOH. — A"E2 : leaflets or tables. 
 Does not decompose tiU heated to 250°. 
 
 CAKBOXY-PEOP y L-ACETIC ACID v. Ethyl- 
 
 SUCCINIC ACID. 
 
 CARBOXY - PYBEYI - GLYOXYLIC ACID 
 
 C4NH3(C02H).CO.C02H. Formed by the oxida- 
 tion of pyrrylene - di - methyl - di - ketone 
 (CH3.CO)2C4H2NH, or of pyrryl-methyl-ketone 
 carboxylic acid, with alkaline EMnO,. Crystal- 
 line; sol. ether, alcohol, and boiling water, 
 insol. benzene. — A"Ag2 : yellow pp. 
 
 Di-methyl ether A"Mej: [145°]; long 
 colourless needles ; m. sol. hot alcohol, si. sol. 
 ether and benzene. Potash-fusion gives pyrrol 
 di-carboxylic acid (Ciamician a. Silber, B. 
 19, 1412, 1957 ; (?. 16, 373, 379). 
 
 CAEBOXY-TAETEONIC ACID v. Di-oxY. 
 
 lABTAEIC ACID. 
 
 CAEBYLO-DIACETONAMINE v. p. 27. 
 
 CAEBYLAMINES v. Cakbamines. 
 
 CAEDAMOMS, OIL OF. Employed in medi- 
 cine as a carminative. 
 
 1. From Ceylon. The seeds of Elettaria 
 major contain 3-5 p.o. of an essential oil which 
 consists of a terpene (170°-178°), terpinene, a 
 solid substance [61°], and terpineol C,|,H,80 
 (205°-220°). The latter is converted by HCl 
 into di-pentene hydrochloride, C,„H,52HC1 [52°] 
 
OARMUFELLIO ACID. 
 
 700 
 
 and by HI into 0,oH,e2HI [76°]. The terpene 
 also gives a hydrochloride C,„H,b2HC1 [52°]. A 
 Bohd tetrabromide could not be got (Weber, A. 
 238, 98). 
 
 2. From Malabar. The oil from Elettaria 
 Cardanumum slowly deposits crystals of 
 C.oHisSHjO (Dumas a. P61igot, A. Ch. [2] 57, 
 
 CAEDOL C„H3„0, (?) An oil, occurring 
 with auacardio acid (q.v.), in the pericarp of 
 the cashew nut {Anacardium occidmtale). It is 
 sol. alcohol and ether. It is not volatile; it 
 blisters the skin. It gives with basic lead 
 acetate a pp. of 02,H2„(PbAc)0,PbO (StSdeler, 
 A. 63, 137). Anaoardio acid 02,H3„(OH)002H 
 in alcoholic solution gives with metallic solu- 
 tions pps. of the salts: AgA'. — CaA' 2aq. — 
 BaA'aq.— MgA'aq.— ItsTOe<%i eth&r is an oil 
 (Euhemann a. Skinner, G. J. 51, 663 ; B. 20, 
 1861). 
 
 CABICIN. An oily substance present in the 
 seeds of the Papaw tree (Garica papaya) 
 (Peckolt, P;i. [3]10, 343). 
 
 CASMIIf APHE V. Naphthoquinone. 
 
 CAKMINIC ACID C„K,,0,,. The colouring 
 matter of cochineal which is obtained from 
 insects of the genus Coccus, chiefly Coccus 
 caaii. Cochineal contains only 10 p.c. colouring 
 matter (Pelletier a. Caventou, A. Ch. [2] 7, 90; 
 8, 255; Warren de la Bue, A. 64, 1, 28; 
 Schutzenberger, A. Ch. [3] 54, 52 ; Sohaller, Bl. 
 [2] 2, 414; M^ne, C. B. 68, 666; Dieterich, 
 C. C. 1867, 287; Liebermann, B. 18, 1969). 
 The lead salt is ppd. on adding lead acetate to 
 an aqueous infusion of cochineal ; by this means 
 the quantity of colouring matter in cochineal 
 may be estimated. Carmine, a red pigment 
 prepared from cochineal, appears to be a com- 
 pound of carminic acid with alumina, lime, and 
 some organic acid. Cochineal also contains a 
 tat (in which are ethers of myristic acid, of 
 CnHjjOj and of CuH^jO^ and a waxy substance, 
 coccerin (Baimann, M. 6, 891; Liebermann, jB. 
 19, 328). 
 
 Properties. — Purple mass, sol. water and 
 alcohol, si. sol. ether. Its solution forms red 
 pps. with the alkaline earths and with acetates 
 of Pb, Zn, Cu, and Ag. Alum and NajCO, give 
 the aluminium lake. 
 
 Reactions. — 1. Boiling dilute HjSOj forms 
 ' carmine-red ' and a sugar CjHjjOj (Hlasiwetz a. 
 Grabowski, A. 141, 329). According to Lieber- 
 mann the formation of sugar is questionable. — 
 2. Potash-fusion gives coccinin, oxalic acid, and 
 succinic acid (H. a. G.). — 3. Cone. HjSOj at 
 130° forms a compound CjjHjjOu and rufioocoin 
 C,bH,„Os (Liebermann a. Dorp, A. 163, 105). — 
 4. HNOj forms nitro - coccic acid 
 C„H5(N02)303. — 5. By distillation with zinc-dust 
 a small quantity of a solid hydrocarbon CuHi^ 
 is produced, this forms plates melting at [187°] 
 (Furth, B. 16, 2169). 
 
 Salt s.— Na^A".— K^A" xaq.— BaA" xaq. 
 
 Coccinin C,4H,205. Prepared as above. 
 Yellow lamin» (from alcohol) ; insol. water, v. 
 Bol. alcohol, si. sol. ether. Sol. alkalis. The 
 alkaline solutions are yellow and absorb oxygen, 
 becoming green and, finally, purple. The solu- 
 tion in cone. HjSO, turns indigo-blue on warm- 
 ing. On distillation with zinc-dust it yields a 
 
 small quantity of a hydrocarbon C|„H,2 whiili 
 forms plates melting at [187°].— CnH||(NHj)0,. 
 Acetyl derivative. Yellow crystals, sol 
 alcohol and acetic acid, insol. water (Furth, B, 
 16, 2169). 
 
 Euflcoccin 0,jH,„08. Formed as above. 
 Brick-red powder, si. sol. warm water and ether, 
 m. sol. alcohol. The ethereal solutions fluoresce 
 green. The alkaline solutions are brown. 
 Cone. HjSOj forms a violet solution. — 
 CaC.^H^O,. 
 
 Compound Gs^U^O,^. Black insoluble pow- 
 der. Forms violet solutions in KOHAq and 
 cono. HjSOj. Both this compound and rufi 
 coecin give O.^Hu [187°] when distilled over 
 zinc-dust. 
 
 Carmine red C„H,20,. Formed by boiling 
 carminic acid with dilute H^SOj (v. suprn). 
 Dark purple mass with green lustre; scarlet 
 when powdered. Alcohol and water form red 
 solutions. Insol. ether. Potash-fusion forma 
 coccinin. Water at 200° forms rufioarmine 
 C„H,A-— Salts: K2CiiH,„0,.—CaC„H,„0,!!;aq 
 — BaO„H,„0, icaq. — ZnC„H,„0, a;aq. — 
 Zn(C|,H,,0jJ2a;aq. 
 
 If carmine-red be dissolved in acetic acid, 
 and treated with bromine two products are ob- 
 tained, named provisionally (a)- and {g)-bromo- 
 carmine. The (o)-bromo-carmine is sparingly 
 soluble in acetic acid and separates in crystals 
 (yield : 10 p.c), whilst the amorphous (;8)-bromo- 
 carmine remains in solution and is ppd. on 
 adding water (the yield is 20 p.c). 
 
 ' (o)-Bromo-carmine ' CmH^BriOj crystalliseg 
 in colourless needles, [248°], v. sol. alkalis. By 
 boiling with strong aqueous KOH it gives 
 
 ' (o) - Sromo - dioxy - carmine,' so called, 
 CioHjBrjOs, which forms colourless crystals, 
 [208°]. By its behaviour on etherifioation it is 
 shown to contain one CO^H and one phenolic 
 OH group. On oxidation with KMnO, it yields 
 two bodies : — (a) An acid CgH^BrjOj which forms 
 colourless crystals [244°]. By its reactions on 
 methylation it is proved to contain one OH 
 and COjH group, whence it probably has the 
 constitution C,(CH3)Br2(OH)(CHO)C02H or 
 C„H(CH3)Br,(0H)C0.C0,H.— (6) A neutral body 
 CjHjBrjO,, [195°], which by its reactions is 
 shown to be a di-bromo-oxy-methyl-phthalio 
 anhydride C„MeBr2(0H)C202:0 [1:2:4:3:5:6]. 
 
 ' (;8)-Bromo-oarinine,' so called, is the second 
 product of the bromination of carmine-red, and 
 separates in yellow amorphous flocks on adding 
 water to the acetic acid solution. It is v. sol. 
 alcohol, acetic acid, &c., but could not be ob- 
 tained in a pure state. By boiling with strong 
 aqueous KOH it is converted into 
 
 ' (/3)-Bromo-oxy-carmine ' CiiHsBrjO^, which 
 forms glistening yellow needles, [232°]. It is a 
 di-basic acid and forms red salts. On oxidation 
 with KMnO^ it yields two bodies: — (a) An acid 
 CipHifBrjOj wHch forms colourless prisms 
 (containing aq), and melts at [230°] with evolu- 
 tion of COj. From its reactions it probably ha» 
 the constitution CjMeBr2(OH)(C02H)CO.C02H. 
 (6) A neutral body OjHjBrjOj identical with that 
 obtained from the ' (o)-bromo-oxy-oarmine ' 
 (Will a. Leymann, B. 18, 3180). 
 
 CARMUFELLIC ACID C.^H^,©,^. An acid 
 said to be formed by the action of HNO, on th« 
 aqueous extract of cloves. Micaceous scales. 
 
710 
 
 CARMUFELLIO ACID. 
 
 iuaol. alcohol, ether, and cold water (Muspratt 
 a. Danson, P. M. [4] 2, 293). 
 
 CABNAtJBA WAX. Obtained from the leaves 
 of Cojpemicia ceri/era in Brazil, and largely used 
 there for making candles. It contains myricy- 
 lic alcohol, C25H53CH2OH [85-5°], a hydrocarbon, 
 [59°] and compound ethers derived from the 
 following alcohols and acids : myricyl alcohol ; 
 an alcohol 02„H,,,CH,OH [76°] ; a di-hydric 
 alcohol C^^Rt^iCB-flJi), [104°]; an isomer- 
 ide of lignooerio acid, OjaH^jCO^H [72-5°] ; an 
 acid isomeric or identical with cerotic acid 
 O28H53CO2H [79°]; and an oxy-acid of the 
 formula C,sH3g(CH20H)(C02H) or its lactone 
 [103-5°]. The alcohol CjsH.BfCH^OH)^ gives on 
 oxidation an acid C23'B.,„(C0.Ji)2 [102'5°] ; and 
 the oxy-acid C,sH3g(CHjOH)(C02H) gives the 
 acid C„Hs,(C02H)2 [90°] (Stiircke, A. 223, 283 ; 
 cf. Lewy, A. Ch. [8] 18, 438 ; Brandos, T. 1811, 
 261 ; Maskelyne, 0. J. 22, 87 ; B^rard, Z. [2] 4, 
 415). The greater part of the wax is myricyl 
 cerotate and myricyl alcohol. 
 
 CABNINE CjHjNjOj. A substance occurring 
 in extract of meat, and in the product of boiling 
 yeast with water (Weidel, A. 158, 353 ; Schutz- 
 enberger, C. B. 78, 493). Obtained by boiling 
 with water the pp. thrown down from meat 
 extract by lead acetate ; the carnine crystallises 
 from the evaporated filtrate (Kruekenberg a. 
 Wagner, C. C. 1884, 107). Crystallises with aq, 
 V. si. sol. cold water, insol. alcohol and ether. 
 Bromine-water converts it into hypoxauthine 
 CsHjN,©.— B'HCl : needles.— B'jH,PtCls. 
 
 CABPENE C^H,,. (156°). Obtained, toge- 
 ther with ^-cresol, by distilling calcium podo- 
 carpate. Oil, smelling of turpentine ; resinifies 
 in the air. Forms an oily compound with bro- 
 mine (Oudemans, B. 6, 1125 ; A. 170, 252). 
 
 CAREOTIN CjeH3j{?) Carrotene. The 
 colouring matter of the carrot (Datccus Carota) 
 (Wackenroder, Oeiger's Mag. 33, 144; Zeise, 
 /. jar. 40, 297; Husemann, A. 117, 200). 
 Occurs also as a normal constituent in the 
 leaves of plants, and in the tomato (Arnaud, 
 C. B. 102, 1119 ; 104, 1293 ; Bl. [2] 46, 487 ; 48, 
 64). Inasmuch as no other coloured hydro- 
 carbon is known, carrotin probably contains 
 oxygen. 
 
 Preparation. — The roots are out up and 
 pressed, dried at 80° and extracted with CSj. 
 The juice is ppd. with lead acetate and the pp. 
 also extracted with CS^. Carrotin, hydrocarrotin, 
 and fat are obtained from the CS2 solutions. 
 The fat is saponified with alcoholic potash. 
 Water and BaCl2 are added. The pp. is dried 
 and extracted with acetone. On recrystallising 
 from methyl alcohol hydrocarrotin separates out 
 first (Eeinitzer, M. 7, 597). 
 
 Properties. — Small red plates, v. sol. CSj, 
 benzene ; v. si. sol. absolute alcohol ; and less 
 sol. 90 p.c. alcohol. Insol. Aq. Bapidly absorbs 
 oxygen from the air. Dissolves in cone. HjSOj 
 giving a deep blue colour. Yields a derivative 
 CjijHjglj with iodine ; this has a deep green 
 colour, and metallic lustre. Chlorine forms a 
 chloro- derivative [120°]. 
 
 Hydiocarrotin Cj^H^O (?) [138°]. [o]o = 
 -37-4° in CHCl, at -3-4°. Prepared as above. 
 Greatly resembles cholesterin. Colourless, insol. 
 water, v. sol. alcohol, acetone ether, CHCl, 
 and CS,. Crystallises from acetone in long 
 
 needles, and from methyl alcohol in plates con- 
 taining water. Besembles Liebermann's choles- 
 tol and Hesse's cupreol but differs from phy- 
 tosterin (Eeinitzer, M. 7, 597). 
 
 Acetyl derivative\\3,S°'\ ; coloured green 
 by H2SO4, and rose by addition of chloroform. 
 
 Benzoyl derivative [145°]. 
 
 CARTHAMIN C„H,80,. The colouring 
 matter of safflower (Oa/rthanms tinciorius) (Chev- 
 reul ; Schlieper, A. 58, 362). Washed safflower 
 is treated with aqueous Na^COj, acetic acid is 
 added and pieces of cotton are put in. The 
 carthamine that has been taken up by the 
 cotton is subsequently dissolved off it by aqueous 
 Na2COs, and ppd. by citric acid. Powder with 
 red lustre (from alcohol) ; si. sol. water, insol. 
 ether, v. sol. alcohol. Its alcoholic solution is 
 purple. Decomposed by boiling with water or 
 alkalis. Potash-fusion gives oxalic and f -oxy- 
 benzoic acids (Malin, A. 136, 117). 
 
 CARVACEOL. C,„H„0 i.e. a„H3MePr(0H) 
 [1:4:2]. Gymenol. Mol. w.150. [o.0°]. (237°i.V.). 
 S.G. 15 -986. hj, 1-5252. H.F. p. 68,181 
 ((0,02) = 94,000; (H2,0) = 69,000) (Stohmann, 
 J.pr. [2] 34, 319). Occurs in the essential oil 
 of Origanum hirtum and, together with cymene 
 and a terpene, in oil of Satureja hortensis and 
 S. montana; in oil of mint and of Thymus 
 Serpyllum (Jahns, Ar. Ph. [3] 16, 277 ; B. 15, 
 816; Haller, Bl. [2] 37, 411; C. B. 94, 132; 
 Beyer, Ar. Ph. [3] 21, 283). 
 
 Formation. — 1. By boiling carvol (50 pta.)p 
 diluted with oil of caraway (50 pts.) with glacial 
 phosphoric acid (12 pts.) for 3 or 4 hours (Lustig, 
 B. 19, 11; c/i Volckel, A. 35, 308; 85, 246; 
 Kekule a. Fleischer, B. 6, 1088 ; Kreysler, B. 18, 
 1704). — 2. From camphor (5 pts.) by boiling with 
 iodine (1 pt.) (Kekule a. Fleischer, B. 6, 934; 
 cf. Claus, J. pr. 25, 264 ; Schweizer, J. pr. 26, 
 118 ; A. 40, 329). — 3. From bromo-camphor and 
 ZnClj (SchiS, B. 13, 1408).— 4. Pure camphor 
 cymene is converted into its monosulphonie 
 acid and the latter carefully fused with 3 pts. 
 of KOH (Jacobsen, B. 11, 1060 ; cf. Pott, B. 2, 
 121 ; H. MuUer, B. 2, 130). 
 
 Properties. — Oil. FCjClj colours its alco- 
 holic solution green. 
 
 Reactions. — 1. On fusing with KOH iso- 
 oxycuminic acid C(,H3(C02H)(OH)C3H, [1:2:4] is 
 first formed and finally oxy-terephthalic acid is 
 produced {B. 11, 1060). — 2. P2S5 gives cymene 
 and thio - carvacrol C|„HuS. — 3. P2O5 forms 
 cresol and propylene. — 4. Fe2Cl8 gives di-carva- 
 crol. — 5. PCI5 forms chloro-cymene. — 6. Diazo- 
 hemene forms CeH2MePr(OH).N2.C,H5 [80°-85°] 
 and C„HMePr(OH)(N2C5H,)2 [126°] (Mazzara, 
 O. 15, 214). — 7. Chloro-acetic acid in presence 
 of an alkali forms carvacryl-glyoollic acid 
 C,„H,30.CH2.C02H.- 8. HjSO, forms one or two 
 sulphouic acids of the form C5H2MePr(OH).S03H. 
 According to Jahns one only is formed, its salts 
 being: KA' aq.— AgA' 2aq.— BaA'j 5aq. S. 12-5 
 at 15°.— MgA'2l2aq. 
 
 Sodium salt. — C^HuONa: white crystal- 
 line powder. 
 
 Methyl ether C,„H,30Me. (217°). S.G. 
 s -954 (Paterno a. Pisati, B. 8, 71 ; Cf. 5, 13). 
 Forms with H^SO^ two acids C,„H,2(S03H)(0Me) 
 whose Ba salts are BaA'2 3|aq : v. si. sol. water, 
 and BaA'2 5aq, v. sol. water. 
 
 Ethyl ether C,„H,30Et: (235°); oilhaving 
 
3ARV0L. 
 
 711 
 
 an odour of carrots (Lustig, B. 19, 11 ; C. C. 
 1884,787). 
 
 Acetyl derivative, C,„H„OAo : (246°). 
 S.G. 2 l-Oll ; colourless liquid heavier than 
 water. 
 
 Benzoyl derivative C,„H„OBz: (above 
 260°) ; thick odourless oil. 
 
 Dicarvacrol. 02„a,„0j. [154°]. Formed by 
 the action of neutral Pe^Cls on carvacrol 
 (Dianin, J. B. 14, 141). Thin silky needles 
 (from dilute alcohol) ; insol. water, v. sol. alco- 
 hol and ether. 
 
 o-CARVACKOTIC ACID C,„H,j(0H)C02H. 
 Oxy-cymene-carboxylic acid. [136°]. Prepared 
 by passing CO^ over heated sodium carvacrol. 
 White silky needles. Sublimable. V. sol. hot 
 water, alcohol, and ether, nearly insol. cold 
 water. Alcoholic FejClj gives a violet coloura- 
 tion (Lustig, B. 19, 18). 
 
 ^-Carvacrotic acid C,„H,2(OH)C02H. Oxy- 
 cymene-carboxylic add. [80°]. Obtained by 
 oxidation of carvacrotio aldehyde (from carvacrol, 
 CHCI3, and NaOH) with KMnO^. Long white 
 silky needles. Can be sublimed and distilled 
 with steam. V. sol. hot water, alcohol, and 
 ether, nearly insol. cold water. Green coloura- 
 tion with alcoholic FejClj (Lustig, B. 19, 10). 
 
 p-CARVACROTIC ALDEHYDE 
 C„H,(CH,)(C3H,)(0H)(CH0) [1:4:2:5] (?) Oxy- 
 aldehydo-cymene. (0. 236°). Formed by heating 
 carvacrol with aqueous NaOH and chloroform. 
 Oil. Volatile with steam (Lustig, B. 19, 14). 
 
 An isomeride [96°] has also been described 
 as ^-carvacrotio aldehyde. It is left as a resi- 
 due after distilling off the volatile aldehyde 
 with steam. White sUky flat plates. Easily 
 soluble in alcohol, ether, and benzene, sparingly 
 in hot water, insoluble in cold water (Nord- 
 mann, B. 17, 2632). 
 
 CARVACRYL-AMINE C.oH.sNHj. Methyl- 
 ■pi-opyl-phenyl-amine. (242°). Formed, together 
 with di-oarvaoryl-amine, by heating carvacrol 
 with ammoniacal ZnBr^ or ZnCl^ and NH^Br 
 or NHjCl at 350°-360°; yield, 25 to 30 p.c. 
 Colourless oil, which solidifies at —16° 
 B'jBLjCljPtClj : yellow prisms, si. sol. hot water. 
 
 Acetyl derivative C,|,H,3.NHAc : [115°]; 
 white glistening tables ; si. sol. hot water, v. sol. 
 warm alcohol. 
 
 Benzoyl derivative C,jH,3.NHBz : 
 [102°] ; flat ghstening crystals ; nearly insol. 
 water, si. sol. cold alcohol, v. sol. hot alcohol, 
 and benzene (Lloyd, B. 20, 1261). 
 
 Di-carvacryl-amine (C,„H|3)2NH. (344°- 
 348°). Formed as above, the yield is 27 to 
 40 p.c. Colourless oil. V. sol. alcohol, ether, 
 and benzene. Its solution in cone. HjSOj is 
 coloured blue by nitrites and nitrates. — B'HGl. 
 — B'jajCU'tCl,. 
 
 Acetyl derivative (C,„H:,3)2KAc : [78°]; 
 white glistening scales ; v. sol. hot alcohol and 
 ligroin, si. sol. in the cold (Lloyd, B. 20, 1261). 
 
 CARVACRYL-GLYCOLI,IC ACID G,^,fi^ i.e. 
 CioHisCCHj-COyH. [140°]. From carvacrol, 
 ohloro-acetic acid and potash (Spioa, 0. 10, 345). 
 Flat needles.— PbA'.—AgA'. 
 
 Ethyl ether EtA.'. [0. 100°]. (289°). 
 
 Amide C.^H.A-NH,. [68°]. 
 
 CARVACRYL-IACTIC ACID C.sH.sOs i.e. 
 C.„H,30.CMeH.C02H. [74°]. From carvacrol, 
 B-'chloro-propionic acid, and potash (Sciohilone, 
 
 O. 12, 49). Prisms, v. e. sol. alcohol, ether, and 
 chloroform, 
 
 CARVACRYL MERCAPTAN C,„HuS i.e. 
 C„H3MePr(SH) [1:4:2]. (236°). S.G. iZi -998. 
 From camphor or carvacrol and PjS, (Flesch, B. 
 6, 478 ; Roderburg, B. 6, 669 ; KekuU a. Fleischer, 
 B. 6, 934). Liquid. HNO3 oxidises it to sulpho- 
 toluic acid (Bechler, J. ^■r. [2] 8, 168). 
 
 Salts.— Hg(C„H,jS)2. [109°] (Fittica, A. 
 172, 327). — C,„H,3S.HgCl. — C,oH,3SAg. — 
 C,„H,3SAgAgN03. 
 
 Methyl ether C,„H,3SMe. (244°). S.G. -99. 
 
 TRI-CARVACRYL PHOSPHATE 
 PO(OC,„H,3)3. [75°]. Colourless prisms or tables. 
 Easily solublein alcohol, ether, and benzene, more 
 sparingly in petroleum-ether. Formed by heat- 
 ing carvacrol with POCI3 ; yield, 55-60 p.c. of the 
 theoretical (Kreysler, B. 18, 1704). 
 
 CARVAGRYL-PHOSPHORIC ACID 
 CjH3MePr.O.P03H2 [1:4:2]. Formed by the action 
 of POCI3 upon carvacrol, and treatment with 
 aqueous K2CO3. The potassium salt A'£5aq 
 forms large silvery plates. By alkaline KMnO, 
 it is oxidised to oxyisopropyl-salicylic acid 
 C„H3(CMe,OH)(OH)C03H [4:2:1] (Heymann a. 
 Konigs, B. 19, 3309). 
 
 TETRA-CARVACRYL SILICATE Si(0C,„H,3),. 
 (380°-390°) at 118 mm. Colourless oil. Formed 
 by heating carvacrol with SiClj; the yield is 
 85 p.c. of the theoretical (Hertkom, B. 18, 1694). 
 
 CARVACRYL-SULPHURIC ACID 
 CsH3MePr.O.S03H [1:4:2]. Cumyl-sulphuric acid. 
 The potassium salt is formed by adding potas- 
 sium pyrosulphate to a warm solution of car- 
 vacrol in aqueous KOH. Silvery plates. V. sol. 
 water and alcohol. By alkaline permanganate 
 it is oxidised to oxyisopropyl-salicylic acid 
 C„H3(CMe20H)(OH)COjH [4:2:1] (Heymann a. 
 Konigs, B. 19, 3309). 
 
 CARVENE. A terpene present in oil of 
 caraway, v. Tekpenes. 
 
 ITitroso-caryene v. Cabvoxiu. 
 
 CARVEOL C,„H,3.0H. (219°). Thick fluid. 
 Formed by reduction of carvol with sodium and 
 alcohol. With phenyl cyanate it reacts to form 
 carveyl-phenyl-carbamate [84°] (Leuchart, B. 
 20, 114). 
 
 CARTEYL PHEITYL-CARBAMATE 
 C.dH.sO.CO.NPhH. [84°]. Formed by the action 
 of phenyl cyanate upon carveol C,„H,5.0H. 
 Slender needles. V. sol. hot alcohol, si. sol. 
 ether and ligroin (Leuchart, B. 20, 114). 
 
 CARVOL C,„H„0. (228°) (E. Sohiff, B. 19, 
 562). S.G. li -9667 (Gladstone, C. J. 49, 621) ; 
 S? -9574 (Fluckiger, Ar. Ph. [3] 22, 361). 
 fi„ 1-5020 (G.). Ba 76-68 (G.). S.V. 190-26. 
 H.F.p. 48,250 ((C,OJ = 94,000; (H2,0) = 69,000) 
 (Stohmann, J. pr. [2] 34, 322). 
 
 Occurrence. — In oil of caraway (oleum carvi) 
 together with carvene (173°) (Volckel, A. 85, 
 246). In oil of diU (Anethum graveolens) and of 
 mint {Mentha crispa). The carvol in the oils of 
 caraway and of dill is dextro-rotatory, but that 
 from oil of mint is IsBvo-rotatory [0]"= —62-46 
 at 2° (Beyer, Ar. Ph. [3] 21, 283). According 
 to Fliickiger (Ar. Ph. [3] 22, 361) the rotatory 
 power of carvol is ld]„ = 58-2°. 
 
 Properties. — Liquid. Carvol from aU three 
 sources forms the same crystalline compound 
 (C,„HnO)2H„S [187°] when H^S is passed into 
 its alcoholic solution. When prepared from oils 
 
712 
 
 CARVOL. 
 
 ol caraway or of dill this compound is dextro- 
 rotatory, [a]D = + 5-5° at 20°, but when obtained 
 from oil of mint it is Itevo-rotatory, [o]d = — 5'5° 
 at 20°. Dilute alcoholic KOH in the cold libe- 
 rates carvol from this compound. Protracted 
 treatiuent with H^S converts carvol in alcoholic 
 solution into the amorphous (C,„H„S)2H2S. 
 
 Reactions. — 1. Distillation over solid KOH 
 or P2O5 changes carvol into the isomeric oarva- 
 crol (Kekul6 a. Fleischer, B. 6, 1088).— 2. P^S, 
 forms cymene. — 3. P^Ss gives thio-carvacrol 
 0,„H,5SH. — 4. Distillation over heated sine-dust 
 gives C,„H,j (173°) and cymene (Arndt, Z. [2] 4, 
 730 ; B. 1, 204).— 5. Sodium in alcohol forms 
 carveol (q. v.). — 6. Dry HCl gas passed into a 
 mixture of carvol (1 mol.) and aceto-acetic ether 
 (1 mol.) forms the compound C15H25CIO4 pos- 
 sibly CaH,5Cl:C(OH).CH(CO.CH3).C02Et. [146°]. 
 Glistening white prisms (Goldsohmidt a. Kisser, 
 JB. 20, 489). — 7. Hydroxyla/imne forms the oxim, 
 V. Cabvoxim. 
 
 Carvol - phenyl - hydrazide CioHHtN^HCjHs. 
 [106°]. Formed by the action of phenyl-hydra- 
 zine on carvol (Goldsohmidt, B. 17, 1578). 
 Slender white needles. Sol. hot water. 
 
 CarTol-cliloro-hydride C,„H,5C10. Hydro- 
 chlorocarvol. Oil. Formed by leading dry HCl 
 into carvol. 
 
 Oxim C,„H,5C1(N0H) : [182°]; tables. 
 Formed by the action of hydroxylamine upon 
 carvol-ohloro-hydride or of HCl upon carvoxim. 
 
 Bemoyl-oxim C,„H,5Cl(N0Bz) : [115°]; 
 needles (from petroleum-spirit) (Goldsohmidt a. 
 Ziirrer, B. 18, 2220). 
 
 Phenyl - hydrazide C,„H,5Cl(NjHPh) : 
 [137°] ; small white prisms. 
 
 Carvol bromo-hydride C,„H,5BrO. Oil. De- 
 composing at about 50°. 
 
 Oxim C,„H,5Br(N0H) : [116°]; prisms 
 (from ligroin). 
 
 Phenyl - hydrazide C,„H,5Br(N2HPh) : 
 [119°] ; slender yellow needles (Goldsohmidt a. 
 Kisser, B. 20, 488, 2071). 
 
 Constitution of carvol. 
 
 HC— CPr =CH 
 
 Carvol I I 
 
 HC— CMeH— CO 
 
 is probably the pseudo-form of 
 
 HC — CPr = CH 
 
 Carvacrol | | 
 
 HC— CMe = C{OH) 
 (Goldsohmidt, B. 20, 490). According to Glad- 
 stone (0. J. 49, 621) the presence of two pairs 
 of doubly-linked atoms of carbon in the mole- 
 cule of carvol is indicated by its molecular re- 
 fraction. 
 
 CAKVOXIM C,„H„:N(OH). Nitroso-hesperi- 
 dene or nitroso-carvene. [71°]. Large colourless 
 transparent plates. Sol. acids and alkalis. 
 
 Formation. — 1. By the action of hydroxyl- 
 amine upon oarvol.^2. By passing nitrosyl 
 chloride into a methyl-alcoholic solution of 
 carvene, and heating to its melting-point the 
 crystalline hydrochloride C,„H,80NC1 which pre- 
 cipitates. 
 
 Reactions. — 1. By heating with dilute H2SO4 
 carvol is regenerated. — 2. By passing HCl gas 
 into its methyl-alcoholic solution the oxim of 
 Earvol chloro-hydride (v. supra) is formed. 
 
 Hydrochloride B'HCl; white crystalline 
 
 solid; decomposed by water; formed by passing 
 HCl into the ethereal solution. 
 
 Methyl ether C,„H,j:N(OMe) : colourless 
 fluid. 
 
 Benzoylderivative CioHn:N(OBz): [95°], 
 white glistening needles, v. sol. alcohol and 
 benzene (Goldsohmidt a. Ziirrer, B. 17, 1577 ; 
 18, 1729). 
 
 Iso-carvoxim C,|,H„(NOH). [143°], possibly 
 
 OPr<^^^- ^(^° (^>CMe. Obtained, together 
 
 with a small quantity of carvoxim, by the action 
 of excess of hydroxylamine on a solution of 
 carvol chlorohydride or bromo-hydride in alcohol 
 (Goldschmidt a. Kisser, B. 20, 2071). Needles, 
 si. sol. alcohol ; sol. acids and alkalis. Unlike 
 carvoxim, it does not combine with HCl or HBr. 
 Dilute HjSOj forms carvacrol and a compound 
 C,„H„NO [94°]. 
 
 Benzoyl derivative 0,„H„(NOBz) : 
 [112°] ; scales, v. sol. alcohol. 
 
 CABVYLAMINE Ci.H.^.NH^. Formed by 
 reduction of carvoxim C,„H„.NOH in alcoholic 
 solution, by sodium-amalgam and acetic acid. 
 Colourless liquid, of strongly aromatic basic 
 odour. Eeadily absorbs COj from the air.— 
 B'HCl: [0. 180°], slender silky needles (from 
 alcohol). 
 
 Benzoyl deri«aii«eC,|,H,5.NHBz: [169°]; 
 white needles (Goldsohmidt a. Kisser, B. 
 20, 486). 
 
 CAKYOPHYLIIN C^H.^O, (?) A substance 
 that may be extracted by alcohol from cloves, 
 the dried flower-buds of Caryophyllus aroma- 
 ticus (Mylius, B. J. 22, 452; Muspratt, Ph. 
 10, 343). Silky needles in stellate groups ; sub- 
 limes at about 285°. SI. sol. cold alcohol, sol. 
 boiling alkalis. PCI5 forms CjjHgjOjCl and 
 CMHjsOjCla. 
 
 Acetyl derivative [184°]. Monoclinio 
 crystals (HjeU, B. 13, 800). 
 
 Caryophyllie acid C„HjjO,2. From caryo- 
 phyllin and fuming HNO, (Mylius, B. 6, 1053). 
 Amorphous; si. sol. water, v. sol. alcohol, ether, 
 and HOAo. May be crystallised from fuming 
 HNO3. 
 
 Salts.— NajA"".—Ag,A"".—Ba.^""liaq. 
 
 CASCAEILLIN C.jH.sO,. [205°]. S. -127 at 
 100° ; S. (alcohol) 3'33 at 8°. Extracted from 
 cascarilla bark (from Groion EleiUheria and 
 Cascarilla) by boiling water (Mylius, B. 6, 1051 ; 
 cf. Tuson, C. J. 17, 195; Duval, J. Ph. [3] 
 8, 91). Minute prisms (from alcohol) ; tastes 
 bitter. Not affected by boiling dilute HCl. Can. 
 carilla bark also contains a volatile oil (173"- 
 180°). 
 
 CASEIN V. Peoteids. 
 
 CASEOSE V. Pboieids. 
 
 CASSONIC ACID C^HjO,. Formed, together 
 with saccharic and oxalic acids, in the oxidation 
 of cane sugar by HNO3 (Siewert, Institut. 21, 78). 
 Also from glyconic acid and HNO, (Honig, j. 
 1879, 667). Syrup. Eeduces ammoniaoal 
 AgNOj to a mirror. — BaA"a;aq. 
 
 CASIOBIN. Castoreum is a hard black sub- 
 stance (soft when fresh) found in a pair of small 
 sacs situated in the genital organs of the beaver 
 (Castor fiber and americanus). An alcoholio 
 extract deposits first fat, and then castorin. 
 Castoreum also contains a volatile pungent oil. 
 
CATECHUTANNIC ACID. 
 
 718 
 
 cholesterin, a resin, proteida, CaCOs, and in- 
 organic salts (Valenciennes, J. 1861, 803). 
 
 CASTOR OIL. A fatty oil obtained by 
 pressure from the seeds of Bicinus communis. 
 It solidifies at about -18°, has S.G. about -969 
 at 12°, and is dextro-rotatory, [a] = 12° (Popp, 
 Ar. Ph. [2] 145; 233). Castor oil consists chiefly 
 of glyoerides of stearic and ricinoleic acids. It 
 is completely dissolved by 5 vols, of 90 p.o. 
 alcohol (Hager, C. C. 1876, 389). Dry distilla- 
 tion gives acrolein, cenanthol (heptoic aldehyde) 
 and an acid (G^.B^fi^)^ (Bussy a. Leoauu, J. Ph. 
 
 13, 57 ; Stanek, J. pr. 63, 138 ; Leeds, B. 16, 
 290; Krafft a. Brunner, B. 17, 2985). HNO, 
 oxidises it to heptoic, oxalic, azela'ic, suberic, 
 and (fl)-pimelic acids (Arppe, A. 120, 288). 
 The products obtained by saponifying castor-oil 
 and distilling the resulting alkaline ricinoleate 
 alone or with NaOH are methyl hexyl ketone, 
 sec-octyl alcohol, and sebacio acid (Neison, C. J. 
 27, 507, 837). Cone. H^SO, converts castor oil 
 into rioinyl - sulphuric acid C.sHsjOjOSOjH, 
 which by the addition of water breaks up into 
 ricinoleic acid and HjSO^. From the fatty acids 
 derived from the Turkey-red oil prepared from 
 castor oil, crystals of a di-oxy-stearic acid sepa- 
 rate after some time (Benedikt a. XJlzer, M. 8, 
 217). 
 
 CATAIPIC ACID C„H,,Oe. [206°]. Ex- 
 tracted by ether from decoctions of the siliqua- 
 ceous capsule of the Bignonia Catalpa,. It may 
 be isomeric with hydrocardenic acid (Sardo, G. 
 
 14, 134). Large white crystals, v. si. sol. water, 
 sol. alcohol and ether. — BaC,jH,20u 6aq : white 
 glistening laminae. — Ag^A" : a white pp. 
 
 CATALYSIS V. Chemicaii change. 
 
 CATECHINS C,gH,gOs8aq (Hlasiwetz; Cross 
 a. Bevan, G. J. 41, 92) ; C„H,80g (Etti, M. 2, 
 547) ; CjiH^jOg (Liebermann a. Tauchert, B. 13, 
 694) ; C,„H,sO,5 and CjjHjsO.s (Gautier, 0. B. 
 86, 668). This name has been given to various 
 compounds contained in catechu or Terra japo- 
 nica which is extracted by boiling water from 
 the fruits or twigs of a variety of plants : Bom- 
 bay catechu from the fruit of Areca Catechu, 
 Bengal catechu from twigs and unripe pods of 
 Acacia (or Mimosa) Catechu, Gambir catechu 
 from Nauclea (TJncaria) Gambir, and Nubian 
 catechu from some Acacia. Catechu is used in 
 dyeing. 
 
 Catechin CjiHibOs (Gautier, O. R. 85, 752) ; 
 C^H.sO, 3aq (C. a. B.) ; C„H,„0,5aq (L. a. T.). 
 [217°]. S. (alcohol) 20 at 15° ; S. (ether) -8 at 
 15° (Wackenroder, A. 37, 311). Obtained from 
 Bombay catechu by washing with water and 
 crystallising from acetic ether (L. a. T. ; Lowe, 
 Fr. 13, 113 ; Zwenger, A. 37, 320 ; Neubauer, A. 
 96, 337 ; Kraut a. Van Delden, A. 128, 285 ; 
 Hlasiwetz a. Malin, A. 134, 118 ; Etti, A. 186, 
 337 ; Schutzenberger, Bl. [2] 4, 5; Saoc, C. B. 
 53, 1102). 
 
 Properties. — Small needles (from water). 
 V. si. sol. cold water, v. sol. hot water and 
 acetic ether. The aqueous solution is coloured 
 green by Fefil^. The solution in KOHAq ab- 
 sorbs oxygen, turning brown. Lead acetate gives 
 in aqueous solution a pp. of (C2,H2„09)23PbO (?) 
 Catechin solutions are ppd. by albumen, but 
 not by gelatin. 
 
 Beactions.—l. Boiling dilute H^SO^ forms 
 cateohuretin.— 2. With HCl and KCIO3 it gives 
 
 C2oH,„C1^0,2 7 (Cross a. Bevan, 0. J. 41, 92) 
 which is turned crimson by Na^SOj. Catechu- 
 tannio acid does the same. — 3. I3r gives bromo- 
 catechuretin CjjHjBrjO,?, a red insoluble powder. 
 4. Water and PI3 give C2,H2„08, an elastic 
 insoluble mass. — 5. HOAc and BaOj give 
 CjiHjjO,,, a colourless powder which melts below 
 100° (Schiitzenberger a. Back, Bl. 4, 8).— 
 6. Aqueous K^Cr^O, forms CjiHi^Oio, a brown 
 insoluble powder. — 7. Potash-fusion gives phlo- 
 roglucin and protocateohuio acid (Hlasiwetz, A. 
 134, 118). — 8. Dry distillation gives pyrocate- 
 chin.— 9. Boiling dilute HjSO, forms insoluble 
 C2,H,eO, (Neubauer, A. 96, 356), or G.^B.^fi,, 
 (Etti).— 10. Boiling diluteKOHformsG2,H,„08(?) 
 a brown powder, sol. alcohol and alkalis. — 11. 
 HI gives iodoform and other products (G.). 
 
 Di-acetyl derivative C..,,H,jO;(OAo)2: 
 [131°] ; needles or prisms. Soluble in ordinary 
 solvents except water and ligroin (L. a. T.). 
 
 Di-benzoyl derivative C2iH,jO,(OBz)j. 
 Flocculent brown substance (S. a. E.). 
 
 Diacetyl-dichloro-catechin 
 C2,H,„Cl2(OAc)20, : [169°]; needles. Sol. al- 
 cohol, si. sol. ether. 
 
 Diacetyl-bromo -catechin 
 C2,H„Br(OAc)20,; [120°]. White needles. Sol. 
 alcohol, si. sol. ether. 
 
 Cateohuretin C^HjoO,, 6aq(?) or C38H,,0„. 
 Formed by passing HCl into a boiling alcoholic 
 liolution of catechin (Kraut a. Delden, A. 128, 
 291). Formed also by heating catechin with 
 cone. HCl at 170° Dark reddish-brown in- 
 soluble powder. Not changed at 190°. 
 
 Di-benzoyl derivative C2,HnBz20,(?) 
 Formed, together with di-benzoyl-catechin by 
 heating catechin with BzCl at 190°. Brown 
 mass. 
 
 Catechin C^H^jO,, 2aq. [205°]. S. 99 at 
 50°. Occurs £/,cording to Gautier (C. B. 86, 
 668) in Gambir-catechu together with the two 
 following catechins ; they are extracted by alco- 
 hol and crystallise after evaporation with exclu- 
 sion of air. Monochnic prisms. 
 
 Catechin C42H3jO, J aq. [177°]. Minute needles 
 {v. supra). 
 
 Catechin Cj„H380,saq. [163°]. S. 5-3 at 50°. 
 Minute needles {v. supra). 
 
 Catechin C„H|jOsaq. According to Etti 
 (M. 2, 547) this is the formula of the catechin in 
 Gambir and Pegu catechins. At 100' it becomes 
 CijHigOg, at 160° catechutannic acid C3bH3^0,5 
 and at 180° C^gR^^Ou- The latter is also got 
 by heating catechin for some time with dilute 
 H^SO^. 
 
 Beactions. —1. Diazobenzene chloride gives 
 (C3H5N2)2C,5H,j08, a red crystalline pp. sol. alco- 
 hol and ether; it dyes wool golden-brown. — 
 2. DUute H2SO4 (1:8) at 140° gives phloroglncin 
 and pyrocateohin. 
 
 Catechin CjjHj^Ois. [165°]. In mahogany 
 (Acajou) (Gautier, Bl. [2] 30, 568). Latour a. 
 Cazeneuve (Bl. [2] 24, 119) give this catechin 
 the formula Ci^L^fi,. 
 
 Catechin CjjHasOu. [140°]. In brown cate- 
 chu (G.). 
 
 CATECHOL V. Pyeooatechin. 
 
 CATECHUIC ACID v. Catechin and Pboto- 
 
 CATECHUIC ACID. 
 
 CATECHUTAKNIC ACID C2,H,(,08(?) or 
 C.|JH3^0,5(?) Extracted by water from catechu. 
 
714 
 
 CATECHUTANNIC ACID. 
 
 Formed also by heating catecMn alone at 130°, 
 with water at 110°, or by boiUng it with alkalis, 
 lime, or Pb(OH), (Etti, A. 186, 332 ; Lowe, J.pr. 
 105, 32, 75; Z. [2] 5, 538; Fi. 12, 285). Dark 
 reddish-brown powder. V. sol. acetic ether, 
 V. e. sol. alcohol, insol. ether ; m. sol. water. It 
 oxidises in the air. It gives a greyish-green pp. 
 with FejClg. It does not pp. tartar-emetic. Its 
 aqueous solution is ppd. by gelatin, albumen, 
 and by dilute H^SOj. At 162° it changes to 
 C„H3jO,5(?) which resembles catechutannic acid 
 in all respects— (C2,H,j08).;3PbO. 
 
 CATHARTIC ACID. The active principle 
 in senna leaves. It is a glucoside. It contains 
 only C, H, and 0. Its Ba and Pb salts are 
 amorphous (Kubly, Bl. [2] 7, 356; Stockman, 
 P7i. [3] 15, 749 ; c/. Lassaigne a. Feneuille, A. 
 Oh. [2] 16, 18 ; Bourgoin, G. B. 73, 1449). 
 
 CATTLOSTEEIN v. Cholesteein. 
 
 CEDAR OIL. Obtained by distilling with 
 water the wood of Juniperus virginiana. Con- 
 tains cedrene and cedar-camphor. According 
 to Bertagnini (C. R. 35, 800) it contains a com- 
 pound which combines with NaHSOj. 
 
 Cedar-camphor C.^H^sO. [7i°'i. (282°). 
 V.D. 8-4 (calc. 7'7). Crystalline mass smelling 
 like cedar-wood. V. si. sol. water, v. sol. alco- 
 hol. Distillation with PjOj splits it up into 
 water and cedrene (Walter, A. Ch. [3] 1, 498). 
 
 CEDBENE CisH^^. (237°). S.V. 7-6. S.G. 
 35 -984. Obtained as above (Walter, l.c.). 
 
 Cedrene. From oil of sage (English). Ci^Hj,. 
 (260°). S.G. IS -915. Yellow or green oil. In- 
 active. Besinified by H-iSOj (4:1) even at 0°. 
 Gaseous HCl turns an ethereal solution purple. 
 The refractive index seems to indicate four C:0 
 groups (M. M. P. Muir, G. J. 87, 686). 
 
 The name Cedrene has been used as a 
 generic name for the hydrocarbons Ci^Hj, which 
 occur in the oils of cedar, cloves, patchouli, 
 cubebs, calamus, cascarilla, rosewood, &c. {v. 
 Tekpenes). Cedrenes closely resemble the ter- 
 penes in their optical properties, which point 
 to the existence of 1^ pairs of doubly linked 
 carbon atoms (Gladstone, C. J. 49, 617). 
 
 CEDRIKET V. Codruliqnon. 
 
 CELLULOSE. „{C,H,„Oj}. "S.G. 1-25-1-45. 
 
 Occurrence. — Cellulose is the basal substance 
 of the skeleton of plants, and indeed may be said 
 to constitute the framework of the vegetable 
 world. The problem of its origin is as much 
 physiological as chemical. It does not appear 
 to be formed as the immediate product of the 
 synthetical action of the cell upon carbonic 
 anhydride and water, but mediately from starch, 
 sugar, and other carbohydrates, through the 
 intervention of the cell protoplasm. The me- 
 chanism of this transformation, as well as the 
 inverse conversion of cellulose into the simpler 
 carbohydrates, has not been elucidated, but is 
 assumed on physiological grounds to be of the 
 simplest character. There is nothing in this 
 assumption which contravenes the evidence 
 afforded by the chemical relationships of the 
 carbohydrate group, which are likewise simple. 
 
 Adapting itself to the infinite variety of 
 structure and function presented by plant tis- 
 sues, cellulose occurs in multitudinous forms : 
 and in any given structure is subject to differenti- 
 ation, modification, or variation of elaboration 
 within very wide limits. The scope of this 
 
 article, however, precludes such a, treatiuent oi 
 the subject as would deal with lesser variations, 
 and we shall therefore confine our attention to 
 those celluloses which constitute the fully ela- 
 borated plant fibres. Plant tissues seldom it 
 ever consist of pure cellulose but contain be- 
 sides other products of growth, either mechanic- 
 ally bound up with the tissue, and therefore 
 frequently removable by mechanical means and 
 by the action of simple solvents, or chemically 
 united to the cellulose; combinations of this 
 latter kind constitute the compound celluloses, 
 and are only resolved by a chemical process. 
 
 Preparation.— The isolation of pure cellulose 
 depends upon its relative insusceptibility of 
 chemical change. The general method of pre- 
 paration from raw fibrous materials consists in 
 exposing the moist fibre or tissue to the action of 
 chlorine gas or bromine-water in the cold and 
 subsequently boiling in a dilute alkaline solu- 
 tion ; repeating this treatment until the alkaline 
 solution no longer dissolves anything from the 
 tissue or fibre. The cellulose is then washed 
 with a dilute acid, water, alcohol, and ether, 
 and dried. 
 
 Properties. — Obtained in this way, or by the 
 ordinary process of bleaching from cotton or 
 linen (flax), or in the form of Swedish filter 
 paper, the typical cellulose is a white substance 
 more or less transparent,' retaining the micro- 
 scopic features of the raw fibre. 
 
 The elementary composition is expressed by 
 the percentage numbers (F. Schulze) : 
 
 C 44-0 44-2 
 
 H 6-4 6-3 
 
 O 49-6 49-5 
 
 or by the corresponding empirical formula 
 CsHidOj. These numbers represent the com- 
 position of the dry and ash-free cellulose. 
 Nearly all celluloses contain a certain propor- 
 tion, however small, of mineral constituents ' and 
 the union of these with the organic portion 
 of the fibre or tissue is of such a nature that 
 the ash left on ignition preserves the form of 
 the original. It is only in the growing point of 
 certain young shoots that the cellulose tissue 
 is sometimes found free from mineral constitu- 
 ents (Hofmeister). The proportion of hygrosco- 
 pic moisture, which is an essential constituent 
 of cellulose under ordinary atmospheric con- 
 ditions, varies from 7 to 9 p.c. ; the mean variation 
 due to variations in the hygrometric state of the 
 air is about 1 p.c. 
 
 Cellulose is insoluble in all simple solvents ; 
 it is dissolved by certain reagents but only by 
 virtue of a preceding constitutional modification. 
 The most remarkable solvent of cellulose is 
 cuprammonia (Schweitzer's reagent) in which it 
 dissolves without essential modification, being 
 recovered by precipitation in a form which is 
 chemically identical with the original (Erdmann, 
 J. pr. 76, 385), though differing in being amor- 
 
 ' Cellulose in its earlier stage of elaboration lias no 
 action upon light, but witli age it acquires fclie property of 
 double refraction. This action is independent of the state 
 of aggregation of the cellulose and is therefore an essen- 
 tial property of the substance itself (Sachs, Exp. Phys. d. 
 Pflanzen, p. 398). 
 
 " The ^organic constituents of bleached cotton amount 
 to 0'l-0'2 p.c. of its weight. In the manufacture of the 
 eo-called Swedish paper, the proportion is reduced liy 
 special treatment of the cellulose with acids. 
 
CELLULOSE. 
 
 715 
 
 phous. This reagent has been employed in a 
 variety of forms, a fact whioh explains the dis- 
 crepancies in the statements as to the solubili- 
 ties of the various celluloses in ouprammonia. 
 The following methods of applying the reagent 
 are to be recommended. » 
 
 The substance to be operated upon is inti- 
 mately mixed -with copper turnings in a tube 
 which is narrowed below and provided with a 
 Btopooek. Strong ammonia is poured upon the 
 contents of the tube and after standing for sonae 
 minutes is drawn off and returned to the tube ; 
 the operation is several times repeated untU the 
 solution of the substance is effected. 
 
 Perhaps the most convenient solution, though 
 not so effective in all oases as the former, is that 
 prepared by dissolving ppd. ouprio hydrate in 
 ammonia. In preparing the reagent in this 
 way it is important that the hydrate should be 
 thoroughly washed, preferably out of contact with 
 the air, before dissolving in the strong aqueous 
 ammonia. Cotton is rapidly dissolved by this 
 solution. The soluble compound formed is re- 
 presented by Mulder as {0|,Hi|,05)2Cu(NH4)2.0. 
 It has been doubted whether this compound 
 exists actually dissolved in the viscous solution ; 
 an investigation of the osmotic properties of 
 the liquid, however, shows it to be a true solution 
 (Cramer). Prom an extended investigation of 
 the optical properties of the solution B^champ 
 concludes that the solution of the cellulose is 
 not simple but is accompanied by progressive 
 molecular transformations, the optical activity 
 (dextrorotatory) of the products increasing to a 
 maximum corresponding to a condition of equili- 
 brium ultimately attained (C. B. 100, 117, 279, 
 368). 
 
 The soluble bases (NaOH, KOH) added to the 
 solution give blue gelatinous pps. having the com- 
 position(C|iH,„05)2CuM"0. Digested withfinely di- 
 vided lead oxide the solution yields the compound 
 C8H,„05.PbO. Cellulose is reppd., as a gelatinous 
 hydrate, on the addition of acids, as well as of 
 many neutral bodies such as alcohol, sugar, and 
 common salt, or even on largely diluting with 
 water and allowing to stand. • The pp. dried in 
 vacua is obtained as a transparent mass re- 
 sembling gum-arabic. On digesting the ammo- 
 nia-cuprio solution upon metallic zinc, this 
 metal pps. the copper, replacing it in the solu- 
 tion and producing the corresponding ammonia- 
 zincio solution of cellulose, which is colourless. 
 The property of cellulose of being dissolved by 
 ouprammonia receives an important technical 
 application. A sheet of paper left for a short 
 time in contact with the cuprammonia, so that 
 the constituent fibres are superficially attacked, 
 and then passed between rollers and dried, be- 
 comes impervious to water and its cohesion is 
 not affected at the boiling heat. Two sheets 
 thus treated adhere firmly together, and with a 
 sufficient number, artificial boards are produced. 
 A variety of materials are now produced in this 
 way, on the manufacturing scale, useful for 
 roofing and other purposes (0. E. A. Wright, 
 Journ. Soc. Chem. Ind. 1884, p. 121). 
 
 Reactions. — Cellulosehas already been spoken 
 of as a comparatively inert substance, and its 
 characteristic reactions are consequently few. 
 One of these is available for its identification 
 and is chiefly used in the microscopical exami- 
 
 nations of tissues : this is its reaction with 
 iodine. The reaction, although similar to that of 
 starch, differs in requiring for its determination 
 the presence of an auxiliary (dehydrating) reagent 
 such as sulphuric or phosphoric acid or zinc chlor- 
 ide. The most effective solution is prepared in the 
 following way : zinc is dissolved to saturation 
 in hydrochloric acid and the solution evaporated 
 to the sp. gr. 2-0 ; to 90 pts. of this solution are 
 added 6 pts. potassium iodide dissolved in 10 pts. 
 water ; and in this solution iodine is dissolved to 
 saturation. By this reagent cellulose is coloured 
 instantly a deep blue or violet. 
 
 Compounds oi? Cellulose. — Cellulose is gene- 
 rally inactive towards compounds contained in 
 dilute aqueous solution ; hence its extensive em- 
 ployment in the filtration of solids from solu- 
 tions. Nevertheless it exhibits a tendency to 
 incipient combination even with acids and 
 alkahs (Mills, C. J. 43, 153) ; with metallic salts 
 it forms compounds of sufficient stability to cause 
 their removal from solution, but the combination 
 is of an indefinite and unstable order (Erdmann, 
 J. pr. 76, 385). (C/. Gladstone, /. pr. 56, 247 ; 
 Muller, Fr. 1, 84 ; O'Shea, 0. J. Proc. 1, 206.) 
 Certain carbon compounds, such as the organic 
 astringents, and many of the colouring matters 
 natural and artificial, unite with cellulose to 
 form compounds of various orders of stability ; 
 of these we would more particularly instance 
 amongst others many of the derivatives of di- 
 phenyl which possess a specific power of direct 
 combination with cellulose. Although such com- 
 binations are of great technical importance, being 
 the foundation of the arts of dyeing and printing 
 they are not sufficiently systematised to deserve 
 more than this passing notice. On the other 
 hand some of the substitution-compounds of cel- 
 lulose with acid radicles are both definite and 
 stable. 
 
 Acetyl-ccUalose, — The tri-substituted com- 
 pound C5H,(0^H,O)aO5 is formed by heating 
 cellulose with 6-8 times its weight of acetic 
 anhydride at 180°, and separates as a white 
 flocculent pp. on diluting the syrupy product. 
 Tri-acetyl-oellulose is insoluble in alcohol and 
 in ether, and is soluble in glacial acetic acid. 
 It is saponified by boiling with alkaline solutions, 
 the cellulose being regenerated. No derivative 
 containing more than three acetyl groups has 
 been obtained ; but a mixture of the mono- and 
 di-acetyl cellulose is formcid by treating cellulose 
 with only twice its weight of acetic anhydride, 
 the formation of these bodies being unattended 
 by their solution. 
 
 Cellulose nitrates. (Pyroxylins — Nitrocellu- 
 lose.) — Whenever cellulose in any form is brought 
 into contact with strong nitric acid at a low 
 temperature, a nitro-product or nitrate is formed. 
 The extent of the nitration depends upon the 
 concentration of the acid, upon the duration of 
 its contact with the cellulose, and on the state 
 of the physical division of the cellulose itself 
 The first investigation of these substances 
 dates from 1838, whenPelouze showed the iden- 
 tity of several of these products obtained from 
 paper, linen ic. and starch. Knop and 
 also Kamarsoh and Heeren found that a mix- 
 ture of sulphuric and nitric acids also formed 
 nitrate of cellulose ; and still later (1847) Millon 
 and Gaudin employed a mixture of sulphuric 
 
718 
 
 CELLULOSE. 
 
 acid and nitrate of potash and soda, which they 
 found to have the same effect. Although gun- 
 cottons or pyroxylines are generally spoken of 
 as nitro-celluloses, they are more correctly de- 
 scribed as cellulose nitrates, since they have not 
 heen found to yield amido- bodies on reduction 
 with nascent hydrogen. The following are the 
 general properties of these compounds (Eder)_ : 
 ^1) When warmed with alkaline solutions, nitric 
 acid is removed in varying quantities, dependent 
 upon the strength of the solution employed. 
 
 (2) Treatment with cold concentrated sulphuric 
 acid expels almost the whole of the nitric acid. 
 
 (3) On boiling with ferrous sulphate and hydro- 
 chloric acid, the nitrogen is expelled as nitric 
 oxide; this reaction is used as a method of 
 nitrogen estimation in these bodies. (4) Po- 
 tassium sulphydrate, ferrous acetate, and many 
 other substances, reconvert the nitrates into 
 cellulose. 
 
 Several weU-characterised nitrates have been 
 obtained, but it "is a matter of difficulty to pre- 
 pare any one in a state of purity and without 
 admixture of a higher or lower nitrated body. 
 The following have been described under a no- 
 menclature having reference to a C,2 formula : 
 
 Hexa-nitrate. — C,2H,4(N03)b04 (gun-cotton). 
 Prepared by treating cotton with a mixture of 
 HNO3 (S.G. 1-5) 3 parts, and Hj,SO, (S.G. 1-84) 
 1 part, for 24 hours, at a temperature not exceed- 
 ing 10° ; 100 parts of cellulose yield about 175 
 of the compound (oalc. 183). Insoluble in alco- 
 hol, ether, or mixtures of both, and glacial 
 acetic acid ; with acetone it forms a jelly and is 
 slowly dissolved. It is the most explosive of the 
 Eeries igniting at 160°-170°. Mixtures of sul- 
 phuric acid and nitre do not give this nitrate 
 (Eder). Ordinary gun-cotton may contain as 
 much as 12 p.c. of nitrates soluble in ether- 
 ■alcohol ; the hexa-nitrate seems to be the only 
 one quite insoluble in this menstruum. 
 
 Penta-nitrate. — C,2H,5(N03)505. This com- 
 |)Osition has been .very commonly ascribed to 
 gun-cotton. It is impossible to prepare it in a 
 j state of purity by the direct action of the acid 
 on cellulose. It is prepared by dissolving the 
 hexa-nitrate in nitric acid at 80°-90°, cooling to 
 0°, and adding concentrated sulphuric acid, by 
 which the penta-nitrate is precipitated ; after 
 mixing vrith a large volume of water and wash- 
 ing the precipitate with water and alcohol, it is 
 dissolved in ether-alcohol and finally re-pre- 
 cipitated by water. This nitrate is slightly 
 soluble in acetic acid, nearly insoluble in alco- 
 hol containing only a small proportion of ether. 
 •Strong potash solution converts it into the di- 
 nitrate. 
 
 Tetra- and tri- iiitrates (collodion pyroxyline) 
 are generally formed together when cellulose is 
 treated with a more dilute acid at a higher tem- 
 perature and for a shorter time than in the case 
 of the hexa-nitrate, e.g. 4 vols. HNO3 (1'38), 
 5 vols. HjSO, (1-84) at 65°-70° for 5 10 minutes. 
 They are freely and equally soluble in ether- 
 alcohol, acetic ether, and mixtures of acetic acid 
 and wood spirit, or alcohol, and are therefore 
 inseparable. They are insoluble in pure alcohol, 
 ether, or acetic acid. On treatment with con- 
 centrated nitric and sulphuric acids they are 
 converted into the higher nitrates. Potash and 
 ammonia convert them into the dinitrate. 
 
 Di-nitrate 0, jH,8(NO,)20s is formed as already 
 indicated, and also by the action of hot dilute 
 nitric acid on cellulose. Freely soluble in ether- 
 alcohol, acetic ether, acetic acid, wood spirit, 
 acetone, and absolute alcohol. The further 
 action of alkalis on the dinitrate results in a 
 complete resolution of the molecule. 
 
 The cellulose nitrates have generally much 
 stronger absorption-affinities for colouring mat- 
 ters than the celluloses. They are much 
 less susceptible of attack by acid oxidants 
 than cellulose Itself, and are therefore used in 
 the filtration of solutions containing e.g. chro- 
 mic acid, permanganates, and, of course, nitric 
 acid of any degree of concentration. Nitric acid 
 of S.Gr. 1'42 has a remarkable toughening ac- 
 tion upon filter paper : the modification is effec- 
 ted by simple immersion, and the paper so 
 treated is increased in strength tenfold, under- 
 going at the same time a contraction amounting, 
 in circles, to about ^ diameter. The cellulose 
 so treated contains no nitrogen (Francis, 0. J. 
 47, 183). 
 
 Cellulose and sulphuric acid. — Cellulose is 
 disintegrated and dissolved by the concentrated 
 acid to a colourless solution. The products are 
 sulphates of a series of compounds of which the 
 celluloses and the dextrins may be regarded as 
 the extreme terms. They are easily isolated in 
 the form of Ba salts. The composition of the 
 sulphates may be expressed by the general for- 
 mula Cs„H,„„05„_j,(S0Ji. The variations in 
 composition and in physical properties are func- 
 tions of the temperature (5°-33°) and duration 
 of the action. The limits of specific rotation 
 of these sulphates are [a]j = — 3'65 and + 72-99. 
 These ethereal salts are entirely decomposed 
 by boiling with alcohol : the resulting carbo- 
 hydrates may be regarded as the corresponding 
 alcohols. In composition and properties {e.g. 
 their reactions with iodine) they constitute an 
 extended series, beginning with soluble cellu- 
 loses and terminating in achrodextrin (Honig a. 
 Schubert, M. 7, 465). While it is impossible to 
 determine the mechanism of these successive 
 resolutions of the cellulose molecule with the 
 precision attainable where such changes may be 
 reversed, and therefore completely studied, they 
 certainly establish the typical connection of the 
 celluloses with the simpler carbohydrates, and 
 in a much more complete way than the coinci- 
 dence of empirical formulae. 
 
 Prior to the researches above detailed the 
 initial terms of the transition series had been 
 similarly obtained and described under the term 
 Amyloid, a term selected to indicate their resem- 
 blance to starch. 
 
 A practical application of the reaction of 
 cellulose with sulphuric acid is found in the 
 manufacture of parchment paper. The process 
 consists in the rapid passage of the paper 
 through the strong acid (S.G. l-5-l'6) followed 
 by copious washing. The result may be de- 
 scribed as a superficial conversion of the cellulose 
 into amyloid, whereby it acquires the properties 
 which have obtained for it the designation in 
 question (c/. Hofmann, A. 112, 248). 
 
 Cellulose and chlorine. — Dry chlorine has 
 no action upon cellulose ; the presence of w^ater 
 determines an indirect oxidising action, but 
 there ia no direct combination of cellulose with 
 
CELLULOSE. 
 
 717 
 
 chlorine. By heating cellulose nitrates with phos- 
 phoric pentachloride and oxychloride at 200° 
 and evaporating the excess of the reagents at 
 170°, a viscous liquid is left, miscible with al- 
 cohol and ether, which appears to be composed 
 of, or to contain, a chloride of cellulose or a 
 cellulose derivative (Baeyer, B. 2, 54). Bromine 
 is without action upon cellulose : specimens left 
 for several months in contact with strong bro- 
 mine-water were not sensibly attacked (H. Miiller, 
 Pflanzmfaser, p. 27 ; cf. Pranchimout, iJ. T. C. 
 2, 91). 
 
 Cellalose and Oxygen. Oxycelluloses. — Two 
 of these compounds or series of compounds have 
 been described. 
 
 {a)-Oxycellulose (Witz, Bull. Bouen, 10, 416 ; 
 11, 189) is formed by the action of solutions of 
 the hypochlorites upon cellulose. Exposed to the 
 action of a solution of bleaching powder (5 p.c.) 
 for 24 hours, the fibre is converted into a friable 
 modification having the composition C 43-0, 
 H 6-2, O 50-8. Other oxidising agents produce 
 similar results ; even by exposure to air and 
 light cellulose is slowly converted into these 
 oxidised derivatives. Their formation is accom- 
 panied by molecular resolution, as is shown by 
 their reducing action upon alkaline copper solu- 
 tions : the product giving this reaction is dis- 
 solved by alkaUs to a yellow solution. These 
 oxycelluloses have a strong attraction for basic 
 colouring matters : also for vanadium com- 
 pounds, attracting these from a solution con- 
 taining so minute a quantity as 1 pt. in 
 1,000,000,000. Upon this property a method 
 has been founded for the quantitative estimation 
 of minute traces of vanadium in aqueous solution 
 (Witz a. Osmond, Bull. Bouen, 14, 30). The 
 study of these oxycelluloses is of great import- 
 ance to the manufacturer of textile materials. 
 
 (Pi)-Oxycellulose C^^B^fi^^ (Cross a. Bevan, 
 G. J. 43, 22) is the residual product (insoluble) 
 of the prolonged digestion of cellulose with nitric 
 acid (20-30 p.c.) at 90° C. On washing with 
 water to remove the acid the substance gela- 
 tinises. It dries to a horny colourless mass. It 
 is characterised by its reaction with sulphuric 
 acid : on gently warming it dissolves with develop- 
 ment of a bright pink colour, the reaction re- 
 sembling that of mucic acid, to which, on other 
 grounds, it is probably related. A fresh pre- 
 paration, treated with a mixture of nitric and 
 sulphuric acids, dissolves, and on pouring into 
 water the nitrate Ci8Hj3(N03)30,3 separates as 
 a white flocculent pp. 
 
 Chromic acid. — Cellulose treated with potas- 
 sium dichromate in presence of acetic acid is 
 converted into glucose, dextrin, and formic acid. 
 Permanganates under the same condition effect 
 B similar decomposition. 
 
 Chromic anhydride in presence of sulphuric 
 acid decomposes cellulose rapidly and completely, 
 the carbon being entirely converted into the 
 gaseous compounds CO and COj. It has been 
 proposed to apply this to the quantitative esti- 
 mation of carbon in celluloses and cellulosio 
 mixtures (Cross a. Bevan, C. N. 52, 207). 
 
 Alkaline oxidations. — The permanganates 
 and hypochlorites in presence of alkalis oxidise 
 cellulose to a syrupy mixture of acids of the 
 peotio series (H. Miiller, Pflamenfaser, v. also 
 S. O. I. 3. 206, 291). Fused vfith potassium 
 
 hydrate the cellulose is oxidised to oxalic acid, 
 malic acid being obtained as an intermediate 
 product. 
 
 Electrolytic oxidants. — The nascent oxygen 
 and other electronegative ions liberated in the 
 electrolysis of various saUne solutions have a very 
 powerful action upon cellulose. These actions 
 have been made the subject of interesting re 
 searches by P. Goppelsroeder {D. P. J. 254, 42). 
 
 Cellalose and Hydrolytlc Agents. 
 
 (1) Dilute acids. A large number of acids, 
 organic as well as mineral, attack cellulose, 
 producing hydration changes, attended by dis- 
 integration of the fibre. The action is gradual 
 at ordinary temperatures, and is of course ac- 
 celerated by applying heat. The study of these 
 actions is of the first importance to the cellulose 
 technologist (Girard, O. B. 81, 1105 ; Cross a. 
 Bevan, S. G. I. 1885 ; Crookes, Handbook of 
 Dyeing and Calico-printing, p. 19). 
 
 It is worthy of note here that the cellulose 
 isolated from grass and hay, and many others 
 less highly elaborated than the celluloses which 
 we are at present considering (cotton and linen), 
 are decomposed on boOing with dilute mineral 
 acids with formation of furfural. 
 
 (2) Alkalis. — Dilute solutions of the alkalis 
 are without sensible action upon cellulose, even 
 at temperatures considerably above the boiling 
 point : when, however, oxidising conditions are 
 superadded, molecular resolution sets in. The 
 joint action of calcium hydrate and air at the 
 boiling temperature is especially powerful, oxy- 
 cellulose being produced (Witz, loc. cit.). Con- 
 centrated solutions of the alkalis (NaOH, KOH) 
 at ordinary temperatures act in a very remark- 
 able way upon ceUulose. There appears to be a 
 ' molecular ' combination of the reagents in the 
 proportion C,2ll3jO,„:Na20 (Mercer) which how- 
 ever is easily resolved by washing with water. 
 But the characteristics of the fibre and the fibre 
 substance are found to have undergone a per- 
 manent modification. There is a considerable 
 shrinkage in linear dimensions : in cotton fabrics 
 treated with caustic soda solution of S.G. 1-225 
 this amounts to 25 p.c. The corresponding 
 modifications in microscopic features have 
 been investigated by Crum (0. J. 1863), the 
 changes being found similar to those which 
 take place in the ripening of the fibre in the 
 plant, viz. from a flattened tube with large cen- 
 tral cavity, to a thick-walled cylinder with 
 small lumen. The chemical change produced 
 is, so far as has been ascertained, entirely one 
 of hydration, and it is remarkable that the only 
 evidence of the change is the increased capa- 
 city for hygroscopic moisture. This amounts to 
 5 p.c. of the weight of the cotton, the proportion 
 calculated for the formula CijH^jOnj.HjO being 
 5-5 p.c. From this fact we may also infer that 
 the normal attraction of cellulose for atmo- 
 spheric moisture is a residual manifestation of 
 the molecular combinations which are seen in 
 the multitudinous hydrates of cellulose found 
 in, or constituting, growing tissues. Mercer, 
 who appears to have first investigated these 
 phenomena, further found that the addition of 
 hydrated oxide of zinc very much increased the 
 action of the caustic solution : thus a solution 
 of sodium hydrate of S.G. I'lOO, which is with- 
 out marked action, is rendered very active by 
 
718 
 
 CELLULOSE. 
 
 the addition of tlie oxide in the proportion 
 ZnO:2Na„0. He also found that the actions 
 wore favoured by low temperatures {v. Life of 
 John Mercer by E. A. Parnell, London, 1886). 
 
 By these characteristics the hydration phe- 
 nomena in question are seen to be closely 
 related to those attending the action of the 
 Schweitzer reagent {supra). The more powerful 
 action of the latter we must refer either to the 
 specific action of the ammonia upon the con- 
 densed aldehydio molecules of which cellulose 
 appears to be constituted,' or to the particular 
 relationship of the molecular weight of the 
 cuprammonia in solution to that of the cellu- 
 lose or cellulose hydrate which it forms. 
 
 The action of concentrated solutions of zinc 
 chloride is similar to that of the alkaline hy- 
 drates above hydrates. It is remarkable on the 
 other hand that a saturated solution of zinc 
 nitrate is without action (Mercer). 
 
 (3) Water. — Heated in contact with water, 
 cellulose is attacked at 160°, but not below 150° 
 (Scheurer a. Grosseteste, Bull. Mulhouse, 1883, 
 62-85). Heated at 200° in contact with water 
 in sealed glass tubes it is fundamentally re- 
 solved, being converted into highly-coloured 
 products, insoluble for the most part, with a 
 small proportion of soluble derivatives amongst 
 which are furfural and pyrocateohol (Hoppe- 
 Seyler, B. 4, 15). 
 
 (4) Ferments. — There are, it can scarcely be 
 doubted, endless transformations of cellulose 
 determined by the so-called soluble ferments, 
 though but few have been investigated. The 
 soluble ferment of the foxglove is stated to con- 
 vert cellulose into glucose and dextrin (Kos- 
 mann, Bl. [2] 27, 246). The fluid from the ver- 
 miform appendix of the rabbit has also been 
 found to digest cellulose with liberation of marsh 
 gas and formation of a soluble compound which 
 reduces cupric oxide in alkaline solution. 
 
 Froximate Syntheses of Cellulose. — Trans- 
 formations of the soluble carbohydrates into cel- 
 lulose, which we may regard as a proximate 
 synthesis of this body, are, as already stated, an 
 important feature in the life of plants. The 
 mechanism of these changes has been thus far 
 but slightly studied, and they are of a kind to 
 elude chemical investigation. Of those which 
 have been studied we may notice (a) There is a 
 ohangesetup ' spontaneously' in beet juice which 
 resultsinthe formation of a hard white substance, 
 having the properties of cellulose. On trans- 
 ferring these lumps to a solution of pure cane 
 sugar, a further transformation of the saccharose 
 into the same substance is brought about. At 
 the same time there is produced a gummy sub- 
 stance which is ppd. by alcohol as a white caou- 
 tchouc-like substance of the same composition 
 as cellulose but swelling up with water and other- 
 wise differing in its physical properties from 
 cellulose. This latter derivative is also formed 
 by the action of diastase upon a solution of 
 saccharose. A similar transformation takes place 
 under the influence of certain fatty seeds, e.g. 
 those of rape and colza, and it is probable that 
 the formation of cellulose from saccharose in 
 the plant takes place under the influence of 
 ferments similar to those above described (Durin, 
 C. B. 82, 1108). 
 
 (b) More recently A. Brown has investigated 
 
 the formation of cellulose by the ' vinegar-plant,' 
 growing in solutions of the carbohydrates, e.g. 
 dextrose in yeast- water. The cells elaborate an 
 extra-cellular film, which acts as a ' cell-collect- 
 ing rdedium,' and they possess, therefore, a two 
 sided activity, i.e. the property above mentioned, 
 in addition to their strictly fermentative activity. 
 The cellulosic film in question was found to 
 contain 50-60 p.o. pure cellulose. It is note- 
 worthy that in a solution of levulose the growth 
 of the 'plant ' is unattended by fermentative 
 action, 38 p.c. of the substance being on the 
 other hand transformed into cellulose (G, J. 
 48, 432). 
 
 OlHBB FOEMS OF CELLULOSE. 
 
 We cannot attempt to enumerate the multi- 
 tudinous varieties of cellulose which the plant 
 world presents. Some of these, when isolated 
 in the pure state, resemble the typical cellulose 
 above described, e.g. the cellulose of hemp and 
 rhea. Others, especially such as require a drastic 
 process of resolution, e.g. the cellulose isolated 
 from jute and wood by the chlorination method 
 {infra), resemble rather the (o)-oxycelluloses. 
 Thus jute cellulose (SCjHiuOj.HjO) reduces 
 cupric oxide in alkaline solution, and is much 
 more susceptible of degradation by hydrolytic 
 reagents than those of the cotton type. Cellu- 
 lose from pinewood is similar in composition 
 and properties. 
 
 Cellulose from esparto and straw, isolated by 
 treatment of the plant substance with alkaline 
 solutions boiling under pressure — which are 
 amongst the most important of the staple ma- 
 terials of the paper-maker — are distinguished 
 by their reaction with aniline salts, being coloured 
 a deep pink on boiling with solutions of these 
 compounds. Many of the celluloses are decom- 
 posed on boiling with dilute acids with formation 
 of furfural and formic acid : hay cellulose yields 
 under certain conditions a volatile crystalline 
 body, which appears to be a furfural derivative, 
 but is still under investigation. 
 
 It may be mentioned here that the term cellu- 
 lose is applied by plant physiologists and agri- 
 cultural chemists to substances which would not 
 come under the definition, upon which this 
 article is based, of cellulose as the (irhite) in- 
 soluble residue which survives the exhaustive 
 treatment of plant substances alternately with 
 chlorine, bromine, or oxidising agents, and boil- 
 ing alkaline solutions. 
 
 Animal cellulose. — The mantles of the Pyro- 
 somidse, Salpides, and Fhallusia mammilaris, 
 freed from chondrigen by boiling in a Papin's 
 digester and further purified by prolonged boiling 
 with potash solution, yields a residual substance 
 which not only has the ultimate composition of 
 cellulose, but has identical properties, e.g. dis- 
 solves in cuprammonia, is converted by nitric 
 acid into an explosive nitrate soluble in ether 
 (Schafer, A. 160, 312). According to Virchow 
 cellulose is found in degenerated human spleen 
 and in certain parts of the brain {0. B. 37, 
 492, 860). 
 
 Compound Celluloses. 
 
 Plant tissues, always containing a propor- 
 tion of cellulose more or less large, frequently con- 
 tain other constituents so intimately united to 
 
CELLULOSE. 
 
 719 
 
 the cellulose as to mask its reactions. From the 
 ciroumstauoea of their occurrence and formation 
 It IS not to be expected that the line can be 
 Bharply drawn between mixtures and (xnnbina- 
 tions of cellulose with non-oeUulose constituents 
 of either fibres or tissues. Frfimy (Ann. Agro- 
 nomiques, 9, 529) recognises the existence of the 
 foUowing compounds distinguished from cellu- 
 lose chiefly by their different behaviour to hydro- 
 lytic reagents and ouprammonia; (1) Fibrose, 
 constituting the membranes of wood cells; 
 (2) Paracellulose, constituting the membrane of 
 the pith and medullary rays, and (3) Vasculose 
 constituting the membranes of the vessels. 
 The value of this somewhat arbitrary classi- 
 fication is questionable (Sachsse, Farbstoffe, 
 Kohlehydrafe, Ac, p. 150), and the distinctions 
 which it seeks to establish have not been gene- 
 rally recognised. On the other hand, there are 
 certain groups of substances widely distributed 
 throughout the plant world, which, while they 
 have certain features in common with the cel- 
 luloses, are sufiioiently distinct to admit of che- 
 mical classification apart from them. Generally 
 speaking, these substances are made up of a 
 cellulose and a non-cellulose portion, the latter 
 conferring the special features of distinction. 
 The compound cellulose thus constituted is re- 
 solved, by treatment with reagents according 
 to the methods to be described, into cellulose or 
 a cellulose residue on the one hand, and soluble 
 derivatives of the non-cellulose on the other. Of 
 these groups we shall consider typical members. 
 The foUowing are the compound celluloses 
 sufficiently characterised to warrant special de- 
 scription under class names : the nomenclature 
 of these compounds is explained by their cha- 
 racteristic resolutions. 
 
 Fectocelluloses 
 
 Eesolved by hydrolysis (alkalis) 
 into 
 
 / \ 
 
 Fectic acid and cellulose. 
 
 Type : Baw flax 
 
 (Kolb, Bull. Mulh. 1868, A. Oh. [4J 14, 348). 
 
 Lignocelkiloses 
 
 Besolved by ohlorination 
 
 into 
 
 / \ 
 
 Chlorinated derivs. : ^ 
 
 Aromatic I and cellulose. 
 
 Soluble in alkalis i 
 
 Type: Jute 
 (Cross a. Bevan, 0. J. 41, 90). 
 
 Adipocelluloses 
 
 Besolved by oxidation 
 
 (Nitric acid) 
 
 into 
 
 Similar derivs.: % 
 as by the oxidation [ and cellulose, 
 of the fats. > 
 Type : Cutioular tissue of leaves and fruits 
 (Fi&mj, 0. B. 48, 667; Sachsse, Fa/rbstoffe, &a.). 
 Fectocelluloses. — The purified bast of a Eus- 
 eian flax investigated by Kolb was found to have 
 the aggregate composition : 
 
 C 43-7 
 H 5-9 
 O 50-4. 
 
 The non-cellulose constituent is therefore a 
 substance of lower carbon percentage than cellu- 
 lose. From its yielding pectio acid on boiling 
 with alkalis, it is obviously a substance allied to 
 pectin. Since the fibre yields about 20 p.o. of 
 its weight of the acid derivative we infer inde- 
 pendently that it is a substance containing 
 approximately 41 p.o. carbon, which confirms 
 the view of its constitution above expressed. 
 Many other plant fibres are made up of or con- 
 tain pectooelluloses (Webster, C. J. 43, 23) ; 
 pectic derivatives were identified by Schunck in 
 the products of the action of boiling alkaline 
 solutions upon raw cotton (Proc. Manchester 
 Lit. Phil. [3] vol. iv ). 
 
 The cellular tissue of a large number of 
 fruits, e.g., the apple and pear, and roots, e.g., 
 turnips and carrots, is composed of pecto-ceUu- 
 
 Lignocelluloses. — The course of lignification 
 in plants is marked by profound alterations in 
 the physical properties of the tissues undergoing 
 this modification ; the tissues lose their elas- 
 ticity, become coloured from grey to brown, and 
 the substance of the tissues manifests the 
 chemical properties about to be described. 
 
 Jute. — Aggregate percentage composition : 
 C. 47'0-48'0, H. 5-9-5-7, 0. 47a-46-3 (C^H.^),,. 
 It may be regarded as composed of 
 Non-oellulose(Lignin)C|5H2,0,|,(55'5p.o. C) 25 p.c. 
 and Cellulose C„H3„0,5 (44-4 „ ) 7S „ 
 though the cellulose isolated from the fibre by 
 chemical resolution differs in composition as 
 already stated from normal cellulose, appearing 
 rather as an oxycellulose. The mineral con- 
 stituents of the raw fibre (purified) vary from 
 0'5 to 2 p.c. of its weight ; the hygroscopic 
 moisture from 10-12. Attacked by concentrated 
 solutions of the alkalis similarly to cotton ; 
 freely soluble in cuprammonia, but is incom- 
 pletely precipitated on acidifying ; the body re- 
 maining in solution gives the reactions of the 
 original substance, and may, therefore, be re- 
 garded as a hydrated modification. Jute com- 
 bines freely with the organic astringents (tan- 
 nins) and the majority of aromatic colouring 
 matters. It is coloured a bright yellow by 
 solutions of salts of aniline and other aromatic 
 bases. This reaction is probably due to a pro- 
 duct of oxidation, since it does not take place 
 with jute which has been boiled for some 
 time in solutions of sulphites. It is coloured 
 brown by iodine solutions. Moistened with a 
 solution of phlorogluoin and treated afterwards 
 with hydrochloric acid it gives a deep red 
 colouration ; with pyrrol also in presence of 
 hydrochloric acid it gives a deep carmine 
 colour. A mixture of sulphuric and nitric acids 
 nitrates the fibre, the gain in weight being ap- 
 proximately equal to that of cellulose under the 
 same conditions. The products are orange- 
 coloured and are soluble in acetone. Like the 
 cellulose nitrates, they give no amido-derivatives 
 on reduction. Iodine is absorbed by the fibre, 
 the quantity taken up being constant under 
 constant conditions ; the resulting compound is 
 not more stable than the iodide of starch. This 
 
720 
 
 OELLULOSE. 
 
 reaction may be made use of for the quantita- 
 tive estimation of the lignocelluloses in cellulosio 
 mixtures. Bromine attacks the fibre in presence 
 of water, forming ill-defined compounds which 
 are dissolved by alkaline solutions^ The opera- 
 tion once or twice repeated eliminates the whole 
 of the non-cellulose ; the resulting cellulose 
 amounts to 72-75 p.o. of the weight of the fibre. 
 Chlorine does not act upon the dry fibre, even 
 when the temperature is raised to 100°, but in 
 presence of water combines rapidly at ordinary 
 temperatures with evolution of heat. The 
 chlorinated derivative is yellow coloured ; 
 it is soluble in alcohol, and from the solution 
 water precipitates the compound C,9Hi8Cl40g, as 
 a yellow floeculent mass. This compound gives 
 a characteristic magenta colouration with sodium 
 sulphite solution similar to that of mairogallol ' 
 (Webster, G. J. 45, 205). It dissolves in solu- 
 tions of the caustic alkalis with a brown colour, 
 evolving the characteristic odour of the chloro- 
 quinones. It yields chloropicrin on distillation 
 with nitric acid. Fused with potassium hydrate 
 it yields protocatechuic acid. It is therefore 
 an aromatic derivative, and appears to be allied 
 to the trihydric phenols. The chlorinated fibre 
 when boiled with sodium sulphite solution is 
 entirely resolved into cellulose, and soluble deri- 
 vatives of the non-cellulose or lignin constituent. 
 This constitutes the simplest and most rapid 
 method of cellulose estimation in the fibre. The 
 proportion of cellulose obtained is somewhat 
 higher than by the bromine method (75-78 p.c.) 
 and is further increased by preventing rise of 
 temperature in the chlorination. 
 
 Digested with dilute nitric acid at 80° jute 
 is resolved directly into cellulose (oxycellulose) 
 oxalic and carbonic acids and a peculiar acid 
 derivative of the lignin constituent. This 
 body has the formula C25H4„(N02)023 ; it is of an 
 intense yellow colour, and dyes the animal fibres 
 to a similar shade. It forms salts with the 
 earthy bases (C25H3j(N02)023.M"4) which are pre- 
 cipitated by alcohol from aqueous solutions in 
 the form of bright yellow flocks.' 
 
 Sydrolytic agents. — Jute and the lignocel- 
 luloses generally are much more susceptible of 
 hydrolysis than the simple celluloses. The 
 dilute acids effect a simple hydrolysis at 80°, 
 i.e. the portion dissolved has the same composi- 
 tion and properties as the original ; on raising 
 the temperature to boiling, furfural is obtained 
 in considerable quantity. Boiling dilute alkalis 
 effect a simple hydrolysis. When the hydrolysis 
 is complicated by the introduction of either re- 
 ducing or oxidising conditions, resolution into 
 cellulose and non-cellulose (soluble derivatives) 
 is determined. Thus sulphurous acid, the 
 bisulphites, and the normal sulphites (alkaline) 
 attack and resolve the lignocelluloses when 
 heated with their solutions under pressure. The 
 temperatures necessary for efficient resolution, 
 
 ' Aocording to Hantzsch a. Sohniter (5. 20, 2033), 
 mairogallol' is a species of condensed quinone chloride— 
 the characteristic molecule being derived from quinone 
 by replacement of one of its typical atoms by Cla, the 
 aromatic Uniting being at the same time partially re- 
 solved. Such a view accords equally well with the pro- 
 perties of the derivative in question. 
 
 ' It is worthy of note that the addition of urea to the 
 diluteacid considerably modifies its action, which becomes 
 one of simple hydrolysis as in the case of sulphuric and 
 hydrochloric acids (f^ra). 
 
 i.e. for the isolation of cellulose, are with sul- 
 phurous acid (7-5 p.o. SOj) 90°-100°, with bisul- 
 phites (4 p.c. SO2) 150°, with normal sulphites! 
 (4 p.c. SO2)170°-180°, the increase of temperature- 
 corresponding with the diminution of hydrolytio 
 power by progressive neutralisation of the acid. 
 The hydrolysis is aided by combination of tha- 
 reagents with the soluble derivatives, which pre- 
 vents the reversal of the action at the high 
 temperature, which would otherwise occur. In- 
 heating with solutions of the caustic alkaMs; 
 under pressure, a high temperature is necessary 
 for complete resolution ; a considerable propor- 
 tion of the reagent is necessary for combining- 
 with the products, which under the oxidising 
 conditions are of an acid nature. These facts- 
 are of importance in the preparation of cellulose^ 
 from lignocelluloses, which is now a widely ex- 
 tended industry (Forestry Exhibition Beports^ 
 Edinburgh, 1885). 
 
 Animal Digestion. — It has long been known 
 that the urine of the herbivora contains hippuric 
 acid as a normal constituent, and it has been 
 shown that the benzoyl radicle necessary tO' 
 form this body is a prodtict of the digestion of 
 lignoceUulose (Meissner). Since the lignocellu- 
 lose molecule contains no aromatic compounda 
 in the strict sense of the term (Stutzer, B. 8, 575) 
 the process of digestion must effect the con- 
 version. 
 
 Decomposition by Heat. — Cumulative Beso-- 
 lution. The celluloses bum in the air with a. 
 quiet luminous flame. When heated out of contact 
 with the air they are completely resolved into 
 gaseous and volatile products on the one hand, 
 and a residual black mass, containing a high 
 percentage of carbon. Eegarding these car- 
 bonaceous substances as the products of con- 
 densation of cellulose molecules with elimination 
 of water, the process may be viewed as, in tha 
 main, one of cumulative resolution by dehy- 
 dration (Mills, P. M., June, 1877) ; the cumu- 
 late containing hydrogen and oxygen in chemical 
 union with carbon is still in every sense a com- 
 pound ; taking into consideration, at the same 
 time, its approximation in appearance and pro- 
 perties to the element itself it may be termed 
 a pseudo-carbon.' Dehydrating reagents effect 
 similar resolutions, the lignocelluloses under- 
 going condensation more readily than the cellu- 
 loses. The tendency to carbon accumulation 
 which is the main feature of these resolutions 
 is well marked in the vast series of natural 
 products of the decay of cellulosic tissues, from 
 humus to the coals. Though not of pyrogenio 
 origin they nevertheless deserve mention in this 
 connection from considerations of general re- 
 semblance. 
 
 It is noteworthy that the products of chlori- 
 nating ulmic substances (Sestini, Oaz. It., 1882, 
 292) are closely similar to those obtained from 
 the lignocelluloses. Similar products are also 
 yielded by the cannel coals. 
 
 Other forms of LignoceUulose. Two other 
 varieties of lignoceUulose deserve mention, viz. 
 glycoUgnose, CjjH^Oj,, the substance of fir 
 woods ' gVycod/rupose,' CjjH^Oai, the substance 
 of the stony concretion of pears (Srdmann, 
 A. 138, 1 ; Suppl. 5, 223 ; Bente, B. 8, 476 ; 
 Saohsse, Farbstoffe, 151). On boiling with dilute 
 
 '/>A«.Jl/otr., 1882,326. 
 
CELLULOSE. 
 
 721 
 
 hydrochloric acid these compounds are said to 
 be resolved into a sugar and an insoluble residue, 
 lignoa6 = C,sH2sO,„ and drupose = 0„HjbO,2, re- 
 spectively. On comparing these formulse with 
 those of the original substances, the differences 
 are so slight as to be negligible. The action of 
 the acid is probably therefore one of simple 
 hydrolysis. The reactions of these substances 
 are also in other respects identical with those 
 of the jute substance. Although therefore dif- 
 fering from the ligno-cellulose, above described, 
 in ultimate composition, they are essentially of 
 the same order of compounds. 
 
 Crude fibre. This terra is applied by agri- 
 cultural chemists to the residual product of the 
 treatment of fodder plants with boiling solutions 
 of certain acids and alkalis, applied successively. 
 The process is a crude imitation of the process 
 of digestion in the animal, and the results which 
 it yields are of purely empirical value. Crude 
 fibre will be found on examination, in most 
 cases, to be a ligno-cellulose and to be further 
 resolved by chlorine in the manner indicated. 
 
 AcrpooELLULosES. CorJcand Outicular Tissue. 
 From the mode of formation of these tissues it 
 has been concluded, on physiological grounds, 
 as in the case of the lignoceUuloses, that they 
 are modified celluloses (Sachsse, Farbstoffe, &c. 
 p. 153). The ultimate composition of cork is 
 represented by the following percentage num- 
 bers: C 65-7, H 8-3, N 1-5, 24-5. Unlike the 
 lignoceUuloses, however, it is by no means a 
 simple or homogeneous substance, but is re- 
 solved by the action of mere solvents into a 
 number of proximate constituents, some of 
 which are crystalhue. The residue from the 
 action of these solvents may be regarded as 
 the true cork substance. It is resolved by 
 the action of boiling nitric acid (20-30 p.c.) 
 into cellulose on the one hand — only a small 
 proportion (8-5 p.c), however, surviving so 
 severe a treatment — and a series of fatty acids 
 (or products of their decomposition) such as 
 Buberio and adipic acids, on the other ; the latter 
 amount to about 40 p.c. of the weight of sub- 
 stance treated. If cork be resolved by treatment 
 with sodium sulphite solution, at 166° a soft 
 mass is obtained preserving the structural 
 features of the original, but which on sUght 
 pressure breaks down into a cellular mass. On 
 slight purification this yields a pure cellulose ; 
 the proportion obtained being from 9 to 12 p.o. 
 of the original cork. From these resolutions 
 into cellulose, and products of decomposition 
 similar to those obtained from the fats and waxes 
 under simUar treatment, the substance of cork 
 has come to be regarded as a compound of such 
 molecules ; and this view of its constitution, as 
 well as that of the entire group of substances simi- 
 lar in composition and function, is summed up in 
 the group term Adipocellulose, by which it is 
 proposed to designate them. The cuticular 
 tissues, such as constitute the covering of fleshy 
 fruits and leaves, while similar in many respects, 
 are simpler in composition. When purified they 
 are non-nitrogenous and appear to be homo- 
 geneous. 
 
 Fr6my and Urbain have developed (0. B. 
 100, 19) a somewhat different view of the con- 
 stitution of these tissues. Taking the protective 
 tissues of the leaf of the agave as the type, in 
 
 Vol. I. 
 
 addition to an interior epidermal layer, whioh 
 is cellulosic, and is soluble in cuprammonia 
 after treatment with boiling hydrochloric acid, 
 they distinguish the external or true epidermis, 
 which they term Cutose. The substance com- 
 posing this tissue has the following properties : 
 it is resolved by alkaline saponification into two 
 fatty acids, oleocutic C^jH^Og a liquid oily body, 
 and siearocutic CjgHjgOj, a solid body melting 
 at 76°, soluble in benzene and glacial aoetio 
 acid, and slightly soluble in boiling alcohol, the 
 solution gelatinising on cooling. The following 
 numbers give the percentage composition of the 
 original cutose and of the two derivatives. 
 
 Cutose Oleocutic acid Stearocutic acid 
 C 68-4 66-6 75-5 
 
 H 8-7 8-2 10-8 
 
 22-9 25-2 14-2 
 
 Whence it is concluded that the molecule of 
 cutose is composed proximately of oleo- and 
 stearo-outio acids in the molecular proportion 
 of 5:1. 
 
 The two derived acids above described are 
 marked by a curious instability or tendency to 
 reversion, passing under certain conditions, 
 notably by exposure of their solutions to light, 
 into modifications closely resembling the original 
 cutose. 
 
 With regard to the distribution of cutose in 
 the plant world, while it is the main constituent 
 of the external protective tissues of leaves, 
 fleshy fruits and the stems of annuals, it is 
 found also in the interior tissues, e.g. the bast 
 and fibro-vascular bundles. 
 
 These researches are an important contribu- 
 tion to the subject ; and while there is no 
 reason to doubt the authors' conclusions in the 
 main, it is probable that they have overlooked 
 the presence of cellulose as a constituent of 
 cutose which occurs as an organised i.e. cellular 
 tissue. We need scarcely observe that the 
 chemistry of these adipooelluloses has been 
 but little investigated. 
 
 OoNSTiTuiioK or Cellulose. 
 The physical properties of cellulose throw 
 but little light on the problem of its molecular 
 constitution. We have seen, moreover, that 
 cellulose is chemically inert ; its derivative com- 
 poimds are few, and of these indeed the nitrates 
 alone appear to merit such a description, their 
 formation being unattended by molecular reso- 
 lution. From their composition and propertiea 
 we infer the presence of alcoholic OH groups in 
 the cellulose molecule. The gradual resolution 
 by the action of sulphuric acid, through a series. 
 of compounds terminating with achroodextrin, 
 indicates a certain constitutional relationship 
 to the simpler carbohydrates of which the latter 
 is a typical representative. The exact mechan. 
 ism of the resolution not having been elucidated, 
 it is impossible to draw any bat the general 
 inference from the products to the original 
 cellulose molecule, viz., that the latter is a com- 
 plex of molecules resembling these simpler and 
 better known carbohydrates. We also infer that 
 the bond whioh unites them is one of dehydra- 
 tion, but the exact nature of this bond is for the 
 present entirely conjectural. (For a discussion 
 of the probabilities involved in this problem the 
 reader is referred to a paper by Baeyer entitled 
 
 3A 
 
723 
 
 CELLULOSE. 
 
 •Wasserentziehung a. ihre Bedeutung fiir daa 
 Pflanzenlebeu und die Giihrung,' B. 3, 63.) 
 That such molecules are to be regarded physio- 
 logically as well as chemically, as the proximate 
 constituents of the cellulose molecule, is a con- 
 clusion which has perhaps been somewhat pre- 
 maturely drawn. Its ultimate origin is of course 
 to be traced to the carbonic anhydride and water 
 of the air and soil, the synthesising agencies 
 being the protoplasm and chlorophyll of the 
 plant, aided by the supplies of energy from 
 without. It has been supposed that the mediate 
 source of the vegetable carbohydrates is formic 
 aldehyde, and the recent researches of Loew 
 {B. 20, 141) upon the condensations of this alde- 
 hyde have at least confirmed the probability 
 of this supposition. The products of resolution 
 of cellulose, moreover, clearly indicate the pre- 
 sence of aldehydio groups in the molecules. 
 Apart from conjecture, we may, to sum up this 
 brief review, regard the cellulose molecule as a 
 complex of simpler carbohydrate groups, con- 
 taining alcoholic and aldehydic oxygen {v. also 
 Bowman, B. A. 1887). 
 
 The most striking features of the empirical 
 formula of cellulose OjHiuO., are those character- 
 istic of the entire group of carbohydrates, the 
 molecule containing some multiple of Oj and 
 the hydrogen and oxygen having the ratio 2 : 1. 
 At present these relationships are merely sugges- 
 tive of conditions of molecular equilibrium to 
 be elucidated by future investigation. 
 
 The prevalence of the Cj group is remarkable 
 and suggests a relationship to the aromatic 
 group, which is confirmed by the undoubtedly 
 cellulosic origin of the benzene compounds. 
 On the other hand we have no evidence of the 
 existence of closed chains of C atoms in the 
 cellulose molecule, nor have any simple transi- 
 tions from the one group to the other been as yet 
 discovered. If we turn, however, from the typical 
 cotton cellulose to other forms of cellulose, such 
 as those isolated from growing tissues, we find in 
 the ease with which many of them yield furfural 
 as a product of acid hydrolysis, some evidence 
 of a more complex union of the C atoms, than 
 the normal type usually assumes. Passing on 
 further to the lignooelluloses we find a molecule 
 in the constitution of which a furfural group 
 undoubtedly plays a part, and in which the 
 linking of the C atoms is such as permits a 
 simple transition, in part at least, to products of 
 undoubtedly ' aromatic ' composition. 
 
 We have, in this brief statement of the evi- 
 dence which we have upon which to found our 
 views of the constitution of cellulose, endea- 
 voured rather to indicate the main lines upon 
 which the investigation of the problems involved 
 is proceeding, than to draw premature conclu- 
 sions. The subject will be enormously developed 
 in the future, and will constitute an important 
 foundation of the natural history of the carbon 
 compounds ; a department or view of the science 
 which can scarcely as yet be said to be within 
 reach. 
 
 NoMENOtATUEE. 
 
 Considerable confusion has been imported 
 into this subject by the indiscriminate employ- 
 ment of the terms, cellulose, lignin, woody 
 fibre, lignose, 'crude fibre,' in describing the 
 
 various products, natural and artificial, of which 
 this article treats. The want of uniformity 
 arises from the division of the subject amongst 
 physiologists, agriculturists and chemists. That 
 which we have adopted appears to bring about 
 a certain simplification. 
 
 The application of the term cellulose we 
 have already defined and limited. To denomi- 
 nate the compound celluloses, which correspond 
 with the chief modifications of cellulose recog- 
 nised by physiologists, we use a compound 
 term consisting of cellulose as the substantive 
 portion with a qualifying prefix. To specially 
 distinguish the characteristic constituent of 
 these compounds, that to which we have ap- 
 plied the neutral term non-cellulose, we employ 
 the root of the prefix with the termination m, 
 thns pectin, lignin. 
 
 In conformity with this plan it may be ex- 
 pedient to introduce such terms as subero- 
 cellulose, cuto-cellulose, suberin, cutin, and many 
 others : but this should be left to be determined 
 by the progress of investigation. The special 
 classification and nomenclature proposed by 
 Fr6my has been already discussed. C. F. 0. 
 
 CUBASIIT, the meta- acid {v. Abasic acid) 
 existing in cherry-tree and plum-tree gums, and 
 in the gums of other trees of the same family. 
 Gum arable yields cerasin when heated to 150° 
 (G61is, G. B. 44, 144). Cherry-tree gum is said 
 to contain 52'lp.o. arabin, 34-9 cerasin, 12 water, 
 and lash. Treated with nitric acid cerasin 
 yield 15'5 p.c. mucic acid. C.O'S. 
 
 CESATIN v. Pkoteids. 
 
 CERATOPHYLLIN. [147°]. Extracted by 
 lime-water from the Uohen Parmelia cerato- 
 phylla (Hesse, A. 119, 365). Thin prisms, si. 
 sol. cold, V. sol. hot, water ; v. sol. alcohol, 
 ether, and aqueous alkalis. Pe-^Clj colours its 
 alcoholic solution purple. Bleaching-powder 
 gives a red colour. 
 
 CERBEEIN. A poisonous, crystalline gluco- 
 side occurring in Cerbera Odollam (Oudemans, 
 J.pr. 99, 407; de Vrij, B. T. C. 3, 167). 
 
 CEEEBEIN C.69-08, H.11-47, N.213, 0.17-32 
 (Parous. Prom these numbers the formulas 
 C,„H,„N20„; CjsH^^N^O,,; or C^H.^jN^O,, may 
 be calculated). The body called Ph/renosin by 
 Thudichum {J. pr. [2] 25, 19) is probably the 
 same body in an impure state. The name 
 cerebrin was used fiurst by Kiihn (1828) and ap- 
 plied to a mixture of cholesterin and lecithin. It 
 was used by Lassaigne (1830) to denote the 
 entire substance that can be extracted from 
 brain by alcohol. It was employed by Gobley 
 (1850) to denote so-called 'protagon;' and by 
 Muller to denote the nitrogenous substance free 
 from phosphorus that can be extracted from 
 the brain by alcohol, to which he gave the 
 formula C„H,sNOs. 
 
 Beferences. — Fourcroy, A. Ch. 16, 282 ; Fr^my, 
 J. Ph. 27, 453 ; Liebreich, A. 134, 29 ; Gobley, 
 J. Ph. [4] 19, 346 ; W. Muller, A. 103, 131 i 
 105, 361. 
 
 Preparation. — Ox-brain is freed from mem- 
 branes, washed with water, squeezed and heated 
 with baryta to boiling. The clear liquid is 
 poured off and the coagulated residue washed 
 with nearly boiling water, dried and extracted 
 with alcohol. The first extract deposits very 
 
CEKIUM. 
 
 723 
 
 little on cooling, but cerebrin mixed with eholes- 
 terin separates from the subsequent extracts. 
 The cholesterin is removed by solution in ether. 
 So prepared, cerebrin is free from phosphorus 
 but contains inorganic matter. 250 grms. were 
 got from 90 brains. It is redissolved in alcohol 
 at 60° which leaves a barium salt undissolved. 
 The barium that goes into solution is removed 
 by a current of CO^. The cerebrin is purified by 
 frequent recrystaUisations from alcohol. The 
 earlier mother-liquors deposit on standing a 
 gelatinous pp. By reorystallisation from alcohol 
 this pp. may be separated into cerebrin (spheri- 
 cal crystals), homoeerebrin (needles), and en- 
 cephalin (E. Parous, J. ^. 132, 310). 
 
 Properties. — Separates as a white crystalline 
 powder composed of transparent globules from 
 a boiling alcoholic solution. Soluble in acetone, 
 chloroform, benzene, and glacial acetic acid. 
 Insoluble in ether. Separates from acetone 
 partly as globules, partly as matted threads. 
 Cerebrin dissolves in cone. H^SO^. On standing 
 exposed to the air, the liquid becomes covered 
 ■with a purple skin, which afterwards turns green. 
 Cerebrin does not combine with acids, bases, or 
 salts. It is not affected by boiling for a short 
 time with baryta. It is but sUghtly decomposed 
 by bbUing alcoholic potash. Cerebrin swells up 
 but slightly in boiling water. It is very slightly 
 hygroscopic, absorbing 2 p.o. of water from the 
 air. It is decomposed by boiling for a long 
 time with baryta. Boiled for some hours with 
 dilute HCl it forms a solution that can reduce 
 Fehling's solution. 
 
 Homoeerebrin C. 70-1 p.c. ; H. 11-6 ; N. 2-2 ; 
 O. 16-1. The yield is J- that of the cerebrin. 
 Soluble in the same liquids as cerebrin ; soluble 
 also in boiling ether. Swells up in hot water, 
 but does not form a paste. Is not decomposed 
 by boiling water. Treated with hot HCl, it 
 forms a solution that reduces Fehling's solution. 
 Boiled for a long time with baryta, it is decom- 
 posed. It is not hygroscopic. Its solutions are 
 neutral. It does not combine with acids, bases, 
 or salts. It separates from alcoholic solutions 
 in very fine needles. After separation from 
 alcohol and drying, it is not a white powder (like 
 cerebrin) but a waxy mass. It is more soluble 
 in absolute alcohol than cerebrin. 
 
 Encephalin. C. 68-4; H. 116; N. 3-1; 0. 16;9. 
 Eesembles homoeerebrin rather than cerebrin. 
 It separates from solutions in flexible plates. 
 From acetone it separates in granular masses. 
 It swells up with hot water forming a complete 
 paste. Boiled with HCl, it forms a solution 
 that can reduce Fehling's solution. 
 
 CERIC ACID. C. 64-2 p.c; H. 8-8 p.o. ; 0. 270 
 p.c. Obtained by the action of HNO3 on cerin, or 
 according to Kiigler on phellonio acid C22H42O3 
 [96°]. Phellonio acid is obtained, together with 
 glycerin and stearic acid, by the action of alco- 
 holic KHO on cork that has previously been 
 exhausted by chloroform and alcohol (Dopping, 
 A. 45, 289). 
 
 CEEIN C2„H320(?). [250°]. A substance that 
 may be extracted by chloroform from cork, the 
 bark of Quercus Suber, in which it occurs to the 
 extent of 2 p.c. (Kugler, Ar. Ph. [3] 22, 217; 
 ef. Chevreul, A. Ch. 96, 170 ; Dopping, A. 45, 
 289). Needles, insol. water, sol. other solvents. 
 According to Siewert (^. 3-?^!8,383) an alcoholic 
 
 extract of cork contains phellyl alcohol 
 C„H2sO [100°], a neutral, crystalline substancB, 
 si. sol. alcohol. 
 
 CERIUM. Ce. At. w. 139-9. Mol. w. un- 
 known as element has not been gasified. S.Gr. 
 (abt. 18°) 6-63 to 6-73 (Hillebrand a. Norton, P. 
 156, 471). M.P. considerably above that of Sb 
 (450°) but below that of Ag (950°) (H. a. N.). 
 S.H. (0°-100°) -04479 (H., P. 158, 7). S.V.S. 
 21-1. Chief lines in emission-spectrum ; 5352-2, 
 5273-2, 4628-2, 4572-6, 4562-1, 4296, 4289 (Tha- 
 16n). In 1803 Klaproth, and independently 
 BorzeUus and Hisinger, separated a new earth 
 from a Swedish mineral and called it Ceria 
 (from the then recently discovered planet Ceres) ; 
 in 1839-41 Mosander {P. 11, 406) proved that 
 ceria was a mixture of at least three metalUo 
 oxides, oxides viz. of Ce, La, and Di. The metal 
 cerium was first obtained by Mosander in 1826, 
 it was more fully examined by Wohler, Bunsen, 
 and other chemists. 
 
 Occurrence. — In many Swedish minerals, 
 more especially in cerite a silicate of Ce (abt. 
 56 p.c. CCjO,) ; occurs as silicate, phosphate, 
 carbonate, fluoride, &o., also in many apatites ; 
 generally accompanied by La, Di, Fe, Al, &o. 
 It has been recently found that clay used for 
 brickmaking at Hanistadt (near Seeligenstadt 
 in the neighbourhood of Frankfurt) contains 
 from 8 to 12 p.o. of Gefi^ (Strohecker, /. pr. [2] 
 33, 133 a. 260). 
 
 Preparation. — Cerite is heated to redness, 
 powdered, mixed with considerable excess of 
 cone. H2SO4, and the mixture is gradually heated 
 to incipient redness in a Hessian crucible ; after 
 cooling, the mass is powdered and then added, 
 little by little, to ice-cold water, whereby sul- 
 phates of Ce, La, and Di are dissolved ; the 
 treatment with H^SO, &c. is repeated with the 
 portion insoluble in cold water ; the aqueous 
 solution is heated to boiling, whereby basic sul- 
 phates are ppd. ; solution in ice-cold water and 
 ppn. by heating to boiling are repeated several 
 times (Marignac ; Bunsen ; Wohler). The solu- 
 tion in cold water is ppd. by addition of oxalio 
 acid solution; the oxalates are washed with 
 water, dried, and heated in a Pt dish until com- 
 pletely converted into oxides. The mixed oxides 
 (of Ce, La, and Di) may now be treated in many 
 different ways. The following method was used 
 by Brauner (O. J. 47, 884) in order to prepare 
 pure CejSSO^ for atomic weight determinations ; 
 it is based upon the formation of basic Ce 
 nitrate insoluble in water. The mixed oxides were 
 dissolved in moderately cone. HNOjAq, excess 
 of acid was removed by evaporation, and the 
 syrup-like liquid was poured into much pure 
 boiling water ; the ppd. basic eerie nitrate was 
 washed (on a funnel connected with a pump) 
 with boiling water containing a little nitric acid. 
 The nitrate was dissolved in HNOjAq, excess of 
 acid was removed by evaporation, the liquid 
 was poured into boUing water, &c., as already 
 described. This treatment was repeated 10 or 
 11 times. From the pure basic eerie nitrate 
 thus obtained other Ce compounds may be pre- 
 pared. Brauner prepared Cej3S04by dissolving 
 the basic nitrate in dilute HjSO^Aq, and HjSOsAq, 
 evaporating to dryness in a Pt dish, and heating 
 with due precaution, dissolving in a little ice- 
 oold water, ppg. by absolute alcohol, washing 
 
 3a2 
 
724 
 
 CERIUM. 
 
 with abs. alcohol, dissolving in ice-cold water, 
 ppg. by alcohol, dissolving again, heating to 
 100° and stirring with a glass rod ; CejSSOj.eHjO 
 was thus obtained ; it was dehydrated by heat- 
 ing for some weeks at 440° in molten sulphur ; 
 at full redness the sulphate gives off SO^ and 
 SOj and leaves pure CeO^. 
 
 Bobinson (Pr. 37, 150) prepared pure Cefil,. 
 The mixed oxides from cerite were dissolved in 
 HNO^Aq {v. supra), and the liquid, after concen- 
 tration to a syrup, was poured into boiling dilute 
 HjSOjAq ; the basic sulphates were dissolved in 
 HNOJAq, the Ce salt oxidised by boiling with 
 PbO^ (Gibbs, Am. S. [2] 37, 352), the liquid 
 evaporated, and La and Di salts removed by 
 treatment with HNOjAq; the pure basic cerio 
 nitrate remaining was converted into chloride by 
 treatment with HClAq, from this Ce oxalate was 
 obtained by ppn. with oxalic acid ; the oxalate 
 was heated in dry HCl, and pure CBjCIj was 
 thus obtained (for details v. original). Bobin- 
 son (I.e.) also recommends evaporating the nitric 
 acid solution of the mixed nitrates to complete 
 dryness, heating the brown mass to full redness 
 until the residue is pale-yellow, and treating 
 this with boiling dilute HNOjAq ; Ce basic 
 nitrate remains while nitrates of Di and La 
 dissolve. 
 
 Other methods for preparing more or less 
 pure Ce salts are described by Bunsen, P. 155, 
 375 ; Czudnowicz, J. pr. 80, 16 ; Watts, O. J. 
 2, 147 ; Holtzmann, J. 1862. 136 ; Jolin, Bl. [2] 
 21, 533 ; Erk, Z. [2] 7, 100 ; Popp, A. 131, 361 ; 
 Pattison a. Clark, C. N. 16, 259. Wohler (A. 
 144, 251) prepared Ce by adding pieces of Na 
 to a molten mixture of Ce^Clj, KCl, and NH4CI ; 
 the product, however, was impure. Hillebrand 
 a. Norton (P. 155, 633 ; 156, 466) by electrolysing 
 CejClj, covered with NH^Cl, using a thick iron 
 wire as negative electrode (4 Bunsen's cells) 
 obtained approximately pure cerium. (For details 
 V. original papers.) 
 
 ProperHes and Reactions. — Steel-grey, very 
 lustrous, very ductile, metal ; malleable, un- 
 changed in dry air, but in moist air is super- 
 ficially oxidised; heated in air burns to oxide 
 with production of heat and much light ; burns 
 in CI, Br, I vapour, S vapour, P vapour, forming 
 compounds with these elements ; easily dissolved 
 by HClAq, dilute HNO3 or BLjSOjAq, no reaction 
 with cold cone. HNO3 or HjSOjAq. Ce slowly 
 decomposes cold water, quickly decomposes hot 
 water. As the V.D. of no Ce compound 
 has yet been determined, the At. w. of the 
 metal must be fixed by chemical considerations 
 and by S.H. The value given to the At. w. for 
 many years was abt. 92, and the formulte of the 
 oxides, and chloride, &c., were CeO, Cefi^, 
 CeClj, &c. ; Ce was thus placed, along with La 
 and Di, in the same class as Al and the earth 
 metals. Considering the relations between the 
 properties of compounds of Ce, La, Di, and of 
 other elements, Meudelejeff {A. Supplbd. 8,186) 
 thought that Ce ought to be classed with those 
 elements which form well-marked oxides MO2, 
 i.e. with Ti, Zr, Sn, &c. If this were done the 
 At. w, of Ce would become 92 x |. Further in- 
 vestigation has completely justified Mendelejeff's 
 proposal ; Ce is now classed with C, Si, Ti, Zr, 
 Sn, Pb, and Th ; La is placed with Al and the 
 earth metals, and Di is classed with the elements 
 
 of Group V. whose characteristic highest oxide 
 is M2O5. 
 
 The At. w. of cerium has been determined 
 (1) by estimating SO, in oerous sulphate (Be- 
 ringer, A. 42, 134 ; Eammelsberg, P. 55, 65 ; 
 Hermann, J. pr. 30, 184 ; Marignac, A. Ch. [3] 
 27, 209; 38, 148). (2) by estimating CI in 
 cerous chloride (Beringer, l.c.; Bobinson, Pr. 
 87, 150). (3) from combustions of cerous 
 oxalate (Jogel, A. 105, 45; Bammelsberg,P. 108, 
 44). (4) by conversion of Ce23S04 into CeOj by 
 heat (Brauner, C. J. 47, 879). (5) by determining 
 S.H. of approximately pure Ce (Hillebrand a. 
 Norton, P. 156, 471). The most accurate deter- 
 minations are those made by Bobinson and 
 Brauner, respectively: both lead to the number 
 139-90 (0=15-96). 
 
 Cerium is distinctly metallic in its physical 
 and chemical properties ; it forms the oxides 
 Gefl, and CeOj (and probably also CeOj), both 
 of these are salt-forming in their reactions with 
 acids, but the well-marked salts (cerous salts) 
 are those corresponding to Ce^Oj, e.g. CejSSO^ 
 &c. ; in this respect Ce differs from Ti, Zr, Th, 
 Sn, and Pb, the salts of which metals belong to 
 the forms MX and MX2(X= SO,, CO3, 2NO3, &e.), 
 and shows analogies with the elements of 
 Group HI. (Al &c.). Ce does, however, form a 
 eerie sulphate Ce2S04 ; besides the oxide CeOj, 
 a fluoride CeF, analogous to TiF„ ZrF,, &c., is 
 known Qv. Caebon oboup oi- elehents ; also 
 Titanium group oi- elements.) 
 
 Detection and Estimation. — Ce salts are 
 generally soluble in water: alkalis pp. white 
 hydrated Ce^Oj ; NaClOAq pps. yellow hydrated 
 CeOj which dissolves in HClAq in presence of 
 alcohol to form a colourless liquid ; solutions of 
 Ce salts are ppd. by oxalic acid, the ppd. oxalate 
 is white and insoluble in NH4 salts ; saturated 
 KjSOjAq pps. a white crystalline double sulphate, 
 scarcely soluble in cold water, decomposed and 
 dissolved by hot water containing a little HCl ; 
 Ce salts boiled with PbOz and a little HN03Aq 
 give a yellow solution. When a slightly acid 
 solution of a Ce salt is mixed with ammonium 
 acetate, a little H^OjAq is added, and the whole 
 is warmed, a yellowish pp. is formed (Hartley, 
 C. J. 41, 202) ; if this pp. is moistened with 
 NHjAq, again treated with H202Aq, and warmed, 
 an orange solid (? CeOj) is produced (de Bois- 
 baudran, C. B. 100, 605). Ce can be separated 
 from La and Di only by very prolonged treat- 
 ment, V. Preparation. Ce is usually estimated 
 as CeOj, but it is very difficult to obtain this 
 oxide pure. For methods of separation and 
 estimation a manual of analysis must be con- 
 sulted. 
 
 Cerium, carbide of. Said to be obtained as 
 a dense black powder, insoluble in hot cone. 
 acids, by heating cerous formate or oxalate in a 
 stream of H, and treating with HClAq to dis- 
 solve out any oxide formed. Analyses agree 
 approximately with composition CeOj (Dela- 
 fontaine, J. 1865. 177). 
 
 Cerium, haloid and oxyhaloid compounds of. 
 Cerium forms cerous haloid compounds, Ce^X, 
 or CeXj, corresponding to the oxide Ce^O, ; and 
 also a oeric fluoride CeP, : the molecular weight 
 of none of these compounds has been deter- 
 mined. 
 
CERIUM. 
 
 726 
 
 Cbroxis bkomide. CeaBrj or CeBrj. Known 
 as the hydrate CeBr3.a;H.,0. Obtained by dis- 
 solving cerous oxide, Gefi,, in HBrAq and 
 evaporating. Deliquescent needles ; unchanged 
 by heating out of contact with air; heated in 
 air, partially decomposed with loss of Br. Forms 
 double salt CeBr3.AuBr3.8H2O (Jolin, Bl. [2] 21, 
 
 _ Ceeous CHioErDE. CesClj or CeClj. Ob- 
 tained by heating Ce in 01; or by dissolving 
 CejOa in HClAq, adding NH^Cl, evaporating to 
 dryness, and driving off NH,C1 by heating; or 
 by passing a mixture of dry CO and 01 over hot 
 Ce^Oj (Didier, G. R. 101, 882). Pure CeCla was 
 prepared by Bobinson {Pr. 37, 150) by heating 
 pure Ce2(C20,)3 in pure dry HCl gas to 120°-130° 
 for some time, then to 200°, and then to low 
 redness ; the small quantity of C separated was 
 removed by heating at low redness in mixed 
 CO2 and HCl ; finally the temperature was 
 raised to a full red heat and the 00^ stream 
 was stopped. The chloride was allowed to cool 
 in HCl gas, transferred to a small flask, and 
 kept in vacuo, over H^SOj and surrounded by 
 CaO, until all HCl was removed. S.G. ||| 3-88 
 (Robinson, l.c.). A white, deliquescent solid; 
 easily soluble in water with production of heat ; 
 decomposed by O, or by steam, to Ce^Oj (Didier). 
 A hydrate, CeCl3.7H20, is said to be formed by 
 digesting Ce203 in HClAq and evaporating. 
 Various double salts are described ; e.g. 
 
 CeCl3.4HgCl,.10H2O, CeCls.PtClj.l3H30, 
 CeCl3.AuCl3.13H20 (John, l.c.). 
 
 Cebous oyANiDE (and double cyanides) v. 
 
 CyANIDES. 
 
 Cekohs fluobide. CeFj. Obtained as a 
 gelatinous pp. (2CeP3H20) by adding NaFAq to 
 CeCl3 in HClAq (Jolin). 
 
 Cemo fluobide. CeFi.HjO. An amorphous 
 brown powder, insoluble in water, obtained by 
 treating CeOj-CHjO with HFAq, washing, and 
 drying at 100°. Decomposed by heat with loss 
 of H2O and HF and formation of CeF3 ; heated 
 strongly in contact with moist air CeOj and HF 
 are formed. Combines with KF (by treatment 
 with KF.HF) to form 2CeF4.3KF.2H2O (Brauner, 
 C. J. 41, 69). 
 
 Cekous iodide. 062X5 or Celj. Obtained as 
 the hydrate Cela.gHjO, in colourless crystals, by 
 dissolving Ce203 in HIAq, evaporating in a 
 current of HjS, and placing in vacuo over 
 HljSOj: soluble in water and alcohol, very 
 quickly decomposes in air (Lange, /. pr. 82, 
 134). 
 
 Cekium oxychlobides. The compound 
 CejOaClj ( = Ce203.2CeCl3) is said to be formed 
 when CeCl3 is heated with Na (in preparation of 
 Ce) and the mass is treated with water. Dark 
 purple, lustrous, powder; insoluble in water 
 (Wohler, A. 144, 254). The same oxychloride 
 is said to be obtained, as iridescent scales, by 
 passing a mixture of steam and N over a fused 
 mixture of CeCls and NaCl ; easily soluble in 
 dilute acids ; heated in air gives CojOj and HOI 
 (Didier, C. B. 101, 882). 
 
 Cerium, hydroxides of, v. Ceeicm, oxtdes of. 
 
 Cerium, oxides and hydrated oxides of. 
 The best studied oxides are cerous oxide Cefl,, 
 and oerio oxide CeOj; a peroxide Ce03 also pro- 
 bably exists. Other oxides, e.g. Cefi^ and Ce^Og, 
 
 have been described, but their existence is verj 
 doubtful. 
 
 Cbeous oxide. 00203. (Cerium ses^uioxide.) 
 Mol. w. unknown. The white, bulky pp. ob- 
 tained by adding KOHAq to a solution of a 
 cerous salt is hydrated cerous oxide ; as the pp. 
 at once begins to take up and CO2 from the 
 air the hydrate has not yet been obtained pure. 
 The oxide Gefi^ is prepared by heating cerous 
 oxalate in a stream of pure H. The oxalate is 
 prepared from the basic nitrate [v. Ceeium, Pre- 
 paration) by dissolving in a little HNOjAq ana 
 ppg. by oxalic acid (Popp, A, 131, 361 ; Eam- 
 melsberg, B. 6, 86). 
 
 Properties and Reactions. — A grey solid ; 
 unchanged by heating in H. Dissolves in many 
 acids to form cerous salts of the form 002X3, 
 X= SOj, CO3, 2NO3, 2010,, &a. 
 
 Cebic oxlde. CeOj. (Cerium dioxide). The 
 pale yellow pp. obtained by suspending 
 Ce203.a;H20 in KOHAq and passing in 01 is hy- 
 drated eerie oxide (2Ce02.3H20 ; Bammelsberg, 
 P. 108, 40). 
 
 Formation.— 1. By washing the hydrate with 
 water containing a little acetic acid until KOIf 
 is removed, drying and heating. — 2. By heating 
 cerous sulphate 0028804 to full redness in air. 
 3. By heating CeF4 in air (Brauner). 
 
 Preparation. — Cerous oxalate is prepared 
 from the basic nitrate from cerite (v. Ceeium, 
 Preparation) ; it is heated to redness in a Pt 
 dish with free access of air. Nordenskiold (P. 
 114, 616) obtained colourless, transparent, 
 tesseral crystals of CeOj by heating 0bO2 for 
 24 hours with a little borax in a porcelain oven, 
 and treating the mass with HOlAq: S.G-. at 
 15° = 6-94. 
 
 Properties and Reactions. — Very pale yellow 
 solid (Wolf, Brauner, Bobinson [C. N. 54], 
 Crookes, Pr. 38, 414). S.G. 6-74 (Nilson a. Pet- 
 tersson, B. 13, 1459). S.V.S. 25-45. S.H. 
 •0877 (N. a. P., Pr. 31, 46). Dissolves in cone. 
 HjSOjAq with production of much heat, and 
 evolution of some ; on crystallising, the salt 
 Ce23S04.Ce(S04)2.24H20 separates (Mendelejeff, 
 A. 168, 45) ; from the mother-liquor of this 
 salt eerie sulphate Ce2S04.4H20 is obtained. 
 This reaction shows that part of the CeOj is re- 
 duced by the H2SO4 to 00203, and part reacts 
 with the acid to form Ce2S04. Dissolves in 
 HNOjAq; on adding NH4NO3 and crystallising in 
 vacuo the double salt 20e(NO3)4. 4NH4NO,.3H20 
 is obtained. Scarcely soluble in HClAq ; but 
 dissolves in this acid, and also in other dilute 
 acids, in presence of reducing bodies, e.g. filter 
 paper, alcohol, SOjAq, &o. 
 
 Ceeium ibioxide. Ce03. (Cerium peroxide.) 
 Said to be obtained as a reddish pp. by adding a 
 slight excess of NH3Aq to Ce23S04Aq, and di- 
 gesting with hydrogen peroxide (de Boisbaudran, 
 0. R. 100, 605 ; Cleve, Bl. [2] 48, 58). 
 
 Othee oxides of ceeium are described by 
 Popp (A. 131, 361) ; Hermann (J. pr. 80, 184 ; 
 82, 385 ; 92, 113) ; the formula Ce40s and CejOj 
 are assigned to these oxides, respectively ; but 
 experiments made by Bammelsberg (P. 108, 40) 
 and others tend to show that the only oxides 
 which have been isolated are Csfi„ CeO,, and 
 Ce03. 
 
 Cerium, oxychlorides of, t;. under Cebiuic, 
 
 haloid and OXYHAIiOID COMPOUNDS OF. 
 
726 
 
 CERIUM. 
 
 Cerinm, salts of. — Salts obtained by replacing 
 H ol acids by Ce. Two series of salts are known, 
 cerous salts represented by CejSSOj, and oerio 
 salts represented by Ce2S0i. The cerous salts 
 correspond to the oxide Ce^Os, the general form 
 of these salts is Ce^Xj where X = SO4, CO3, 
 2NO3, 2C10„ &B. ; the oerio saJts correspond to 
 the oxide CeOj, their general form is CeXj where 
 X = SO4 &o. The cerous salts are considerably 
 more stable than the cerio salts ; the latter are 
 readily reduced to the former; but few cerio 
 salts have been obtained, the principal salt is 
 Ce2S04 ; several double salts are known of the 
 form Ce2SOj.!i;M2S04, and CeiNOs-xMNOj, when 
 M is an alkali metal. Many double cerous salts 
 are known. A few basic salts are also known. 
 Some salts have been isolated which appear to 
 belong to the mixed form xCe.^X^.yCeX^; and 
 one of the so-called basic nitrates is probably 
 KCejeNOj.j/CeOj. Por descriptions of the indi- 
 vidual salts V. the articles on the various groups 
 of salts, CAKBONATES, SULPHATES, &c. ; the chief 
 salts are the bromate, carbonates, iodate, nitrates, 
 oxalate, perchlorate, phosphates, selenate, sul- 
 
 Cerium silicide. Described by UUik (Z. [2] 
 2, 60) as a brown powder ; obtained by passing 
 an electric current from 8 Buusen-cells through 
 a fused mixture of EF and Ce^Pj in a porcelain 
 crucible, and treating with water the brownish 
 mass formed at the negative pole. The Si was 
 derived from the crucible which was strongly 
 attacked. Analysis gave numbers nearly agree- 
 ing with the formula Ce^Sis. 
 
 Cerium, sulphides of. Only one sulphide is 
 known, cerous sulphide, Ce^Sa. It is best ob- 
 tained by passing dry H^S over CeO^ heated to 
 full redness in a porcelain tube. S.G. 5-1. Ver- 
 milion to black according to the temperature 
 at which prepared. May also be obtained in 
 red translucent crystals by passing dry H^S 
 over a fused mixture of dry NaCl and dry Ge.fi\, 
 and then washing with water. Unchanged in 
 ordinary air ; but burnt to SO2 and CeOj below 
 a red heat in air. Dissolves easily in dilute 
 acids with production of H„S ; very slowly de- 
 composed by warm water (Didier, G. B. 100, 
 1461 ; V. also Lange, J. pr. 82, 129 ; and Mo- 
 sander, P. 11, 406). 
 
 Cerium, sulphocyanide of; v. strLPHO- 
 CYANiDES, under Cyanides. M. M. P. M. 
 
 CEROl'IC ACID Cj^H^jOs (?) In the leaves 
 of the Scotch fir (Pinus sylvestris), from which 
 it may be extracted by dilute alcohol. Minute 
 needles.— BaA"aq (Kawalier, A. 88, 360). 
 
 CEEOSIN OjiH^O. [82°]. A waxy sub- 
 stance found on the stem of the sugar-cane. 
 Nacreous laminse (from alcohol). Heating with 
 potash-lime oxidises it to cerosic acid 
 CjbHjbOs (?) [93°], which may be crystallised 
 from petroleum (Avequin, A. Ch. 75, 218 ; Dumas, 
 A. Ch. 75, 222 ; Lewy, A. Ch. [3] 13, 438). 
 
 CEROTENE Cj^Hj^. [58°]. A product of 
 the distillation of Chinese wax (Brodie, P. M. 
 [3] 33, 378; A. 67, 210). Eesembles paraffin. 
 Chlorine forms C^U^filje, Cj^HsjClj,, and 
 CjiHa^Cljj. A similar body [66°] occurs in hay ; 
 it is perhaps C^,^ (Eonig a. Eiesoff, B. 6, 
 600). 
 
 CEEOTIC ACID C^H^O, or C^sHjA- [78°]. 
 
 Occurrtiice. — 1. As oeryl cerotate in Chinese 
 
 wax ; whence it is obtained by distillation, or, 
 better, by treatment with alcoholic EOH. — 2. In 
 the free state in bee's wax (John, Chemische 
 Schriften, 4, 38 ; Boudet a. Boissenot, J. Ph. 
 13, 38; Ettling, A. 2, 267; Hess, A. 27, B; 
 Gerhardt, Bev. scient. 19, 5 ; Lewy, A. Ch. [3] 
 13, 438; Brodie,^. 67, 180; Zatzek, M. 3, 677). 
 
 formation. — By oxidation of paraiBn with 
 dilute HNO3 or with chromic mixture (Gill a. 
 Meusel, O. J. 21, 466). Also by heating oeryl 
 alcohol with soda-lime (Schwalb, A. 235, 141). 
 
 Preparation. — The alcoholic extract from 
 bee's wax is recrystallised till it melts at 70°. 
 This is dissolved in alcohol and the lead salt 
 thrown down by alcoholic lead or cuprio ace- 
 tate. 
 
 Salts. 
 
 -NaA'. — CuA' at 100°. — PbA'~ 
 
 [113°].— EA'.— MgA'2 ? [140°-145°].— AgA'. 
 
 Methyl ether MeA'. [60°] (Nafzger, 4. 224, 
 233). 
 
 Ethyl ether EtA'. [60°]. Fatty plates 
 (from alcohol). Soluble in ether. May be 
 distilled m vacuo. On distillation it gives off 
 CjHj and COj and the distillate contains cerotio 
 acid and a paraffin [44°] (C25H54 or Cj^Hsj) while 
 in the retort there remains a ketone [92°] which 
 is (C,,H„),CO or {GJi^yfiO. 
 
 Geryl ether CjjHss.O.CjjHssO. [82°]. 
 Occurs almost pure as Chinese wax (Brodie). 
 Occurs also in opium-wax (Hesse, B. 3, 638), 
 and in yolk, the sweat of sheep (Buisine, Bl. [2] 
 42, 201). 
 
 An acid [79°] isomeric or identical vrith 
 cerotic acid is the chief acid present in the 
 product of saponification of carnaiiba wax. From 
 alcohol it separates as a jelly, but from other 
 solvents (ether, benzene, light petroleum) as a 
 crystalline powder (Stiircke, A. 223, 283 ; cf. 
 B6rard, ^. [2] 6,465). 
 
 Salt.— PbA'j [116°]. Sol. boiHng glacial 
 acetic acid and toluene. Insol. boiling alcohol 
 or ether. 
 
 CEEOTOlfE C,3H„,0 i.e. (C.,3H,3)2CO (?) 
 [62°]. Formed by distilling lead cerotate (Briiok- 
 ner, J.pr. 57, 17). Plates (from ether). 
 
 Cerotone (C^,S.,s)fiO (?) [92°]. Formed by 
 distilling cerotic acid or its ethyl ether (Nafzger, 
 A. 224, 237). Plates (from acetone). 
 
 CEKYL ALCOHOL C^jHssO or Cj^Hj A- [79°]. 
 
 Occurrence. — Chinese-wax consists almost 
 entirely of ceryl cerotate (Brodie, A. 67, 180 ; 
 Schwalb, A. 235, 141). Ceryl cerotate also 
 occurs in the sweat on the wool of sheep. The 
 wax outside ripe heads of the opium poppy 
 contains ceryl cerotate and oeryl palmitate, [79°] 
 (Hesse, B. 3, 637). 
 
 Preparation. — Chinese- wax is saponified with 
 alcoholic potash, the product mixed with bario 
 chloride solution and the ceryl alcohol separated 
 from baric cerotate by solution in alcohol. 
 
 Beactions. — Is oxidised to cerotio acid 
 CjjHjjOj by heating with soda-lime. 
 
 Iso-ceryl alcohol CjiHssO. [62°]. The por- 
 tion of the wax of Ficus gummiflua which ia 
 insoluble in cold ether (Eessel, B. 11, 2113). 
 
 Acetyl derivative C^j'B.^flAo. [57°]. 
 
 CESPITIKE C3H,3N(?). (95°). Occurs in coal 
 tar, and in the product of the distillation of peat 
 (Church a. Owen, P. M. [4] 20, 110 ; Fritzsche, 
 J. 1868, 402). Liquid, miscible with water. 
 Combines with EtI. Its platinochloride is do- 
 
CETYL CHLOEIDE. 
 
 727 
 
 tomposed by boiling water (De Coninck, Bl. [2] 
 45, 131). Goldsohmidt a. Constam {B. 16, 2978) 
 suggest that it is wet pyridine. 
 
 GEXANE V. Hexadeoane. 
 
 CETENE C„H,, i.e. CH3.(CH,).,.CH:CH,. 
 Cetylene. Hsxadecylene. [4°]. (275°) ; (155°) 
 Bt 15 mm. S.G. |-7917; t^ -7842. V.D. 8-0. 
 Formed by distilling cetyl alcohol withP.,05 
 (Dumas a. P^ligot, A. Ch. [2] 62, 4 ; Smith,'^. 
 Ch. [3] 6, 40). Also by distilling oetyl palmi- 
 tate or commercial spermaceti (cf. Krafit, B. 
 16,3018). Oil ; sol. alcohol and ether. Accord- 
 ing to Berthelot {A. Ch. [3] 51, 81) it forms un- 
 stable compounds with HBr and HCl. It forms 
 a^ dibromide C,5H,^r2 [14°] whence alcoholic 
 KOH forms oily bromo-cetene (Chydenius, A. 
 143, 267). HCIO forms ohloro-cetyl alcohol 
 C„Hs,,Cl(OH) (c. 300°) (Carius, A. 126, 195). 
 SO3 forms C.jHs.SOaH [18°],iusol. water.— KA': 
 [106°J ; S. 1 (Lasarenko, B. 7, 125). 
 
 An iBomeride of cetene, [42°], (284°) is got 
 by distilling azelaio acid with baryta (Schorlem- 
 mer, A. 136, 265). 
 
 CETENE GLYCOL The di-acetyl deri- 
 vative C,iH3.,(OAo)2 is formed by the action of 
 AgOAo on cetene dibromide. It cannot be dis- 
 tiUed (Chydenius, A. 143, 270). 
 
 CETENE OXIDE CisHj^O. [below 30°]. 
 (below 300°). From chloro-cetyl alcohol {v. 
 Cetene) and aqueous KOH (Carius, A. 126, 202). 
 Minute needles. 
 
 CETIC ACID C.^HjoOj. [55°]. The glyceryl 
 derivative occurs in the oil expressed from the 
 seeds of Jatropha Gurcas (Bonis, J. 1854, 462). 
 According to Heintz (P. 90, 137) a very small 
 quantity of this acid is found in the products of 
 saponification of spermaceti. 
 
 Ethyl ether EtA'. [21°] (B.). 
 
 CETINENECisHjo. Cetylene. Hexadecinene. 
 Hexadecylidme. [20°]. (284°). (160°) at 15 mm. 
 S.G. \° = -804 ; »j° = -797. H.F. 118,000 (Berthe- 
 lot). Large colourless tables. Formed by heat- 
 ing cetene (hexadecylene) bromide (natural or 
 synthetical) with alcohoUc KOH (Krafft, B. 17, 
 1373 ; cf. Chydenius, O. B. 64, 180). 
 
 CETBARIC ACID C,8H,sO,. Contained, to- 
 gether with lichenostearic acid, in Iceland moss 
 (Cetraria islandica) (Berzelius, Schw. J. 7, 317 ; 
 A. Ch. 90, 277 ; Herberger, A. 21, 137 ; Knop a. 
 Schnedermann, A. 55, 144). Hair-like needles 
 (from alcohol), v. si. sol. water, si. sol. ether, v. 
 Bol. boiling alcohol. Tastes bitter. Decomposed 
 before melting. Its solutions turn brown on 
 boiling, especially in presence of alkali. FOjClj 
 gives a red pp. in neutral solutions. — (NHJjA". — 
 PbA". 
 
 DICETYL CsjHbs. Dotnacontane. [70°]. 
 (above 360°). V.D. 15-8. Formed by treating 
 an ethereal solution of oetyl iodide with sodium 
 (Sorabji, 0. J. 47, 37 ; cf. Lebedeff, /. B. 1884, 
 [2] 299). Scales, v. si. sol. ether, v. sol. boiling 
 glacial HOAc. 
 
 CETYL ACETATE CuHsjOAo. n-Prim-hexa- 
 decyl acetate. [19°] (Becker, A. 102, 220) ; [23°] 
 (KrafEt, B. 16, 1721). (278°) at 190 mm. ; (200°) 
 at 15 mm. (K.). S.G. ij -8640 ; 1 -8612. MM. 
 18-772 at 20-7° (Perkin, G. J. 45, 421). Needles ; 
 si. sol. cold alcohol. 
 
 CETYL - ACETIC ACID is identical with 
 Eteatiic acid (a.t).). 
 
 Di-oetyl-acetio acid CajHTOO^ t.e. 
 (C,sHj3)2CH.CO.^. [70°]. Formed by heating 
 di-cetyl-malonio acid at 150° (Guthzeit, A. 206, 
 365). Crystalline scales, si. sol. alcohol. — AgA': 
 amorphous pp. 
 
 CETYL ALCOHOL C.jHs^O. Mthal. n-Prim- 
 hexadecyl alcoJwl. Mol. w. 242. [50°]. (844°) ; 
 (190°) at 15 mm. S.G. (liquid) \° = -8176j 
 f = -8105 ; w = -7837. H.F. 112,000 (Berthelot). 
 
 Occurrence. — Spermaceti is cetyl pabnitate 
 (C|sH33)C,i;H3,02 (Chevreul, Becherches sur les 
 corps gras, p. 171 ; Dumas a. P^ligot, A. Ch. [2] 
 82, 4 ; Dumas a. Stas, A. Ch. [2] 73, 124 ; Smith, 
 A. Ch. [3] 6, 40 ; A. 42, 247 ; Heintz, P. 84, 232; 
 87, 553). In the sebaceous glands of geese and 
 ducks (De Tonge, S. 3, 225). 
 
 Formation. — By the distillation of bario 
 sebacate (Schorlemmer, Pr. 19, 22). 
 
 Preparation. — 1. Spermaceti (10 pts.) is 
 boiled with alcohol (5 pts.) and potash (2 pts.) 
 until saponified. The product is poured into 
 water and the cetyl alcohol crystallised from 
 ether. The crude commercial cetyl alcohol con- 
 tains in addition to hexadecyl alcohol also n-p- 
 octadecyl alcohol and probably small quantities 
 of other homologues (Krafft, B. 17, 1627).— 
 2. The acetate is formed by reducing palmitic 
 aldehyde (obtained by distiUing barium pabni- 
 tate with barium formate) with zinc-dust and 
 acetic acid (Krafft, B. 16, 1721). 
 
 Properties. — Small crystalline plates (from 
 alcohol). Gives palmitic acid on oxidation. 
 
 Sodium CetylateC.eHajNaO. [110°] (Fri- 
 dau, A. 83, 1). 
 
 Ethyl ether C,5H3,OEt. [20°] (Becker, 
 A. 102, 220). 
 
 TBI-CETYL-AMINE C«H„N i.6. (C^^B.^)^. 
 [89°]. From cetyl iodide and gaseous NE^ at 
 150° (Fridau, A. 83, 25). Needles. Its salts are 
 insol. water, sol. alcohol and ether. — B'HCl. — 
 (B'HCy^PtCl^ : yellow pp. 
 
 CETYL-ANILINE CjjHjjN i.e. 
 N(CjH5)(C,jH33)H. Phenyl-cetyl-amine. [42°]. 
 From cetyl iodide and aniline at 100° (Fridau, 
 
 A. 83, 29). Silvery scales (from alcohol). Has 
 no action on litmus, and does not pp. metallic 
 salts. -B'sHjPtCls. 
 
 Di-cetyl-aniline N(CbH5)(C,8H33)2. From 
 cetyl-aniline and cetyl iodide at 110° (F.). 
 Crystalline.— B'jHjPtClj. 
 
 CETYL-BENZENE CsH5(C,jH33). Hexadecyl- 
 benzene. [27°]. (230° at 15 mm.) Formed by 
 the action of sodium upon a mixture of iodo- 
 benzene and oetyliodide (Krafit, B. 19, 2988). 
 
 CETYL-BENZENE-STTLPHONIC ACID 
 C8H4(C,sH3s).S03H. Sexadecyl-bemene-sulpho- 
 nic acid. Formed by sulphonating cetyl-benzeno. 
 The sodium salt A'Na is sparingly soluble (Krafft, 
 
 B. 19, 2988). 
 
 CETYL BENZOATECisHsjOBz. [30°] (Becker, 
 A. 102, 219). Crystalline scales. 
 
 CECYL BORATE C.sHajBO,. [58°] (Schill, 
 A. Suppl. 5, 198). 
 
 CETYL BROMIDE C,BH33Br. [15°]. From 
 cetyl alcohol.Br, and P(Fridau,.4. 83, 15). Insol. 
 water, v. sol. alcohol and ether. 
 
 CETYL CHLORIDE C,sH33Cl. S.G. is -841. 
 From cetyl alcohol and PCI5. Oil, insol. alco- 
 hol, sol. ether. Boils above 280° with decompo 
 sition (Dumas a. Pffigot, A. Ch. 62, 4 ; Tiitt- 
 Bcheff, S^. Ghim. pwre, 2, 463). 
 
728 
 
 OETYL CYANIDE. 
 
 CETTL CYANIDE C.eHsjCN. Margaro- 
 nitrile. [53°] (?) Pormed by heating potassium 
 cetyl sulphate with KCN and extracting with 
 ether. Crystalline solid (Eohler, Z. d. gesammt. 
 Naturw. 7, 252). According to Heintz (P. 102, 
 257) it is a liquid, but is accompanied by a solid 
 mixture [55°]. 
 
 CETTL ETHEE v. Cettl oxide. 
 
 CETYLIDE C22H42O5. [c. 65°]. A substance 
 Baid to be formed by dissolving oerebrin in eono. 
 H2SO4 and pouring the solution into water 
 (Geoghegan, H. 3, 332). Insol. water ; v. sol. 
 hot alcohol, v. e. sol. ether. Potash -fusion gives 
 palmitic acid, hydrogen, and CH^. 
 
 CETYL IODIDE G.^J.. [22°]. From cetyl 
 alcohol, phosphorus, and iodine. Laminae (from 
 alcohol). [22°] (Pridau, 4. 83,23). 
 
 CETYL-MALOmC ACID C,sH33.CH(C02H)j. 
 Eexadecyl - malonic acid [117°] (G.); [121°] 
 (Krafft, B. 17, 1630). Formed by heating alco- 
 hol (40 g.), in which Na (2'9g.) has been dissolved, 
 ■with malonic ether (20 g.) and oetyl iodide 
 (44 g.) ; the resulting solid ether being saponified 
 by aqueous KOH (Guthaeit, A. 206, 357). Gran- 
 ules ; m. sol. cold alcohol. Decomposed by heat 
 into CO2 and oetyl-acetio acid. — Salts. — Ag^A". 
 — BaA". 
 
 Di - cetyl - malonic acid (C,eH33)2C(C02H)2. 
 [87°]. Prepared in the same manner as cetyl- 
 malonic acid, using half the quantity of malonic 
 ether (Guthzeit, A. 206, 362). Aggregate of mi- 
 nute crystals (from alcohol) ; si. sol. cold alco- 
 hol. Split up at 150° into CO2 and di-cetyl 
 acetic acid. — AgjA" : voluminous white pp. 
 
 CETYL MEBCAPTAN C.^Hja-SH. [51°]. 
 From oetyl chloride and alcoholic KSH. Silvery 
 scales (from ether) ; does not attack HgO but 
 gives white pps. with alcohoHo AgNOj and 
 HgCl2(Fridau,4.83, 18). 
 
 CETYL NITEATE CisHajNO,. [12°]. S.G. -91. 
 From cetyl alcohol, H2SO4, and HNO3. Long 
 flattened needles, si. sol. cold alcohol (Cham- 
 pion, Z. 1871, 469). 
 
 DI-CETYL OXIDE (C,3H33)20. [55°]. (300°). 
 From sodium cetylate and cetyl iodide at 110° 
 (Fridau, A. 83, 22). 
 
 CETYL PALMITATE v. Paimitic acid. 
 
 CETYL-PHENOL C5H,(C,5H33).OH. Hexa- 
 decyl-phenol. [77§°]. (260°) at 15 mm. 
 Formed by fusing cetyl-benzene-sulphonic acid 
 with KOH. Colourless, tasteless and odourless 
 crystals (Krafit, B. 19, 2984). 
 
 CETYLPHENYL-AMIN E CeH,(C,8H33) .NH^. 
 Anddo-cetyl-bemene. Amido-hexadecyl-bemeiie. 
 [c. 53°]. (254°) at 15 mm. Colourless crystals 
 (from benzene). Formed by reduction of nitro- 
 oetyl-benzene (Erafft, B. 19, 2984). 
 
 CETYL STEAEATE v. Steaeic acid. 
 
 CETYL SULPHIDE (CisH33),S. [58°]. From 
 cetyl chloride and K^S. Scales (from ether- 
 alcohol) (Fridau, A. 83, 16). 
 
 CETYL SULPHURIC ACID C.sHij.O.SOjH. 
 From cetyl alcohol and H^SO, (Dumas a. P^ligot, 
 A. 19, 293 ; Kohler, J. 1856, 579 ; Heintz, P. 
 102, 257). — EA': soft nacreous laminae composed 
 fd interlaced needles (from alcohol). 
 
 CETYL DI-THIO-CAEBONATE OF POTAS- 
 SIUM (C,sH33)O.CS.SK. From cetyl alcohol, 
 KOH, and CSj at 70°. Unstable, hygroscopic 
 scales. Gives a yellow pp. with alcoholic AgNO,, 
 
 quietly turning black (Desains a. De la Pro- 
 vostaye, ji. Ch. [3] 6, 494). 
 
 CEVADILLINE v. Veratrum aikaloids. 
 
 CEVADINE V. Veratbum alkaiiOids. 
 
 CEVINE V. Vebatkum alkaloids. 
 
 CHAMOMILE OIL. An essential oil distilled 
 from chamomile flowers. Both the English or 
 Eoman oil of chamomile (from Anthemis nobilis) 
 and the oil from Matricaria Ohamoniilla are blue, 
 or greenish blue, and boil between 105°-800°. 
 In the oil from Matricaria Chamomilla Kaohler 
 (-B. 4, 36) found a Uquid C,„H,80 (150°-170°), a 
 terpene (165°-185°) (c/. Bizio, Sits. B. 43 [2] 
 292), and a blue liquid (C,„H,„0)j (270°-300°), 
 whence K forms a terpene (OjjHjj) and PjOj 
 forms cymene (c/. Borntrager, A. 49, 243). 
 English (or Eoman) oil of chamomile consists 
 of isobutyl isobutyrate (149°), isobutyl angel- 
 ate (177°), amyl angelate (200°), amyl tiglate 
 (205°), hexyl angelate, hexyl tiglate, and an- 
 themol {g. v.) (Fittig a. Kobig, A. 195, 106 ; 
 van Eomburgh, B. T. G. 5, 220 ; cf. Demarpay, 
 O. B. 77, 360). Petroleum ether extracts from 
 chamomile flowers {Anthemis nobilis), in addi- 
 tion to the above liquids, very small quantities 
 of two solids [64°] and [189°] ; the former is 
 possibly CisH,, (Naudin, Bl. [2] 41, 483). 
 
 CHABACIIT. A white unctuous substance, 
 soluble in ether, occurring in Palmella cruenta, 
 Vaucheriaterrest/ris, andother OsciHosncB present 
 in fresh water (Phipson, G. N. 40, 86). 
 
 CHARCOAL V. Caebon. 
 
 CHEBULIC ACID CjE^O^ (?) Occurs in the 
 fruit of Terminalia Ghebula (Fridohn, C. G. 
 1884, 641). Trimetric prisms, sol. alcohol and 
 hot water ; has a sweet taste. Eeduoes Fehling's 
 solution. Fe^Clj gives a blue-black pp. Difiers 
 from gallic acid in giving no colour with aqueous 
 KCy. 
 
 CHELEEYTHRINE C.jH.^NO^. [160°]. S 
 (alcohol) -33 at 17°. Occurs in very small 
 quantity in the root and unripe fruits of tha 
 common celandine [GheUdonium majus), and in 
 the root of the yellow sea-poppy {Qlaucium lu 
 teum) (Probst, A. 29, 120 ; 31, 250). Sanguinaria 
 canadensis contains an alkaloid, sanguinarine, 
 which is possibly identical with chelerythrine 
 (Schiel, Am. S.[2] 20,220; but cf. Nasehold, Z. 
 1870, 119; Henschke, O. 0. 1887, 243). KH, 
 throws it down from solution in dilute acids as a 
 floceulent pp., v. sol. ether, CSj, chloroform, and 
 benzene. Its solutions fluoresce violet. Acida 
 turn it red.— B'HCl aq : red, v. sol. water and 
 alcohol. — B'jHjPtClo aq. — (B'HI)54Hgl2. — 
 (B'HCy),,4PtCy,. 
 
 CHELIDONIC ACID C,Ufl^ i.e. 
 .CHiC.COjH 
 CO^ >0 (Haitinger a. Lieben) or 
 
 \CH:C.COjH 
 
 
 
 0:C.C(C0,H).CH:C:CH.C02H (Leroh). [220°]. 
 S. -6 at 8° ; 3-9 at 100°. Occurs as calcium salt 
 in the sap of the celandine GheUdonium majus 
 (Probst, A. 29, 116 ; Lerch, A. 57, 273 ; M. 5, 
 367 ; Lietzenmayer, Dissertation, 1884). 
 
 Reactions. — 1. By warming with water and 
 bromine it is split up into oxalic acid, bromo- 
 form, and penta-bromo-acetone (Wilde, A. 127, 
 165).— 2. Agueous alkalis in the cold turn it 
 yellow, forming xanthochelidonic acid C,H,0, ; 
 
CHELIDONIO AOm 
 
 72* 
 
 on boiling it is split up into oxalio acid and 
 acetone : 0,H A + 3H,0 = 2H,0,0, + C3H.O.— 
 rf. Ammonia forms ohelidamio (oxypyridine di- 
 carboxyUc) acid (Lieben a. Haitinger, B. 16, 
 Z /''T ■^*"'' ^°^ acetic acid reduce it to 
 hydrocbelidonio acid C,H,„0..— 5. HI forms 
 pimeho acid 0,H,„(C0,H),.-6. SodAum amalgam 
 gives nydro-xanthochelidonio acid.— 7. At 220°- 
 230° It gives off CO2 forming comanio acid 
 
 Salts — Cbelidonic acid is dibasic. It dis- 
 solves zinc and iron and decomposes carbonates. 
 The normal salts are mostly soluble in water 
 and crystallisable ; those of the alkalis and 
 alkaline earths are readily transformed into salts 
 of xanthoohelidonio acid (this led formerly to 
 the belief that the acid was tribasio). The acid 
 salts crystallise in needles, are soluble in water, 
 and redden litmus.— K2A".—(NH,)2A" 2aq.— 
 NaiA."3Jaq. — NaHA"2aq (at 100°). — 
 NaH3A"j2iaq. — CaA"3aci. — CaH,A'' 4aq. ~ 
 BaA" aq. — BaH^A", 5aq. — PbA"aq.— Ag^A".— 
 AgHA" aq. 
 
 Mono-ethyl ether EtHA" [224°] (H. a. 
 L.) ; [184°] (Lerch). White needles ; gives with 
 AgNOs the salt EtAgA" : trimetric prisms. 
 
 Di- ethyl ether 'm^k". [63° cor.]. Golden 
 triclinic prisms, sol. water, alcohol, and ether. 
 
 Xanthochelidonic acid C,H|iO,. Ghelihydro- 
 nie acid. 
 
 Preparation. — When oheUdonic acid is dis- 
 solved, at ordinary temperatures, in excess of 
 aqueous alkalis or alkaline earths it assimilates 
 water and the resulting yellow solution contains 
 a salt of xanthochelidonic acid (Haitinger a,. 
 Lieben, M. 5, 347 ; Lerch, M. 5, 377). On adding 
 aqueous KOH to an aqueous solution of calcium 
 ohelidonate CaC^H^Oj, a yellow jelly CaKCjHjO, 
 separates, and ultimately coagulates. This salt 
 is acidified with H^SOj and the xanthochelidonic 
 acid extracted by ether that contains alcohol. 
 
 Properties. — Amorphous, transparent, hygro- 
 scopic mass. Its aqueous solutions give lemon 
 yellow pps. with bases. FeaClj gives a dark red 
 colouration. AgNOj gives in neutral solutions 
 a yellow pp. turned chocolate brown by boiling. 
 Xanthochelidonic acid gives the iodoform re- 
 action. Sodium-amalgam reduces it to hydro- 
 xanthochelidonic acid (0,H,20, ?). Its salts 
 readily change into those of chelidonic acid. 
 
 Salts. — CajA"": yellow powder. — 
 Ag3HA""4aq: yellow pp. — AgjA"": chocolate- 
 brown powder. — ^Ag^CaHjA"", 4aq : yellow. — 
 AgsCaA""^ : chocolate.— Pb5Ca3A"'V—BaCaA"". 
 — Ca3K2A""2 4aq. 
 
 Hydro-chelidonic acid C,H,„05. [142°]. Pre- 
 pared by reducing cheUdonic acid with zinc and 
 acetic acid, and purified by means of its zinc 
 salt (Haitinger a. Lieben, M. 5, 353). Groups 
 of colourless leaflets (from water) ; sol. alcohol, 
 el. sol. ether. It does not give the iodoform re- 
 action. KMnO, oxidises it to oxalic and succinic 
 acids. HI reduces it to pimelio acid. 
 
 Salts. — ZnA''2aq: monoclinic six-sided 
 tables ; aib:a = 1-029 : 1 : 1-737 ; iS = 80°8' 
 (Zepharovich, M. 5, 355).— CaA" aq.— Ag^A". 
 
 Chelidamic acid C,HjNOs i.e, 
 O.HjN(OH)(CO,H)j or 
 
 „„ x.C(CO,H):CH^. (jQ 
 
 ;\C.OH 
 
 C(C02H):CH' 
 
 Ammonchelidonic acid. {Py. l)-Oxy-pyridine 
 (Py. 3, 5)-di-carboxyUc acid. Prepared by eva- 
 porating chelidonic acid with excess of ammonia 
 and ppd. by HCl (Haitinger a. Lieben, M. 6, 283 ; 
 Lerch, M. 5, 383). Six-sided trimetric prisms 
 (containing aq) ; si. sol. cold water and alcohol, 
 insol. ether. Its solutions give a red colouration 
 with Fe^Clj and a gelatinous pp. with AgNOj. 
 
 Beactions. — 1. Split up by heat at 230°, or 
 by water at 196° into CO2 and oxy-pyridine.— 2. 
 Distillation with zinc-dust gives pyridine. 
 
 Salts. — H2A"HC1 aq. - PbA" : minute 
 prisms. — Pb3(C,H2NOs)2 : silky needles. — 
 Pb(NHj)(C,H2N03) : needles.— PbAgO^H^NO,.- 
 BaPb,(C,H,N0,)2 3aq. — PbECH^NO^. - Ag^A". 
 — CaA" 2aq. — Ca3(C,HjN0s)j 8aq. — 
 Ca(NHJO,H,N03 2aq. ^ ' ' ''^ 
 
 Di-ethyl ether Et2A"aq. [81°]. Needles. 
 Di-bromo-ohelidamic acid CjHaBrjNOs 2aq. 
 Di-iromo-oxy -pyridine di-carboxylic acid. From 
 chelidamio acid, water, and Br. Deliquescent 
 needles or prisms ; si. sol. alcohol. Gives a purple 
 colouration with Fe^Clj. — Ag^A". 
 
 Di-ohloro-chelidamio acid C,H3Cl2NO,, aq. 
 From chelidamic acid, KOHAq, and CI. Tri- 
 metric prisms.— Ag;A".—Pb3(C,Cl2N05)2. 
 
 Di-iodo-cbelidamic acid O^HjIaNOs. From 
 chelidamio acid, KOH, and I. Slender needles. 
 
 Methyl-chelidamic acid CjH^NOs i.e. 
 C5HMeN{0H)(C0jH)j. Oxy-methyl-pyridine di- 
 carboxylic acid. From chelidonic acid and 
 methylamine. Gives a yellow colour with FejClj. 
 AgN03 pps. neutral solutions, but not solutions 
 of the free acid (difference from chelidamio acid). 
 Heating with HClAq does not split oft MeCl 
 showing absence of methoxyl. Heat splits it up 
 into CO2 and oxy-methyl-pyridine. Bromine 
 gives a di-bromo-derivative CsHjBr^NOs which is 
 split up by heat into CO^ and di-bromo-oxy- 
 methyl-pyridine [196°]. 
 
 Phenyl-chelidamic acid C,3H5N05aq i.e. 
 C5H(CsH5)N(OH)(C02H)2. From chelidonic acid 
 and aniline. Silky needles. Gives a golden 
 colouration with FejClj. When heated it yields 
 oxy -phenyl-pyridine. 
 
 Chelamine v. Oxt -pyridine. 
 CHELIDONINE CjoH.jNsOj aq. [136°]. Occurs 
 in the root of Chelidonium majus and separated 
 from ohelerythrine by ether in which it is less 
 soluble (Probst, 4.29, 123 ; Healing, A. 29, 131 ; 
 Will, A. 35, 113 ; Henschke, G. C. 1887, 243). 
 Tables (from acetic ether). Insol. water, sol. 
 alcohol and ether. Gives a green colour with 
 Erdmann's solution (Eijkman, B. T. C. 3, 190). 
 — B 2H2PtClg. 
 
 Preparation.— The expressed juice (1 kilo.), 
 clarified by albumen, is acidulated with HNO3 
 (7 g. of S.G. 1-3) and ppd. by lead nitrate. The 
 pp. is decomposed by calcium hydrosulphide, 
 the filtrate is acidified by HCl, decolorised by 
 animal charcoal, and evaporated. The Ca salt 
 that crystallises out is purified by conversion 
 into the Ag salt, whence the acid is liberated by 
 HCl (Lietzenmayer, M. 5, 341). 
 
 Properties. — Needles containing 2aq (from 
 water) ; m. sol. hot water ; v. si. soL alcohol. 
 It gives the iodoform reactioa. 
 
780 
 
 CHEMICAL AND PHYSICAL PROPERTIES. 
 
 CHEMICAL AND PHYSICAL PROPERTIES 
 OF BODIES, CONNEXIONS BETWEEN. 
 Certain properties are common to all kinds of 
 matter, othera are characteristic of this or that 
 kind only. Thus, every material substance is 
 acted on by the force of gravity in exactly the 
 same manner, but only a few liquids rotate 
 the plane of polarisation of a ray of light. 
 Properties belonging to the second of these 
 classes are subdivided into two groups, physi- 
 cal and chemical properties. Chemistry deals 
 with those changes in the properties of material 
 bodies wMch are accompanied by changes in 
 the composition of the bodies. Physics deals 
 with changes in the properties of bodies the 
 composition of which remains the same. When 
 the totality of properties by which a body is 
 known remains unaltered throughout any pro- 
 cess, that process is called physical ; when 
 the result of any process is a body or bodies 
 ■with properties so different from the totality 
 of those of the original that the original can 
 no longer be said to exist, that process is 
 called chemical. Physical and chemical pro- 
 cesses are always closely connected in their 
 occurrence ; no chemical change takes place 
 without some accompanying physical change, 
 and it is probable that every physical change is 
 to some extent accompanied by chemical 
 change. Many physical properties are quanti- 
 ties which may be accurately measured ; e.g. 
 melting- and boiling-points, specific gravity, &a., 
 &c. Change of composition of a body or sys- 
 tem of bodies is very frequently accompanied by 
 change in the value of one or more of these 
 measurable quantities ; in other words, the 
 physical constants of a body are conditioned, 
 among other circumstances, by changes in the 
 variable, chemical composition. By the chemi- 
 cal composition of any homogeneous kind of 
 matter is meant, in the first place, a statement of 
 the elements, and of the mass of each element, 
 in a given mass of that body : in this meaning 
 of the term the chemical composition of a 
 body or system can be accurately stated, and 
 definite relations can be determined between 
 changes in the composition and changes in the 
 values of such physical properties as melting- 
 and boiling-points, specific rotatory power, spe- 
 cific refractive energy, and so forth. When the 
 relations between the two groups of changes 
 have been studied and generalised, it may be- 
 come possible to infer the amount and cha- 
 racter of a change of composition from measure- 
 ments of the changes in the values of a few 
 physical properties. It would be impossible to 
 study the relations between every chemical 
 change and the accompanying variations in the 
 physical properties of the bodies forming the 
 changing system ; it is necessary to select 
 typical cases, and to study these as accurately 
 and minutely as possible. As a rule, one physi- 
 cal property is chosen for measurement ; the 
 composition of the system is defined to begin 
 with ; the system is allowed, or caused, to pass 
 into another definite state ; and the variation 
 in the value of the chosen property is determined. 
 But when it is found that several distinct 
 kinds of matter exist, each homogeneous, each 
 distinguished by definite properties, and each 
 containing in a given mass the same masses of 
 
 the same elements, it becomes necessary to 
 widen the meaning of the expression chemical 
 composition. It becomes necessary to frame an 
 hypothesis to account for the observed facts 
 The hypothesis generally adopted asserts that 
 matter has a grained structure, that a mass of 
 any kind of homogeneous matter is composed of 
 a vast but not indefinite number of minute 
 parts ; and that the properties of the mass are 
 conditioned by the properties of these parts. 
 These minute portions of matter are called 
 molecules. But the molecule is not necessarily 
 itself without parts. The chemist asserts that 
 every molecule is built up of a definite number 
 of smaller parts either of one or of several 
 kinds of matter. These parts of molecules are 
 called atoms. The atoms of elements are the 
 ultimate forms of matter with which chemistry 
 at present concerns itself. The hypothesis 
 goes on to assert that the properties of a 
 molecule, and hence the properties of any 
 portion of homogeneous matter composed of 
 molecules of this kind, are conditioned by the 
 nature, the number, and the relative arrange- 
 ment, of the atoms which together form the 
 molecule. In other words, the hypothesis 
 declares that the molecule is itself a structure. 
 On this hypothesis, by the chemical composi- 
 tion of a body is meant a statement of the na- 
 ture, number, and relative arrangement, of the 
 atoms which form a molecule of the body. We 
 know as yet almost nothing about the configu- 
 ration of atoms in molecules ; but chemistry 
 has formed certain more or less clear hy- 
 potheses, and attempts are constantly being 
 made to connect changes in the values of 
 various physical properties with variations in 
 the relative arrangement of atoms in molecules, 
 as this arrangement is conceived by the hy. 
 potheses in question. 
 
 But the physical conception of the molecule 
 is derived from the study of various gaseous 
 phenomena : the physicist deals with the mo- 
 lecule as a whole ; he pictures the molecules as 
 performing certain vibrations, on the form, 
 amplitude, and rate, of which the physical 
 properties of bodies depend. The two concep- 
 tions, the chemical and the physical concep- 
 tion, of the molecule are therefore to a great 
 extent mutually independent. In how far then, 
 one may ask, can a development of the chemical 
 conception be looked for by using physical 
 methods of inquiry? Looking at recent re- 
 searches, it seems probable that the chemical 
 conception of the molecule must be very con- 
 siderably modified, and must be brought more 
 into harmony with the physical conception. 
 The latter is itself to some extent being changed 
 by the development of the theory of vortbx 
 atoms. But it must not be forgotten that the 
 physical conception, in so far as it is a clear 
 conception, has been developed almost wholly 
 from the study of gaseous laws, more especially 
 of the laws which express the relations of the 
 volumes of gases to temperature and pressure ; 
 these relations are dependent on the states of 
 combination of the parts of molecules, and are 
 in no way affected by the nature or number of 
 these parts. The chemical conception, on the 
 other hand, must be made sufficiently elastic to 
 cover the phenomena presented by gaseous, 
 
CHEMICAL CHANGE. 
 
 731 
 
 KquiJ, and solid, compounds ; and most of the 
 chemical processes which occur among com- 
 pounds belonging to these classes are con- 
 ditioned both by the nature and number, and by 
 the states of combination, of the atoms which 
 form the chemical molecules of the reacting 
 bodies. The chemical conception of the mole- 
 cule -will probably be modified when we know 
 more of those properties which, like the relation 
 between the volumes of gases and the tempera- 
 ture and pressure of these gases, are to a great 
 extent, if not altogether, independent of the 
 nature and numbers of the constituent parts of 
 molecules. The physical conception will pro- 
 bably be modified as we learn more of those 
 properties which, like specific heat, are for 
 the most part dependent on the nature and 
 numbers of the constituent parts of molecules. 
 
 (v. MoLECniiAB STEUCTUKB OF MATTER, THEORIES 
 EEaAKDINO). 
 
 Chemistry regards not only changes in the 
 composition, but also changes in the properties, 
 of bodies ; she attempts to generalise not only 
 the laws of composition, but also those of the 
 mutual actions, of bodies. The study of the 
 connexions between changes of composition 
 and variations in physical properties of chemi- 
 cally reacting bodies will throw light on the 
 nature of chemical change. When accurate 
 measurements have been made of the quantities 
 of heat which disappear or are produced in a 
 series of typical chemical processes we shall be 
 able to apply to these processes the knowledge 
 of heat-energy which is generalised in the ther- 
 modynamioal laws. Chemical change may then 
 perhaps be shown to be a special instance of the 
 working of these laws. The conditions of che- 
 mical change on the one hand, and of physical 
 change on the other, must be studied, in order 
 that the laws which express these conditions 
 may be gained ; the relations between these two 
 groups of laws must then be ascertained ; thus 
 it may become possible to attain to clear mental 
 images of natural phenomena as wholes which 
 now present one aspect to the physicist and 
 another to the chemist. 
 
 For accounts of the various physical methods 
 employed in chemistry, and r6sum6s of the more 
 important results, v. PnYsiOAi methods. 
 
 M. M. P. M. 
 
 CHEMICAL CHANGE. Chemical science 
 is based upon the hypothesis that matter is con- 
 stituted of extremely small particles or atoms, 
 and that these atoms are capable of aggregating 
 together by virtue of certain inherent properties 
 or forces, their affinities, to form complex atomic 
 structures or groupings. 
 
 The recognition of this distinctive force by 
 the older chemists led them to propound various 
 theories to account for its existence and explain 
 the phenomena of chemical action (v. Affinity). 
 
 With the nature of this force we are not con- 
 cerned here, but only with the phenomena that 
 accompany its exhibition and the circumstances 
 that modify its action. 
 
 By a chemical change, therefore, is meant any 
 alteration either (1) of the character of a per- 
 mutation in an atomic group, such for instance 
 as is exhibited in the change of ammonium 
 cyanate, NH^CNO, into urea (NH2)jC0 ; or (2) 
 a permutation between two or more such groups, 
 
 as AB + CD = AD + BC, which groups may be of 
 various degrees of complexity ; or (3) the change 
 may arise from a combination such as 
 AB + CD = ABCD, or the converse of this, as is 
 seen in the phenomena of dissociation. 
 
 The majority of chemical changes may be 
 formulated as permutations between two sets of 
 atomic groups ; such as the action of bases on 
 acids, the decomposition of one salt by another, 
 or the combination between gaseous elements as 
 H„ + Cl2 = 2HCl. Examples of chemical change 
 according to ease (3) are of less frequent occur- 
 rence than the last ; such are the formation of 
 double salts like the alums, the combination of 
 certain gaseous molecules with oxides, &c., as 
 CaO-hC02 = CaC03 and CO + Clj = COCl,. The 
 number of strikingly marked instances that 
 could come under the head of permutations in an 
 atomic group is very small, but such changes- 
 may be of frequent occurrence, producing altera- 
 tions in physical and chemical properties too- 
 slight to be recognisable. 
 
 There are several bodies which are known to 
 undergo remarkable and highly interesting 
 physical, and consequently no doubt chemical, 
 changes, when heated, but whether such changes 
 come under class (1) or class (3) is undecided. 
 -Among such substances are phosphorus, para- 
 cyanogen, and cyanuric acid. In the case of 
 phosphorus, the change from the yellow to the- 
 red modification, caused by heat or light, is 
 probably due to an alteration in the state of 
 aggregation of the atoms ; that is to say, if the 
 molecule of yellow phosphorus be P„ that of the 
 red modification is probably P^ ; for solid para- 
 cyanogen, which is converted by heat intO' 
 gaseous cyanogen, and for cyanuric acid, the 
 same may be true, with or without a re-arrange- 
 ment among the constituent atoms of the- 
 molecules (v. Allotbopy and Isomerism). 
 
 The study of the phenomena attending a 
 chemical change shows that in many instances 
 there is an accompanying evolution of energy,, 
 from the changing system, in one form or 
 other, either as heat, or light, or as electrical, 
 currents. In other cases to produce a chemical 
 change expenditure of energy is necessary. 
 
 What may be the nature of the chemical 
 force or affinity that acts between atoms is not 
 known, but it is characterised from gravitative 
 force by this difference, that whereas gravitation 
 acts upon all kinds of matter alike, depending 
 merely on the masses of the bodies, chemical 
 attraction or affinity depends upon the kinds of 
 matter that are presented to each other, as well 
 as upon the conditions under which the bodies 
 are brought together ; in other words, it is an- 
 elective attraction modifiable by circumstances.. 
 For instance, at aredheatmetallicironis oxidised 
 by water vapour and hydrogen is set atliberty, but. 
 at a lower temperature oxide of iron is reduced 
 by hydrogen with the formation of metallic iron 
 and water vapour ; a. mixture of hydrogen and 
 chlorine will remain unchanged for any length 
 of time in darkness, but exposure to sunlight 
 will cause almost instantaneous combination^ 
 and the resulting compound (hydric chloride) may- 
 be again converted into its original constituents 
 by heat. If to a solution of silver nitrate a piece- 
 of metallic copper be added, metaUic silver is 
 ppd. , and copper nitrate formed ; and if now to th&' 
 
733 
 
 CHEMICAL CHANGE. 
 
 copper nitrate a piece of zinc or iron be added, 
 metallic copper is ppd., and zino or iron nitrate 
 is formed. 
 
 These illustrations are sufficient to show the 
 relativity of chemical affinity as depending both 
 upon the conditions to which the system is sub- 
 jected as well as upon the qualities of the materials. 
 
 Under whatever conditions a chemical 
 system may exist in which a change is happen- 
 ing, the atomic forces at work will continue to 
 act until a state of more or less stable equili- 
 brium is reached, after which no further action 
 will take place ; and the ultimate limit reached 
 will depend upon (1) the relative quantities of 
 the reacting bodies ; and (2) the conditions to 
 which the system is subjected. As the system 
 passes from the initial to the final configuration 
 there will be a loss or gain of energy equal in 
 amount to the difference between the total 
 energy of the system in the two states. The 
 rate at which the change takes place will depend 
 also upon the same two circumstances. These 
 two statements amount to this ; that, represent- 
 ing a chemical change by the equation A + B = 
 A' + B', all the atomic forces at work producing 
 the transformation have not invariably the same 
 ratios, but that the ratios vary with variations in 
 the conditions as regards heat, light, &c. ; and, 
 consequently, any determinations of the relative 
 affinities of the members of the system can only 
 be looked upon as expressing certain ratios that 
 hold good under special conditions. The final 
 state reached by the system, and the rate at 
 which the change progresses towards that state, 
 vary with the relative masses of the reacting 
 bodies, other things being equal, although the 
 atomic forces or the affinities remain the same. 
 In other words the final configuration, and the 
 speed of attaining it, are each a function of the 
 reacting masses and of the atomic forces, the 
 latter being a function of the physical conditions 
 to which the system is subjected. 
 
 The phenomena of dissociation furnish many 
 examples of these facts ; as do also those 
 systems which are limited by inverse actions and 
 do not properly come under the term dissociation, 
 wherein both the masses of the constituents as 
 well as the conditions, especially as regards heat, 
 influence the change in its amount and rate. 
 The great field offered for investigation by 
 fractional pptn. will, no doubt, afford many strik- 
 ing instances of the variations of the affinity 
 values under diverse circumstances when the 
 subject is worked out. 
 
 From the foregoing considerations it is clear 
 that a chemical system may or may not undergo 
 change by virtue of any intrinsic forces acting 
 among the constituents, but that such will 
 happen only according to the conditions to which 
 it ia subjected. Eeactions which at moderate 
 temperatures take place with evolution of much 
 energy may be completely suspended by lowering 
 or increasing the temperature, excluding light, 
 or altering the pressure; in other words, the 
 forces or affinities resisting change, if greater 
 than those tending to produce an alteration 
 under some circumstances, may be reversed 
 when these circumstances are altered. 
 
 There are, however, a number of interesting 
 examples in which the stability of a system 
 seems to be overturned by the mere presence 
 
 of an extraneous body which itself undergoes 
 no apparent change. For instance, oxygen and 
 SOj do not combine when moderately heated, 
 but if passed over spongy platinum combination 
 readily occurs. Sometimes again the inter- 
 mediate body does undergo change, as when 
 chlorine is passed over a strongly heated mixture 
 of carbon and silica, whereas without the addi- 
 tion of carbon the silica is not acted upon by the 
 chlorine ; or, platinum, which itself is insoluble 
 in nitric acid, may be rendered soluble in the 
 same acid by alloying it with silver (u. post, 
 Catalytic changes, p. 750). 
 
 Some equally remarkable instances of the 
 apparent necessity of the presence of a third 
 body in order to bring about chemical action 
 between two others have been noticed. Wanklyn 
 (0. N. 20, 271) found that perfectly dry chlorine 
 gas has no action upon metallic sodium. Couper 
 (G.J.iS, 153), starting from Wanklyn's observa- 
 tion, has examined the action of dry chlorine on 
 several metals that are acted upon vigorously by 
 the moist gas. He found that dry chlorine has 
 no perceptible action on Dutch metal, whereas 
 with the moist gas combination takes place, 
 with production of heat and light ; or on touching 
 the metallic surface when in an atmosphere of 
 dry chlorine with a drop of water, instant com- 
 bination occurs. Couper examined a number ol 
 metals in the same way with the following re. 
 suits : the chlorine gas used was allowed -to 
 stand over CaCIj for several days to thoroughly 
 dry it. Zinc, and magnesium, showed no action ; 
 silver, slight action ; bismuth, combination 
 slow ; arsenic, antimony, and tin, rapidly acted 
 upon. It is worthy of note that these last three 
 metals form volatile chlorides liquid at ordinary 
 temperatures. With mercury, combination 
 equally rapid, with dry or moist chlorine. 
 Potassium showed slight action, probably due 
 to adhering KHO ; with proper precautions 
 against moisture, action was slow. Dixon 
 (T. 1884, 617) has observed a somewhat ana- 
 logous fact relating to the combination of gasea 
 under the influence of the electric spark. He 
 has shown that if a mixture of CO and be 
 perfectly dried by P2O5, and be then subjected 
 to the spark from a large Leyden jar or a 
 Buhmkorff 'a coU, union does not take place ; if, 
 however, the slightest trace of moisture be 
 admitted to the mixture, and the spark again 
 made to pass, combination occurs. The hypo- 
 thesis Dixon advances to account for these facts 
 is that the intervention of water molecules is 
 necessary to bring about combination, a molecule 
 of water being decomposed under the influence 
 of the spark by one of carbonic oxide to form 
 carbonic acid and free hydrogen, the latter in 
 its turn combining with the oxygen to form 
 water: this cycle of operations being repre- 
 sented by the equations H2O + CO = !^ + CO2 ; 
 Hj + = H20; consequently a comparatively 
 small number of water molecules are necessary 
 to effect complete combustion. (See also 0. 3. 
 49, 94.) Phosphorus and carbon have been 
 shown by Baker (O. /. 47, 349) to combine with 
 oxygen less energetically in the absence of mois- 
 ture than when moisture is present ; and Earn- 
 say and Young (O. J. 45, 93) observed that if a 
 mixture of dry H and N is passed through a 
 tube containing iron filinge at a red heat no 
 
CHEMICAL CHANGE. 
 
 733 
 
 ammonia is formed; with the moist gases, how- 
 ever, a trace of NHj is obtained. 
 
 Allotbopio Change. 
 
 Several of the elementary bodies are known 
 to exist in two or more difterent modifications, 
 such for instance as sulphur, selenion, carbon, 
 phosphorus, and oxygen : the several forms of 
 each element exhibit more or less strongly 
 marked differences in chemical as well as physical 
 properties. It is probable that such different 
 modifications of one elementary body consist, as 
 in the case of oxygen and ozone, of different 
 atomic groupings or aggregates of atoms. The 
 means by which the change from one modifica- 
 tion of an element to another is brought about 
 are various. Oxygen is converted into ozone by 
 the electric spark or ' silent discharge,' and ozone 
 is changed again into oxygen by heat; yellow 
 phosphorus is converted into the red modification 
 either by light or by heat, and the red modifica- 
 tion is again reconverted into yellow phosphorus 
 at a higher temperature ; sulphur and selenion 
 undergo several changes under the infiuence of 
 heat ; in the ease of carbon, the conditions ne- 
 cessary to bring about metamorphoses are not 
 fully known. 
 
 The study of certain isomeric compound 
 bodies (v. Isomebism) . has shown that the 
 transformation of one isomeride into another is, 
 in some cases, somewhat analogous to the 
 phenomena of dissociation. If solid para- 
 cyanogen (CN)„ is heated in a closed vessel to 
 860° it is entirely converted into cyanogen gas 
 (CN)^ ; the pressure increases until the gas con- 
 denses and is liquefied on the cooler parts of the 
 apparatus. At temperatures below 500° little 
 or no decomposition occurs. As the para- 
 cyanogen is heated above this temperature a 
 slow transformation takes place into gaseous 
 cyanogen, and the transformation continues 
 until the pressure of the cyanogen gas attains a 
 certain definite limit beyond which it does not 
 rise, and there is no further evolution of gas. 
 Exhausting the apparatus and maintaining the 
 temperature, the pressure again rises to its 
 previous limit and remains stationary however 
 long the heating is continued. For every such 
 temperature there is a maximum pressure 
 reached which limits the further decomposition 
 of the paracyanogen into gaseous cyanogen. If 
 now when the pressure has attained its limit, 
 at a given temperature, a quantity of cyanogen 
 gas is forced into the apparatus, the pressure 
 slowly faUs to the initial limit with the trans- 
 formation of gaseous cyanogen into solid para- 
 cyanogen. Troost a. HautefeniUe (C. B. 66, 735, 
 795) have found the following values for these 
 pressures of transformation at different tem- 
 peratures : — 
 
 Temp. 
 
 Pressure of transformation 
 
 502° 
 
 54° 
 
 mm. 
 
 506 
 
 56 
 
 
 659 
 
 123 
 
 
 575 
 
 129 
 
 
 587 
 
 157 
 
 
 599 
 
 275 
 
 
 601 
 
 318 
 
 
 629 
 MO 
 
 868 
 1310 
 
 If 
 
 •• 
 
 The transformation of solid paracyanogen 
 into gaseous cyanogen is seen to be analogous 
 to the volatiUsation of a liquid in presence of 
 its own vapour ; but the formation of red phos- 
 phorus from the yeUow material or vice-versd is 
 a more complex process. If a quantity of yeUow 
 phosphorus is heated in a closed vessel (say to 
 500°), the mass of phosphorus being more 
 than sufficient to volatilise in the space, a maxi- 
 mum pressure is quickly attained. After a time 
 the pressure gradually falls, more or less quickly 
 according to the temperature, till it reaches a 
 minimum at which it remains constant. Pro- 
 vided there is no change of temperature, the 
 vapour of the phosphorus is gradually converted 
 into the red modification which condenses on the 
 sides of the apparatus. If the quantity of phos- 
 phorus introduced into the apparatus is just 
 sufficient to volatilise and fill the vessel with 
 vapour at the first pressure (the heating being 
 continued), red phosphorus begins to form after 
 a time, and the pressure continues to fall until 
 the minimum limit is reached as before. If, 
 however, only sufficient ordinary phosphorus 
 is used to fill the apparatus with vapour at the 
 lower limit of pressure, no red phosphorus is 
 formed, however long the heating may be con- 
 tinued. These two pressures — the maximum is 
 first attained, and the final minimum limiting 
 the transformation of yellow into red phos- 
 phorus — depend solely upon the temperature. 
 Troost and HautefeniUe {A. Ch. [5] 2, 153) found 
 the following numbers relating to these pheno- 
 mena : 
 
 
 Pressui-eof 
 
 vapour of 
 
 Maximum 
 
 pressure 
 
 Temp. 
 
 p limiting the trans- 
 
 of p vapour first 
 
 
 formation 
 
 produced 
 
 360° 
 
 •12 atms. 
 
 3-2 
 
 atms. 
 
 440 
 
 1-75 
 
 
 7-6 
 
 
 487 
 
 6-80 
 
 
 — 
 
 
 494 
 
 
 
 
 18 
 
 ,f 
 
 503 
 
 — 
 
 
 21-9 
 
 
 510 
 
 10-8 
 
 
 
 
 
 511 
 
 — 
 
 
 26-2 
 
 
 631 
 
 16 
 
 
 — 
 
 
 650 
 
 31 
 
 
 — 
 
 
 677 
 
 56 
 
 )j 
 
 — 
 
 
 The rates at which the transformation takes 
 place as well as other phenomena exhibited 
 during the change have been studied by Lemoine 
 {A. Ch. [4] 24, 194). He gives the following 
 numbers illustrative of the progress of the 
 change in time : 
 
 Ordinary 
 
 Quantities of ordinary P remaining at 
 
 litre. 
 
 440°, after 
 
 Grams. 
 
 Smins. 
 
 ih. 
 
 2h. 
 
 8h. 
 
 17h. 
 
 24h. 
 
 3211. 
 
 41h. 
 
 2-9 
 
 
 
 
 
 
 
 2.9 
 
 
 
 „ 
 
 5-9 
 
 
 
 — 
 
 — 
 
 5-3 
 
 — 
 
 — 
 
 4-9 
 
 47 
 
 16-0 
 
 
 
 — 
 
 — 
 
 5-0 
 
 — 
 
 — 
 
 — 
 
 — 
 
 24-0(Hittorf) 
 
 15-5 
 
 11-1 
 
 7-0 
 
 4-4 
 
 — 
 
 — 
 
 — 
 
 
 
 30-5 
 
 — 
 
 — 
 
 5-4 
 
 4'0 3-7 
 
 3-6 
 
 — 
 
 — 
 
 Lemoine (O. B. 73, 990) has given a mathe- 
 matical theory of the changes that red or yellow 
 phosphorus undergoes when heated in a closed 
 vessel, and has compared his formulsB with the 
 results of experiment. Let p be the ^tal mass 
 
734 
 
 CHEMICAL CHANGE. 
 
 of material introduced into a space v, and let y 
 be the mass of yellow phosphorus formed or 
 existing at time t ; if the red phosphorus be 
 supposed to remain in the same state of divi- 
 sion throughout, its free surface will be sensibly 
 proportional to its mass v — y. The quantity of 
 yellow phosphorus evolved, Sj/,, in time St is 
 equal to a{B — y) Tit, and the quantity of the ordi- 
 nary phosphorus, Sy^, transformed into the red 
 
 modification in the same time is 6(p — !/) " 8i ; the 
 
 V 
 
 total effect is therefore the difference between 
 these two quantities, or 
 
 V 
 
 which may be written ~M=f(g — y) (h-y), re- 
 presenting the rate of change in terms of the 
 ordinary phosphorus existing. 
 
 For further account of Allotropio Changes 
 
 V. AIjLOIBOPY. 
 
 Influence op Pkessube on Gaseous Chanoes. 
 
 Many bodies when subjected to the influence 
 of heat in the gaseous state, undergo marked 
 changes either in their physical or chemical 
 properties, or in both ; such changes result more 
 particularly in a diminution of molecular den- 
 sity or a disruption of molecular structure. 
 Among such bodies may be cited, mercurous 
 chloride, chloral hydrate, phosphoric chloride, 
 hydriodic acid, nitric peroxide, hydric selenide, 
 amylic bromide, and acetic acid. In the case of 
 some of these bodies the changes in question 
 have been proved to be the accompaniment of 
 disruption or dissociation of their molecules 
 (v. Dissociation) ; in other cases, such as nitric 
 peroxide and acetic acid, there is no complete 
 proof that the changes in density which these 
 bodies suffer when heated in the gaseous state 
 are really occasioned by a dissociation of their 
 molecules, or are due to the fact of their vapours 
 not obeying the dilatation-law even when suffi- 
 ciently far removed from the liquid state as to 
 place them under the category of gases. Con- 
 sidered from these two points of view, it is evident 
 that the dilatation of a gas under the influence 
 of heat may be of a twofold character, arising 
 from two distinctly separate causes ; firstly, the 
 expansion may be purely physical, varying or not 
 according to the dilatation-law, and secondly, 
 there may be expansion as the accompaniment 
 of a chemical change, viz., separation of the 
 gaseous molecules into simpler groups of atoms. 
 An observed variation of density at different 
 temperatures may be produced by either of these 
 two causes, or by both combined, and it becomes 
 therefore a matter of great importance to be 
 able if possible to discriminate these two actions, 
 and to say to which of them the observed results 
 are to be ascribed. If it could be shown that a 
 diminution of pressure produced the same varia- 
 tion in the densities of certain gases as has 
 been observed under the influence of heat, a 
 great point would be gained in favour of the dis- 
 sociation-theory in settling the oases under 
 dispute. It would seem possible that a dis- 
 crimination between the two possible phenomena 
 accounting for abnormal densities might be made 
 by introducing the element of time into such 
 
 investigations. To make this clear, take the gas 
 nitrogen tetroxide, whose vapour density at lo\y 
 temperatures has been found to be approxi- 
 mately represented by the formula NjO,, while 
 at high temperatures it corresponds to NO^ (the 
 vapour densities being 3-18 and 1-59 respec- 
 tively). Now Troost (C. B. 86, 1394) found the 
 vapour density of nitrogen tetroxide at 27° and 
 at low pressures to be as follows : 
 
 Pressure. 
 35 mm. 
 16 „ 
 
 Density. 
 1-6 
 1-59 (NOj 
 
 = 1-59). 
 
 These results show that the same change takes 
 place under diminished pressure as occurs under 
 the influence of heat at ordinary atmospheric 
 pressures ; that is to say, these numbers indicato 
 that, if the observed changes in density are duo 
 to dissociation of the molecules NjO, into the 
 molecules NO,, then under a pressure p the ratio 
 of the number of molecules of NjO, to NOj is dif- 
 ferent from the ratio when the pressure is altered 
 to p', temperature being the same in each case. 
 The proof of this assertion is of considerable 
 importance in the theory of dissociation; 
 whether the change in density is or is not to be 
 attributed to the supposed fact, that the gas 
 N2O4 forms an exception to the dilatation-law, 
 would seem to be capaljle of indisputable proof 
 by introducing the element of time into the ex- 
 periments. If the gas N2O, is really dissociated 
 into NO2 under diminished pressure, 2 vols. 
 N2O4 would give 4 vols. NOj ; now, by the 
 kinetic theory of gases it is conceivable that 
 this dissociation would take place practically in- 
 stantaneously when the temperature was in- 
 creased or the pressure was diminished, whereas 
 on reversing the process the molecules of NOj 
 would require some time before meeting with 
 the requisite number of partners to re-form the 
 molecules of NjO,. Such an experiment might 
 form a crucial test of the truth of the dissocia- 
 tion-hypothesis for this particular gas, and it 
 might also be applied to other cases, for it is 
 scarcely conceivable that the coefficient of dila- 
 tation of a gas should alter in time. Natanson 
 (W. 24, 454) has determined the ratio between 
 the specific heats of nitrogen tetroxide by 
 means of Eundt's dust-figure method ; his results 
 seem to show that as the pressure decreases this 
 gas passes from a more to a less complex mole- 
 cular structure. 
 
 In the determination of the vapour densities 
 of several bodies whose abnormal dilatations are 
 almost undoubtedly to be ascribed to the disrup- 
 tion or dissociation of their molecular struc- 
 tures, the influence of time on the phenomenon 
 has been several times observed, and has been 
 made the subject of investigation by Naumann 
 for the particular case of ammonium carbamate 
 (v. next page). 
 
 Wurtz (O. B. 60, 728), when determining the 
 vapour density of amylic bromide (b.p. 113°) 
 between 153° and 360°, noticed that when the 
 vapour was suddenly heated to 225° the density 
 was 4'69, whereas in another experiment when 
 the vapour had been maintained at this tem- 
 perature for ten minutes the density was 3-68. 
 These results show undoubtedly that the diminu- 
 tion in density, or the dissociation produced by 
 heating, rec[uired time to be effected, and hence was 
 
CHEMICAL CHANGE. 
 
 735 
 
 due to a chemical change and not to a variation 
 m the coeffioient of dilatation of the gas. 
 
 Naumann {A. 160, 1) studied the influence of 
 tune on the dissociation and re-formation of 
 ammonium carbamate; the following tables 
 Illustrate the general bearing of his experi- 
 ments : — o r 
 
 Speedof dissociation of NHs)j002 at 46°. 
 
 Pressure under 
 
 
 
 the flissooiatioa- 
 
 Increase ol 
 
 Time of 
 
 pressure, 
 
 which 
 
 pressure 
 
 increase 
 
 =854 mm. 
 
 
 
 124 
 
 [mn. 
 
 ,^_ 
 
 
 37 
 
 
 87 mm. 
 
 5 min. 
 
 17 
 
 
 20 
 
 5 
 
 10 
 
 
 7 
 
 5 
 
 6 
 
 
 4 
 
 5 
 
 4 
 
 
 2 
 
 5 
 
 3 
 
 
 1 
 
 5 
 
 2-5 
 
 •5 
 
 5 
 
 2 
 
 
 •5 
 
 5 
 
 1-5 
 
 •4 
 
 5 
 
 
 
 
 1-5 
 
 17 
 
 Speed of f 
 
 armation a com 
 
 bination of 
 
 
 2] 
 
 ii(H3-i-OOj)at20 
 
 °. 
 
 Bxoeas of pressure 
 
 
 
 over dissociating- 
 
 Decrease of 
 
 Time o£ 
 
 pressure 
 
 pressure 
 
 decrease 
 
 (=62-4 mm 
 
 .)at20° 
 
 
 
 185 mm. 
 
 
 
 _ 
 
 140 
 
 If 
 
 45 mm. 
 
 2-5 mins. 
 
 90 
 
 If 
 
 50 „ 
 
 5 .1 
 
 63 
 
 If 
 
 27 „ 
 
 5 ,1 
 
 45 
 
 ff 
 
 18 ,1 
 
 5 f, 
 
 30 
 
 ff 
 
 15 ,1 
 
 5 „ 
 
 21 
 
 tf 
 
 9 ,1 
 
 5 1, 
 
 15 
 
 ji 
 
 6 „ 
 
 5 ,1 
 
 10 
 
 ff 
 
 5 „ 
 
 5 „ 
 
 6 
 
 ff 
 
 4 „ 
 
 5 „ 
 
 4 
 
 If 
 
 2 „ 
 
 5 If 
 
 1 
 
 tf 
 
 3 „ 
 
 10 „ 
 
 
 
 ff 
 
 1 ,. 
 
 6 1, 
 
 
 
 ff 
 
 „ 
 
 5 fi 
 
 In these two examples it is seen that, starting 
 with a mass of solid ammonium carbamate (Nau- 
 mann showed by his experiments that at all tem- 
 peratures the gas evolved consists of 2NH,-i-C02) 
 and suddenly increasing the temperature, a con- 
 siderable time is required before the normal 
 pressure of dissociation corresponding to that 
 temperature is reached. In like manner, by sud- 
 denly diminishing the temperature, the recombi- 
 nation of the ammonia with the carbon dioxide 
 to form the solid (NH3)2C02 does not take place 
 instantaneously, but a considerable time elapses 
 before the pressure corresponding to the 
 lower temperature is arrived at. Although ana- 
 logous in some respects to the volatilisation and 
 condensation of a liquid, the phenomena exhi- 
 bited by (NH3)2C02 when heated are characterised 
 by their greater slowness. 
 
 In experiments relating to vapours of vary- 
 ing densities — such as those of Troost on acetic 
 acid and nitric tetroxide at low pressures — it is 
 important to determine whether diminution of 
 prjssure acts in a manner similar to that of heat 
 
 in bringing about dissociation, or disruption, of 
 the molecules of the gas. By introducing the 
 element of time into the experiments, and by 
 suddenly varying the pressure, dissociation 
 might be shown to occur in the case of nitric 
 tetroxide as already remarked, the process in this 
 case being doubtless reversible ; whereas with 
 say, ozone, or a mixture of ozone and oxygen, 
 the amount of change produced by increasing 
 the volume, say, twenty-fold, could be determined 
 by the usual methods of analysis (c/. also Dis- 
 sociation, and Equilibkium, ohemioal). 
 
 ChEMIOAIi STiSTEMS. 
 
 Considering the three physical states in which 
 bodies are capable of undergoing chemical chanj/e, 
 either as gases, liquids, or solids, it is evident that 
 there are two distinct kinds or classes of chemical 
 systems possible, according to the states in which 
 the active substances exist, and which may be 
 termed heterogeneous and homogeneous systems. 
 The former name is applied to all reactions in 
 which the active members of the system are in 
 different physical states, a solid and a liquid, or 
 a solid and a gas, or a liquid and a gas ; as 
 examples of each of these may be mentioned the 
 action of acids on metals or on carbonates, the 
 dissociation of calcic carbonate or ammonio car- 
 bamate by heat, and the oxidising action of free 
 oxygen on solutions of stannous or ferrous salts. 
 By homogeneous systems are to be understood 
 those in which all the active members exist in 
 the same physical state, either as liquids ol 
 gases ; it is inconceivable that two sohd bodies, 
 however finely powdered and well mixed, could 
 come under this category. Examples of homo- 
 geneous systems are shown in the numerous 
 etherification processes, the oxidising action of 
 potassic chlorate on ferrous salts, the action of 
 oxalic acid on potassic permanganate, among 
 liquids, and for gaseous systems, the action of 
 iodine or selenion on hydrogen, and the influ- 
 ence of light on a mixture of chlorine and hy- 
 drogen or on gaseous hydriodic acid. Many valu- 
 able facts have been brought out by the study 
 of heterogeneous chemical systems, especially as 
 regards dissociation-phenomena ; but the great 
 field in which the most fundamental facts con- 
 cerning chemical action will be gathered is 
 naturally that embracing homogeneous systems, 
 for here the most intimate contact exists among 
 the acting substances, affording free play to the 
 various chemical forces at work, and the secon- 
 dary physical changes which interfere with the 
 primary chemical change are reduced to a mini- 
 mum. 
 
 Heterogeneous Systems. — Gladstone and 
 Tribe (Pr. 19, 498) have investigated the rate at 
 which H, more positive metal immersed in a 
 solution of a salt of a less positive one displaces 
 the latter, and the relation which exists between 
 the rate of action and the mass of salt in the 
 solution. Employing a solution of argentic 
 nitrate, the displacing metal being copper, and 
 allowing the action to continue for ten minutes 
 under varying conditions of concentration, they 
 found that by doubling the amount of silver salt 
 in solution the amount of action that took place 
 during this interval of time was trebled. Zina 
 and cupric chloride, zinc and cuprio sulphate, 
 zinc- and lead nitrate, iron and cuprio sulphate, 
 
736 
 
 CHEMICAL CHANGB. 
 
 and other oombiuntions, showed in every case, 
 when the solutions were sufficiently diluted, that 
 this 2-3 law holds good. Expressed algebraic- 
 ally, if y be the mass of metal dissolved, and x 
 the concentration of the solution, then the above 
 
 lagi 
 
 2-3 law is y=aa;'°?^ where » is a constant. 
 
 These experiments have been repeated and ex- 
 tended by Langley (C. J. 45, 663), who con- 
 firms the truth of Gladstone's law ; but when 
 the method of experimenting is modified, as by 
 continually moving the metal about in the so- 
 lution or by brushing its surface so as to keep 
 the solution uniform throughout, Langley con- 
 siders that the rate of action is proportional 
 solely to the amount of salt in solution. More- 
 over, Langley's experiments indicate that the 
 law observed by Gladstone and Tribe arises 
 from two causes, viz., chemical action, and 
 gravitative action, the latter producing slow 
 currents through the solution because of the 
 changing densities of the original salts and of 
 those which are produced in the change. 
 
 In studying the rate of evolution of carbon 
 dioxide from marble by the action of acids, 
 Bojuski and Eajander (B. 10, 34) found that 
 the rate of action is proportional to the concen- 
 tration of the acid, but varies according to 
 the nature of the acid employed ; moreover, they 
 concluded that, for the three acids HCl, HBr, 
 and HNO3, the speed of the action is inversely 
 proportional to the molecular weights of the 
 acids when the solutions are of equal degrees 
 of concentration. Pawlewski {B. 13, 334) has 
 continued these experiments, employing differ- 
 ent carbonates (BaCOj, CaCOj, SrCOj) with the 
 same acid ; although his results are not very 
 regular, yet he considers them sufficient to show 
 that the speed of the reaction is inversely pro- 
 portional, not to the molecular weights of the 
 carbonates, but to the atomic weights of the 
 metals whose carbonates were employed. 
 
 Of a somewhat similar nature to the experi- 
 ments of Gladstone and Tribe is the work of 
 Thorpe (C. J. 41, 287) on the behaviour of zinc, 
 magnesium, and iron, as reducing agents, with 
 acidulated solutions of ferric sulphate. Known 
 weights of these three metals in the form of 
 thin foil were introduced into acidified solutions 
 of ferric sulphate, and the amount of reduction 
 effected— part of the liberated hydrogen coming 
 off as gas — under varying conditions of tempe- 
 rature, amount of free acid, and strength of 
 the ferric solution, was determined. The re- 
 sults obtained showed that the reduction effec- 
 ted when a, given mass of zinc dissolves in an 
 acidified solution of ferric sulphate increases 
 with increase of temperature, other conditions 
 being the same. Provided a sufficiency of acid 
 to dissolve the zinc be present, the maximum 
 reducing action is obtained by concentrating 
 the ferric sulphate solution, and diminishing the 
 amount of free acid. 
 
 When magnesium is employed, the reduction 
 effected is scarcely one-fourth of that for zinc, 
 while the time required for solution is compara- 
 tively very short ; by diminishing the quantity 
 of free acid the amount of reduction effected is 
 increased. The diminution in the rate of solu- 
 tion with a decrease in the quantity of free acid 
 
 was found to be much greater in the case o£ 
 magnesium than in that of zinc; with zino 
 the rates were approximately in the ratios 
 1 : 1*5 : 2, and, under like conditions with magne- 
 sium, the rates were as 1:6: 36. When the ferric 
 sulphate is reduced by iron, the rate of solution 
 becomes extremely slow, and the reducing action 
 appears to decrease with increase of tempera- 
 ture. These reduction-experiments, considered 
 as a whole, seem to be in harmony with the 
 the view that the reducing action of so-called 
 nascent hydrogen is connected with the existence 
 of atoms, as distinguished from molecules of 
 this gas ; and that any conditions which tend 
 to prevent the mutual combination of these 
 atoms tend also to increase the amount of 
 reduction effected by the hydrogen. 
 
 When phosphorus oxychloride acts upon 
 certain nitrates, it has been found that the 
 ratio between the chlorine and phosphoric 
 pentoxide in the residue obtained after all 
 action has ceased has a certain definite value. 
 Mills {P.M. [4] 40, 134, and 44, 506), who has 
 studied this reaction for several nitrates, has 
 designated these ratios by the symbol a, or 
 weight of chlorine 
 
 rather he has taken a as = 
 
 01 
 
 weight of P2O5 
 
 When one aitrate fixes 
 
 _ weight of 01 . „o 
 
 weight of P2O5 
 more chlorine, per unit of P^Oj, than another 
 nitrate, Mill says that the affinity of the former 
 is greater than that of the latter nitrate ; inas- 
 much as this chlorine-fixing action can be 
 measured for several nitrates, the values of o, 
 on Mill's view, represent the 'elective attractions' 
 of the nitrates. 
 
 If o be divided by the formula-weights, 2, of 
 the several nitrates, calculated to a uniform 
 mass of NO3, the following numbers (under q) 
 are obtained : — 
 
 
 a 
 
 s 
 
 Q 
 
 Thallous nitrate . 
 
 8-78 
 
 265-30 
 
 30-29 
 
 SUver „ 
 
 5-48 
 
 169-94 
 
 31-01 
 
 Lead „ . 
 
 5-17 
 
 165-56 
 
 3202 
 
 Eubidium „ . 
 
 2-38 
 
 147-40 
 
 61-93 
 
 Caesium „ . 
 
 2-21 
 
 195-01 
 
 88-24 
 
 Potassium „ . 
 
 1-99 
 
 101-14 
 
 50-82 
 
 Sodium „ . 
 
 1-70 
 
 85-05 
 
 50-03 
 
 Lithium „ . 
 
 1-60 
 
 69-00 
 
 42-86 
 
 These numbers show that the affinity-co- 
 efficients are directly proportional to the formula- 
 weights of the nitrates, and that (with one 
 exception) a and 2 increase and diminish in 
 regular order. The quotients, Q, therefore, re- 
 present the masses of nitrates which correspond 
 with what Mill calls a ' unit of elective attrac- 
 tion.' 
 
 Chemical Systems of limited action. 
 
 When a chemical reaction is expressed sym- 
 bolically either as ab + on = AO -f ed or a' + b' = 0', 
 it is usually understood that for the complete 
 decomposition of the mass ab all that is neces- 
 sary is to bring it into suitable contact with the 
 definite mass of the second body cd, or that the 
 
CHEMICAL CHANGE. 
 
 737 
 
 mass a' if presented to b' under proper condi- 
 tions-will unite witli it to form o'. In many 
 chemical changes this is true, at least within the 
 limits of experimental error, and if sufficient 
 tune be given ; and it may be said that many 
 processes of quantitative chemical analyses are 
 based on this assumption. There are, however, 
 many instances known in which the statement 
 does not hold good. For example, if mol. weights 
 of ethylio alcohol and acetic acid are mixed 
 and heated for some time, say at 100°, only 
 about 66 p.c. of the total action possible takes 
 place, no matter how long the operation is 
 allowed to continue ; or again, if mol. weights of 
 iodine and hydrogen are heated at 440° in a 
 closed vessel, even after an indefinitely long 
 period of time there will still exist a certain 
 fraction of these elements uncombined. The 
 limitation of these and many other similar 
 changes appears to be due to the fact that the 
 products of the first action tend, under the con- 
 ditions of the experiment, to re-form the original 
 substances, and the two reactions proceed simul- 
 taneously with different degrees of intensity, 
 depending upon the masses of material, until a 
 stage is reached at which a state of equilibrium 
 is attained, the first action at this stage being 
 balanced by the second. The mutual action of 
 alcohol and acetic acid would thus be repre- 
 sented by the equations, 
 
 (1) CHjCOjH + C.^,OH = CHsCOAHs + H^O, 
 
 (2) CH3C0^02H,-^H,0 = CH3C02H + C^H,0H. 
 The theory of such limited actions was for- 
 mulated by Guldberg and Waage, in 1867 
 (6tvdes sur les AffiniUs chimiques) and applied 
 by them to the determination of the ' coefficients 
 of affinity' for several reactions. These 
 chemists concluded from the results of their 
 experiments that in a system undergoing change 
 the amount of action in a unit of time between 
 two or more active bodies — ^in other words, the 
 rate of the change — is proportional to the 
 product of the active masses. This same as- 
 sumption was made by Berthelot in 1862, based 
 on the results of his etherification experiments ; 
 and in 1866 Harcourt and Esson showed that 
 tor certain chemical systems the rate of change 
 is proportional to the product of the active 
 masses of the changing bodies. In the above 
 statements the ' active masses ' of the various 
 bodies means the number of equivalents of each 
 present in the reacting system. There are in- 
 stances, however, in which bodies introduced 
 into a chemical system either accelerate or 
 retard the reaction without 'themselves under- 
 going change (v. post, p. 714). Guldberg and 
 Waage assume that, in the reaction a -^ b = a' -H e', 
 if the masses of A and B be ^ and q, then the 
 force tending to produce the change varies as the 
 product pq, whatever may be the kinds of mat- 
 ter ; for two particular substances this force is 
 equal to lepq, where k is the 'coefficient of 
 affinity ' depending upon the kinds of matter, 
 and probably upon the conditions of the experi- 
 ment (v. ante and also Affinity, pp. 70-75). 
 This, however, is not the only force acting; there 
 are others of a secondary character tending to 
 retard or accelerate the formation of a' and b'. 
 Neglecting these secondary forces for the pre- 
 sent, let the masses of a' and b' be p' and q', 
 and the coefficient of affinity for the reverse 
 
 Vol. I. 
 
 action a' -^ b' = a -i- B be «', then the force tending 
 to re-form A and B equals ic'p'q'- When equili- 
 brium is attained these two forces are equal, or 
 Kpq = K'pfq', so that if the four quantities 
 p,qj?',q', are determined experimentally, the ratio 
 
 — ; of the coefficients of affinity may be found. 
 
 Expressed in another way, if p,q,p',q', be the 
 number of equivalents of the four substances in 
 the system at the beginning of the reaction, and 
 if X be the number of equivalents of p and Q 
 transformed into p' and q' when equilibrium is 
 reached, or no further change takes place in the 
 system, aU expressed in terms of unit volume, 
 then p = r — x, q = Q-x, p' = F' + x, and 
 q' = Qi' + x; inserting these values, the equation 
 becomes k(p-ce)(q-!i;) =k'(p'4 x)(Q' + a:). 
 
 Such is the simplest representation of the 
 theory of limited actions. The presence, how- 
 ever, of extraneous salts, or even the secondary 
 actions among the four bodies themselves, 
 doubtless materially influence the ultimate limit 
 when a state of equilibrium is reached. For 
 instance, if a body x be introduced into the sys- 
 tem, Guldberg and Waage assume that the force 
 produced by the action between x and A, and 
 influencing the change between a and b, is propor- 
 tional to the product of x and a, or is equal to 
 OAX, and they term a the ' coefficient of action.' 
 Assuming that there are coefficients of action be- 
 tween all the four bodies — these coefficients being 
 a, 6, c, and d, for a and a', a and b, b and a', and 
 B and b', respectively, and a', b', c', d', for a' and 
 A, b and A, a' and a, and b' and b, respectively — 
 then the total force for the reaction betweea 
 A and B wiU be equal to 
 
 KP2 + app' + bpgl + cjp' -v dqq', 
 and that between a' and b' will be equal to 
 
 Kf^q' + a'p'p + b'pq' + c'p'q + d'q'q. 
 But that there may be equilibrium these forces 
 must be equal. Writing a-a'=a,b-b' = P,&B.,. 
 the equation of equilibrium becomes 
 
 Kpq = /c'p'q' -^ app' + Ppq' + yqp' + Sqq'. 
 If it is desired to study the rate at which tha 
 reaction progresses, then this rate is assumed; 
 to be measured by the difference between tha 
 two forces or 
 
 -£=icpq- lep'q' - app' -0qq'-yp>q-dqq', 
 
 Owing to their complicated character, these 
 equations for the hmit or the rate of a chemical 
 change are of little value from an experimental 
 point of view ; it would seem scarcely possible 
 to determine the numerous secondary forces 
 Guldberg and Waage introduce into their for- 
 mulffi. In such a case as the action between 
 barium sulphate and potassium carbonate the 
 secondary actions to be taken into account are 
 between BaSO, and BaCOj, BaSO, and K,SO., 
 KjCO;, and BaCOj, KjCOj and KjSO„ and be- 
 tween the water and each of the four salts. For 
 a full discussion of this theory in its simpler 
 form applied to experimental results see Guld- 
 berg and Waage, J. pr. [2] 19, 69 (v. also 
 Affinity, p. 75). 
 
 Berthelot and Saint-GUles (A. Ch. [3] 65 
 385 ; 66, 1 ; 68, 225) were the first to make a 
 complete study of the reactions between carbon 
 acids and alcohols, as regards the influenca 
 exerted by variations of temperature, pressure 
 
 8D 
 
738 
 
 CHEMICAL CHANGE. 
 
 amounts of material, and time. They found 
 that these reactions are characterised by three 
 important features : (1) the combination proceeds 
 slowly, with a velocity depending upon the 
 influences to which the system is submitted ; 
 (2) the combination is never complete, however 
 long the duration of contact ; (3) the proportion 
 of ethereal salt formed under dift'erent conditions 
 always tends towards a limit. 
 
 The inverse action limiting the formation of 
 the ethereal salt, viz. its decomposition by the 
 water formed during the reaction, was found to 
 be much less rapid than the combination. In 
 other words, if two systems are employed— one 
 consisting of ethylic alcohol and acetic acid, the 
 other of ethylic acetate and water — all in 
 equivalent proportions, the first of these will 
 attain the limit of equilibrium more quickly 
 than the second under like conditions. Berthelot 
 (A. Ch. [3] 66, 113) concluded that in the forma- 
 tion of the ethereal salts ' the quantities of 
 acid and alcohol that combine at each instant 
 are proportional to the product of the reacting 
 masses.' He gave the formula for expressing 
 
 the rate of formation as -l'=mi'/i( 1—1 ] ', for 
 
 at \ I I 
 
 equivalent quantities of alcohol and acid, where 
 I is the Umit, which for acetic acid is = 66'5. 
 
 According to the theory of mass-action, the 
 rates of formation of ethereal salts, as well as 
 the magnitude of the limits, ought to be in- 
 creased by an increase in either the amount of 
 alcohol or of acid. As regards the ultimate 
 limits, this was found to be true by Berthelot 
 and Saint-Gilles, but for the speed of etherifica- 
 tion they found that with n equivalents of alcohol 
 and one of acid there was (at least for part of 
 the course) little or no increase over that for 
 equivalent quantities ; in fact, a diminution in 
 the rate was observed. On the other hand, with 
 n equivalents of acid and one of alcohol the 
 rate of etherification was greatly accelerated. 
 The following two tables illustrate these 
 points {A. Ch. [3] 66, 90, 98) :— 
 
 1 eq. acetic acid + n eq. alcohol. Temp. 100°. 
 
 
 n=l, 
 acid =190, 
 limit=100 
 
 n=2, 
 aoid=100, 
 rimit=100 
 
 n=5, 
 acid=100, 
 limit=100 
 
 4h. 
 15 „ 
 83 „ 
 
 25-8 
 47-4 
 60-6 
 
 38-8 
 71-3 
 91-1 
 
 27-8 
 44'0 
 72-2 
 
 33-8 
 53-2 
 87-1 
 
 17-5 
 31-3 
 72-2 
 
 19-3 
 34-5 
 79-4 
 
 1 eq. alcohol + n eq. acid. Temp. 100°. 
 
 
 aoi(l=100, 
 limit =10a 
 
 n=2, 
 acid=100, 
 limit=100 
 
 n=5, 
 aold=100, 
 limit=100 
 
 4h. 
 15 „ 
 83 „ 
 
 25-8 
 47-4 
 60-6 
 
 38-8 
 71-3 
 91-1 
 
 47-1 
 74-4 
 79-2 
 
 54-9 
 86-7 
 92-5 
 
 57-6 
 96-6 
 96-6 
 
 59-4 
 100 
 100 
 
 The variation produced in the limit, or 
 tnaximum amount of ethereal salt formed, by 
 employing excess of one or other of the con- 
 stituents is illustrated by the following tables 
 {A. Ch. [3] 68, 274, 286) :— 
 
 1 en. aoid+n eqs. alcohol. 
 
 neqs. acid+1 
 
 eq. alcohol 
 
 fl 
 
 limit 
 
 n 
 
 limit 
 
 1-0 
 
 66-5 p.o. 
 
 1-0 
 
 66-5 p.0. 
 
 1-5 
 
 77-9 
 
 •67 
 
 51-9 
 
 20 
 
 82-8 
 
 ■60 
 
 41-4 
 
 2-8 
 
 85-6 
 
 •36 
 
 30-6 
 
 30 
 
 88-2 
 
 •33 
 
 29-3 
 
 4-0 
 
 902 
 
 •25 
 
 22-6 
 
 5-4 
 
 92-0 
 
 •18 
 
 171 
 
 12-0 
 
 93-2 
 
 •08 
 
 7-8 
 
 190 
 
 95-0 
 
 •05 
 
 50 
 
 500-0 
 
 neutral to 
 litmus. 
 
 
 
 The action of inorganic acids on alcohols has 
 been investigated by Viliiers (A. Ch. [5] 21, 72); 
 but in these processes secondary reactions that 
 are liable to occur complicate matters somewhat. 
 With a given alcohol, the speeds of etherification 
 of the acids HI, HBr, HCl, and H^SO^, were 
 found to be widely different. HI etherifies more 
 quickly than HBr, and each more quickly than 
 acetic acid; whereas HCl acts with extreme 
 slowness, even much more slowly than acetic 
 acid. HjSOj etherifies almost immediately 
 under ordinary conditions, but the speed is 
 diminished by dilution, as weU as by lowering 
 the temperature. The etherification limits at 
 100° are different for the three hydracids, and 
 are greater than the correspondmg limits at 
 lower temperatures. The limits also depend 
 upon the proportion of water which exists in 
 the initial mixture, but while the limit diminishes 
 in the case of organic acids in a continuous 
 manner as the water increases, without actually 
 becoming nil, the etherification by hydracids 
 ceases completely with a certain dilution, and 
 this limit of dilution is not fixed but rises rapidly 
 as the temperature rises. With HjSO,, the 
 etherification is completely stopped with a cer-, 
 tain proportion of water, but, contrary to what 
 occurs with the hydracids, increasing the tem- 
 perature to 100° does not cause the reaction to 
 take place. From a consideration of the work 
 of Berthelot and Saint-CriUes on the rate and 
 conditions limiting the etherification of alcohols 
 by organic acids, it would seem natural to con- 
 clude that the application of the methods em- 
 ployed by these chemists to the various cases of 
 isomerism among alcohols and acids would yield 
 important results relating to the structure of 
 such bodies. For the purpose of discovering 
 whether any relation exists between the rate and 
 limit of etherification and the isomeric structure 
 of either of the two active bodies taking part in 
 the reaction, Menschutkin {A. Ch. [5] 20, 289 ; 
 23, 14 ; J.pr. [2] 24, 49 ; 25, 193) has made an 
 elaborate study of the action of organic acids 
 on alcohols. In order to render all the results 
 comparable with each other it was necessary to 
 assume two standards for reference, one for the 
 alcohols and another for the acids. Methylio 
 alcohol was chosen as the standard alcohol; 
 and formic acid as the standard acid. The two 
 characteristics chosen for measurement were 
 (1) the initial speed of etherification, or the 
 amount of action that takes place in the first 
 hour, and (2) the final limit of the process ; these 
 Menschutkin terms the ' etherification-data.' 
 For the ' methylic-acetic ' system Menschutkin 
 took the limit as equal to 100 ; that is to say, 
 out of equal numbers of molecules of metbyUa 
 
CHEMICAL CHANGE. 
 
 739 
 
 alcohol and acetio acid (in tUs case 144) only 
 100 molecules were converted into methylic 
 acetate when the system reached a state of 
 equilibrium; of these 100 molecules, 80 were 
 formed during the first hour of action. 
 
 The following table contains the 'etherifioa- 
 tion-data ' for the primary alcohols employed: — 
 
 Alcohol 
 
 Speed 
 
 Limit 
 
 Methylic, HCH.,OH . , 
 EthyUo, CHjCH^OH . . 
 Propylic, C^HsCHjOH . 
 Butylic, C,H%CH,OH . . 
 Octylio, O^.^CH^OH . . 
 
 80 
 
 67-3 
 
 66-9 
 
 67-4 
 
 67-0 
 
 100 
 95-6 
 96 
 96-6 
 ? 
 
 The influence of isomerism on etherification 
 among the primary alcohols was investigated for 
 the case of isobutylio alcohol ; the data obtained 
 were 
 
 Isobutylio, C,B.^,CRfiB., speed = 64-61imit = 96-6. 
 These numbers show that the limit is unaffected, 
 but that there is a small decrease in the speed. 
 The unsaturated primary alcohols showed less 
 facility for forming ethers, the reaction in their 
 case progressing much less rapidly, as the follow- 
 ing numbers show : — 
 
 speed limit 
 AUyUo alcohol, C^HjCHjOH, 51-9 85-3 
 Propargylic alcohol, C^HCHjOH, 29-5 ? 
 Benzylic alcohol, CsHsCHjOH, 54 6 87-3 
 
 For the secondary alcohols, the phenols, and 
 some other alcohols, the following etherification- 
 data were obtained: — 
 
 Dimethyl carbinol 
 
 Methylethyl „ 
 
 Diethyl „ 
 
 Isopropylmethyl „ 
 
 Isobutylethyl „ 
 
 Hezylmethyl „ 
 
 Ethylvinyl „ 
 
 Diallyl „ 
 
 Ethylphenyl „ 
 
 Diphenyl „ 
 
 Phenol „ 
 
 Faracresol „ 
 
 Thymol „ 
 
 a-Kaphthol „ 
 
 Glycol „ 
 
 Glycerin „ 
 
 Erythrite h 
 
 Kannite „ 
 
 
 Speed 
 
 Limit 
 
 (CH,).CHOH . . 
 
 38-2 
 
 86-9 
 
 (OH,)(O.H.)CHOH. 
 
 32-6 
 
 85-2 
 
 (C,H.),CHOE . . 
 
 24-3 
 
 84-2 
 
 (CH.)(C,H/9,)CH0H 
 (C.H.)(C.H^.)CHOH 
 
 27-2 
 
 85'2 
 
 26-2 
 
 ? - 
 
 (CH.)(C.H„)OHOH 
 (0,H.)(C,H,5CH0H. 
 
 34-1 
 
 ? 
 
 21-3 
 
 75-1 
 
 (O.H.),CHOH . 
 (C,H.3(C.H.)CH0H. 
 
 16-3 
 
 72 
 
 27-2 
 
 ? 
 
 (CH.XCHOH . . 
 
 81-6 
 
 ? 
 
 C,H..OH . 
 
 2-0 
 
 12-4 
 
 C.H.CH..OH . , 
 
 3-7 
 
 13-7 
 
 C.H,CH,C.H,.OH . 
 
 1-4 
 
 13-6 
 
 0,„H,.OH . . 
 
 ? 
 
 8-8 
 
 CH^OH.CH,OH. 
 
 61-7 
 
 77-4 
 
 (CH,OH),CHOH . 
 
 62-2 
 
 66-2 
 
 O^H.(OH). 
 
 34 
 
 67-6 
 
 C.H.(0HJ. . . 
 
 29-8 
 
 38 
 
 Menschutkin (J", ^w. 25, 193) has also determined 
 the initial speeds and limits for different organic 
 acids, employing one alcohol (isobutylio), and 
 taking formic acid as the standard of reference. 
 The following results were obtained : 
 
 
 Acid 
 
 Speed 
 
 Limit 
 
 /PormioOH.O 
 
 100 
 
 100 
 
 ." 
 
 Acetio OaH.0 
 
 71-9 
 
 104-8 
 
 H, 
 
 Propionic CaHaOa 
 
 66-7 
 
 106-9 
 
 W 
 
 Butyric O.H,0, 
 
 B3-9 
 
 108-2 
 
 rS 
 
 OaprOiC OaH,aOa 
 
 63-6 
 
 108-7 
 
 
 CapryUo 0.H,.O, 
 
 60-0 
 
 110-3 
 
 Hydrosorbic C.H„0 
 
 
 
 Phenylaoetic 0,H,0 
 
 79-1 
 
 116 
 
 Phenylproplonio C,H,„0 
 
 
 
 Dlmethacetio CH(OH,),CO,H . . . 
 Methethaoetic OH(OH,)(0,H.)OO.H 
 
 43-4 
 
 108-2 
 
 30-3 
 
 114-8 
 
 Crotonic 0,H,.CO,H 
 
 19'6 
 
 112-3 
 
 Oinnamio 0,H.(O.H.)00^ . . . 
 
 18-7 
 
 116-3 
 
 Trimethacetio 0,H,„0, . . . . 
 
 11 8 
 
 
 Dimethethaoetic C,H„0, . . . ■ 
 
 4-8 
 
 116-4 
 
 Bor 
 
 bloOAO 
 
 
 
 Acid 
 
 Benzoic 0,H,0, . 
 Nitrobenzoio C,H:,(N0,)0, 
 Paratoluylio O.H.O, . 
 Cuminic CoHuOj 
 
 Speed Limit 
 
 13-9 
 40-1 
 10-7 
 10-1 
 
 112-9 
 114-3 
 119-1 
 118-1 
 
 From the foregoing numbers it is seen that 
 the rates of etherification' of the secondary 
 acids are much less than those of the primary 
 acids, but that the limits show only slight varia- 
 tions. The speeds of etherification of the ter- 
 tiary acids are less than those of either the 
 primary or secondary acids, but on the other 
 hand the limits are greater. For a fuU disoud- 
 sion of the value of etherification-data as a 
 means of determining isomerism among 
 alcohols and acids see Menschutkin (<7'. pr. 
 [2] 26, 103 ; also Z. P. C. 1, 611). 
 
 The theory of limited chemical reactions has 
 been formulated in a simple manner by Van 't 
 HofE {B. 10, 669) for the particular case of 
 etherification, but essentially in the same 
 manner as Guldberg and Waage have done in 
 their general treatment of this chemical pro- 
 blem. If the system initially consists of one 
 equivalent of acetio acid, k of alcohol, and q of 
 water, then when the quantity e of ether has 
 been formed, there wUl still remain of acid 1 — e, 
 of alcohol K— e, and of water q + e; consequently 
 the rate at which ether is still being formed is 
 expressed by 0,(1 — 6)((c — 6), and the rate of de^ 
 composition of the already formed ether by the 
 water by C^e (g + e). When equilibrium is at- 
 tained these two expressions must be equal, or, 
 C| (1-e) (ic-e) = C^(q + e). For equivalent quanti- 
 ties of acetic acid and ethylic alcohol, or k=1 
 and q = 0, Berthelot and St. Gilles found the 
 
 2 
 limit to be about 66-6 p.c, or 6= .-. Inserting 
 
 o 
 
 these values in the equation, the ratio of the two 
 constant C, and Cj is found; or C, = 402. The 
 equation now becomes 4(t-e)(K-e) = s(g-(-e) from 
 which the maximum quantity of ether capable 
 of being formed when various amounts of alco- 
 hol or water are employed can be calculated. For 
 instance, if k = a> , i.e. if the alcohol is unlimited 
 in amount, c = l, that is, all the acid is changed 
 into ethereal salt ; if g = oo , i.e. if the water is un- 
 limited in amount, e = 0, or no ether is formed. 
 These results are merely the extreme cases of 
 what experiments have proved to be true between 
 those limits of k and q which have been tried. 
 
 Formation of AcetaniUde. — ^In a study of the 
 formation of acetanihde, according to the equa- 
 tion CjHsNHj -I- C2H,02= 05H5(0jH30)HN + Afl, 
 Menschutkin (J.pr. 26, 208) found that, although 
 in the processes of etherification the final limit 
 of the reaction attained after an indefinitely 
 long interval of time is practically uninfluenced 
 by change of temperature, in this example the 
 limit is materially decreased as the tempera- 
 ture increases. The following results show this 
 decrease : — 
 
 Temp. 
 
 Limit. 
 
 
 100° 
 
 85-05 p.o. 
 
 
 125" 
 
 8311 
 
 
 136° 
 
 82-39 
 
 
 145° 
 
 81-22 
 
 
 155° 
 
 79-68 
 
 
 Another remarkable fact 
 
 was noticed in 
 3b2 
 
 this 
 
740 
 
 CHEMICAL CHANGE. 
 
 reaction, and one which is apparently at variance 
 with most experiments relating to the action of 
 mass (see Berthelot's etherification experiments, 
 ante) . In any chemical system undergoing change, 
 comprising two or more active bodies, the rate 
 of change is generally accelerated [v. p. 744) 
 by an increase in the amount of any of the 
 active bodies, and this increase in the rate is 
 more or less proportional to the quantity of 
 active substance added. But in the formation 
 of acetanilide, with a constant amount of acetic 
 acid, an increase in the quantity of aniline re- 
 tards the action, according to Menschutkin, 
 although the final limit is increased as the 
 theory of mass-action requires. The numbers 
 under ' speed ' showing this fact represent the 
 amount of action after 15 mins. 
 
 Moleonles aniline with 
 one mol. acid 
 
 Speed 
 
 Limit 
 
 1 
 
 2 
 3 
 
 4 
 8 
 
 34-71 
 28-71 
 23-45 
 
 17-13 
 
 79-68 
 91-65 
 94-61 
 96-17 
 97-22 
 
 However, when the aniline remains constant 
 and the acetic acid is increased, the law of mass- 
 action appears in the normal way (v. also Ar- 
 Form, p. 85). 
 
 Molecules acid with 
 one mol. aniline 
 
 Speed 
 
 Limit 
 
 1 
 2 
 4 
 
 34-71 
 57-30 
 78-08 
 
 79-68 
 96-88 
 99-80 
 
 Division of a base between two acids. 
 When a mixture of two acids acts on a base, 
 or two bases act on one acid, the two acids in the 
 first case being more than sufiScient to combine 
 with the base, or the two bases in the second 
 case with the single acid, it is usually granted 
 that the base divides itself between the two acids 
 or the acid between the two bases in definite 
 ratios. Or if an acid acts upon a salt in solu- 
 tion, as nitric acid on potassic sulphate, a defi- 
 nite amount of change takes place resulting in 
 this instance in the formation of potassic nitrate 
 and sulphuric acid. If the ratios in which such 
 divisions occur were known they might afford 
 measures of the relative afiinities of the acting 
 bodies for the particular conditions of the experi- 
 ments. Such ratios have been determined for 
 a great many acids by Ostwald, with most im- 
 portant results. (For an account of this work 
 
 V. AlTlNITY.) 
 
 Pattison Muir (C. J. 33, 27; 35, 311; 36, 60) 
 has studied the conditions affecting the equili- 
 brium of certain chemical systems wherein pps. 
 are formed, with the view of determining the 
 relationship between the concentrations of the 
 solutions, the ratios between the active bodies, 
 and the infiueuce of heat on the equilibrium 
 ratios. An investigation somewhat similar to 
 this was conducted by Morris {A. 213, 233). 
 
 Fractional Precipitation. 
 It has been shown {ante ; and v. Affinitt) 
 that if a mixture of two acids is allowed to 
 
 act upon a single base, or of two bases on a 
 single acid, the ratio in which the base divides 
 itself between the two acids, or the acid between 
 the two bases, depends upon the relative quanti- 
 ties or masses of the materials in the system, as 
 weU as upon the strength of the affinities acting 
 between the several bodies. In like manner, if 
 a pptant. is added to a solution, containing two 
 or more salts of different metals, the mass of 
 the pptant. being less than is required for com- 
 plete ppn. of aU the salts in the solution (being, 
 
 say, ith of the total necessary) then the ratios 
 
 of the quantities of the salts decomposed — or of 
 the hydrates, carbonates, &c. formed — depends 
 on (i) the relative masses of the substances in 
 solution, (ii) the relative affinities of the salts 
 or the basic powers of the oxides with reference 
 to the pptant., and also (iii) on the fraction of the 
 total material that is ppd. 
 
 This highly interesting subject of fractional 
 ppn. has been as yet investigated but to a very 
 shght extent ; it would, however, seem to promise 
 in the future a fertile field for the determination 
 of what might be caUed the relative basic 
 powers of different oxides or hydrates. If, for 
 example, a solution contains two salts of different 
 metals, the basic powers of whose oxides are 
 different, and if a small fraction is ppd. (say as 
 hydrate), there wiU be a tendency on the part 
 of- the less basic material to accumulate in the 
 pp. in preference to the more basic, and this 
 tendency will be greater as the difference between 
 the basic powers is greater. If the basic powers 
 differ but slightly, then the increase in the ratio 
 of the less to the more basic material wUl 
 progress very slowly by repeated application of 
 the process of fractional ppn. If in the extreme 
 case no such difference exists under the condi- 
 tions of the experiment as regards temperature 
 and quality of tiie pptant. (the ratio of the basic 
 powers may and probably does vary with the 
 temperature), then the ratio of the two materials 
 in the small pp. will be the same as that in the 
 original solution, and consequently, however 
 frequently the process may be repeated on each 
 fraction formed, no separation will be effected. 
 
 At the present time there are a number of 
 elements known belonging to the earths, for 
 the separation of which the only method that 
 has yet been discovered is that of fractional 
 ppn., or fractional fusion ; in both cases the 
 separation depends on the differences of the 
 basic powers of the various bodies. Such, 
 for instance, is the separation of the three 
 elements, samarium, didymium, and lanthanum, 
 from each other; or holmium, thulium, and 
 erbium ; or again terbium from yttrium. These 
 separations are so extremely tedious, requiring 
 the application of fractional ppn. to be repeated 
 a very great number of times with but relatively 
 infinitesimal yields of finally pure material, 
 that it is evident that the differences in basic 
 powers must be extremely small, more particu- 
 larly in the oases of samaria-didymia, yttria- 
 terbia, and hohnia-thulia. This process for 
 effecting the separation of these earths is 
 rendered all the more uncertain and difficult 
 owing to the want of facts drawn from the study 
 of fractional ppn. of other bodies bearing upon 
 
CHEMICAL CHANGE. 
 
 741 
 
 the best conditions nnder which the process 
 should be conducted {v. Eakths). 
 
 Ohizyfiski (A. Suppl. 4, 226; J. 1866. 12) 
 has investigated the subject of fractional ppn. 
 for the case of magnesium and calcium chlorides 
 by phosphoric acid. This chemist employed 
 solutions containing the two salts in varied 
 proportions; to these solutions he added a 
 constant quantity of phosphoric acid insufficient 
 for complete ppn., then ammonia was added, 
 and he determined the amounts of calcic and 
 magnesic oxides in the pps. The composition 
 of the pps. was found to vary with the ratio 
 of the amounts of calcic and magnesic chlorides 
 in the solutions, but to be nearly independent 
 of the quantity of water used for dilution. By 
 increasing the amount of calcic chloride in the 
 solution, the magnesic chloride remaining con- 
 stant, it_ was found that the lime passed into 
 the pp. in greater quantity, while the amount 
 of magnesia decreased; with the calcium salt 
 constant, the magnesic chloride being increased, 
 the reverse occurred, but to a less marked 
 degree. These variations took place in a 
 regular manner as the composition of the solu- 
 tions varied. 
 
 Mills, in conjunction with others (P. M. [5] 
 13, 169, 177; and "Pr. 29, 181), has studied 
 the fractional ppn., by means of sodium hydrate 
 or carbonate, of several sulphates, taken in 
 pairs under varying conditions of mass, with 
 the view of determining the relative facility 
 with which one sulphate is decomposed in 
 presence of another when an insufficiency of a 
 pptant. is added to the solution. 
 
 In one set of experiments in which nickel 
 and manganese sulphates were employed, the 
 following numbers were obtained ; each solu- 
 tion contained 1 gram of material made up to 
 100 c.c, and 10 c.c. of a solution of Ka^COj 
 (•5715 gram NajCOj) were added: — 
 
 NISO. 
 
 MnSO. 
 
 NiSO. 
 ppd. 
 
 MnSO. 
 ppd. 
 
 Temp. 0." 
 
 •1 grm. 
 
 •9 grm. 
 
 •0953 
 
 •5850 
 
 12-9 
 
 •2 
 
 •8 
 
 •1852 
 
 •4616 
 
 13-6 
 
 •3 
 
 ■7 
 
 •2799 
 
 •3766 
 
 12-5 
 
 •4 
 
 •6 
 
 •3588 
 
 •2976 
 
 13 
 
 •5 
 
 •5 
 
 •4305 
 
 •2450 
 
 13-6 
 
 •6 
 
 •4 
 
 •4788 
 
 •1536 
 
 . 12-8 
 
 •7 
 
 •3 
 
 •4991 
 
 •1089 
 
 17 
 
 •8 
 
 •2 
 
 •5584 
 
 •0722 
 
 17 
 
 •9 
 
 •1 
 
 •5841 
 
 •0363 
 
 152 
 
 From these numbers it is seen that the ratio 
 of the quantities of material ppd. varies con- 
 tinuously, and in the same manner as the ratio 
 of the amounts of salts employed ; with equal 
 masses of the two sulphates in solution the pp. 
 oontains much more nickel than manganese; 
 hence it is at once inferred that the basic power 
 of manganous hydrate or oxide is greater than 
 that of nickel, since the less basic a material 
 the greater its tendency to be affected by the 
 pptant. 
 
 Extending these experiments performed in a 
 similar manner to mixtures of nickel and cobalt 
 sulphates, but employing sodic hydrate instead 
 of carbonate, it was found that these two salts 
 
 have almost equal degrees of precipitability ; that 
 is to say, if the two salts exist in the solution in 
 equal amounts they will accumulate in the pp. 
 in about equal quantities ; or, with varying 
 quantities of material, the ratio of the amounts 
 of the two salts ppd. will be approximately 
 equal to the ratio initially in the solution ; in 
 other words, the basic powers of the two salts 
 are about equal. (For the theory of fractional 
 pptn. see Hood, P. M. 1886.) 
 
 Beduction of Oxides. 
 
 The conditions that affect the reduction of 
 metallic oxides by hydrogen, carbon monoxide, 
 and carbon, have been examined by Wright and 
 Luff (C. J. 33, 1, 509 ; 35, 475 ; 37, 757), the 
 type of the reactions being represented by the 
 equation a-fbo^ab + o. The results have 
 important practical bearings on metallurgical 
 operations. The temperature at which reduc- 
 tion commences is a function of (1) the physical 
 conditions of the bodies experimented with, 
 (2) and the chemical nature of the substances. 
 With CO as the reducing agent, the temperature 
 at which action begins in the case of cupric 
 oxide varies from 60° to 146° according to the 
 state of aggregation of the copper oxide; for 
 ferric oxide the temperature ranges between 90° 
 and 220°. The reduction by CO of copper oxide, 
 prepared by ppn., is well marked at temperatures 
 below 100°, but at 100° it becomes very ener- 
 getic. The initial action of H on copper oxide 
 was found to take place at temperatures ranging 
 between 85° and 172°, and on ferric oxide be- 
 tween 195° and 265°. When carbon was em- 
 ployed as the reducing agent, the temperature of 
 initial action varied not only with the physical 
 nature of the metallic oxide, but also with the 
 quality of the carbon ; the temperature limits for 
 copper oxide were 350° and 440°, and for ferric 
 oxide 480° to 450°. By comparing the tempera- 
 tures of initial action for a given kind of me- 
 tallic oxide, it was invariably found that that 
 reducing agent begins to act at the lowest tem- 
 perature which has the greatest heat of combus- 
 tion, so that the heat disturbance during its 
 action has (algebraically) the greatest value. 
 Thus H always begins to act at a lower tempera- 
 ture than carbon, and CO at a lower temperature 
 than H, as the following table shows for different 
 specimens of metallic oxides : — 
 
 
 00 
 
 H 
 
 Sugar 
 
 
 from 
 00 
 
 Cupric oxide A . 
 
 60° 
 
 85° 
 
 390° 
 
 350° 
 
 B . 
 
 125 
 
 175 
 
 430 
 
 350 
 
 . 
 
 146 
 
 172 
 
 440 
 
 430 
 
 Cuprous oxide 
 
 110 
 
 155 
 
 390 
 
 345 
 
 Ferric oxide A . 
 
 202 
 
 260 
 
 450 
 
 430 
 
 „ B . 
 
 90 
 
 195 
 
 450 
 
 
 
 . 
 
 220 
 
 245 
 
 450 
 
 480 
 
 Comparing cupric and ferric oxides prepared 
 by analogous processes, and therefore pre- 
 sumably in much the same physical state, it 
 was uniformly found that the temperature of 
 initial action of a given reducing agent is lower 
 on oxide of copper than on oxide of iron, as the 
 following numbers sho^ : — 
 
742 
 
 CHEMICAL CHANGE. 
 
 Copper 
 Iron 
 
 Oxides pre- 
 pared by pre- 
 cipitation . . 
 
 ^Jared ^I^OPP; 
 h e a t i n g I Iron < 
 salts . . J '- 
 
 00 
 
 60° 
 90 
 
 125 
 202 
 220 
 
 85= 
 195 
 
 175 
 260 
 245 
 
 Sugar 
 
 
 390' 
 450 
 
 430 
 450 
 450 
 
 Ofrom 
 CO 
 
 350° 
 430 
 
 390 
 430 
 430 
 
 The extension of these experiments to the oxides 
 of nickel, cobalt, lead, manganese, ferrous and 
 ferroso-ferrio oxides, resulted in the following 
 conclusions, among others. DifEerences in physical 
 state are attended with correlative differences in 
 the temperatures at which the actions of the re- 
 ducing agents CO, H, and C, are first manifested. 
 For the several oxides of the same metal the tem- 
 perature of the initial action of a given reducing 
 agent is sensibly the same unless the differences 
 in physical structure are very marked. In no 
 case was any exception found to the rule that 
 the temperature of initial action of CO is lower 
 than that of H, and that of H lower than that 
 of C, on the same sample of metallic oxide. 
 For a large number of cases the rule holds that 
 the greater (algebraically) the heat production 
 during the occurrence of a reaction the lower is 
 the temperature at which this action is first 
 manifested. 
 
 During the investigation of the rates of 
 action of CO and H, it was noticed that in many 
 instances ' chemical induction ' manifested 
 itself ; i.e. the reducing action of the gas on the 
 metallic oxide at a given temperature was at 
 first slight or nil ('period of incubation'), but 
 after a longer or shorter time the reduction 
 commenced and proceeded at an increasing rate, 
 until the retarding influences of the products of 
 the action caused the rate of reduction to cease 
 increasing, and subsequently to diminish. The 
 'period of incubation,' when measurable, was 
 found to be shorter the higher the temperature. 
 
 A similar phenomenon has been observed by 
 Bunsen and Eoscoe in their investigation of the 
 action of light on a mixture of chlorine and 
 hydrogen (t). influence of light, j)os<), and it is 
 interesting to note that in a heterogeneous 
 system consisting of a sohd oxide and a gas 
 chemical induction should also manifest itself. 
 The question naturally arises whether or not it 
 is a general phenomenon accompanying all 
 chemical changes. 
 
 Homogeneous TTnlimited Systems. — Consider- 
 ing the simplest chemical system undergoing 
 change, that of a single body either decomposing, 
 like ammonium nitrate when heated, or suffering 
 molecular rearrangement, as ammonic cyanate 
 into urea, it is evident that unless the products 
 interfere as retarding agents the amount of 
 change in unit of time, that is to say the rate of 
 change, will be proportional at any time to the 
 amount of active substance then existing. When, 
 however, a system comprises two or more active 
 members reacting on each other, such as an 
 alcohol on an acid, or hydric peroxide on an 
 acidulated solution of a soluble iodide, the cir- 
 cumstances are much more complicated. The 
 general experiments on the rate of chemical 
 
 change, when not limited by inverse action, 
 prove that in such complex systems the rate of 
 change of any one of the members is increased 
 or diminished by an increase or decrease in the 
 quantity of any of the other constituents, and 
 is more or less proportional to such varia- 
 tion. For example, if the system comprises 
 A,A2A3,...A„ (different bodies reacting one with 
 the other), the rate at which A« changes is in- 
 creased or diminished by a simUar variation in any 
 other member, as Af. The statement of this law 
 of mass by MiUs (P. M. [5] 1) in the words ' no 
 matter what may be the masses of the substances 
 reacting the entire mass of each takes part in 
 the process,' requires to be limited by the further 
 statement that the law applies only to homo- 
 geneous systems in the sense in which these have 
 been before defined. It could not be asserted for 
 instance that the entire mass of the marble in 
 Bojuski and Kajander's experiments affects the 
 rate of action of the acid, or that a hollow sphere 
 of zinc dissolves less rapidly in acid than a soHd 
 sphere of similar external dimensions. 
 
 Berthelot in 1862 (A. Ch.) showed that the 
 rate of reaction of alcohol with acetic acid is 
 proportional to the product of the two active 
 substances. Harcourt and Esson in 1866 {Pr. 
 14, 470) estabUshed several formulsB representing 
 various experimental conditions based on the 
 same hypothesis, but the reaction they employed 
 for verification of the theory (permanganate on 
 oxalic acid) proved to be of so complex a 
 character as to give but imperfect results. These 
 chemists, however, were more successful subse- 
 quently (Pr. 15, 262) with the reaction 
 HA + 2IH = 2H20-Hl2. 
 
 The theory of Guldberg and Waage relates 
 more particularly to cases of limited action, but 
 in its application to the study of the rate of 
 change the introduction of so many ' coefBcients 
 of action ' {v. ante, p. 737) renders the equation 
 of little practical use for such investigations. 
 (But V. article ArnNiTT, p. 70). Except in the 
 theory of Guldberg and Waage, the influence of 
 the products of the change either as accelerating 
 or retarding agents is generally overlooked in 
 attempts to formulate chemical action ; but it is 
 easy to introduce these effects in an equation to 
 represent the rate of change of a complex system, 
 on the hypothesis that the rate is directly pro- 
 portional to the product of aU the active mem- 
 bers and is inversely proportional tp the amount 
 of chemically inactive bodies formed (v. beiabda- 
 
 TION OF CHEMICAL CHANGE, p. 744). 
 
 In a complex system, consisting of n members, 
 undergoing change, let the masses of the initial 
 active bodies be represented by A,A2A,...A„, and 
 let the masses of these bodies that have become 
 changed or rendered chemically inactive up to a 
 time t, be represented by a„a2,a^...a^; then, ac- 
 cording to this hypothesis, the rate of change of 
 any member of the system, say A„ is 
 
 dt '^B±{\\ + \"ai...\'a^ •••W 
 
 Where ft, and b, are constants, and \', \" X» 
 
 are the retardation or accelerating coefficients 
 of the products of the action, the -H or — sign 
 being taken according as these products all act 
 as retarding or as accelerating agents. Which 
 of these actions was performed by any specified 
 
CHEMICAL CHANGE. 
 
 743 
 
 product of the primary action could be deter- 
 mined experimentally, by introducing a known 
 mass of the body into the system, and com- 
 paring the rate of the change with that observed 
 when no more of the specified body was present 
 than was_ formed during the primary reaction. 
 Since a, is the member of the system whose 
 rate of change is the object of measurement, 
 let the amount that remains unchanged at time t, 
 that is A,— a., be taken as y ; then— if the initial 
 
 quantities of the other members be v,, f^ v^ 
 
 tquivalents of a„-a, = 6,i/,a., i^ = f^v^„ a„ 
 
 = *n''ii^i and a, = f,o„ ttj = e2a,, o„ = e„o<. In- 
 serting these values in the above equation it 
 becomes 
 
 _'^y-„/ y{(''i-l)A+yl{(y2-l)A+i/{...ete. 
 
 (2) 
 
 dt '~ b' T 2/ 
 
 In this equation ju.' and b' are constants to be 
 determined experimentally, a being the initial 
 value oty; /i' is proportional to the rate and is 
 dependent on the temperature {v. influence op 
 
 HEAT ON CHEMICAL CHANGE, p. 744). 
 
 Numerical examples of this equation for a 
 system comprising the three bodies, ferrous 
 chloride, hydrio chloride, and potassic chlorate, 
 have been given by Hood (P. M. [5] 20, 444), but 
 the solutions he employed were so dilute that 
 the products of the action appeared to influence 
 the rate inappreciably, consequently the term 
 in the equation relating to these effects was 
 neglected, and the equation was taken as : 
 
 -§=/*'2/(v,-l)A + 2,)((.',-l)A + 2/) .(3) 
 
 for the system of three bodies. 
 
 It is possible to arrange the experimental 
 conditions in such a way that, neglecting the 
 action of the products, the course of the change 
 may be much simpler than is represented by 
 equation (2). This may be done, (1) by having 
 all the active substances present m very large 
 excess over that one which is made the object 
 of measurement, so that they undergo but slight 
 diminution between the beginning and the finish 
 of the change taking place in the body measured ; 
 or (2) by arranging the constituents so that one 
 or more of them, although taking part in the 
 reaction, remains constant in amount, one con- 
 stituent only diminishing in value. The equa- 
 tion for the rate of change of one member in 
 either case would be by (2) 
 
 dt 
 
 Where a„A2,...a„ are the masses of the chemically 
 active constituents which remain constant or 
 nearly so ; or integrating, y = Be-"', o being equal 
 to yltAi, A2...A„. 
 
 Harcourt and Eason (T. 157, 117) proved 
 the truth of this exponential formula for the 
 action between a soluble iodide and hydrio 
 peroxide. The fundamental change in this 
 case is represented by HA + 2HI = 2H2O + 1^. 
 By the simple device of adding a known con- 
 stant amount of sodic thiosulphate to the active 
 solution each time the liberated iodina made 
 its appearance, the amount of hydric iodide was 
 kept constant, while the H2O2 alone dimi- 
 nished. The successive additions of thiosulphate 
 measured the amount of change of the hydric 
 peroxide (or y), and the intervals between each 
 allitxon, or rather the appearances of free 
 
 -M^A,Aj...A.. 
 
 iodine, measured the times of action. From their 
 experiments relating to the influence of variational 
 of temperature, and variations of the masses of 
 the acting substances, Harcourt and Esson con- 
 cluded that 'whether the solution contains in 
 Ic.c. 746 millionths of a gram of hydric sulphate 
 or 150 times that quantity, 604 nullionths of a 
 gram of KI or 9 times that quantity, or whether 
 HCl or hydrio sodic carbonate be substituted for 
 HjSOj, whether the temperature be 0° or 50°, 
 and whether the portions of change require for 
 their accomplishment intervals of one or two 
 minutes, or intervals of half an hour or an hour, 
 this reaction stiU conforms to the law that the 
 amount of change is at any moment proportional 
 to the amount of changing substance.' 
 
 Harcourt and Esson {T. 156, 193) had pre- 
 viously employed the reaction between potassic 
 permanganate and oxalic acid for investigating 
 the laws according to which a chemical change 
 progresses. Although this investigation was not 
 quite successful in its primary object, it serves 
 well to illustrate the anomalous results that may 
 be obtained by the interfering action of the pro- 
 ducts formed in a reaction, or by extraneous 
 salts. The reaction under examination may be 
 represented at its beginning and its conclusion hj 
 the two sides of the equation : 
 K^MnPs + 3H,S0j + 5HiOj04 
 
 = K,SO, + 2MnSO,-hl0COj + 8H2O.. . 
 The reaction progresses with moderate rapidity 
 at temperatures easily kept under control. By 
 varying the mass of any one of the constituents 
 a corresponding variation occurs in the rate of 
 oxidation. The influence of HjSOf is shown in 
 the following table ; the reaction was allowed to 
 go on in each case for four minutes, and was 
 then suddenly stopped by the addition of KI, the 
 amount of change that had taken place being 
 obtained by estimating the iodine liberated: — 
 
 Mole- 
 
 Per cent. 
 
 
 Per cent. 
 
 cules 
 
 change in 
 
 H^SO. 
 
 change in 
 
 H,SO. 
 
 4min. 
 
 i min. 
 
 2 
 
 21-8 
 
 10 
 
 71-6 
 
 4 
 
 86 
 
 12 
 
 77-4 
 
 6 
 
 51-1 
 
 14 
 
 82-4 
 
 8 
 
 63-5 
 
 16 
 
 85-7 
 
 
 
 22 
 
 92-3 
 
 The principal secondary reaction in the oxida- 
 tion of C2H2O4 by KjMujOs arises from the de- 
 composition of K2Mn208 by the MnSO, 
 
 (J^MnA + SMnSOj + 2H2O 
 = KjSOj + 2H2S04 + SMnOj) ; this reaction in- 
 fluences the rate of oxidation in a remarkable 
 manner. With the materials in the proportions 
 of KjMnuOstlOHjSO^tSHjOjOj, it was found that 
 when no manganous sulphate was added only 
 eight p.c. of chemical change took place in 
 4 mins., but by gradually increasing the mass of 
 MnSO, the amount of change taking place in 
 this interval of time increased, until it reached 
 85 p.c. when 3MnS0, was present. Further in- 
 crease of the MnSOj only sHghtly altered the rate 
 of oxidation. Harcourt and Esson likewise found 
 that by varying the masses of H2SO4 and C^HjO,, 
 the K^MujOg and MnS04 remaining constant, 
 the percentage of chemical change in a definite 
 time (3 mins.) gradually increased till it reached 
 
744 
 
 CHEMICAL CHANGE. 
 
 a maxunum, then diminished to a minimum, 
 and again increased on addition of more 'H.fifi,. 
 Experiments on the relation between the time of 
 continuance of the action and its amount showed 
 that after a certain interval the course of the 
 change was represented by an hyperbola. The 
 reason of this regularity only occurring after the 
 action had proceeded some time was traced to 
 the double changes that take place, first between 
 the MnSO, and KjMnjO,,, and then between the 
 MnOj produced and the CjBLjO,. Both changes 
 are, however, comparatively slow ; but if either 
 of them occurred very rapidly compared with the 
 other, in presence of equivalent quantities of 
 materials, the whole course of the change would 
 doubtless be represented by an hyperbola. 
 
 Hood (P. M. [5] 6, 371 ; 8, 121) has studied 
 the rate of oxidation of JEerrous sulphate by 
 potassic chlorate, and the iniluence exerted on 
 the process by variations (i) in the amounts of 
 acid used and (ii) in the temperature. The 
 equation for equivalents being 
 
 BFeSOi + KClOj + SH^SO, 
 = 3Pej(S04), + ECl + SH^O, it is evident that the 
 rate of change wiU be the product of three 
 factors. The acid being in large excess and 
 KC10,:6FeS04 = i':l, the rate of change by equa- 
 tion (3) is ^=— /»B2/(y— l)A + y wheresequals 
 
 the amount of acid ; or log. 
 
 (n-l)k + y 
 /ib(»-1)a(c-«) ; if,however,KC103:6FeS04= 1:1, 
 
 then ^ =—iiBy\or y{a + t)'= . By a series 
 
 of determinations of y (c.c. of permanganate) at 
 indefinite intervals of time, the constants in 
 either of these equations {/is and o, and /j.b and a) 
 were found for different conditions of tempera- 
 ture, amount of acid (b), &c., and consequently a 
 measure was obtained of the changes produced 
 in the rate of oxidation by such variations. 
 Hood found that for this reaction both these 
 formulee hold good, and, as theory indicates, the 
 rate of oxidation, within certain limits, is pro- 
 portional to the amount of free acid ; as the 
 amount of acid, however, becomes comparatively 
 very great the oxidation progresses much more 
 rapidly than the acid increases. When HCl 
 replaces HjSO,, in order to produce the same 
 rate of oxidation the amounts must be as 36-5 : 80. 
 
 Ostwald {J.pr. 27, 1) has studied the interest- 
 ing reaction E.CONH2 + H20 = E.CO.ONH4 with 
 reference to the accelerating influence acids have 
 upon the rate of the change. This reaction is a 
 striking instance of so called ' predisposing ' 
 affinity, the reaction being a very slow one when 
 water alone is employed. (For details of this in- 
 vestigation, V. the article Affinity, p. 79.) 
 
 The decomposition of the ethereal salts, e.g. 
 methyUc acetate, by water, affords an example of 
 chemical change somewhat analogous to that of 
 the acetamides. The difference between the two 
 cases is that in the former the water resolves the 
 compoimd into two others, alcohol and acid, 
 whereas in the latter the water is assimilated to 
 form a more complex compound. The presence 
 of acids greatly accelerates the decomposition of 
 the ethereal salts, as is the case with the acet- 
 amides ; the relations between speed of action and 
 
 quality of acid have been investigated by Ostwald 
 (J.pr. 28, 449), v. Affinity. 
 
 Eetaedation and Aoceleeation op Chemioax. 
 Chakoes.— In the reaction that takes place when 
 an alcohol and an organic acid are mixed, the 
 amount of change is limited by the inverse actioi; 
 that arises between the products of the change, 
 ethereal salt and water, which inverse action 
 tends to the re-formation of the original alcohol 
 and acid ; it is consequently evident that the 
 rate at which the etherification progresses is re- 
 tarded by this inverse action. In like manner if 
 BaSOj is acted on by KjCOj, the rate of the de. 
 composition is retarded by the inverse action 
 that occurs between the BaCOa and K^SOj which 
 results in the formation of the original bodies. 
 
 The same may be said as regards the rate of 
 all those reactions which are limited in extent by 
 inverse chemical changes. 
 
 There is, however, another kind of retarda- 
 tion possible, not arising from any secondary 
 chemical changes taking place in the system, but 
 of a purely physical origin. If in a homogeneous 
 system undergoing change, such for instance as 
 is represented by the equation A-^B = AB, the 
 chemically active bodies be considered to be in 
 a state of continual motion, the rate of formation 
 of AB will be proportional to the number of im- 
 pacts between the a's and b's in a unit of time. 
 It is conceivable then that if the molecules ab 
 are not removed from the sphere of action their 
 mere presence will hamper the movements of the 
 remaining A's and b's, and by so doing will 
 diminish the number of impacts between them 
 in a unit of time, that is to say, will retard their 
 rate of combination. That retardation of a 
 chemical change does, arise by the addition of a 
 quantity of one of the products has been shown 
 to be true in several instances ; but whether the 
 effects are to be interpreted on a physical basis, 
 as is done here, or on a chemical basis, cannot 
 be decided with certainty until much more ex- 
 perimental evidence has been obtained. The 
 study of the influence of chemically inactive 
 bodies on systems undergoing change, that is to 
 say of bodies which probably do not take part 
 chemically in the reactions, forms a wide field 
 for research ; and there is no doubt that the re- 
 sults obtained will have an important bearing on 
 chemical science considered in its dynamical 
 aspect. 
 
 An acceleration in the rate of a chemical 
 change may be brought about by an increase in 
 the amount of any one of the active constituents 
 of the system ; such an acceleration, as has been 
 already shown, is easily explained by the law of 
 mass-action, viz. that the total mass of each 
 constituent takes part in the reaction. 
 
 There are instances, however, somewhat more 
 difficult of explanation, such as the inversion of 
 cane sugar, or the decomposition of methylic 
 acetate, by acids, wherein the addition of an 
 acid merely accelerates the change, the mass 
 of the acid remaining the same at the finish as 
 at the beginning of the reaction. The tendency 
 to undergo change in these instances is merely 
 increased by the presence of the acid, and this 
 tendency, measured by the speed of the change, 
 is dependent on the character of the acid em- 
 ployed {v. Ostwald's experiments detailed in 
 Affinity, p. 79). The difficulties that are here 
 
OIIEMIOAL CHANGE. 
 
 745 
 
 Encountered would seem to be similar to those 
 that arise in the consideration of so-called ' con- 
 tact actions ' or catalysis. 
 
 Guldberg and Waage (Etudes), in their inves- 
 tigation of the rate of production of hydrogen by 
 ■the mutual action of metals and acids, found 
 that the presence of salts in the acid solution 
 exercised a remarkable influence on the speed, 
 80me_ salts^ accelerating, others retarding, the 
 reaction; the salts themselves remaining un- 
 altered. Mills and Walton (Pr. 28, 268) observed 
 an acceleration in the rate of formation of am- 
 monia from potassic nitrate and zinc amalgam 
 by the addition of either K^SO, or NaaSO^, the 
 increase of speed being practically the same for 
 equal masses of the two sulphates. If a dilute 
 acidulated solution of ferrous sulphate is oxidised 
 by potassic chlorate at the ordinary tempera- 
 ture, these two bodies being present in equiva- 
 lent quantities, and the free acid (HjSOJ being 
 much in excess, the rate of the oxidation (v. ante) 
 
 is expressed by the equation ^- = —1-, or 
 
 at o 
 
 y(rt + t) = b, where t is time in minutes, and y is 
 CO. permanganate equivalent to ferrous iron re- 
 maining at time t. Since in these equations 
 
 -joc 6"' (or the rate of change is inversely pro- 
 portional to 6), by performing two experiments 
 under like conditions of temperature, dilution, 
 amount of acid, of iron, and of chlorate, except 
 that to one of the solutions a known mass of a 
 sulphate is added, it is easy to calculate the 
 equations, y(a + t) = h, for each of the systems ; 
 and, by comparing the two values for 6, to get a 
 measure of the retarding action of the particular 
 sulphate employed. In other words, the time 
 required to oxidise the iron from y' to y" is pro- 
 portional to h, and if this time for the blank 
 experiment be taken as 100 minutes, the value 
 
 of —- — (where 6 corresponds to the blank 
 
 o 
 and 6' to the retarded experiment) gives the 
 number of minutes required to perform the 
 same amount of oxidation in the presence of 
 the added sulphate. The annexed table con- 
 tains the results obtained by Hood (P. M. [5] 13, 
 419) in studying the retardation of various 
 sulphates in the above manner ; the temperature 
 being 21°C. in each experiment. 
 
 The numbers show that the retardation 
 occasioned by the presence of a chemically 
 inactive salt in the system employed is pro- 
 portional to the mass of the salt added, and 
 that some salts of analogous character produce 
 for equal masses the same retarding effect. 
 Thus the potassium, sodium, and ammonium 
 sulphates each produce a retardation of about 10 
 p.c. per gram, and the two alums about 6 p.c. 
 per gram. The differences in the effects of 
 magnesium and zinc sulphates are, however, too 
 great to allow of their being classed together 
 as analogous salts from a dynamical point of 
 view with reference to this particular case of 
 retardation. 
 
 Considering the alkali-sulphates and the 
 alums, it is clear that, since equal masses of the 
 several members of each group produce the 
 same effect, the retardation produced by a mole- 
 cule of one of the salts is proportional to its 
 
 
 z,so. 
 
 Na^SO. 
 
 (NH.),SO. 
 
 Weight 
 
 salt 
 
 
 Per 
 cent. 
 
 
 Per 
 cent. 
 
 
 Per 
 
 cent. 
 
 looy 
 
 retar- 
 
 1006' 
 
 retar- 
 
 1006' 
 
 retar- 
 
 h 
 
 dation 
 
 6 
 
 dation 
 
 i 
 
 dation 
 
 
 
 fori 
 
 
 lorl 
 
 
 fori 
 
 
 
 gram 
 
 
 gram 
 
 
 gram 
 
 2 grams . 
 
 120-3 
 
 10-1 
 
 120-6 
 
 10-3 
 
 120-8 
 
 10-4 
 
 3 „ . 
 
 130-8 
 
 10-2 
 
 131-6 
 
 10-6 
 
 132-4 
 
 10-8 
 
 4 „ . 
 
 143-1 
 
 10-8 
 
 143-3 
 
 10-8 
 
 146-3 
 
 11-3 
 
 6 „ . 
 
 163-4 
 
 10-7 
 
 161-9 
 
 10-4 
 
 164-9 
 
 10-9 
 
 6 „ . 
 
 167-1 
 
 11-2 
 
 166-6 
 
 11-1 
 
 166-2 
 
 11-0 
 
 8 „ . 
 
 195-8 
 
 11-9 
 
 190-6 
 
 11-3 
 
 193-2 
 
 11-6 
 
 10 „ . 
 
 221-7 
 
 13-2 
 
 212-4 
 
 11-2 
 
 213-9 
 
 11-4 
 
 
 KA1(S0.). 
 
 (NH.)A1(S0.). 
 
 Weight 
 
 
 Per cent. 
 
 
 Per cent. 
 
 salt 
 
 1006' 
 
 retarda- 
 
 1006' 
 
 retarda- 
 
 
 b 
 
 tion for 
 Igram 
 
 b 
 
 tion for 
 1 gram 
 
 2 grama . 
 
 112-2 
 
 6-1 
 
 111-8 
 
 6-9 
 
 3 „ . 
 
 118-1 
 
 6-0 
 
 118-3 
 
 6-1 
 
 4 „ . 
 
 124-7 
 
 6-2 
 
 124-4 
 
 6-1 
 
 B „ . 
 
 129-6 
 
 6-9 
 
 129-7 
 
 5-9 
 
 6 „ . 
 
 138-1 
 
 6-3 
 
 137-4 
 
 6-2 
 
 8 „ . 
 
 146-2 
 
 6-8 
 
 144-6 
 
 6-6 
 
 10 >, . 
 
 155-2 
 
 6-5 
 
 1631 
 
 6-3 
 
 
 MgSO. 
 
 ZnSO. 
 
 WeigM 
 salt 
 
 
 Per cent. 
 
 
 Per cent. 
 
 1006' 
 
 retarda- 
 
 1006' 
 
 retarda- 
 
 h 
 
 tion for 
 
 6 
 
 tion for 
 
 
 
 1 gram 
 
 
 1 gram 
 
 2 grams , 
 
 114-9 
 
 7-4 
 
 110-1 
 
 5-0 
 
 3 „ . 
 
 123-e 
 
 7-8 
 
 116 
 
 6-0 
 
 4 „ . 
 
 128-4 
 
 7-1 
 
 117-6 
 
 4-4 
 
 6 „ . 
 
 134 
 
 6-8 
 
 123 
 
 4-6 
 
 6 ., . 
 
 140-9 
 
 6-8 
 
 127 
 
 4-5 
 
 8 „ . 
 
 lSO-9 
 
 6-4 
 
 132-7 
 
 4-1 
 
 10 „ . 
 
 161-1 
 
 6-1 
 
 138-4 
 
 3-3 
 
 mass ; in other words, the greater the mass of a 
 molecule the more it retards the rate of the 
 chemical change. 
 
 Judging by these facts, it would seem not 
 improbable that chemical bodies might be 
 classified on a dynamical basis as regards their 
 retardation-effects. With this aim, Hood (P. M. 
 [5] 20, 444) has continued these experiments 
 in relation to soluble chlorides, but the anoma- 
 lous results obtained do not justify the assump- 
 tion started with. The results show that the 
 sulphates of the alkali metals in the oxidation 
 of ferrous chloride by KCIO3 produce an equal 
 retarding effect, about 17 p.c. per gram, but that 
 MgSOj, ZuSOj, and CdSO, (although usuaUy 
 classed together from a statical point of view) 
 differ greatly in their retardation-effects ; the 
 results for the first two sulphates are in about 
 the same ratio as in previous experiments with 
 ferrous sulphate instead of ferrous chloride. 
 Experiments with MgSOj showed that these 
 ' retardation coeificients ' vary slightly with in- 
 crease of temperature. 
 
 An examination of the effects of chlorides on 
 this reaction showed strikingly anomalous re- 
 sults ; no two chlorides gave the same retarda- 
 tion-effect. Sodic chloride practically produced 
 no effect on the speed of the oxidation, while 
 zinc, magnesium, and cadmium chlorides pro- 
 duced an acceleration. It seems difficult to 
 reconcile these results with a theory that should 
 account for the action of a chemically inactive 
 
r46 
 
 CHEMICAL CHANGE. 
 
 ialt in a system undergoing change on the basis 
 of molecular interference with the movements 
 of the changing constituents of the system. It 
 may be, however, that the presence of such 
 extraneous bodies induces secondary reactions 
 in the system which occasion either an accelera- 
 tion or a retardation of the principal change. _ 
 
 Influence of Heat.— The study of the in- 
 fluence exerted by heat on chemical changes, as 
 illustrated by the phenomena of dissociation, 
 and by such phenomena as occur when phos- 
 phorus or sulphur are heated, forms an im- 
 portant factor in the vast problem of chemical 
 action. Starting with the fundamental notions, 
 that heat is a form of energy, and that all 
 external material phenomena comprise two 
 factors, matter and motion, which it is the aim 
 of chemistry to investigate, with the molecular 
 theory of the constitution of matter for a basis, 
 it is evident that the relations between the 
 action of heat and chemical change will be most 
 advantageously studied by examining in what way 
 the rates and the limits of chemical changes, 
 occurring in homogeneous systems, are affected 
 by heat, and by determining the influence 
 exerted on such changes by extraneous bodies. 
 
 What is already known regarding the in- 
 fluence of heat in bringing about chemical com- 
 binations and decompositions would seem to 
 indicate that such action is of a twofold cha- 
 racter, more particularly in systems possessing 
 free mobility either in the gaseous or liquid 
 states ; for, besides accelerating the motions of 
 translation of the molecules of the system, and 
 BO multiplying the chances of collision in a 
 given time, and consequently increasing the 
 rate at which the change takes place, the action 
 of heat also accelerates the rate of change by 
 diminishing the stabilities of the reacting mole- 
 cules, and thus increasing their tendency to 
 undergo change. Thus, representing the mole- 
 cules of gaseous iodine and hydrogen respectively 
 as Ij and Hj, the amount of HI produced in 
 unit time at a given temperature, by the mutual 
 action of Hj and Ij, will depend upon the num- 
 ber of molecular coUisions, the velocities of 
 translation of the molecules (or the temperature 
 of the gas), as well as upon the facility with 
 which the molecules become separated into 2H 
 and 21. It is easy to understand in this way 
 why there are deflnite limits of temperature 
 within which chemical changes take place ; and 
 how some reactions which occur very rapidly 
 at one temperature may be prevented by suifi- 
 oiently cooling the reacting bodies. 
 
 Although as a general rule the action of heat 
 is such as to induce chemical combination at 
 moderately low temperatures and decomposition 
 at higher temperatures, instances are known of 
 bodies being more staljle, under certain condi- 
 tions, at high, than at low temperatures. Troost 
 and Hautefeuille (C. E. 73, 443 ; 84, 946) have 
 shown that by passing SiCl^ over strongly heated 
 silicon the latter is volatilised and is again con- 
 densed on the cooler parts of the tube. This 
 apparent volatilisation of silicon was found to be 
 brought about by the formation of SijClj at the 
 higher temperature, and decomposition of this 
 compound into the original bodies at a lower 
 temperature (281201, = 3SiClj + Si). The com- 
 paratively complex body SijCl, is thus resolved 
 
 by diminishing the temperature into the com- 
 paratively simpler bodies SiCl^ and Si. 
 
 A somewhat analogous reaction is asserted to 
 occur by Ditte vfith SeH^ (C.B. 74, 980). This 
 chemist says that if selenion is heated with hy- 
 drogen in a closed vessel, the amount of SeHj 
 formed increases with increase of temperature up 
 to 520°, but that any further increase in the 
 temperature is accompanied by a decrease in the 
 amount of SeH^ formed. If two tubes are heated 
 under like circumstances until the amount of 
 SeHj formed is constant, and one of them is then 
 cooled rapidly while the other is allowed to 
 return gradually to the lower temperature, Ditte 
 says that the second tube contains less SeHj than 
 the first, and so much less as the cooling has 
 been slower. On the other hand, SeHj submitted 
 to the action of heat suffers sensible decomposi- 
 tion even at 150° ; above 270° the amount of de- 
 composition gradually decreases untU it reaches a 
 minimum at 520°, after which the decomposition 
 continuously increases as temperature rises. 
 
 Chemical systems which are limited by reason 
 of inverse actions may be represented in terms of 
 
 their rates by the equations -^ ' = /(6);^(ab), and 
 
 —— =/(fl)i|'(0D), in which the accelerating influ- 
 ence of temperature is expressed by the functions 
 /(fl) and/(fl), and the absolute rate by the differ- 
 ence, or ^ =/(9)if'(AB)-/(e)i^(cD). When equi- 
 
 librium is attained, or no further change takes 
 place, /(e)+(A'B')-/(e)^(o'D') = 0; a', b', c', d', 
 being the quantities of active substances that can 
 exist together in stable equilibrium at tempera- 
 ture fl°- If the temperature functions be the 
 same in both cases,then /(fl) {"KaV) - i)'(o'd') } = 0, 
 or i('(a'b') = i|'(o'd'), or the limits are independent 
 of temperature. This would seem to be true 
 between certain limits for the simpler etherifioa- 
 tion processes, as Berthelot and Saint-GiUes' 
 experiments have shown. Menschutkin, how- 
 ever, has examined certain limited reactions 
 which show a marked variation in the limits 
 with temperature, and seem to indicate that the 
 ratio of /(fl) to/(9) is not constant. 
 
 From a study of certain reactions which are 
 not affected by limiting conditions, and of other 
 reactions which are so limited, attempts have 
 been made to determine the accelerating action 
 of heat, that is to say, to determine the form of 
 the temperature-function /(fl) in the equation 
 
 % = fiemT.a.b.c....). 
 
 Hood (P. M. [5] 6, 371), from experiments on 
 the rate of oxidation of ferrous sulphate solution 
 by KClOs, considered that /(9)oc fl^, or that the 
 rate of oxidation varied as the second power of 
 the temperature ; but the experiments were not 
 sufficiently numerous to place this conclusion 
 beyond doubt. 
 
 Warder {Am. [3] 203) studied the influence 
 of heat on the rate of the action 
 
 OjHjO.CjHsO + NaHO = NaCjHsO^ + CjHjHO, 
 in dilute aqueous solutions, the temperature 
 limits being 3'6° and 37-7°. The results obtained 
 agreed well with the formula (7'5 + a) (62-5° — f) = 
 521'4 ; t being temperature, and a the number of 
 gram-equivalents per litre which would (accord- 
 
CHEMICAL CHANGE. 
 
 747 
 
 ing to the theory of mass) react upon each other 
 per minute in a solution kept of normal strength. 
 The formula could be written as a = i. + Bf', 
 indicating the rate to vary nearly as the square of 
 the temperature. Menschutkin {J^.^r. [2] 29,437) 
 employed three somewhat analogous reactions 
 tor the study of this subject ; (1) formation of 
 ethylio acetate from acetic acid and ethylio 
 alcohol, (2) formation of acetanilide from acetic 
 acid and anihne, (3) formation of acetamide 
 from acetic acid and ammonia. Molecular quan- 
 tities of the materials were heated for one hour 
 at different temperatures, and the amounts of 
 ether, anilide, and acetamide formed were deter- 
 mined, and taken as measures of the speeds. The 
 following are his results : — 
 
 Temp. 
 
 Ether 
 formed 
 
 Temp. 
 
 Anilide 
 formed 
 
 Temp. 
 
 Aceta- 
 mide 
 formed 
 
 90 
 
 7-50 
 
 82° 
 
 6-08 
 
 100° 
 
 
 
 102 
 
 18-50 
 
 90 
 
 8-50 
 
 110 
 
 1-27 
 
 112 
 
 19-02 
 
 102 
 
 14-59 
 
 121 
 
 4-41 
 
 122 
 
 24-78 
 
 112 
 
 21-51 
 
 130 
 
 9-02 
 
 182 
 
 32-60 
 
 122 
 
 80-71 
 
 140 
 
 21-36 
 
 142 
 
 40-65 
 
 132 
 
 39-91 
 
 150 
 
 86-96 
 
 152 
 
 46-82 
 
 142 
 
 47-65 
 
 152 
 
 40-66 
 
 162 
 
 52-99 
 
 152 
 
 55-49 
 
 155 
 
 50-90 
 
 172 
 
 67-45 
 
 162 
 
 61-57 
 
 160 
 
 68-67 
 
 182-5 
 
 60-99 
 
 172 
 
 66-39 
 
 172 
 
 72-33 
 
 212-5 
 
 63-98 
 
 182-5 
 
 68-87 
 
 182-5 
 
 78-31 
 
 
 
 212-5 
 
 72-19 
 
 212-5 
 
 82-83 
 
 These numbers all agree in this respect, that 
 the differences in the amounts of action during 
 one hour, for equal differences of temperature, 
 gradually increase, pass through a maximum at 
 a definite temperature, and then decrease. As 
 regards the general inferences that might be 
 drawn from these experiments relative to the 
 connection between action of heat and rate of 
 change, it must be remembered that the re- 
 actions labour under the disadvantage of being 
 cases of only limited action, and that the pro- 
 ducts of the change no doubt retard the prin- 
 cipal reaction, and tend to complicate matters. 
 Besides this, the method of allowing the change 
 to proceed in each case for the same interval of 
 time is objectionable, for at the higher tempera- 
 tures the amounts of the products formed before 
 the expiration of one hour are so very much 
 greater than the amounts formed at the lower 
 temperature that their presence must exercise a 
 considerable retarding influence on the further 
 progress of the reaction up to the time-limit. 
 
 Unlike some of the etherification processes 
 the limits of formation of acetanilide and acet- 
 amide are influenced very considerably by heat, 
 as the following numbers show : — 
 
 Acetanilide 
 
 Acetamide 
 
 Temp. 
 
 Limit 
 
 Temp. 
 
 Limit 
 
 100° 
 
 80-05 
 
 125° 
 
 75-10 
 
 125 
 
 83-11 
 
 140 
 
 78-18 
 
 185 
 
 82-39 
 
 155 
 
 81-46 
 
 145 
 
 81-22 
 
 182-5 
 
 82-82 
 
 155 
 
 79-68 
 
 212-5 
 
 84-04 
 
 182-5 
 
 78-85 
 
 
 
 212-5 
 
 77-75 
 
 
 
 In order to determine the temperature- 
 function influencing the rate of a chemi(ia^ 
 change. Hood (P. M. [5] 20, 323) has again, 
 studied the oxidation of ferrous sulphate solu- 
 tion by potassic chlorate. This reaction is 
 well adapted for work of the kind, as it is com- 
 pletely under control, and can be rendered as quick 
 or as slow as may be desired by altering such' 
 conditions as dilution, temperature, amount of 
 free acid, &c. The progress of the oxidation can 
 also be followed with the greatest precision by 
 means of permanganate. 
 
 Each experimental solution consisted of -5637' 
 gram of iron as ferrous sulphate, and 3-099 
 grams of free H^SOj, made up to a volume of 
 250 c.c. To this solution 10 c.c. of a solution of 
 KCIO3 were added, equal to -2057 gram, being 
 the oxidising equivalent of the iron. From such 
 a solution, maintained at a constant temperature,. 
 10 o.e. were withdrawn at indefinite intervals of 
 time, and titrated by permanganate, and from 
 several such observations the constants in the' 
 equation y{a+t) = b were calculated ; y being c.c. 
 of permanganate, and t being time in minutes. 
 
 Since b is inversely proportional to the rate- 
 
 of change, or -M = — 1_ = —kf{e)y^, by compar- 
 
 ing the values of b obtained from a series of ex- 
 periments in which everything remains the same- 
 except the temperature, a measure is obtained 
 of the influence of heat on the rate of the oxida- 
 tion, and consequently a means of finding the 
 probable nature of the temperature-function /(fl). 
 The following table contains the results of 
 Hood's experiments ; the values for a and b for 
 the equation ylfl + t) = b being the means ot 
 several experiments : — 
 
 Temp. C. 
 
 a 
 
 i 
 
 Ratio *-i— 
 
 10° 
 
 330-8 
 
 3327-8 
 
 
 11 
 
 301-6 
 
 8025 
 
 1-100 
 
 12 
 
 274-7 
 
 2752-9 
 
 1-098 
 
 18 
 
 250 
 
 2508 
 
 1-099 
 
 14 
 
 227-5 
 
 2282-7 
 
 1-096 
 
 15 
 
 206-6 
 
 2055-7 
 
 1-110 
 
 16 
 
 194-3 
 
 1920-8 
 
 1-07* 
 
 17 
 
 174-2 
 
 1783 
 
 1-109 
 
 18 
 
 159 
 
 1577-4 
 
 1-098 
 
 19 
 
 147-1 
 
 1452-6 
 
 1-086 
 
 20 
 
 184-4 
 
 1325-4 
 
 1-096 
 
 21 
 
 124 
 
 1216-8 
 
 1-089 
 
 22 
 
 114-9 
 
 1128 
 
 1-083 
 
 23 
 
 102-6 
 
 1002-3 
 
 1-120 
 
 24 
 
 94-8 
 
 924-5 
 
 1-084 
 
 25 
 
 89-9 
 
 869 
 
 1-064 
 
 28 
 
 68-5 
 
 654-8 
 
 1-099 
 
 30 
 
 58-7 
 
 551-2 
 
 1-090 
 
 82 
 
 50-3 
 
 465-3 
 
 1-088 
 
 
 
 Mean 
 
 1-093 
 
 From the numbers under 
 
 6n 
 
 6»M 
 
 it appears) 
 
 that this ratio has as nearly as possible a con- 
 stant value, the mean of all the experiments' 
 being 1-093 : it would seem, therefore, that for 
 this reaction at least the temperature-function' 
 has an exponential form, and that the rate ofr 
 
748 
 
 CHEMICAL CHANGE. 
 
 change may be written .—5 = —iia? y'', 6 being the 
 
 at 
 temperature. Calculating the rates of oxidation 
 on this assumption, or /> = /i(l-093)*, where /> is 
 irate and 8 temperature, and comparing them 
 with the rates found by experiment from the 
 
 values of 5, or -^ the rate at 10°C. being taken 
 
 Ot 
 
 •as unity, the following numbers are obtained : — 
 
 
 Bate of 
 
 Oalculated rate 
 
 Temp. 0. 
 
 oxidation 
 
 of oxidation 
 
 10° 
 
 1-00 
 
 
 11 
 
 1-10 
 
 i-'og" 
 
 12 
 
 1-21 
 
 119 
 
 13 
 
 1-33 
 
 1-31 
 
 14 
 
 1-46 
 
 1-43 
 
 15 
 
 1-62 
 
 1-56 
 
 16 
 
 1-73 
 
 1-70 
 
 17 
 
 1-92 
 
 1-86 
 
 18 
 
 211 
 
 2-04 
 
 19 
 
 2-29 
 
 2'23 
 
 20 
 
 2-51 
 
 2-43 
 
 21 
 
 2-73 
 
 2-66 
 
 22 
 
 2-96 
 
 2-91 
 
 23 
 
 382 
 
 3-18 
 
 24 
 
 8-59 
 
 8-47 
 
 25 
 
 8-83 
 
 8-80 
 
 28 
 
 5-08 
 
 4-96 
 
 80 
 
 6-04 
 
 5-92 
 
 32 
 
 7-15 
 
 7-07 
 
 Investigations of many reactions must be 
 made before it can be determined how far it may 
 be true in general that the rate of a chemical 
 'Change increases in geometrical progression as 
 the temperature varies arithmetically. Lemoine 
 {litttdes sur Us 6guilibres cMmiques, 178) has 
 expressed the opinion that the temperature- 
 function is of an exponential form ; and this he 
 considers to be correlative with the nature of the 
 internal movements which constitute the tem- 
 perature of a body. 
 
 Influence of Lioht. — A survey of the prin- 
 cipal facts that are known relating to the influ- 
 ence of light on chemical changes, or in 
 producing such changes, would seem to indicate 
 the possibility of classifying these chemical 
 changes into (1) such as are only induced by the 
 action of light, or light and heat combined, and 
 (2) reactions which, taking place under ordinary 
 -conditions in darkness, are accelerated by the 
 •action of light. To the first class of actions 
 belong par excellence the photographic processes 
 ipt which unfortunately so little is known), and 
 Buoh reactions as the combination of H with CI, 
 the dissociation of HI, or the reduction of ferric 
 oxalate solution. From the experiments of 
 Amato it would seem tha tsome of these typical 
 changes produced by light can only take place 
 a,bove a certain limit of temperature, indicating 
 that heat as well as light is necessary. To the 
 second class probably a great many, if not all, of 
 the chemical changes that have been studied 
 ^th reference to their rates, limits, &c., will be 
 lound to belong when they have been examined 
 in this respect, but as yet little or nothing has 
 been done. As an instance of the latter class of 
 reactions may be cited the oxidation of oxalic 
 
 acid by potassic permanganate, Harcourt and 
 Esson {T. 156, 194) observed that the rate of this 
 oxidation (which under ordinary conditions is 
 moderately quick) is greatly accelerated in direct 
 Bimlight; the amount of this acceleration waa 
 not, however, determined. 
 
 Hydriodic acid exposed to sunlight for one 
 month at ordinary temperatures is decomposed 
 to the extent of 80 p.c. ; but when this gas is 
 heated night and day for the same length of 
 time at 265° in a dark chamber, scarcely 2 p.o. 
 of the hydrogen is liberated. 
 
 The analogy between the chemical effects of 
 light and heat is very striking : both agencies 
 act in such a way as to break down or simplify 
 chemical structures, as weU as to buUd up com- 
 plex molecules from simpler constituents. Many 
 instances might be cited to exemplify these state- 
 ments ; such as the disruption of HI into free 
 iodine and hydrogen, the formation of HCl and 
 of COCI2 by light ; and the formation, and at a 
 higher temperature the dissociation, of HI, HjSe, 
 HjO, and numberless other bodies, by heat. 
 
 There seems, however, to be one marked 
 difference in the modes of action of heat and 
 light. Whereas, in those chemical changes pro- 
 duced by heat which are termed dissociations 
 or disruptions of molecular structures, a limit is 
 reached depending upon the pressure and tem- 
 perature to which the system is subjected, in 
 similar changes produced by light there seems 
 to be no limit, but the process goes on until 
 complete decomposition is attained. This is 
 easily understood when it is remembered that 
 in such reactions, under suitable conditions, 
 heat tends to destroy as well as to re-form the 
 molecular structures ; but that when light acts 
 in such a way as to break down complex mole- 
 cules the inverse action has not yet been 
 observed to occur under any conditions. For 
 example free H and I exposed for one month to 
 sunlight suffer no measurable change ; but HI 
 in the same interval of time is decomposed to 
 the extent of 80 p.c. Beaotions of a limited, 
 and perhaps reversible, character, induced by 
 light, analogous with the dissociation-pheno 
 mena produced by heat, may yet be discovered. 
 Light rays of different refrangibilities induce 
 chemical changes with greatly different in- 
 tensities, and probably with different effects. 
 Lemoine (O. E. 93, 514) has shovm that HI is 
 decomposed with facihty in vessels made of 
 blue glass, but is very slowly changed in red 
 glass vessels. For those bodies which heat 
 alone decomposes at low temperatures, the 
 extreme red of the spectrum appears much less 
 efficacious than the extreme violet. In the 
 cases of bodies which are stable at high tem- 
 peratures, if the time of action be long enough, 
 the red rays ultimately produce the same result 
 as the violet. Chastaing {A. Ch. [5] 11, 145) 
 concludes that it is not necessary that white 
 light should act more energetically in a given 
 way than any particular part of the solar 
 spectrum, for it is possible that some rays pro- 
 duce the inverse action of others. The cliemical 
 action of the solar spectrum on binary metalloid 
 and metallic compounds ought, he thinks, to be 
 represented by two curves, one reducing on the 
 side of the violet, the other of an oxidising 
 character on the red side ot the spectrum, and, 
 
CHEMICAL CHANGE, 
 
 749 
 
 he says, there probably exists a point where 
 photochemical aotion is nil or equal to that 
 which takes place in darkness 
 
 An elaborate study of the influence of light 
 in producing chemical changes was made by 
 Bunsen and Eoscoe in 1857 ; some of the facts 
 which their investigations brought out are of a 
 highly important character. Draper in 1843 
 had observed that the action of light on a 
 mixture of H and CI does not begin to show 
 itself instantaneously, and he concluded that 
 the first action of light was to bring about a 
 change in the CI, probably producing an allo- 
 tropio modification, before combination could 
 take place between it and hydrogen. Bunsen 
 and Eoscoe made this observation by Draper 
 the subject of many experiments and measure- 
 ments. They considered that whatever may be 
 the cause of the resistance to combination which 
 the gaseous mixture shows for some little time 
 after submitting it to the action of a constant 
 source of light. Draper's assumption is not 
 borne out by facts. 
 
 The following measurements exemplify this 
 resistance-effect as obtained by these chemists 
 with a constant source of light (T, 147, 363) : — 
 
 Time in mins. 
 
 Observation 
 
 Action during 1 
 min. 
 
 
 
 100 
 
 
 1 
 
 100-5 
 
 •5 
 
 2 
 
 102-1 
 
 1-6 
 
 3 
 
 102-6 
 
 •5 
 
 4 
 
 103-2 
 
 •6 
 
 6 
 
 105-3 
 
 2-1 
 
 6 
 
 119-9 
 
 14-6 
 
 7 
 
 139-1 
 
 19-2 
 
 8 
 
 170-2 
 
 81-1 
 
 9 
 
 200-6 
 
 80-4 
 
 These numbers show that about 8 mins. 
 exposure is required before the rate of combi- 
 nation reaches a constant maximum. It was 
 found that the time that elapses, from the first 
 insolation until the first trace of photochemical 
 induction becomes visible, and until the maxi- 
 mum action is attained, varies much according 
 to the experimental conditions. It was also 
 found that the resistance to combination, once 
 overcome by the influence of light, is soon 
 restored when the gaseous mixture is allowed to 
 stand in darkness, but that the increase of the 
 induction from exposure to light takes place 
 much more rapidly than the diminution of the 
 same on darkening. The presence of a foreign 
 gas, or of excess of CI or H, influences the 
 induction-effect in a remarkable manner. Thus 
 the maximum of the induction of a normal 
 mixture was reduced from 100 to 37-8 by the 
 presence of j^^ °^ hydrogen, and in the presence 
 of 1^05 and Ji- of oxygen it diminished from 
 100 to 9-7 and 2-7 respectively, and for j^j of 
 CI from 100 to 60-2. By insolating the gases 
 separately no appreciable effect was produced 
 on the induction effect when the gases were 
 afterwards mixed. ., ^ .^ ^,- v • 
 
 It is interesting to note that if this prehmi- 
 nary resistance to undergo change is a universal 
 law in such actions as are brought about by 
 light in bodies in the liquid or solid state, it 
 
 would evidently place a limit to so-called instan- 
 taneous photography. 
 
 Marchand (A. Oh. [4] 30, 302) has studied the 
 influence of light on a mixture of oxalic acid and 
 ferric chloride in aqueous solution. Such a solu- 
 tion placed in darkness sufiers no change, but 
 when exposed to light it evolves CO^ with the 
 reduction of the ferric chloride. Heat alone has 
 no visible effect on the mixture even at a boiling 
 temperature, but if the solution is exposed to solar 
 radiations and is then heated, decomposition takes 
 place with explosive violence. Of the different 
 parts of the spectrum, the blue rays exercise the 
 most energetic action, even more so than the 
 violet rays. Some highly interesting facts have 
 been noticed by Lemoine (C. B. 97, 1208), bearing 
 on the chemical changes produced by light with 
 the above mixture. He employed a number of thin 
 vertical glass tubes, 15 mm. diameter, each con- 
 taining 20 c.c. of a mixture of ferric chloride and 
 oxalic acid; the solutions were saturated with 
 COj, and contained equivalent quantities of the 
 reacting bodies. The evolved gas was collected 
 over glycerine. The speed of the reaction in- 
 creased in proportion to the intensity of the 
 light, but for equal intensities of light the speed 
 was at first approximately constant, and only 
 began to slacken when the liquid had disengaged 
 half the possible quantity of gas. If the two re- 
 agents are exposed separately to strong sunlight 
 and are then mixed, the decomposition goes on 
 much more rapidly than if the mixture is ex- 
 posed to light before separate insolation. The 
 following numbers illustrate this fact; the 
 measurements, which were made after the same 
 intervals of exposure, show an acceleration of 
 obout ten p.o. in the latter case : — 
 
 &as disengaged. 
 24 6-2 ei 83 93 100 107 
 
 24 68 70 91 103 110 117 
 
 1 1-11 1-09 1-10 1-11 1-10 1-09 
 
 Liquids not insolated 
 Liquids insolated for ) q 
 nine hours ... J 
 Batios . . 
 
 A remarkable point noticed in these experi- 
 ments was that the addition of water increased 
 the rate of action of the light. This anomalous 
 effect may have been due to the partial decom- 
 position of the ferric salt, as well as to the fact 
 that the upper layers of the ferric chloride 
 absorb much of the light and prevent it pene- 
 trating far into the liquid. 
 
 According to Amato (0. 14, 67), many re- 
 actions which are produced by sunlight are not 
 really due to this agency. Amato considers that 
 light only acts under certain determinate con- 
 ditions of temperature, and that consequently 
 there are limits of temperature within which 
 light does not act in a chemical way. He found 
 that a mixture of CI and H if cooled to — 12° 
 could be exposed to the direct rays of the sun 
 for hours without combination taking place. In 
 this experiment care must be taken that the CI 
 is not exposed to the sun's rays before cooling, 
 as insolation renders ctlorine capable of com- 
 bining with hydrogen even in the dark. 
 
 Influence or Pkessube. — Many substances 
 when subjected to the influence of heat in a 
 closed vessel, such for instance as calcic car- 
 bonate, ammonic carbamate, or paracyanogen, 
 are decomposed or changed to an extent which 
 is found to be limited, for a constant tempera- 
 ture, by the pressure of the resulting gaseous 
 
750 
 
 CHEMICAL CHANGE. 
 
 products. When the pressure of the evolved 
 gases has reached a definite value no further 
 alteration takes place. If, however, the pressure 
 is maintained below this limit, by allowing the 
 gases to escape, complete decomposition results. 
 The consideration of the influence of gaseous 
 ■pressure in such instances belongs to dissocia- 
 tion (q.'v.). There are, however, a few chemical 
 ■changes known, other than those of dissociation, 
 which occur only under considerable pressures, 
 and others again which are prevented, or at 
 least greatly retarded, by pressure. 
 
 Cailletet (C. B. 68, 395) found that, repre- 
 senting the amount of action between zinc and 
 HClA.q of a definite strength under ordinary 
 .atmospheric pressure by 10, the action was 
 reduced to 4'7 under a pressure of 60 atmo- 
 spheres, and under 120 atmospheres the amount 
 ■of action in the same time was only "1. The 
 nmouut of action between HNO3 and CaCO, 
 omder pressures of 1 and 150 atmospheres he 
 iound to be as ll-OO : 1. 
 
 Beketoff (C. R. 48, 442) reduced solutions of 
 silver nitrate and sulphate, and ammoniacal 
 silver chloride, by hydrogen, under pressure— re- 
 actions which do not take place at atmospheric 
 pressure. 
 
 By mere mechanical pressure Spripg (B. 17, 
 1218) caused several of the metals, such as 
 copper and lead, to combine with sulphur, and 
 also brought about the formation of many 
 alloys. 
 
 Contact-actions. — Catalysis. Cyclical Ac- 
 tions. — Catalysis, or contact-action, is the name 
 given to a numerous class of chemical changes 
 that are induced in certain chemical systems by 
 a substance which does not itself undergo any 
 permanent alteration, but which by its mere 
 presence under suitable conditions brings about 
 a re-arrangement among the molecules of the 
 bodies with which it is placed in contact. The 
 material which acts in this manner, without 
 apparently being affected itself by the changes it 
 induces, has been termed a catalytic or contact- 
 agent. 
 
 According to the theory of BerzeHus, who 
 was the first to study this class of reactions, such 
 bodies are possessed of a peculiar property or 
 power which he termed ' catalytic force,' or the 
 power to bring about chemical changes. Berze- 
 lius assumed this catalytic force to be of the 
 character of an electrical force. It seems sim- 
 pler, however, to regard such actions as being 
 merely manifestations of the same property or 
 power that is exhibited by aU forms of matter 
 undergoing chemical change, or the manifesta- 
 tion of the affinities of one kind of matter for 
 another. It is reasonable to suppose that in 
 every chemical system there is a tendency to 
 undergo change of some definite character, such 
 for instance as hydrogen and oxygen to unite, 
 caue sugar and water to form glucose, potassio 
 chlorate to give off oxygen, &o. The conditions 
 under which the system exists may be such that 
 the affinities are in a state of stable equilibrium 
 among themselves. Every system may be re- 
 garded as having a weak point, or point of least 
 resistance, at which an alteration will most 
 easily take place. For instance, in the reduction 
 of certain metallic oxides, the oxides are first 
 reduced to lower oxides and then to the metal ; 
 
 or, certain salts are decomposed when heated, 
 but one phase of the change takes place at a 
 lower temperature, or more easily, than another 
 phase. It would seem probable, therefore, that 
 if a suitable material were introduced into a 
 chemical system, it might so react with certain 
 constituents of the system as to upset the pre- 
 vious equilibrium to such an extent that what 
 was before merely a tendency to undergo change 
 would become an actual change, beginning at 
 the point which before the introduction of the 
 catalytic agent was the weakest point of the 
 system. The catalytic agent may be regarded 
 as tending to form, with one of the constituents 
 of the system, a compound too unstable to exist 
 under the conditions, which compound imme- 
 diately breaks up, leaving the so-called catalytic 
 agent in its original condition, free to react with 
 a fresh portion of the system. 
 
 Contact-action would seem to be rather an ill- 
 chosen term for this class of reactions, since 
 all chemical combinations imply contact. It 
 is also well known that many soluble salts if 
 placed in contact with insoluble salts or pps. 
 adhere tenaciously to these. A striking instance 
 of this kind of contact-action is exhibited by 
 metastannio acid. If a small quantity of this 
 powder be shaken up with a highly ferruginous 
 solution of aluminium sulphate, the ferric oxide 
 in solution is seized upon by the insoluble meta- 
 stannio acid, leaving a solution of aluminium 
 sulphate in which scarcely a trace of iron can be 
 detected. 
 
 From the evidence that exists relating to 
 what is strictly known as catalytic action, if a 
 word were necessary to distinguish this kind of 
 change from ordinary chemical reactions, cyclical 
 action or cyclical change would seem to be near 
 the mark. 
 
 The instances that are known among gases 
 in which the presence of a body brings about 
 chemical action in an otherwise stable gaseous 
 mixture seem to be explained by assuming that 
 contact action merely causes a condensation of 
 the gases upon the surface of the material that 
 brings about their union. Faraday {T. 1834. 55) 
 found that if a plate of perfectly clean platinum 
 is brought into a mixture of hydrogen and 
 oxygen, combination of the gases begins to take 
 place, at first slowly, but at a gradually in- 
 creasing rate, until combination occurs with 
 explosive violence. This combination was con- 
 sidered by Faraday to be due to the condensa- 
 tion of the gases upon the metallic surface, 
 whereby the molecules of oxygen and hydrogen 
 were brought into such close contact that 
 chemical union took place. The presence of 
 smaU quantities of CO or CS^ prevents the com- 
 bination of the oxygen and hydrogen by aid of 
 a platinum surface, although the metal is not 
 found to lose its power if afterwards plunged 
 into a pure mixture of the gases. SmaU quanti- 
 ties of such gases as HjS or HCl, however, so 
 alter the platinum-surface that the metal is now 
 incapable of effecting the combination of H with 
 0. Other substances, such as charcoal, pumice, 
 rook crystal, <fec., act in a similar manner to, 
 but less rapidly than, platinum. Platinum also 
 brings about the combination of SO^ and to 
 form SOj, of NH, and O to form HNO, and 
 HjO, &o. 
 
DHEMIOAL CHANGE. 
 
 751 
 
 Konowalow (B. 17, 1360; 18, 2808), when 
 determining the vapour density of tertiary 
 amyiacetate, found that the dissociation-pheno- 
 mena exhibited by the vapour of this body are 
 influenced in a stiikiag manner by the presence 
 of many finely divided substances such as silica, 
 magnesia, calcium sulphate, &o. The effects 
 varied with the chemical, as well as with the 
 physical, characters of the substances placed 
 in contact with the vapour. To such a slight 
 extent have these contact actions been studied 
 that it seems as yet impossible to interpret them 
 in the same way as those chemical actions which 
 are here termed cyclical. Faraday's theory for 
 the action of platinum in bringing about the 
 union of oxygen and hydrogen by a mere con- 
 densation of the gases would seem to be the 
 most reasonable explanation in the face of the 
 facts at present known. 
 
 Examples of catalytic actions are known 
 among liquids, which may be e iplained on the 
 theory of cyclical change ; such are the evolu- 
 tion of oxygen from a solution of a hypochlorite 
 when warmed with cobaltous or manganic 
 oxide, and the decomposition of hydrogen per- 
 oxide by manganese dioxide, finely divided 
 platinum or silver, or by oxide of silver. The 
 last case is remarkable, for here oxygen is 
 evolved both from the silver oxide and from the 
 hydrogen peroxide; to explain this, and a 
 number of analogous reactions, Brodie (T. 140, 
 759) assumed that atoms of the same body may 
 have an attraction for each other or be in a 
 state of polarisation. Brodie expressed the 
 
 +- 
 reaction of AgjO with Kfl.^ thus, HjOO + Ag.,0 = 
 
 HjO-hOO + Ag,. 
 
 The change of cane sugar and water into 
 glucose, and of ethereal salts and water into 
 acids and alcohols, in the presence of acids 
 which themselves remain unchanged, are other 
 instances of catalytic action probably of a 
 cyclical character (see Affinity, pp. 71 et seq.). 
 
 If potassic chlorate is heated alone it melts at 
 about 345°C. and on increasing the temperature 
 to about 370°C. oxygen begins to be produced. 
 Many substances in a fine state of division when 
 mixed with this salt cause an evolution of oxygen 
 much below the temperature at which the chlor- 
 ate decomposes when heated alone, and without 
 the salt entering into a state of fusion. The 
 substances which facilitate this decomposition 
 do not themselves appear to undergo any chemi- 
 cal change. It is probable that the theory pro- 
 pounded by Mercer {B. A. 1842. 32) to explain 
 analogous chemical changes is the true one, viz. 
 that the material which facilitates the decompo- 
 sitioii has a tendency to pass into a higher state 
 of oxidation, and that an unstable compound is 
 formed, but is decomposed at the temperature of 
 the experiment. On this hypothesis the potas- 
 sium chlorate is regarded as being decomposed at 
 the lower temperature by the double effect of 
 heat and the affinity of the contact substance — 
 as MnOj — for the oxygen of the chlorate. Heated 
 by itself, potassium chlorate passes through an 
 intermediate stage in its decomposition with 
 the formation of perchlorate ; this intermediate 
 Btage is represented according to some chemists 
 by the equation 2KCIO3 = KCIO^ + KCl + Oj, but 
 it appears to be more correctly expressed by the 
 
 equation 10KC10a = 6KC104 + 4KOI + 30j (Teed, 
 O. N. 52, 248). If, however, manganese dioxide 
 is heated with the chlorate, no perchlorate is 
 formed ; this fact may be explained and used as 
 an argument in favour of Mercer's view, by sup- 
 posing that KCIO3 when decomposed by itself 
 forms EGl and 0„ and that the nascent ozone 
 oxidises a second molecule of chlorate to per- 
 chlorate, whereas in the presence of MuO^ a 
 higher but very unstable oxide of manganese 
 is formed, and is almost simultaneously decom- 
 posed. The oxides which most markedly facilitate 
 the decomposition of potassium chlorate are as a 
 rule those the metals of which form several 
 oxides. It is a well-known fact that the oxygen 
 prepared from KCIO3, either by heating the salt 
 alone or mixed with MuO^, liberates iodine from 
 an alkaline iodide ; this is usually considered to 
 be due to a trace of free chlorine ; it may, how- 
 ever, be occasioned by a little ozone that escapes 
 decomposition by the MnOj or the KClOs. 
 
 Contact chemical action, whatever be its true 
 cause, plays a highly important part in several 
 industrial operations, as the inversion of cane 
 sugar, the conversion of starchy matters into 
 glucose, the decolorisation of sugar solutions by 
 charcoal, and probably in the purification of 
 waters by filtration through porous media. For- 
 merly the great industrial processes of fermenta- 
 tion in the formation of alcoholic liquors were 
 referred to this cause, but it seems now certain 
 that such changes are phenomena connected 
 with organic life and not with those of unorgan- 
 ised matter. 
 
 (For a theoretical consideration of catalysis 
 see MendeUeff, B. 19, 456.) 
 
 A consideration of the facts that are known 
 relating to chemical change shows that in the 
 study of the subject not only must the kind or 
 quality, and the mass, of the reacting matter, be 
 taken into account, but attention must also be 
 given to the intrinsic forces that come into play, 
 as well as to the notion of molecular or atomic 
 motions. It is not at present so much the 
 relative values of these forces that one desires to 
 know, in whatever way they may be measured, 
 as the circumstances under which the forces act, 
 or are modified in their action. It has been seen 
 that all atomic structures are possessed of rela- 
 tive degrees of stability, as is shown when sub- 
 mitted to the action of physical agencies, or 
 when they play an active part in chemical sys- 
 tems, this BtabOity being due to the interaction 
 of the affinities holding the structure together. 
 These forces or affinities offer different degrees of 
 resistance to the action of different agencies, and 
 it would seem to be only by the study of such 
 influences that a rational conception of the 
 nature of chemical action wiU be arrived at. 
 
 That the ultimate constituents of matter — 
 the atoms or molecules —are in continual motion, 
 the interdiffusion of gases, and of salts in solu- 
 tion, seems to prove ; and the fact that, in a 
 chemical system undergoing change, such change 
 is more or less gradual, taking fractions of 
 seconds or whole years to be accomplished, seems 
 to offer conclusive proof that the atomic consti- 
 tuents are in a continual motion of interdiffusion. 
 But whether or not the change going on in a 
 chemical system is brought about by simple 
 
762 
 
 CHEMICAL CHANGE. 
 
 oollisions among the moying molecules camiot 
 be asserted. For instance, anhydrous alcohol and 
 acetic acid, when mixed in equivalent proportions 
 react upon each other at ordinary temperatures 
 with extreme slowness ; in fact, it takes months 
 to accomplish what at 100° requires only 
 minutes, and yet it is highly probable that very 
 many more collisions occur between the alcohol 
 and the acid molecules than the rate of change 
 would lead us to conclude. It may be that in 
 these and similar cases the molecules of the 
 two constituents of the system must be moving 
 with a definite velocity if chemical action is to 
 occur. But the kinetic theory of gases teaches 
 that in a space of uniform temperature some 
 molecules have high and others low velocities, 
 and that the ratio between the numbers of mole- 
 cules having high and those iaving low veloci- 
 ties varies with the temperature; consequently 
 the chemical change which occurs may be but 
 a process of selection among the molecules 
 according to the velocities they possess, those 
 with velocities below a certain limit colliding, but 
 not reacting chemically with, each other. 
 
 As chemical reactions are generally formu- 
 lated, the phenomena of change are for the most 
 part at present viewed only in the light of the 
 distribution of certain masses of matter of 
 various kinds, and no cognisance is taken of the 
 changes in the energies of the systems as these 
 pass from the initial to the final states. In the 
 blank that is at present occupied by the sign ' = ' 
 lie all the real phenomena of the science of 
 matter. Attempts have been made to fill up 
 this blank by the investigation and measurement 
 of the heat-disturbances that arise when a 
 chemical system passes from the state repre- 
 sented by one side of the equation to that repre- 
 sented by the other side. By virtue of the 
 inherent forces or affinities, as well as by the 
 particular motions of the ultimate particles or 
 atoms of matter, aU substances may be looked 
 upon as possessing a certain definite amount of 
 energy, potential as well as kinetical, and con- 
 sequently as capable of performing a definite 
 amount of work. The tendency of the constitu- 
 ents of a system is invariably towards a state 
 the attainment of which involves a degradation 
 of energy ; in other words the total energy of the 
 system tends to fall from a higher to a lower 
 level. (For the general inferences that have been 
 drawn from the study of thermal phenomena 
 bearing on the applications of the laws of energy 
 to chemical change reference must be made to 
 the section on ihebmaii phenomena of the article 
 Phtsioaii methods used in chemistkt.) 
 
 It is much to be desired that a classification 
 of the elements, or, what seems more possible, 
 of their compounds, should be attempted, based 
 
 upon some particular dynamical propertiesi 
 which should include not only the conception of 
 mass but also the conceptions of time and work -^ 
 it is evident, however, that the difficulty lies ini 
 the kind of phenomena to be observed and. 
 measured. Mills (P. M. [5] 1) has propounded 
 certain ideas relating to chemical phenomena,, 
 making motion the basis of the science ; and he- 
 considers that chemical substances should be- 
 valued not for what they are conceived as beings 
 but for what they are capable of doing. Doubt- 
 less, however, the being as well as the doing 
 must be considered together. The masses of 
 various bodies necessary for the performance of 
 unit of work Mills terms the dynamic equiva- 
 lents, or the ' bergmannics,' of the respective- 
 bodies ; these may vary according to the sort of 
 doing, or work, the several substances are em- 
 ployed to effect ; such as the power of various 
 acids to invert sugar, or to decompose ethereal 
 salts, the precipitability of salts, the coefficients, 
 of diffusion, (fee, &o. For many valuable deter- 
 minations of dynamical effects of substances in 
 inducing or accelerating chemical changes, see 
 the work of Ostwald. For a full account of this 
 work V. the article Afeinitt. (In connexioa 
 with this article, v. the articles : Affinity ; 
 
 ALLOTBOPT ; ChEMIOAIi and PHYSICAIi pbopekties. 
 OE BODIES, CONNEXIONS BETWEEN ; COMBINATION, 
 
 CHEMICAL ; Dissociation ; Equilibbiuii, chemi- 
 cal; ISOMEEISM.) 
 
 Additional Beferences. 
 
 Essai de Micanique cMmigue, Berthelot. 
 Etudes de Dynamique cMmigue, Van 't Hoff. 
 Mudes sur les iSguilibres cMmiques, Lemoine 
 (a very full work on the subject). Modemen 
 Theorien der Chemie, Meyer. Principles of 
 Chemistry, Pattison Muir. Lehrlmch der dllge- 
 meinen Chemie, Ostwald. Chemical Action, 
 Gladstone {T. 1855). Chemical Equilibrium, 
 Gibbs (Trans. Connecticut Academy of Arts 
 and Sciences, 1875. 1878). Chemical Change 
 determined optically, JeUett {Trans. B. Irish 
 Acad., vol. XXV.). Speed of Inversion of Cane 
 Sugar, Influence of Acids, Heat, dc, Urech (B. 
 15, 2457 ; 16, 762, 2825 ; 17, 495, 1539) ; also 
 Ostwald (J. pr. vols. 29 and 31) and Fleury (O. B. 
 1875). Influence of Pressure on Combustion, 
 Frankland (T. 1861). Speed of Substitution of 
 Bromine in the Fatty Acids, Hell and Urech 
 {B. 13, 531). Speed of Absorption of Oases, 
 Heurter {Monit. Saientifique, 1878) ; also Hood 
 (P. M. 1884). Action of Oxides on Carbonates, 
 Mallard {A. Ch. 1879) ; also Mills (O. J. 1879, 
 1881, and 1882). Chemical Changes in Oases 
 (Mathematical Theory), J. J. Thomson (P.M 
 [5] xviii.). 3, J. H, 
 
 END OF THE FIEST VOLUMH. 
 
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