m ■ . ■ H ■ ■ ^H WORKS OF ELLEN H. RICHARDS PUBLISHED BY JOHN WILEY & SONS 43-45 East Nineteenth Street, New York Laboratory Notes on Industrial Water Analysis: A Survey Course for Engineers. 8vo, 52 pages. Cloth, 50c net. The Cost of Cleanness. l2mo, v + 109 pages. Cloth. $1.00. The Cost of Living as Modified by Sanitary Science. Third Edition, Revised. 12mo. 164 pages. Cloth. $1.00. Air, Water, and Food; From a Sanitary Standpoint. By Ellen H. Richards and Alpheus G. Woodman, Assistant Professor of Food Analysis, Massachusetts Institute of Technology. Third Edition, Revised and Enlarged. 8vo. 278 pages. Cloth. $2.00. The Cost of Food : A Study in Dietaries. 12mo. 161 pages. Cloth. $1.00. The Dietary Computer. By Ellen H. Richards, Instructor in Sanitary Chem- istry, Massachusetts Institute of Technology, assisted by Louise Harding Williams. $1.50 net. Pamphlet separately, $1.00 net. The Cost of Shelter. 12mo. vi + 136 pages. Illustrated. Cloth. . $1.00. " Cost of Living " Series. 1. Cost of Living. 2. Cost of Food. 3. Cost of Shelter. 4. Cost of Cleanness. 12mo. Cloth. 4 vols, in a box. $4.00. Published by WHITCOMB & BARROWS Huntington Chambers The Chemistry of Cooking and Cleaning. By Ellen H. Richards and S. Maria Elliott. 158 pages. Cloth. $1.00. Food Materials and their Adulterations. 183 pages. Cloth. $1.00. Home Sanitation. Revised Edition. Edited by Ellen H. Richards and Marion Talbot. 85 pages. Paper. 25c. Plain Words about Food. The Rumford Leaflets. Illustrated. 176 pages. Cloth. $1.00. First Lessons on Food Diet. 52 pages. Cloth. 30c net. The Art of Right=Living. 50 pages. Cloth. 50c net. Sanitation in Daily Life. 82 pages. Cloth. 65c. net. AIR, WATER, AND FOOD FROM A SANITARY STANDPOINT. BY ELLEN H. RICHARDS AND ALPHEUS G. WOODMAN. Instructor in Sanitary Chemistry. Assistant Processor of Food Analysis, Massachusetts Institute of Technology. Massachusetts Institute of Technology. "These cannot be taken as sufficient ... in these times whei) every word spoken finds at once a ready doubter, if not an opponent. They are. however, specimens, and will serve to- make* comparisons in time to come." — Angus Smith. "The ideal scientific mind, therefore, must always be held in a state of balance which the slightest new evidence may change in one direction or another. It is in a constant state of skepticism, knowing full well that nothing is certain."— Henry A. Rowland. THIRD EDITION, REVISED AND ENLARGED. FIRST THOUSAND. NEW YORK: JOHN WTLEY & SONS. London : CHAPMAN & HALL, Limited. 1909. V X ** Copyright, 1900, 1904. 1909, BLLBN H. RICHARDS and ALPHEUS G. WOODMAN. ©GI.A25TI99 (ftp fcrfentttir ?rrs« Kdbrrt Brutmtwn& anil (Bompang Htm fork LC Control Number tmp96 028456 PREFACE TO THE THIRD EDITION. The great increase of attention to the relations of physical environment to mental and moral welfare leads the authors to hope that this revised and enlarged edition will meet with approval by the body of seekers after truth along these lines of study and investigation. More clearly than any one else they recognize the omis- sions and shortcomings of any book dealing with so compre- hensive a subject under the limitations of a short school course. Therefore a suggestive rather than a complete treatment has been adopted, and a certain conservatism has governed the discussion of some subjects which to treat fully would require too much space as well as a previous training impossible to assume. The chapters on analytical methods have been con- siderably enlarged; the character of the matter added tends to make the work more adapted to the needs of the chemical and sanitary engineer as well as to the general student and householder. In a subject so rapidly advanc- ing the printed page can hardly hope to keep fully abreast of the times, but all the methods have been reviewed or modified, and tentative ones have been retained or dropped as experience has indicated their value. The bibliography has been revised and brought up to date. CONTENTS. :haptsr page I. Three Essentials of Human Existence i II. Air: Composition, Impurities, Relation to Human Life 10 III. The Problem of Ventilation 19 IV. Methods of Examination -. 27 V. Water: Source, Properties, Solvent Power, as a Carrier. 57 VI. The Problem of Safe Water and Interpretation of Analy- ses 76 VII. Methods of Examination 96 VIII. Food in Relation to Human Life, Definition, Sources, Classes, Dietaries 142 IX. Adulteration and Sophistication of Food Materials 157 X. Methods of Food Analysis 167 Appendices, Tables, Reagents 235 Bibliogp.aphy .- 263 AIR, WATER, AND FOOD, CHAPTER I. THREE ESSENTIALS OF HUMAN EXISTENCE. Air, water, and food are three essentials for healthful human life. Sanitary Chemistry deals with these three com- modities in their relation to the needs of daily existence: first, as to their normal composition; second, as to natural variations from the normal; third, as to artificial variations — those produced directly by human agency with benevolent intention, or resulting from carelessness or cupidity. A large portion of the problems of public health come under these heads, and a discussion of them in the broadest sense includes a consideration of engineering questions and of municipal finances. This, however, is beyond the scope of the present work. The following pages will deal chiefly with such portions of the subject of Sanitary Chemistry as come directly under individual control, or which require the education of indi- viduals in order to make up the mass of public opinion which shall support the city or state in carrying out sanitary measures. A notable interest in the subject of individual health as ■2 AIR, WATER, AND FOOD. a means of securing the highest individual capacity both for work and for pleasure is being aroused as the application of the principles governing the evolutionary progress of other forms of living matter is seen to extend to mankind. Will power may guide human forces in most economi- cal ways, and may concentrate energy upon a focal point so as to seem to accomplish superhuman feats, but it cannot create force out of nothing. There is a law of conservation of human energy. The human body, in order to carry on all its functions to the best advantage, especially those of the highest thought for the longest time, must be placed under the best conditions and must be supplied with clean air, safe water, and good food, and must be able to appropriate them to its use. The day is not far distant when a city will be held as responsible for the purity of the air in its school- houses, the cleanliness of the water in its reservoirs, and the reliability of the food sold in its markets as it now is for the condition of its streets and bridges. Nor will the years be many before educational institutions will be held as respon- sible for the condition of the bodies as of the minds of the pupils committed to their care; when a chair of Sanitary Science will be considered as important as a chair of Greek or Mathematics; when the competency of the food-purveyor will have as much weight with intelligent patrons as the scholarly reputation of any member of the Faculty. Within a still shorter time will catalogues call the attention of the interested public to the ventilation of college halls and dor- mitories, as well as to the exterior appearance and location. These results can be brought about only when the stu- dents themselves appreciate the possibilities of increased mental production under conditions of decreased friction, such as can be found only when the requirements of health are perfectly fulfilled. THREE ESSENTIALS OF HUMAN EXISTENCE. 3 Of the three essentials, air may well be considered first, although its office is to convert food already taken into heat and energy. Its exclusion only for a few minutes causes death, and in quantity used it far exceeds the other two. Again, so important is the action of air that the quality of food is of far less consequence when abundant oxygen is present, as in pure air, than when it is present in lessened quantity, as in air vitiated by foreign substances. Individual habit has much to do with the appreciation of good air, and as our knowledge of the value of an abun- dance of this substance in securing great efficiency in the human being increases, we shall be led to attach more im- portance to the sufficiency of the supply. In northern climates air is not free to all in the sense of costing nothing, for the coming of fresh air into the house means an accompaniment of cold which must be counter- acted by the consumption of fuel. A mistaken idea of econ- omy leads householders, school boards, and college trustees to limit the size of the air-ducts as well as of the rooms. It is therefore necessary to emphasize the facts which science has fully established, in order to secure the survival of the fittest of the race under the present pressure of economic conditions, which take so little account of the highest wel- fare of the human machine. Air, water, and soil are the common possessions of man- kind. It is impossible for man to use either selfishly without injury to his neighbor and without squandering his inheri- tance. Primitive man could leave a given spot when the soil became offensive, and neighbors were then too few to require consideration; but neither man nor beast could with impunity foul the stream for his neighbor who had rights below him. The soil is permanent; one knows where to look for it and its pollution. Air is abundant and is kept in con- 4 AIR, WATER, AND FOOD. stant motion by forces of nature beyond human control, so that, save in the neighborhood of an exceptionally offensive factory, man does not often foul the free air of heaven; it is. only when he confines it within unwonted bounds that it becomes a menace. Water is the next precious commodity of the three. Without it man dies in a few days; without it the soil is bar- ren; without it air in motion parches all vegetation and carries clouds of dust-particles; without it there is no life. As population increases it becomes necessary to collect as much of the rainfall as possible, to store it until needed, and to use it with discretion. After use it is often loaded with impurities and sent to deal death and destruction to those who require it later, and yet, in nature's plan, it is the carrier of the world, and rightly treated and carefully husbanded there is enough for the needs of all. Its presence or absence has been the controlling force in determining the habitations of men. In its office of carrier it not only brings nourishment in solution to the tissues of the human body, but also carries away the refuse material. It is a cardinal principle in all sanitary reforms to get rid of that which is useless as soon as possible. Too little water allows accumulation of waste material and a clogging of the bodily drainage system. The average quantity needed daily by the human body is about three quarts. Of this a greater or less proportion is taken in food, so that at times only from a pint to a quart need be taken in the form of water as such. Next in importance to quantity is the quality, dependent somewhat upon the uses to which it is to be put. As a rule, the moderately soft waters are the best for any purpose. For drinking purposes water must be free from dangers to health in the way of poisonous metals, decomposing matters, and disease-germs. For domestic use economy requires; THREE ESSENTIALS OF HUMAN EXISTENCE. 5 that it should not decompose too much soap. Manufactur- ing interests require that it should not give too much scale to boilers; for agriculture there should not be too much alkali. From the nature of things, no one family or city can have sole control of a given body of water. Those on the high- lands may have the first use of the water, which then perco- lates to a lower level and is used by the people on the slopes over and over before it reaches the sea to start again on its cycle of vapor, cloud and rain, brook and river. Al- though receiving impurities each time, there are many beneficent influences at work to overcome the evils resulting from this repeated use. That which is dissolved from one portion of earth may be deposited on another. As the plant is the scavenger of the air, withdrawing the carbon dioxide with which it would otherwise become loaded, so the water lias also its plant life, purifying it and withdrawing that which would otherwise soon render it unfit for any use. Pure water is found only in the chemical laboratory; the most that can be hoped for is that human beings may secure for themselves water which is safe to drink, which will not impair the efficiency of the human machine. The importance of the third essential for human life, food, and the close interdependence of all three, may be clearly shown. Of little use is it to provide pure air and clean water if the substances eaten are not* capable of com- bining with the oxygen of the air or of being dissolved in the water or the digestive juices; of less use still is it to par- take of substances which act as irritants and poisons on the tissues which they should nourish, and thus prevent healthful metabolism and respiratory exchange. And yet a large majority of those who have acquired some notion of the meaning and importance of pure air and 6 AIR, WATER, AND FOOD. are beginning to consider it worth while to strive for clean water pay not the least attention to the sanitary qualities of food; the palatable and aesthetic aspects only appeal to them. Steam-power is produced by the combustion of coal or oil. Human force is derived by releasing the stored energy of the food in the body. The delicately balanced mechansm of the human body suffers even more from friction than the most sensitive machine, and the greatest loss of potential human energy occurs through ignorance, carelessness, and reckless disregard of nature's laws in regard to food. It is necessary to know, first, what is the normal compo- sition of a given food-material. This is found by analyses of many typical samples. Second, is the sample under con- sideration normal? To answer this requires an analysis of it, and a comparison of the results with standards. If it is not normal, in what way does it depart from the standard both in healthfulness and in quality? Third, if a food-substance is normal, what are its valuable ingredients and in what pro- portions are they to be used in the daily diet? In regard to meat, milk, and fish, the sanitary aspect for the chemist resolves itself into two questions: Is the sub- stance so changed as to become a possible source of poison- ous products? Or has anything in the nature of a preserva- tive been added to it? If so, is it of a nature injurious to man? There is, however, a great range of quality in some of the most abundant foodstuffs, such as the cereals, especially in the nitrogen content. This is most important to the vege- tarian and to institutions where economy must be practised. The following variations in the composition of leading cereals will illustrate: THREE ESSENTIALS OF HUMAN EXISTENCE f ,, T ■ Nitrogenous Crude Carbo- i?;w;«. a„v, Water - Substance, rat. hydrates. Flbre " Ash ' Oats, maximum. ..... . 20.80 18.84 10.65 64.63 20.08 8.64 " minimum 6.21 6.00 2. 11 48.69 4.45 1.34. «• American hulled. 12. 11 13.57 7-68 63.37 1.30 2.03 Corn, maximum 22.20 14.31 8.87 52.08 7.71 3.93 " minimum. .. 4- 6 § 5-55 i-73 72-75 0.99 o.Sz One sample of wheat flour may contain 14 per cent, of nitro- genous substance, another may yield only 9. A day's ration, 500 grams, will give 70 grams of gluten, etc., in the one case and only 45 in the other. This difference of 25 grams, would be a serious factor in the dietary of an institution where little additional proteid is given, and it alone might be the cause of dangerous under-nutrition. The next step would naturally be to determine how definitely these varying percentages mean varyine nutrition.. To this end a study of vegetable nitrogenous oroducts in their combination or contact with cellulose, starch, and min- eral matter is needed. Much work remains to be done before these questions can be even approximately answered. At the low cost of one cent a pound, common vegetables yield only about one-fifth as much nutriment as one cent's- worth of flour, yet they contain essential elements and de- serve to be carefully studied. Dried fruits and nuts are much undervalued as articles of food, as are rice and lentils. (See table, page 150.) The discussion of food values will be found in Chapter Yin. Probably the widest field for the sanitary chemist to-day is the study of the so-called predigested foods, infant foods, " hygienic " preparations, two-minute cereals, and the count- less proprietary packages, which, designed to meet the de- mand for quick results, prove traps for the unwary. Therefore the sanitary aspect of food demands a study 8 AIR, WATER, AND FOOD. of normal food and food value even more than of adulterants or of poisonous food, ptomaines and toxines. The cultiva- tion of intelligent public opinion is most important, and each student should go out from a sanitary laboratory a mission- ary to his fellow men. That is, the office of a laboratory of sanitary chemistry should be so to diffuse knowledge as to make it impossible for educated people to be deluded by the representations of unprincipled dealers. Freedom from superstition is just as important in this as in the domain of astronomy or physics. So long as chemists are employed by manufacturing concerns in making adulterated and fraudulent foodstuffs, so long must other chemists be em- ployed in protecting the people until the public in general becomes wiser. A part of the common knowledge of the race should be the essentials of healthful living, in order that the full measure of human progress may be enjoyed. There is needed a greater respect for food and its func- tions in the human body, a better knowledge of its effect on the daily output of energy, its absolute relations to health and life, and the enjoyment of the same. The familiarity with these facts which is given by a few hours' work in the laboratory will make a lasting impression and will enable the student to benefit his whole life, even if he never uses it pro- fessionally. It is purely scientific knowledge, just as much as that derived from a study of the phases of the moon or the formulae of integration. The variety of operations in such work, calling for great diversity of apparatus and methods, is an educational factor not to be overlooked in laboratory training. For all detailed discussions and methods the reader *s referred to such works as those of Wiley, Allen, Leach, etc., but for the student who needs to study, as a part of general education, only typical substances, and such methods as can THREE ESSENTIALS OF HUMAN EXISTENCE. 9 be carried out within the limits of laboratory exercises in a college curriculum, the following pages are written. Not enough is given to frighten or discourage the student, but enough, it is hoped, to arouse an interest which will impel him at every subsequent opportunity to seek for more and wider knowledge. Food is too generally regarded as a private, individual matter rather than as a branch of social economy; it is, however, too fundamental to the welfare of the race to be neglected. Society, in order to protect itself, must take cognizance of the questions relative to food and nutrition. Formerly each race adapted itself to its environment and trained its digestion in accordance with the available food supply. In America to-day the question is not how to get food enough, but how to choose from the bewildering variety offered that which shall best promote the health and develop the powers of the human being, and, what is of equal im- portance, how to avoid over-indulgence, which weakens the moral fibre and lessens mental and physical efficiency. In spite of all preaching, few really believe that plain living goes with high thinking. Professor Patten says that the ideal of health is to obtain complete nutrition. Over-nutri- tion as well as under-nutrition weakens the body and sub- jects it to evils that make it incapable of survival. Xo other form of social service will give so full a return for effort expended as the help given toward better diet for children and students. Fortunately help is coming fast. The United States Government is giving much study to food problems, and by publications is making available the work of other countries. The later bulletins listed in the bibliography at the end of this volume are especially valu- able. What is now needed is a general recognition of the importance of the subject. CHAPTER II. air: composition; impurities; relation to human- life. The average adult human being makes about eighteen involuntary respirations per minute. The tidal volume of air is from 300 to 500 cubic centimeters (30 cu. in.), about 2800 cubic centimeters (170 cu. in.) remaining in the lungs unless voluntarily expelled by deep breathing. The total volume expelled is often called the vital capacity, and is about 3400 cubic centimeters for men and 2500 for women. Even when at rest a volume of 7000 to 12,000 liters (250 to 420 cu. ft.) of air passes through the lungs of each individual in twenty-four hours. Under conditions of exercise more or less prolonged or violent this volume may be doubled. The composition of the normal inspired air by volume is approxi- mately: nitrogen and argon 79 per cent., oxygen 20.9 per cent., other constituents 0.1 per cent. The air as it leaves the lungs contains nitrogen 79.5 per cent., oxygen 16.0 per cent., carbon dioxide 4.4 per cent., and is saturated with water-vapor. There has therefore taken place an inter- change of gases (called the respiratory exchange), by which oxygen has passed into the fluids of the body, and carbon dioxide into the air contained within the lung-cells. Only about one-fifth of the total oxygen is abstracted during each tide. If the composition of the inspired air varies from the air: relation to human life. ii normal, this exchange is disturbed, owing to the difference in gaseous pressure and in rate of absorption which this variation causes. So delicate is the balance of the active forces that serious disturbance of the functions of the living organism occurs if the percentage of oxygen is lessened by one or two tenths, or if the pressure is raised or lowered by a fraction of an atmosphere. It is true that, like a tree bending before the wind, the organism soon adapts itself to changed circumstances, provided the change is not too great nor too suddenly made; but, like the exposed tree, the living being is never quite so vigorous and symmetrical as it would have been without the effort to overcome disadvantageous conditions. That a permanent or habitual lowering of the oxygen in inspired air must be harmful will be readily seen from a con- sideration of the office of this gas in the body. To Lavoisier and Laplace we owe the knowledge that animal heat is de- rived from a process of combustion. Lavoisier held, how- ever, that the seat of this combustion was in the lungs, and it is to Pfliiger and his pupils that we are indebted for the proofs that it is in the tissues themselves, while the lungs serve as a clearing-house or centre qf exchange. By the union of the oxygen with the substances found in the tissues and brought to them by the circulating fluids of the body from the digested food, the heat necessary for the life and work of the body is produced. This heat is needed to keep the tissues at the temperature at which they can best accomplish their work, to give mechanical power for the in- voluntary action of heart and lungs, for the processes of assimilation, and to furnish the energy for all voluntary work and thought. Thus both water and food are intimately con- cerned in the processes in which air is an essential factor. The statement made in the first sentence of Chapter I is 12 AIR, WATER, AND FOOD. therefore justified, namely, that air, water, and food together are three essentials of human existence. A certain relation between the three means health, and any disturbance of this relation means unhealth, by which term may be designated a condition of less than perfect health not yet so serious as to be called sickness. Air being a mere mixture of the gases nitrogen and oxy- gen, in no definite atomic proportions, and carrying varying amounts of other substances, gaseous and suspended parti- cles, no definite composition can be given. The difference between the air over sea or forest plateau and that of city streets or of crowded tenements seems only slight if expressed in per cent. From 20.98 per cent, of oxygen in the first to 20.87 an d 20.60 in the last; from .022 per cent, of carbon dioxide in the purest air to .045 in cities and .33 in rooms, are the common variations; and yet the effect of these apparently small differences on human beings subjected to them is very noticeable. It is customary to enhance these differences by expressing the results in parts per 10,000. That the carbon dioxide is of itself a disturbing factor is indicated by the observed fact that air which has had the per cent, of oxygen reduced by combustion to a point at which a candle will no longer burn may be made again a supporter of combustion by the removal of the cafbon dioxide. A practical application of this principle is made in the devices used in diving and in entering mines filled with irre- spirable gases. There is a sensible effort in breathing, and a feeling of discomfort is usually experienced, if the carbon dioxide ac- cumulates to ten times the normal amount, or 40 parts per 10,000 instead of 4. This is probably due to its solubility and to its interference with the respiratory exchange, since the interchange of gases is influenced by their " partial pres- air: relation to human life. 13 sures." Each gas forming part of a mechanical mixture exerts a partial pressure proportional to its percentage of the mixture. For example, if atmospheric air, containing 20.81 per cent, of oxygen, is at 760 millimeters barometric pres- 20.81 sure, the partial pressure of the oxygen would be X 760=158.15 millimeters. The following partial pressures of oxygen and carbon dioxide in inspired air and in the lung- cells show the extent of variation in different parts of the respiratory tract: Inspired Air. Lung-cells. Oxygen 158.15 mm. 122 mm. Carbon dioxide 0.30 mm. 38 mm. Gas will always tend to diffuse from the region of high- est to that of lowest pressure. Hence the reason for the great influence of pressure in causing the diffusion of oxygen from the inspired air into the lung-cells and for the converse movement of carbon dioxide. That variation in pressure has much to do with the discomfort is shown in the so-called mountain-sickness, experienced at high altitudes in rarefied air, and in the so-called caisson-disease, developed in men working in compressed air. If the passage from the caissons to the open air is made gradually, there is little trouble, but a quick change is often dangerous. A sort of mountain- sickness is experienced by many on entering a close room from the outside air. Usually this passes away in a measure as the organism accommodates itself to the new conditions. Even if the symptoms are not severe, there is a dulness or an irritability which is not conducive to the best apprehen- sion of a difficult subject or to the fullest enjoyment of an entertainment. This lessening of mental capacity is especially to be de- 14 AIR, WATER, AND FOOD. plore'd in the case of school-children, who are at an age when respiration is most frequent and the need of pure air the greatest, and also when economy of effort is most demanded. It has been said that from the study of the physiological effects of close air it seems to be indicated that the evil is due to the change in the respiratory quotient and to the con- sequent change in blood-pressure, which interferes with the circulation. The respiratory quotient is obtained by divid- ing the volume of carbon dioxide given off by that of the oxygen absorbed, and indicates how much of the oxygen has combined with carbon to form carbon dioxide, since one vol- ume of oxygen combines with caroon to form one volume of carbon dioxide. The rate of exchange is influenced by questions of pressure, exposure, temperature, and water- vapor or moisture, muscular activity, and the like. Water-vapor is the most variable constituent, due to the changing capacity of air for moisture at different tempera- tures and to the character of the earth's surface. Whether over land or water, cultivated or forest region, air at o° C. contains only 4.87 grams of water per cubic meter, while air at 6o° F. (15 C.) can take up 12.76 grams, and at 90 F. holds 33.92 grams. Since the human body is constancy giving off moisture from skin and lungs, and since this exhalation is an important factor in the bodily economy, the presence of ex- cessive moisture in the air exercises a decided effect. On clear, invigorating days the moisture in the air may be only 30 or 50 per cent, of that required for complete satu- ration at the given temperature, and although the ther- mometer reading may indicate 85 ° F. on a hot day, little discomfort follows; but let the humidity rise to 90 or 95 per cent, while the' temperature remains the same, and oppres- sion, restlessness, or languor results. Much the same effects are seen in the case of close rooms and crowded halls. The air: relation to human life. 15 watery vapor given off (about 20 grams per person per hour) soon saturates the air, and the consequent drowsiness and headache usually attributed to carbon dioxide will be felt; while if this moisture is removed, the same proportion of carbon dioxide would hardly inconvenience the occupants. A relative humidity of 60 per cent, is said to be the most comfortable for house temperature. In normal man, exposure to cold increases the respiratory exchange; but if he represses shivering and keeps still by force of will, it apparently does not. Politely sitting still in- creases the probability of taking cold. A high temperature lessens the production of carbon dioxide and therefore saves food. This may in part account for the oppressiveness felt by well-fed and warmly clothed persons in public places none too warm for those with a more restricted diet. Muscular activity increases respiratory exchange and causes a demand for food. A class of students passing across the campus, up several flights of stairs, into a lecture-room vitiate the air for the first ten minutes at a rate higher by one part of carbon dioxide per 10,000 than half an hour later. The exchange is also stimulated by a meal. Not only the oxidation of the food itself, but the muscular activity of the alimentary canal and probably other accompanying activities call for an expenditure of energy which is supplied by in- creased heat production. Sodium sulphate is said to increase the various respira- tory activities, and some have held this, fact to be one reason for the beneficial effects of certain mineral waters. The amount of carbon dioxide expired is estimated by Pettenkofer .at .006 to .012 cubic foot per pound of body weight, according to the degree of exertion. Rubner con- siders that, in general, metabolic processes depend also upon the proportion of superficial area to the total volume of the 1 6 AIR, WATER, AND FOOD. body, hence the smaller the animal the greater the surface to the whole mass. Children give off in proportion to their body weight about twice as much carbon dioxide as adults. Another estimate gives the output of carbon dioxide as .0027 gram per hour per square centimeter of surface. Ammonia is also a constant component of the air of in- habited places and is washed out by rain and snow, as will be shown in Chapter VI. Of the occasional impurities, probably the most fatal is carbon monoxide arising from leaking gas-fixtures or de- fective furnaces. This gas has 250 times the affinity for haemoglobin and therefore forms with it a more stable compound than does oxygen, and hence its presence causes a deficiency of the latter gas in the blood, giving symp- toms like those observed in mountain-climbing or bal- loon ascensions. When the blood-corpuscles become about one-third saturated the effect becomes sensible; but if the quantity of gas is considerable, the symptoms are hardly noticeable before insensibility occurs. For this reason, glow- ing charcoal and open gas-jets are the favorite forms of cowardly self-destruction. In the neighborhood of factories, smelting-works, ore- heaps, and of cities burning soft coal there is a noticeable amount of sulphurous and sulphuric acids, sometimes so con- siderable as to destroy vegetation. In places where gas is burned, oxides of nitrogen are formed in small quantity, the effect of which is known to be harmful. Minute quantities of hydrogen sulphide and of com- pounds of carbon and hydrogen and of other gases may be present, especially in houses with defective plumbing or in the neighborhood of barns, cesspools, and filthy back yards. These may reach dangerous proportions, but, like carbon air: relation to human life. 17 monoxide, should not be permitted in or near any well-regu- lated household. Soot, being insoluble, accumulates in the lungs, as a post- mortem examination of persons who have lived for some time in a smoky city proves; nevertheless no definite ill effects have been as yet attributed to this cause. This again con- firms the inference that it is the gaseous constituents, and the varying temperature and pressure, which seriously affect the respiratory exchange The following results, obtained on the air of a large man- ufacturing city, will be of interest in this connection: * GRAMS PER 1,000,000 CUBIC METERS OF AIR.f Soot. H 2 S0 4 . FreeNH 3 . Alb. NH 3 . HNO,. HN0 2 . 1000 to 40000 7000 to 63000 1 100 to 1000 97 to 557 45 to 1063 o to 155 1 Partly H a SO s . It is probable that much of the danger ascribed to sewer- air arises from other causes. Since the atmosphere in sewer- pipes is always moist, the only probable source of organisms is the splashing of the water. Only about one-half as many organisms have been found in the air a'bove flowing sewage as in out-door air. Professor Carnelley and Dr. Haldane found only one-half as much carbon dioxide and one-third as much organic matter in such air as in that of the streets above. Beyond individual control, and in a measure beyond gen- eral control, there exists suspended matter in the air: fine volcanic dust, pollen, spores of moulds and algae, dried bac- teria, diatoms, small seeds of plants, soot and the finely pulverized earth from roads and cultivated and barren lands. To this portion of the air we owe beautiful sunsets and dis- agreeable fogs. To it manv affections of the throat and * Mabery: /. Am. Chem. Soc, 17 (i8qs). 105. f See also Bailey: " The Air of Large Towns," Science, Oct. 13, 1893. Irwin: "The Soot Deposited on Manchester Snow,"y. Soc. Chem. bid* (1902), 533. 18 AIR, WATER, AND FOOD. eyes are due, and by it disease may be transmitted. Some kinds of dust lodge in the air-cells and by irritation render tke individual liable to disease, as statistics of the mortality in dust-producing trades show. In the air of houses this impurity increases a thousand-fold by means of the wear of furnishings and the accumulation on them of deposited par- ticies, by means of furnace-ashes and dried debris of all kinds. Only recently have the dangers of this part of the air we breathe been distinctly pointed out. Aitken * estimated that a cubic inch of air may carry 2000 dust-particles in the open country, 3,000,000 and more in cities, and 30,000,000 in inhabited rooms. Among these millions there may be found from ten to several hundred micro-organisms, moulds, and bacteria, and, under certain conditions, pathogenic germs. As methods of culture become more satisfactory and tests more universal, it may be demonstrated that many old or long-inhabited buildings furnish several varieties of patho- genic germs constantly to the air. According to some authorities, the most dangerous con- tamination of the air is the " crowd-poison," or organic matter given off with the carbon dioxide and moisture in the breath. References will be found in the bibliography to dis- cussions of the subject. No evidence has ever been found in the course of investigations in this laboratory, covering a period of twenty-five years, that the healthy human lung gives off any toxic substance. The same conclusion is reached by Dr. Emanuel Formanek of the Hygienic Institute at Prague after a long series of critical experiments.f * Nature, 31 (187 o), 265; 41 {1886) t 394. f Archlv fur Hygiene, 38 (igoo), 1. CHAPTER III. THE PROBLEM OF VENTILATION. From the preceding chapter it will be seen how impor- tant is the purity of the air to human well-being, and how essential is the diffusion of the knowledge of the methods by which it can be secured. It is often said that artificial ventilation is a modern necessity. Remains of aqueducts and sewers have testified to the sanitary intelligence of his- toric peoples, but the ventilating fan does not seem to have been included, although natural ventilation by shafts and flues has been practised since man came out of cave-dwellings. It is true that customs have changed as to many items of daily life. In cities more people live on an acre of ground, thus fouling the air above and the ground beneath ; more factories are belching smoke; more coal is burned; houses are built with smaller rooms and less pervious walls; schools and lecture-halls are more crowded; people are better fed, con- sequently there is more garbage; streets are macadamized, allowing finely ground particles to fill the air with every puff of. wind; gas-pipes traverse the walls of every house and pass under every street; carpets, draperies, and much passing in and out cause an accumulation of dust unknown fifty years ago. Kerosene lamps require more oxygen than manv candles. Besides, people -are becoming less hardy and more sensitive physically, so that well-ventilated living-spaces are a modern necessity if human efficiency is to be maintained. 19 20 AIR, WATER, AND FOOD. As we have seen, the air of open spaces presents only very slight variation at the same level or for several thousand feet above it. The movement of the air caused by the wind is usually so rapid, and the reservoir of air for many miles above the earth is so immense in comparison with the thin vitiated layer, that there are only to be considered enclosed spaces in which human beings remain for a period of time. To supply the 7000 to 12,000 liters (250 to 430 cube feet) of tidal air per person in maximum purity, there must be brought to the person at rest some 1800 cubic feet of air per hour. If he were in an air-tight chamber 12 feet square and 8 feet high, a man would reach the limit of purity in 38 minutes; but no ordinary room is air-tight, and when the difference between inside and outside temperature is consid- erable, a rapid exchange is taking place even with doors and windows shut. To secure the passage of this large volume of air through a small space without causing a draft that will be objected to by the abnormally sensitive victim of modern luxurious habits is the problem of ventilation — one not yet satisfactorily solved. The sanitary engineer is expected to design the appara- tus and to aid the architect in so placing and proportioning flues, inlets, and outlets as to accomplish the desired results. Unfortunately it is too common, especially in the case of school and college buildings, to economize in the first cost by dispensing with the services of the expert and to leave to the builder and " practical " architect all such details. In any case, it often becomes necessary to call in the chemist to prove the need of reform, or to show by the composition of the air whether or not the ventilating plant is doing its work efficiently. The sanitary inspector, whose business it is to decide air: the problem of VENTILATION. 21 upon the legal questions connected with tenements and fac- tories, must often rely upon chemical examinations of the air. The validity of these depends not only upon the per- fection and delicacy of apparatus and methods used, but also upon the judgment and intelligence with which the samples are taken. Many errors in the construction of buildings have been perpetrated because of an ignorance of the physical proper- ties of air and, consequently, a mistaken notion of the be- havior of a vitiated atmosphere. The lecturer on popular science who some forty years ago enlightened (?) the com- munity on the chemistry of daily life was accustomed to use, as a striking illustration, a glass jar in which a small lighted candle was instantly extinguished on pouring into the jar a tumblerful of carbon dioxide which had been collected for the purpose. The inference was plain: carbon dioxide was heavier than air, therefore it falls to the floor and must be allowed to flow out as if it were a stream of water. Further confirmation of this inference was found in the frequently observed fact that a candle lowered into a well often went out just before the water was reached. Hence for many years the habits of thoughtful persons were formed on a belief in the heaviness of carbon dioxide or " bad air," and in its tendency to go to the bottom of the room and into any holes it could find. This is only another instance of danger in half a truth. When do we find cold carbon dioxide generated in living-rooms? And how warm must the gas be in order to be lighter than the ordinary air? How quickly does diffusion take place? Until within a very few years the almost unanimous belief among the so-called educated classes was that the bad air could be let out by opening a window at the bottom, and, in spite of the lessons w 7 hich might have been learned by any observant person in 22 AIR, WATER, AND FOOD. hanging pictures or Christmas greens, the common practice in private houses, churches, and schools is to open the win- dows at the bottom. All ordinary vitiation of the air proceeds from a heated source. Human breath and warm air are lighter than cold air and rise even with their burden of carbon dioxide. It is only when they impinge on a very much colder surface, as on the window-pane on a very cold day, that they become suffi- ciently chilled to fall without mixing with the neighboring air. The freedom with which the gases of the air mix, as well as the rapidity of the action, may be illustrated in a variety of ways. Open a bottle of any volatile and pungent substance, as ammonia or hydrogen sulphide, in one corner of a room, and almost instantly it may be perceived in the most distant part. In natural ventilation we have only to avail ourselves of these characteristic properties of gases; and whether we wish to get rid of the light gases escaping from furnace, stove, or gas-pipe, or of the specifically heavier carbon dioxide, or of the most dangerous dust, we must furnish an outlet at the place to which the fleeing enemy first arrives, lest it turn and rend us for our ignorance. It is usually sufficient to furnish this opportunity, the current caused by this willing escape drawing in sufficient fresh air to take its place except in very crowded rooms, and even these might be so ventilated provided the whole roof were one large ventilating flue. If, however, the air is to be drawn from the bottom of the room, its unwilling current must be pulled by a superior force, as by an open fire on the hearth, which heats the air above it so that, in rushing into. the free air above, it draws after it all things movable within reach. Then, indeed, even the top of the room becomes quickly cleared and no corner can escape; but if the fire be air: the problem of ventilation. 23 long gone out and the chimney cold, the reverse takes place and cold, heavy air sinks to the floor, helping to confine the bad air at the top of the room. What the cold chimney cannot accomplish the mechani- cally driven fan can do, namely, by a slight compression force a draught even up a cold chimney. In this case the very unwillingness of the air to take the prescribed path helps in the result as water forced through a miil-wheel de- velops mechanical work. The warmed fresh air forced in near the top of the room loses its velocity as it mingles with that already present, and finds its way along the line of least resistance to the opening provided at the bottom of the room, into the flue, but only in case there is no easier way. Open doors or windows interfere with the prescribed course, and blindness to this fact on the part of the occupants of mechanically ventilated buildings has caused unjust com- plaints of the system. The necessity of regulating the con- sumption of fuel and admission of fresh air in accordance with variations of temperature, as well as the great care and trouble this involves, renders the " natural " system of ventila- tion practicable only in less crowded dwelling-houses where intelligence can control the varying factors. For schools, lecture-halls, or any enclosed spaces occupied by numbers of persons at one time, some form of mechanical ventilation offers the only hope of good air in cold climates. What form that shall take is for the engineer to decide. The chem- ist's part is to devise means of readily determining whether the persons in charge of the apparatus are using it to gain the results designed by the expert. As a test of how nearly practice approaches the theoreti- cal value, carbon dioxide is taken as the indicator, since it is present in a thousand times larger quantitv than any other impurity and since it is easily determined. If the air has 24 AIR, WATER, AND FOOD. only the normal amount of carbon dioxide, it is but rarely that it contains enough of anything else to be harmful. The presence of hydrogen sulphide or of coal-gas is betrayed by the odor. Where the gas-supply is " water-gas," contain- ing 30 to 40 per cent, of carbon monoxide, there is greater danger; but if legal restrictions are complied with, the pres- ence of this can be detected in the same way, viz., by the odor. Danger may also arise from the presence of so-called " sewer-gas," which, however, is not a single gas, but a most complex and variable mixture of the more volatile products of decomposition. For the detection of " sewer-air " chemi- cal tests are of little value, since it contains no constituent in sufficient quantity and with sufficient regularity to serve as an index of its presence. Ill-smelling gases are given off only when sewage is about eighteen hours old, hence dirty house-pipes are the chief cause of foul air. The delicate sense of smell is of value here. Indeed, an edu- cated nose is most essential in all examinations of house- air. " Crowd-poison," if it exists, keeps company with the increase of the products of respiration, and if the incoming air is strained or taken from a place free from dust, the par- ticles added to the air which is in the rooms will also be re- moved with the carbon dioxide. From nearly all points of view, carbon dioxide is an indi- cator of the efficiency of ventilation, especially if combined with observations of temperature and moisture. It is an in- dicator also readily understood and accepted by the public. The principles of ventilation may be readily illustrated to a class by means of simple apparatus. Such an apparatus, using candles and designed to illustrate the section of an ordinarv room, is shown in Fig. I. In testing the efficiency of ventilation of any room or AIR: THE PROBLEM OF VENTILATION. 25 building, it is necessary to determine first the direction of the air-currents, for there can be no ventilation without currents. If the architect who designed the building, or the engineer who advised the architect, is responsible, then the chemist has only to follow directions in taking the samples; but fre- quently the chemist, as well as the sanitary engineer, is called Fig. 1. — Apparatus to Illustrate the Principles of Ventilation. upon to make tests of rooms and buildings of which no plans are available. In the examination of such rooms, then, the position of flues or conduits, both inlets and outlets, which were intended to convey air or which serve without such intention, should first be located. Possible avenues of ingress and egress by means of loose windows, cracks around doors, etc., are to be considered. When there is great difference of temperature between outer and inner air, these allow of quite rapid change of air. Some means of rendering visible these currents is de- sirable, such as smouldering paper, magnesium powder, or fumes of ammonium chloride. 26 AIR, WATER, AND FOOD. When the direction and intensity of these air-currents have been determined, the places from which the air-samples are to be taken may be chosen. It will be evident in what part of the room stagnation occurs and where eddies are formed, also where the air escapes. In a room or building without artificial ventilation the air-currents are seen to be ascending until they become chilled, when they fall. An empty room will not show so decidedly the rise of air-currents as will an occupied one in which the vitiated air, being much warmer, rises more rap- idly and cools less quickly. In taking the samples all acci- dental means of contamination must be avoided and the occupants must be quiet, for the moving of persons causes disturbance in the air-current. There is room for great in- genuity in this part of the examination, as circumstances greatly modify the method of procedure. A fair sample, or a sufficient number of samples to give a fair average, must be taken. Having secured and analyzed the samples of air, the de- cision as to the efficiency of ventilation must be rendered. If the room examined is a study- or recitation-room, the stratum of air at the level of the students' heads should not contain over 8 or 9 parts per 10,000 of carbon dioxide, should not show a temperature of over 70 F., nor a humidity of over 35 or 50 per cent., and these conditions should be main- tained for hours at a time. For lecture-halls and spaces occupied for only one hour at a time, with ample time between occupation, it is admis- sible to allow 9 to 11 parts. If fan ventilation is used, the outlet should give the average degree of contamination. If no system is used, the air at the top of the room is first vitiated; only at the end of twenty minutes to half an hour do the lower layers begin to show it. CHAPTER IV. ANALYTICAL METHODS. DETERMINATION OP CARBON DIOXIDE. General Statements. — Since the earliest crude attempts at the determination of carbon dioxide all chemical methods have been based on its absorption by alkalies or alkaline earths. It may be the -diminution in volume of the air through absorption of the carbon dioxide that is measured ; the carbon dioxide may be separated as barium carbonate and weighed ; the reduced alkalinity of the absorbing liquid may be determined ; or the carbon dioxide may be set free from the absorbing solution and its volume determined directly ; all of these methods have been used with more or less success. For determining with great exactness the amount in out-door or " fresh " air it is customary to aspirate large quantities of air, sometimes as much as 600 liters, through the absorbing solution. For determining the amount in the air of rooms a much smaller sample, collected in calibrated vessels, of from one to eight liters, is preferable. Where it is necessary to absorb large quantities of the gas in a slight volume of solution, potassium or sodium hy- droxide is used. For nearly all of the " popular tests " cal- cium hvdroxide, lime-water, is used because of its harmless nature and the ease with which it can be obtained from the corner drug store, or from the quicklime procured from the mason's barrel. For volumetric methods barium hydroxide is generally preferred, because of the less solubility of the 27 28 AIR, WATER, AND FOOD. barium carbonate, it being only about two-thirds as soluble as the calcium salt. The very avidity with which these substances take up carbon dioxide is a hindrance to the preparation of standard solutions in an atmosphere already rich in it. When once prepared the solution must be pre- served with especial care, since contact with the hands or a whiff of the breath will reduce its strength and vitiate the results. All such solutions are best kept in bottles well pro- tected from the air by tubes filled with soda-lime and de- livered from a burette, as described on page 36. Pettenkofer Method. — The method which for many years was generally employed for the estimation of carbon dioxide in the air of rooms is some modification of that originally devised by Pettenkofer.* Principle.— In principle this consists in absorbing the carbon dioxide from a known volume of air in barium hy- droxide solution and titrating the excess with standard sulphuric acid. It is essential for the complete absorption of the carbon dioxide that the barium hydroxide be largely in excess, so that not more than one-fifth of it is neutralized ; furthermore, the absorbing solution must be shaken up with the air for a considerable time. Collecting the Samples.- — The samples are collected in four- or eight-liter bottles, the volume of which is accurately known, the bottles having been calibrated by weighing them filled with water. These bottles are provided with a rubber stopper carrying a glass tube over which a rubber nipple is slipped. They are filled with the air to be tested by means of a pair of nine-inch blacksmith's bellows, fitted with valves so arranged as to draw the air cut of the bottle. The bellows is connected with a three-quarter-inch brass * Pettenkofer: Annalen, 2, Supp. Band (1862), p. 1. Gill: Analyst, 17 (1892), 184. AIR: ANALYTICAL METHODS. 29 tube reaching nearly to the bottom of the bottle ; fifteen or twenty strokes should be sufficient to replace the air in a four-liter bottle. At the time of collecting the samples the following observations should be recorded: Room, date, time, weather, place in room, number of people present, number of gas-jets or lamps burning, condition of the doors, windows, and transoms; in short, everything that would tend to affect the amount of carbon dioxide in the air,, or to cause currents or eddies. The bottles should be distinctly labelled and their volumes recorded. If the temperature at the point where the samples are collected should be essentially different from that of the laboratory, the bottles should be allowed to stand in the laboratory for half an hour, or until they have attained its temperature. Directions for Laboratory Work. — The solutions of barium hydroxide and sulphuric acid which are used are approxi- mately of equal strength; but since it is impracticable to prepare exact solutions of barium hydroxide and to keep them without change, the exact value of the barium hy- droxide solution must be found by titration against the standard sulphuric acid, which is made of such a strength that 1 cubic centimeter is equivalent to exactly 1 milligram of C0 2 . This standardization, as well as the subsequent titration, is best made in a small flask to lessen the error from absorption of carbon dioxide from the air. It will be found most generally satisfactory to measure into the flask about 25 c.c. of the barium hydroxide, add. a drop of phen- olphthalein solution, and titrate with the sulphuric acid to the disappearance of the pink color. In all cases the first end-point should be taken as the correct one, because the pink color will sometimes return on standing. This is due to the presence of minute quantities of potassium or sodium hyd^.'^ide in the solution. The alkali sulphates will react 30 AIR, WATER, AND FOOD. with any barium carbonate which may be suspended in the liquid with the formation of alkali carbonates which give a pink color with phenolphthalein.* The standardization should be repeated until consecutive results are obtained which check within 0.2 per cent, of each other. Determination. — Remove the cap from the tube in the stopper of the bottle, insert the tube-tip of the burette so that it projects into the bottle, and run in rapidly 50 c.c of barium hydroxide from the burette. Replace the cap and spread the solution completely over the sides of the bottle while waiting three minutes for the burette to drain. In doing this take care that none of the solution gets into the cap. Note carefully the temperature and barometric pressure. Place the bottle on its side and roll or shake it at frequent intervals for forty-five minutes, taking care that the whole surface of the bottle is moistened with the solution each time. At the end of this time thoroughly shake the bottle to mix the solution, remove the cap, and pour the solution into a stoppered bottle of hard glass of 40 c.c. capacity, taking care that the solution shall come in contact with the air as little as possible. Under these conditions a full well-stoppered bottle may safely stand for days before titration. For the titration, measure out with a pipette 25 c.c. of the clear liquid into a 7 5 -c.c. flask and titrate it with the sulphuric acid as in the standardization. The differ- ence between the number of cubic centimeters of standard acid required to neutralize the total barium hydroxide before and after absorption gives the number of milligrams of dry carbon dioxide in the sample tested. The results may be expressed in parts per 10,000, by volume, under * This action can be largely prevented by including a small amount of barium chloride when making up the barium hydroxide solution (see p. 247.) air: analytical methods. 31 standard conditions (o° and 760 mm.), saturated with moisture (Method 1) or dry (Method 2). Tables for this purpose will be found in Appendix A.* Example. — Data: Standardization, I c.c. Ba (0H) 2 = 1.020 c.c. H 2 S0 4 volume of bottle = 8490 c.c; Ba(OH);j used = 49.9 c.c. ; H 2 S0 4 used = 21. 1 c.c. ; temperature and pressure = 21 and j66 mm. Before absorption 49.9 c.c. Ba(OH) 2 = 49.9 X 1.020 = 50.90 c.c. H 2 S0 4 . After absorption 49.9 c.c. Ba(OH) 2 = 42^2. x 21. 1 = 42.12 c.c. H 2 S0 4 . . '. (8490 — 49.9) = 8440. 1 c.c. air contain 50.90— 42. 12 = 8.78 mg. C0 2 . Method 1. — I c.c. C0 2 saturated with moisture at 2 1° and 766 mm. weighs 1.79624 mg. (Table II, Appendix A). 8 78 .-. 8.78 mg. = —7 — =4.887 c.c. C0 2 saturated with moisture. tt r ■ 1 4.887 Hence in 10,000 c.c. of air there are -^ — X 10,000 = 8440. 1 5.79 parts C0 2 . Method 2. — In this method the volume of air is reduced to standard conditions of temperature and pressure, under which conditions the weight of a cubic centimeter of dry C0 2 is a constant quantity. Thus v' — v{\ + o.oo366(/ / — *°)]. 1/ = 8440.1, f = 21 , t° = o° ; hence v = 7837.7 c.c. * Dietrich's Table, the one in general use, is not absolutely correct, the weight of a cubic centimeter of carbon dioxide at o° C. and 760 mm. being somewhat different from that given at present by the best authorities, but it is sufficiently close for any but the most exacting work. 32 AIR, WATER, AND FOOD. Also, v : v"=H"\H> or 7837.7 : ^=760: (766— 18.5). (18.5 = tension aqueous vapor at 21 .) Then v" = 7709 c.c. = volume of air at o° and 760 mm. 1 c.c. CO2 at o° and 760 mm. weighs 1.9643 mg. 8.78 4-469 = 4.469 c.c. CO. — X 10,000 =5.79 parts 1.9643 " * 7709 C0 2 per 10,000. Two samples are to be taken, closely following the notes, and the results calculated by both methods before collecting- more samples. Then some one room may be taken and the quality of the air determined for the different hours of the day, or a comparison of different rooms may be made, or a building may be tested as a whole. All data and results ob- tained should be arranged in tabular form on a separate page of the note-book. Notes. — This method of collecting the air in a large bottle possesses a decided advantage over the method of slowly drawing the air through barium hydroxide contained in a long tube, in that a sample represents the condition of the air at a given time and not its average condition for a period of an hour or so. In collecting samples, care must be taken to avoid cur- rents of air or the close proximity of people. Duplicate samples can be obtained only in empty or nearly empty rooms. Even two sides of the same room will probably show differences, but two samples taken carefully side by side ought to agree within 0.05 part per 10,000. While the Pettenkofer method is convenient, and for a long time has been the favorite, it is now quite generally recognized that it contains inherent sources of error which can be obviated only by the use of complicated apparatus and extreme skill in manipulation. That the method can be employed to obtain results of the highest degree of accu- AIR: ANALYTICAL METHODS. 33' • racy has been shown by Letts and Blake* in an exhaustive study of the question. The refinements found necessary, however, place their modification out of consideration for ordinary use. The principal source of error lies in the necessity for titrating the alkaline liquid within the "area of contamina- tion," the exhaled breath containing on an average from 50 to 100 times as much carbon dioxide as the air under examination. Other important sources of error which have been found to lead to erroneous results are the action of the caustic alkali on the glass of the large bottle, and the presence of small amounts of the precipitated barium car- bonate in the solution during the titration. It should therefore be borne in mind that results obtained by this method may be too high even though agreeing closely among themselves. The small bottle to which the solution is transferred for settling should be of such a size (40 c.c.) that the volume which drains readily from the large bottle when the glass tube is flush with the stopper shall a little more than fill it. That is, no air-space should be left to serve as a medium for transpiration from the surrounding air if the bottle stand for some hours. On the other hand, there should be a sufficient excess over the 25 c.c needed to ensure the filling of the pipette at the first trial. This pipette is globular in shape, with a stem of small diameter above and below the bulb. The last drop is taken off by touching the neck of the flask after counting ten from the time it is empty. It is then set upright to drain; the drop which collects is gently shaken out before the next titration. The error is less than if it were rinsed with water each time. All rubber stoppers which are used should first be boiled * Proc. Royal Dublin Sec., 9, 107 (iqoo). 34 AIR, WATER, AND FOOD. in dilute caustic soda, then in a dilute solution of potassium bichromate and sulphuric acid and thoroughly washed. Walker Method. — A comparatively simple method in which the errors inherent to the Pettenkofer process are avoided has been proposed by Walker.* The method has been carefully studied in this laboratory f and found to be capable of great accuracy Principle. — To a definite volume of air, usually i to 2 liters, is added a measured amount of standard barium hydroxide, care being taken to avoid contact of the solution with the air. After the absorption of the carbon dioxide, the solution is filtered under reduced pressure through as- bestos and the clear barium hydroxide received into a known excess of standard hydrochloric acid. The absorp- tion vessel is rinsed out with water free from carbon dioxide. The excess of acid is then determined by titration with barium hydroxide. Reagents and Apparatus. — The standard solutions used are N/50 hydrochloric acid, and barium hydroxide, approxi- mately N/100, its exact strength relative to the acid being found daily by titration. It will be found advantageous to use solutions of this strength, somewhat more dilute than those recommended by Walker, on account of the increased accuracy with air nearly free from carbon dioxide. The decreased range of usefulness is readily compensated ' by the employment of smaller samples of the impure air. The barium hydroxide, which is usually made up in quantities of 8 liters at a time, is preserved with especial care. The hard-glass bottle containing it, placed on a high shelf so that the measuring apparatus can be filled directly .by gravity, is heavily coated on the inside with barium * J. Chem. Soc, jj t IIIO {iqoo). ■f Woodman : /. Am. Chem. Soc, 25, 150 (iqoj). air: analytical methods. 35 carbonate. The bottle is closed by a rubber stopper with two holes, one of which carries the siphon tube dip- ping to the bottom of the bottle and supplying the meas- uring burette, while the other carries a fairly large glass T (Fig. 2). A I W Fig. 2. From one-half the horizontal arm of this projects a glass tube carrying the device for protecting the solution. This device is shown drawn on a somewhat larger scale in the same sketch. The horizontal tube enters the T tube far 36 AIR, WATER, AND FOOD. enough to support the apparatus. Connection is made, by a closely fitting rubber tube. The longer tube, reaching nearly to the bottom of the test-tube, carries a fairly good- sized "calcium chloride tube" which contains soda-lime, enclosed in the usual manner by pings of cotton. The test- tube contains 5 to 10 c.c. cf dilute (about N/50) caustic potash colored with phenolphthalein, the whole serving to indicate the efficiency of the soda-lime. From the other end of the horizontal arm of the T projects in the same way a long tube bent at right angles fitting by a rubber stopper into the top of the burette, thus making the whole a closed system, much after the manner of Blochmann.* Any air entering the bottle when the solution is drawn from the burette or when the burette is filled again must have come through the protecting apparatus. This will be found efficient if care is taken in the selection or preparation of the soda-lime. t The burette used for the barium hydroxide is a glass- stoppered one, differing somewhat from the ordinary form. The lower portion below the graduations is narrowed and bent at right angles. This horizontal part is fitted with an ordinary glass stop-cock. This gives no trouble when kept well vaselined. The tip of the burette is kept covered with a little rubber cap when not in use to prevent clogging from the formation of carbonate. The apparatus could easily be arranged with a special pipette for the delivery of a definite charge of baryta solution if desired. The bottles used for the collection of samples are of hard glass of about 2 liters capacity, the exact volume being determined in each case to a cubic centimeter. The bottle * Ann. Chem. (Liebig), 237, 39 (1887). f Directions for preparing a good quality of soda-lime are given by Benedict and Tower: /. Am. Chem. Soc, 21, 396 (i8qq). AIR: ANALYTICAL METHODS. 37 is olosed by a rubber stopper through which pass two glass tubes about 7 mm. in diameter. The longer tube reaches almost to the bottom of the bottle; the shorter tube ends internally just flush with the stopper. Both tubes project externally about two inches and are provided with stop- Fig. 3. cocks at slightly different levels so as to permit of convenient manipulation. There is permanently attached to the upper end of the longer tube a piece of rubber tubing 1 inch in length which serves to connect it with the tip of the baryta burette. The stop-cocks may be replaced by rubber tubing and Mohr pinch-cocks if desired. 38 AIR, WATER, AND FOOD. The apparatus used for filtering off the barium carbonate is shown in Fig. 3. To the base of a ring-stand is firmly clamped an ordinary filter-bottle of about 250 c.c. capacity closed by a rubber stopper with two holes. Through one of these passes a tube leading to the suction-pump, through the other the tube of a Gooch filtering-funnel, the upper part of which is cut off so that the remainder above the constriction is about an inch long. The tip projecting into the bottle is bent so that the liquid shall flow down the side and not spatter. A rather close coil of stout platinum wire placed above the narrow portion serves as a support for the asbestos filter, or can be removed if it is desired to use a cotton plug instead. In the upper part of the tube is tightly fitted a rubber stopper through which passes a narrow glass tube extending to within one-eighth inch of the asbestos layer and provided above the stopper with a stop-cock. Connection is made with the short tube of the inverted bottle by means of a rubber tube about 8 inches in length. Procedure. — (a) The Absorption. — Insert the tip of the baryta burette into the short piece of rubber tubing and run in approximately 50 c.c. with both stop-cocks open. Close the outlet cock, pinch the rubber tube with the fingers, detach it from the burette and insert a bit of glass rod to keep out the air. Finally close the stop-cock. Drain the burette three minutes and take the reading as usual. Carry out the absorption of the carbon dioxide as described in the Pettenkofer method, except that 25-30 minutes is ample for the absorption. ib) The Filtration. — While the absorption is in progress prepare the filter. Apply slight suction and add enough asbestos fiber suspended in water to form a felt about a sixteenth of an inch thick over the platinum coil. Wash it air: analytical methods. 39 once or twice with distilled water. If properly done the water should flow from the filter-tube in a continuous stream when the pump is running at good speed, but should drop only slowly when the suction is slight. Prepare also about ioo c.c. of " wash- water " by adding to distilled water i c.c. of a 10 per cent, barium chloride solution and three drops of phenolphthalein, then titrating with the barium hydroxide to a faint permanent pink. Keep in a stoppered flask until wanted. Measure into the filter-bottle 25 c.c. of the hydrochloric acid. The arrangement of the bottle and filter during filtration is shown in the figure. Open the stop-cock of the shorter tube and turn on the pump. Now slowly open the filter stop-cock and control the flow of liquid entirely with this cock. The barium carbonate remains on the asbestos, and the clear baryta solution which passes through is at once neutralized by the hydrochloric acid. When all the liquid has passed through allow the pump to act for a few minutes to partially exhaust the bottle, then close the filter-cock. Pour some of the wash-water into a small beaker, dip the end of the longer tube into it, .and by opening the stop- cock allow about 20 c.c. to flow into the bottle before again closing it. Unclamp the bottle and shake thoroughly while held horizontally and still attached to the filter. Clamp it in place again, turn on the pump, and drain off the wash- water. Repeat this twice. Generally at the third washing" the wash-water is no longer turned pink, showing that the barium hydroxide has been completely removed. Remove the stopper and cock from the filter-tube and draw the re- mainder of the wash-water through the filter to wash down the sides of the tube. 40 AIR, WATER, AND FOOD. (c) The Titration. — Transfer the acid solution tea 6-inch porcelain dish and run in barium hydroxide to the produc- tion of a distinct pink color. Return the solution to the filter-bottle and pour it again into the dish. One or two drops of the alkali solution will suffice to finish the titra- tion. Note. — It will be seen that in this method the errors of the other are largely avoided. The alkali solution is made weaker, and its time of contact with the glass of the bottle is shorter; the barium carbonate is entirely removed if the filtration is properly conducted ; the titration is not carried out in an alkaline solution, but in one that is acid. For a discussion of the results obtained the papers cited above may be consulted. Strong potassium hydroxide is undoubtedly the best absorb- ent for carbon dioxide and in all cases where delicate manipula- tion and expensive apparatus are not hindrances, some form of gas absorption apparatus is best. The measurement of the gas should be made over mercury and in a finely calibrated tube. Eimer and Amend now supply a modification of the Petterson and Palmquist apparatus which gives good results. General Tests. — In addition to the above methods for determining carbon dioxide just described, there are general tests which can often be used with advantage. If within the space of a few hours some fifty or more tests are to be made, and comparative results rather than great accuracy are required, some simpler form of apparatus is desirable. Such an apparatus, to be satisfactory, should meet, so far as possible, the following requirements: (i) It should be sufficiently compact and portable to be carried in the hand from place to place. air: analytical methods. 41 (2) It should be as simple in construction as possible, and its use should not involve delicate measurements. (3) If possible, the apparatus should be made entirely of glass, avoiding prolonged contact of corks or of rubber connectors with any dilute solution which may be used. (4) It should be so constructed as to protect the solution at all times from the carbon dioxide of the air, especially while the determination is being made, because of necessity such an apparatus must be used within the area of contami- nation. (5) The complete apparatus should be sufficient for fifty or more determinations. (6) It must be capable of giving results of a reasonable degree of accuracy, say within 0.5 part of carbon dioxide in 10,000 parts of air, in the hands of persons having little or no chemical knowledge and minimum skill in manipula- tion. (7) If a solution be used in the apparatus it should be one which can be prepared easily from chemicals readily obtained; the solution must maintain its efficiency for a reasonable length of time, if protected from external influ- ences; and the solution should be one that is not at all dangerous or obnoxious to use. Simplicity of apparatus is much to be desired, but it should not be gained at too great sacrifice of accuracy. Even when no greater precision is required than is necessary to meet the demands of practical work, it is out of the question to measure the test solution by means of an ordinary pipette or to preserve it for any length of time in stoppered vials; the strength of the solution is almost certain to be reduced by contamination with the breath, by contact with rubber or cork. 42 AIR, WATER, AND FOOD. It must ever be borne in mind that extreme care is necessary in the preparation and rise of these very dilute solutions, the strict observance of conditions which might well be neglected in ordinary analytical procedures being here an essential factor of success. For the preservation and measuring of the test solution the authors have devised an apparatus which appears to answer the above requirements, and in actual practice has been found satisfactory.* The essential feature of this apparatus consists of an automatic pipette for measuring the test solution. This is a modified form of the pipette first pro- posed by G. P. Vanier and in use in this laboratory for a number of years. A gen- eral idea of it may be had from Fig. 4. The manner of using it is extremely simple. The test solution is preserved in a 1 -liter bottle of hard glass provided with a doubly perforated rubber stopper. Through one opening passes the siphon tube of the pi- pette, which is sufficiently long to reach to the bottom of the bottle ; through the other passes a glass tube ending just below the stopper and connected with a small bottle containing fresh soda-lime. By means of the three-way cock the solution is allowed to flow into the small inside pipette until it overflows. The stop-cock is then turned and the solution allowed to flow out at the lowest point. The pipette is made of such a size as to deliver exactly 10 cubic centimeters. The entrance of atmospheric car- * Air Testing for Engineers. A. G. Woodman and Ellen H. Richards: Tech. Quar., 14, 94 ^9 01 )- Fig. 4. — Automatic Pipette. AIR: ANALYTICAL METHODS. 43 bon dioxide as the solution flows out is prevented by the small tube containing soda-lime or bits of caustic potash, The excess of liquid which accumulates in the overflow reservoir may be drawn off when desired. The bottle and pipette are contained in a wooden case about 20X8x7 inches, outside dimensions, and with the solution weigh about 8 pounds. The case is furnished with a handle at the top so that it may be carried readily in the hand from place to place. The bottle is fastened to the case, and the lower end of the pipette is clamped to a wooden support to keep it from swinging. The stopper should be firmly fastened to prevent loosening. The bottle should be thoroughly cleaned and washed with potassium bichromate and sulphuric acid, and it is best also to steam it for half an hour or so. As a further measure of precaution the rubber stopper is boiled with dilute caustic potash and thoroughly washed, although the solution can come in contact with it only through splashing while the case is being carried. This measuring apparatus may be used with a variety of methods and with various strengths of solution. The general tests are based on two fundamental principles. For instance, the Fitz and Wolpert methods are carried out by shaking a small quantity of dilute lime-water, colored pink by phenolphthalein, with successive portions of air until the solution is decolorized. The greater the amount of carbon dioxide in the air the less will be the volume of air required to neutralize the lime-water, and vice versa. That is, the amount of lime-water remaining constant, the amount of carbon dioxide will vary in a certain inverse ratio to the volume of air. 44 AIR, WATER, AND FOOD. The method of Cohen and Appleyard* is based upon the fact that if a dilute solution of lime-water, slightly colored with phenolphthalein, is brought in contact with a sample of air containing more than enough carbon dioxide to com- bine with all the lime present, the solution will be gradually decolorized, the length of time required depending upon the amount of carbon dioxide present. That is, the quantity of lime-water and the volume of air remaining the same in each case, the rate of decolorization will vary inversely with the amount of carbon dioxide. The method is scientific in principle because it recognizes the fact that the absorption of carbon dioxide by dilute alkali solutions is a time- reaction. The method of preparation of the solutions and the manner of making the tests which have been found to give the best results will be described in detail, since experience has shown that these directions cannot be too minute. Preparation of the Test Solution. — The solution used is a dilute solution of lime-water colored with phenolphthalein. To freshly slaked lime add twenty times its weight of water in a bottle of such size that it is not more than two-thirds full. Shake the mixture continuously for 20 minutes, and then allow it to settle over night or until perfectly clear. The resulting solution is the stock lime solution, or "satu- rated lime-water." If made in the manner indicated, each cubic centimeter of it ought to be very nearly equivalent to 1 milligram of carbon dioxide. If, however, it is desired to know the strength of it more exactly, it may be deter- mined by standard acid. To prepare the "test solution," pour into the 1 -liter bottle of the testing apparatus 1 measured liter of distilled * Chem. News, 70, (1894), in. air: analytical methods. 45 water, and add 2.5 ex. of a solution of phenolphthalein (made by dissolving 0.7 gram of phenolphthalein in 50 c.c. of alcohol and adding an equal volume of water). Stand the bottle on a sheet of white paper and add the "saturated lime-water " drop by drop from a pipette, shaking the bottle thoroughly after each addition until a faint pink color is produced which is permanent for one minute. Now add 6.3 c.c. of the " saturated lime-water," shake, and imme- diately connect the bottle again to the apparatus. For accuracy in testing air which is high in carbon dioxide, it is found advantageous to use a solution twice as strong as the above. This double solution is prepared in precisely the same way, using 5.0 c.c. of the phenolphthalein solution and 12.6 c.c. of the " saturated lime-water." While this procedure does not give an exact volume of solution, it is believed to be the best for the preparation of this dilute test solution, since it obviates the necessity for pouring the prepared solution from the measuring-flask into the bottle in which it is kept; 12.6 c.c. of the stock lime solution is added rather than 10 c.c, in order to keep the values obtained with the resulting solution more nearly comparable with the older values calculated on the suppo- sition that 10 c.c. of " saturated lime-water " was equivalent to 12.6 milligrams of carbon dioxide. Method of Making the Test. — The Fitz shaker or appara- tus for measuring the volume of air used, consists of a tube of about 30 cubic centimeters capacity, closed at one end, and graduated for a distance of 20 cubic centimeters from the closed end. In this tube, by means of a rubber collar, slides a smaller tube which is contracted at the outer end so as to be more readily closed by the finger. The appa- ratus is shown full size in Fig 5. 4 6 AIR, WATER, AND FOOD. See that the inner tube of the shaker slides readily in the outer one, moistening the rubber collar slightly if necessary. Have the inner tube pressed down to the bottom of the larger one, and measure into the apparatus 10 cubic centimeters of the test solu- tion from the automatic pipette, or from a burette, as in Fig. 2. Pull the inner tube up to the 5-c.c. mark (the bottom of the inner tube serv- ing as the index) and close the end of the tube with the finger. Hold the apparatus horizontally, and shake it vigorously for exactly 30 seconds. The amount of air that is thus brought in contact with the solution is equivalent to approximately 30 cubic centimeters, as there are 25 cubic centimeters of air above the liquid when the small tube is forced to the bottom of the larger. Re- move the finger, press down the small tube again to the bottom of the larger and draw it up to the 20-c.c. mark. Shake the apparatus again for 30 seconds. The amount of air brought in contact with the solution is now 30 + 20 = 50 c.c. Repeat the shaking, using 20 c.c. of fresh air each time, until the pink color is discharged. The amount of carbon dioxide corresponding to the number of cubic centimeters of air used will be found in Table A. 10 Fig. 5-— Fitz Shaker. Full Size. air: analytical methods. 47 Acting on the same principle is the Wolpert shaker shown in Fig. 50. This cylinder is easier to manipulate and results obtained with it by students are more consistent than those obtained with the Fitz. TABLE A. Double Standard Test Solution. CO2 in 10,000. Cubic Centimeters of Air. Solution. CO2 in 10,000. 22.2 5° 15-6 18.O 70 12.4 I5- 1 90 10.2 13.O no 8.7 "•3 13° 7-5 9.9 15° 6.6 8.8 170 5-8 8.0 190 5- 2 7-3 210 4.8 6.8 230 4-5 6-3 250 4-3 5-9 270 4.1 5-6 290 3-95 5-4 310 3-8 5-i 33° H 4.8 35° 3.6 4-7 31° 4-5 39o 4.4 410 4.2 45° 4.0 490 3-9 53o I The following notes and precautions feiV - apply to both forms of the shaker. Care should be taken that the finger used to close the end of the tube is perfectly clean, since on a warm day FlG " 5a ' the free acid in the perspiration might easily vitiate the results. Some may find the use of a rubber stopper prefer- able. If greater accuracy is desired, the shaker should be filled \rith the air to be tested before running in the test solution. 48 AIR, WATER, AND FOOD. This may be done readily by filling the shaker with water and emptying it. The apparatus should be shaken vigorously and contin- uously during the 30 seconds in order to absorb practically all of the carbon dioxide in the enclosed air. The number of shakings ought not to be less than 100 during this time. Care should be taken not to contaminate the air while the sample is being taken. The breath should be held momen- tarily while the air in the apparatus is being replaced, and the sample should be collected as far to one side of the body as possible. It ought not to require over 10 seconds to replace the air, and the entire test, with air containing, say, 8 parts of carbon dioxide per 10,000, should not require over 6 minutes. If less than 90 c.c. of air is required to discharge the pink color, the test should be repeated, using 10 c.c. of air each time after the first 30 c.c. It is not necessary to rinse out the shaker after making each test, but it should be carefully washed and dried after using, and the parts kept separate when not in use. The " double solution " is used in exactly the same manner and amount as the regular test solution, reference being made to the appropriate portion of the table. For the Cohen method the same solutions may be used and measured from the same apparatus. The samples are collected in white, glass-stoppered bottles of one-half liter capacity. This may be done by aspirating the air with a bel- lows, or the bottles may be completely filled with water, which is then emptied at the place where the air is to be tested. A convenient modification of this is the water siphon method. — Two bottles (diameter one-third the height) of nearly equal capacity are fitted with rubber stoppers carrying small glass tubing, connected by several feet of rubber connector with air: analytical methods. 49, clamps (Fig. 6). One bottle is completely filled with water, nearly free from carbon dioxide. The pair of bottles is taken to the place from which the air is to be collected. The inlet tube may be long to reach to near Fig. 6. the ceiling, or short; if long, the first siphoning should be rejected, to secure filling the inlet tube with the air desired, the stoppers exchanged, and the sample taken. The air-filled bottle is stoppered and taken to the laboratory; or the test solution is at once added, the bottle stoppered and shaken, noting minutes and seconds. One bottle of water with a small .5° AIR, WATER, AND FOOD. reserve will serve for a number of takings before absorbing a deleterious amount of C0 2 . (See Fig. 6.) A method involving more preparation but less trouble in the field is the steam vacuum method. The steam is supplied by a 500 c.c. flask serving as a boiler with a Tirrill burner to Fig. 7. — Steam- Vacuum Apparatus. From the thesis of Carl E. Hanson, 1908. supply the heat. The flask (Fig. 7) is fitted with a rubber stopper carrying a No. 6 glass tube bent so that one end extends within one half-inch of the bottom of the bottle when placed in position on the stand. The bottles used are of about 500 c.c. capacity, made for a ground-glass stopper but fitted with a rubber stopper. air: analytical methods. 51 To prepare the jet, the water in the flask is allowed to boil for five minutes in order to expel completely the air in the water and the flask. The pressure should be sufficient to throw the vaporized steam at least one foot above the exposed end of the tube. The empty bottle is placed on the stand in an inverted position and allowed to remain for three minutes. In the mean- time a thin coating of vaseline is applied half way up the sides of the stopper. The vaseline acts as an unguent, reducing the coefficient of friction to such an extent that the principal resistance is due to the reaction of the stopper against com- pression. This enables one to force the stepper in far enough t:o bring the glass and rubber into intimate contact, which is essential. The vaseline also fills the interstices between the rubber and the glass, which makes leakage impossible. Protecting the hand with a cloth, the bottle is raised from the stand, and the instant it clears the end of the tube the stopper is inserted while the bottle is still inverted. The stopper may be pushed in more securely by pushing it against the table with a few pounds pressure while the bottle is still in the inverted position. The stopper is kept in under this pressure for a few minutes until the vacuum begins to form, after which the atmospheric pressure will keep it in place. All the bottles required are treated in the same way. The rubber stoppers should be at least one size larger than would ordinarily be used for the bottles, and should project three- eighths of an inch or more to be easily removed when the sample is to be taken. Sample bottles may be tested for completeness of vacuum by holding them in an inverted position under water at 70 F., free from carbon dioxide, and removing the stopper. After the water has replaced the vacuum, the stopper is inserted and the bottle removed. 5 2 AIR, WATER, AND FOOD. In making the test 10 c.c. of the test solution are run in from the automatic pipette, or from a burette as in Fig. 2, the time noted, and the bottle shaken continuously and vigorously with both hands until the pink color vanishes. From the time required the amount of carbon dioxide in the air may be found by referring to Table B. TABLE B. Double Solution. Time, Minutes and "Test Solution.' ' Double Solution. Time. Minutes and CO2 in 10,000. Seconds. CO2 in 10,000. CO2 in 10,000. Seconds. .... O.15 .... 4.0 5-45 O.30 15-6 6.00 o-45 12. 1 3-9 6.15 16.O 1. 00 9.9 6.30 i3-i i-i5 8.4 3*8 6-45 11.4 1.30 7.2 7.00 IO.I i-45 6.3 7-i5 9.1 2.00 5-5 3-7 7-3° 8-3 2.15 4.9 7.6 2.30 4.4 7.0 2.45 4.0 6-5 3.00 3-8 6.1 3-i5 3-7 5-7 3-3° 3-6 5-4 3-45 5-i 4.00 4.9 4-i5 4-7 4-3° 4-5 4-45 4-3 5.00 4.2 5-*5 4.1 5-30 Carbon Monoxide. — The detection and estimation of carbon monoxide in the very minute quantities in which it is found in the air of ordinary rooms is a problem of considerable difficulty. Detection. — Probably the most convenient test for detect- ing small quantities is the blood test. Dilute a large drop of human blood, freshly drawn by pricking the finger, to 10 c.c. with water. Divide the solution into two equal portions, and shake one portion gently for ten minutes in a bottle containing about 100 c.c. of the air to be tested. Compare the tints of the two portions by holding them against a well- air: analytical methods. 53 lighted white surface. The presence of carbon monoxide is indicated by the appearance of a pink tint in the blood which has been shaken with air. One part in 10,000 can be de- tected in this way.* The delicacy of the test can be increased by examining- the blood, after shaking with the air, with a spectroscope. By collecting the sample in an 8-liter bottle and examining it in this way 0.01 part m 10,000 may be detected. Determination. f — Principle. — Oxidation of the carbon monoxide to carbon dioxide by iodine pentoxide, iodine being liberated according to the following equation: I 2 5 + 5 CO = I 2 + $co 2 . N The iodine is titrated with sodium thiosulphate. 1000 r Directions. — Place 25 grams of iodine pentoxide, free from iodine, in a small U tube which is suspended in an oil-bath and connected with a small absorption-bulb containing 0.5 gram of potassium iodide dissolved in 5 c.c. of water. Heat the oil-bath to 150 C, and pass the air, previously drawn through U tubes, — one containing sulphuric acid and the other solid potassium hydroxide, — through the apparatus at the rate of a liter in two hours. Titrate the liberated iodine N bv sodium thiosulphate and starch. J 1000 l Notes. — The temperature and barometric pressure should be noted and all volumes reduced to o° C. and 760 mm. pressure. Using 1000 c.c. of air, it is possible to determine in this way 0.25 part per 10,000, by volume, of carbon monoxide. The use of tubes containing sulphuric acid and potassium hydroxide is to free the air from unsaturated hydrocarbons, hydrogen sulphide, sulphur dioxide, and similar reducing gases. * Clowes: " Detection and Estimation of Inflammable Gas and Vapor in Ihe Air," p. 138. t Kinnicutt and Sanford: Jour. Am. Chem. Soc, 22 (1900), 14 54 AIR, WATER, AND FOOD. Nitrites- — The determination of the amount of nitrites or nitrous acid in the air can be readily made as follows: Collect a sample of the air in a calibrated eiodit-liter bottle, as in the determination of carbon dioxide. Add ioo c.c. of N approximately — sodium hydroxide solution. (This should be free from nitrites and is best made by dissolving metallic sodium in redisti led water.) Shake the bottle occasionally and let it stand for about twenty-four hours. Take out 50 c.c. of the solution and determine the amount of nitrites as directed on page 108. Micro-organisms. — For the quantitative determination of the number and distribution of the micro-organisms in air, the method employed by Tucker * in the examination of the air of the Boston City Hospital answers very well. The apparatus used consists essentially of three parts: (1) a special glass tube called the aerobioscopc, in which is placed the filtering material; (2) a stout copper cylinder of about sixteen liters capacity, fitted with a vacuum-gauge; (3) an air-pump. The filtering medium which is used to retain the micro-organisms is a narrow column of sterilized granulated sugar about four inches long. In using the apparatus, the required amount of air is first drawn from the cylinder by means of the air-pump. A sterilized aerobioscopc is then attached to the cylinder and the air is slowly drawn through it, leaving its germs in the sugar- filter. After the air has been drawn through, the aerobioscopc is taken to the culture-room and the sugar dissolved in melted sterilized nutrient gelatine. The ge'atine is con- gealed in an even film on the inside of the tube, where, after * Report State Board of Health, Mass., 1889, 161. air: analytical methods. 55. 'four or five days, the colonies will develop, and can be counted by the aid of squares engraved upon the glass. This method possesses several peculiar advantages. The use of a vacuous cylinder allows a known volume of air to be readily aspirated, and the rate of flow through the filter is easily controlled. Another great advantage is the use of a soluble filter (sterilized granulated sugar), since insoluble substances seriously interfere with the counting. Further- more, the removal or transference of the filter and its germs is avoided. The apparatus is portable, and the method, as compared with others, is exceedingly rapid of execution. Organic Matter. — In regard to the presence of organic matter in the air there is at present considerable variance of opinion. While some investigators have obtained results- which indicate the presence of such organic matter, it has been found also that the amount which is obtained is very much less when the dust of the air is first removed by filtra- tion. The quantity of organic matter is therefore closely re- lated to the amount of dust, and there is strong evidence that this dust in the air is the source of the greater part, if not all,, of the organic matter, unless there are present persons with decayed teeth, diseased lungs, etc. The methods of determination that are in general use may be divided into two groups. In the first group are those methods in which the organic matter is converted into ammonia and determined by Nessler's reagent. In the sec- ond group the organic matter is oxidized by boiling with dilute potassium permanganate, the excess being titrated with oxalic acid. No one method gives results which are wholly satisfactory, the chief difficulties being to secure an absorbing material which shall itself be free from organic matter, and to avoid the introduction of minute particles of organic matter or dust during the analytical process. 56 AIR, WATER, AND FOOD. Remsen * and Bergey f recommend the use of freshly- ignited granular pumice-stone contained in a narrow glass absorption-tube. After aspirating a known volume of air, the pumice-stone is transferred to a flask, the ammonia dis- tilled off from alkaline permanganate and estimated by Ness- ler's reagent. Experience with the method in this labora- tory has shown that it is practically impossible to prepare the pumice-stone so that it shall be absolutely free from organic matter, and that the mere act of transference of the absorb- ing material resulted in a considerable error. Miss Talbot J iound, furthermore, that all of the organic matter is not con- verted into ammonia by a single distillation, but that a second and third redistillation of the distillates uniformly gave higher results. She found it preferable to draw the air directly through the boiling permanganate, having the ap- paratus so arranged that the condensed steam was returned to the flask. In this way the particles of organic matter were returned again and again to be acted upon by the perman- ganate. Experience with all these methods is well summed up by Professor Remsen when he says: " It would be useless to have examinations of air made by any but the most careful workers. It would be time thrown away to have such an- alyses made by the average practical chemist.'* Dust and Soot — The dust in the air may be estimated by drawing a measured volume through tubes packed with cot- ton and noting the increase in weight. Soot may be deter- mined by drawing the air through combustion-tubing partly filled with ignited asbestos, and then determining the carbon by the ordinary methods of combustion. * National Bd. Health Bulletin, I, 233; II, 517. f Mis. Coll. of Smithsonian Institution, No. 1037 (1896). X Tech. Quart., 1 (1887), 29. CHAPTER V. WATER : ITS SOURCE, PROPERTIES, AND RELATION TO LIFE AND HEALTH. {From the Householder' s Standpoint.) The metabolism which produces human energy is depen- dent upon the presence of water in the tissues. This water is derived in part from food which, as eaten, contains from 30 to 95 per cent.; in part from boiled water, as in tea and coffee; or raw from well or city tap. The total daily supply per person for this purpose from all sources is five or six pints. Water is also necessary to all forms of vegetable and animal life, even the lowest types, including those inim'cal to human health. Man has always used water as his beast of ourden: to carry ships to the ocean, to turn mill-wheels, to generate electrical power. He has also forced it to be his scavenger, carrying the refuse of his activities out of his sight. Unless compelled by legal restrictions, he has given little thought to the effect on his neighbor of this treatment of their common property. In common law, water is held to be a gift of nature to man for use by all, and therefore not to be diverted from its natural channels for the pleasure or profit of any one to the exclusion of the rest. Neither has one the right to return to the channel water unfit for the use of his neighbor farther down the stream. That is, there is no private ownership in 57 5« AIR, WATER, AND FOOD. surface-waters flowing in natural channels. But this inter- pretation of eminent jurists has not always been strictly fol- lowed. Many cases have been decided, especially since the rapid growth of large cities, in direct contradiction to this law. As population increases, cities need to go farther and farther into the country for their water-supply, and they often take from the few settlers found there the right to the water which passes their doors, for the benefit of far-away thousands. The law in regard to that portion which never enters, or which escapes from visible channels, is less clear. It is usu- ally held that this water goes with the soil, and that rights to it may be bought and sold: that wells may be driven and drains dug, even if a neighbor's supply is cut off; but it is always maintained that no man has a right to place any sub- stances on or in the ground which shall render his neighbor's well unfit for use. The changes in conditions of life have rendered impera tive a careful study of the ways and means of practically com- plying with the law's demand without a serious restraint upon the progress of civilization. The daily quantity required for each person has increased from the two ^o four gallons drawn by bucket from the farm- house well to thirty or forty gallons taken from the town sup- ply by the turning of a faucet, and in cities where much is used for manufacturing purposes, for running elevators and motors, the daily amount may reach ioo gallons per inhabi- tant. This constantly increasing use of water for other than cleansing purposes has enormously increased the difficulty of securine dean water for domestic use. Not only is a larger quantity of polluting material deposited in the water, but it is carried farther from its source by the dilution. This fact, as well as the demand for higher standards of water: source, properties, and relation to life. 59 purity, has made the abandonment of private water-supplies a necessity, and has demanded from municipalities the best scientific knowledge and the most careful supervision of the quality of the public supply. A city or town is under as strict obligation to furnish a safe supply of water as it is to provide safe roads. To this end, the proper construction and maintenance of reservoirs and a sufficient police surveillance of the watershed is as im- portant as abundance of supply. Education of the people at large is still necessary, not only that those who depend in whole or in part upon springs and wells may know how to protect themselves, but also that the necessary cost of the larger public (municipal) supply may be cheerfully paid for by the citizens. Leaving out of the present discussion such considerations as belong only to the engineer and specialist, the problem of potable water will be treated in this chapter from the point of view of the intelligent citizen and educated individual who cannot afford to remain ignorant of so important a factor in the general welfare. The reason why this education is needed lies in the fact that primitive habits of thought, influencing action in every-day life, survive long after the race has passed beyond the original conditions. In no respect is this more true than in regard to water. The ideal drinking-water of most persons is the dear,, colorless, sparkling water of a spring, refreshing in its cool- ness and satisfying the aesthetic sense by its suggestion of purity. So strong a hold has this ideal that it is most diffi- cult to convince the average person that any water which has these characteristics can be other than wholesome and, con- versely, that w r ater lacking in any of these qualities is suitable for human consumption. Early man drank clear cool water 60 AIR, WATER, AND FOOD. wherever he found it. If there was not a spring at hand, he scooped out a hole in the sand. Pioneer settlers dug the well as near the kitchen door or the barnyard as they could find water, with a blind faith in the protecting power of mother earth, not wholly misplaced so long as the require- ments of the household did not exceed two or three gallons per person daily, and so long as the nearest neighbor was half a mile away. So persistent is this confidence in nature that in the light of this day a majority of intelligent people, even, will quaff at a roadside well or drink freely at a country hotel or go to live in a city without ever taking thought for the quality of the water. Water is water, and he who pauses with his glass half-way and asks whence comes the supply is scouted as a weak-minded crank. So, too, when town au- thorities have spared no pains or expense to secure a safe supply from a distant lake, and have guarded it by all means known to science, the primitive habit of thought requiring colorless water of an even coolness of temperature leads those who can afford it to purchase " spring "-water in jugs and bottles, with the blind faith of the savage that what comes out of the ground must be good. Fundamental race-habits are taken advantage of by the dealer in spring-waters as well as by the vendor of patent medicines — the missionary has no chance against him. From the schools and colleges there should, however, be sent out a generation of more intelligent persons who, learning to weigh evidence, will not take chances and will help to develop a public opinion on sanitary matters, especially in regard to water-supplies. For not until there is an intelligent public can the present reckless use of water and ground be stopped. While no^ everv man may be a chemist, he can have that modicum of knowledge which will enable him to understand the need of chemical tests of water: source, properties, and relation to life. 6i water and to distinguish between the work of the expert and the amateur. However safe this ideal of clear, colorless water may have been in early times, it must now be relegated, with the un- barred door and unwatched treasure, to the mountain fast- nesses. As the country becomes settled, appearance and taste are no longer sufficient guides; therefore scientific tests must be applied and the results interpreted by trained ob- servers to whom the individual subordinates his private judgment. The ideal water should be above suspicion, for if it has once been contaminated, who can tell how soon it will find bad company again? Not the analyst in his laboratory. In fact, the laboratory verdict is worth very little without a knowledge of outside conditions and without a keen detec- tive insight which scents out the most unlikely causes. Nevertheless the evidence given by analytical results is needed to procure conviction. Although " pure " water is found only in the laboratory, " safe " water, that which is reasonably free from objection- able substances, mineral and organic, may be obtained with sufficient care and knowledge. A clear understanding of the problem requires a close study of the circulation of water on the earth. Let us trace the course of water from sky to ocean, in view of its availa- bility for domestic use, and note the dangerous properties it may acquire, considering also the changes in condition which it may undergo in its course from mountain to sea. Water-vapor rising from sea and land is condensed in the upper air, then falls to the earth, absorbing, as it does so, ammonia, carbon dioxide, sulphur oxides, and other soluble gases, if present, and washing the air free from dust-particles, mineral and organic. 62 AIR, WATER, AND FOOD. This meteoric water (rain or snow), although nearly free from dissolved mineral substances, is therefore by no means pure. Furthermore, rain falling on insoluble rocks, bare or lichen-covered, or on loose, sandy soils, washes them also, giving up to the vegetation the ammonia and taking in re- turn carbon dioxide and dissolved albuminoid ammonia. Water thus enriched has increased solvent power on cer- tain rocks and soils. This rain-water soon forms rivulets which, passing down from the highlands into the forest, spread over the moss-covered area, soaking the leaves and peaty soil and extracting organic substances. Mountain brooks, as well as lowland streams, draining a region free from limestone, are thus colored brownish-yellow and furnish " meadow-tea/' as Thoreau happily named it. As the stream flows on it re- ceives contributions of many kinds — the overflow of springs, the under-drainage from cultivated fields, the surface-wash from pasture and meadow. Scavengers are, however, con- stantly at work. Brought as dust by the ever-passing air- currents, seeds of tiny plants freely sprout in the water and grow rapidly whenever a quiet pool or lake gives oppor- tunity. The products of organic decay and the ammonia of the rain may be thus removed and the water pass on to the reservoir clear and soft and as nearly pure as nature furnishes. It is, however, becoming rare to find even a mountain stream or forest brook which has not been subjected to modification by human agencies. Three kinds of contamination may take place. First: A farmhouse high up on the hillside lays trib- ute for drinking purposes upon that water finding its way beneath the sand which appears in the form of a spring. The overflow is made into a duck-pond, or passes through the watering-trough by the roadside before it joins other water tumbling over the rocks as a rapid stream. The brook thus grown larger widens out a little below the farmhouse into a water: source, properties, and relation to life. 63 shallow pool, in which one or two cows frequently seek com- fort. The water has become rich in organic matter and sup- ports a thick growth of tiny plants; the stones, even, may be coated with green slime. This vegetation serves as a warning to the hunter and the woodsman, who wisely drink only of water from clear pools with bottom of shining sand. The heavy material stirred up by the cattle soon settles, leaving the water in the stream below clear, although probably a little yellow in color. It still tastes well and looks all right, and may be used by human beings with probable impunity. Second: The little stream next passes other farm build- ings, where the privy is put over it to save the trouble of cleaning, or, even if not so close, is placed in such a way as to allow of a possible wash into it, especially in times of sudden rain. A case of typhoid fever develops at this farm. No pre- caution is taken to disinfect the discharges, and a portion of the dangerous material is carried into and along with the water. Some two or three miles below, another farmhouse, having no spring, uses this same little stream for its supply, perhaps damming it up into a little pond or pumping it into a tank. All unconscious of what has happened above, or ignorant of consequences, this water with a history is freely used, and perhaps the whole family come down with the dis- ease, perhaps only the delicate one may have it. It may be that they will all escape, owing to the fact that they were particularly robust, or that they drank no water raw, or that the conditions on the stream have been favorable to purifica- tion of the water by storage and consequent growth of the green plants, which are our friends in such cases; but if the water were pumped into a covered tank and used soon after, the chances are nine to one that some deleterious results followed. 64 AIR, WATER, AND FOOD. Third: A part of the water sinks through the sand, and by this filtration becomes freed from all suspended matter and consequently from the germs of disease, if present. In its course if it is intercepted and collected in a shallow well it may again be of great organic purity and free from danger, but it will surely bear the telltale marks of its progress in the increase of chlorine and solids which will have escaped all the agents of purification, and in the nitrates, the result of the process. It will be noticed that it is only after contamination with the " waste of human life " that danger comes to other human beings and that many circumstances modify that danger. The chances are about equal to those of fire; and as most householders think it worth while to insure against possible fire, so they should hold the chemist's certificate as a sort of water insurance; but since the fire policy does not protect from carelessness, the knowledge that the water-supply is once good does not absolve the householder or the citizen from the greatest care in protecting his premises. Duty to his neighbor should lead him to see that this coin of the world is passed on in as good condition as possible, and he should at least give notice of danger when he knows that it exists. But this general movement of water on and near the sur- face is not all the story. From 25 to 40 per cent, of the annual rainfall, in temperate regions, soaks at once into the ground, and passing downward through the soil to hard-pan, to clayey or impervious layers, or to rock surface, thence through crevices, broken joints, or glacial drift-deposits to the water-table, flows along the slope for many miles, until it finds its way again to the surface, either from the bottom of a lake, the bed of a river, the side of a hill, supplying wells or appearing as a spring free from all organic and suspended water: source, properties, and relation to life. 65 matter but often rich in gases. In any one of these courses it may be intercepted by man and caught or pumped for his use. Such water may never have been far from the surface;, it may have been used and returned to the ground many times; it may have appeared as surface-water and again dis- appeared to great depths. It has been estimated that water moves in the ground at rates varying from 0.2 to 20 feet per day. This long contact with rocks will, of course, bring min- eral substances into solution which may be precipitated as new rocks are reached or other streams encountered, so that the same gallon of water may have had many stages in its course and may have held many different substances in solu- tion. An example of how much can be so held is found in the waters of the alkali belt (page 241). It is no wonder that so active a solvent as water should take with it much substance whenever it remains long in con- tact with soil or rock, for it may be many months before that which has once sunk out of sight again appears. In fact, great rivers are supposed to flow into the sea from under the sur- face. Then, too, the acquisition of dissolved gases favors the solution of many substances; for instance, water carrying carbon dioxide dissolves limestone as well as lead and cop- per, and when at low temperature and containing ammo- nium carbonate water may dissolve ferric iron. Water carrying organic acids dissolves among other sub- stances iron compounds which may or may not be in the ferrous condition, and therefore may or may not be precipi- tated on coming to the surface. And as we have seen that the ground below a certain level is permeated with moving water, whatever is buried in the earth is likewise liable to enter the watercourses in one form or another. An understanding of this movement of water under- 66 AIR, WATER, AND FOOD. ground, with the accompanying changes in its character, cannot be too strongly insisted upon, for the lack of com- prehension of it is at the root of most of the troubles from well-waters. For example, the leaching cesspool, the primi- tive " septic tank," delivers its more or less filtered water rich in nitrogen compounds into the general circulation at a depth below the most efficient action of the nitrifying or- ganisms, hence it may permit the passage of organisms of putrefaction into underground streams or into the well, when access is direct. Even when filtration is perfect, the products of decay are yet carried with it and so tell the story of the past. The difficulty is to determine the state of the filter which may be on a neighbor's land many hundred feet away, and to be sure that its action is uniform. Experience with artificial filters shows how difficult it is to maintain efficiency with rapid use; hence heavy rains or wet years may cause a state of danger not ordinarily existing. The relation of water to human health must be consid- ered chiefly in the light of the changes which go on in the substances held suspended or dissolved in it, and the effect of these changes on the wholesomeness of the water. The suspended matter may be either inert, as clay or sand; dead vegetable, as fragments of plants; living vegetable, as plants floating on the surface, diatoms, desmids, a'gse, etc.; dead or living animal, as infusoria, small crustaceans, etc. Wherever these occur there are found the lower orders of vegetable organisms, fungi, moulds, bacteria, ready to do the necessary work of decomposition preparatory to solu- tion. The mere presence of these forms of living matter does not of itself mean danger to those using the water, but among these may be found pathogenic organisms which are, at present, considered as liable to cause disease. Such mi- crobes do not find in water a congenial habitat, and, fortu- water: source, properties, and relation to life. 67 nately, do not thrive on the vegetable diet and in the cool tem- perature of natural waters, hence the other organisms soon overpower them; danger decreases not only in proportion to distance, time, and dilution, but also, probably, to the abun- dance of other vegetable life. Under favorable circum- stances the danger is, however, a very real one. The presence of certain living plants may, moreover, give rise to unpleasant, if not dangerous, tastes and odors, due to the presence of extremely pungent oils or other aromatic substances formed in the process of growth. When these plants are decaying putrefactive odors are also present, some- times rendering the water too offensive for use. These or- ganisms are described in Whipple's " Microscopy of Drink- ing-water," and in Chapter VII a short list of those which give characteristic odors will be found. The presence of much decaying vegetable matter in drinking-water is to be avoided, since it is not known what effect it may have upon the general health of the individual, rendering him perhaps more susceptible to disease. Food-supply is a necessary condition for life, and there cannot be abundant growth in a water without a correspond- ingly large amount of dissolved substances furnishing the food for this living fauna and flora. As has been stated, water usually carries considerable mineral substance and is often supplied with organic and gaseous compounds, while nitro- gen is furnished from many sources, most abundantly from sewage, so that it is not strange that water-life is so abundant, but rather that it is not more so. Most of the difficulties in securing a satisfactory water-supply are connected with the cycle of nitrogen in its relation to organic life. This may be briefly stated as follows: Nitrogen is found as an essential constituent of all living matter. When thus combined, it is the so-called organic nitrogen, and is found 68 AIR, WATER, AND FOOD. in undecomposed vegetable or animal substances. As soon as dead, these substances may become food for micro-organisms and the nitrogen then appears in a form from which it can be obtained as ammonia; for instance, from decaying beans, from putrefying broth, and from fresh sewage. This process takes place with or without much air and may be accompanied by very bad odors. As soon, however, as the nitrogen has passed from the insoluble organic form into the soluble compounds from which ammonia is obtained, then, if oxygen is present, and only then, another set of micro-organisms take up the work and nitrites appear; when still another set have done their work the nitrogen is found only in combination as ni- trates, fully oxidized and mineralized, no longer organic or capable of sustaining the life of the lower forms of vegetation, but, on the other hand, the most valuable food for chlorophyll- bearing plants which convert nitrates again into organic nitrogen. This cycle may be arrested or broken at certain stages. If the soluble ammonia compounds are set free out of contact with air or below the layers of soil containing the nitrifying organisms, they may remain indefinitely un- changed. If nitrates have been carried below the reach of the roots of the chlorophyll-bearing plants, or if they are con- fined in a space deficient in oxygen, then an access of decom- posable organic matter with micro-organisms will cause a, reduction of the nitrates to nitrites and free nitrogen, through the action of these lower plants which, in the absence of air, take the little oxygen they need from mineral com- pounds. These micro-organisms are not the only ones at work, however. In any sudden prominence of one factor others are apt to be overlooked; thus in the present case the in- finitely small has so powerfully affected men's minds tha f r partly because the micro-organisms are beyond their range WATER: SOURCE, PROPERTIES, AND RELATION TO LIFE. 69 of vision, such forms of life as are evident to the naked eye or with low powers of the microscope have been overlooked to an extent. As agents of putrefaction and of decay the micro-organ- isms have their work to do, but the final purification — the finishing up of the work — belongs to another order of life. The still minute but visible green plants — those which float free in water or attach themselves to larger growths — have now their part to play. The life-history of these forms has been little studied, and the work they do in the actual puri- fying of polluted water has been almost overlooked. The impression left on reading most books is that when foul mat- ter has been dissolved and converted into ammonia, carbon dioxide, and nitrates the work is done, but these compounds only furnish food for the next class, and these again for in- fusoria, tiny crustaceans, etc. In some cases these organisms succeed each other with great rapidity; in one case the fauna and flora of a given pond varied each week of a season, certain rare forms being found only once. There is needed, almost more than anything else, a con- secutive study of the green plants found in water-supplies, since by their cultivation greater purity might be attained and possibly a way might be found of exterminating the dis- agreeable ones. The most unexpected results may follow the long study of a single organism, such as has been given to Oscillaria prolifica of Jamaica Pond for a period of fifteen years. Weekly, sometimes daily, observations have been made for several years.* It is organisms of this class which give tastes and odors to water, and which, if enough were known concerning them, * Trans. A. A. A. S., 1898. Technology Quarterly, 14 {igoi) t 302; 15 <{jgo2) y 308. JO AIR, WATER, AND FOOD. would probably give perfectly trustworthy evidence as to the past history or source of contamination. The two classes of organisms work in opposite directions, and so long as food is present for either, life will increase with proportional rapidity. This connection of cause and effect should be made familiar to the intelligent citizen. When a ground- water free from all organic matter but rich in nitrates is exposed in an open basin the rich growth of chlorophyll-bearing algae follows as a matter of course; later, decay sets in and products of decomposition abound, the air above being the source of a constant supply of spores of all kinds. When a house- or barn-drain empties into a small slug- gish stream, it soon becomes filled with green plants thriving on the ammonia, and it is often possible to trace the source of pollution of a large lake by the line of green anabaena leading to the insignificant ditch. A curious blindness on the part of managers of water- works to the movements of water and its action in transport- ing material is seen not only in the almost universal proximity of cemeteries to reservoirs, but also in the common practice of dressing the sloping banks of turf with a heavy coating of manure. Even if this was derived from clean stables and was not liable to be contaminated with night-soil, the abun- dant food for plants which inevitably finds its way into the reservoir occasions as fruitful results in the water as on the banks, and is undoubtedly the cause of much of the trouble in storage basins. It is evident, therefore, that a once polluted water cannot be said to be purified so long as food for green plants re- mains, for the moment the temperature and other conditions be^nf favorable growth will begin. The term "purifica- tion" f aken in a chemical sense, should not be looselv used. water: source, properties, and relation to life. 71 Complete purification can take place only when all traces of former impurity, in any form, have been removed. Chemical precipitation of sewage leaves the soluble ammonia, and sand filtration leaves nitrates to serve for abundant life and sub- sequent decay in the streams into which the effluents flow. Such effluents are clarified and the organic matter may have been mineralized, but this is not purified water. Only when growing plants have removed this food and have themselves been removed can the water approach a purified condition. The effect of storage of water containing high nitrates in open tanks or reservoirs exposed to the collection of dust will be that spores of chlorophyll-bearing algae, diatoms, desmids, etc., will soon develop and will increase as long, as the food (nitrates, mineral matter, etc.) lasts. Only by pro- tection from dust and light can such water be kept free from unpleasant accumulations of suspended organisms or from disagreeable tastes. Unpolluted surface-waters, on the other hand, improve on storage, as a general rule, if the basin is a clean one. The storage of polluted or clarified water is thus forbidden, since not infrequently the first indication of the pollution of a surface supply is given by the appearance of some member of that richly nitrogenous group of algae called cyanophycecc, or " blue- greens," from the presence of blue or purple coloring matter along with the yellow-green chlorophyll. Since this group of plants contains from seven to eleven per cent, of nitrogen, while other groups contain only one or two, it is evident that, if it is to flourish, more nitrogenous food must be supplied. This may be derived from fertilized fields, from decay of other vegetable life, as well as from the richer source of direct sewage; but, in anv case, the growth of these plants is a sign of abundant food- supply which must be cut off if they are to be starved out, as they must be unless they are removed while fresh by strain- 72 AIR, WATER, AND FOOD. ing or skimming, for the odor of their decay is so intolerable as to preclude the use of the water. In some cases the odor accompanying their growth renders the water quite objec- tionable, and neither natural nor artificial filtration is able to remove it. Either natural or artificial basins may have a collection of vegetable matter on the bottom which slowly decomposes in summer, and since the bottom water is colder, the resulting ammonia remains until the late fall overturn, when it is brought to the surface, where it favors the growth of diatoms and other cold-water plants. Certain diatoms, as asterio- nella, cause disagreeable odors. Such basins show the least ammonia in early October and the most in late November. In order to make any predictions as to the pro'bable de- velopment of this flora and fauna of water, experience and at least a year's watching of any given supply are required until more is known of the life-history of these forms of life. Nothing is more needed to-day than work along these lines. When may disagreeable odors and tastes be expected? What precaution or measures may be taken in each case to prevent them? These are the questions the water-works superintendent, equally with the consumer, is asking, for the most part vainly as yet. As has been stated, surface-waters often carry stable or- ganic matter in connection with color, so that while the organic nitrogen shows high, no free ammonia or nitrates are formed on standing. These weak meadow-teas are now largely used for town supplies, and a word as to the source of the color may not be amiss. Many carbonaceous sub- stances, sugar, for example, when partially broken up become caramelized and give a brown solution, the color being due to substances richer in carbon; this color is deeper as the decomposition is more complete. There is no reason to sup- water: source, properties, and relation to life. 73 pose that such compounds have any deleterious effect on health. Indeed, experience has proved that such waters are more reliable than many others. The chlorine of unpolluted natural waters is derived from the sea in past or present times. Waves breaking on a rocky shore send finely divided salt-spray high into the air; dust-particles becoming coated with it carry their burden of salt around the world. The rain brings to earth now more, now less of this salted dust, each region receiving in the course of the year an amount fairly proportional to its dis- tance from the seacoast and to the rainfall. No mountain lake or stream has yet been found free from this element. Where evaporation and rainfall nearly balance, the normal chlorine will be that of the rain for the year, but where evapo- ration is in excess it may exceed that for any given year. In the absence of salt-springs and industries using much salt, the source of chlorine in excess of the normal is the do- mestic life of man. Mr. F. P. Stearns has estimated that the chlorine in the annual drainage of any watershed is increased one-tenth part per million by 20 inhabitants per square mile. Chlorine may serve to prove not only the presence but the amount of sewage pollution in any case where the other factors are known. Otherwise chlorine has no sanitary significance. Of the mineral constituents in waters there is little to say except that, like climate, water is to be taken as It is found — hard, high in mineral matters if derived from a lime- stone region, soft if from archean formations. Physicians are not agreed as to the effects of hard water, or of the brown soft waters. Fortunately the human system possesses remarkable adaptability, so that if slowly accustomed to a given condi- tion, as we have seen in the case of air, and as we shall have 74 AIR, WATER, AND FOOD. occasion to remark when food is considered, it can safely bear what would be a serious shock if suddenly encountered from an opposite condition. Natives of a hard-water region are made ill on coming to a soft-water region, and vice versa. Inhabitants of a city with a polluted water-supply seem to acquire a certain immunity. The safety from organic contamination secured by the use of distilled water has brought up the question of a pos- sible danger in too little mineral contents for the best cellular interchange wherein lies life. With the superabundance of mineral salts in ordinary diet, there would seem to be little cause for alarm; but if the food were poor in these substances, it is quite conceivable that evil results might follow a free use of distilled water. A word as to the care of water in the house may not seem amiss, in view of the tendency it has to absorb gases, to collect dust, to favor chemical and vital changes, to dis- solve metals. Too great care cannot be taken in all these directions to secure water freshly drawn from the main pipe beyond the lead or brass house-pipes and to avoid thos,e traps for the un- wary householders — faucet filters. When the water-supply is cafe, but warm and flat to the taste, ice is frequently used to cool it. Much has been said about the dangers of ice when used in drinking-water and on or about food. The latter is prob- ably the most serious danger, since people are not so careful about the quality of ice for that purpose. Certain rules may be broadly stated as guides to the householder: Crystal-clear ice, free from crevices, bubbles, etc., is probably pure, for it has been formed from slow freezing in a thin layer, over a deep mass of water, as 20 to 30 inches of water: source, properties, and relation to life. 75 ice in a pond 40 or 60 feet deep. In this case the impurities have been excluded. This crystal ice is impermeable to air and therefore to what air carries, and of course to water and what it carries. An equally safe rule is to discard all "snow-ice" made from snow saturated with water. The increasing difficulty of obtaining safe water has caused an increasing use of distilled water obtained either from domestic stills or in bottles or carboys from manu- facturers. The latter is often a desirable source of drink- ing-water if the glass does not scale off from the bottles. A very little common salt may be added if the consumer prefers, or even a drop or two of the druggists' "lime- water." The domestic still, if made from a poor quality of metal, may bring an evil second only to that of polluted water. Lead should not enter into its construction. CHAPTER VI. THE PROBLEM OF SAFE AND ACCEPTABLE WATER AND THE INTERPRETATION OF ANALYSES. {From the Chemist's Standpoint.) From what has been said it will be evident that the prob- lem of safe water for domestic use is not so much concerned with the water itself as with its property as a carrier and its part in chemical changes. We have seen how a great variety of vegetable and ani- mal matter finds its way into the water of a settled region; and as it is constantly being transformed from one form to another by the agency of multitudes of organisms, it is evi- dent that the exigencies of modern life render impossible the exclusive use of water of great organic purity. It is useless, therefore, to fight over again the battles of the past as to the source and kind of " organic matter " in water. We have also seen that it is not the mere presence of compounds of carbon, hydrogen, and nitrogen in drinking- water which gives the element of danger. It is not even the fact that these have taken part in animal life; fish and frogs continually die in ponds and streams, to say nothing of countless cyclops and mosquito larvae. Well authenti- cated cases are on record in which one drink of a polluted water has proved fatal; while, on the other hand, it is equally sure that highly contaminated water has been used with ap- parent impunity. 76 water: the problem of SAFE WATER. J7 When water has received excreta of diseased human beings, disease-germs are very likely to be conveyed by it to other human beings. In a city there are. always cases of disease, therefore all city sewage is to be considered danger- ous. But besides the living germs there are other accom- paniments of decaying organic matter which, when in con- centrated form, sometimes show toxic properties. Certain facts and many conjectures lead to the conclusion - that a water is " safe " only when free from decaying substances. Along with the millions of harmless micro-organisms engaged in the work of conversion there may be a few score inimical to the health of man, and for the education of the still skeptical public it is often advisable to speak somewhat strongly of the possible dangers from water-borne disease- germs. -\ •„ Nitrogen as the Essential Element in Living Matter. — All organisms from the lowest to the highest thrive only in the presence of food; therefore only that organic, matter which serves to support life or which, as a product of life, may be deleterious to man is rightly to be held as dangerous. The element common to both kinds is nitrogen; therefore the water-analyst seeks evidence not only of its presence or ab- sence, but of the forms in which it is found and their relation to one another. It may be assumed that any water which shows no change in the relative amount of its nitrogenous compounds at the end of a week either does not contain the organisms necessary to effect this change or is wanting in the food upon which they can thrive. As, however, it is inconvenient to wait a week before deciding this point, other methods are used. The so-called a 1 buminoid ammonia is supposed to indicate the amount of decomposable nitrogen- ous matter, but, as a matter of fact, taken by itself it gives little information of value. While its absence is conclusive, j8 AIR, WATER, AND FOOD. its presence is not equally so; but a proof of its variability from- day to day is really valuable. Whether used in the final interpretation or not, " organic nitrogen " (or that portion of it appearing as albuminoid ammonia) is always deter- mined, together with the other forms, as soon as the sample is received. A nitrogenous organic compound is dangerous from one of two causes: first, because it is already decaying and har- bors pathogenic germs or is giving off toxines; or, second, because it will furnish food for a further development of bac- terial life. As to its derivation from animal or from vegetable mat- ter, there need be little discussion, especially since the recog- nition of the high nitrogenous content of the blue-green algae and the nitrogenous character of " soil-humus " and the close approximation of animal and vegetable protoplasm. But it is most important to know if it is stable, since one of the best aphorisms ever contributed to the literature of water- analysis is given by Dr. Drown's statement, " A state of change is a state of danger." Results of the Decay of Nitrogenous Organic Matter. — The products of the first stage of decay of this class of organic matter are carbon dioxide and ammonia. It is to the latter that we turn for the proofs sought, by reason of the methods at hand for detecting such small amounts as one part in a billion parts of water, and because it is for the nitro- gen compound that we seek. The mere presence of free ammonia is not a sufficient in- dication of recent pollution from human sources. Rain-water, as shown in Table III, contains considerable quantities; decaying blue-green algae furnish it in still larger amounts, and moreover it offers acceptab!e food to plant-life and may therefore disappear in the form of combined nitrogen. water: the problem of safe water. 79 Nevertheless, it is to be held as one of the chief witnesses, for it is found in sewage in a thousand times the quantity in which it occurs in ordinary potable water. While putrefac- tive decay takes place by stages, the lines of division are not sharply drawn, and nitrites, the result of the second stage, may be and usually are found in polluted waters together with ammonia. So frequently is this the case that it is considered circumstantial evidence sufficient to convict when both am- monia and nitrites are found together. (See Tables V and VI, p. 241.) The reason is not far to seek. Both are not only prod- ucts of decay, but both are in that unstable condition which indicates active processes, and which therefore means the presence of micro-organisms. Certain exceptions will be noted later. The fourth form of nitrogen, that found in nitrates, is no longer classed as organic; it is now become food for green plants and cannot nourish the class to which bacteria and pathogenic germs belong, hence it is fair to presume that for lack of food the latter have succumbed or have been other- wise removed. The value of this test is the proof it sometimes furnishes of previous sewage pollution, since the nitrogen present in excess of that brought down by rain must have been furnished either by fertilizers, by decaying matter, or by sewage. (See Tables V and VI, p. 241.) Organic Carbon. — Since by far the largest constituent of organic matter is carbon, some fifty per cent., it might seem as if this was the best indication of pollution. Indeed, it was formerly so considered, and many methods have been de- vised to show its presence quantitatively. As our knowledge of the slight differences between many forms of animal and vegetable substances grows, the probability of any conclusive evidence from this source, either as to past history or present 8o . AIR, WATER, AND FOOD. condition, decreases. In short, although for many years water-analysts have been striving to perfect methods of de- tecting certain substances and certain organisms, it would seem as if they were no nearer a discovery of one simple de- cisive test, but, in most cases, were driven to a somewhat elaborate examination in which one test only furnishes one link in the chain of evidence. Sanitary Analysis. — The examination of a water to deter- mine its safety for domestic use is called a sanitary analys's, in distinction from that examination which determines its fitness for manufacturing purposes, for use in steam-boilers, or its medicinal value. Four points are to be determined: First, the amount, if any, of organic matter in a living or dead condition, sus- pended or dissolved in the water; second, the amount and character of the products of decomposition of organic mat- ter, and their relative proportions to one another; third, the stability of the undecomposed organic substances; fourth, the amount of certain mineral substances dissolved. From these results we draw conclusions as to the present condition and past history of the water. These conclusions are not in- fallible, but there are enough unavoidable risks in human life without taking unnecessary ones; and if pollution is proved, the cause should be removed or the supply aban- doned. Preliminary Inspection. — So long as the eye can re-enforce the other tests and the whole course of the water may be clearly traced, it is comparatively easy to judge of the charac- ter of a supply and of its safety for human use; but when a hole in the ground is the visible source, or the actual history of the water is hidden in unknown distances and depths, the diagnosis is more difficult. First, the geological horizon and superficial soil must be water: the problem of safe water. 8r studied; the direction and flow of underground water, not the slope of the surface only; the possible sources of danger, occasional as well as constant, within at least a quarter of a mile radius. The composition of unpolluted water of the same region should always be at hand for consultation. Safe Water. — As has been said, we can no longer require pure water; the most that we can demand is that the supply shall be safe. To the uninitiated one sample of clear, color- less water seems very like any other. The safe, colored or muddy water of a stream or pond seems less desirable than the clear, cold water of a badly polluted well. A water may be normally safe and yet, from exceptional circumstances, be for a time a source of danger. In one case the mouth of a well at a factory was overflowed by a con- taminated brook raised above its usual level by a heavy shower for half an hour only. Some thirty cases of typhoid fever resulted, so close to one another and so suddenly ceas- ing as to leave no doubt of the fact that for only a few hours was the water unsafe. How, then, shall a chemist tell if at some past time a water may have been or at some future time may become a source of disease? Only by carefully weigh- ing all the testimony attainable — ocular, chemical, biological, bacteriological — in the light of past experience. The day of the vest-pocket sample, usually in a flavoring- extract bottle, cork and all, is nearly past, but that of the fruit-jar, with a sticky rubber ring and corroded zinc top, is still with us. That admiration for chemical knowledge and belief in chemical clairvoyance which expects the chemist to decide from a sample while you wait if a certain water caused the death of a person a month since in a distant town under unknown conditions is very trying to the man who knows his own limitations. The market value of an analysis cannot well be appre- 82 AIR, WATER, AND FOOD. dated until a juster estimate of the professional training of the analyst is a part of common knowledge. Safe and Acceptable Water. — It is not enough that a supply shall be free to-day from disease-germs; it should re- main free from changes for a reasonable period of time. Therefore the advice desired by the towns seeking for sup- plies implies much more than mere analysis; it includes esti- mates of future changes, of variations due to possible further developments, and of the effect of these variations on accept- ability as well as safety. To be fully acceptable, a water should be free from color, odor, turbidity, sediment, and of a uniform temperature so low as to admit of use without ice. Only such water as has been earth-filtered and earth-cooled can meet this demand, but the supply of this class is becoming drawn upon to its limit; besides there are difficulties in the conveyance and storage of ground-water which offset many of its advantages. From the foregoing paragraphs it will be seen not only that waters carry every possible degree of safety or danger according to the country they drain, the num'ber and habits of the people living on the watershed, and the presence or absence of factories, slaughter-houses, etc., but that many elements enter into the judgment of a water-supply, and how different these elements are in different waters. Safe water is that which carries neither seeds of disease nor such sub- stances as are deleterious in any way to mankind in general. A brown water may yield 20 parts per million organic matter and show 10 parts oxygen consumed, and yet be a safe and wholesome water. A ground-water may show 5 parts nitrates, and yet for ten or twenty years prove a safe supply. Since, however, water is so universally made a carrier of refuse, it is difficult to find a stream or well which fulfils the water: the problem of safe water. 83 above exacting requirements, and a compromise is made which sets certain arbitrary limits and so keeps the chances small. Such limits are very misleading of themselves, espe- cially if used over a wide extent of territory. The English standards, for instance, are not applicable to eastern North America. Only a study of all local conditions and a wise in- terpretation of all results can make standard figures of any significance. This is true, also, of bacterial results in surface- waters. In the natural condition of lakes and streams there are so many varieties of bacteria present and in such varying numbers, according to wind and rain and watershed, that taken alone the numerical count gives no more convincing proof than is found in chemical figures. While it is quite within the limits of possibility that a culture-tube of typhoid bacilli might be emptied into the middle of a river or be washed into a reservoir, and chemical analysis give no sign, yet no continuous natural means of contamination is known which is not accompanied by sub- stances readily detected by suitable chemical examination. In either case an epidemic may or may not result, dependent upon causes other than the mere presence or absence of the micro-organisms. If drainage from a house or barn is seen entering a stream, it does not need a dozen plate-cultures to prove that there is possible danger. Such tests may, however, when used with skill, serve to trace contamination back to its source, and is another means at the service of the trained water-works superintendent whereby he can keep a close watch over the character of his supply. As a means of control of the efficiency of filter-plants the bacterial examination is invaluable, and as a knowledge of the forms which accompany pathogenic germs becomes more certain the value of these tests will increase, even if the 84 AIR, WATER, AND FOOD. classification and identification is not perfected to scientific accuracy. It is one of the penalties of living in a large city that the water-supply must of necessity be surface-water which has been caught and stored at a distance or that which has been filched from a stream, filtered and made passable. Conse- quently education must take the place of instinct, and custom must make that acceptable which circumstances render necessary. THE INTERPRETATION OF ANALYSES. Experience in cutting through glacial moraines for rail- ways or in driving levels for mining operations does not qualify a man for exploration of a Babylonian or prehistoric mound. Human occupations have left upon the sand and clay evidences which, although so slight as to be unnoticed by the casual observer, are like an open book to him who patiently acquires a knowledge of the meaning of the dis- placements, discolorations, and enclosed fragments. Flowing water, like sand and clay strata, bears evidences of its previous history no less intelligible to him who has the key to the cipher and who adds to the keen eye of the detective and ready wit of the interpreter the sound judgment of the engi- neer. Reasoning upon insufficient premises will as often fail in the one case as in the other, while lucky guesses fre- quently encourage superficiality in both. After the analyst has entered on the blank (page 141) the six to ten records needed for a ground-water, or the fifteen to twenty for a surface-water; after the columns headed Bacteria, Diatoms, Algae, etc., have been filled in, there still remains the summing up of the case by the judge. The correct interpretation of results means a knowledge of the source, geological horizon, surroundings, probable water: the interpretation of analyses. 85 changes, and the significance of each item in this particular case. Each class of water has its own characteristics. The presence, in quantity, of any given element is interpreted according to the kind of water under consideration. Spring- water is, of course, colorless; lake-water of equal safety is probably colored. Spring-water must be, as a rule, free from ammonia; lake-water may at times contain considerable amounts without detracting from its good character. Classification of Waters. — To facilitate examination, therefore, w r aters may be divided Into three classes: first, cistern, brook, pond, and river water — so-called surface- water; second, spring and deep-well water; and third, shal- low wells and sewage effluents. Water of the last two classes has been for greater or less periods of time in contact with rock and filtered through sand, hence is designated as ground-water. A few examples taken from the different kinds of water showing the varying conditions to which they are subjected may serve to make the rules of interpretation clearer. Surface-Waters. — When rain-water falls on slated or shingled roofs and is conducted into cisterns, it carries with it whatever deposits lave collected, the pollen of forest-trees or disease-germs from city slums many miles away; from metal roofs it takes either the metal itself or the pain" used to protect the surface. In all cases, lower forms of animal life, small insects, and soot from chimneys may be present. These foreign substances should be at once filtered out with- out allowing time for organic decay, unless there is an auto- matic device for wasting the first washings of the collecting surface. There are still substances in solution which would be better away; therefore the water is allowed to stand quietly in order that the changes may have time to take place — to ferment, as it is often technically expressed. After 86 AIR, WATER, AND FOOD. this season of purification the water is again filtered and stored ready for use. There is usually color and a little am- monia, but rarely nitrates. The soluble meta's, if once pres- ent, still remain. It goes without saying that all such cisterns must be absolutely impervious to surface drainage. For lack of one or all of these precautions, cistern-water has. often been found to be contaminated from cesspools, from leaden or painted roofs, or from decaying organic mat er. Brook-water. — The rain that falls on mountain slopes of granitic or other insoluble rocks washes from them whatever- loose earth may have fallen there, and from the firmly fixed lichens the small insects and other animal forms which they harbor. These are transported in brooks to the lower lands where the organisms decay, the heavier earthy particles fall- ing out by the way. If the upland rocks and soil yield a portion of mineral salts to the water, it may come out clear and colorless even if it has not penetrated to an appreciable depth. The water from these forest brooks, after remaining im- pounded in a clean lake or reservoir, exposed to sunlight and air, often becomes the safest source of supply. As with cis- terns, so with reservoirs, filtration, natural or artificial, may take place previous or subsequent to storage, or both before and after. Lake or Mixed Water. — Lakes are fed by springs as well as by brooks, or by that portion of rainfall which passes a few inches below the surface, and is filtered before reaching the' main body. If the banks are sandy and uninhabited, the water will show good effects from this filtration; but if the seepage-water comes from a settled country, it will bring either ammonia or nitrates. The analysis will quickly show this if the water sample can be taken before it has mixed with that bearing the spores of plants which are fed by water: the interpretation of analyses. 8y nitrates. Often the very presence of these plants furnishes the proof sought. River-waters. — A large stream, especially a muddy one, may receive the drainage of half a dozen cities a hundred miles distant and yet not give conclusive evidence of dangerous contamination, while a small river with a rapid current may become unsafe from the presence of a few villages a dozen miles away. Northeastern America is so well supplied with uninhab- ited high lands for collecting-grounds, and with basins in the glacial drift for storage in natural or artificial lakes, that very few rivers need to be used after they have become polluted. The Merrimac and the Hudson are, however, so used. In other parts of the country the use of rivers is an increasing necessity, requiring municipal filter plants. From every point of view organic matter should be kept as far as possible out of running streams which may at any- time be needed for public supplies, or the natural purifica- tion by algae should precede the final filtration and storage. It is quite probable that this double treatment may be more frequently required as unpolluted water becomes more scarce. What the method of filtration shall be depends upon the character of the water, whether clear or turbid with clay, whether certainly polluted or only with a remote possibility of contamination. Each problem must be studied by itself without prejudice in favor of any one method. It is the re- sult which must be kept in mind, namely, the furnishing of safe and acceptable water to the community. Effect of tJie Storage of Surface-water. — In interpreting his results, the analyst should take into acccunt the influence which the keeping of water in basins has upon its character. Storage of surface-water is of utmost importance in all cases- gg AIR, WATER, AND FOOD. of doubt. Most disease-germs find such water an unfavor- able medium for prolonged life, since exposure to sunlight soon destroys the darkness-loving bacteria, and a certain sterilizing effect results from the growth of green alg?e, so that water considerably polluted becomes purified if given time for the various agents to do their work; but time is essential. Odors. — For surface-waters one of the links in the chain of evidence is found in the odor, cold and hot, which to the trained and sensitive nose often gives convincing testimony. A musty odor, unmistakably different from a mouldy vege- table smell, betrays sewage contamination even when the chemical analysis might not be convincing. This odor is not always taken out. by filtration, neither is that of certain or- ganisms growing in stored water, notably Anabcena and Synurd. A study of these organisms is invaluable to the routine observer who watches the seasonal and annual changes in his reservoir. Turbidity and Sediment. — The determination of turbid- ity and sediment, added to the odor, tells much to the expert, but very little to the inexperienced student. Turbidity may be due to drainage contamination, to growth of bacteria, to clay, to iron, to swarms of micro-organisms. Sediment may be sand, zooglea, fragments of plants or animals, or ferric oxide. Filtration. — The subject of filtration has been so exten- sively treated elsewhere that the student is referred to the bibliography on page 263. There are cases in which it is preferable to run the risk of too much alum in the drinking- water, and too much sulphuric acid in boiler feed-water, rather than of too many micro-organisms with the accom- panying organic matter. It will have been noticed that the ideal natural water is water: the interpretation of analyses. 89 that which has been earth-filtered, and thus all suspended matter, including microbes, has been removed. This sup- poses that sufficient time has elapsed so that all decomposing organic matter has been destroyed. Man tries to imitate nature's processes, but expects to accomplish it in moments instead of months. The era of house-filters, those admirable culture-grounds for bacteria, is happily nearly past. Taxpayers are becoming convinced that a good original water-supply in competent hands is worth paying for. Where straining only is needed, a flannel bag washed daily is as efficient as any faucet-filter. If the latter takes out color as well, it should be closely watched. Water should not be first boiled and then filtered, but first filtered and then boiled. Summary. — Surface-water. — In general it may be said that the waters of the first class found in New England are generally more or less colored, and contain more or less sus- pended organic life and its debris, which often impart a de- cided odor to the water. These waters, draining for the most part wooded and sparsely populated regions, are low in free ammonia, nitrates, and nitrites; low, also, in mineral salts, and with only a slight excess of chlorine over the normal. They are usually high in organic matter and albuminoid am- monia even when entirely free from pollution. In other parts of the United States surface-waters may be low in color, but with much suspended clay and silt, and may hold in solution notable quantities of mineral salts. The latter aid greatly in the clarification by artificial filtration, which is so often rendered necessary by the excessive turbid- ity even if not by sewage contamination. In Table IV, page 239, will be found examples showing at a glance how profoundly the character of a water is affected by the geological horizon, whether its source is in the glacial 90 AIR, WATER, AND FOOD. drift of the Appalachian region, or in the limestone of the Hudson River Valley, or in the saline deposits of the sub- sided areas. Deep Wells and Springs. — The waters of the second class are derived from the depths of the earth, far below any pos- sible surface contamination, and have long been imprisoned in the dark and cold, and often subjected to great pressure, The influence of pressure on organisms has not been entirely worked out, but from what is known it is probably very un- favorable to the life of the lower organisms. The results of many bacterial examinations have been vitiated by the diffi- culty of securing a sample from great depths without con- tamination by surface exposure — pipes open to the air har- boring many forms of life. Deep wells, 700 feet and more, are not likely to be dan- gerous. They may often contain ammonia from prehistoric coal-fields or tertiary deposits, but rarely nitrates. This is accounted for by the fact that " the result of the changes of the nitrogenous organic substances which fall into the earth is, without doubt, frequently the formation of gaseous nitro- gen." Also, that " salts of nitric acid on penetrating into the depths of the earth give up their oxygen." * Owing to their long sojourn in the depths of the earth, these waters are higher in mineral substances than surface- waters. Since their origin is unknown, the chlorine cannot be correctly gauged, especially as there are saline waters deep down in rock cavities in all parts of the world. It is usually believed that these deep wells furnish a safe, palatable water when the kind and amount of mineral matter is not objectionable. Shallow Wells. — It is not to be wondered at that waters * Mendeleeff : "Chemistry," p. 223. water: the interpretation of analyses. 91 of the third class — ground-water, taken from just beneath the surface layers of the soil — should contain many sub- stances foreign to the waters about them as well as to those at greater depths. The shallow wells, which are practically more or less diluted sewage effluents, present the greatest variety. They may be clear and colorless and show as great organic purity as the best mountain spring. In other cases, the overworked filter permits the passage of organisms and undecomposed material. In either case there will be found those compounds which, being soluble and stable, are car- ried with the water as signs to be read by him who knows the language. A complete history of each specimen of this class of ground-water is desirable, and with sufficient patience and care it may be obtained with reasonable accuracy, if the principles governing the circulation of water and the changes of the organic matter it carries be kept well in mind. It is certain at once that absence of color, of organic mat- ter in any form, and of odor should be insisted upon, for ground-water is filtered water and the filter should be doing its work. A modicum of geological knowledge is essential, as the presence of shaly or slaty rock will permit the passage into underground water of surface drainage with less purification than will a granite or sandstone region. A clayey soil is a less efficient filter than a sandy loam and permits the pollution to travel farther. Nitrogen in Well-water — It may be taken as an axiom that the only form of nitrogen permissible in a good ground- water is that of nitrates, a fully oxidized or mineralized food for green plants. If nitrites are also present, a source of pollution is at hand, for, as has been said, nitrites indicate either a stage of oxidation not completed or one of reduction from nitrates in the presence of organic matter. If free am- 92 AIR, WATER, AND FOOD. monia be present, it is safe to say that the source is not only near but in actual contact, since but a few hours' time is needed to oxidize the ammonia in any soil not waterlogged. It may also be pretty safe to assume that bacteria are present, since ammonia is the first stage of that decomposition which they accompany. It is the part of prudence, therefore, to avoid any water which contains both free ammonia and nitrites above .200 or .300 parts per million of the first, and .020 or .030 of the second. The absorption of nitrogen by plants is rarely complete, so that it usually appears in far larger quantities in contami- nated ground-waters than could be obtained from purified rain-water. The leaching cesspool discharges its liquid con- tents below the zone of green-plant life; fertilized soil also yields a portion of its food value to the lower layers. A small portion of the nitrogen of vegetable origin may appear as nitrates, but only as a derivative of soil rich in humus is it likely to play any considerable part. In eastern America nitrates above 0.5 parts per million would arouse suspicion, ;and above 5 parts would in most cases prove previous por- tion. It is evident that in the use of nitrogen as an indicator of the conditions of a water we are limfted, by the changeful character of the compounds, to certain not-to-be-mistaken amounts, and that in the majority of cases the evidence given is not decisive. v Chlorine in Well-water. — Fortunately there is another ele- ment not so eagerly sought for by plants and not liable to so many transformations. Thanks to the great solubility of its common compounds and to their stability, chlorine, once a constituent of a given body of water, is not extracted there- from and remains as a telltale to reveal the past history of a stream or spring. If a man is judged by the company he ./? J vnt y># STATE BOARD OF HEALTH MAP OF THE STATE OF MASSACHUSETTS. ^^£^1 SHOWING The ** NORMAL CHLORINE. WATER: THE INTERPRETATION OF ANALYSES. 93 keeps, much more a water-supply. From sewage all the nitrogen may be removed and the chlorine still remain. But in order to use this information with any degree of certainty the normal chlorine of the locality must be known. If a map showing isochlors has been made of the region or State, and if there are no geological deposits to interfere, this is easy; but if the chemist or engineer has an unknown coun- try to report upon, it will be necessary to examine the local conditions and to choose six, eight, or ten samples of prob- able freedom from contamination and to test them for com- parison. The sources of the excess of chlorine over the normal are usually the sink-drain with its burden of salted water from domestic operations; the house-drain, with its chlorine-containing excreta; and the stable-drain, with a slight chlorine content in comparison with the other two. Mineral Substances. — Since water Is a universal solvent, it is not surprising to find considerable amounts of mineral matter in the two columns " Total Solid Residue on Evapo- ration " and " Hardness." How much calcium sulphate or magnesium chloride or other soluble mineral is allowable in a potable water is for the physician rather than the chemist to say. As has been said, the human system possesses great adaptability, not only for different foods, but for mineral sub- stances water-carried. Not so the steam-boiler or the laundry- tub, which reacts very sensitively and affects the pockets of the consumers. In a region of soft water, high solids with chlorine and nitrates indicate sewage pollution. Silica is much more commonly present even in surface- waters than is often supposed. What its effect may be is unknown. Iron is not uncommonly found in combination with organic matter in either surface or imperfectly filtered waters in contact with soils poor in calcium salts. It is fre- quently accompanied by free ammonia, which causes an 94 AIR, WATER, AND FOOD. abundant growth of Crenothrix. It is also present in deep wells in the form of carbonate, which precipitates on exposure to warm air. In a considerable number of cases of public water-supply there is a mixture of surface and ground water which com- plicates the verdict, requiring a most delicate balancing of probabilities. The mineral contents often aid in this deci- sion. Well-waters, too, are often exposed to surface-wash because of poor protection at the mouth. Cyclops or other surface-water organisms often indicate this. Water-pipes. — After all, if the pipes conveying the water are of lead or brass, an additional danger appears. Gen- erally speaking, the purer the water the greater the risk. No common metal seems to withstand the action of soft water; six to eight years being the average age of galvanized pipe, and eight to ten of iron pipe. It would seem as if wooden pipe must come into greater use until some kind of glass is invented which will withstand this corrosive action and yet admit of plumber's connections. Value of Tests. — It is often asked if some tests cannot be made by the ordinary person of average intelligence which will enable him to tell the quality of a water as well as the expert to whom he pays ten or twenty dollars for an opinion. A careful perusal of the preceding pages will have answered the question in the negative. There is no assay of water as there is of gold and silver. Not one but ten or twenty tests must be made. Not only must the tests be made with the utmost care and cleanliness of person, utensils, and room, but the results must be studied in the light of other experience and other knowledge, geological and biological, and after all this is done there is an array of circumstantial evidence which must be carefully weighed by one whose judgment and experience enable him to read clearly where another might water: the interpretation of analyses. 95 see nothing. The value of a water-analysis is in direct pro- portion to the knowledge and experience of the one who interprets it. Clinical skill in addition to theoretical knowl- edge is required to interpret the figures obtained in the course of a water-analysis, as in the symptoms of a disease: and the analogy goes still further, for as some diseases are clearly defined, others are so complicated that only those who have had long experience can outline a safe course, of treatment; so some waters bear the marks of their character so plainly as not to admit of mistake, while others require most careful study. For these reasons the value of water-analysis should not be decried because the fears aroused by reports given by unskilled analysts prove groundless, any more than the prac- tice of medicine should be discarded because inexperienced men make mistakes. Is the water in any given case safe for drinking? To an- swer this question there is needed a knowledge wider than a chemist's of the relation of decaying organic matter and of the germ-carrying power of water to outbreaks of disease. There must be added the knowledge of the biologist, the en- gineer, and the sanitarian. CHAPTER VII. ANALYTICAL METHODS.* General Statements. — Water-analysis cannot be carried on in an ordinary laboratory. In order to obtain satisfactory results it is necessary to have a room set apart for the pur- pose, and to exclude rigidly all operations which tend to the production of fumes or dust. Where such minute traces of substances are dealt with as in water-analysis, too much care cannot be taken to insure the absolute cleanliness of the ap paratus and the surroundings. It is desirable that the room be well lighted, and if possible the windows should face toward the north. The methods for the examination of water which are de- scribed in this chapter by no means comprise all that are in use. The directions are given for the use of students in our own laboratory under the conditions obtaining, i.e., of large classes and of several courses of study, with especial reference to educational rather than purely technical needs, and in some cases, no doubt, the traditions of thirty years may have unduly persisted. The methods have been so selected as to intro- duce a variety of apparatus and to illustrate principles. They have also been subjected to a thorough test in meeting the demands of practical work. Collection of Samples.— -F or the collection of water sam- ples, glass-stoppered bottles of about a gallon capacity are best. Those used in this laboratory are of white glass, fifteen inches high to the top of the stopper, five and a half inches * See Report of Committee on Standard Methods of Water-analysis, Jour, of Infectious Diseases, Supplement No. I, May, 1905. 96 water: analytical methods. 97 in diameter, and weigh about three pounds. They have flat,, mushroom stoppers, on which is engraved a number to corre- spond with that on the bottle. The bottles, before being sent out, are thoroughly cleaned with potassium bichromate and sulphuric acid, washed with distilled water and dried. If glass-stoppered bottles are not at hand, new demijohns fitted with new corks may be used. A glass bottle or a demijohn is much to be preferred to an earthenware jug, because, if for no other reason, it is so much easier to be sure that the interior is clean. It should always be borne in mind that in water- analysis the question is one of very minute quantities of mate- rial, and that the methods to be employed are extremely delicate. Hence, in the case of many waters, careless hand- ling of the sample would contaminate the water to a sufficient: extent to render valueless the results obtained in the labora- tory. In collecting samples, the following directions should be closely followed: * Directions for Collecting Samples for Analysis — From a Water-tap. — Let the water run freely from the tap for a few minutes 'before collecting the sample. Then place the bottle directly under the tap and rinse it out with the waler three times, pouring out the water completely each time. Place it again under the tap; fill it to overflowing and pour out a small quantity so that there shall be left an air-space under the stopper of about an inch. Rinse off the stopoer with flowing water; put it into the bottle while still wet and secure it by tying over it a clean piece of cotton cloth. Seal, the ends of the string on the top of the stopper. Under no circumstances touch the inside of the neck of the bottle or the stem of the stopper with the hand, or wipe it with a cloth. From a Stream, Pond, or Reservoir. — Rinse the bottle and. * Ann. Rep. Mass. State Board of Health, 1890, p. 520. 98 AIR, WATER, AND FOOD. stopper with the water, if this can be done without stirring | up the sediment on the bottom. Then sink the botlle, with the stopper in place, entirely beneath the surface of the water and take out the stopper at a distance of twelve inches or more below the surface. When the bottle is fu 1 replace the stopper, below the surface if possible, and secure it as directed above. It will be found convenient, in taking samples in this way, to have the bottle weighted so that it will sink be- low the surface, and to remove the stopper by a cord. It is important that the sample should be obtained free from the -sediment at the bottom of a stream and from the scum on the surface. If a stream should not be deep enough to admit of this method of taking a sample, dip up the water with an absolutely clean vessel and pour it into the bottle after the latter has been rinsed. The sample of water should be collected immediately be- fore shipping by express, so that as little time as possible shall intervene between the collection of the sample and its examination. All possible information should be furnished •concerning the source of the water and of possible sources of contamination. For example, in the case of a well, the prox- imity of dwellings, cesspools, or drains should be recorded, and the character and slope of the soil, whether toward or away from the well, should be noted. In the case of a sur- face-water, mention any abnormal or unusual conditions; as, for instance, if the streams or ponds are swollen by recent heavy rains, or are unusually low in consequence of prolonged drought, or if there be a great deal of vegetable growth in or on the surface of the water. Record, in short, any circum- stantial evidence which by any possibility may aid in the final judgment. The question of proper collection of samples is an impor- tant one, and the chemist is perfectly justified in refusing to water: analytical methods. 99 give an opinion in regard to the purity of a water which he has not himself collected. The ignorance and carelessness shown by people who send samples for analysis are often- times quite amusing. Samples have been received at this laboratory in almost every kind of container imaginable, from an imperfectly rinsed whisky-bottle to a discarded syrup-jug, with about an inch of maple sugar in the bottom. One sam- ple was sent all the way trom Georgia in a stone jug with a corn-cob inserted for a stopper. Others are received with the stopper carefully (?) protected by a mass of sealing-wax or candle-grease. A favorite way is to send the sample in a fruit-jar packed in sawdust or straw. Opinions evidently differ greatly, too, in regard to the size of sample that is needed. It is no uncommon occurrence to have a person come into the laboratory with the remark, " Here is a sample of water that I want analyzed," supplemented by the produc- tion from a coat-pocket of a homoeopathic vial or a sample of half a pint or so of water. Of course, in cases like these practically nothing can be done. Preparation of the Sample for Analysis. — Since changes in the composition of a contaminated water are constantly going on, the analysis of the sample should be begun without •delay. The bottle is held under the tap, and the neck and stopper are washed free from adhering dust. The stopper Is rinsed off with some of the water from the bottle. Qualita- tive tests should be made for ammonia, nitrites and chlorine. With waters containing much suspended matter, and in the case of surface-waters in which it is desired to distinguish between the organic matter in solution and that in suspen- sion, a portion of the water should be filtered. In most cases the suspended matter can be removed by filtration through paper. For this purpose only the best Swedish filter-paper should be used, and the filters should be first IOO ATR, WATER, AND FOOD. thoroughly washed with ammonia-free water. With some waters containing very finely divided clay in suspension, fil- tration through paper will not be satisfactory, and the sample must be filtered by suction through a cylinder of ung'azed porcelain, such as an ordinary Chamberland-Pasteur hi er- tube. In the filtered water it is customary to determine the dissolved solids, the albuminoid ammonia, or the organic nitrogen, and the color. Determination of Free and Albuminoid Ammonia — Apparatus* — The apparatus used for the determination of ammonia is that shown in Fig. 8. It consists of a round-bottomed flask of 900 c.c. capaci- ty, with square shoul- ders and a narrow neck five inches long, and an ordinary Liebig con- denser fitted with an. inner tube of block tin,, 3 / 16 of an inch in diame- ter. The flask is closed by a cork carrying a glass tube bent nearly at right angles, which slips for some distance within the tin tube cf the condenser. A tight joint is made by means of a large cork, which is shown in section in Fig. 9. The large cork serves the double purpose of making a tight joint with the ScaleJHin.= lfoot. Fig. 8. — Apparatus for Ammonia Dis- tillation. * A. H. Gill : /. Anal, and App. Chem., 6 {1892), 669. WATER: ANALYTICAL METHODS. IOI condenser and also as a convenient means for handling- the small glass tube. In order to remove the cork from the dis- tilling-flask, the glass tube carrying it is simply turned to one side, using the large cork as a pivot. The flasks are heated with the free flame of a Bunsen burner. New flasks are treated with boiling dilute sulphuric acid and potassium bichromate before they are used. New corks should be steamed out for one or two hours. A good, sound cork will last for several months with daily use. The dis- ssssssssssssssssssss/ss/.'/ . n - "~-.^'"-~~ ■ - , ■— 7-.,./. , ' — CORK JO I NT Full Size Fig. 9. tillates are received into small 50-c.c. flasks and poured into Nessler tubes for nesslerization. The Nessler tubes are 11 inches long and f-inch internal diameter, the 50-c.c. mark being about two inches from the top. It is desirable to so arrange the apparatus as to collect the distillates directly in the Nessler tubes and at the same time render the apparatus more compact by having several condenser tubes run through a common cooling tank. For class work, however, the appa- ratus just described has been found most suitable. Directions. — Free the apparatus from ammonia by dis- tilling off the water in the flask, testing each 50-c.c. portion of the distillate until no color is given with the Nessler re- agent. When the distillate is free from ammonia, pour the 102 AIR, WATER, AND FOOD. water left in the flasks into the bottle marked " Ammonia- free residues." Shake the bottle thoroughly to mix the sample. For determining the ammonia measure out in a calibrated flask a portion, usually 500 ex., the amount taken depending upon the result of the qualitative test. Pour this into the distilling- flask, and distil over three portions of 50 c.c. each into Nessler tubes or into the graduated flasks. In dealing with sewage or sewage effluents, which are very high in free ammonia, if the ammonia were collected in three portions, so much would distil over in the first portion that the color given with Nessler's reagent would often be too deep to read or a precipitate might form. To avoid this the total distillate of 150 to 175 c.c. is collected in a 200-c.c. graduated flask, made up to the mark, thoroughly mixed by pouring, and then 50 c.c. of it taken for nesslerization. In this way the ammonia is distributed more evenly in the distillate and the determination is not sacrificed. Notes. — When the amount of ammonia shown by the quali- tative test is high — i.e., shows a color equivalent to I. c.c. of the standard ammonia solution — a less quantity than 500 c.c. should be taken for the distillation, 100 c.c. or, in the case of sewage, even 10 c.c. being diluted to 500 c.c. with water free from ammonia. Sewage and soils may be distilled with steam in the apparatus figured on page 106 under the Kjeldahl pro- cess. After the free ammonia has been distilled off, allow the contents of the flask to cool slightly; then add 40 c.c. of alka- line permanganate through a funnel, taking care that none of the alkaline soluion touches the neck of the flask, and proceed with the distillation of the albuminoid ammonia; that is to say, the determination of the nitrogen of the undecomposed organic matter. With colored surface-waters distil off five water: analytical methods. 103 portions of 50 c.c. each; with waters of low organic content three or four portions will suffice. In order to obtain about one half the total organic nitrogen regulate the height of the flame so that the time of distilling 50 c.c. shall not be more than eight and not less than five minutes. It is impossible to convert all of the organic nitrogen into ammonia by boiling with alkaline permanganate. The amount of ammonia which is thus obtained depends not only upon the character of the substances, but also upon the concentration of the solution and the rate of boiling. In order that the albuminoid ammonia in potable waters shall bear some definite relation to the total organic nitrogen, it is necessary that these conditions shall be duplicated as nearly as possible in different determinations; that is, the alkaline permanganate must be added to a definite volume of the water, and the boiling must be carried on at a definite rate. Some of the highly colored surface-waters give up their nitrogen very slowly by this treat- ment; polluted waters, on the other hand, yield the ammonia more rapidly, so that the observation of the relative amounts found in the successive portions is of the utmost importance in forming a judgment. Have the Nessler tubes clean and thoroughly rinsed with ammonia-free water. Unless permanent standards are used prepare standards by adding to Nessler tubes nearly filled. with ammonia-free water varying quantities of the standard, ammonium chloride solution; for instance, 0.1, 0.3, 0.5, 0.7, 1.0, 1.3, 1.5, 2.0, 2.5, 4.0, 6.0 c.c. The standard ammonium chloride solution contains .00001 gram N in one cubic centimeter. Mix the contents of the tubes by rotating them between the palms of the hands (never shake them like a test-tube or stir them with a rod), allow them to stand for two or three minutes, and add 1 c.c. of the Nessler' s reagent to the whole io4 AIR, WATER, AND FOOD. set, and to the samples to be tested, as rapidly as possible. At the end of ten minutes match the colors and record the amount of ammonia. As an example of a colored surface-water may be given the following results from distilling 500 c.c: Free Ammonia. Albuminoid A mmonia. 1st 50 C.C, 0.7 C.C. 1st 50 c.c, 4.5 c.c 2d 50 C.C, 0.3 C.C 2d 50 c.c, 2.8 C.C 3d 50 C.C, 0.0 c.c. 3d 50 c.c, 4th 50 c.c, 5th 50 c.c, 1.5 C.C. 1.0 C.C 0.5 c.c 1.0 c.c. 10.3 cc. In this case the free ammonia would be 0.020 and the albuminoid ammonia .206 parts per million. In the case of water from suspicious wells and of sewage effluents, about 0.5 gram of freshly ignited sodium carbonate should be added before distillation, in order to make sure that the reaction of the water is not acid, and to decompose any urea which may be present. This will not be necessary with ordinary surface-waters, as experience has shown that they almost always have a slight alkaline reaction. A depth of color given by 6 c.c. of the standard ammonium chloride with the Nessler reagent is about the limit of satis- factory comparison in the 11-inch 50 c.c. tubes. The color given by 10 or 12 c.c. of the standard may be matched in the 100 c.c. tubes with a depth of 5 inches and a diameter of ij inches. For most cases where great exactness is not essential it is possible to divide the 50 c.c. or the 100 c.c. into two equal parts by pouring into a tube the exact counterpart of the standard tube and matching the color. It is even possible to closely approximate the correct result by the use of a foot rule. The standard is, we will assume, 5 c.c. The height of liquid in water: analytical methods. 105 the tube to be tested, we will call 9 inches. If the height of the column left which matches 5 c.c. is 3 inches, then the reading was 15 c.c. of the standard. The limit of solubility of the mercur-ammonium iodide is reached at 25 or 30 c.c. of the standard in 50 c.c. The incipient precipitate not only changes the color of the solution but causes a slight milkiness or turbidity which prevents a sharp reading of the color. The test is an excellent example of quantitive color work when carried out under strictly comparable conditions. It should perhaps be stated that in both the ammonium and nitrite determinations, as also in that of iron, dilution of the sample in which the color is already developed does not give a correct result. Therefore dilution if necessary must be made before the reagents are added. In order to secure the most accurate results it is impor- tant that the temperature of the distillates to be nesslerized and of the standards be the same, since the warmer solutions give a more intense color with the Nessler reagent. The compounds produced by the action of ammonia on mercuric solutions are considered as substitutions of 1 Hg for 2H in NH 4 , and are called mercur-ammoniums. Tetra- mercur-ammonium iodide (NHg 2 I), the compound formed by addition of the Nessler reagent, is a brown precipitate, sol- uble in excess of KI in the presence of KOH with a brown- ish-yellow color proportional within certain limits to the amount of NH 3 : NH 3 + (2HgI 2 + 2KI + 3KOH) = NHg 2 I + 5KI + 3H2O. The " free ammonia " in all probability does not exist in the water in a free state or as the hydroxide; it is probably present in the form of carbonate or of chloride. When water containing these or similar compounds of ammonia is boiled, they are decomposed and free ammonia passes off with the io6 AIR, WATER, AND FOOD. steam and is found in the distillate; hence the origin of the name. Determination of Total Organic Nitrogen by the Kjeldahl Process — Directions. — Measure 500 c.c. of the water into a round-bottomed flask of 750 c.c. capacity and Fig. 10. — Apparatus for Distilling Ammonia by Steam. boil until about 200 c.c. have been driven off. (The free ammonia which is thus expelled may be determined, if de- sired, by connecting the flask with a condenser.) Allow the water remaining in the flask to cool, and add 10 c.c. of pure concentrated sulphuric acid free from nitrogen. Mix by shaking; place the flask in an inclined position on wire WATER. ANALYTICAL METHODS. IO7 gauze under the hood and boil cautiously until the water is all driven off. Place a small funnel in the neck of the flask to prevent the escape of acid fumes, and continue the heating for at least half an hour after the sulphuric acid becomes white. Meanwhile rinse out the distilling apparatus (see Fig. 10), and free it from ammonia as usual. Then, after the acid in the digestion-flask has cooled, rinse down the neck of the flask with ioo c.c. of ammonia-free water and attach the flask to the distillation apparatus. Add ioo c.c. of potassium hydroxide solution through the separatory funnel and distil off the ammonia by steam, receiving the distillate in a 250-c.c. graduated flask. Conduct the distillation rather slowly until the first 50 c.c. have distilled over, then distil more rapidly until about 175 c.c. have been collected. Make the volume of the distillate up to 250 c.c. with ammonia-free water, mix it thoroughly and take 50 c.c. for nesslerization. Notes. — The principles involved in the method consist in the oxidation of the carbon and hydrogen of the organic mat- ter by boiling sulphuric acid, the nitrogen being converted into ammonia and held by the acid as ammonium sulphate. The ammonia is then liberated and distilled off. from an alka- line solution. The use of mercury and of. potassium per- manganate to assist in the oxidation has been found to be unnecessary, as the organic matter in natural waters is much more easily oxidized than in other substances,- — flour, for in- stance. The presence of nitrates and nitrites in waters has not been found to interfere with the accurate determination of the organic nitrogen. The error which has been found by Kjeldahl and Warrington to be caused by the presence of nitrates seems to disappear when the organic material is diluted to the considerable extent that exists in natural waters. The high chlorine found in some well-waters does 108 AIR, WATER, AND FOOD. not interfere with the method to any extent, but this deter- mination does not possess much value in this class of waters, which are low in organic nitrogen. In carrying out the digestion with sulphuric acid, the greatest care must be taken to prevent access of ammonia or dust from any source. The acid solutions will absorb am- monia from the air or from the dust of the laboratory if they are allowed to remain uncovered for any length of time. This source of error may in some instances be sufficiently large to render a determination valueless, even in a room which is to all appearances free from ammonia-fumes. Hence the operation should, if possible, be carried to com- pletion within twenty-four hours, and for every set of deter- minations a blank analysis should be made with ammonia- free water in order to make a correction for the ammonia in the reagents, and for that accidentally introduced during the process. As the result of many hundred comparative determina- tions of the organic nitrogen and of the albuminoid ammo- nia in natural waters which take their origin in the glacial drift, it has been found that the nitrogen given by the albu- minoid-ammonia process as directed in the previous pages is about one-half of the total organic nitrogen as given by the Kjeldahl process; in the case of sewages and polluted waters it is very variable owing to their irregular composition. Determination of Nitrogen in the Form of Nitrites. — Directions. — When the determination of the free and albuminoid ammonia is well under way, the estimation of nitrogen in the next stage of decay, that of nitrites, should be begun. If the water is colorless, measure out the required amount, usually ioo c.c, into a ioo-c.c. tube. If the water possesses color which cannot be removed by simple filtra- tion, it should be decolorized as follows: Thoroughly rinse water: analytical methods. 109 with the water a 250-c.c. glass-stoppered bottle; pour into it about 200 c.c. of the sample, add about 3 c.c. of the milk of alumina and shake the bottle vigorously. Let the bottle stand for ten or fifteen minutes and filter through a small plaited filter which has been thoroughly washed with water free from nitrites. From this filtrate take 10 c.c. for nitrates (see p. no). To 100 c.c. of the filtered sample or of the origi- nally colorless water add 10 c.c. of sulphanilic acid in acetic acid and 10 c.c. of naphthylamine acetate. After standing 5 to 10 minutes, not longer, compare with the standards made with the nitrite solution or, better, with 2x4 inch pieces of Milton Bradley's standard papers* the VR, violet-red tint 2 which is an exact match for the color given by 5 c.c. or VR, tint 1, which matches 10 c.c. of the stand- ard nitrite solution in a ioo-c.c. Nessler tube with a depth of 5 inches to the graduation. If 100 c.c. of the sample is used this measures the nitrites in parts per million. Good waters show considerably less than .005, suspicious waters between .005 and .010, bad waters may show from .000 to .300 or even more. The same use of the foot rule and aliquot part may be made as above in the ammonia determination. One cubic centimeter of the standard nitrite solution contains 0.0000001 gram N as nitrite. The determination must be completed within half an hour, since the air of a room in which gas is burned contains nitrites. f Notes.— If the color obtained is more . than . that given by 20 c.c. of the standard solution, as it may. be in the case of water from bad wells and sewage effiuents,. the water should be diluted with nitrite-free water, 10 c.c. or even 1 c.c. being made up to 100 c.c. before adding the reagents, since colors * Mulliken's "Identification of Pure Organic Compounds,"' Sheet A, Color Standard. f Defren: Tech. Quart., g (1896), 238; Axson: loc. cit., 12 (1899), 219. IIO AIR, WATER, AND FOOD. above 20 c.c. are too deep for accurate comparison. In many- cases, however, it may be more convenient and sufficiently accurate, where the colors are not very much greater than 20 c.c, to read the color in an aliquot part, as described in the determination of ammonia on page 104. The reactions which take place consist first in the diazotiz- Ing of the sulphanilic acid by the nitrite present in acid solu- tion, forming diazobenzenesulphonic anhydride. This reacs with the naphtylamine hydrochlorate, forming azo-or-amido- naphtylic parabenzol-sulphonic acid, which gives the pink color to the solution, the amount formed depending upon the amount of nitrite present. ' N ■ N H I: J i H— C C— H H— C C C— H II I I II I H— C C— H H— C C C— H v/ \/\// c c c I I I SO3H NH a H Determination of Nitrogen in the Form of Nitrates.* — Directions. — Nitrogen in the fourth stage, that of nitrates, is next determined. In the case of ground-waters, or sewage effluents, measure 2 c.c. from the bottle with a capillary pipette, into a three-inch porcelain evaporating-dish; for surface- waters, always low in nitrates, take 10 c.c. from the portion already decolorized in the determination of the nitrites. Place the dishes on the top of the water-bath and let their contents evaporate gently until one or two drops are left; then set them away in a place free from dust, that the remainder may evapo- rate spontaneously. Do not let them go quite to dryness on the bath. * Sprengel: Pogg. Ann., 121, 188. Grandval and Lajoux: CompL rend. y 101, 62. Gill: J. Am. Chent. Soc, 16 {1894), 122. water: analytical methods. hi When the water is entirely evaporated, drop six drops of phenol-disulphonic acid directly upon the dry residue and rub it around with a glass rod to insure complete contact of the acid and the residue in the dish. Dilute the acid with 7 ex. of distilled water and add 3 c.c. of ammonium hydrate (1:1) or if only one laboratory is available KOH (1:3) since no ammonium hydrate solutions should be allowed in a distilling laboratory. To prepare the standards to be matched in the small porce- lain dishes, measure out the varying amounts of the standard nitrate solution, for instance 0.5, 1.0 c.c. to 8 c.c, add enough water to make the volume 10 c.c. and two or three drops of the alkaline hydrate. For very low or very high colors the matching is most satisfactorily done in 50-c.c. Nessler tubes, diluting to 50 c.c. or reading an aliquot portion. For matching the lowest colors, which in this case is safely done, 5 or 6 inch high tubes cut from broken Nessler tubes are very satisfactory. To prepare standards in Nessler tubes. A portion of water is made alkaline, and the standard is run in little by little until it matches the lowest color. Then more is added until the next color is matched, and so on to the highest color. Notes. — It will be found that if 10 c.c. of a colored water be evaporated directly, the color obtained with the reagents will be much deeper as well as browner than that given by the standards; hence the necessity for first decolorizing. Chlorides interfere with the accuracy of the method, but not to any extent when chlorine is present in less than 20 parts per million. If the amount of chlorine be more than this, the evaporation should be made in vacuo over sulphuric acid. Nitrites do not interfere with the test. The reaction is generally considered to consist in the formation of picric acid. While this is not quantitatively true, it offers the best explanation of the changes that occur. II 2 AIR, WATER, AMt> FOOD. Trinitrophenol (picric acid) is formed by the action of the nitrates in the cold, dry residue upon the phenol-disulphonic acid with which it is moistened: OH OH l A H— C C— SO,H NO,— C C— NO, || | J- 3 HNO,= II | +2H,SO. H— C C— H H— C C— H \ // \ / + H,0 C C I I SO.H NO, Phenol-disulphonic acid. Picric acid. The addition of an excess of caustic alkali converts the picric acid to the alkali picrate, which imparts an intense yel- low color to the liquid. The best color is obtained by the use of ammonia. Large quantities of nitrates in colorless water may be de- termined by reduction to ammonia by sodium amalgam, or by any reaction which yields nitrogen, this being measured as gas. Determination of the Carbonaceous Matter or " Oxy- gen Consumed." KubeVs Hot Acid Method. Reagents. — Ammonium oxalate 0.888 gram in one liter distilled water. One c.c. is equivalent to 0.0001 gram of oxygen. Potassium permanganate 0.4 gram in one liter dis- tilled water, standardize against the ammonium oxalate solution and make the necessary correction. If exact, 1 c.c. is equivalent to 0.0001 gram available oxygen. Directions. — Measure 100 c.c. of the water into a 250-c.c. flat-bottomed flask, add 10 c.c. of sulphuric acid (1:3) and about 10 c.c. of the potassium permanganate. Place the flask oh wife gauze and heat it quickly to boiling. Boil the solution for exactly two minutes; remove it from the flame; let it cool one minute, and add 10 c.c. of the ammonium oxalate. Titrate water: analytical method. 113 with the permanganate to a faint permanent pink color. Each c.c. of the exact permanganate used in excess of the oxalate solution used represents 0.0001 gram of oxygen consummed by the sample. Notes. — For highly colored surface-waters 25 c.c. are taken and diluted to 100 c.c. with water free from organic matter; for sewages 10 c.c. are diluted in the same way. The oxygen given up by the permanganate combines with the carbon of the organic matter and perhaps to a cer- tain extent with the hydrogen, but not with the nitrogen. The amount of oxygen consumed bears some relation, there- fore, to the amount of organic carbon present in the water r but this relation certainly cannot be taken as a definite one in every case, the results varying even with the time of boiling. The method has its greatest value when it is used to compare waters of the same general character and having the same origin; for example, in making periodical tests of the purity of the effluent from a filter. Furthermore^ in order that the results shall have this comparative value, it is absolutely necessary that the process shall always be carried out in exactly the same way, even to the minutest detail of quantity, time, and temperature. In some cases it may be found advantageous to heat the solution upon the water-bath for half an hour instead of boil- ing it for five minutes. The results, however, will not be exactly comparable with those obtained by boiling. - Different kinds of organic matter behave differently with various oxidizing agents, so that a comparison of the results obtained with different oxidizing agents may throw light upon, the character of the organic matter, as well as i f s amount.* In waters from the watersheds of eastern Nor^h America the color and the oxygen consumed have a certain, though somewhat varying, relation, , I < Determination of Chlorine, r^The chlorine is deter- mined in natural waters by the method in general use; * Woodman: /. Am. Chem. Soc, 20 (rSgS), 497. 114 AIR > WATER, AND FOOD. namely, titration with a solution of silver nitrate, using potas- sium chromate as an indicator. Since the exact change of color which constitutes the end-point will vary with the sensitiveness of the eyes of different observers to red, each person should standardize the silver nitrate solution for him- self. To do this, measure into a six-inch porcelain dish 25 c.c. of distilled water; add 5 c.c. of sodium chloride solution (1 c.c. — 0.001 gram CI) from the burette and three drops of potassium chromate solution. Titrate with the silver nitrate solution until the yellow color of the liquid assumes the faint- est tinge of reddish brown. Directions. — Waters which are high in chlorine, i.e., which contain 20 or more parts per million, are titrated directly, using 25 c.c. either with or without the addition of 5 c.c. of the salt solution. Waters which are low in chlorine are con- centrated before titration, 250 c.c. being evaporated to 25 c.c. on the water-bath. Brown surface-waters should be decol- orized as follows: Pour into a 750-c.c. flat-bottomed flask about 500 c.c. of the water. Add 3 c.c. of the milk of alumina; shake and heat the water quickly to boiling on an iron plate. When the liquid comes to a full boil, at once remove the flask from the plate to avoid loss by evaporation. Place it in an inclined position to allow the alumina to settle. Decant off 250 c.c. of the colorless water into a six-inch dish for concentration to 25 c.c, using a flask calibrated for both the hot and the cold solution. Before making the titration, rub down the sides of the dish above the liquid with a small quantity of distilled water free from chlorine, using a clean feather. Rinsing alone will not always dissolve the chlo- rides which adhere to the sides of the dish. Notes. — For titration by this method the solution must be as nearly neutral as possible If the water is alkaline to .any extent, it should be neutralized with dilute sulphuric acid, water: analytical methods. 115 using phenolphthalein as an indicator. The solution will then contain alkali only as bicarbonate, which does not interfere with the titration. Acid water must be made neu- tral by the addition of sodium carbonate. It is important that the process be carried out essentially as described, since it has been found that the results vary with the volume of solution in which the titration is made, the amount of chromate used, and the amount of precipitated silver chloride present.* A correction for volume can be made by means of the formula given by Hazen. E. G. Smith t recommends titration in a volume of 100 c.c., making a correction of .1 c.c. more or less as found for the error due to dilution of the reagents. Color is removed by agitation with milk of alumina as before described. Determination of the Residue on Evaporation and the Loss on Ignition. — Directions. — Ignite and weigh a platinum dish. Measure into it 100 c.c. of the water (200 c.c. in the case of surface-waters), and evaporate to dryness on the water-bath. When the water is all evaporated heat the dish in the oven at the temperature of boiling water for two hours, then let it remain in a desiccator over sulphuric acid for several hours and weigh.J The increase in weight gives the " total solids " or " residue on evaporation." If from a ground-water, save the residue for the determination of the iron. In the case of surface-waters the residue should be ignited and the loss on ignition noted. Heat the dish in a " radia- tor," which consists of another platinum dish enough larger to allow an air-space of about half an inch between the two dishes, the inner dish being supported by a triangle of plati- num wire. Over the inner dish is suspended a disk of * Hazen: Am. Chem. Jour., 11 (iSSg), 409. \ Trans. Wis. Acad. Sciences, Arts, and Letters, Vol. XIII, 359. Jin some laboratories it is the practice to dry at no° or 130 C. n6 AIR, WATER, AND FOOD. platinum-foil to radiate back the heat into the dish. The larger platinum dish is heated to bright redness by a triple gas-burner. Heat the dish in the radiator until the residue is white or nearly so. Note any blackening or charring of the residue and any peculiar " burnt odor " which may be given off. After the dish has cooled, slightly moisten the residue with a few drops of distilled water to secure weighing under the same conditions. Heat the residue in the oven for half an hour; cool in a desiccator and weigh. This gives the weight of " fixed solids," the difference being the " loss on ignition." Notes. — Before the introduction of modern methods of water-analysis the determination of " loss on ignition " was the only method for the estimation of organic matter in water. In order, however, that the determination shall pos- sess any real value, it is necessary to regulate carefully the heat during the ignition, so as to destroy the organic matter with- out decomposing calcium carbonate or volatilizing the alkali chlorides. This is what the use of the radiator is intended to accom- plish, and in the case of surface-waters, with low mineral con- tent and considerable organic matter, the method gives gen- erally satisfactory results. But in the case of ground-waters having little or no organic matter and high mineral content the loss is often very great on account of the decomposition of nitrates and chlorides of the alkaline earths and the loss of water of crystallization. In waters of this class the determi- nation of " loss on ignition " is, therefore, generally meaning- less, although an approximation to the amount of organic matter can be obtained by the addition of sodium carbonate to the water before evaporating to dryness. By this means the alkaline earths are precipitated as carbonates, the chlorine and nitric acid are held by an alkaline base, and there is no water of crystallization in the residue. Even with this modi- fication the loss is considerable when magnesium salts are present, owing to the loss of carbonic acid. ,0 - r; water: analytical methods. 117 The behavior on ignition is oftentimes significant. Swampy or peaty waters give a brownish residue on evapora- tion to dryness, which blackens or chars, and this black sub- stance burns off quite slowly. The odor of the charring is like that of charring wood or grain; sometimes sweetish, but not at all offensive. Waters much polluted by sewage blacken slightly; the black particles burn off quickly and the odor is disagreeable. Any observations on this point should be re- corded in the report (p. 141 ) under the heading " Change on Ignition." Determination of the Hardness. 1. By Soap. — Clark's Method. Directions. — Measure 50 c.c. of water into a 200-c.c. clear glass-stoppered bottle and add the soap solution from the burette, two or three tenths of a cubic centimeter at a time, shaking well after each addition, until a lather is obtained which covers the entire surface of the liquid with the bottle lying on its side, and is permanent for five minutes. The number of parts of calcium carbonate corresponding to the volume of soap solution used is found in the table in Appen- dix A. This will give the total hardness. If it is desired to find the permanent hardness also, dilute 50 c.c. of the water to about 200 c.c. and boil down to 50 c.c. in a beaker, cool and determine the hardness as before. This will give the per- manent hardness, and the difference will be the temporary hardness. Notes. — When potassium or sodium soap is added to water containing calcium and magnesium salts, the soap is decomposed, and insoluble compounds with the fatty acids are formed. The importance of adding the soap in small quan- tities cannot be too strongly emphasized, especially in the presence of magnesium compounds. The presence of mag- Il8 AIR, WATER, AND FOOD. nesium salts will be recognized by the peculiar curdy appear- ance of the precipitate formed and by the occurrence of a false end-point, the lather lasting about three minutes when the titration is about half done. If much carbonic acid be 'liberated, it is better to follow Dr. Clark's original directions and remove it by suction. By reference to the table it will be observed that values are not given fcr more than 16 c.c. of the soap solution. If in any case the water under examination requires more than 10 c.c. of the standard soap solution, a smaller portion of 25 c.c, 10 c.c. or even 2 c.c, as the case may require, is meas- ured out and made up to a volume of 50 c.c with recently distilled water. If the volume of soap used is always about 7 c.c, this will keep the results comparable with each other, although the element of dilution introduces an error. Potable waters, in the eastern United States, at least, are rarely so high in mineral matter as to require excessive dilution. In the case of extremely hard waters, however, the acid method is to be preferred. Distilled water itself, containing no calcium salt whatever, requires the use of a considerable quantity of soap to produce a permanent lather. The cause for this seems to exist in the dissociation of the greater part of the soap at the extreme dilution to which it is subjected,, and the slow accumulation of a sufficient quantity of undis- sociated soap to allow of the increase of surface tension to a point at which soap-bubbles will persist. By the temporary hardness of water is meant the hardness which is removed by boiling. It is due to the carbonates of calcium and magnesium held in solution by the carbonic acid in the water, probably in the form of bicarbonates. Perma- nent hardness is that which is not removed by boiling. It is. caused by the presence of soluble salts of calcium and mag- nesium, not carbonates, but chlorides and sulphates princi- pally, held in solution by the solvent power of the water itself.. WATER: ANALYTICAL METHOD. II9 2. By Acid. — Hehner's Method* ALKALINITY. Directions. — For the determination of the " alkalinity," measure ioo c.c. of the water into a clear bottle such, as is used for the soap test, and add 2.5 c.c. of the erythrosine indicator, 0.1 gram of the sodium salt in 1 liter of distilled water, and 5 c.c. of chloroform neutral to erythrosine. Mix well by shaking N . and add — sulphuric acid from the burette in small quantities, shaking thoroughly after each addition. The pink color grad- ually grows lighter until the addition of a drop or two of the acid causes it to disappear entirely. Each tenth of a cubic centimeter of acid used represents one part of CaC0 3 in 1,000,000. Make a correction for the indicator by carrying out a blank determination with distilled water. The alkalinity may be determined more quickly as follows. Measure 100 c.c. of the water to be tested into a No. 6 evapo- rating dish, add two drops of sensitive methyl orange and titrate with the — sulphuric acid. Lacmoid and phenacetolin can also be used in the determination of the alkalinity, but they necessitate titration in a hot solution on account of their sus- ceptibility to carbonic acid. ■Notes.— This method is especially useful for waters which require clarification by alumina and subsequent filtration. i The use of chloroform is essential to secure a sharp end- point. The non-ionized erythrosine formed by the addition of the acid to its alkali salt is soluble in the aqueous solu- * Hehner: Analyst, 1883, 8, 77; Draper, Chem. News, 1885, 51, 206: Ellms: Jour. Am. Chem. Soc, 1899, 21, 239. 120 AIR, WATER, AND FOOD. tion with a slight rose color. It is, however, more soluble in the chloroform, and when it is thus removed as fast as formed the neutralization of the alkali becomes at once apparent.* If a water contains sodium or potassium carbonate, there will not be any permanent hardness, and hence more acid will be required for the filtrate than corresponds to the amount of sodium carbonate added. From the excess the amount of sodium carbonate in the water may be determined. Any alkali carbonate present would be calculated as temporary hardness by the direct titration; hence it should be calculated to calcium carbonate and subtracted from the results found by the direct titra- tion. Determination of Phosphates. f — Directions. — Evapo- rate 50 c.c. of the water and 3 c.c. of nitric acid (sp. gr. 1.07) to drvness in a 3 -inch porcelain dish on the water-bath. Heat the residue in an oven for two hours at the tempera- ture of boiling water. Treat the dry residue with 50 c.c. of cold distilled water, added in several portions and poured into the comparison-tube. It is not necessary to filter the solution. Add 4 c.c. of ammonium molybdate (50 grams per liter) and 2 c.c. of nitric acid, mix the contents of the tube and compare the color, after three minutes, with stand- ards made by diluting varying quantities of the standard phosphate solution (1 c.c. =0.0001 gram P 2 5 ) to 50 c.c. with distilled water and adding the reagents as above. Carry out a blank determination on the distilled water used for dilution, especially if it has stood for any length of time in glass vessels. * Ellms: /. Am. Chetn Soc, 21 (i8qq), 359. fLepierre- Bull. Soc. Chim., 15 (1896), 1213 Woodman and Cayvan: J. Am. Chem. Soc, 23 (iqoi), 96. Woodman- ibid. (1902), 735. WATER: ANALYTICAL METHODS. 12 1 Notes. — The method as described will be sufficient for ordinary work. If a more exact determination of the phos- phate is required, a slight correction should be made in each case. For a table showing these corrections reference may be made to the paper by Woodman and Cayvan previously cited. The evaporation and heating w T ith nitric acid is for the purpose of removing silica, which gives with ammonium molybdates a yellow color similar to that given by phos- phates. The determination of phosphates in a drinking-water is a matter which has not received the attention from water analysts that has been given to the estimation of various other constituents. Any one who looks through the litera- ture cannot help noticing how few are the published results of quantitative estimations of the phosphate con- tent of natural waters, apart from mineral waters. Yet this determination, by reason of the conversion of organic phosphorus compounds into phosphates through the processes of decay, is one which might reasonably be expected to throw considerable light on the question of the pollution of natural waters by objectionable ma- terial. The reasons for this dearth of published data are not far to seek. To be of value the amount of phosphate must be known within rather narrow r limits. Qualitative tests are not sufficient. The mere presence of phosphates is by no means definite or even confirmatory evidence of organic pollution. Rocks and minerals containing phosphates are found nearly everywhere, and traces, at times even con- siderable quantities, may be dissolved, especially by waters rich in carbonic acid. This, however, does not constitute 122 AIR, WATER, AND FOOD. a serious objection to the utility of the determination. The same is true of many if not most of the constituents upon which reliance is placed in judging of the quality of a water. Unpolluted waters often contain notable amounts of nitrates and chlorides, and a true judgment can be rendered only after comparison with samples from adjacent but unpol- luted sources. The chief reason, however, has been the lack of an accu- rate and simple method, sufficiently delicate, and of enough data to work out a standard for comparison. This reason can hardly hold true now, for enough work has been done on the colorimetric method to indicate its value as another link (of which we have none too many, any- way) in the chain of circumstantial evidence by which we are often compelled to judge the purity of a water. The amount of phosphate and its variation seem to fol- low the same general line as the other mineral constitu- ents which either accompany the polluting material or are produced by its decay, especially the nitrates and chlorides. It is not, however, so delicate an indicator as these. In general it may be said that the amount (expressed as P 2 5 ) in an unpolluted water will seldom be over i.o part per million. Determination of Iron.* — Directions. — Evaporate iooor 200 c.c. of the water to dryness in a platinum dish. (The weighed residue from the determination of total solids may be used if desired.) Treat the residue with 5 c.c. of hydro- chloric acid (1:1), being careful to carry the acid to the edge of the dish. In some cases it may be necessary to heat the dish gently on the water-bath in order to bring all the iron * Thomson: J. Chem. Soc, 67 (1885), 493. WATER: ANALYTICAL METHODS. 123 into solution. When all is dissolved with the exception of silica, rinse the solution into a ioo-c.c. tube and make it up to about 50 c.c. with distilled water. Add a solution of po- tassium permanganate drop by drop until the solution re- mains pink for 10 minutes. Meanwhile prepare a blank standard with 5.0 c.c. of dis- tilled water and about a cubic centimeter of hydrochloric acid. Add 15 c.c. of potassium sulphocyanide solution to the waters and to the blank standard. Add the standard iron solution, in small quantities, .02 c.c. if necessary, from a capillary pipette, mixing thoroughly by pouring the solu- tion back and forth from one tube to another after each addition, until the color of the standard matches that of the water. One cubic centimeter of the standard iron solu- tion is equal to 0.000 1 gram of Fe. Notes. — In the case of some river-waters it will be fpund necessary to add a few cubic centimeters of hydrochloric acid to the water while evaporating, in order to facilitate the solution of the iron. This should be done on a separate portion from that used for the determination of total solids. The colors should be matched immediately after adding the sulphocyanide, since the color fades appreciably on standing. The highest standard should not contain more than 3 c.c. of the iron solution, since the color then becomes too deep for accurate comparison. Determination of the Dissolved Oxygen. Method of L. W. Winkler* Collection of Samples. — The samples are collected in glass-stoppered bottles of known capacity, holding about * Berichte, 21 (1888), 2843. 124 AIR » WATER, AND FOOD. 250 cubic centimeters. When water is taken from a faucet the bottle is filled by means of a tube which passes to the bottom of the bottle. A considerable amount of water is allowed to pass through the bottle and overflow at the top. It will be almost impossible to obtain duplicate samples unless the bottles are filled at the same time by means of a T tube, owing to variations in pressure in the pipes. In taking samples from a stream or pond, a stopper with two holes is used. A tube passing through one of these holes is sunk in the water to the desired depth, and the other is connected with a larger bottle of at least four times the capacity of the smaller one, and fitted in the same way. From the larger bottle the air is exhausted by the lungs or by an air-pump until it is nearly filled with water. Unless the determination is to be made at once, the rubber stopper of the smaller bottle is quickly replaced by the glass stopper so that no air is left in the bottle. The temperature of the water at the time of sampling should be noted. The apparatus which has been used in connection with work in this laboratory for collecting samples at various depths down to 75 feet is shown in outline in Fig. 11. A gal- vanized-iron can of such size as to hold one of the gallon bot- tles is weighted with lead and provided with ears at the top for suspending. The bottle, which is securely wired in, is pro- vided with a rubber stopper carrying two brass tubes, one ending just below the stopper and projecting for about 8 or 9 inches above it, the other extending to the bottom of the bottle and connected by heavy rubber tubing with the sample bottle. This is held by brass brackets, which are fastened by means of a wooden cleat to the side of the can. The neck of the bottle is put into the slot in the .upper WATER: ANALYTICAL METHODS. 125 bracket and then it is firmly clamped by the thumb-screw of the lower one. The arrangement of tubes in the sample bottle is obvious. In using the apparatus it is quickly Fig. lowered to the desired depth by means of a rope marked off in feet. The water enters the sample bottle and flows through it into the other. When the bubbles cease to rise, indicating that the larger bottle is full, thus replacing the water in the sample bottle a number of times, the apparatus is drawn to the surface. The temperature is read from a thermometer fastened to the tube inside the gallon bottle. The Determination. — Remove the stopper and add 2 c.c. of manganous sulphate solution with a pipette having a long capillary point reaching to the bottom of the bottle, and in the same way add 2 c.c. of the solution of sodium hydroxide and potassium iodide. Insert the glass stopper, leaving no bubbles of air, and mix the contents of the bottle. 126 AIR, WATER, AND FOOD. f Allow the precipitate to settle, and add 3 c.c. of strong hydrochloric acid with another pipette ; add also one or two small glass beads and again insert the stopper. When the white portion of the precipitate is entirely dissolved, pour out a part of the solution into a flask, put back the stopper and shake the bottle vigorously. Then rinse out the con- tents of the bottle into the flask and titrate the liberated N iodine with approximately — sodium thiosulphate until the color becomes a faint yellow. Then add starch solution and titrate to the disappearance of the blue color. The first end-point should be taken, as the color will return on account of the reducing action of the organic matter present. OXYGEN DISSOLVED. From Report on Standard Methods. Sulphuric Acid. — Specific gravity 1.4 (dilution 1:1). Sodium Thiosulphate Solution. — Dissolve 6.2 grams of chemically pure recrystallized sodium thiosulphate in one N - liter of distilled water. This gives an — solution, each c.c. 40 pf which is equivalent to .0002 gram of oxygen or .1395 c - c - of oxygen at o° C. and 760 mm. pressure. Inasmuch as .this solution is not permanent, it should be standardized N "occasionally against an — solution of potassium bichromate as described in almost any work on volumetric analysis. The keeping qualities of the thiosulphate solution are im- proved by adding to each liter 5 c.c. of chloroform and 1.5 grams of ammonium carbonate before making up to the prescribed volume. . r "Calculation of Results.— The standard method of ex- water: analytical methods. 127 pressing results shall be by parts per million of oxygen by weight. "It is sometimes convenient to know the number of c.c. of the gas per liter of o° C. temperature and 760 mm. pres- sure, and also to know the percentage which the amount of gas present is of the maximum amount capable of being dissolved by distilled water at the same temperature and pressure. All three methods of calculation are therefore here given: Oxygen in parts per million 0.0002N X 1 .000,000 200N V ~ V in c.c. per liter 0.1395NX: [OOO i39-5 N V V Oxygen in per cent, of saturation 200N X 100 2o,oooN = vxo = "~vo N Where N = number of c.c. of — thiosulphate solution, V = capacity of the bottle in c.c. less the vol- ume of the manganous sulphate and potas- sium iodide solution added (i. e., less four c.c). = the amount of oxygen in parts per million in water saturated at the same temperature and pressure." 128 AIR, WATER, AND FOOD. QUANTITIES OF DISSOLVED OXYGEN IN PARTS PER MILLION BY WEIGHT IN WATER SATURATED WITH AIR AT THE TEMPERATURE GIVEN. Temp. C. Oxygen. Temp. C. Oxygen. Temp. C. Oxygen. Temp. C. Oxygen. o 14.70 8 11.86 16 9-94 24 8.51 I 14-28 9 11.58 17 9-75 2 5 8-35 2 13.88 10 II. 31 18 9.56 26 8.19 3 I3-50 11 11 05 19 9 37 27 8.03 4 13 14 12 10.80 20 9.19 28 7.88 5 12.80 13 IO-57 21 9 01 29 7-74 6 12.47 14 IO-35 22 8.84 30 7.60 7 I2.l6 15 IO.14 2 3 8.67 Notes. — This determination is a good illustration of an indirect volumetric process. A precipitate of manganous hydroxide is formed in the bottle by the reaction of the manganous sulphate and the sodium hydroxide. This imme- diately combines with the oxygen in the water to form a cer- tain amount of manganic hydroxide. The hydrochloric acid which is added reacts with the manganic hydroxide to form chlorine, which in turn liberates iodine from the potassium iodide, the amount thus set free depending primarily upon the quantity of oxygen dissolved in the water. The presence of considerable amounts of organic matter or of nitrites in- troduces an error. In such cases the method must be modified or a correction made. Details of the method used in such cases are given in the paper by Winkler previously cited. A correction is made for the volume of the reagents added, but since the precipitated hydroxides had settled before the acid was added, no allowance should be made for the amount of acid, since the water it displaces contains neither oxygen nor iodine. water: analytical methods. 12 o> is a constant for any particular bottle, and its logarithm may be recorded in a note-book or upon the bottle itself. If water is collected in the ordinary way and transferred. to the apparatus by pouring, there will inevitably be an ab- sorption of oxygen unless the water is already saturated. Thus a process which gives excellent results when the water is nearly or quite saturated may fail entirely to give accurate results when the dissolved oxygen is low or absent. The water may be supersaturated with oxygen, in which case the per cent, of saturation may be more than one hundred.* Determinations of dissolved oxygen in ponds and streams are best made on the spot, or at least the re- agents should be added. The very simple apparatus re- quired for the Winkler process can be packed in small space, and the entire determination requires only a few minutes. The absorption of the oxygen by the manganous hydroxide- is complete almost at once, and it is unnecessary to allow it to settle for a long time before adding the acid. The titra- tion can be made with a small burette or pipette with accurate results. Determination of Free Carbonic Acid. — Reagent. — Stand- N ard — solution of sodium carbonate. Dissolve 2.41 grams of dry sodium carbonate in one liter of distilled water which has been freed from carbonic acid by cautious addition of dilute solution of sodium carbonate. Add 5 c.c. of phenolphthalein indicator (7 grams in a liter) to the distilled water before neutralizing and measuring. Preserve this solution in bottles of resistant glass, protected from the air by tubes filled with- soda lime. One c.c. equals 0.001 gram of C0 2 . ♦Gill: Tech. Quart., 5 (1892), 250. 130 AIR, WATER, AND FOOD. Procedure. — Measure 100 c.c. of the sample into a tall, narrow vessel, preferably a 100 c.c. Nessler tube, and titrate N rapidly with the — sodium carbonate solution, stirring gently until a faint but permanent pink color is produced. N The number of c.c. of — sodium carbonate solution used in 22 titrating 100 c.c. of water, multiplied by 10, gives the parts per million of free carbonic acid as C0 2 . Owing to the ease with which free carbonic acid escapes irom water, particularly when present in considerable quanti- ties, it is highly desirable that a special sample should be collected for this determination, which should preferably be made on the ground. If the analysis cannot be made on the spot, approximate results from water not high in free carbonic acid may be obtained from samples collected in bottles which are completely filled so as to leave no air space under the stopper. Notes. — The reaction consists in the formation of acid sodium carbonate: Na 2 C0 3 + H 2 4-CO2 = 2NaHC0 3 . The acid carbonate does not give a pink color with phenol- phthalein. Determination of the Color. — The amount of color is generally determined by direct comparison of the water with some definite standard of color. Various standards of color have been proposed, the objection to most of them being that they are not sufficiently general in their application, Being adapted only for the color of some particular class of waters. water: analytical methods. 131 Nesslerized Ammonia Standards .—The yellowish-brown "tint of the surface-waters of the Atlantic watershed corre- sponds, except in the lowest grades, very closely to that of nesslerized ammonia, so that the standards for reading ammonia can be used also for the determination of the color. The comparison is made in the same kind of 50-c.c. tubes that are used for the ammonia determinations, but the tubes used for this purpose are kept separate from those used for the ammonia, since the least amount of alkali re- maining in a tube (from imperfect washing, for instance) ■alters the color of the water. The scale used corresponds quite closely with the amount of the standard ammonium chloride solution in the standards. Thus a color of 1.0 is nearly the same as that produced by the nesslerization of 1 c.c. of the standard ammonia; c.i is about the color pro- duced with 0.1 c.c. of the ammonia solution. In the higher grades of color, above 1.0 or 2.0, the tint varies considerably from that of the nesslerized ammonia, and the degree of color is then better determined in wider tubes and in less depth. The degree of correspondence of the ammonia standards with the natural waters is dependent largely upon the sensi- tiveness of the Nessler's reagent, a solution which is so sen- sitive as to precipitate in two hours, matching the colors more closely than one which will remain for twenty- four hours. This is perhaps due to the reddish tinge given to the solution by the incipient precipitation of the mercuric iodide. Natural Water Standards. — To avoid these variations in •color, standards made from dark-colored water from swamps by various degrees of dilution, and verified by direct com- parison with suitably prepared nesslerized ammonia stand- 132 AIR, WATER, AND FOOD. ards, are used. They have the same hue as the waters to be matched, as well as a degree of turbidity which corresponds well with that of surface-waters ; once prepared, they will keep for a fairly long time if protected from the light and from the dust. These are the standards that are in use in this laboratory. They are periodically standardized by comparison with the permanent glasses of a Lovibond Tintometer. Platinum Standards. — For ground-waters which have only very little color and considerable hardness, and for fil- tered waters, the platinum color standards are convenient.*" According to this scale, the color of a water is the amount of platinum in parts per ten thousand, which, together with enough cobalt to match the tint, must be dissolved to pro- duce an equal color in distilled water. In practice, a stand- ard having a color of 5.00 is prepared by dissolving 1.246' grams of potassium platinic chloride (equivalent to .5 gram platinum), 1.000 gram of cobalt chloride (equivalent to .25 gram cobalt), and 100 c.c. of strong hydrochloric acid in dis- tilled water and diluting to one liter. Dilute standards for use are made by diluting varying amounts of this standard to 50 c.c. with distilled water. Thus, by diluting 1 c.c, 2 c.c, and 3 c.c. to 50 c.c, colors of 0.1, 0.2, and 0.3 are obtained. It is claimed that the platinum stand- ards are permanent if protected from the dust. Iodine Standards. — A standard for color which could be made up at the moment when wanted and without the use of costly apparatus would be a desideratum. Experiments made in this laboratory indicate that an aqueous solution containing a definite weight of iodine offers the best solution of the prob- lem. Owing, however, to the volatility of iodine even in dilute aqueous solution it is better to liberate it directly in * Hazen : Am. Chem. /., 14 (1892), 300. water: analytical methods. 133 the comparison-tube itself. For this the following solutions are required: Potassium iodide, 0.1 gram per liter; potas- sium bichromate, 0.09 gram per liter; picric acid, 0.2 gram per liter. For a color of 5.0, 50 c.c. each of the iodide and of the bichromate solutions are used; for lower colors proportional amounts are taken and diluted to 100 c.c. with distilled water. To each tube is added 1 c.c. of the picric acid solution, and just before the colors are to be matched add 2 c.c. of strong sulphuric acid. The color develops, as in the case of nessler- ized ammonia, within ten minutes and can be relied upon for about half an hour. A very slight milkiness aids in match- ing the color; a great hindrance to the use of metallic solu- tions being their clearness or brightness as compared with natural waters. The comparison-tubes which give the most satisfactory results with colors from 5.0 to 0.5 on the natural water scale are 15 / 16 inch wide and 9V4 inches high to the 100-c.c. mark, For lower colors, narrower tubes, n /i6 mcn diameter and the same depth, give closer readings. Determination of the Odor. — Cold. — Shake violently the sample in one of the large collecting-bottles when it is about half or two-thirds full, then remove the stopper and quickly put the nose to the mouth of the bottle. Note the character and degree of intensity of the odor, if any. An odor can often be detected in this way which would be en- tirely inappreciable if the water were poured into a tumbler. Hot. — Pour into a beaker about five inches high enough water to one-third fill it. Cover the beaker with a well-fitting watch-glass and place it on an iron plate which has been pre- viously heated, so that the water shall quickly come to a boil. When the air-bubbles have all been driven off and the water is about to boil, take the beaker from the plate and allow it to cool for about five minutes. Then shake it with a rotary 134 AIR, WATER, AND FOOD. movement, slip the watch-glass to one side and put the nose into the beaker. Note the odor as before. The odor may or may not be the same as that of the water when cold; it can be perceived, as a rule, for only an instant. Notes. — It is inevitable that a certain personal equation should influence this test. Each laboratory will have its own .standards for routine work, but a certain familiarity with the more common odors will tend to allay public anxiety and to aid in a more watchful habit on the part of consumers. Good ground-waters do not give distinct odors unless they are de- rived from clayey soil, but the odor often betrays a contami- nated wei! more surely than any other test. Surface-waters will nearly always yield a characteristic odor. This odor may be due to the organic matter contained in the water, or to the presence of minute plants or animal organisms. Among the odors which are frequently met are the " earthy," " vegetable," " musty," " mouldy," " disagree- able," and " offensive." The " earthy " odor is that of freshly turned clayey soil. u Vegetable " is the odor of many normal colored surface-waters; it may be described as swampy or marshy, pond-like, and is often strengthened by heating. " Musty " can be likened to the odor of damp straw from stables; it is fairly characteristic of sewage con- tamination, and by the trained observer is distinctly distin- guishable from the mouldy odor. " Mouldy " is the odor of upturned garden or forest mould, or of a moist hot-house; it is somewhat allied to the earthy odor. " Disagreeable " is a term which is capable of wide variation among different observers. It may include certain characteristic odors which are peculiar to the growth or decay of certain organisms, as the " pigpen " odor of Anabcena, the " fishy " or " cucum- ber " odor of Synura, etc. The term " offensive " is generally reserved for the sewages. These terms can be taken only as broad illustrations of the character of the particular odor, WATER ANALYTICAL METHODS. 13$ since the odor will very likely be described by different per- sons in different ways, and each laboratory will have its own characterization. The odor which often accompanies an abundant development of diatoms is a good illustration of this. It will be called by various inexperienced observers offensive, rotten, fishy, geranium-like, aromatic, in one and the same sample of water. The terms generally used to signify the degree of inten- sity of the odor are " very faint," " faint," " distinct," and " decided." The exact value to be placed on each of these terms will, as a matter of course, vary with the individual analyst, but in a general way it may be said that the " very faint " odor is one that would not be detected except by the trained observer; the " faint " odor would be recognized by the ordinary consumer if his attention were called to it; the " distinct " odor is one that would be readily noticed by the average consumer, but would not interfere with the use of the water; while the " decided " odor is one which would, in all probability, render the use of the water unpleasant. Biological Examination — The close relation of the odor to the living fauna and flora of the water makes it desirable that the chemist shall be able to recognize the more common forms of water plants and animals even if he makes no pre- tensions to a knowledge of cryptogamic botany or of zo- ology. Therefore a microscope and a concentration appara- tus should be in every water-laboratory. A full description will be found in Whipple.* The bacteriological examination belongs to the expert rather than to the student, certainly in the present state of our knowledge of the lower organisms. It may be desirable for the student to be familiar with the simpler methods of plate and tube culture, and the water-works laboratory should, as in the above case, be provided with means for plain * " Microscopy of Drinking-water." 2d ed. N. Y., Wiley. H36 AIR, WATER; AND FOOD. number counts, and directions for avoiding errors due to variations in temperature, time of culture, etc., consult Frankland's "Micro-organisms in Water"; "Manual of Bacteriology," Muir and Ritchie; "Water Bacteriology," Prescott and Winslow. Determination of the Turbidity and Sediment — The suspended matter remaining in the water after it has rested quietly in the collecting-bottle for twelve hours, or more, is called its turbidity, and that which has settled to the bottom of the bottle, its sediment. Good ground-waters are often entirely free from turbidity and sediment, the suspended matters having been filtered out during the subterranean passage of the water, but this is rarely true of surface-waters. The turbidity is various in character and amount, sometimes milky from clay or ferrous iron in solution; usually it consists of fine particles, generally living algae or infusoria. These often collect on the side toward or from the light, and a practised eye can, not infre- quently, recognize their forms. Some of the lower animal forms can also be seen by the naked eye, and the larger En- tomostraca are quite noticeable in many waters. The sediment may be earthy or flocculent; in ttie latter case it is generally debris of organic matter of various kinds. The degree of turbidity is expressed by the terms " very slight," " slight," " distinct," and " decided," and the degree of sediment by " very slight," " slight," " considerable," and " heavy." These determinations, again, are of value only to the routine worker, and for him there are various methods in use. The papers of Parmelee and Ellms * and of Whipple and Jackson f should be consulted for a description of these. Permanent standards, however desirable for a routine laboratory where many samples are tested daily, are not very reliable for students' work where the tests are made * Tech Quart., 12 {1899), 145. \Ibid. t 283. waier: analytical methods. 137 only at intervals and for educational rather than technical purposes. Determination of Alum. — On account of the use of alum or aluminum sulphate as a coagulant in the filtration of water, a determination of alumina in the effluent water is often necessary. This may be readily made by the log- wood test.* Directions. — The logwood solution is made as follows: Take two grams of logwood chips and boil one minute in a platinum dish with 50 c.c. of distilled water. Decant the solution and boil again for one minute with 50 c.c. of water. Decant this and similarly boil a third time with 50 c.c. of water. Decant this into a platinum receptacle for use. Take three drops for each test. Kept in platinum, the solu- tion will last for several days at least. Test the water as follows: Boil 50 c.c. of the water in a platinum dish for a short time to expel carbon dioxide. Add three drops of the logwood solution and continue boiling for a few seconds to develop the color. Decant into a glass flask and cool quickly under the tap (so as not to keep the hot solution too long in the glass). Transfer to a No. 2 beaker and blow in carbon dioxide from the breath by means of a glass tube until there is no further decolorization. Pour the water into a Nessler tube for comparison with standards similarly prepared. Allow them to stand several hours before taking the final reading. No wash-water is used at any of the decantations. The test shows one part of aluminum sulphate in 8,000,000 parts of water. A blank made with distilled water, if not completely decolorized by the C0 2 , will show a tint perceptibly fainter * E. H. Richards: Tech. Quart., 4 (1891), 194. A. H. Low, Tech. Quart., 15 (1902), 351. 1 3$ AIR, WATER, AND FOOD. than that produced by one part in 8,000,000 of aluminum sulphate. It should be noted that carbon dioxide must be kept absent until the point prescribed. The solution is therefore transferred to a beaker in order to keep the flask free from carbon dioxide for the next test. The main points are: 1. Any kind of logwood appears to answer. 2. The solution is good for several days, at least, if kept in platinum. 3. The use of platinum instead of glass for boiling the test, 4. The use of carbon dioxide instead of acetic acid. Aluminum hydrate, as pointed out by the late Professor A. R. Leeds in 1893, will produce a tint almost as strong as if it were in solution, but of a distinctly differing tint. Mr. Low's method of procedure is as follows: First, test the water as above described. If no tint, or none ex- ceeding that of the blank, remains after standing several hours or over night, that is sufficient. If, however, a tint persists, or a colored precipitate settles out, it is necessary to determine if this is due to aluminum hydrate. Pour a sample of the water several times through a double Swedish filter, and finally test the filtrate. If the tint produced is weaker than that given by the unfiltered water, repeat the operation on a fresh portion of the water, using the same filter, and continue repeating with new portions of the water and always using the same filter, until it is apparent that no further diminution of the tint can be effected. For a less delicate test in school laboratories where platinum is not available, the following alternative method may be used: Dissolve about 0.1 gram pure hematoxylin in 25 c.c. water ; this solution will keep for two weeks and works best water: analytical methods. 139 after being made several hours. To 50 c.c. of the water, placed in a four-inch porcelain dish, add two drops of the haematoxylin solution, allow the solution to stand for one or two minutes, then add a drop of 20 per cent, acetic acid. The standards are prepared at the same time, using 50 c.c- of distilled water and the required amount of a stand- ard alum solution. The comparison must be made imme- diately, since the color fades on standing. In this way the presence of one part of aluminum sulphate in five million can be determined directly in the water and with ease. Logwood may be used instead of the haematoxylin, the solution being prepared as above. Notes. — This test will show the presence of all soluble salts of aluminum which enter into combination with the coloring matter of the logwood to form a " lake." The alkalies and alkaline earths give a purplish color with logwood extract, hence the test for alum can be made only in acid solution. Determination of Lead. — Lead in the minute quantities in which it ordinarily occurs in water is best estimated by comparing the color of the sulphide with standards. Directions. — If the water is colorless, acidify the clear solu- tion, concentrated if need be, with two or three drops of acetic acid, and pass in hydrogen sulphide to saturation. If a color is produced, compare it in a 100-c.c. tube with the color given by varying quantities of a standard lead solution. If the water is too highly colored to estimate the lead di- rectly, evaporate three or four liters in a porcelain dish to about 25 c.c, add 10 c.c. of ammonium chloride solution and a considerable excess of strong ammonia. Then add hydro- gen sulphide water and allow the dish to stand some hours. JBoil the contents of the dish for a few moments to expel the 140 AIR, WATER, AND FOOD. excess of hydrogen sulphide, and filter. The precipitate con- tains all the lead, iron, and suspended organic matter, also copper and zinc if present, while the soluble color goes into the filtrate. Wash once with hot water, transfer the filter to the original dish, and dissolve the sulphides by boiling with dilute nitric acid (i part acid, sp. gr. 1.2, to 5 parts water). Filter and wash; evaporate to 10-15 c.c, cool, add 5 c.c. con- centrated sulphuric acid and evaporate until copious fumes are given off". Then, if the original water contained less than 0.25 part iron per million, add acetic acid and ammonia, boil, filter, and read the' amount of lead in the alkaline filtrate, making the standards (page 260) also alkaline with ammonia. If the water contained over .25 part iron, wash the lead sulphate into a beaker with alcohol and water, and let it set- tle overnight. Filter, wash free from iron with 50 per cent, alcohol, dissolve the precipitate by boiling with ammonium acetate, filter, and determine the lead as above. Note. — If more than .25 part of iron is present, some of the lead will be held by the precipitated ferric hydroxide; and if 25 parts are present, all of the lead may be lost in this way; hence the modification of the method in the presence of con- siderable quantities of iron.* When copper is also present it is detected by the blue color given to the ammoniacal filtrate from the iron precipi- tation. Statement of Results — In reporting water analyses the results are best expressed in milligrams per liter, which for the majority of waters is equivalent to " parts per million." Occasionally it may be desirable to express the results in " grains per gallon." Parts per million may be converted into grains per U. S. gallon by multiplying by 0.058. For con- * Ann. Rep. State Bd. Health, Mass., 1898, 577. water: analytical methods. 141 venience the results should be arranged in tabular form, such an arrangement being suggested below: sanitary water-analysis. (Parts per 1,000,000.) Date. Physical. Residue on Evaporation. No. Color. Turb. Sed. Odor. Total. Loss. Fixed. Change Cold. Hot. Ignition. X2I 3-9-'oo .50 0.0 0.0 Dec. None Cons. None None F. Veg. None 42.5 64.0 9740.0 12.5 30.0 (Slight \ black "3 Nitrogen as No. Total Organic. Alb. Ammonia. Free Am. Nitrite. Nitrate. Ox. Cons. Total. Sol. Susp. 121 .598 .306 .014 .032 .170 .136 .056 .000 .560 .003 .000 .003 .220 .1.40 1. 14 4.83 •41 3.23 123 Hardness Chlorine as Chlo- rides. Iron. Biological (per c.c.) No. Bac. Plants. Diatoms. Cyano- phyceae. Alg«e. Animals. 20.0 23.0 560.0 1.8 6.3 1198.0 ■ 229 .01 .46 123 No. 121 is from a pond; 122 from a spring; 123 from an artesian well. CHAPTER VIII. FOOD IN RELATION TO HUMAN LIFE: COMPOSITION, SOURCES, DIETARIES. Life itself is conditioned on the food-supply. Wholesome food is a necessity for productive life. Man can and does exist on very unsuitable, even more or less poisonous, food, but it is merely existence and not effective life. This is true not only of the wage-earner, but of the business-man, the professional man, the scholar. To be well, to be able to do a day's work, is man's birthright. Nevertheless a too large proportion of the American people sells this most valuable possession for a mess of pottage which pleases the palate for three minutes and weights the diges- tive organs for three hours. With the products of the world ex- posed in our markets, the restraints of a restricted choice, as well as inherited instincts or traditions, lose their force. The buyer, unless he has actual knowledge to guide him, is swayed by the caprices of the moment or the condition of his purse, and often fails to secure adequate return in nutritive value for the money paid. The fact that so much manipulated material is put upon the market renders this choice of food doubly difficult, since the appearance of the original article is often entirely lost, and to city-bred buyers even the natural product conveys little idea of its money value. It is now even more necessary that an elemen- tary knowledge of the proximate composition and food value of the more common edible substances should be recognized as an essential part of education. 142 FOOD IN RELATION TO HUMAN LIFE. 1 43 Food: Definition and Uses. — Food is that which builds up the body and furnishes energy for its activities: that which brings within reach of the living cells which form the tissues the elements which they need for life and growth. Only such available sub- stances can be called food, no matter what their chemical compo- sition may be. Soft coal contains carbon and hydrogen and is food for the furnace, but is not available for the animal body. This food which is taken into the body is used in various ways. It forms and builds up new tissues, besides repairing and making good the waste of tissues due to bodily activity; it is stored up in the body to meet a future demand; it supplies the needed heat by the transformation of its stored up or potential energy into the muscular energy required by the body; it may be used to protect the tissues of the body from being themselves consumed as food. Composition of Food. — We determine what chemical elements enter into the composition of the body by an analysis of the various organs and tissues. We learn what combinations of these ele- ments serve as food by determining those present in mother's milk and in foodstuffs which experience has proved to furnish perfect nutrition. From these studies it is apparent that about fifteen chemical elements are constant constituents of the human body; that about a thousand natural products are known to have food value; that of these, one hundred are of world-wide importance (see table, page 150), and that ten of them form nine-tenths of the food of the world. The composition of food, as shown by chemical analysis, is not, however, the only factor that must be known to determine its value. The digestibility of the material must be taken into account as well. "We live not upon what we eat, but upon what we digest." It is more important to know the amount of available nutrients than the amount of total nutrients. Food Principles. — W^hile the foodstuffs present great variety, the food principles may be grouped under four headings; 144 AIR, WATER, AND FOOD. viz., nitrogenous substances or proteids, fats, carbohydrates, and mineral salts. Each group contains many members with minor but often essential differences. To make these sub- stances available, there is needed an ample supply of air and of water, — of water for solution and circulation, of air for the oxygen needed to liberate the stored energy of the food in the place where it will accomplish its purpose. Nitrogenous Substances. — Since, in some way as yet un- known to us, nitrogen is essential to living matter, such sub- stances as contain this element in an available form are of the first importance. Some, as albumen, are so closely allied to human protoplasm that probably they need only to be dis- solved to be at once assimilated. Others, as gluten and sim- ilar vegetable products, undergo a greater change; while still others, as gelatine, have a less profound but marked effect in protecting the tissues from waste. The enzymes, " ferments," in part, of the older nomencla- ture, are also highly nitrogenous substances present in some form in nearly all foodstuffs of natural origin. The nearer the composition of the food approaches that of the protoplas- mic proteid, presumably the greater its food value, since each cleavage, each hydrolysis, each step in the breaking down of the highly complex molecule, consisting of hundreds of atoms, is supposed to liberate the stored energy. Therefore it is not a matter of indifference in what form this essential is taken. So little is known, however, with scientific accuracy that stu- dents will find a fruitful field of research along these lines of investigation. Also together with this element, nitrogen, go others, in small quantity to be sure, but evidently of great value. Such are sulphur, iron, phosphorus. One difference between the several groups of proteids is seen in this com- bination with the metallic elements which seems to carry with it certain effects. Until greater progress has been made in FOOD IN RELATION TO HUMAN LIFE. 1 45 determining the availability in the organism of the various known substances, we must be content with a wide margin in the calculated quantities necessary for the daily efficiency, except in the very few instances of nearly pure substances, as white of egg. It is evident also that the manner of prepara- tion and the kind of mixtures used in food will afreet most profoundly so unstable and complex a class of substances. One thing is certain, that the body cannot take nitrogen from that which does not contain it. Therefore a cer- tain quantity of highly nitrogenous food should form "a portion of the daily supply. It is usually held that the body seems to be sufficiently nourished when the food contains an amount of digestible proteid equivalent to about ioo> grams of dry albumen per day for the average adult, although recent work has shown that this figure is probably too high. An excess appears to have a stimulating effect and overloads the system with the waste, since the end-products are not purely mineralized substances, as are carbon dioxide and water from the carbohydrates, but are compounds of an or- ganic nature, as creatin, urea, and uric acid, which have deleterious effects when accumulated in the system. A de- ficiency of nitrogen is made good, to a limited extent, by the protective agency of the other foodstuffs which offer them- selves for all the offices except the final one of tissue-building. Fats. — For this protective action, as well as for many other purposes, the fats are most valuable, and if they occur in about the same proportion as do the nitrogenous elements, the needs of the organism seem to be well met. Thus, in mother's milk, in eggs, and in meat from active animals these two are in nearly equal proportions, while in the cereals the fat is less; in nuts and in meat from fattened animals, as a rule, it is higher than the nitrogen. Little is known as to the varying food value of these fats from different sources. Certain 146 AIR, WATER, AND FOOD. physical conditions of solidity, melting-point, etc., seem to have more influence than mere chemical composition. What- ever the source, it is certain that the stored-up energy which is to serve the organism in cases of loss of income from any cause is in the form of fat, a form which is not subject to the action of agents which so readily decompose proteids and •carbohydrates and yet is readily converted into available food whenever called for. That it is not absolutely necessary that the food should contain fat as such seems to be proved by experiment, but from the fact that all nearly natural food- substances do contain it, and that it appears to be more economical of human energy to take it from these foods than to manufacture it from the proteids and carbohydrates, we may safely assume fat to be an essential of the human dietary. That the equality in amount of fat with nitrogenous com- pounds is not essential is proved by the fact that the strong draft animals, as horses and oxen, take food in which the per cent, of fat is not more than half as much as of proteid; never- theless it is present in the food of all animals and doubtless, in its turn, is protected by an excess of the third class of foodstuffs, the carbohydrates, characteristic of the vegetable kingdom — a class which in the final decomposition yield clean volatile products, water and carbon dioxide, and which, there- fore, do not clog the system so readily as do urea and other wastes. Carbohydrates. — The number of more or less well-defined substances under this head is legion: starches from scores of plants, sugars from as many more, gums, pectins, and dextrins, all with a certain food value, dependent prob- ably upon the utilization of the various mixtures with which they are taken into the alimentary canal. These foodstuffs are very liable to " fermentation," that is, to an' acid decomposition which prevents their absorption by FOOD IN RELATION TO HUMAN LIFE. 147 the delicate lining of the walls of the intestines and which causes digestive disturbance. The sugars, which are very soluble, and therefore liable to be present in excess, are es- pecially subject to this change. This class of food-substances is found in the diet of civilized man, free to choose, in an amount about equal to the sum of the other two classes, with a tendency to less rather than more. It may be said that sugar and fat increase over starch in the diet of a people of unrestricted choice, but it is not certain that the qualities of body which make for hardihood and resistance to disease are correspondingly increased. There is, indeed, much evi- dence to show that power of digesting vegetable foods indi- cates a general well-being of body conducive to long life. A ready adaptation renders possible the changes of habitat re- quired by civilization. Unless one is to be confined to a nar- row range it is wise to cultivate a strength of digestion as well as a strength of muscle, and for the best brain power we believe it to be more essential. Mineral Salts. — The fourth class, mineral salts, comes into the food largely from the vegetable substances eaten, for in these the union is an organic one readily assimilated. As we have seen, certain elements go with the nitrogenous portion, as, for example, in gluten and its congeners are found sul- phur and phosphorus. Potassium, found in barley, is a con- stant constituent of protoplasm, while sodium is found in blood-serum. A lack of vegetable foods seems to impoverish the blood-corpuscles. For children, a deficiency in lime causes serious disease. Sugar, olive-oil, corn-starch, and other prepared food-substances cannot take the place of asparagus, cabbage, carrots, etc. To sum up briefly, then, wu may say that the protein or nitro- genous portion of the food forms tissue, such as muscle, sinew and fat, and furnishes energy in the form of heat and muscular strength ; I48 AIR, WATER, AND FOOD. the fats build up fatty tissue, but not muscle, and supply heat; the carbohydrates are changed into fat and supply heat. Another im- portant use of the nutrients is to protect each other from being used in the body. The carbohydrates, especially, in this way protect the protein, including muscle, etc., from consumption. Change in Composition Due to Cooking. — The composition of cooked food is in general not the same as the raw material on ac- count principally of chemical and physical changes brought about by the heat employed in the cooking process. The total nutrients, calculated on a water-free basis, may be practically the same, but the structure is often quite different. Starch is hydrolyzed and rendered soluble by heating in the presence of moisture, and at higher temperatures it may be con- verted into the brown, soluble dextrin. The sugars are changed, being, in the case of sucrose, partly converted into other forms, such as invert sugar, by the heating, with the help of the organic acids present in many foods. Some of the proteids tend to become less soluble through heating and at higher temperatures may be even partly decomposed with possible loss of food value. Heat of Combustion. — Until a more definite knowledge of the processes of metabolism (the transformations of matter and energy in the animal organism) is obtained the potential energy of food is calculated in terms of mechanical work — expressed in heat-units or calories. One calorie is the amount of heat required to raise the tempera- ture of one gram of water one degree centigrade. A gram of fat, as actually digested and oxidized in the body, affords enough heat to raise the temperature of about 9000 grams of water one degree. In like manner a gram of protein has an energy- producing power expressed in calories of about 4000, and for carbohydrates the average value is also 4000. Allowance is made in these figures for the fact that to digest com- pletely any part of our food results in a decrease of the amount of FOOD IN RELATION TO HUMAN LIFE. 1 49 energy to be derived from it, and this affects the protein more than it does the other two. It is probably true that under favorable con- ditions the fat and carbohydrates can be completely utilized in the body and consequently their energy-producing power can be correctly estimated from their heat-producing power outside the body, In the case of protein, however, the digestion within the body is never so complete as to furnish all the energy that would be obtained by a complete combustion of these nitrogenous materials outside of the body. The fact remains, however, that all experiments yet made go to show that within practical limits We are safe in using the heat of combustion (expressed in calories) of any food-substance at a controlling measure of food values. Nutritive Ratio. — The requisite number of calories must, how- ever, be obtained by the utilization of such substances as contain all the elements needed by the body, and in such ratio as has been found available for the balance of nutrition. In carrying on its multifarious activities the body loses about 20 grams of nitrogen per day, which must be replaced by the same element in the food taken. Thus while the requisite number of calories may be fur- nished by fat or starch, these substances alone will not suffice for complete nutrition. The nutritive ratio, or the proportion of nitrogeneous to non-nitrogenous food, must be maintained in the proportion of 1 to 3, or at least 1 to 5. The following table of one hundred common food-mate- rials is arranged in the order of calorific or energy-giving power, but in considering the food value of any one substance its nitrogen content must also be considered, and such com- binations made as will yield the requisite elements for a well- oalanced ration. From even a cursory examination of the table it will be seen how widely some of the foodstuffs differ under differing conditions of soil moisture, fertilization in the case of plants, J5o AIR, WATER, AND FOOD. COMPOSITION OF SOME COMMON FOOD-MATERIALS AS PURCHASED* I. Fuel Value 3000-4000 Calories* per Pound. Food -material. Butter Lard (refined) Oleomargarine. . . . Salt fat pork Suet Walnuts (shelled) Refuse. Per cent. Water. Per cent. I I o 9-5 0.3 to 12.2 4.3 t° 21 9 3-5 Nitroge- nous Substances. Per cent. 0.2 to 5.0 i.r to 7.5 16.6 Fat. Per cent. 85.0 100.00 83.0 80.3 to 94.1 70.7 to 94.5 63.4 Carbo- hydrates. II. Fuel Value 2000-3000 Calories per Pound. Bacon Cheese (American pale). Chocolate Doughnuts Mutton Hank (fat) Peanut butter Sausage (farmer) 8.7 3 9 10.4 31.6 ,5 to 10.5 o to 25.8 28.9 2.1 22.2 9-5 28.8 12.5 to 13.4 5.1 to 7.6 10.7 20 3 27.9 59-4 35-9 47.1 to 50.2 16.4 to 25.7 59.8 46.5 40.4 III. Fuel Value 1500-2000 Calories per Pound. Barley (pearled) Beans (dried) Cake average (except fruit). Candy Cheese (Neuchatel) Corn-meal Corn-starch Crackers (average) Fat meats Gelatin Ham (smoked, medium fat) Infants' and invalids' foods Macaroni Oats Peanuts Peas (dried) Pop-corn Rice Rye flour Sugar (granulated) Wheat (entire) flour Wheat flour (white bakers'). Wheat (shredded) Zwieback 11. 7 4.5 to 28.4 9.8 to 12.9 I 9.6 to 15. 5 19.9 4.0 42.7 to 57.2 8.8 to 17.9 10. o 6.8 38.3 13.6 27.3 to 42.5 2.4 to 12.3 7.0 to 12.3 7.8 6.9 6.9 to 15.0 4-3 9.1 to 14.0 11. 9 to 13 6 7.0 to 10. 1 19.9 to 26.6 6.3 6.4 to 13.1 lo.i to 13.3 7.2 to 10.7 5.0 to 7.7 * Including fibre. 15. 1 to 22.3 6.7 to 11.6 10.7 13.0 84.2 10.2 to 21.9 2.0 to 22.5 7.9 to 16.6 16. s 19. 5 20.4 to 28.0 10 7 5.9 to 11.3 4.9 to 8.8 12.2 to 14.6 10.3 to 14.9 9.6 to 11. 4 8.6 to 11. 7 0.7 to 1.5 1 4 to 3.1 9.0 22.3 to 32.5 1.0 to 5.3 24.5 to 39.9 0.3 to 10.9 0.0 to 4.9 7-3 29.1 0.8 to 1.3 5.0 0.1 to 0.7 0.2 to 1.3 Perci 26.8 to 33.8. 45.8 to 63.2 .5 to 2.1 .9 to 2.0 .3 to 1.6 .1 to 1 1. 3 [7.1 77.3 to 78.1* 57.2 to 63.5* 63-3 96.0 2 tO 2.9 68.4 to 80.6* 90 o* 71.9* 66.9 to 89.4 67.2 to 78.4*. 66.5* 18. 5 58.0 to 67.4* 78.7 75.4 to 81.9* 77.6 to 80.2* IOO 69.5 to 77.0* 70.3 to 75.5 75.0 to 79.7* 72.1 to 74.2 IV. Fuel Value 1000-1500 Calories per Pound. Apples (dried) Bread (white) Corn-bread Dates Figs Fresh pork (ribs and shoulder). Medium fat mutton and beef... Mince-meat (commercial) Mince-meat (home-made) .. ., Pies Prunes (dried) Raisins , Sandwiches Sardines (canned) Salt mackerel [5.9 to 20.3 [4.4 to 27.8 15.0 IO. o 5-o 22.9 8. 6 to 47.4 35.3 28 4 10 48.0 1.3.8 1 1 6 to 25.0 4° .1 to 43.6 3« to 44.9 27.7 54-4 44.9 19.0 13 1 44-9 53 6 32.5 T 2 to 2.5 6 9.2 5 to io.'i 2 i-9 .6 to 5.7 1- .710 14.5 .4 to 12.9 6.7 4.8 4.4 1.8 »-3 10.9 23-7 16.3 0.1 to 5.0 »-3 2.3 to 9.8 2.5 0.3 25.4 to 25.6 19.8 to 31.2 14 6.7 9.4 30 9.0 48.6 to 86.91. 53.1 40.31054.3 70.6 68.3 to 83.1 60.2 32.1 39-2 62.2 68.5 33-3 * One Calorie equals 1000 calories. FOOD IN RELATION TO HUMAN LIFE. I5F COMPOSITION OF SOME COMMON FOOD MATERIALS. — Continued. V. Fuel Value 500-1000 Calories pek Pound. Food-material. Beef (round) Beef (sirloin steak). Chicken (fowls) . . . Cream Eggs Herring (smoked) . Meats (lean) Olives Salmon (fresh) . . . Salmon (canned)... Tapioca pudding. . Tongue (beef) Turkey Veal (breast) Refuse. Per cent. 8.5 12.8 18.0 to 42.7 44-4 0.5 to 11. 3 19.0 23.8 to 35.:. 11. 7 to 16.9 9.2 to 55 3 17.1 to 32.4 15.7 to 25.4 Water. Per cent. 62.5 54.0 38 3 to 53.7 74.0 65-5 19.2 59.9 to 69.2 52.4 45.0 to 51.2 54.6 to 58.2 52.0 to 71.6 32.4 to 69.2 41. 1 1044.7 48.5 to 55.7 Nitroge- nous Substances. Per cent. 19.2 16.5 11. 5 to 16.0 2-5 11.9 20.5 18. 1 to 21.4 i-4 12.6 to 15.0 18.6 to 20.2 2.8 to 4.2 7.8 to 20.2 15.8 to 16.8 14.2 to 16.9 Fat. Per cent. 9.2 16. 1 6.9 to 21.5 18.5 9-3 8.8 7.8 to 14.2 21.0 6.6 to 9.5 5.6 to 9.8 2.3 to 4.8 0.7 to 15.3 5.9 to 25.5 9.4 to 12.8 Carbo- hydrates. Per cent. 21.9 to 38.1 VI. Fuel Value 400-500 Calories per Pound. Beans (canned red kidney). Calf 's-foot jelly Salt cod (boneless) Succotash (canned) Sweet potatoes 1.6 20.0 72.7 77-6 54-8 71.4 to 79.9 55-2 VII. Fuel Value 300-400 Calories per Bananas .. . Butter beans Fish (fresh) . Grapes Hash Milk Potatoes . 3 r -o 50.0 25.2 to 46.0 25.0 48.9 29.4 46.1 to 49.1 58.0 80.3 87.0 62.6 7.0 0.2 18.5 4-3 17 4 27.7 2.9 to 4.4 o-3 0.7 to 1.7 14.9 to 22.4. i-4 0.6 21.9 [ES PER Pound. 8 °-4 14-3 4-7 o-3 14.6 1.9 to 12.0 1.8 to 5.9 1.0 1.2 14.4 6.0 1-9 9-4 3-3 4.0 5-o 1.8 O.I 14.7 VIII. Fuel Value 2^0-300 Calories per Pound. Apples Chicken (broilers) Cranberries Onions . Oysters (solid) . . . Parsnips , Pears 25.0 3*-4 to 55. 20.0 10. o 63.3 44-6 to 52.4 87.6 to 89.5 78.9 82.2 to 92.4 66.4 76.0 9.0 to 15.7 0.4 to 0.5 1.4 4-5 to 7.3 i-3 o-5 to 1 to c o-3 to 1 0.4 0.4 10.8 IX. Fuel Value 100-200 Calories per Pound. Beets Cabbage Carrots Green corn ... Lemons Oranges Soups (canned) Spinach , Squash Tomatoes (canned). 70.0 77 7 70.6 29.4 62.5 6^.4 91.0 to 92.8 91.6 to 92.8 44 2 92.5 to 07.9 O.7 0.6 2.9 to 5.0 1.8 to 2.4 o 7 0.3 to 1.7 0.5 to 0-8 to 0.5 9.3 to 10.9 8.9 1.5 to 6.2 10.8 7-7 4.8 7-4 7-7 5-9 8.5 0.6 to 5.7 3.1 to 3.4 4-5 1.4 to 8.1 X. Fuel Value 10-100 Calories per Pound. Asparagus Bouillon (canned) Celery Cucumbers Watermelons 20.0 15.0 59-4 94.0 96.5 to 96.7 75-6 .7 to 2.6 0.9 0.7 0.2 0.2 0.0 to 0.2 0.2 O.I 3-3 to 0.3 2.6 2.6 i5 2 AIR, WATER, AND FOOD and of fatness or leanness in animals, of method of prepara- tion or of combination in cooked foods. Therefore examinations of materials are imperative if there is to be any basis of calculation. In an institution where, for instance, flour forms two-thirds of the daily ration, if it contains the lowest per cent, of nitrogen it may not furnish sufficient proteid for a well-balanced ration, or if the meat used is very lean there may not be fat enough for the best nu- trition. The great variation in the proportion of water leads to many surprises, and the amount of unedible material is to be considered. The uneducated provider buys oysters under the impression that he is furnishing food of high value, and does not distinguish between potatoes and rice. In the present state of our knowledge, the best use to which we can put such tables and analyses is as a check against gross errors of diet, which are found with alarming frequency especially among children and students, those who can least afford to make them. References will be found in the Bibliography to works for further study along these lines. Dietaries. — A dietary is simply a known amount of food of known composition per person per day, week, or month. What is called a standard dietary is such a combination of food-materials as shall furnish the amounts held to be neces- sary. The following are examples of such standard dietaries: Approximate Amounts required daily by Nitrogenous, grams. Fats, grams. Carbohydrates, grams. Calortes. 62 78 IOO IOO 125 45 45 75 90 125 200 28l 380 450 500 1593 1890 2665 3092 3725 Adult at moderate work Adult at hard work... (In feeding experiments from 10 to 20 per cent, more must be allowed for waste and indigestibility.) FOOD IN RELATION TO HUMAN LIFE. 1 53 From the table on p. 150 may be selected such food as will give the required quantities in variety enough to suit any taste. That which the table cannot give is the per cent, of each which, tinder any given condition, will be utilized by the person fed. The strength of the digestive juices, exercise, fresh air, the cooking, the mixing of the foods, the habits of mind as to food, the customs of the family, all influence this utilization, so that other means must be resorted to in order to gain an idea of what is practicable. This is done by taking account of the food of persons free to choose ; of those in different countries, in different circumstances, and using a great variety of materials. Since Voit made his standard dietary in 1870, many hundreds, at least, have been so gathered in the United States alone — more than two hundred since 1886. All the information thus gained goes to confirm the theoretical standard, and also to show how much depends upon suitable preparation and combination. These last two things help each other. As food is ordinarily prepared, about 10 per cent, must be deducted for indigestibility in a customary mixed diet, and about 10 per cent, more for the refuse or waste of food as purchased, so that of the total pounds of meat, vegetables, and groceries some 20 per cent, is of no final service in the body. It is immaterial whether this amount is subtracted from the final calculation or whether the higher figures be taken, that is, whether 125 grams of proteid as purchased or 100 grams final utility is used. There will be an unknown limit in either case. According to late experiments 100 grams of proteid is high. The waste of fats is less in propor- tion as the dietary is a restricted one. Knowledge of Food Values Necessary. — The most serious aspect of the food question is that the taking of it is volun- tary, not, like air, a necessity beyond control, and that the 154 a: most fantastic ideas are allowed to rule. The day-laborer is in little danger, since his food demand is made strong by out- of-door exercise; but the student who shuts himself up in hot, close rooms, and who does not look upon food as his capital, but only as a disagreeable task or an amusement, is in great danger, as is he who, having heard that one can live on a few cents a day, proceeds to try it without knowledge, and suffers a loss of efficiency for years or for all his life. It is not nearly so difficult to acquire a working knowl- edge of food values as of whist or golf, so that on entering a restaurant a suitable menu may be made up within one's al- lowance. It is only necessary to correct prevailing impres- sions and reinforce one's experience. Figs, dates, raisins, and prunes are apt to be regarded as luxuries instead of as rich food-substances of a most di- gestible kind when freed from skin and seed. Nuts are a much neglected form of wholesome food, admirably suited to a winter table from their richness in fat, and also furnish- ing muscular energy, as is seen in the agile squirrel, and is proved by many human examples. With nuts, however, must be taken fruits or other bulky foods, to balance the con- centration. The somewhat compact and oily substance must be finely divided and freed from its astringent skin. In distinction from these rich foodstuffs, we find oranges, apples, etc.; the usual garden vegetables, asparagus, lettuce, etc., which, while they fill an important place in the dietary, add little directly to the energy of the 'body and need not be considered except as, by their flavor or aesthetic stimulus, they add to the efficiency of the rest. The foods which furnish the greatest nutrition for the least money are such materials as corn meal, wheat flour, milk, beans, cheese and sugar. The expensive cuts of meat, high- priced breakfast cereals and the like, add but little to the FOOD IN RELATION TO HUMAN LIFE. 1 55 nutritive value but greatly increase the cost of living. A meal of lettuce dressed with oil, eaten with bread and cheese, fulfils all the requirements of nutrition, and may cost five cents. The same food value from sweet breads, grape-fruit, etc., might cost a dollar. Incorrect ideas in regard to food values, and prejudice inherited or acquired against certain foods, have too often resulted in exclud- ing wholesome and nutritious articles from the dietary and de- creasing thereby the efficiency of the human machine. CHAPTER IX. THE PROBLEM OF SAFE FOOD. ADULTERATION AND SOPHISTICATION. Adulteration grows largely, if not almost entirely, from exces- sive competition. Nearly every article of common food has been found at one time or another to be adulterated, yet manufacturers testify that they willingly would stop this addition of foreign material if they could be sure that their competitors would stop also. Other causes there are also: the demand for goods out of season; for perishable products which must come many miles; the failure of the supply of a given substance to meet a continu- ing demand; all of these lead to adulteration, imitation and sub- stitution. To many people otherwise intelligent, the term adulterated food is synonymous with poisoned food. With others, thanks to alarm- ing newspaper articles, not wholly disinterested, the general im- pression is far beyond the reality. It is not necessary to use poison- ous or even deleterious material : it needs only to mix with the food material some substance cheaper but harmless, to make some change in the outward appearance of the article so that people shall not recognize the familiar substance, and then to herald far and wide the discovery of a new process by which the food value is greatly enhanced. "Things are not what they seem" is nowhere more true than in the case of foods. Definition of Adulteration. — To adulterate is "to debase" "to make impure by an admixture of baser materials." The word "adulterated refers to any food to which any foreign substance, not a proper portion of the food, has been added. It does not 156 THE PROBLEM OF SAFE FOOD. T57 matter whether the added material is of greater value than the food itself. The addition of coffee to cereal or substitute coffees, is properly held to be an adulteration. Deterioration should not be mistaken for adulteration. People who are not wholly familiar with the appearance of a food or the chemical and physical changes which it may undergo, think that if it does not taste just right or look just right that it must be adulterated. Appearance has slight relation to the purity of the article in these days of paint, polish and powder. Some forms of adulteration are more properly described under the head of misbranding, that is, referring to foods incorrectly de- scribed by the label. While the significance is not exactly the same as that of the word adulterated, yet the two may sometimes be applied to the same product. For instance, the addition of starch to sausage to conceal the use of excessive amounts of water and of fat constitutes an adulteration, which would not be the case if the article were properly branded to show the presence of the added "filler." To adulterate the coin of the realm or the liquor of the bar with a baser metal or an imitation whisky is a heinous offence. So is the mixture of milk with the baser article, water, which thereby lowers its food value. But the " wretched sophistry" which ob- scures the nature of things on a package of prepared food mis- leads more persons and inflicts more injury upon the community than the other, yet goes unrebuked. The most barefaced asser- tions are printed in magazines, and "pure-food shows" only whet the appetite for something new. Legal Definition of Adulteration and Misbranding. — In the Federal Pure Food Law, commonly known as the Food and Drugs Act of June 30, 1906, adulteration and misbranding are thus defined : Sec. 7. That for the purposes of this Act an article shall be deemed to be adulterated : 158 AIR, WATER, AND FOOD. In the case of food : First. If any substance has been mixed and pacjked with it so ■as to reduce or lower or injuriously affect its quality or strength. Second. If any substance has been substituted wholly or in part for the article. Third. If any valuable constituent of the article has been wholly or in part abstracted. Fourth. If it be mixed, colored, powdered, coated, or stained in a manner whereby damage or inferiority is concealed. Fifth. If it contains any added poisonous or other added dele- terious ingredient which may render such article injurious to health: Provided, That when in the preparation of food products for shipment they are preserved by any external application applied in such manner that the preservative is necessarily removed me- chanically, or by maceration in water, or otherwise, and directions for the removal of said preservative shall be printed on the covering or the package, the provisions of this Act shall be construed as applying only when said products are ready for consumption. Sixth. If it consists in whole or in part of a filthy, decomposed, or putrid animal or vegetable substance, or any portion of an animal unfit for food, whether manufactured or not, or if it is the product of a deceased animal, or one that has died otherwise than by slaughter. Sec. 8. That the term " misbranded," as used herein, shall apply to all drugs, or articles of food, or articles which enter into the composition of food, the package or label of which shall bear any statement, design, or device regarding such article, or the ingredients or substances contained therein which shall be false or misleading in any particular, and to any food or drug product which is falsely branded as to the State, Territory, or country in which it is manufactured or produced. That for the purposes of this Act an article shall also be deemed to be misbranded : THE PROBLEM OF SAFE FOOD. 1 59 In the case of food : First. If it be an imitation of or offered for sale under the dis- tinctive name of another article. Second. If it be labeled or branded so as to deceive or mislead the purchaser, or purport to be a foreign product when not so, or if the contents of the package as originally put up shall have been removed, in whole or in part, and other contents shall have been placed in such package, or if it fail to bear a statement on the label of the quantity or proportion of any morphine, opium, cocaine, heroin, alpha or beta eucaine, chloroform, cannabis indica, chloral hydrate, or acetanilide, or any derivative or preparation of any of such substances contained therein. Third. If in package form, and the contents are stated in terms of weight or measure, they are not plainly and correctly stated on the outside of the package. Fourth. If the package containing it or its label shall bear any statement, design, or device regarding the ingredients or the sub- stances contained therein, which statement, design, or device shall be false or misleading in any particular: Provided, That an article of food which does not contain any added poisonous or deleterious ingredients shall not be deemed to be adulterated or misbranded in the following cases: First. In the case of mixtures or compounds which may be now or from time to time hereafter known as articles of food, under their own distinctive names, and not an imitation of or offered for sale under the distinctive name of another article, if the name be accompanied on the same label or brand with a state- ment of the place where said article has been manufactured or produced. Second. In the case of articles labeled, branded, or tagged so as to plainly indicate that they are compounds, imitations, or blends, and the word "compound," "imitation," or "blend," as the case may be, is plainly stated on the package in which it is l6o AIR, WATER, AND FOOD. offered for sale: Provided, That the term blend as used herein shall be construed to mean a mixture of like substances, not ex- cluding harmless coloring or flavoring ingredients used for the purpose of coloring and flavoring only: And provided further , That nothing in this act shall be construed as requiring or compelling proprietors or manufacturers of proprietary foods which contain no unwholesome added ingredient to disclose their trade formulas, except in so far as the provisions of this act may require to secure freedom from adulteration or misbranding. Extent of Adulteration. — In any discussion of the extent to which adulterated foods are sold it must be borne in mind that the adulterated articles make up only a relatively small proportion of the food that actually passes over the counter. Flour, for ex- ample, is seldom adulterated ; pepper, mustard and vanilla extract often are. For one pound of these substances sold, iooo pounds or more of flour go out from the store. Figures given in official reports of food inspection do not represent the case exactly, be- cause the inspectors are trained men, and purchase samples of those lines of goods which experience has shown them to be most likely to be adulterated. Brands of foods which they have reason to believe are pure they do not sample. Estimated on the total quantity sold, it is doubtful if more than 5 to 10 per cent, of the food sold is adulterated in any way, and these figures would un- doubtedly be much too high for those states in which there is a well-enforced system of food inspection. Character of Adulteration. — Much of the present propaganda in the interests of pure food and the movement for the protection of the consumer can be summed up in three words: "An Honest Label." In many cases an accurate and true statement of the contents of the can or package is the only protection needed by the consumer, and is fully as efficient as well as much cheaper than prosecutions or restrictive measures. Many of the terms used on food packages deceive only the ignorant purchaser. THE PROBLEM OF SAFE FOOD. l6l "Strictly pure" is a well-understood trade term, with a meaning known to the initiated; the words " Home-Made" may cover some of the most highly developed products of synthetic organic chemistry. The cases in which the adulteration is of a character dele- terious to health are fortunately few. The use of canned goods brings certain dangers in the dissolved metals from the cans or from the solder, also from a careless habit of allowing food to stand in the opened tins. The liking for bright green pickles and peas leads to coloration by copper salts. So rapidly do new substances come upon the market that it is of little use to put into a general text-book definite statements of the quality of many foods. A baking-powder or a spice which is honestly made to-day may next week pass into the hands of un- scrupulous dealers who please the public and thereby salve their consciences. To furnish what the people think they want has been the rule from the days of an earlier generation of grocers, who divided a barrel of cooking-soda in halves and set one-half on one side of the store for "saleratus" and the other on the opposite side for soda, so that there should be no suspicion in the mind of the cus- tomer that the packages came from the same barrel, and yet each might satisfy his individual preference. Names that have passed down from a former generation as being above reproach are now found to cover adulterated goods. The trademark has passed into other and less scrupulous hands, and the new owners do not hesitate to trade upon the reputation earned by their predecessors. There are, however, several phases of the subject that should be briefly mentioned. Breakfast Foods, — The craving for something new to stimulate a jaded appetite already spoiled by endless variety and bad com- binations has led to the manufacture of a cereal preparation for nearly every day in the year, regarding some of which the state- 1 62 AIR, WATER, AND FOOD. ment is made that they are "predigested." No better comment- ary on the laziness or wilful ignorance of American providers could be made than this. Little do the people know about wheat or cooking if they suppose that grain can be changed by manipula- tion in any kind of machine so as to give greater food value than was contained in the grain. While it is true that some of these preparations are far better than the half-cooked grains found on so many tables, the fact remains that it is the cook and not the substance which is poor. The false statements on food packages of all kinds are so absurd that they would defeat their own pur- pose were they viewed in the light of common sense. It is not always best to have food which is too easily digested. A predigested food is quickly absorbed into the circulation, and hence a small quantity causes a sensation of fulness and satis- faction, which, however, soon passes away and a faintness results. This is especially true of the sugars and dextrins. Frequent meals should go with easily absorbed foods. The rapid digestion is the cause of much pernicious eating of sweets between meals, which satisfies the appetite for the time being and prevents substantial quantities of other foods being taken at the time they are offered. From a study of analyses of a large number of foods the fol- lowing conclusions are drawn by F. W. Robison : * i. The breakfast foods are legitimate and valuable foods. 2. Predigestion has been carried on in the majority of them to a limited degree only. 3. The price for which they are sold is as a rule excessive and not in keeping with their nutritive values. 4. They contain as a rule, considerable fibre which, while prob- ably rendering them less digestible, at the same time, may render them more wholesome to the average person. 5. The claims made for many of them are not warranted by the facts. * Mich. Agr. Expt. Sta., Bull. 211 (1904). THE PROBLEM OF SAFE FOOD. 1 63 6. The claim that they are far more nutritious than the wheat and grains from which they are made is not substantiated. 7. They are palatable as a rule and pleasing to the eye. 8. The digestibility of these products as compared with highly milled goods, while probably favorable to the latter, does not give due credit to the former, because of the healthful influence of the fibre and mineral matter in the breakfast foods. 9. Rolled oats or oatmeal as a source of protein and of fuel is ahead of the wheat preparations, excepting of course the special gluten foods, which are manifestly in a different class. In general, the cost of these foods is low if they are considered merely as confections to please the taste, but they are expensive foods regarded as substitutes for the ordinary cereal products. This is well shown in the following table in which the fuel value of breakfast foods and other common food products is graphically compared. Colors and Preservatives in Food. — For many years such sub- stances as alcohol, vinegar, sugar, salt, and the like, have been used to preserve food. Such materials are commonly held to be harmless to persons of sound digestion if used in moderate amounts. Within recent years, however, there has been a constantly increas- ing tendency toward the use in food products of such powerful antiseptics as formaldehyde, salicylic and benzoic acids and their salts, and boric acid. An important distinction to be borne in mind between this class of preservatives and those first named is that the former when used in food in quantity sufficient to pre- serve it make their presence known to the consumer by either their taste or odor. With the chemical preservatives, however, an intimation of their presence is conveyed to the consumer only by a statement on the label. It is the general feeling among those engaged in the enforcement of the food laws that the common use of these preservatives should be forbidden, or that they should be allowed only under certain definite restrictions. The question 164 AIR, WATER, AND FOOD. ■ 1 <*• CD co CM CO O O CO CM O O ' <*- CM O O ' O CM O O — CO 1 f- 1 1 CM 1 ■ T— ll O O 1 1 1 CO 1 ^i- II J 1 ° 1 j co O 1 j H 1 1 O 1 u - Z 1 1- < X < 1 co 1 1 * 1 h 1 1 < 1 j C ) 1 : t- < 1 ' < < LU 1 LJ ! n j U) ' ■ I 1 t 1 5 I 3 < ce O 1 O I 1 * i 1 1-' 5 1 "*. c 1 LU -1 O Ul CO LU D STEAK_. E NUTS__. A VITA -SALT Q < 1 ul Ul 1 * I ; i j 1 l j 1 j 1 1 O X 5 t LU ,Ti DC O < O Ul 1 3 CO u. z ' 9 P 1 c 1 LU Q ° 2 II > 1 : ui 1 l J CO cr O LU Q O CO MEAL TOES_ IE WH E WHI HzEl-^:o^coi S :'<^ LlJ Fat. — Since the fat is so important a constituent of milk, an endless variety of methods and modifications for its deter- mination have been devised. The processes which are in most general use may be divided into three classes: i. Estimation of the fat by simple extraction of the milk, best dried on some absorbent material. 2. Volumetric estimation of the fat liberated by chemical treatment from the milk and collected by centrifugal force. 3. Estimation of the fat by extraction from the milk itself after solution of the casein by acid. A typical method from each class will be described in de- tail. (t) Adams' Method. — Directions. — Roll a strip of fat- free blotting-paper, 22 inches long and 2-J inches wide, into a rather loose coil and fasten it by a bit of copper wire. Hold the coil in one hand and carefully run on to the upper end of it 5 c.c. of milk from a burette pipette. Place the coil, diy end downward, in the water-oven and dry it for an hour. When dry remove the wire and place the coil in the Soxhlet extractor. If preferred, the strip of paper may be held hori- zontally in a frame and the milk run on to it. When dry the paper is rolled into a coil and extracted. Weigh the extraction- flask, place in it 75 to 100 c.c. of petroleum ether and connect the extractor with the condenser. After the coil has been extracted for at least two hours remove the extractor and evaporate the petroleum ether at low temperature, taking care to avoid the vicinity of free flames. Dry the flask with the extracted fat in the water oven to constant weight. Avoid pro- tracted heating, which would cause partial oxidation of the fat. Notes. — Absorbent paper exercises a selective action on the constituents of milk so that the fat is left on the surface of the paper, mixed with only about one-third of the non-fatty solids, and hence it is more easily extracted; further, owing to the greatly increased surface exposed, the extraction of the fat is practically complete. 176 AIR, WATER, AND FOOD. Ethyl ether may be used instead of petroleum ether, but care should be taken that the ether is perfectly dry, otherwise other substances than fat, principally milk-sugar, will be extracted. On the other hand, substituted glycerides may not be dissolved out by ether. For these reasons the petroleum ether is to be preferred as a solvent, although its action is considerably slower than that of the other. Owing to the inflammable nature of the solvents employed, Fig. 12. — Apparatus for Fat Extraction. it is best not to use a flame as the source of heat, but to heat the flask by means of a steam- or water-bath. In this labora- tory small electric heaters about 4 inches in diameter are used and have been found safe and convenient. The complete apparatus is shown in Fig. 12. In using these it should be borne in mind that considerable quantities of ether or petroleum ether in contact with the heatea surface may ignite, and caution should be taken not to evaporate any quantity of these solvents from an open vessel. (2) Babcock Method. — Directions. — Measure 17.6 ex. of the milk from a pipette into the long-necked, graduated whirling- food: analytical methods. 177 bottle. Measure out 17.5 c.c. of sulphuric acid 1^0, gr. 1.83 ) r and add it gradually to the milk, mixing the t\*-« thoroughly after each addition. Take care that none of the liquid spurts into the neck of the bottle. After mixing the milk and acid, and while the bottles are still hot, place them in opposite pockets in the centrifugal machine, in even numbers, and whirl them for five minutes, at full speed. Then remove the bottles and add hot water up to the necks, after which whirl them again for one minute. Again add hot water until the fat rises to the 8 mark on the stem. Place the bottles in the machine and whirl them at the same rate as before for one minute. Then measure the length of the column of fat by a pair of dividers, the points being placed at the extreme limits of the column, the fat being kept warm, if necessary, by standing the bottle in hot water. If now one point of the dividers is placed at the zero mark of the scale on the bottle used, the other will indicate the per cent, of fat in the milk. Notes. — When the acid and milk are mixed the mixture becomes hot from the action of the acid on the water in the milk and turns dark-colored on account of the charring of the milk-sugar. The casein is first precipitated and then dissolved. The fat is thus separated in a pure state from the other constituents of the milk. The fat obtained should be of a clear, golden-yellow color, and distinctly separated from the acid solution beneath it. If the fat is light-colored or whitish, it generally indicates that the acid is too weak, and a dark-colored fat with a stratum of black particles below it indicates that the acid is too strong. The best results will be obtained by the use of acid of the strength noted above. A violet color is sometimes produced when the first por- tions of the acid and milk are mixed. This frequently indi- cates the presence of formaldehyde. (See p. 187.) 1 7 8 AIR, WATER, AND FOOD. (3) Gottlieb Method. — Directions. — Measure 5 c.c. of milk into a glass-stoppered 50-c.c. cylinder and add the following reagents, being careful to add them in the order given and to shake the stoppered cylinder thoroughly after the addition of each reagent: 1 c.c. of ammonia, sp. gr. 0.96, 5 c.c. of alcohol, 12.5 c.c. of ethyl ether and 12.5 c.c. of petroleum ether. Let the cylinder stand until the lower layer is free from bubbles, over night if necessary. With ordinary milk the separation takes place rapidly, but with sweetened condensed milk the longer time may be necessary. Transfer the upper layer to a tared flask by means of the apparatus shown in Fig. 13. This consists of a cork carrying an ordinary glass T tube. Through the straight limb of the T tube slides a bent glass tube, which is turned up at the lower end. The tube is adjusted by sliding it through the rubber collar (C) so that the lower end rests just above the junction of the two layers. On then blow- ing gently in the side arm (5), the upper layer is forced out into the flask. Repeat the extrac- tion once, using 10 c.c. each of ether and pe- troleum ether and blowing it off into the flask. Distil off the solvent and dry the residual fat to constant weight in the water oven. Notes. — It is almost useless to try to extract the fat from milk by shaking it directly with .a solvent. An emulsion is formed with the other constituents of the milk, and it is impossible to get a good separation of the solvent even with the centrifugal machine. This is prob- ably due to the action of the colloidal casein, because it is found that when a complete or partial solution of the casein is effected it is comparatively easy to extract and separate the fat by a solvent immiscible with water. food: analytical methods: milk. 179 The method is applicable to whole milk but is especially valuable in determining fat in such products as skim milk or butter milk, which are low in fat. It is also of value in the analysis of sweetened condensed milk. Relation between Specific Gravity, Fat, and Solids in Milk. — As has been stated already, the specific gravity of milk is, in the main, a function of two factors, namely, the percentage of solids not fat and that of the fat. The former raises it, the latter lowers it. Taken by itself it affords very little indication of the composition, but if any other item be known, it should be possible to find, by calculation, the other quantities, provided the assumption is true. The solids not fat are made up of several fluctuating constituents, but " nor- mal milk " seems to contain them in such a constant ratio that a calculation serves at least to detect an abnormal sam- ple. For example, given the specific gravity and solids to calculate the fat: Specific gravity = Gr. The amount which each per cent, of solids not fat raises the specific gravity = s. The amount which each per cent, of fat lowers the specific gravity = f. Total solids = T. Solids not fat = 5\ Fat = F. Gr = Ss — Ff; or, substituting for 5 its value T — F; Gr = (T — F) s — Ff. The uncertainty of the calculation lies in the val- ues of s and f, which have not been quite satisfactorily deter- mined. At different times various formulae have been proposed for this calculation, varying, as a matter of course, with tha method of fat extraction employed. The one most extensively used is that of Hehner and Richmond,* which is based on extensive observation and perfected process * Analyst, 13 {1888), 26; 17 (1892), 170. i8o of fat extraction. This formula is generally stated as fol- lows: F = 0.8597 — 0.2186G, where F represents the fat, 7"the total solids, and G 1000 X (specific gravity — 1.000). The simple formula —F = T — — answers within the F 5 4 limits of experimental error for normal milk, but not for skimmed or watered milk. Example. — Data: Gr = 1.0323; G = (Gr — 1) X 1000 = 32.3; T= 12.90. 6 32. ^ —F= 12.90 — . F — 4.02 calculated, 3.99 found. A similar relation has been worked out for the poteids and sugar, so that from three determinations the whole com- position may be calculated. Example as above: Ash = .70 = A. Q Formula: P= 2.ST + 2.$A — 3.33F — .68—-, Gr. or P=z 36.12 + 1.75 — 13.32 — 21.28 = 3.27. Sugar = T-{A + P+F) = I2.90 - (.70 + 3.27 + 4.02) z= 4.9I. Where a number of calculations are to be ma^e, Rich- mond's milk-scale will be found convenient. This is an in- strument based on the principle of the slide-rule, having three scales, two of which, for the fat and the tota 1 solids, are marked on the body of the rule, while that for the spe ific gravity is marked on the sliding part. Extended tables are also used for the same purpose. Analyst, 13 {1888), 26; 17 {i8g2), 170. food: analytical methods: milk. 181 Milk-sugar. — The methods for the determination of the sugar in milk may be divided into two general classes: (i) those depending on the reducing power of the sugar upon an alkaline copper solution; (2) those which are based upon observations of the degree of rotation of the plane of polarized light. (1) Determination by Fehling's Solution according to Munson and Walker.* Directions. — The milk must first be clarified to remove substances other than sugar which would exert a reducing action on the Fehling's solution. Measure 25 c.c. of milk into a 500-c.c. calibrated flask. Add about 400 c.c. of water, 10 c.c. of Fehling's copper sulphate N solution, then 35 c.c. of — NaOH, and make up to 500 c.c. Mix thoroughly and filter through a dry filter. Determination. — In a No. 3 beaker mix 25 c.c. of the Fehling's copper sulphate solution and 25 c.c. of the alkaline tartrate solution. Add 50 c.c. of the milk sugar solution, prepared as above, cover the beaker with a watch glass, and heat it upon wire gauze. Regulate the flame so that boiling shall begin in four minutes, and continue the boiling for exactly two minutes. Filter the cuprous oxide without delay through asbestos in a weighed Gooch crucible, wash it with hot water until free from alkali, pour out the hot nitrate, then wash with 10 c.c. of alcohol and finally with 10 c.c. of ether. Dry the crucible for 30 minutes at the temperature of boiling water and weigh. Find the milligrams of lactose monohydrate corresponding to the weight of cuprous oxide from Table XII on page 248 and •calculate the percentage present in the milk. * J. Am. Chem. Soc. (1906), 663; (1907), 541. l82 AIR, WATER, AND FOOD. Notes. — The general principle upon which all these methods depend is based on the fact that certain sugars, among which is lactose, have the power of reducing an alkaline solution of copper to a lower state of oxidation in which copper is separated as cuprous oxide. The copper salt which is found to give the most delicate and reliable reaction is the tartrate. The two solutions which make up the Fehling's solution are best preserved separately, and rrixed only when wanted for use, as otherwise the reducing power of the solution is liable to change. The amount of reduction of the copper salt to the cuprous oxide is affected by the rate at which the sugar solution is added, the time and degree of heating, and the strength of the sugar solution; hence the necessity for adopting a definite procedure and for taking the results from a table determined by exactly the same procedure for varying amounts of the sugar. The asbestos which is used should be previously boiled in nitric acid and then in dilute sodium hydroxide and thoroughly washed. A layer about a centimeter thick should be used in the crucible, and a " blank " determination made with the Fehling's solution should not show a change in weight greater than one-half milligram. After the precipitated cuprous oxid: has been weighed it may be dissolved in hot dilute nitric acid, the asbestos in the crucible washed and dried as described, when it is again ready for use. Do not remove the asbestos from the crucible. (2) Determination by the Saccharimeter. — For the optical determination of milk-sugar the method of double di- lution, as described by Wiley and Ewell,* will be found satis- factory. Directions. — Into each of two flasks, marked at 100 and 200 c.c, respectively, put 65.52 grams of milk, add 10 c.c. of acid mercuric nitrate, fill to the mark, and mix by shaking. * Analyst, 21 (ySg6), 182. food: analytical methods: milk. 183, Filter through dry filters and polarize in a 400-millimeter tube, using the Schmidt and Haensch saccharimeter. Cal- culate the results as in the following example: Weight of milk used = 65.52 grams; Reading from 100-c.c. flask = 2o°.84; " " 200-c.c. flask = io°. 15. Then 10. 15 X 2 = 20.30; 20.84 — 20.30 = 0.54; 0.54 X 2 = 1.08; 20.84 — 1.08 = 19.76; 19.76 —■ 4 = 4.94, which is the per cent- of milk-sugar. Notes. — The object in using the method of double dilu- tion is to avoid the necessity of making corrections for the volume of the precipitate of casein and fat. The method is based on the fact that, within certain limits, the polarizations of two solutions of the same substance are inversely propor- tional to their volumes. The flasks should be filled at nearly the same temperature as that at which the polarizations are made, and the tem- perature of the room should be kept as nearly as possible at 20 to avoid errors arising from marked changes in tem- perature. PROTEIDS OF MILK. Determination of Total Proteids. — Weigh 5 grams of milk into a digestion flask and determine the nitrogen by the Kjeldahl process, as directed on page 206. Multiply the per cent, of nitrogen by the factor 6.38 to obtain the per cent, of proteids. The frothing of the alkaline solution during the distillation may be prevented by the addition of a piece of paraffin about the size of a bean. 184 AIR, WATER, AND FOOD. Determination of Casein and Albumin.* — Directions. — To 10 grams of milk add 90 c.c. of water at 40-42 C. and then 1.5 c.c. of 10 per cent, acetic acid. Agitate and warm at the above temperature until a flocculent precipitate sepa- rates, leaving a clear supernatant liquid. Filter, wash, and determine the nitrogen in the washed precipitate and filter by the Kjeldahl process. Multiply by 6.38 for the casein. To determine the albumin neutralize the filtrate with caustic alkali and phenolphthalein and heat it at ioo° C. until the precipitate settles clear. Filter, wash, and determine the nitrogen as before. Nitrogen multiplied by 6.38 equals albumin. Notes. — The principal proteid bodies present in milk are casein and albumin. Others are present in much smaller quantity, such as fibrin or globulin. Different observers at various times have claimed the presence of other nitrogenous bodies, but these have not been entirely substantiated. It is now generally held that the colloidal state in which the casein is held in milk is due to the combination with it of certain mineral compounds, chiefly those of calcium. The action of precipitants is on these mineral matters, breaking up the com- bination and releasing the insoluble casein. Interpretation of Results. — The most common forms of adulteration of milk are the addition of water and the removal of cream. Occasionally some foreign material may be added. A good idea of the form of adulteration may usually be gained from the relation between the fat and the solids not fat. In watered milk both of these are low, but the ratio between them is about the same as in normal milk. In skimmed milk the solids not fat may be nearly normal while the fat is very low. If the total solids and the solids not fat are both below standard, * Van Slyke and Hart: Am. Chem. J., 29 (1903), 170. food: analytical methods: milk. 185 while the proportion of fat to solids not fat is very small, it is a fair assumption that the milk is both skimmed and watered. Leach * states that it is nearly always safe to condemn a milk as watered, if the total solids are below 10.75 per cent., with a corresponding amount of fat. Direct Determination of Added Water. — This may be done by determining the specific gravity of the milk-serum after coagulation and removal of the casein. f The casein is coag- ulated by dilute acetic acid, filtered off on a dry filter, and the specific gravity of the nitrate taken at 15 C. by the West- phal balance. The specific gravity of the serum from normal milk is never below 1.027, an( ^ oruv rarely below 1.029. The addition of each ten per cent, of water lowers tne specific gravity by 0.0010 to 0.0035. A more convenient method of determination is Dy the Zeiss immersion refract ometer if this instrument is available. (See Bur. of Chem., Bui. 107 (Revised), p. 120; also 1-eacn, Food Inspection and Analysis, p. 766.) The Abbe reiractometer, page 202, can also be used. The determination is often of importance since it enables the analyst to distinguish readily between milk which is directly adulterated on the one hand, and that which is only below standard on the other. In legal prosecutions the amount of penalty imposed is sometimes dependant on whether the analyst can show evidence of the actual addition of water. Cane-sugar. — To detect the presence of cane-sugar boil about 10 c.c. of the milk with 0.1 gram of resorcin and 1 c.c. of rrydrochloric acid for five minutes. The liquid will be colored rose-red if cane-sugar be present. The quantitative determination may be made by means of the polariscope. * "Food Inspection and Analysis." f Woodman: J. Am. Chem. Soc, 21 (1899), 503; Leach: "Food Inspection and Analysis," p. 765. l86 AIR, WATER, AND FOOD. Cane sugar is occasionally found in the milk through the use of diluted condensed milk to eke out the supply. Starch. — Heat 10 c.c. of the milk to boiling in a test-tube, and when cold add a few drops of the solution of iodine in potassium iodide. The presence of even 0.2 per cent, of starch will be shown by the characteristic blue coloration. Coloring-matters. — The principal coloring-matters added to milk are annatto, caramel, and coal-tar dyes. In general, coloring-matters are added only to watered milk, but general, coloring-matters are added only to watered milk, but occasionally samples which were of standard quality have been found to be colored. Directions .—Put about 100 c.c. of the milk into a small beaker, add 2 c.c. of 25 per cent, acetic acid and allow the beaker to stand quietly for about ten or fifteen minutes in a water-bath kept at 70 C, the casein being thus separated as a compact cake. Decant off the whey, squeezing the curd as free from it as possible by means of a spatula. Trans- fer the curd to a flask and let it remain covered with ether for an hour or more. Evaporate the ether extract, which contains the annatto if present, add 5 c.c. of water, and dilute sodium hydroxide until the mixture, after thorough beating and stirring with a glass rod is faintly alkaline to litmus paper, and filter through a wet filter. If annatto is present, it will permeate the filter and give it an orange color when the fat is washed off under the tap. Treat the filter with stannous chloride. If annatto is present, a pink color will be produced. After pouring off the ether examine the milk-curd for caramel or aniline orange. If the curd is left white, neither of these colors is present. If caramel has been used, the curd will be of a pinkish-brown color; if the color is due to the aniline dye, the curd will have a yellow or orange tint In doubtful cases the curd should be compared with one from a food: analytical methods: milk. 187 milk known to be uncolored. To distinguish between the two colors shake a small portion of the curd in a test-tube with strong hydrochloric acid. The caramel-colored curd will act similarly to an uncolored curd, that is, it will gradually produce a deep blue color in the solution. On the other hand, the coal-tar color will immediately produce with the hydrochloric acid a pink color. Note. — It is to be regretted that there is no positive test for caramel sufficiently delicate to serve here. The test as described is a negative one, the only indication of caramel being the occurrence of a colored curd in which the color is not given by the coal-tar dye. Preservatives. — The preservatives usually added to milk are formaldehyde and borax or boric acid. Carbonate of soda is added in some cases to disguise the acidity of sour milk. Formaldehyde. — This is generally used as a 40 per cent, aqueous solution, sold under the name of formalin. Several simple tests commonly used for the detection of formaldehyde will be described. (1) When the sulphuric acid is added to the milk in making the Babcock test for fat, a bluish- violet ring will be noticed at the junction of the two liquids when formaldehyde is present. One part of formaldehyde in 200,000 parts of milk can be detected by this test, but it fails when the formaldehyde amounts to 0.5 per cent. The test is more delicate if the sulphuric acid contains a trace of ferric chloride. (2) To 10 ex. of milk in a small porcelain dish add an equal volume of hydrochloric acid (1.20 sp. gr.). Add one drop of ferric chloride solution and heat the dish with a small flame, stirring vigorously, until the contents are nearly boiling. Remove the flame and continue the stirring for two or three minutes, then add about 50 c.c. of water. The presence of formaldehyde will be shown by a violet color which appears in i88 the particles of the precipitated casein, the depth of color depending on the amount of formaldehyde present. The color should be observed carefully at the moment of dilution. This test readily shows the presence of one part of formaldehyde in 250,000 parts of milk, if fresh. Boric Acid or Borax. — Make 25 c.c. of the milk distinctly alkaline with lime water and evaporate to dryness on the water bath. Char the residue over a flame but do not neces- sarily heat it until white. Digest the residue with 15-20 c.c. of water and add hydrochloric acid (1.12) until the mixture is faintly acid to litmus paper. Filter, and add 1 c.c. of acid fn excess. Place a strip of turmeric paper in the solution and evaporate to dryness on the water bath. If boric acid or borates are present, the paper takes on a peculiar red color, which is changed by ammonia to a dark blue-green, but is restored by acid. Excess of hydrochloric acid should be avoided, as it turns the paper a dirty green when evaporated. This test can also be applied to the hydrochloric acid solution of the ash. Sodium Carbonate. — Detected in the milk-ash, as on page 174. If effervescence occurs, test the original milk with rosolic acid as follows: Mix 10 c.c. of milk with an equal volume of alcohol, and add a few drops of a one per cent, solution of rosolic acid. The presence of sodium carbonate is indicated by a more or less distinct pink coloration. A comparative test should be made at the same time with milk known to be pure. CONDENSED MILK. . It may in some cases afford an interesting variation to carry out the tests on condensed milk, this having within recent years become an important article of food. With the unsweet- ened condensed milk, commonly sold as " evaporated milk," the methods as used with whole milk can be applied directly to food: analytical methods: milk. 189 the diluted sample. In the case of sweetened condensed milk, which is usually meant by the term condensed milk in this country, the methods must in some cases be modified, on account of the large proportion of cane sugar present. The following are analyses of a few typical samples of sweetened condensed milk: COMPOSITION OF SWEETENED CONDENSED MILK. Degree of Con- densa- tion. Fat in Total Solids. Water. Milk Solids. Cane- sugar. Lac- tose. Pro- tein. Fat. Ash. Origi- nal MUk. I 1 72.95 27.05 30.01 42.94 11.28 7-85 9-3 1.58 2.26 4. II 2 2 71 .03 28.97 27.49 43-45 11.78 7-51 6.6 1.60 2.29 2.88 3 J 7i-5« 28.42 24.24 47-34 13.08 9.04 0.15 1.97 2.8 0.05 Normal. 2 Not made from standard milk. 3 Condensed from skimmed milk. Preparation of the Sample. — Transfer the entire contents of the can to a large evaporating dish, scraping it out clean, and work it thoroughly with a pestle until homogeneous. Weigh out 40 grams of the mixed sample and dilute to 100 c.c. in a calibrated flask. Total Solids. — Dilute 10 c.c. of the 40 per cent, solution with an equal volume of water and evaporate 5 c.c. of the diluted mixture, corresponding to 1 gram of the sample, to dryness in a weighed platinum dish, as directed on page 173. It is of importance to have the sample very dilute in order to get an accurate determination of the solids and this can best be accomplished in the manner described. Ash. — Ignite the residue from the determination of total solids, as in the case of ordinary milk. Fat. — The fat is the determination of most importance since judgment of the quality of the sample is based more largely on this factor than on any other. Its determination, however, is 190 AIR, WATER, AND FOOD. attended with some difficulty on account of the large amount of cane sugar present. The Babcock method, for instance, does not give satisfaction since the charring of the sugar by the sulphuric acid prevents a clean separation of the fat. The Adams method, moreover, is unreliable because the cane sugar dries on the paper coil, enclosing the fat so that it is not readily extracted by the solvent. Several modifications of these methods have been proposed, however, by which fairly good results may be obtained. Babcock Method as modified by Leach. — Leach has modified the Babcock test so as to make it available for sweetened con- densed milk by precipitating the proteids and fat with copper sulphate and then removing the interfering sugar by several extractions with water. Directions for carrying out the test will be found in Leach: Food Inspection and Analysis, p. 149, or in Bur. of Chem., Bui. 107, p. 123. Adams Method. — This can be applied in the following manner: Dry 5 c.c. of the 40 per cent, solution on the paper coil, as described on page 175. Extract with petroleum ether in the usual manner; dry, soak the coil in 500 c.c. of water for several hours; dry, extract again for five hours and weigh the fat as usual. Gottlieb Method. — Use 10 c.c. of the 40 per cent, solution and carry out the determination exactly as described on page 178. In many ways this method will be found to give the best results on condensed milk. Proteids. — Determine nitrogen in 5 c.c. of the 40 per cent, solution and multiply by 6.38. Lactose. — Use the method described on page 181 on 25 c.c. of the 40 per cent, solution. Cane Sugar.— This may be determined with sufficient accuracy for most purposes by difference, subtracting the milk solids (the sum of the lactose, fat, protein and ash), from the food: analytical methods: milk. 191 total solids. The direct estimation of the cane sugar in the presence of lactose may be carried out with the polariscope by the choice of a suitable inverting agent. The writer has obtained good results by inversion with acid mercuric nitrate, as described by Harrison.* BUTTER. General Statements .—Butter consists of the fat of milk, together with a small percentage of water, salt, and curd. The curd is made up principally of the casein of the milk. These various ingredients are present in about the following proportions : Fat 78.00-90.0 per cent. ; average, 82 per cent. Water 5.00-20.0 " " " 12 " " Salt 0.40-15.0 " " " 5 " " Curd 0.11- 5.3 " " " 1 " The fat consists of a mixture of the glycerides of the fatty acids. The characteristic feature of butter-fat is the extraordinarily high proportion of the glycerides of the solu- ble and volatile fatty acids when contrasted with other fats. Tl e following may be taken as the probable composition of normal butter-fat: Acid. Per cent. Acid. Per cent. Triglycerides. Dioxystearic 1 .00 1 .04 Oleic 32.50 33.95 Stearic 1.83 1.91 Palmitic 38.61 40.5 1 Myristic 9.89 10.44 Laurie 2.57 2.73 Capric 0.32 0.34 Caprylic 0.49 0.53 Caproic 2.09 2.32 Butyric 5.45 6.23 Total 94-75 100.00 Accordiug to this, the proportion of volatile acids in butter (butyric, caproic, caprylic, and capric acids) amounts to 8.35%. The amount of volatile acid in lard, for example, is about 0.1%. "■Analyst, 29, 248. f Browne, /. Am. Chem. Soc, 21 (1899), 807. 192 AIR, WATER, AND FOOD. The usual examination of butter consists in the examina- tion of the butter-fat, in order to detect the presence of foreign fats. The determination of the amount of curd may be of value also in some cases, more especially from a sanitary standpoint. The chief danger to health probably lies in the possible decomposition of the nitrogenous portion, for it is quite generally recognized that the substitution of oleomargarine is not injurious to health. It is a not infre- quent practice, however, as remarked in the previous chap- ter, to incorporate a large amount (sometimes as high as 33 per cent.) of curd and other nitrogenous matters in fresh butter. If this is kept for any length of time, a decomposi- tion is liable to occur which may have serious effects. Other determinations that are usually made are the water and salt. The term " oleomargarine " is usually applied to a mixture of refined lard, " oleo oil," which is mainly the olein of beef fat, and cottonseed oil. Ordinarily a small proportion of butter is added and the product is generally churned with milk. A comparatively recent form of butter substitute which finds extensive use in some sections of the country is "process," or "renovated," butter. The raw material, or " stock," used for the manufacture of this consists of butter which cannot be sold as butter either because of deteriora- tion through rancidity or moulding or because, through care- lessness on the part of the makers, it possesses an unattractive appearance or flavor. The chief recruiting-ground for this material is the country grocery store. The fat, separated from the curd by melting and settling, is aerated to remove disagreeable odors and leave it nearly neutral. This is then emulsified with fresh milk which has been inoculated with a bacterial culture, and the whole is chilled, granulated, and churned. The butter is then worked and packed for market in the usual manner. The character of the prod- food: analytical methods: butter. 193 uct has much improved since the early days of the industry, the best grades now approximating- the lower grades of creamery butter. The " aroma " of butter seems to be connected with the decomposition produced by the action of bacteria on the casein and the small amount of milk-sugar that is present, and not with any change in the fats; there is no evidence, however, that any unwholesome effect is produced by the aroma-giving organisms. The rancidity of butter-fat is generally considered to be due to decomposition and oxidation of the fatty acids, espe- cially the unsaturated ones, the amount of change depending" on conditions of light, heat, and exposure to air. Examination of the Fat. — The fat is first separated from the other constituents of the butter so that it may be weighed out for the various tests. Directions. — Melt a piece of butter, about two cubic inches, in a small beaker placed on top of the water-bath so that the temperature shall not rise above 50°-6o°. After about fifteen minutes the water, salt, and curd will have set- tled to the bottom. (A better separation may be secured by dividing the melted sample equally between two test-tubes and whirling them for 3-4 minutes in a centrifugal machine.) Place a bit of absorbent cotton in a funnel, previously waimed, and decant off the clear fat through the cotton into a second beaker, taking care that none of the water or curd is brought upon the filter. When the filtered fat has cooled to about 40 place a small pipette in the beaker and weigh the whole. By means of the pipette the desired amount of fat is taken out, the pipette replaced in the beaker, and the whole again weighed. The difference in weight gives the exact amount of fat taken. It is a saving of time, however, if several por- tions are to be weighed out, to make the weights one after 194 AIR, WATER, AND FOOD. another, so that one weight will suffice for a determination. Weigh out thus : Two portions of 5 grams each into 250-c.c. round-bottomed flasks for the Reichert-Meissl method, one portion of 2,5 to 3 grams into a 500-c.c. beaker for Hehner's process, two portions of about .35 to .5 gram each into 300-c.c. .glass-stoppered bottles for determination of the iodine value. In the case of the larger portions, weigh only to the nearest milligram. (1) Reichert-Meissl Number for Volatile Fatty Acids. — Directions. — To the fat in the 250-c.c. flasks add 2 c.c. of strong caustic potash (1:1) and 10 c.c. of 95 per cent, alcohol. Connect the flask with a return-flow condenser and heat on a water-bath so that the alcohol boils vigorously for 25 minutes. At the end of this time disconnect the flask and evaporate off the alcohol on a boiling-water bath. After the complete removal of the alcohol add 140 c.c. of re- cently boiled distilled water which has been cooled to about 50 . The water should be added slowly, a few cubic centi- meters at a time. Warm the flask on the water-bath until a clear solution of the soap is obtained. Cool the solution to about 6o° and add 8 c.c. of sulphuric acid (1:4) to set free the fatty acids. Drop two bits of pumice, about the size of a pea, into the flask, close it by a well-fitting cork, which is tied in with twine, and immerse it in boiling water until the fatty acids have melted to an oily layer floating on the top of the liquid. Cool the flask to about 6o°, remove the cork, and immediately attach the flask to the condenser. Distil no c.c. into a graduated flask in as nearly thirty minutes as possible. Thoroughly mix the distillate, pour the whole of it through a dry filter, and titrate 100 c.c. of the N . mixed filtrate with — ■ sodium hydroxide, using phenol- phthalein as an indicator. Multiply the number of cubic centi- food: analytical methods: butter. 195 meters of alkali used by eleven-tenths, and correct the reading also for any weight of fat greater or less than 5 grams. For example, if 5.3 grams of butter-fat are used, and 100 N c.c. of the distillate require 27.4 ex. of — NaOH, no c.c. would require 2.7.4X^=30.14 c.c. Then 5.3 : 30.14 = 5 : x . #=28.4. x is the Reichert-Meissl number. Notes. — The Reichert-Meissl number for genuine butter varies from 24 to 34; the average usually taken is 28.8. Cocoanut oil gives a value of 6-8; other edible fats and oils have a value usually less than 1 . The presence of cocoanut oil is readily shown by the Reichert- Meissl number taken in connection with the saponification value, that is, the number of milligrams of potassium hydroxide required to saponify one gram of the fat. (For a description of the method of determining this see Lewkowitsch: Oils, Fat, and Waxes, or Gill: A Short Handbook of Oil Analysis). The Reichert-Meissl number is higher in butter fat than in cocoanut oil, while the saponification value is lower. In pure butter fat the value of the expression (Saponification value — Reichert- Meissl number — 200) varies from 3.4 to 4.1; in pure cocoanut oil it runs from 47 to 50.7.* When the fat is treated with potash it is decomposed, the glycerine being set free, and the potassium salts of the fatty acids, that is to say, the potassium soaps are formed. Hence the process is called saponification. For butyric acid the reaction may be expressed C 3 H 5 (C 3 H T COO) 3 + 3KOH = 3 C 3 H 7 COOK + C 3 H 5 (OH) 3 . The alcohol is used to dissolve the fat. But at the moment the butyric acid is set free it tends to combine with the alcohoi to form a volatile ether: C 3 H 7 COOH + C 2 H 5 OH = QHCOOC 2 H 5 + H 2 0. Juckenack and Pasternack: Ztschr. Nahr. Genussm., 7 (1904), 193. I96 AIR, WATER, AND FOOD. The object of the return-flow condenser is to prevent the escape of this volatile ether and to allow of its complete saponification. If the water used to dissolve the soap is added too rap- idly, the soap may be decomposed with the liberation o c the fatty acids: C 3 H 7 COOK + H 2 = C 3 H 7 COOH + KOH. The fatty acids are set free at the proper time by means of sulphuric acid, and the volatile acids distilled off and ntrated. The pumice is added to prevent explosive boiling. The whole of the volatile acids do not pass over into the distillate, but only a part, the amount depending upon the rate of distillation and the volume of the distillate Hence, m order to get uniform results, it is necessary to follow the pre- scribed procedure with great care. (2) Hehner's Method for Direct Determination of the Fixed Fsttv Acids. — Directions. — To the portion of 2.5 grams weighed out into the 500-c.c. beaker add 1 c.e. of caustic potash and 20 c.c. of 95 per cent, alcohol. Cover the beaker with a watch-glass and heat it on the water-bath until the liquid is clear and homogeneous. As it is not essen- tial to prevent the escape of the volatile acids, the use of a return-flow condenser is not necessary. Evaporate off the alcohol on the water-bath and dissolve the soap in about 400 c.c. of warm distilled water. When the soap is com- pletely dissolved add 10 c.c. of hydrochloric acid (sp. gr. 1.1 2), and heat the beaker in the water-bath almost to boil- ing until the clear oil floats. Meanwhile dry and weigh a thick filter in a small covered beaker. Allow the solution to cool until the fat forms a solid cake on top ; filter the clear liquid and finally bring the solid fats upon the weighed filter. Wash the beaker and fat thoroughly with cold water, then wash out the fat adhering to the beaker with boiling water, which is poured through the filter, taking care that food: analytical methods: butter. 197 the filter is never more than two-thirds full. If the filter paper is of good texture and thoroughly wet beforehand it will retain the fatty acids completely. If, however, oily particles are noticed in the filtrate, cool it by adding pieces of ice, remove the solidified particles with a glass rod and transfer them to the filter. Cool the funnel by plunging it into cold water, remove the filter, place it in the weighing-beaker and dry it at ioo° to constant weight. The fat should be heated about an hour at first, then for periods of about thirty minutes, until the weight is constant within 2 mgs. Notes. — 87.5 per cent, is usually taken as the proportion of fixed fatty acids in butter-fat ; 88 and 89 per cent, have been frequently found. All other fats yield from 95 to 96 per cent, of insoluble fatty acids. (3) Determination of Iodine Value. — This method is based on the fact that certain of the fatty acids, notably the "unsaturated acids," as oleic acid, C 17 H 33 COOH, take up the halogens with the formation of addition products. Directions. — Dissolve the fat in the 300-c.c. bottles in 10 c.c. of chloroform. Add 30 c.c. of the iodine solution from a pipette or glass-stoppered burette, and allow the bottles to stand with occasional shaking for fifteen minutes. Add 10 c.c. of 20 per cent, potassium iodide solution, then 100 c.c. of distilled water, and titrate the excess of iodine N with — sodium thiosulphate until the solution is faintly yellow. Add 2-3 c.c. of starch solution and titrate to the disappearance of the blue color. Calculate the result in grams of iodine absorbed by 100 grams of fat. This is called the Iodine Number, or Iodine Value. At the time of making the determination carry out two * ' blanks ' ' in exactly the same way except that no fat is used and only 20 c.c. of the iodine solution is added. Standardization of the Thiosulphate Solution. — As this is 198 AIR, WATER, AND FOOD. not permanent, its strength should be determined by means of the standard potassium bichromate solution, 1 c.c. of which is equivalent to 0.0 1 gram of iodine. Measure 20 c.c. of the potassium bichromate from a pipette into an Erlenmeyer flask. Add 5 c.c. of potassium iodide, 100 c.c. of water, and 5 c.c. of strong hydrochloric acid. Titrate the liberated iodine with the thiosulphate solution until the color has almost disappeared, then add starch solution and continue the titration until the blue color changes to a sea-green, due to the formation of chromium chloride. The iodine is liberated in accordance with the following equation: K 2 Cr 2 7 + 14HCI + 6KI = 8KC1 + 2 CrCl 3 + 7 H 2 + 61. Calculation of Results. — Example. — From the standardi- zation, 16.07 c.c. thiosulphate = 20 c.c. bichromate =0.200 gram I; 1 c.c. thiosulphate =0.0125 gram I. Also, from blank, 20 c.c. iodine solution =42.40 c.c. thiosulphate; 1 c.c. iodine solution = 2.12 c.c. thiosulphate. If 30 c.c. iodine solution have been added to 0.6542 grams of fat, then 30X2.12=63.60 c.c. is the equivalent amount of thiosulphate solution; and if 44.85 c.c. thio- sulphate were used to titrate excess of free iodine, 63.60 — 44.85 = 18.75 c.c. is the amount of thiosulphate equivalent to the iodine combined with the fat. Then, since 1 c.c. thiosulphate is equivalent to 0.0125 gram free iodine, — —^-7 — '■ X 100 =35.83 grams of iodine combined with 0.0542 100 grams fat. Notes. — It is assumed that 100 grams of pure butter-fat absorb 30-40 grams iodine; oleomargarine, 63-75 grams; olive-oil, 83 grams; and cottonseed-oil, 106 grams. food: analytical methods: butter. 199 The products formed by the action of iodine on the fats are mainly addition products with a slight proportion of substituted bodies. Thus the unsaturated olein, (C 17 H 33 COO) 3 C 3 H 5 , takes up six atoms of iodine, forming an addition product^ di-iodo-stearin, (C 17 H 33 I 2 COO) 3 C 3 H 5 . The method in general use for determining the iodine value of fats and oils has been that of Baron Hubl,* an alcoholic solution of iodine and mercuric chloride being used as the reagent. The method here described, due to Hanust, has the advantage that the solutions keep better, remaining practically unchanged for several months, and that the action is about sixteen times as rapid. For the fats and for oils with low iodine values the results are very close to the figures obtained by the Hubl process. If it is desired to carry out the determination by the older method, directions can be found in any standard work on the analysis of oils. Great care should be taken that there is no change in temperature between the time of measuring the solution of iodine for the blanks and for the determinations, since the high coefficient of expansion of acetic acid may cause a material error. The Spoon Test or " Foam " Test. — Melt a piece of the sample as large as a small chestnut in an ordinary tablespoon or a small tin dish. A test-tube can be used if desired. Use a small flame and stir the melting fat with a splinter of wood (such as a match). Then increase the heat so that the fat * Ding. Poly. J., 253, 281; /. Soc. Chem. Ind., 3 {1884), 641. •j" Ztschr. Unters. Nahr. u. Genussm., 4 (ipoi), 913. 200 AIR, WATER, AND FOOD. shall boil briskly, and stir thoroughly, not neglecting the outer edges, several times during the boiling. Oleomargarine and renovated butter boil noisily, usually sputtering like a mixture of grease and water when boiled, and produce little or no foam. Genuine butter usually boils with much less noise and produces an abundance of foam. The difference in regard to the foam is very marked. Note also the appearance of the particles of curd after the boiling. With genuine butter these will be very small and finely divided, hardly noticeable in fact, while with oleomargarine and renovated butter the curd gathers in much larger masses or lumps. Notes. — This simple method is of value for giving a quick decision regarding a sample, and is especially useful for the detection of renovated butter. The differences in the composi- tion of butter-fat brought about by renovation are so slight that chemical methods are here of no avail. The spoon test, however, will distinguish in the great majority of cases between genuine butter on the one hand and oleomargarine and renovated butter on the other; the index of refraction or the chemical methods just described readily distinguish between the two latter. Physical Methods. — Microscopic Examination. — Pure, fresh butter is not ordinarily crystalline in structure. Butter which has been melted, however, and fats which have been liquefied and allowed to cool slowly show a distinct crystalline structure, especially by polarized light. If only fresh butter were sold, and all adulterants had been previously melted and slowly cooled, this method would be all that would be necessary for the detection of adulteration. As it is, however, it is most useful in making comparative examinations of samples which have been subjected to the same conditions. From an examina- tion of the accompanying plate,* which shows the appearance * From photomicrographs by A. G. Woodman and A. I. Kendall, 1900. food: analytical methods: butter. 201 by polarized light of four samples of known origin which were melted and cooled slowly under exactly similar conditions, it will be seen that, while the differences are noticeable, they are not sufficient in all cases to form a basis for absolute identi- fication. About the most that can be said is that if a small bit, about the size of a pin-head, of the fresh, unmelted sample, is taken from the center of the mass and pressed out on a slide by gentle pressure on the cover glass, it ought to show a fairly uniform field if examined with a one-sixth objective, using polarized light and a selenite plate. Other fats melted and cooled, and mixed with butter, generally show a crystalline structure and a variegated color with the selenite plate. For a further discussion of this point the student is referred to Bulletin 13, U. S. Dept. Agric, Part I, pp. 29-40; Part IV, pp. 449-455- Specific Gravity. — This is most conveniently determined at ioo° C. by means of the Westphal balance (see Allen, The Analyst, n, 223; also Bull. 13, Part IV, pp. 430-431). The pyknometer method is, however, the one adopted by the Asso- ciation of Official Agricultural Chemists as the official method. See Bulletin 107, p. 130. Melting Point. — This may be determined by the capillary- tube method as generally employed for organic substances and described in text books on organic analysis. (See for instance, Mulliken: Identification of Pure Organic Compounds, Vol. I, p. 218.) Wiley's method, however, which is the official method of the A. O. A. C, has the advantage that it avoids the incorrect results which are sometimes obtained with other methods due to the adherence of the melting fat to solid surfaces. A descrip- tion of the method will be found in Bull. 107, p. 133. Refractive Ina]ex. — The determination of the refractive index is especially valuable in food analysis on account of the ease 202 AIR, WATER, AND FOOD and rapidity with which the determination can be made and the fact that so little of the substance is necessary for the determination. Various forms of refractometers are used for the purpose, a fairly complete description of which will be found 1 [l 'H fl Fig. 14. in some of the larger works, such as Leach: Food Inspection and Analysis, or Vaubel:' Quantitative Bestimmung organischer Verbindungen. The instrument having the widest range is the Abbe refractometer, in which the index of refraction is determined by measuring the total reflection produced by a very thin layer of the melted fat, placed between two prisms food: analytical methods: butter. 203 of flint glass. This instrument, fitted with water- jacketed prisms is shown in Fig. 14. Directions. — Revolve the whole instrument on the axis b until it reaches the stop provided, then open the prism casing AB by giving the pin v a half-turn (to the right). Be sure the prism surfaces are clean. It not, clean them carefully with a soft cloth and a little alcohol. Place a few drops of the melted sample directly on the surface of the prism and clamp the two together again by turning the pin v in the opposite direction. Now turn the instrument back (toward the observer) as far as possible and bring the " critical line " into the field of vision of the telescope. This is done by holding the sector 5 firmly with the hand and revolving the double prism by means of the alidade / until the field is divided into a light and a dark portion. If the line is not sharp focus the ocular 01 the tele- scope. If it is colored it is due to dispersion of trie light by the liquid and should be corrected by revolving tne compen- sator T by the milled screw M. The correction is made by a system of two revolving Amici prisms in the lower part of the telescope. Adjust the critical line so that it falls on the inter- section of the cross hairs of the telescope. Observe the temper- ature by the thermometer inserted in the prism casing. In the case of solid fats a sufficiently high temperature should be maintained by a current of warm water to keep the sample well above its melting point. A temperature of 30-40 C. is usually sufficient. Do not let the temperature rise above 70 or the prisms may be injured. Read the index of refraction directly through the small lens L, estimating the fourth decimal. Calculate the value for the refractive index at 25 ° C. Notes. — The index of refraction decreases with rising tem- perature. With the common oils and lats the change for each degree is very nearly a constant, amounting to 0.000365. Leach and Lythgoe* have devised a sliding scale by means of * J. Am. Chem. Soc. (1904), 1193. 204 AIR, WATER, AND FOOD. which the temperature correction may be readily made without reference to tables. The values of wff for genuine butter lie between 14590 and 1.4620; for oleomargarine the values range from 1.4650 to 1.4700. The correctness of the adjustment of the instrument may be tested by the " test-plate " which comes with it, using monobromnaphthalene, or by means of distilled water. The theoretical value for the refractive index of water at 18 C. is 1.3330. Determination of Water. — Directions. — Weigh 2 grams of butter into a shallow metal dish having a flat bottom two inches in diameter and containing a slender stirring-rod two and a half inches long. Heat the butter in the oven at ioo° C. for thirty minutes, cool in a desiccator, and weigh. Heat again for periods of fifteen minutes, until the weight remains constant within 2 or 3 milligrams. During the process of heat- ing stir the butter frequently to hasten evaporation of the water. Determination of Salt.- -Directions. — Weigh 10 grams of butter in a small beaker, add 30 c.c. of hot water, and when the fat is completely melted transfer the whole to a separately funnel. Shake the mixture thoroughly, allow the fat to rise to the top, and draw off the water, taking care that none of the fat-globules pass the stopcock. Repeat the operation four times, using 30 c.c. of water each time. Make the washings up to 250 c.c, mix thoroughly, and titrate 25 N c.c. in a six-inch porcelain dish, using — silver nitrate with potassium chromate as an indicator. Complete Analysis of Butter in One Sample. — Direc- tions. — Weigh about 2 grams of butter into a platinum Gooch crucible, half-filled with ignited fibrous asbestos, and dry it at ioo° C. to constant weight. The loss in weight is the amount of water. Then treat the crucible repeatedly A. Butter X 30. C. Oleomargarine X 30. B. Beef-fat X 30, D. Lard X 30. food: analytical methods: butter. 205 with small portions of petroleum ether, using- gentle suction, and again dry it to constant weight. The difference between this and the preceding weight will be the amount of fat. Now carefully heat the crucible over a sma 1 l flame or in a muffle until a light grayish ash is obtained. The loss in weight is the amount of curd, and the residual increase in weight over that of the crucible and asbestos is the ash. If de- sired, the salt may be washed out of the ash and determined by titration with silver nitrate after neutralizing the solution with calcium carbonate. FLOUR, PREPARED CEREALS, ETC. This class of foodstuffs is usually in a dry form and not liable to rapid change by micro-organisms, and the examina- tion consists in the determination of their " food value." This may require a simple analytical process, as in the case of the quantity of nitrogen in a sample of " gluten " sold for diabetic patients, or in the case of a brand of flour to be used in a hospital or State institution. It may also require an estimation of the available food-material, as in the case of two kinds of beans or corn. The results of chemical analysis will often put the statements made on packages of breakfast cereals in a different light. Owing to the extensive use at present of various cereal breakfast foods, many of which are modified from their original composition by cooking or treatment with malt, the extent to which the starch has by this treatment been converted to soluble forms is also an important question for consideration. The actual determination of digestibility belongs to physio- logical chemistry and need not be taken into consideration here. Moisture. — Directions. — Spread about 2 grams of the finely ground material in a thin layer on a watch-glass and dry it in the oven at ioo° C. for five hours. On account of the ready 206 AIR, WATER, AND FOOD. absorption of moisture by the dried sample, the use of clipped. watch-glasses will be found advantageous. Note. — With some substances drying in a current of hydrogen or some inert gas may be necessary, but for most cereals the method given will be found satisfactory. Ash. — Directions. — Weigh about 2 grams into a platinum dish, such as is used for the determination of solids in milk, and char it carefully. Ignite at a very low red heat until the ash is white, preferably in a muffle. Notes. — If a white ash cannot be obtained in this manner, exhaust the charred mass with water, collect the insoluble residue on a filter, burn it, add this ash to the residue from the evaporation of the aqueous extract and heat the whole at a low red heat until the ash is white. Some cereals, such as whole wheat and bailey, will act destructively on platinum dishes, on account of the phosphates present but can be ignited safely in platinum in the muffle. Ether Extracts: Fats and Oils. — Directions. — Place the residue from the determination of moisture, as described above, in an extraction-cone and extract it with pure anhydrous ether for sixteen hours. Evaporate off the ether and dry the residual fat at the temperature of boiling water to constant weight. The ether extract of cereals is not pure fat but may contain more or less coloring matter or resins. Petroleum ether can be used for the extraction, giving results not essentially different from those obtained with anhydrous ethyl ether. Total Proteids: Determination of Nitrogen by the Kjeldahl Process. *— --Principle. — Oxidation of carbon and hydrogen, and conversion of organic nitrogen to ammonium sulphate by means of boiling sulphuric acid in presence of * Ztschr. anal. Chem., 22 {1883), 366. food: analytical methods: butter. 207 mercury, the latter acting as a carrier of oxygen, and being converted to mercuric sulphate. Precipitation of mercury by potassium sulphide to prevent the formation of mercur-ammo- nium compounds when the solution is made alkaline. Setting free of ammonia by neutralization of the acid by potassium hydroxide. Distillation of ammonia into a measured quantity N of — acid. Titration of excess of acid. 10 Directions. — Transfer about 0.5 gram of the finely divided substance from a weighing-tube to a pear-shaped digestion flask, add 10 c.c. of concentrated sulphuric acid free from nitrogen, and 0.2 gram (three small drops) of metallic mercury. Place a small funnel in the neck of the flask, which should be supported in an inclined position on wire gauze and heated with a small flame until frothing has ceased and the liquid boils quietly. Then increase the heat and boil the solution for at least half an hour after it becomes colorless. Allow the flask to cool for a minute or two, and add a few crystals of potassium permanganate until the liquid has acquired a slight green or purple color. N Measure 25 c.c. of — acid from a burette into a 300-c.c. Erlenmeyer flask and place the condenser-tip beneath the surface of the liquid, adding a little water, if necessary, to seal it. Transfer the digestate with several small portions of distilled water to the distilling flask of the apparatus, add 20 c.c. of potassium sulphide solution, and connect the flask with the condenser. Add 50 c.c. of caustic potash through the separa- tory funnel, and distil off the ammonia by steam. When 200 c.c. have distilled over, remove the collecting-flask, after rinsing off the condenser-tip with distilled water, and titrate the excess N of acid with — sodium hydroxide, using methyl orange or 2o8 cochineal as indicator. If using new reagents, a blank deter- mination should be made with 0.5 gram of cane-sugar in order to reduce any nitrates present which might otherwise escape detection. Notes. — The temperature during the digestion must be maintained at or near the boiling-point of the acid, since at a lower temperature the formation of ammonia is incomplete. The process is considered by Dafert * to take place in four steps: (1) the sulphuric acid takes the elements of water from the organic matter; (2) the sulphur dioxide produced by the action of the residual carbon on the sulphuric acid exercises a reducing action on the nitrogenous bodies; (3) the nitro- genous substances formed in this way are converted to am- monia by a process of oxidation; (4) the ammonia formed is fixed by the acid as ammonium sulphate. In some cases the potassium permanganate is necessary to insure the complete conversion of the nitrogenous bodies into ammonia, although it is probable that its use is unneces- sary in the majority of analyses. The Kjeldahl process in the form outlined above is not applicable to the determination of nitrogen in the form of nitrates. In order to render it of more general application various modifications of the method have been proposed, the one generally used in this country being that suggested by Scovell.t In this method salicylic acid is used with the sul- phuric acid, being converted by the nitrate into nitro-phenol. By the use of sodium thiosu'phate or zinc-dust this is reduced to amido-phenol. The amido-phenol is transformed into am- monium sulphate by the heating with sulphuric acid, the use of mercury being absolutely necessary in this case to secure * Ztschr. anal. Chem., 24 (1885), 455- t U. S. Dept. Agr., Bull. 16 (1887), 51 food: analytical methods: cereals. 209 the complete transformation. It is true also that certain other nitrogenous bodies, notably the alkaloids and certain organic bases, do not yield all their nitrogen to the Kjeldahl process without modifications which complicate the method. For a discussion of the efficiency of these various modifications the student is referred to a paper by Sherman and Falk.* The per cent, of proteids may be found by multiplying the per cent, of nitrogen by an appropriate factor, the one in general use being 6.25. Recent work has shown, however, that most of the proteids of cereals contain more than 16 per cent, of nitrogen, so that the factor 6.25 gives results that are too high. Because all the older work was calculated on this factor, it is still generally used, nevertheless. Kjeldahl-Gunning Method. — The Gunning method can be used in all cases where the Kjeldahl-Wilfarth modification, just described, is employed, and in some ways it is simpler. The digestion and distillation are carried out as described on page 207, using the same amount of sample, together with 20 c.c. of concentrated sulphuric acid and 10 grams of powdered potassium sulphate. No mercury and consequently no potas- sium sulphide is used. 100 c.c. of the potash should be added instead of 50. Note. — The potassium sulphate is added to raise the boiling point of the sulphuric acid and thus shorten the time required for the digestion. Carbohydrates. — The total carbohydrates, often stated in analyses as " nitrogen-free extract," may be readily obtained by subtracting from 100 the sum of the percentages of the other constituents, viz., moisture, ash, ether extract, and nitrogenous bodies. In many cases, however, espe- cially with the cooked or treated cereals and with such * J. Am. Chem. Soc. {1904), 26, 1469. 2IO AIR, WATER, AND FOOD. classes of cereal preparations as infant or invalid foods, a further study of the carbohydrates is desirable. These are made up of two general classes: (a) soluble carbohydrates, including sugars, as sucrose, dextrose and maltose, dextrin and soluble starch, by the latter term being meant starch which is soluble in water but still gives the characteristic blue color with iodine, in distinction from some of the more completely broken-down forms like dextrin, which no longer give blue or purple colors with iodine; (b) insoluble carbohydrates, including starch, pentosans, lignin bodies, and cellulose. The three latter occur chiefly in the husk or envelope of the grain or in the woody fibre of the plant. The pentosans or gums are distinguished from one another by the formation of specific sugars upon hydrolysis with acids. For ordinary analytical purposes it is sufficient to determine the lignin and cellulose together as " crude fibre." Since the exact procedure to be followed in the determina- tion of the carbohydrates varies largely with each specific case, only a general outline can be presented here. Sugars. — The finely ground material, previously dried and extracted with ether for the removal of crude fat, is extracted with 85 per cent, alcohol. In the extract the reducing sugars may be determined by means of Fehling's solution as described on page 181, and the sucrose deter- mined in the same way after inversion with hydrochloric acid. Dextrin and Soluble Starch. — The residue from the ex- traction of the sugars is treated for eighteen to twenty-four hours with water at laboratory temperature with frequent agitation, made up to definite volume, and filtered. This may be tested with iodine, and if no blue color is produced, evaporated to small volume, and the dextrin converted to dextrose by dilute hydrochloric acid and determined by food: analytical methods: cereals. 211 Fehling's solution. In some few cases, however, a blue color with iodine may indicate the presence of soluble starch, in which case an aliquot part of the filtrate may be treated with an excess of barium hydroxide to precipitate the starch. In the filtrate from this precipitate the dextrin is deter- mined by inversion and copper reduction as before. The difference between the dextrin thus found and the first determination gives the soluble starch. Starch. — The methods for the determination of starch vary with the condition in which the starch is found. In the case of nearly pure starch it may be converted into dextrose by boiling with dilute acid, the dextrose being then deter- mined by Fehling's solution in the usual way. Hot acids, however, cannot be used to convert starch in the natural state, as it is found in cereals, because other carbohydrate bodies, especially the pentosans, become soluble under these conditions and the results are too high. In such cases the starch is brought into solution by treatment with diastase or by heating with water under pressure. The results obtained by direct acid hydrolysis, however, in cases where the highest accuracy is not required, may be sufficient and the method is much quicker and easier of execution than the digestion with diastase. Direct Acid Hydrolysis. — Directions. — Weigh out from 2 to 5 grams of the sample, depending upon the amount of starch present, and wash on a filter with five successive portions of 10 c.c. each of ether. Allow the ether to evaporate from the residue and then wash it with 10 per cent, alcohol until free from soluble carbohydrates. 150 c.c. of the dilute alcohol is generally sufficient, but if much reducing sugar or dextrin is present, as may be the case with malted cereals, more will be necessary. Wash the residue from the filter with 200 c.c. of water into a 500 c.c. graduated flask, add 20 c.c. of hydrochloric acid, sp. gr. 1.125, place a funnel in the neck of the flask to 212 AIR, WATER, AND FOOD. retard evaporation, and heat in a boiling water bath for two and one-half hours. Cool, nearly neutralize with sodium hydroxide and make up to 500 c.c. Filter, and determine dextrose in an aliquot portion, 25 or 50 c.c., of the filtrate, using the method described on page 181. Convert dextrose to starch by the factor 0.9. Note. — The washing to remove soluble carbohydrates is performed with dilute alcohol rather than with water because the former is less likely to carry starch granules through the paper. The sugar solution when added to the Fehling's solution should be clear and only faintly acid. It should in general contain not more than 0.5 per cent, of reducing sugar. Determination with Diastase. — Directions. — Treat 2 to 5 grams of the sample with ether and dilute alcohol, as in the previous method, and wash the residue into a 250-c.c. flask with 50 c.c. of water. Heat slowly to boiling, or immerse the flask in boiling water, until the starch gelatinizes, stirring constantly to prevent the formation of lumps. Cool to 55 ° C, add 20-40 c.c. of malt extract, and keep the solution within two degrees of the stated temperature for an hour or until the solution no longer gives the starch reaction with iodine under the microscope. In either case heat the solution again to boiling to gelatinize any remaining starch granules, test again and if starch is found, cool to 55 C, and treat as before, using a fresh portion of malt extract. Continue this treatment until, when carefully examined under the microscope, a drop of the solution fails to give the iodine reaction for starch. Cool, make up to 250 c.c. and filter through a dry filter. Transfer 200 c.c. of the filtrate to a 500-c.c. graduated flask, add 20 c.c. of hydrochloric acid, sp. gr. 1.125, and carry out the determina- tion as described in the preceding method. A blank determination must be carried through, using 50 c.c. of water and exactly the same amount of malt extract as food: analytical methods: cereals. 213 vised in the regular procedure, in order to correct for the cupric reducing power of the malt extract. Malt Extract. — Treat 40 grams of fresh coarsely ground malt several hours with 200 c.c. of water, shaking occasionally. Filter and add a few drops of chloroform to prevent the growth of molds. Notes. — The action of the diastase on the gelatinized starch is to convert it into maltose and dextrin, that is, into soluble bodies that can be separated by filtration from the pentosans and other carbohydrates that give the high results in the direct acid method. By the action of acid (hydrolysis) the maltose and dextrin are converted to dextrose. The determination should, if possible, be carried through without interruption. In case this cannot be done salicylic acid may be used to prevent fermentation, not adding it, how- ever, until after the digestion with diastase. If the malt itself is not readily procurable, certain forms of prepared diastase are on the market and may be found more convenient either for analytical use or for purposes of illustra- tion. When possible, however, it is preferable to use the freshly prepared malt extract, as the prepared diastase, made at different times and from separate portions of malt, may show great differences in hydrolytic power. It is sometimes convenient to use freshly collected saliva, this being free from carbohydrate. In this case the digestion should be carried out at 38 C. instead of 55 C. Pentosans. — These are determined usually directly upon the original material. The methods in general use depend upon the conversion of the pentose substance into furfural by distillation with strong acid and the subsequent precipi- tation and estimation of the furfural. The latter may be done by treatment with phenylhydrazine acetate and formation of the furfural hydrazone, or by the formation of an insoluble 214 AIR, WATER, AND FOOD. condensation product with phloroglucin according to the method of Councler. For the details of these methods reference may be made to Wiley, " Principles and Practice of Agricultural Analysis," Vol. Ill, p. 178 et seq., also an article by Sherman.* The phloroglucin method is given as a provisional method in BulL 107 of the Bureau of Chemistry. Crude Fibre. — The Weende method, the method adopted by the Association of Official Agricultural Chemists, is based on the assumption that the starch and other digestible carbo- hydrates and proteid will be removed from the cereal by succes- sive digestion at a boiling temperature with acid and alkali of a definite strength. The complex body thus obtained is not a definite chemical compound, but may be considered as being composed largely of cellulose. Use 2 grams of .the finely ground sample and wash on a niter with 5 portions of 10 ex. each of ether. (The residue from the determination of " ether extract " can be used if desired.) Transfer the washed material to a 500-c.c. Erlenmeyer flask, add 200 c.c. of boiling 1.25 per cent, sulphuric acid, place a funnel in the neck of the flask and boil gently for 30 minutes. Filter on a ribbed filter and wash with several portions of boiling water. Transfer the precipitate by means of 200 c.c. of boiling 1.25 per cent, sodium hydroxide in a small wash-bottle to the same 500-c.c. Erlenmeyer flask, and boil again gently for 30 minutes. Filter on ignited asbestos in a Gooch crucible, wash with boiling water until free from alkali, then with 10 c.c. of alcohol, and finally with 10 c.c. of ether. Dry at the temperature of boiling water to constant weight. Ignite carefully at first, * /. Am. Chem. Soc, 19 {1897), 291. food: analytical methods: cereals. 215 then at a low red heac until the organic matter is destroyed. Calculate the loss on ignition as " crude fibre." Note. — The filtration will be found to proceed fairly rapidly if the solution is filtered hot and care is taken to keep the residue from the filter as long as possible. The sulphuric acid and sodium hydroxide should be carefully prepared and the strength determined by titration. EXAMINATION OF FERMENTED LIQUORS. WINE. General Statements. — The object of a wine analysis is ordinarily to determine whether or not a wine is pure and unadulterated, or whether it has been properlv made. Special works furnish sufficient information concerning pro- cesses of manufacture, and it is essential to know here onlv the general composition of the grape-juice or "must" and how, by the natural process of fermentation, this may be altered in the finished product. The "must " contains sugars (mainly dextrose) ; dextrin; organic acids and salts, mainly tartaric and malic acids; salts of inorganic acids, chiefly phosphates, sulphates, and chlorides. Various extractive matters, which largely affect the color and flavor of the wine, together with a little tannin and albuminous substances, are also present. The wine will contain then, besides water, the following : Alcohol, glycerine, frequently some sugar that has escaped fermentation, ethers, which determine largely the "bouquet" of the wine, and more or less of the acids, salts, coloring and extractive mat- ters of the must, together with varying amounts of carbonic, acetic, and succinic acids. According to differences in their composition wines may be divided into various classes, such as " dry " w T ines, which 2l6 AIR, WATER, AND FOOD. contain very little sugar, as distinguished from the sweet wines, in which a notable quantity of sugar has escaped fermentation, or to which an addition of sugar has been made subsequent to the main fermentation. Or they may be divided according to the content of alcohol into natural wines and those fortified by addition of alcohol, as port, sherry, and madeira. The composition of the wine may be changed, moreover, by the various methods which are used for its "improve- ment," such as fortification already mentioned, plastering, petiotization, etc. Information regarding these methods will be found in some of the larger works mentioned in the bibliography. The determinations of most value in judging the purity of wine are alcohol, glycerine, extract, ash, total and volatile acids. The actual percentages of these substances are not of so great value as certain relations between them, such as the ratio of ash to extract, extract to alcohol, alcohol to glycerine, alcohol to acids, and volatile to total acids. Examination for preservatives and foreign coloring matters should also be made. It should be remembered, however, in judging the quality of American wines that the standards of European practice are not entirely applicable and that further study will be necessary before even tentative stand- ards can be fixed. Specific Gravity. — This is to be taken by means of the Westphal balance or Sprengel tube at i5°.5 C. Notes. — Where the specific gravity of the sample is known, the various portions taken for analysis can be more conven- iently measured than weighed. The results can be calculated to per cent, by weight by dividing the results expressed as grams per ioo ex. by the specific gravity. Effervescing wines should, before analysis, be vigorously food: analytical methods: fermented liquors. 217 shaken in a large flask to hasten the escape of carbon dioxide. The liquid may then be poured from under the foam into another vessel. Alcohol. — Principle. — The alcohol is obtained freed from everything but water, and its amount determined by ascertain- ing the specific gravity of the mixture, and taking the per cent, from the tables. Directions. — Measure (or weigh) 100 ex. of the wine into a 500-c.c. round-bottomed flask. Add 50 c.c. of water, neutralize N free acid with — sodium hydroxide, and add 0.5 gram of tannic acid, if necessary, to prevent foaming. Distil off about 95 to 98 c.c. into a ioo-c.c. graduated flask. Fill up to the mark with distilled water, mix thoroughly, and take the specific gravity of the distillate at 15 °. 5 C. with a pyknometer. The percentage of absolute alcohol by volume corresponding to the observed density will be found in Table X, page 244. To find the alcohol by weight in the sample, multiply the per cent, of alcohol in the distillate as taken from the table, by the weight of the distillate and divide the result by the weight of the sample used. Notes. — The object of neutralizing the wine with sodium hydroxide is to prevent the distillation of volatile acids, prin- cipally acetic. A certain amount of volatile ethers may also pass over into the distillate, but in most cases it is so slight that its influence may be neglected. Normal wines ordinarily contain between 4.5 and 12 per cent, of alcohol except in the case of " fortified " wines, where the amount may be even 20 per cent. Fermentation does not yield more than about 14 per cent, of alcohol. Extract. — The method to be employed depends on the proportion of extract. A preliminary calculation should be made by the aid of the formula x = i+d— &'\ 2.1 8 AIR, WATER, AND FOOD. where x is the specific gravity of the dealcoholized wine, d the specific gravity of the wine, and d' the specific gravity of the distillate obtained in the determination of alcohol. The value for x is found from Table XI, page 247. Dry Wines. — (Having an extract content of less than 3 per cent.) Evaporate 50 c.c. on the water-bath to a sirupy consistency in a flat-bottomed platinum dish. Heat the residue in the oven at ioo° C. for two hours and a half, cool in a desiccator and weigh. Sweet Wines. — When the extract content is between 3 and 6 per cent, treat 25 c.c. of the sample as described under dry wines. When the amount of extract exceeds 6 per cent, it is best to accept the result found from the table and not to determine it gravimetrically. Notes. — The gravimetric determination will be inac- curate with wines high in extract on account of the serious error caused by drying levulose at high temperatures. The figures in the table are based on determinations made at 75 C. in vacuo. Wine made from the juice of ripe grapes rarely contains less than 1.5 per cent, of extract in the case of white wines and about 2.0 per cent, in the case of red wines. The amount of extract decreases of course with age. Alcohol-extract Ratio. — The municipal laboratory of Paris considers a wine "fortified" if the alcohol exceeds 4.5 times the extract for red wines and 6. 5 for white wines. The amount of added alcohol is calculated by the municipal laboratory by subtracting the "natural" alcohol (extract X4.5 or 6.5) from the total alcohol. Ash. — Ignite the residue from the extract determination as described on page 206. Note. — The amount of ash in a natural wine averages about 10 per cent, of the extract, varying ordinarily be- tween 0.14 per cent, and 0.35 per cent. food: analytical methods: fermented liquors. 219 Glycerine. — Evaporate 100 c.c. of wine in a porcelain dish on the water-bath to a volume of about 10 c.c, and treat the residue with about 5 grams of fine sand and with from 1.5 to 2 c.c. of milk of lime (containing 40 grams Ca(OH) 2 per 100 c.c.) for each gram of extract present, and evaporate almost to dryness. [With wines whose extract exceeds 5 grams per 100 c.c, heat the portion to be used in the determination of glycerine to boiling in a flask, and treat with successive small portions of milk of lime until it becomes, first, darker, and then light in color. When cool, add 200 c.c. of 96 per cent, alcohol (sp. gr. 0.81 18), allow the precipitate to subside, filter, and wash with 96 per cent, alcohol (sp. gr. 0.81 18). Evaporate the filtrate to about 10 c.c, add about 5 grams of sand and from 1.5 to 2 c.c of milk of lime, and proceed as before.] Treat the moist residue with 5 c.c of alcohol (96 per cent, by vol- ume), remove the substance adhering to the sides of the dish with a spatula, and rub the whole mass to a paste, with the addition of a little more alcohol. Heat the mixture on the water-bath, with constant stirring, to incipient boiling, and decant the liquid into a flask graduated at 100 and no c.c. Wash the residue repeatedly by decantation with 10 c.c. portions of hot 96 per cent, alcohol. Cool the con- tents of the flask to 15 , dilute to the no-c.c mark with 96 per cent, alcohol, and filter through a folded filter. Evaporate 100 c.c. of the filtrate to a sirupy consistency in a porcelain dish, on a hot, but not boiling, water-bath,, transfer the residue to a small glass-stoppered graduated cylinder with 20 c.c of absolute alcohol, and add three portions of 20 c.c each of absolute ether, with thorough shaking after each addition. Let stand until clear, then pour off through a filter, and wash the cylinder three times or more with a mixture of one part absolute alcohol to one 220 AIR, WATER. AND FOOD. and one-half parts of absolute ether, pouring the wash- liquor also through the filter. Evaporate the filtrate to a sirupy consistency, dry for one hour at the temperature of boiling water, weigh, ignite, and weigh again. The loss in ignition increased by one-tenth gives the glycerine. Notes. — The ratio of glycerine to alcohol is of great importance in judging the purity of a wine. According to European standards in pure wines the glycerine-alcohol ratio varies from between 6 and 14 parts by weight of the former to 100 of the latter. The little work done on American wines indicates a lower ratio. Free Acids : Total Acidity Calculated as Tartaric N Acid. — Titrate 10 c.c. of the wine with — sodium hydroxide. The end-point is reached when a drop of the liquid placed upon faintly-red litmus paper produces a blue spot in the middle of the portion moistened. Calculate the results as N tartaric acid. One c.c. — sodium hydroxide =0.0075 gram of tartaric acid. Volatile Acids Calculated as Acetic Acid. — Measure 50 c.c. of wine into a 3 00 -c.c. flask provided with a cork having two perforations. One is fitted with a tube 6 mm. in diameter and blown out to a bulb 40 mm. in diameter a short distance above the cork; this tube is connected with a con- denser. The other perforation carries a tube reaching nearly to the bottom of the flask and drawn out to a small aperture at its lower end; this is connected with a 500-c.c. flask con- taining water. Heat both flasks to boiling ; then lower the flame under that containing the wine, adjusting the flame so that the volume of liquid remains constant, and continue the distillation by means of steam until 200 c.c. have gone over. food: analytical methods: fermented liquors. 221 N Titrate the distillate with — sodium hydroxide, using phe- nolphthalein as an indicator. Calculate the results as N acetic acid. One c.c. — sodium hydroxide =0.0060 eram 10 of acetic acid. Fixed Acids Calculated as Tartaric Acid. — These may be found by calculating the volatile acids as tartaric and subtracting the result from the total tartaric acid found by direct titration. Note. — The total acids in a wine vary usually between 0.45 per cent, and 1.5 per cent. The acid content is fre- quently diminished by aging or by the separation of cream of tartar. The volatile acid should, in general, not be over 0.12 to 0.16 per cent., depending upon the age of the wine. A wine properly made should not have the volatile acid, estimated as acetic, exceed one-fourth of the total free acid, calculated as tartaric. Coloring Matters: Detection of Coal-tar Dyes. — Double Dyeing Method of Sostegni and Carpentieri* — Fifty c.c. of the sample are diluted to 100 c.c. with water, filtered if necessary, acidified with from 2 to 4 c.c. of 10 per cent, solution of hydro- chloric acid, and a piece of woolen cloth which has been washed in a very dilute solution of boiling potassium hydroxide, and then washed in water, immersed in it and boiled for five to ten minutes. The cloth is removed, thoroughly washed in water, and boiled with very dilute hydrochloric acid solution. Then after washing out the acid the color is dissolved in a solution of ammonium hydroxide (1 to 50). With some of the dyes solution takes place quite readily, while with others it is neces- sary to boil some time. The wool is taken out, a slight excess of hydrochloric acid is added to the solution, another piece * Ztschr. anal. Chem., 35 (1896), 397. 22 2 AIR, WATER, AND FOOD. of wool is immersed and again boiled. With vegetable coloring matter this second dyeing gives practically no color, and there is no danger of mistaking a fruit color for one of coal-tar origin. Notes. — It is absolutely necessary that the second dyeing should be made, as some of the coal-tar dyes will dye a dirty orange in the first acid bath which might be easily passed for vegetable color but on treatment in alkaline bath and second acid bath becomes a bright pink. Another advantage in the second dyeing is that if a large piece of woolen cloth is used in the first dyeing, and a small piece in the second dyeing, small amounts of coloring matter can be brought out much more decidedly in the second dyeing, where practically all of the vegetable coloring matter has been excluded. Several colors which are not coal-tar dyes, notably archil, archil derivatives, and sulphonated indigo, give reactions by this method and are liable to be confused with coal-tar colors. For hints as to the method for detecting these reference may be made to Bulletin 107, Bureau of Chemistry, page 190. Methods for the further separation and identification of the artificial colors cannot be taken up here for lack of space. The student is referred to Leach: "Food Inspection and Analysis," p. 628 et seq.\ Mulliken: " The Identification of Commercial Dyestuffs;" and a paper by Green, Yeoman, and Jones on " The Identification of Dyestuffs on A nimal Fibres."* Preservatives. — The preservatives most commonly em- ployed in wines are salicylic and benzoic acids. Sulphurous acid and sulphites are also used. For methods of detecting other substances less commonly employed, such as abrastol, beta-naphthol, etc., reference may be made to Bulletin 107 of the Bureau of Chemistry. Boric acid is occasionally used, * /. Soc. Dyers and Colourists, 1905, 236-243. food: analytical methods: fermented liquors. 223 but since a small amount of it is normally present in wines, tests, to be of value, should be quantitative. Salicylic Acid. — Acidify about 50 c.c. of the wine with 5 c.c. of dilute (1:3) sulphuric acid and extract in a separatory funnel with 25 c.c. of ether. Draw off the lower layer, wash the ether twice with water, using 10 c.c. each time and finally evaporate the ether in a porcelain dish at room temperature. To the residue in the dish add 2 to 3 drops of ferric alum solu- tion (p. 261). or very dilute ferric chloride. A deep purple or violet color indicates salicylic acid. Notes. — Not more than 50 c.c. should be used for the test, since a trace of salicylic acid seems normally present in some wines. The washing with water is to free the ether from traces of sulphuric acid which interferes w r ith the development of the violet color. Benzoic Acid* — Acidify about 100 c.c. of wine with sul- phuric acid, extract with ether, and evaporate the ethereal solution as in the detection of salicylic acid. Treat the resi- due with 2 or 3 c.c. of strong sulphuric acid. Heat till white fumes appear; organic matter is charred and benzoic acid is converted into sulpho-benzoic acid. A few crystals of ammonium nitrate are then added. This causes the for- mation of metadinitrobenzoic acid. When cool the acid is diluted with water and ammonia added in excess, followed by a drop or two of ammonium sulphide. The nitro-compound becomes converted into ammonium metadiamidobenzoic acid, which possesses a red color. This reaction takes place imme- diately, and is seen at the surface of the liquid without stirring. Sulphurous Acid and Sulphites.- — See directions under Beer, page 225. * Mohler: Bull. Soc. Chim. [3], 3, {1896) 414. 224 AIR J WATER, AND FOOD. BEER AND OTHER MALT LIQUORS. Before analysis the sample must be thoroughly shaken in a large flask, in order to remove carbon dioxide. Specific Gravity. — Taken with a pyknometer or Sprengel tube at I5°.5 C. Alcohol. — Determined as in the analysis of wine. It will not be necessary to neutralize the free acid before distilling. Extract. — Determine the extract content corresponding to the specific gravity of the dealcoholized beer according to Table For this purpose employ the formula in which Sp is the specific gravity of the dealcoholized beer, g the specific gravity of the beer, and g f the specific gravity of the distillate obtained in the determination of alcohol. Instead of using this formula the residue from the distillation of alcohol is sometimes diluted to the original volume, and its specific gravity taken. This is often impracticable owing to the necessity of employing tannic acid to prevent foaming in the distilling flask, and owing to the coagulation of proteids during the distillation. Note. — The extract of beer cannot be accurately deter- mined by evaporation and drying at the boiling-point of water because of the dehydration of the maltose. Ash. — Evaporate 25 c.c. to diyness and determine as in the analysis of wine. Free Acids. — Heat 20 c.c. to incipient boiling to expel carbon dioxide and titrate as in the analysis of wine. Fixed acids, consisting principally of lactic and succinic, are calcu- N lated as lactic acid. One c.c. of — sodium hydroxide =0.0090 gram of lactic acid. food: analytical methods: fermented liquors. 225, Reducing Sugar. — Dilute 25 c.c. of the beer, freed from carbon dioxide, to 100 c.c. Determine the reducing sugar in 25 c.c. of this solution as directed on page 181, enough water being added to make the total volume of the Fehling's solution- sugar mixture 100 c.c. Express the results in terms of maltose, as given in Table XII. Preservatives. — The preservatives most commonly em- ployed in beer are benzoic and salicylic acids and their sodium salts, sulphites and fluorides. Benzoic and Salicylic Acids. — Detected as described under Wine. Sulphites. — Qualitative Test. — Use an apparatus similar to that described for the determination of volatile acids in wine. To 50 c.c. of the sample add about a gram of sodium bicarbonate, 20 c.c. of 20 per cent, phosphoric acid, and immediately con- nect the flask with the condenser. Pass steam through the flask until about 20 c.c. have collected in the distillate. To the distillate add bromine water in slight excess and boil. Expel the excess of bromine and test for sulphuric acid with hydrochloric acid and barium chloride in the usual manner. Notes. — The method described does not distinguish between free sulphurous acid and that present in the form of sulphites. The former can be distilled without the addition of phosphoric acid. The presence of sulphites in a sample should not be con- sidered evidence of added preservatives unless an excessive amount is found since the use of sulphured malt or hops may introduce a small amount. To obtain conclusive data a quan- titative determination of the amount present should be made. This can be done by a method very similar to that used for the detection, taking greater precautions against oxidation and absorbing the sulphurous acid in standard iodine solution. Care should be taken also to avoid the distillation of iodine- 2 26 AIR, WATER, AND FOOD. reducing substances other than sulphurous acid. For a detailed discussion of the determination reference may be made to the following papers: Bureau of Chemistry, Bull. 107, p. 187; Gudeman: /. Ind. Eng. Chem., 1909, p. 81; Woodman and Gadsby: /. Ind. Eng. Chem., 1909. Fluorides. — The well-known qualitative test for fluorides by etching a glass plate may be modified by the use of a suitable condenser and made sufficiently delicate to be used here. It is possible also by suitable regulation of the temperature to make the test approximately quantitative.* FLAVORING EXTRACTS. The work on alcoholic liquids can be pleasantly varied by substituting for it in some cases the determination of alcohol and other important components of the usual flavoring essences, the most important of which are vanilla and lemon. Several important types of food methods, such as the determination of essential oils and quantitative extraction with volatile solvents, are also brought to the attention of the student. VANILLA. Vanilla extract is a dilute alcoholic tincture of the vanilla bean, the fruit of a climbing plant of the orchid family. The best grades are made by allowing the cut and bruised beans to macerate in the alcohol for several months, the liquid thus obtained being deep brown in color, with a delightful perfume and flavor. Sugar is added to assist in the extraction and to sweeten the product. The cost of a quart of the pure extract, according to Winton,f * Woodman and Talbot: J. Am. Chem. Soc, 1906, 1437; 1907, 1362. t Conn. Agr. Exp. Sta. Report, 1901, 150. food: analytical methods: flavoring extracts. 227 is from about 60 cents to S2.50, depending chiefly upon the grade of beans used. The composition of five pure vanilla extracts, made from beans of different grades, is given in the following table, * the results being expressed in per cent, by weight: Grade of Bean. Specific Gravity. Vanillin. , Alcohol. Total Residue. Cane- sugar. Mexican (whole) Mexican (cut) South American (whole) Bourbon (whole) Tahiti (whole) 1. 0159 1. 0146 1 .0109 1 .0166 1. 0104 0.125 0.065 0.215 0.138 0.108 37-96 39-92 38-58 38.32 38-84 22.60 23.10 22.00 23-13 75 21 19.90 19.20 19.00 20.40 20.00 The adulteration of vanilla extract consists principally in the use of extract of Tonka bean, a cheap substitute somewhat resembling vanilla in its flavor, in the use of artificial prepara- tions of the active principles of vanilla and tonka, vanillin and coumarin, and in the addition of artificial color, usually cara- mel. A cheap extract may be entirely an artificial mixture, made of artificial vanillin or coumarin, or both, in weak alcohol, colored with caramel. An occasional adulteration is the use of alkali, such as potassium bicarbonate, to hold the resin in solution and permit the use of a more dilute alcohol. Analytical Methods. — Alcohol. — Measure 25 c.c. of the sample, add 100 c.c. of water, and determine the alcohol by volume, as directed on page 217, omitting the use of sodium hydroxide or tannic acid. Vanillin and Coumarin. — (Method of Hess and Prescott, modified by Winton and Bailey. f) Weigh 25 grams into a 200-C.C beaker with marks showing volumes of 25 and 50 c.c. Dilute to the 50-c.c. mark and evaporate in a water-bath to * Conn. Agr. Exp. Sta. Report, 1901, 150. f J. Am. Chem. Soc, 1905, 719; Bur. o/Chem., Bull. 107, 156. 2 28 AIR, WATER, AND FOOD. 25 c.c. at a temperature in the bath of not more than yo° C. Dilute a second time to 50 c.c. and evaporate to 25 c.c. Add neutral lead acetate solution drop by drop until no more pre- cipitate forms. Stir with a glass rod to facilitate flocculation of the precipitate, filter through a moistened filter, and wash three times with hot water, taking care that the total filtrate does not measure more than 50 c.c. Cool the filtrate and shake with 20 c.c. of ether in a separatory funnel. Remove the ether to another separatory funnel and repeat the shaking of the aqueous liquid with ether three times, using 15 c.c. each time. Shake the combined ether solutions four or five times with 2 per cent, ammonium hydroxide, using 10 c.c. for the first shaking and 5 c.c. for each subsequent shaking. Set aside the combined ammoniacal solutions for the determination of vanillin. Wash the ether solution into a weighed dish and allow the ether to evaporate at the room temperature. Dry in a desic- cator, and weigh. Stir the residue for fifteen minutes with 15 c.c. of petroleum ether (boiling-point 30 to 40 C.) and decant the clear liquid into a beaker. Repeat the extraction with petroleum ether two or three times. Allow the residue to stand in the air until apparently dry, completing the drying in a desiccator. Weigh, and deduct the weight from the weight of the residue obtained after the ether evaporation, thus obtain- ing the weight of the coumarin. Allow the petroleum ether extract to evaporate at room temperature. If it is coumarin it may be recognized by the characteristic odor, resembling that of "sweet grass," and by Leach's test * as follows: Dissolve the residue in a few drops of N hot water, and add one or two drops of — iodine in potassium * Leach: "Food Inspection and Analysis," 738. food: analytical methods: flavoring extracts. 229 iodide. On stirring with a rod, a brown precipitate will form, which will gather into dark green flocks. The reaction is especially marked if carried out in a white porcelain crucible or dish. Slightly acidulate the ammoniacal solution reserved for vanillin with 10 per cent, hydrochloric acid. Cool, and shake out in a separatory funnel with four portions of ether, as described for the first ether extraction. Evaporate the ether at room temperature in a weighed dish, dry over sulphuric acid, and weigh the vanillin. If the residue is white it may be safely assumed in the majority of cases that it is pure vanillin. If dark colored, however, it should be purified as in the case of conmarin, and the percentage calculated from the loss in weight. Notes. — The separation of vanillin and coumarin is based on the differences in their chemical constitution. Vanillin is hydroxymethoxy benzoic aldehyde, while coumarin is the anhy- dride of orthohydroxycinnamic acid. On account of the aldehydic nature of the vanillin the separation by dilute ammo- nia is possible, the aldehyde ammonia compound of vanillin being readily soluble in water, while the coumarin remains wholly in the ether. Acetanilid has been reported in vanillin extracts, being present as an adulterant of the artificial vanillin employed, but its use is rare. If present, it will be found in the residue from the petroleum ether extraction and can be recognized by its melting-point, 11 2° C, and appropriate tests. Resins. — Evaporate 25 or 50 c.c. of the extract to one-third its volume on the water-bath in order to remove the alcohol. Make up to the original volume with hot water. If no alkali has been used in the manufacture of the extract, the resin should appear at this point as a flocculent brown residue. Add acetic acid in slight excess, allow the evaporating-dish to stand 230 AIR, WATER, AND FOOD. in a warm place for a time to separate the resin completely, and filter. Wash the residue on the filter, and save both the filtrate and residue. Test the resin by placing pieces of the filter, with the resin attached, in a few cubic centimeters of dilute caustic potash. The resin is dissolved with a deep red color, and on acidifying is again precipitated. Test the filtrate by adding to it a few drops of basic lead acetate. A bulky pre- cipitate is formed, on account of the organic acid, gums, etc., present. Confirm the resin test by shaking 5 c.c. portions of the extract in separate test-tubes with 10 c.c. of amyl alcohol and 10 c.c. of ether. With pure extracts the upper layers will be colored, varying from light yellow to deep brown; with artificial extracts, free from resin, the amyl alcohol and ether layers will be uncolored. Note. — While the artificial vanillin, as sold on the market and used in the manufacture of low-grade extracts, is identical with the vanillin of the vanilla bean, it is true that pure extracts owe their value and flavor to other ingredients as well as to the vanillin present. Among these " extractive matters" the resins are important from an analytical standpoint, serving by their presence or absence to determine whether true vanilla is present or the extract entirely artificial. As a quick and ready test, serving to distinguish artificial extracts from genuine prepara- tions of the vanilla bean, the amyl alcohol and ether tests will be found especially useful. Color: Caramel. — Caramel is the color commonly used in vanilla extracts, although coal-tar dyes have been found. The presence of dyes is sometimes indicated by the color of the amyl alcohol in testing for the resin, they being in many cases soluble in amyl alcohol, but insoluble in ether. The two tests for caramel which in the author's experience have proven most satisfactory are the lead acetate test and the paraldehyde test. food: analytical methods: flavoring extracts. 231 Lead Acetate Test. — The coloring matter present in vanilla extracts is almost completely removed when the dealcoholized extract is treated with a few cubic centimeters of basic lead acetate solution. When caramel is present, the filtrate and precipitate, if any, have the characteristic red-brown color of caramel. Paraldehyde Test. — To 15 c.c. of the extract add 2 c.c. of zinc chloride (5 per cent, solution), and 2 c.c. of caustic potash (2 per cent, solution). Filter, wash the precipitate with hot water, and dissolve it in 15 c.c. of acetic acid (10 per cent, solution). Concentrate on the water-bath to one-half or one- third its volume, neutralize the excess of acid, and transfer the clear solution to a rather large test-tube. Add three volumes of paraldehyde and just enough alcohol to make the mixture homogeneous. If caramel is present a brown flocculent pre- cipitate will form on standing over night. Note. — The treatment with zinc hydroxide is to separate the caramel from sugar, which is present in many extracts, and interferes with the paraldehyde test.* The precipitate obtained with paraldehyde is probably caramel and not the product of a chemical reaction. LEMON. Lemon extract is usually made by dissolving oil of lemon, obtained by expression or distillation from the rind of the lemon, in strong alcohol. The product is sometimes colored with the color of lemon peel. The Federal standards f require a content of lemon oil of at least 5 per cent, by volume. The expensive ingredient of the extract is the alcohol, since alcohol of at least 80 per cent, strength by volume must be used to dissolve 5 per cent, of lemon oil; hence in making cheap extracts * Woodman and Newhall: Tech. Quart., 21, 280. \ U. S. Dept. Agric, Office of the Secretary, Circ. iq. 232 AIR, WATER, AND FOOD. the manufacturer endeavors to use a dilute alcohol, even under the necessity of omitting a portion or all of the oil of lemon. The common forms of adulteration of lemon extract are the use of weak alcohol and consequent deficiency of lemon oil, as already noted; the substitution for the lemon oil of small amounts of stronger oils, as oil of citronella, oil of lemon-grass, and the like; the use of citral, the odorous principle of lemon oil, used for making the so-called "terpeneless lemon extracts;" and the coloring of the extracts by coal-tar colors or turmeric. Preliminary Test. — To a little of the extract in a test-tube add seven or eight times its volume of water. A high-grade extract will show a heavy cloud, due to the precipitation of the lemon oil. If no cloudiness or turbidity appears it may be safely inferred that no oil is present. Alcohol. — The determination of alcohol is somewhat com- plicated in this case by the presence of the volatile oil of lemon which must be removed before distilling. Dilute 20 c.c. of the extract to 100 ex. with water, and pour the mixture into a dry Erlenmeyer flask containing 5 grams of light magnesium carbonate. Shake thoroughly and filter through a dry filter. Measure 50 c.c. of the clear filtrate, add about 15 c.c. of water, and distil 50 c.c, as directed on page 217. From the specific gravity of the distillate determine the per cent, of alcohol by volume, and this, multiplied by 5, will give the percentage in the original extract. Note. — The magnesia serves to absorb the precipitated oil and prevent it from passing through the filter. Lemon Oil. — Pipette 20 c.c. of the extract into a Babcock milk bottle; add 1 c.c. dilute hydrochloric acid (1:1); then add from 25 to 28 c.c. of water previously warmed to 6o° C; mix and let stand in water at 6o° for five minutes; whirl in centrifuge for five minutes; fill with warm water to bring the oil into the graduated neck of the flask; repeat whirling for food: analytical methods: flavoring extracts. 233 two minutes; stand the flask in water at 6o° C. for a few minutes and read the per cent, of oil by volume. If the determination is not made in duplicate the flask should be balanced by another containing an equal weight of water. In case oil of lemon is present in amounts over 2 per cent, add to the percentage of oil found 0.4 per cent, to correct for the oil retained in solution. If less than 2 per cent, and more than 1 per cent, is present, add 0.3 per cent, for correction. Refractive Index of the Oil. — With a narrow glass tube remove a few drops of the oil obtained in the neck of the Babcock flask in the previous determination and determine its index of refraction at 25 °, using the Abbe refractometer. The read- ing for pure lemon oil at 25 is 1 .4715-1 .4740. Most of the adulterants give a higher refractive index; oil of turpentine is distinctly lower. Color. — Test for coal-tar colors by evaporating a portion of the extract to dryness on the water-bath. Dissolve the residue in water and carry out the double dyeing method, as described on page 221. To test for turmeric add to a portion of the sample three drops of saturated boric acid solution, one small drop of dilute (1:10) hydrochloric acid, and a piece of filter-paper so arranged that it is only half immersed in the liquid. Evaporate to dryness on the water-bath. In the presence of turmeric the paper will be colored pink and the test may be confirmed as described on page 188, Excess of hydrochloric acid should be avoided, as in testing for boric acid. Citral. — See /. Am. Chem. Soc. y 1906, 1472. APPENDICES. APPENDIX A. Table I. TENSION OF AQUEOUS VAPOR IN MILLIMETERS OF MERCURY FROM 0° TO 30°. 9 C, REDUCED TO 0° AND SEA-LEVEL. o°.o. o°.i. O .2. o°3- o°. 4 . o°. 5 . o°.6. o°. 7 . o°.8. o°. 9 . o° 4-57 4.60 4.64 4.67 4- 70 4-74 4-77 4.80 4.84 4.87 I 4.91 4.94 4.98 5.02 5.05 5 -09 5-12 5.16 5-20 5.23 2 5.27 5.31 5-35 5-39 5-42 5-46 5.5o 5-54 5-58 5.62 3 5-66 5.70 5-74 5-78 5-82 5-86 5-90 5-94 5-99 6.03 4 6.07 6. 11 6.15 6.20 6.24 6.28 6-33 6-37 6.42 6.46 5 6.51 6-55 6.60 6.64 6.69 6-74 6.78 6.83 6.88 6.92 6 6.97 7.02 7.07 7.12 7.17 7.22 7.26 7-31 7.36 7.42 7 7-47 7-52 7-57 7.62 7-67 7-72 7.78 7.83 7.88 7-94 8 7-99 8.05 8.10 8.15 8.21 8.27 8.32 8.38 8-43 8-49 9 8.55 8.61 8.66 8.72 8.78 8.84 8.90 8.96 9.02 9.08 10 9.14 9.20 9.26 9-32 9-39 9-45 9-5i 9.58 9.64 9.70 11 9-77 9-33 9.90 9.96 10.03 10.09 10.16 10.23 10.30 10.36 12 10.43 10.50 io.57 10.64 10.71 10.78 10.85 10.92 10.99 11.06 13 11. 14 11. 21 11.28 11.36 H-43 11 .50 11.58 11.66 H-73 11. 81 14 11.88 11.96 12.04 12. 12 12.19 12.27 12-35 12.43 12.51 12.59 15 12.67 12.76 12.84 12.92 13.00 13.09 13.17 !3-25 13-34 13.42 16 I35I 13-60 13.68 13-77 13.86 13-95 14.04 14.12 14.21 14.30 17 14.40 14.49 14.58 14.67 14.76 14.86 14-95 15.04 15.14 1523 18 15-33 15-43 15-52 15-62 15.72 15.82 15-92 16.02 16.12 16.22 19 16.32 16.42 16.52 16.63 16.73 16.83 16.94 17.04 17.15 17.26 20 I7-36 17-47 17-58 17.69 17.80 17.91 18.02 18.13 18.24 18.35 21 18.47 18.58 18.69 18.81 18.92 19.04 19.16 19.27 19-39 19-51 22 19.63 19-75 19.87 19.99 20.11 20.24 20.36 20.48 20.61 20.73 23 20.86 20.98 21. 11 21 .24 21-37 21. 50 21.63 21.76 21.89 22.02 24 22.15 22.29 22.42 22.55 22.69 22.83 22.96 23. 10 23-24 23.38 25 23.52 23.66 23.80 23-94 24.08 24.23 24-37 24.52 24.66 24.81 26 24.96 25-10 25.25 25.40 25-55 25.70 25.86 26.01 26.16 26.32 27 26.47 26.63 26.78 26.94 27. 10 27.26 27.42 27.58 27-74 27.90 28 28.07 28.23 28.39 28.56 28.73 28.89 29.06 29.23 29.40 29- 57 29 29.74 29.92 30.09 30.26 30.44 30.62 30.79 30.97 31-15 31.33 30 3I-5I 31.69 31.87 32.06 32.24 32-43 32.61 32.80 32.99 33.18 236 APPENDIX A. 237 c vo 2 "3" en « W l H pi w fa K w Q o pq < U fa o . «° W o W « § o W o O M a a P5 O p pi (J fa ' ?1 M -r .0 co i» 00 OS rt (M M "* »o f?4 (M O* iM vM CM ro in Ov ro ro vO CO ro vO Ov ro £ 10 00 CO O ro 10 00 (N ? 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CO OO - CO CO CO CO CO 00 c3 c^ 0> o- C^ •0 LO hs M co 00 CO -» ■4- 8, vo 10 ^*- N N N -2 N, Ov l>» CO 1^ M co vo 00 vO ■0 00 4 co ro Ov o- ro CO 00 00 ro ro ro N CO O CO m VO O CO Ov 00 Ov 00 Ov 06 ro VO 10 IN VO IT) 00 vo" ro fs m ro in Ov In CO N ro ^- M m 00 -_ — IN ■* 0> 2 ro vo CO O VO VO vO t-- OO Ov D» ro CO vo 09 m 8 rt- Ov (vi ro rO VO Ov 00 rO <> rs 1 VC 00 10 VO Ov Ov VO i IN- IN t> r-. in rv In r^ tN e 10 ro Ov 00 CO ro rs, VO CO ro O Ov CO Ov ro 00 Ov 10 VO O 00 IN O O O Ov « t» 00 * °^ 00 ►"» r~- M ** M M M w H M M - M H " H « H 00 in ro co CO u-i CO IN IO £ rs vo ro Ov o> ■s VO vO IN IN 00 00 CO CO CO CO Is. CO IN tN tv vO •s. 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Ono °d 000000000000 O OOOOOOOrj- ii O O f)H t^Otc NO m t r-* N en O to O O «' in « -H in (N «N M CN 11 m MOOminOmcN K c M r-t M M H rfin , . t^ moo in O r^oo to ^O noo coOinOincNO'**- O enGO-iinOOO>-i So £ M U) < OOOOO'-'OOCO'-'Oi-i OOOOOOOOOOOOO wOOOOOOO OOOOOOOOOOOOO OOOOOOOO & X is H rt s H 3 S.'H 1) ooMinooOO'^"* ; l-i-<^-r^u-ico^T)-o*HOOOvO • uih noo mm muitON fflN £ -< 00 r^vo • § 1 ' S w E- H * m m ih M tH i-h tN tN in O m • J O (U CO a «J 5 "o U NOOOOC^inOrfHitHOi- 1 CNOOOOOO«*> *- > (A 03 'o w a« • ed u C/2 oj > ring, off coast of Mai Mooselauke, N. lall stream, Vermont stern, Massachusetts iven well, coast of M ring, Central Massac ia.ll stream, New Yor ke, Adirondack Mts. servoir, Newark, N. iven well, South Car rintr. Georgia ssissippi River, in M ep well near Lake St ssouri River, in Mon ver Sac, Missouri. . . . siniboine, Winnipeg. ep well, Lake Winni] Texas oj u '3 £ c*3 a u 4j •r ex fa — ' i ab «j ij i- PQ co wUQ co v) J 04 Q co - • - f mo r-^co O O m 5 (N f< 240 APPENDIX A. X c 0° X c coo o •+ o 10 o\ o 8 3. o o- §1 > < 3 5 g K n o & efl w< W Ph P W H O o <5 91 Pi r- O On OC GC r^ ~ c - o o M o bo 3. a (u -a •iOoU -S 3 -B S rt O cs ■ s c ^ e *g 03 OJ rt .y x > x c 6 « e o3 o3 C o3 o b o ^ o d en 03 ~j E£ c3 rt > d i_ u w. o; 3 u > t/3.> (/) OJ t" 151 o Tic/} .2 > c rt «" - ° E - at' as a- o b en en S 3 § o3 (fl W)1h O en o3 O ^ - J- " ^ t^.2 ^ .2 be M ^ O ^" O c rt o ^ a be P O n O .5 cj -b tuob cu ^^ cu - — APPENDIX A. 24X <: a - — < Si q C ■£ w *i H — 3 P ^ s 1 hJ , ( > U V a Q CO p-i 7, u < 0000N*O o mm ovo O -"(-roc-vo ■*■<*■ c» Ooo ■ - O- O m mvo m o o o\ o O O ro t~- -J- •toa) "iO ir>M3 *© rn m m 1000 O^ 6 o" 6 6 4J U ■ " 1— > . -' rt 3 3 £ « 2 re^ "r;— »5 , re rj , !"" * C X u 52 {r o £ = s p 2*2 ■ - - o 4; o — > O D „ 4). PQ«0Q ifl>0 f»00 o» o w Cfl h-1 pq li, < O h C/3 H H ►J < Pi H ^ o w S 2^ £x\ ■X if. re " u re q <" ^&| u "re u S S u I I t- re *_> re o v o f t/i f?i ■«J-oo i-l i_) M W £ <, rr, -a- rn | N N M ¥ trt H w Hi Cm S CO O* o* n»o cn H * f- « & K U rr < en ^ m*o >o mti» § « O now t-» c« ct> r " eo £ £.50. "S c rt be . ■_ B- rt— ' O U «J J- XI 3— 4; rt re Px vSigs •CO (/!-*- i) D cj y BlllOO lD^Qc/5 MD 00 \0 ■* u-.AO lO f» N ON O- r<-.00 N m VO m vo ^ H wvo 00 r- 1^ fO N N \o -<»-00 Ml>0 M M -*lfl » 0« M m ►. ■«- w M CI TfVO O •* 10 O>00 "*" H 00 -«■ "1HCO » t^ t-» « N M Jo w - yi -"«C - U£ . Hunter Redston Amsden Sanborn V)« txGO 242 APPENDIX A. Table VII. TABLE OF HARDNESS, SHOWING THE PARTS OF CALCIUM CAR- BONATE (CaC0 3 ) IN 1,000,000 FOR EACH TENTH OF A CUBIC CENTIMETER OF SOAP SOLUTION USED. 0.0 O.I 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 cu. cm. cu. cm. cu. cm. cu. cm. cu. cm. cu. cm. cu. cm. cu. cm. cu. cm. cu. cm. 0.0 O.O 1.6 3-2 1 .0 4.8 6.3 7-9 9-5 II. I 12.7 14-3 15-6 16.9 18.2 2.0 19-5 20.8 22.1 23.4 24.7 26.O 27-3 28.6 29.9 31-2 30 32.5 33-8 35-1 36.4 37-7 39 40- 3 41.6 42.9 44-3 4.0 45 -7 47.1 48.6 50.0 51.4 52.9 54.3 55-7 57-1 58.6 5-o 60.0 61.4 62.9 64-3 65.7 67.1 68.6 70.0 71.4 72.9 6.0 74-3 75-7 77-1 78.6 80.O 81.4 82.9 84-3 85-7 87.1 7.0 88.6 90.0 91.4 92.9 94-3 95-7 97.1 98.6 100. 101.5 8.0 103.0 104.5 106.0 1075 IOg.O no. 5 112. II3-5 1150 116. 5 9.0 118.0 "9-5 Z2I.I 122.6 124. 1 125.6 127. 1 128.6 130. 1 131-6 10. 133-1 134.6 I36. I 137-6 I39-I 140.6 142. 1 143-7 145-2 146.8 11 .0 148 4 150 151. 6 153-2 154-8 156.3 157-9 159-5 161. 1 162.7 12.0 164.3 165.9 I67-5 169.0 170.6 172.2 173-8 175.4 177-0 178.6 13.0 180.2 181. 7 183.3 184.9 186.5 188. 1 189.7 I9I-3 192.9 194.4 14.0 196.0 197.6 199.2 200.8 202.4 204.0 205.6 207.1 208.7 210.3 15-0 211. 9 213-5 215. 1 216.8 218.5 220.2 221.8 223.5 225.2 226.9 Table VIII. SHOWING THE NUMBER OF CUBIC CENTIMETERS OF OXYGEN DIS- SOLVED IN IOOO CUBIC CENTIMETERS OF WATER WHEN SATURATED AT DIFFERENT TEMPERATURES, AS CAL- CULATED BY WINKLER.' * Deg. Cent. Cu. Cm. Deg. Cent. Cu. Cm. Deg. Cent. Cu. Cm. O IO.187 II 7.692 21 6.233 I 9.910 12 7.518 22 6. 114 2 9-643 13 7-352 23 5.999 3 9-387 14 7.192 24 5.886 4 9.142 15 7.038 25 5 • 776 5 8.907 16 6.891 26 5-669 6 8.682 17 6.750 27 5 • 564 7 8.467 18 6.614 28 5.460 8 8.260 19 6.482 29 5.357 9 8.063 20 6.356 30 5.255 10 7.873 * Berichte, 22 (1889), 1772. APPENDIX A. 243 Table IX. FOR CORRECTING THE SPECIFIC GRAVITY OF MILK ACCORDING TO TEMPERATURE. ADAPTED FROM THE TABLE OF VIETH. (Temperature in Degrees Centigrade.) Specific Gravity. I.025 26 27 28 29 30 31 32 33 34 35 24.1 25- 1 26.1 27.0 2S.0 29.0 29.9 30.9 31.8 32.7 33-6 24-3 25.2 26.2 27.2 28.2 29. 1 30. 1 3i-i 32.0 33-o 33-9 24 25 20 27 28 29 30 31-3 32.3 33-2 34-i J-.O - 24.6 24.7 25-5 25-7 26.5 26.7 27.5 27.7 28.5 28.7 29-5 29 -7j 30.4 30.6 31-4 3 1 - ! 32.4 32.6 33-4 33-6 34-4 34-6 24.9 25.9, 26.9: 27. 9I 2S.9 29.9 30.9 3i-9 32-9 33-9 34-9 25.1 26. 1 27.1 28.1 29 30 3i 32 33 34 35-2 37 18 25-3 25-4 26.3 26.5 27.4 27-5 28.4 28.5 29.4 29-5 30.4 30.5 3i-4 31.5 32.4 32.6 33-4 33-6 34-4 34-6 35-4 35-o 25.6 26.7 27-7 28.7; 29.8 30.8 3i-8| 32-9 33-9 34-9: 35-9 25 27 28 29 30 3i 32.2 33-2 34-2 35-2 36.2 Directions. — Find the observed gravity in the left-hand column. Then in the same line, and under the observed temperature, will be found the corrected reading. 244 APPENDIX A. Table X. PERCENTAGE OF ALCOHOL i5°.5 c FROM THE SPECIFIC (HEHNER.) GRAVITY AT Percent Per cent Per cent Per cent Per cent Per cent Sp. Gr. Alcohol Alcohol Sp. Gr. Alcohol Alcohol Sp. Gr. Alcohol Alcohol i5°-5C. by by is°.sc. by by iS°.5 C. bv by Weight. Volume. Weight. Volume. Weight. Volume. I.OOOO 0.00 O.OO 0.9999 0.05 O.07 0.9959 2-33 2-93 O.9919 4.69 5-86 8 O.II 0.13 8 2-39 3.00 8 4-75 5-94 7 0.16 0. 20 7 2.44 3-°7 7 4.81 6.02 6 O. 21 0.26 6 2.50 3-i4 6 4-87 6.10 5 O. 26 °-33 5 2.56 3.21 5 4-94 6.17 4 O.32 0.40 4 2.61 3.28 4 5.00 6.24 3 0-37 0.46 3 2.67 3-35 3 5.06 6.32 2 O.42 o-53 2 2.72 3-42 2 5-12 6.40 I O.47 0.60 1 2.78 3-49 1 5-i9 6.48 O 0-53 0.66 2.83 3-55 5-25 6-55 O.9989 0.58 0-73 0.9949 2.89 3-62 0.9909 5-3i 6.63 8 O.63 0.79 8 2.94 3- 6 9 8 5-37 6.71 7 O.68 0.86 7 3.00 3-76 7 5-44 6.78 6 O.74 °-93 6 3.06 3-83 6 5-5o 6.86 5 O.79 0.99 5 3.12 3-9° 5 5-56 6-94 4 O.84 1.06 4 3-i8 3-98 4 5.62 7.01 3 O.89 1-13 3 3-24 4-o5 3 5-69 7.09 2 0-95 1. 19 2 3-29 4.12 2 5-75 7.17 1 I. OO 1. 26 1 3-35 4.20 1 5-8i 7-25 I.06 i-34 3-4i 4.27 5-87 7-32 0.9979 I. 12 1.42 0-9939 3-47 4-34 0.9899 5-94 7.40 8 1. 19 i-49 8 3-53 4-42 8 6.00 7-48 7 1-25 i-57 7 3-59 4-49 7 6.07 7-57 6 I. 31 1-65 6 3-65 4-5° 6 6.14 7.66 5 i-37 i-73 5 3-7i 4-63 5 6.21 7-74 4 1-44 1. 81 4 3-76 4.71 4 6.28 7-83 3 1.50 1.88 3 3.82 4-78 3 6.36 7.92 2 1-56 1.96 2 3-88 4-85 2 6-43 8.01 1 1.62 2.04 1 3-94 4-93 1 6.50 8.10 1-69 2.12 4.00 5.00 6-57 8.18 0.9969 1-75 2.20 0.9929 4.06 5-o8 0.9889 6.64 8.27 8 1. 81 2.27 8 4.12 5-i6 8 6.71 8.36 7 1.87 2-35 7 4.19 5-24 7 6.78 8-45 6 i-94 2-43 6 4-25 5-32 6 6.86 8-54 5 2.00 2-51 5 4-3 1 5-39 5 6 -93 8.63 4 2.06 2.58 4 4-37 5-47 4 7.00 8.72 3 2. 11 2.62 3 4-44 5-55 3 7.07 8.80 2 2.17 2.72 2 4-5° 5-63 2 7-i3 8.88 1 2. 22 2-79 1 4-56 5-7i 1 7.20 8.96 2.28 2.86 4.62 5-78 7.27 9.04 APPENDIX A. 245 Table X. — Continued. PERCENTAGE OF ALCOHOL. Per cent Per cent Per cent Per cent ! Per cent Per cent Sp. Gr. Alcohol Alcohol Sp. Gr. Alcohol Alcohol Sp. Gr. ! Alcohol Alcohol i5°.S C. by by I5°.SC. by by I5°-SC. ! by by Weight. Volume. 1 Weight. Volume. i Weight. Volume. O.9879 7-33 9-13 4 10.54 i3-°5 O.9789 14.OO 17.26 8 7.40 9. 21 3 10.62 13-15 8 14.09 17.37 7 7-47 9.29 2 10.69 l3- 2 4 7 14.18 17.48 6 7-53 9-37 1 10.77 13-34 6 14.27 17-59 5 7.60 9-45 10.85 J3-43 5 I4-3 6 17.70 4 7.67 9-54 4 14-45 17.81 3 7-73 9.62 0.9829 IO.92 13-52 3 14-55 17.92 2 7.80 9.70 8 11 .00 13.62 2 14.64 18.03 1 7-87 9-78 7 11.08 13-72 1 J 4-73 18.14 7-93 9.86 6 5 11. 15 11.23 13.81 !3-9° 14.82 18.25 0.9869 8.00 9-95 4 11. 31 *3-99 0.9779 14.90 18.36 8 8.07 10.03 3 11.38 14.09 8 15.00 18.48 7 8.14 10.12 2 11.46 14.18 7 15.08 18-58 6 8.21 10.21 1 n-54 14.27 6 I5-I7 18.68 5 8.29 10.30 11.62 J 4-37 5 15-25 18.78 4 8.36 10.38 4 15-33 18.88 3 8-43 10.47 0.9819 II.69 14.46 3 15-42 18.98 2 8.50 10.56 8 11.77 14.56 2 i5-5o 19.08 1 8-57 10.65 7 11.85 14-65 1 15-58 19.18 8.64 IO -73 6 5 11.92 12.00 14.74 14.84 15-67 19.28 | 0.9859 8-71 10.82 4 12.08 14-93 0.9769 15-75 19.39 8 8-79 10.91 3 12.15 15.02 8 15.83 19.49 7 8.86 11.00 2 12.23 15.12 7 15-92 19-59 6 8-93 11.08 1 12.31 15.21 6 16.00 19.68 5 9.00 11. 17 12.38 15-30 5 16.08 19.78 4 9.07 11.26 4 16.15 19.87 3 9.14 ii-35 0.9809 12.46 I5-40 3 16.23 19.96 2 9. 21 11.44 8 12.54 15-49 2 16.31 20.06 1 9.29 11.52 7 12.62 15.58 1 16.38 20.15 9-36 11. 61 6 5 12.69 12.77 15.68 15-77 16.46 20.24 0.9849 943 11.70 4 12.85 15-86 0-9759 16.54 20.33 8 9-5o 11.79 3 12.92 15.96 8 16.62 20.43 7 9-57 11.87 2 13.00 16.05 7 16.69 20.52 6 9.64 11.96 1 13.08 16.15 6 16.77 20.61 5 9.71 12.05 13-15 16.24 5 16.85 20.71 4 9-79 12.13 4 16.92 20.80 3 9.86 12.22 0.9799 13-23 16.33 3 17.00 20.89 2 9-93 12.31 8 13-31 16.43 2 17.08 20.99 1 10.00 12.40 7 13-38 16.52 1 17.17 21.09 10.08 12.49 6 5 13.46 13-54 16.61 16.70 17.25 21.19 0. 0839 10.15 12.58 4 13.62 16.80 0.9749 17-33 21.29 8 10.23 12.68 3 13.69 16.89 8 17.42 20.39 7 10.31 12.77 2 13-77 16.98 7 i7-5o 21.49 6 10.38 12.87 1 13.85 17.08 6 17.58 21-59 5 10.46 12.96 13.92 17.17 5 17.67 21.69 246 APPENDIX A. Table X. — Continued. PERCENTAGE OF ALCOHOL. Per cent Per cent 1 Per cent Per cent Per cent Per cent Sp. Gr. Alcohol Alcohol Sp. Gr. Alcohol Alcohol Sp. Gr. Alcohol Alcohol I5°.5C. by by is°-sc. by by I5°.SC. by by Weight. Volume. Weight. "Volume. Weight. Volume. 4 17-75 21.79 4 20.17 24.68 4 22.54 27.49 3 17-83 21.89 3 20.25 24.78 3 22.62 27-59 2 17.92 21.99 2 20.33 24.88 2 22.69 27.68 I 18.00 22.09 1 20.42 24.98 1 22.77 27.77 O 18.08 22.18 20.50 25.07 22.85 27.86 0.9739 18.15 22. 27 0.9709 20.58 25.17 0.9679 22.92 , 27-95 8 18.23 22.36 8 20.67 25.27 8 23.00 28.04 7 18.31 22.46 7 20-75 25.37 7 23.08 28.13 6 18.38 22-55 6 20.83 25-47 6 23-15 28.22 5 18.46 22.64 5 20 92 25-57 5 23.23 28.31 4 18.54 22,73 4 2I.OO 25-67 4 23-31 28.41 3 18.62 22.82 3 21.08 25 76 3 23.38 28.50 2 18.69 22.92 2 21.15 25.86 2 23.46 28-59 1 18.77 23 OI 1 21.23 25.95 1 23-54 28.68 18.85 23.IO 21.31 26.04 23.62 28.77 O.9729 18 92 23.19 0.9699 21.38 26.13 0.9669 23.69 28.86 8 19 00 23-28 8 21.46 26 22 8 2 3-77 28.95 7 19.08 23-38 7 21-54 26.3I 7 23.85 29.04 6 19 17 23-48 6 21.62 26.4O 6 23.92 29-13 5 l9- 2 5 23 58 5 21.69 26.49 5 24.00 29.22 4 19-33 23.68 4 21.77 26.58 4 24.08 29.31 3 19.42 23-78 3 21.85 26.67 3 24-15 29.40 2 I9-50 23-88 2 21.92 26.77 2 24-23 29-49 1 19.58 23.98 1 22.00 26.86 1 24. 3 1 29.58 19.67 24.08 22.08 26.95 24.38 29.67 0.9719 19-75 24. l8 0.9689 22.15 27.04 0.9659 24.46 29.76 8 19.83 24.28 8 22.23 27- J 3 8 24-54 29.86 7 19.92 24-38 7 22.31 27.22 7 24.62 29-95 6 20.00 24.48 6 22.38 27-31 6 24.69 30.04 5 20 08 24.58 5 22.46 27.40 5 4 3 2 24-77 24-85 24.92 25.00 30.22 30.40 APPENDIX A. 247 Table XL EXTRACT IN WINE. Per Cent by Weight. [According to Windisch.] Sp. Gr. Ex- Sp. Gr. Ex- Sp. Gr. Ex- 1 'Sp. Gr. Ex- Sp. Gr. Ex- Sp. Gr Ex- tract. tract. tract. tract. tract. tract. 1 . 0000 0.00 1 .0200 5-17 1 .0400 10.35 1 .0600 15.55 1 .0800 20.78 1 . 1 00a 26 .04 1 .0005 0.13 1.0205 5.30 1 .0405 10.48 1 .0605 15.68 1 .0805 20.91 1 . 1005 26. 17 1 .0010 0.26 1 .0210 5-43 1 .0410 10.61 1 .0610 15.81 1. 0810 21 .04 1 . IOIO 26.30 1 .0015 0.39 1 .0215 5.56 1-0415 10.74 1 .0615 15-94 1. 0815 21.17 1. 1015 26.43 r .0020 0.52 1 .0220 5.69 1 .0420 10.87 1 .0620 16.07 1 .0820 21.31 1 . 1020 26.56 1 .0025 0.64 1 .0225 5-82 1 .0425 1 1 . 00 1 .0625 16.21 1 .0825 21.44 1 .1025 26.70 1 .0030 0.77 1.0230 5-94 1.0430 11 . 13 1.0630 16.33 1 .0830 21.57 1 . 1030 26.83 1 -0035 0.90 10235 6.07 1 -0435 11.26 1-0635 16.47 1.0835 21 . 70 1 -1035 26 . 96 1 .0040 1 °3 1 .0240 6. 20 1 .0440 n.39 1 .0640 16.60 1 .0840 21.83 1 . 1040 27.09 1. 0045 1. 16 1.0245 6.33 1.0445 11 .52 1 0645 16.73 1.0845 21 .96 1. 1045 27.22 1 .0050 1.29 1 .0250 6.46 1.0450 11 .65 1 .0650 16.86 1 .0850 22 .09 1. 1050 27.35 1.0055 1.42 1-0255 6.59 1.0455 11.78 1-0655 16.99 1-0855 22 . 22 i- 1055 27.49 1 .0060 1. 55 1 .0260 6.72 1 .0460 11. 91 1 .0660 17.12 1 .0860 22 .36 1 . 1060 27.62 1 .0065 1.68 1.0265 6.8s 1 .0465 13 .04 1 .0665 17.25 1.0865 22.49 1 . 1065 27.75 1 .0070 1. 81 1 .0270 6.98 1.0470 12.17 1 .0670 17.38 1 .0870 22 . 62 1 . 1070 27.88 1.0075 1.94 1.0275 7. 11 1 -0475 12 .30 1.0675 17-51 1.0875 22.75 1. 1075 28.01 1 .0080 2.07 1 .0280 7.24 1 .0480 12.43 1.0680 17.64 1.0880 22.88 1 . 1080 28.15 1 .0085 2.19 1.0285 7-37 1 .0485 12.56 1.0685 17.77 1.0885 23.OI 1. 1085 28.28 1 .0090 2.32 1 .0290 7- SO 1 .0490 12 .69 1 .0690 17 .90 1 .0890 23.I4 1 . 1090 28.41 1.0095 2-45 1 .0295 7.63 I.Q495 12.82 1 .0695 18.03 1.0895 23.28 1. 1095 28.54 1 .0100 2.58 1 .0300 7.76 1 .0500 12.95 1 .0700 18.16 1 .0900 23 .41 1 . 1 100 26 .67 1 .0105 2.71 1.0305 7.89 1 -0505 I3.08 1.0705 18.30 1 .0905 23.54 1 . 1105 28.81 1 .0110 2.84 1 .0310 8.02 1 .0510 13-21 1 .0710 18.43 1 .0910 23.67 I . IIIO 28.94 1.0115 2.97 1-0315 8.14 1-0515 13-34 1 -0715 18.56 1. 0915 23.80 I . 1115 29.07 1 .0120 3- 10 1 .0320 8.27 1.0520 13-47 1 .0720 18.69 1 .0920 23.93 I . II20 29.20 1. 0125 3-23 1-0325 8.40 1-0525 I3.6o 1 .0725 18.82 1 .0925 24.07 I . 1125 29-33 1. 0130 3.36 1.0330 8-53 1.0530 13-73 1 .0730 18.95 1.0930 24.20 I.II30 29.47 1.0135 3-49 I-0335 8.66 1. 053S 13-86 I-0735 19.08 1 -0935 24.33 r."35 29. 60 1 .0140 3-02 1 .0340 8.79 1 . 0540 13 -99 1 .0740 19.21 1 .0940 24.46 1 . 1 1 40 2973 1. 0145 3-75 I-0345 8.92 I-054S 14. 12 1.0745 19.34 I.Q945 24.59 1. "45 29.86 1. 0150 3.87 1.0350 9.05 1.0550 14-25 1.0750 19-47 1 .0950 24.72 1.1150 29.99. 1.015s 4.00 I-0355 9.18 I-0555 14.38 I-0755 19.60 1 -0955 24.85 1. "55 30.13 1 .0160 4.13 1.0360 9.3i 1 .0560 14.51 1 .0760 19-73 1 .0960 24.99 1.016s 4. 26 1-0365 9-44 1.0565 14.64 1.0765 19.86 1 .0965 25.12 1. 0170 4-39 1.0370 9-57 1.0570 M-77 1.0770 20.00 1 .0970 25-25 1. 017s 4.52 I-0375 970 I.0575 14.90 1 -0775 20. 12 1 -0975 25.38 1 .0180 4.65 1 .0380 9.83 1 .0580 15-03 1 .0780 20. 26 1 .0980 25-51 1. 0185 4.78 1-0385 9.96 1.0585 15.16 1.0785 20.39 1 .0985 25.64 1 .0190 4.91 1 .0390 10.09 1 .0590 15-29 1 .0790 20. 52 1 .0990 25.78 1. 0195 5-04 1 -0395 10. 22 1 .0595 15.42 1.0795 20.65 I-Q995 25.91 . 248 APPENDIX A. Table XII. TABLE FOR REDUCING SUGAR CONDENSED MUNSON AND WALKER. (Expressed in milligrams.) FROM THAT OF O O u X CD u X p 3 6 «5 u C + A BX s < O aT S3 O - 2 ^ u 6 en 2 Q a bo to u CD > C + A 2X jc5 O 1)8 ISO 9 10 4.0 4-5 4.0 5-9 260 117 .6 121. 4 176.3 203.9 is 6.2 6-7 7-5 9-9 265 120.0 123.9 179-7 207.9 20 8.3 8-9 10.9 13-8 270 122.5 126. 4 183.2 211. 8 25 10.5 11 . 2 14.4 17.8 275 124.9 I28.9 186.6 215.8 30 12.6 13-4 17.8 21.8 280 127.3 I3I-4 190. I 219.7 35 14.8 15.6 21.3 25-7 285 129.8 133-9 193-5 223.7 40 16.9 17.8 24.7 29.7 290 132.3 I36.4 196.9 227.6 45 19. 1 20. 1 28.2 33-7 295 134-7 138.9 200. 4 231.6 SO 21.3 22.3 31-6 37-6 300 137.2 141. 5 203.8 235-5 55 23-5 24.6 35-0 41.6 305 139-7 144.0 207 . 2 239.5 60 25.6 26.8 38.4 45-6 310 142 .2 146.6 210. 7 243-3 65 27.8 29.1 41 .9 49-5 315 144-7 149- 1 214. 1 247.4 70 30.0 31-3 45-4 53-5 320 147.2 I5I-7 217.6 251-3 75 32 .2 33-6 48.8 57-5 325 149-7 154-3 221.0 255-3 80 34-4 35-9 52.3 61 .4 330 152.2 156.8 224.4 2S9-3 85 36.7 38.2 55-7 65.4 335 154.7 159-4 227.9 263.3 90 38.9 40.4 59-2 69 -3 340 157.3 162 .0 231-3 267. 1 95 41. I 42. 7 62.6 73-3 345 159-8 164.6 234-7 271 . 1 100 433 45-0 66.1 77-3 350 162 . 4 167. 2 238.2 275.0 105 45-5 47-3 69.5 81.2 355 164.9 169.8 241 .6 279.0 no 47-8 49-6 73-0 85.2 360 l675 172.5 245-1 282.9 n5 50.0 51-9 76.4 89.2 365 170. I I75-I 248.5 286.9 120 52.3 543 79-8 93-1 370 172.7 177.7 252 .0 290.8 125 54-5 56.6 833 97.1 375 175-3 180.4 255-4 294.8 130 56.8 58.9 86.7 101 .0 380 177.9 183.0 258.8 298.7 135 59-o 61.2 90. 2 105.0 38s 180.5 185.7 262.3 302.7 140 61.3 63.6 93-6 109 .0 390 183. 1 188.4 265.7 306.6 145 63.6 65-9 97-1 112 .9 395 185.7 191 .0 269. 1 310.6 150 659 68.3 100.5 116. 9 400 188.4 193-7 272 .6 3M.5 155 68.2 70.6 104.0 120.8 405 191 .0 196.4 276.0 3IK.5 160 70.4 73-0 107.4 124.8 410 193-7 199- 1 279-5 322.4 165 72.8 75-3 no. 9 128.8 415 196.3 201.8 282 .9 326.3 170 75-i 77-7 114. 3 132.7 420 199.0 204.6 286.3 330.3 175 77-4 80.1 117. 7 136.7 425 201 . 7 207.3 289.8 334-2 180 79-7 82.5 121 . 2 140.6 430 204.4 210.0 293-2 338.3 185 82.0 84.9 124.6 144-6 435 207. 1 212.8 296.6 342.1 190 84.3 87.2 128. 1 148.6 440 209 . 8 215-5 300. 1 346.1 195 86.7 89.6 I3I-5 152.5 445 212.5 218.3 3035 350.0 200 89.0 92 .0 I35-0 156. s 450 215.2 221 . 1 306.9 353-9 205 91.4 94-5 138.4 160. 4 455 218.0 223.9 310.4 3579 210 93-7 96.9 141. 9 164.4 460 220. 7 226.7 313.8 361.8 215 96. 1 99-3 145-3 168.3 465 223.5 229.5 317.3 365.8 220 98.4 101 .7 148.7 172.3 470 226. 2 232.3 320.7 369.7 225 100. 8 104. 2 152 .2 176.2 475 229.0 235-1 324.1 373-7 230 103.2 106.6 155-6 180.2 480 231.8 237-9 327.6 377-6 235 105 .6 109. 1 159. 1 184.2 485 234.6 240.8 33io 381. 5 240 108.0 in. 5 162.5 188. 1 490 237.4 243-6 334-4 385-5 245 no. 4 114. 166.0 192 . 1 250 112. 8 116. 4 169.4 196.0 355 115. 2 118. 9 172.8 200.0 APPENDIX A. Table XIII. EXTRACT IN BEER- WORT. (According to Schultzand Ostermann.) 249 Specific Extract. Specific Extract. Specific Extract. Specific Extract. Gravity at Per cent Gravity at Per cent. Gravity at Per cent. Gravity at Per cent. i 5 ° C. by Weight. >5°C. by Weight. 15° C. by Weight. .5°C. by Weight, 1 .OOOO O.OO I 0235 6.07 I . 0470 II.89 I.0705 17-59 1 .0005 O.13 I . 0240 6.I9 1-0475 I2.0I I .0710 17.70 1 .0010 O.26 I.O245 6.31 I . 0480 12 . 14 1-0715 17.81 1. 0015 0-39 I.0250 6.44 I.0485 12 . 26 I .0720 17.93 1 .0020 O.52 ^0255 6.58 I . 0490 I2.38 I.0725 18.04 1 .0025 O.66 1 .0260 6.71 1-0495 I2.50 I.0730 18.15 I . 0030 O.79 1.0265 6.85 I .0500 I2.63 I 0735 18.26 1-0035 O.92 1 .0270 6.99 1-0505 12-75 I .0740 18.38 1 . 0040 I.05 1.0275 7.12 I. 0510 12.87 I 0745 18.49 1 . 0045 I. 18 1 .0280 7. 26 1-0515 12.99 I.075O 18.59 1 .0050 i-3i 1.0285 7-37 I .0520 13.12 I 0755 18.70 1-0055 1.44 1 .0290 7.48 I.0525 I3.24 I .0760 18.81 1 .0060 1.56 1-0395 7.60 I 0530 I3-36 I.0765 18.91 1 . 0065 1 .69 1.0300 7-7i 1-0535 I3-48 I.0770 19.02 1 . 0070 1.82 I -030 5 7.82 I . 0540 I3.6I I0775 19. 12 1.0075 i-95 1. 0310 7-93 I 0545 13-73 T .O78O I9.23 1 .0080 2.07 1-0315 8.04 I-0550 13-86 I.O785 19.33 1 .0085 2. 20 1.0320 8.16 IO555 I3-98 I .O79O 19.44 1 .0090 2-33 !032 5 8.27 I . 0560 14. 11 I-0795 19-56 1.0095 2.46 1.0330 8.40 1-0565 14.23 I O8OO 19.67 I .0100 2.58 I 0335 8-53 I.0570 I4-36 I.O8O5 ' 19.79 1. 0105 2.71 1.0340 8.67 LO575 74.49 I. 08lO 19.91 1 .01 10 2.84 J0345 8.80 I .0580 14.62 I. O8I5 20.03 1.0115 2.97 1-0350 8-94 I.0585 14-75 I .0820 20. 14 1 .0120 3.10 1-0355 9.07 I . 0590 14.89 I.0825 20.26 1-0125 3-23 1 . 0360 9. 21 1-0595 15.02 I .O83O 20.37 1. 0130 3-35 1-0365 9-34 I . 0600 15-14 LO835 20.48 i- OI 35 3-48 1.0370 9-45 I . 0605 1525 I . O84O 20.59 1 .0140 3-6i 1 0375 9-57 I .0610 1536 I.O845 20. 70 1. 0145 3-74 1.0380 9.69 I. 0615 15.47 I .O85O 20.8I 1. 0150 3-87 1-0385 9.81 I .0620 I5-58 I.0855 20.93 1-0155 4.00 1.0390 9.92 I.0625 1569 I . O86O 21 .06 1 .0160 4-13 !0395 10.04 I . 0630 15.80 I.0865 21 . 19 1. 0165 4.26 1 . 0400 10. 16 IO635 1592 I .O87O 21-33 1 .0170 4-39 1.0405 10.27 I . 0640 16.03 I.O875 21-43 1. 0175 4-53 1 .0410 10.40 I . 0645 16. 14 I.O88O 21-54 1 .0180 4.66 1-0415 10.52 I . 0650 16.25 I.O885 21 .64 1. 0185 4-79 1 . 0420 10.65 I 0655 16.37 I . O89O 21-75 1 .0190 4-93 1.0425 10.77 I . 0660 16.50 IO895 21.86 - 1. 0195 5.06 1.0430 10.90 I . 0665 16.62 I . 0900 21.98 1 . 0200 5.20 J0435 11.03 I .0670 16.74 I . 0905 22.08 1 .0205 5-33 1 . 0440 11. 15 I.0675 16.86 I .O9IO 22. 19 1 .0210 5-45 1.0445 11.28 I . 0680 16.99 I-09I5 22.30 1. 0215 5-57 1 . 0450 11 .40 I.0685 17. 11 I .0920 22.41 1 .0220 5 70 1 0455 1 1 ■ 53 I . 0690 17.23 I . 0925 22.52 1 .0225 5-82 1 . 0460 11.65 1.0695 17-35 I . O93O 22.63 1 .0230 5-94 1.0465 11.77 I .0700 17.48 I 0935 22.73 250 APPENDIX A. Table XIII. — Continued. EXTRACT IN BEER-WORT. (According to Schultz and Ostermann.) Specific Extract. Specific Extract. Specific Extract. Specific Extract. Gravity at Per cent. Gravity at Per cent Gravity at Per cent. Gravity at Per cent. . ..5°C. by Weight. 15° C. by Weight. 15° L- by Weight 15° C. by Weight. I . 0940 22.84 I . I020 24-53 I . I IOO 26. 27 1. 1 180 27.88 1-0945 22.94 I. 1025 24.64 I.IIO5 26.37 1.1185 27.98 1.0950 23-05 I . IO3O 24-74 I . II IO 26.48 I . 1 1 90 28.09 1-0955 23.16 I • IO35 24.85 I.III5 26.58 1. "95 28.19 I . 0960 23.27 I . IO40 24.96 I . 1 1 20 26.68 1 . 1 200 28.28 I.0965 23-37 I . IO45 25.07 I.II25 26.79 1-1205 28.38 I .0970 23.48 I . 1050 25.18 I. 1 130 26.89 1 . 1210 28.48 I.0975 23-59 I IO55 25.29 I.II35 26.99 1.1215 28.58 I . 0980 23.69 I . IO60 25.40 I . I I40 27.09 1 . 1220 28.68 I . 0985 23.80 I. IO65 25-50 I- 1 145 27.19 1. 1225 28.78 I . 0990 23.90 I . IO70 25.61 I.II50 27.29 1 . 1230 28.88 I.0995 24.01 I. IO75 25-71 III55 27.38 1 1235 28.98 I . IOOO 24. 1 1 I . IO80 25.82 I . I l6o 27.48 1 . 1 240 29.08 I. 1005 24.21 I . IO85 25-93 I.H65 27.58 1. 1245 29.18 I . IOIO 24.32 I . IO90 26.05 I . 1 1 70 27.68 1. 1250 29. 28 1.1015 24-43 I . IO95 26. 16 III75 27.78 L1255 29.38 APPENDIX A. LOGARITHMS OF NUMBERS. 251 It « Proportional Parts. £j3 1 2 3 ' 4 5 7 8 9 2 £ 1 2 3 4 5 6 i 7 8 9 IO 0000 0043 0086 0128 0170 1 I 0212 0253 0294 0334 0374 4 S 1 2 17 21 25!2g 33 37 II 0414 0453 0492 0531 0569 0607 0645 0682 0719 0755 4 8 1 1 15 19 23 26 30 34 12 0792 0828 0864 0899 0934 0969 1004 1038 1072 1 106 J 7 10 14 1 21 24 28 3i 13 "39 ii73 1206 1239 1271 1303 1335 1367 1399 1430 3 6 10 13 IC 19 23 26 29 14 1461 1492 1523 1553 1584 1614 1644 ( X6 73 1703 1732 3 6 9 1 2 is 18 21 24 27 15 1761 1790 1818 1847 1875 1903 1931 1 ,1959 1987 2014 3 6 8 1 1 14 17 20 22 25 16 2041 2068 2095 2122 2148 2175 2201 ^227 2253 2279 3 5 8 11 13 16 18 21 24 17 2304 2330 2355 2380 2405 2430 2455 2480 2504 2529 2 5 7 10 1 2 |- IS 17 20 22 18 2553 2577 2601 2625 2648 2672 2695 2718 2742 2765 2 5 7 9 1 2 14 16 19 21 19 2788 2810 2833 2856 2878 2900 2923 2945 2967 2989 2 4 7 9 1 1 13 16 18 20 20 3010 3032 3054 3075 3096 3n8 3i39 3l60 3181 3201 2 4 6 8 1 13 15 17 19 21 3222 3243 3263 3284 3304 3324 3345 33 6 5 3385 3404 2 4 6 8 10 12 14 16 18 22 3424 3444 34 6 4 3483 3502 3522 354i 356o 3579 3598 2 4 6 8 10 1 2 14 15 17 23 3617 3636 3655 3674 3692 37" 3729 3747 3766 3784 2 4 6 7 9 1 1 13 IS 17 24 ' 3802 3820 3838 3856 3874 3892 3909 3927 3945 3962 2 4 5 7 9 1 1 1 2 14 16 25 3979 3997 4014 4031 '4048 4065 4082 4099 4116 4133 2 3 5 7 9 10 12 14 1 5 26 4150 4166 4183 4200 4216 4232 l 4 249 , 4265 4281 4298 2 3 5 7 8 10 11 13 15 27 4314 4330 4346 4362 4378 4393 4409 4425 4440 4456 2 3 5 8 9 1 1 13 14 28 4472 4487 4502 4518 4533 4548 4564 4579 4594 4609 2 3 5 6 8 9 1 1 12 14 29 4624 4639 4654 4669 4683 4698 47134728 4742 4757 I 3 4 7 9 10 12 13 30 477i 4786 4800 4814 4829 4843 4857 4871 4886 4900 3 4 6 7 9 10 1 1 13 31 +914 49284942 4955 4969 4983 4997 501 1 5024 5038 3 4 7 8 io 11 12 32 5051 50655079 5092 5105 5ii9 51325145 5i59 5172 3 4 5 7 8 9 11 12 33 5i85 5198 5211 52245237 5250 52635276 5289 5302 3 4 5 6 8 9 10 12 34 5315 5328.5340 5353 5366 5378 539i 5403 54i6 5428 3 4 5 6 8 9 10 11 35 544i 5453^465 5478 5490 5502 55H 5527 5539 555i 2 4 5 6 7 , 10 11 36 5563 55755587 5599 561 1 5623 5635 5647 5658 5670 2 4 5 6 7 8 1 11 37 5682 5694 57°5 5717 5729 5740 5752 5763 5775 5786 2 3 5 6 » 8 9 10 38 5798 58095821 5832 5843 5855 5866 5877 5888 5899 2 3 5 6 7 8 9 10 39 59i 1 5922 5933 5944 5955 5966 5977 5988 5999 6010 2 3 4 5 7 8 9 10 40 6021 6031 6042 6053 6064 6075 6085 6096 6107 6117 2 3 4 5 6 8 9 IO- 4i 6128 6138 6149 61606170 6180 6191 6201 6212 6222 2 3 4 5 6 7 8 9 42 6232 6243^253 6263 6274 6284 6294 6304 63H 6325 2 3 4 5 6 7 8 9 43 6335 6345 6355 6365 6375 6385 6395 6405 6415 6425 2 3 4 5 6 7 8 9 44 6435 6444 6454 6464 6474 6484 6493 6503 65X3 6522 2 3 4 ' 5 6 7 8 9 45 6532 6542 6551 6561 6571 6580 6590 6599 6609 6618 2 3 4 5 6 7 8 9 46 6628 6637 6646 6656 6665 6675 6684 6693 6702 6712 2 3 4 5 6 7 7 8 47 S721 6730 6739 6749 6758 6767 67761678516794 6803 2 3 4 5 5 6] 7 8 48 6812 6821 6830 6839 6848 6857 68666875 6884 6893 2 3 4 4 5 6 7 8 49 6902 691 1 6920 6928 6937 6946 6955 6964 6972 6981 2 3 - 4 5 6 7 8 50 6990 6998 7007 7016 7024 7033 7042 7050 7059 7067 2 3 3 4 s 6 7 8 5i 7076 7084 7093 7101 7110 7118 7126 7135 7143 7152 2 3 3 4 5 6 1 7 8 52 7160 7168 7177 7185 7i93 7202 7210 7218 7226 7235 2 2 3 4 .5 61 7 7 53 7243 7251 7259 7267 7275 7284 7292 7300 73o8 73I 6 2 2 3 4 5 6 6 7 54 7324 7332 7340 7348 7356 7364 7372 738o l 7388f73 9 6 I 2 2 3 4 5 6 1 6 7 *D* APPENDIX A. LOGARITHMS OF NUMBERS. - t-1 12 3 4 5 6 7 8 9 .OO 1000 1002 1005 1007 1009 1012 IOli 1016 IOIC 1021 1 1 x 1 2 2 2 .01 1023 1026 1028 1030 1033 1035 io 3 £ 1040 1042 1045 1 1 1122a .02 1047 1050 1052 io 54 1057 1059 1062 1064 1067 1069 001 1 1 1 2 2 a .03 1072 1074 1076 1079 1081 1084 1086 1089 1091 1094 1 i 1 1 2 2 3 .04 1096 1099 1 102 1 104 1 107 1 109 III2 1 1 14 1117 1 1 19 1 1 1 12222 .05 1122 1125 1127 1 1 30 1132 1135 1138 1 140 1143 II 46 I I I 12 2 2 2 .06 114811151 1153 1 1 56 1159 1161 I 164 1167 1169 1172 I I I 12 2 2 2 .07 1175J1178 1 180 "83 1186 1189 II9I 1194 1197 11991 I I I 12 2 2 2 .08 1202 1205 1208 1211 1213 1216 1219 1222 1225 1227I0 1 1 1 12 3 2 3 .09 1230 1233 1236 1239 1242 1245 1247 1250 1253 1 256J 1 1 1 12 2 2 3 .IO 1259 1262 1265 1268 1271 1274 1276 1279 1282 1285 1 1 1 12 2 2 3 .11 1288 1291 1294 1297 1300 i3°3 I306 1309 1312 1315 1 1 1 2 2 2 2 3 .12 1318 1321 1324 1327 1330 1334 1337 1340 1343 1346 1 1 1 2 2 2 2 3 .13 1349 1352 1355 1358 1361 1365 I368 1371 1374 1377 1 1 1 2 2 2 3 3 .14 1380 1384 1387 1390 1393 1396 I4OO i4°3 1406 1409 1 1 1 2 2 2 3 3 .15 H J 3 1416 1419 1422 1426 1429 1432 H35 1439 1442 1 1 1 2 2 2 3 3 .16 1445 1449 1452 1455 1459 1462 I466 1469 1472 1476 1 1 1 22233 .17 1479 1483 i486 1489 1493 1496 I5OO 1503 1507 1510 1 1 1 2 2 2 3 3 .18 1514 1517 1521 1524 1528 1531 1535 1538 1542 1545 1 1 1 2 2 2 3 3 .19 1549 1552 1556 1560 1563 1567 I570 1574 1578 1581 o- I I I 22333 .20 1585 1589 1592 1596 1600 1603 1607 1611 1614 1618 1 1 1 22333 .21 1622 1626 1629 1633 1637 1641 1644 1648 1652 1656 1 1 2 2 2 3 3 3 .22 1660 1663 1667 1671 1675 1679 1683 1687 1690 1694 1 1 2 . 2 2 3 3 3 .23 1698 1702 1706 1710 1714 1718 1722 1726 173° 1734 1 1 2 . '2334 •24 1738 1742 1746 I750 1754 1758 1762 1766 1770 1774 1 1 2 5 •2334 .25 1778 1782 1786 1791 1795 1799 1803 1807 1811 1816 1 1 2 : '2334 .26 1820 1824 1828 1832 1837 1841 1845 1849 1854 T858 1 1 2 2 3 3 3 4 -27 1862 1866 1871 1875 1879 1884 1888 1892 1897 19OI 1 1 2 2 3 3 3 4 .28 i9°5 1910 1914 1919 1923 1928 1932 1936 1 941 1945 x 1. a s 3 3 4 4 .29 1950 1954 1959 1963 1968 1972 1977 1982 1986 1 99 I 1 1 2 5 3 3 4 4 .30 1995 2000 2004 7009 2014 2018 2023 2028 2032 2037 1 1 2 2 3 3 4 4 .31 2042 2046 2051 2056 2061 2065 2070 2075 2080 2084 1 1 2 1 3 3 4 4 -32 2089 2094 2099 2104 2109 2113 2Il8 2123 2128 2133 1 1 22 3 3 4 4 •33 2138 2143 2148 2153 2158 2163 2l68 2173 2178 2183 1 1 2 2 3 3 4 4 • 34 2188 2193 219^ 2203 2208 2213 2218 2223 2228 2234 1 1 2 2 3 3 4 1 4 5 • 35 2239 2244 2249 2254 2259 2265 2270 2275 2280 2286 1 1 2 2 3 3 4 4 5 .36 2291 2296 2301 2307 2312 2317 2323 2328 2333 2339 1 1 2 2 3 3 4 4 5 • 37 2344 2350 2355 2360 2366 2371 2377 2382 2388 2393 1 1 2 2 ; 3 4 4 5 .38 2399 2404 24 1 c Hi5 2421 2427 2432 2438 2443 2449 1 1 2 2 ; 3 4 4 5 • 39 2455 2460 246C 2472 2477 2483 2489 2495 2500 2506 1 1 2 2 ; 3 4 5 5 .40 2512 2518 2522 2529 2535 2541 2547 2553 2559 -564 1 1 2 2 ; 4 4 5 5 .41 2570 2576 2582 2588 2594 2600 2606 2612 2618 2624 j ! 2 2 5 4 4 5 5 .42 2630 2636 2642 2649 2655 2661 2667 2673 2679 2685 1 1 2 2 . 5 4 4 5 <•> •43 2692 2698 2704 2710 2716 2723 2729 2735 2742 2748 1 t 2 3 : * ' 4 4 5 *> •44 2754 2761 2767 2773 2780 2786 2793 2799 2805 28l2 J 1 2 3 5 4 4 5 6 •45 2818 2825 2831 2838 2844 2851 2858 2864 2871 2877 a 1 2 3 3 4 5 5 6 .46 2884 2891 2897 2904 291 1 2917 2924 293 1 2938 2944 1 1 2 3 ^4556 •47 2951 2958 2965 2972 2979 2985 2992 2999 3006 30I3 1 1 2 3 3 4 5 5 6 .48 3020 3027 3034 3041 3048 3055 3062 3069 3076 3083 1 1 2 3 4 4 5 6 6 •49 3090 3097 3105 3112 1119 3126 3133 3141 3148131.^ 1 1 2UI 4 4 5 6 6 254 APPENDIX A. I ANTILOGARITHMS. s Proportional Parts. rt-5 1 2 3 4 5 6 7 8 9 o u 12 3 4 5 6 7 8 9 •50 3162 3!7o 3i77 3184 3192 3199 3206 3214 3221 3228 1 1 2 3 44567 .51 3236 3243 3251 3258 3266 3273 3281 3289 3296 3304 1223 45567 •52 33" 3319 3327 33.34 3342 335° 3357 3365 3373 3381 1223 45567 •53 3388 3396 3404 34 ! 2 3420 3428 3436 3443 345i 3459 1223 45667 •54 3467 3475 3483 3491 3499 35o8 35i6 3524 3532 3540 1223 45667 •55 3548 3556 3565 3573 358i 3589 3597 3606 3614 3622 1223 45677 .56 363 1 3639 3648 36-56 3664 3673 3681 3690 3698 3707 1233 45678 •57 3715 3724 3733 374i 3750 3758 3767 3776 3784 3793 1233 45678 .58 3802 381 1 3819 3828 3837 3846 3855 3864 3873 3882 1234 45678 •59 3890 3899 39o8 39*7 3926 3936 3945 3954 3963 3972 1234 55678 .6O 398i 399o 3999 4009 4018 4027 4036 4046 4055 4064 1 2 3 4 56678 .61 4074 4083 4093 4102 4111 4121 4130 4140 4150 4159 1234 5 6 7 8 .9 .62 416914178 4188 4198 4207 4217 4227 4236 4246 4256 1234 5 6 7 8 .9 .63 4266I4276 4285 4295 4305 43 1 5 4325 4335 4345 4355 1 2 3 4 56789 .64 4365I4375 4385 4395 4406 4416 4426 4436 4446 4457 1234 5 6 7 8 .9 .65 4467 4477 4487 449.8 4508 4519 4529 4539 4550 4560 1234 56789 .66 457i 458i 4592 4603 4613 4624 4634 4645 4656 4667 1234 5 6 7 9 10 .67 4 6 77 4688 4699 4710 472i 4732 4742 4753 4764 4775 1 2 3 4 5 7 8 9 10 .68 4786 4797 4808 4819 4831 4842 4853 4864 4875 4887 1234 6 7 8 9 10 .69 4898 49P9 4920 4932 4943 4955 4966 4977 4989 5000 1235 6 7 8 9 10 •70 5012 5Q23 5035 5047 5058 5070 5082 50935105 5117 1245 6 7 8 9 11 .71 5129 5HO 5152 5 l6 4 5176 5188I5200 5212 5224 5236 1245 6 7 8 10 11 .72 5248 5260 5272 5284 5297 53°9l532i 5333 5346 5358 1245 6 7 9 10 n • 73 5370 5383 5395 5408 5420 5433 5445 5458 5470 5483 1345 6 8 9 10 11 • 74 5495 5508 552i 5534 5546 5559 5572 5585 5598 561O 1 3 4 5 6 8 9 10 12 • 75 5623 5636 5649 5662 5675 5689 5702 5715 5728 574I 13 4 5 7 8 9 10 12 .76 5754 5768 578i 5794 5808 5821 5834 5848 5861 5875 1 3 4 S 7 8 9 11 12 • 77 5888 5902 59 l6 59 2 9 5943 5957 5970 5984 5998 60I2 13 4 5 7 8 10 11 12 .78 6026 6039 6053 6067 6081 6095 6109 6124 6138 6152 1346 7 8 10 11 13 • 79 6166 6180 6194 6209 6223 6237 6252 6266 6281 6295 13 4 6 7 9 10 11 13 .80 6310 6324 6339 635'3 6368 6383 6397 6412 6427 6442 1346 7 9 10 12 13 .81 6457 6471 6486 6501 6516 6531 6546 6561 6577 6592 2356 81 9 11 12 14 .82 6607 6622 6637 6653 6668 6683 6699 6714 6730 6745 2356 8 9 11 12 14 .83 6761 6776 6792 6808 6823 6839 6855 6871 6887 6902 2356 8} 9 11 13 14 .84 6918 6934 6950 6966 6982 6998 7015 703 1 7047 7063 2356 8 10 11 13 15 .85 7079 7096 7112 7129 7145 7161 7178 7194 7211 7228 2 3 5 7 8 10 12 13 15 .86 7244 7261 7278 7295 73"" 7328 7345 7362 7379 7396 2 3 5 7 8 10 12 13 15 .87 7413 743° 7447 7464 7482 7499 75 l6 7534 755i 7568 235 7 9 10 12 14 16 .88 7586 7603 7621 7638 7656 7674 7691 7709 7727 7745 2457 911 12 14 16 .89 7762 7780 7798 7816 7834 7852 7870 7889 7907 7925 2457 911 13 14 16 .90 7943 7962 7980 7998 8017 8035 8054 8072 8091 8110 2467 9 11 13 15 17 .91 8128 8i47 8166 8185 8204 S222 8241 8260 8279 8299 2468 9 11 13 i5 17 .92 8318 8337 8356 8375 8395 8414 8433 8453 8472 8492 2468 10 12 14 15 17 •93 85 1 1 853^ 855i 8570 8590 8610 8630 8650 8670 8690 2468 1012141618 •94 8710 8730 8750 8770 8790 8810 8831 8851 8872 8892 2468 10 12 14 16 18 95 8913 8933 8954 8974 8995 9016 9036 9°57 9078 9099 2468 10 12 15 17 19 .96 9120 91:41 9162 9183 9204 9226 9247 9268 9290 9311 2468 11 13 15 17 19 •97 9333 9354 9376 9397 9419 9441 9462 9484 9506 9528 2479 11 13 15 17 20 .98 9550 9572 9594 9616 96^8 9661 9683 9705 9727 9750 2' 47 O 11 13 16 18 20 •99 19772 9795 9817 9840 986^ 98869908 9931 99549977 Ws 1 11 14 16 18 20 APPENDIX B. REAGENTS. AIR ANALYSIS. Barium Hydroxide. — A solution containing about 4 grams of BaO and 0.2 gram of BaCl 2 to the liter. (1 c.c. = 1 mg. C0 2 , approximately.) Sulphuric Acid. — Dilute 45.45 c.c. of normal sulphuric acid to one liter. ( 1 c.c. = 1 mg. C0 2 .) To standardize the solution measure 25 c.c. into a weighed platinum dish, add dilute ammonia- water in slight excess,, eyanorate to dryness on the water-bath, and dry at 120 C. to constant weight. Standard Lime-water. — (For Popular Tests.)— Shake one part of freshly slaked lime with 20 parts of distilled water for twenty minutes and let the solution stand overnight or until perfectly clear. This solution should be very nearly equiva- lent to the above standard sulphuric acid. To a liter of dis- tilled water add 5 c.c. of a solution of 0.7 gram of phenol- phthalein in 100 c.c. of 50 per cent, alcohol and add lime- water drop by drop until a slight permanent pink color is produced. Add 12.6 c.c. of the above calcium hydroxide solution. The resulting solution is the standard lime-water used for the tests. WATER ANALYSIS. For Ammonia. — Water Free from Ammonia. — The am- monia-free water used in this laboratory is made by redis- tilling distilled water from a solution of alkaline permangan- 255 256 APPENDIX B. ate in a steam-heated copper still. The apparatus used is shown in Fig. 15. Only the middle portion of the distillate is collected. Oftentimes the distillate from a good spring- water may be used. Nesslers Reagent. — Dissolve 61.750 grams KI in 250 c.c. distilled water and add a cold solution of HgCl 2 which has been saturated by boiling an excess of the salt and allowing it to crystallize out. Add the HgCl 2 cautiously until a slight permanent red precipitate (Hgl 2 ) appears. Dissolve this Fig. 15. — Still for Ammonia-free Water. slight precipitate by adding 0.750 gram powdered KI. Then add 150 grams of KOH dissolved in 250 c.c. of water. Make up to the liter and allow it to stand overnight to settle. This solution should give the required color with ammonia within five minutes, and should not precipitate within two hours. Alkaline Permanganate. — Dissolve 233 grams of the best stick potash in 350 c.c. of distilled water. Filter this strong APPENDIX B. 257 solution, if necessary, through a layer of glass wool on a por- celain filter-plate. Dilute with 700 to 750 c.c. of distilled water to a sp. gr. of 1.125, add 8 grams of potassium per- manganate crystals, and boil down to one liter to free the solution from nitrogen. Each new lot of reagent must be tested before being used, but when the chemicals used are all good there should be no correction needed for ammonia in the solution. Standard Ammonia Solution. — Dissolve 3.8215 grams . chemically pure NH 4 C1 in a liter of water free from ammo- nia. This is the strong solution from which the s.andard solution is made by diluting 10 c.c. to a liter wkh wa'.er free from ammonia. One c.c. of the standard solution = o.orcoi gram nitrogen. This solution, like the nitrite standard and other dilute solutions, must be preserved in sterilized bottles protected from dust and organic matter. For Nitrites. — Standard Nitrite Solution. — The pure sil- ver nitrite used in making this solution is prepared by the double decomposition of silver nitrate and potassium nitrite, and repeated crystallizations from water of the rather diffi- cultly soluble silver nitrite. 1.1 grams of this silver nitrite are dissolved in nitrite-free water, the silver completely pre- cipitated by the addition of the standard salt solution used in the determination of chlorine, and the solution made up to 1 liter. 100 c.c. of this strong solution are diluted to 1 liter, and 10 c.c. of this last solution again diluted to 1 liter. The- rmal solution is the one used in preparing standards. 1 c.c = 0.000000 1 gram nitrogen. Sulpkanilic Acid. — Dissolve 3.3 grams sulphanilic acid in 750 c.c. of water by the aid of heat, and add 250 c.c. glacial acetic acid. Naphtylamine Acetate. — Boil 0.5 gram of a-naphtylamine in 100 c.c. of w ater in a small Erlenmeyer flask for about five. 258 APPENDIX B, minutes, filter through a plug of washed absorbent cotton, add 250 c.c. glacial acetic acid, and dilute to a liter. For Nitrates. — Standard Nitrate Solution. — Dissolve 0.720 gram of pure recrystallized KN0 3 in 1 liter of water. Evaporate 10 c.c. of this strong solution cautiously on the water-bath, moisten quickly and thoroughly with 2 c.c. of phenol-disulphonic acid, and dilute to 1 liter for the stand- ard solution. 1 c.c. =0.000001 gram nitrogen. Phenol-disulphonic Acid. — Heat together- 3 grams syn- thetic phenol with 37 grams pure, concentrated H 2 S0 4 in a boiling -water bath for six hours. For Kjeldahl Process. — Sulphuric Acid. — Sp. gr. 1,84.. This should be free from nitrogen. May be obtained from Baker and Adamson, Easton, Pa. Potassium Hydroxide. — Dissolve 350 grams of the best stick potash in ..25 liters of water and boil down to some : thing less thai a liter with 3 grams of permanganate crys- tals. When cold, dilute to a liter with water free from am-, monia. For Phosphates. — Ammonium Molybdate. — Dissolve 50 grams of the pure neutral salt in a liter of distilled water. Nitric Acid (sp. gr. 1.07).— One part of acid (sp. gr. 1.42) to five parts of water. Standard Phosphate Solution. — Dissolve 0.5324 gram of pure crystallized sodium phosphate (Na 2 HP0 4 .i2H 2 0) in freshly distilled water, add 100 c.c. of nitric acid (1.07), and dilute to 1 liter. 1 c.c. =0.0001 gram P 2 5 . The solution keeps without change for several months if preserved in well-stoppered bottles of hard glass ; after a longer time it becomes slightly stronger, owing to the silica dissolved from the glass. For Chlorine. — Salt Solution. — Dissolve 16.48 grams of fused NaCl in a liter of distilled water. For the standard APPENDIX B. 259 solution dilute 100 c.c. of this strong solution to 1 liter. 1 c.c. =0.001 gram chlorine. Silver Nitrate. — Dissolve about 2.42 grams of AgNO s (dry crystals) in 1 liter of chlorine-free water. 1 c.c. = .0005 gram CI, approximately. Standardize against the NaCl solution. Potassium Chromate. — Dissolve 50 grams neutral K 2 CrO i in a little distilled water. Add enough AgN0 3 to produce a slight red precipitate. Filter and make the filtrate up to a liter with water free from chlorine. Milk of Alumina for P)e color ization. — Dissolve 125 grams of potash or ammonia alum in a liter of distilled water. Pre- cipitate the Al(OH) 3 by the cautious addition of NH 4 OH. Wash the precipitate in a large jar by decantation until free from chlorine, nitrites, and ammonia. For Hardness. — Standard Calcium Chloride Solution. — Dissolve 0.200 gram of pure Iceland spar in dilute HC1, tak- ing care to avoid loss by spattering, and evaporate to dryness several times, to remove the excess of acid. Dissolve the calcium chloride thus formed in 1 liter of water. Standard Soap Solution. — Dissolve 100 grams of the best white, dry castile soap In a liter of 80 per cent, alcohol. Of this strong solution dissolve 75-100 c.c. in a liter of 70 per cent, alcohol. This solution must have 70 per cent, alcohol added to it until 14.25 c.c. of it give the required lather with 50 c.c. of the above CaCl 2 solution. Erythrosine Indicator. — Dissolve 0.1 gram of erythrosine in 1 liter of water. For Iron. — Standard Iron Solution. — Dissolve 0.86 gram of ferric ammonium alum, (NH 4 ) 2 S0 4 .Fe 2 (S0 4 ) 3 .24H 2 0, or a corresponding amount of the potassium salt in 500 c.c. of water, add 5 c.c. HNO s (1.20), and dilute to 1 liter. 1 c:c. = 0.000 1 gram Fe. Potassium Sulphocyanide. — 5 grams per liter. 26o APPENDIX B. Hydrochloric Acid. — i part HC1 (sp. gr. 1.20) to 1 part of water. Potassium Permanganate. — 5 grams KMn0 4 in 1 liter of water. For Dissolved Oxygen. — (a) 48 grams of MnS0 4 .4H 2 in 100 ex. of water; (b) 360 gra^s of NaOH and 100 grams of KI in 1 liter of water; (c) HC1, sp. gr. 1.20 Sodium Thios^lphate Solution. — Dissolve 2$ grams of pure recrystallized sodium thiosulphate in 1 liter of water. Dilute 200 c.c. to 1 liter and standardize against a known K 2 Cr 2 7 solution. For Lead. — Standard Lead Solution. — To a strong solu- tion of lead acetate add a slight excess of H 2 S0 4 , filter off and wash the precipitate. Dissolve it in ammonium acetate solution, made by neutralizing glacial acetic acid with strong: ammonia. Make up to a known volume and determine the lead in an aliquot part by precipitating with K 2 Cr 2 7 and weigh- ing the lead chromate. Dilute an aliquot part to make a con- venient standard, say about 1 c.c. = 0.001 gram of Pb. FOOD ANALYSIS. Acid Mercuric Nitrate. — Dissolve mercury in double its weight of nitric acid (sp. gr. 1.42) and dilute the solution with five times its volume of water. Pumice. — Bits of ignited pumice, about the size of a pea, dropped while hot into water and bottled for use. Alcohol (for Reichert-Meissl method). — 95 per cent, alcohol redistilled from potassium hydroxide. Potassium Hydroxide (for Reichert-Meissl method). — One part good quality caustic potash dissolved in one part of water. Iodine Solution (for Hanus' method). — This is conven- iently made up according to the directions of Hunt.* Dis- * /. Soc. Chem. Ind., 21 (1902), 454. APPENDIX B. 26 1 solve 13.2 grams iodine in 1 liter of glacial acetic acid (99 per cent., showing no reduction with bichromate and sulphuric acid). This will best be done by adding the acetic acid in portions and heating on the water-bath with frequent shaking. To the cold solution add enough bromine to double the halogen content, as shown by titration. Three c.c. of bromine is suffi- cient. A slight excess of iodine is not detrimental. Potassium Iodide. — Dissolve 200 grams of potassium iodide in 1 liter of water. Anhydrous Ether. — Wash ordinary ether several times with distilled water and add solid caustic potash until most of the water has been removed. Then add small pieces of clean metallic sodium until there is no further evolution of hydrogen gas. The ether thus prepared should be kept over metallic sodium and a tube of calcium chloride should be inserted in the stopper, in order to allow of the escape of any accumulated gas. Potassium Sulphide. — Dissolve 40 grams of the crystallized salt in 1 liter of water and filter through glass wool. Potassium Hydroxide (for Kjeldahl process). — Dissolve 700 grams of the best quality of stick potash in water and dilute to 1 liter. Basic Lead Acetate. — Boil for half an hour 440 grams of lead acetate and 264 grams of litharge in 1500 c.c. of water. Cool and dilute to 2 liters. Allow to settle and siphon off the clear liquid. (Sp. gr. about 1.27, containing about 35 per cent, of the basic salt.) Ferric Alum. — Dissolve 2 grams of ferric alum in 100 c.c. of water, boil the solution until a precipitate appears, and filter. Fehling's Solution. — (a) Dissolve 69.28 grams of C.P. crys- tallized copper sulphate, carefully dried between blotting-paper, in water and make up to 1 liter, including 1 c.c. of strong sul- phuric acid; (b) Dissolve 346 grams of sodium potassium tar- trate and 100 grams of sodium hydroxide in water and make up to a liter. BIBLIOGRAPHY. The following list comprises some of the more important works bearing on the subjects treated in the preceding pages. A bibliography of the chemistry of foods com- plete to 1882 may be found in the Second Annual Report of the New York State Board of Health, and more or less complete bibliographies are to be found in Sadtler's ''In- dustrial Organic Chemistry," Blyth's " Composition and Analysis of Foods," and Leach's " Food Inspection and Analysis." AIR. Air and Rain. R. Angus Smith. Longmans, Green & Co. London. 1872. Air and its Relations to Life. Walter N. Hartley. D. Appleton & Co. New York. 1875. Report on the Air of Glasgow. E. M. Dixon. Robert Anderson. Glas- gow. 1877. Recherches sur l'Air Confine. A. Braud. Bailliere et Fils. Paris. 1880. Air Analysis. J. A. Wanklyn and W. J. Cooper. Kegan Paul, Trench,. Trubner & Co. London. 1890. Les Poisons de l'Air. N. Grehaut. Bailliere et Fils. Paris. 1890. Treatise on Hygiene and Public Health. Vol. I. Thomas Stevenson and S. F. Murphy. Blakiston, Son & Co. Phila. 1892. Air and Water. Vivian B. Lewes. Methuen & Co. London. 1892. Methods for the Determination of Organic Matter in Air. D. H. Bergey. Smithsonian Institution. Washington, D. C. 1896. The Detection and Measurement of Inflammable Gas and Vapor in the Air. Frank Clowes. Crosby, Lockwood & Son. London. 1896. Sanitation in Daily Life. Ellen H. Richards. Whitcomb & Barrows. Air Currents and the Laws of Ventilation. W. W. Shaw. Cambridge, at the University Press. VENTILATION, Heating and Ventilation of the New Building, Mass. Inst. Tech. S. H. Woodbridge. Tech. Quart., 2, 76. 1888. 263 264 BIBLIOGRAPHY. Heating and Ventilation. J. S. Billings. Sanitary Engineer. New York. 1893. Heating and Ventilating Buildings. Rolla C. Carpenter. John Wiley & Sons. New York. 1895. WATER. Report of the Royal Commission on Water Supply. Great Britain Par- liamentary Documents. London. 1869-70. Sixth Report of Rivers Pollution Commission, Great Britain. London. 1876. Water Softening and Scientific Filtration. Walter George Atkins. E. & F. N. Spon. London. 1880. National Board of Health Report for 1882. Water Supply (Considered mainly from a Chemical and Sanitary Standpoint). W. R. Nichols. John Wiley & Sons. New York. 1883. Water Analysis for Sanitary Purposes. E. Frankland. John Van Voorst. London. 1890. "The Organic Analysis of Potable Waters. J. A. Blair. 1890. Drinking Water and Ice Supplies. T. Mitchell Prudden. G. P. Putnam & Sons. New York. 1891. Potable Water. Floyd Davis. Silver, Burdett & Co. New York. 1891. The Action of Water on Lead. John Henry Garrett. H. K. Lewis. London. 1891. Treatise on Hygiene and Public Health. Vol. I. Thomas Stevenson and S. F. Murphy. Blakiston, Son & Co. Phila. 1892. Sewage Disposal in the United States. Geo. W. Rafter and M. N. Baker. D. Van Nostrand Co. New York. 1894. Xes Eaux-d' Alimentation, Epuration, Filtration, Sterilization. Edm. Guinochet. Bailliere et Fils. Paris. 1894. Micro-Organisms in Water. Percy F. Frankland and Mrs. Percy F. Frank- land. London. 1894. The Filtration of Public Water Supplies. Allen Hazen. John Wiley & Sons. New York. 1895. Examination of Water for Sanitary and Technical Purposes. Henry Leff- man. Blakiston, Son & Co. Phila. 1895. Sewage Disposal on the Farm and Protection of Drinking Water. Theo- bald Smith. U. S. Dept. Agr., Farmers' Bull. 43. 1896. Water Supply (Considered Principally from a Sanitary Standpoint). W P. Mason. John Wiley & Sons. New York. 1903. Water Analysis. J. A. Wanklyn and E. T. Chapman. Tenth Ed. Kegan Paul, Trench, Triibner & Co. London. 1896. Examination of Water and Water Supplies. John C. Thresh. H. A. Churchill & Co. London. 1896. Mikroskopische Wasseranalyse. Carl Mez. J. Springer. Berlin. 1898. A Simple Method of Water Analysis. John C. Thresh. J. & A. Churchill. London. 1898. BIBLIOGRAPHY. 265 Water Purification at Louisville, Ky. Geo. W. Fuller. D. Van Nostrand Co. New York. 1898. Report on Water Purification at Cincinnati, O. Geo. W. Fuller. Board of Trustees, Cincinnati. 1899. Report of Filtration Commission, Pittsburgh, Pa. 1899. Examination of Water (Chemical and Bacteriological). William P. Mason. John Wiley & Sons. New York. 1899. The Microscopy of Drinking Water. Geo. C. Whipple. John Wiley & Sons. New York. 1 899. Geological Survey. State of Washington. 1901. Report of Streams Examination, Sanitary District of Chicago. 1902. Chemical Survey of the Waters of Illinois. 1 897-1902. Water and its Purification. S. Rideal. Crosby, Lockwood & Son. London. 1902. Report on Water Purification Investigations. New Orleans Sewerage and Water Board. 1903. Elements of Water Bacteriology. S. C. Prescott and C.-E. A. Winslow. John Wiley & Sons. New York. 1904. State Board of Health Reports for Massachusetts, Michigan, Illinois, Ohio. The Mass. Reports for 1872-75 and 1890-1900, especially, contain many valuable papers, the following being some of the most important of them : Chemical Examination of Water and Interpretation of Analyses. Thomas M. Drown. Rep. Mass State Board of Health, 1892, 319. Discussion of Special Topics Relating to the Quality of Public Water Sup- plies. F. P. Stearns and T. M. Drown. Rep. Mass. State Board of Health, 1890, 717. On the Amount of Dissolved Oxygen contained in Waters of Ponds and Reservoirs at Different Depths. Thomas M. Drown. Rep. Mass. State Board of Health, 1891, 373. On the Amount of Dissolved Oxygen contained in Waters of Ponds and Reservoirs at Different Depths in Winter under the Ice. Thomas M. Drown. Rep. Mass. State Board of Health, 1892, 333. On the Mineral Contents of Some Natural Waters in Mass. Thomas M. Drown. Rep. Mass. State Board of Health, 1892, 345. The Effect of the Aeration of Natural Waters. Thomas M. Drown. Rep. Mass. State Board of Health, 1891, 385. In addition to the above the following papers contain much information of value on special topics relating to water supply and water analysis: Chemical Examination of Drinking Water. Thomas M. Drown. Proc. Soc. Arts., M. I. T., 1887-8, 87. 266 BIBLIOGRAPHY*. THe^ Analysis of Water — Chemical, Microscopical, and -Bacteriological Thomas M. Drown. J. N. E. Water Works Assoc, 4 (1889) ,79. Uti the Boss on Ignition in Water Analysis. Thomas M. Drown. Tech. Quart., 2 (1888), 132. The Odor and Color of :] Surface Waters. Thomas M. Drown. Tech. Quart., 1 (1888), 256;^ -■ Reduction of Nitrates by Bacteria. Ellen H. Richards and George W. : V Rolfe! Tech. Quart:; 9 (1 896) , 40. The Purification of Water by Freezing. Thomas M. Drown. J. N. E. Water Works Assoc, 8 (1893), 46. The Filtration of Natural Waters. Thomas M. Drown. J. of the Assoc. of Eng. Soc, 9 (1890), 356. - A Study of Self-Purification in the Sudbury River. A. G. Woodman, C.-E. A. Winslow, and P. Hansen. Tech. Quart., 15, 1902. Normal Distribution of Chlorine in Connecticut. H. E. Smith and F. 'SI Hollis. Rept. Conn. State B'd Health, 1902. ' Water Supplies of S. E. Alaska and the Black Hills of S. Dak; E. H. Richards. Tech. Quart., 16,-1903. Notes on the Potable Waters of Mexico. E. H. Richards". Trans. Ami J Inst. Min. Eng., 1901. ; ; ' ' -Rainfall on the Pacific Coast and the Factors of Water Stlpply in California. J. Assoc. Eng. Soc, 1903. , j WATER. Department of Interior. U. S. Geological Survey. Underground Water f Water 1 Supply and Irrigation Paper. No. 160. Myron L.' Fuller. ' Field Assay of Water. No. 151. Marshall O. Leigntoh. Value of Pure Water. George C. Whipple. Published by John Wiley- & Sons. ■ l: New York. ' ' ■ '" ' " ; ' " iv »- : :; " : ''-■ M" «0 Report of the Commission on Additional Water Supply for the City of New York. Appendix VI. ! Report of the Committee on Standard Methods of Water Analysis td the Labora- tory Section of the American Public ' Health Association. (Reprinted from the journal of Infectious Diseases, Supplement No. i.- May, 1965:) Disposal of Dairy and Farm Sewage and Water Supply. Oscar Erf. 'Kansas State Agricultural College Experiment Station Bulletin. BIBLIOGRAPHY. 267 •'-^ -■■ '-."- ; ■- ;; -m -- FOOD.- •; l'. ; .-!m.-,;m,-! •,;; K-;-: ;-. •.-; The list given here is limited to, , books published since 1890. •/•-* Traite General d' Analyse des Beurres. A. J. Zune. H. Lamartin. r; : ? ; Paris. 1892. «.* Die Menschlichen Nahrungs- u. Genussmittel. J. Konig. Julius Springer. j Berlin.- 1893. Foods and Dietaries. R. W. Burnet, M.D. . P. Blakiston, Son & Co. .,];,, lEhila; £893,, , . . -., , l: ri ■ . f ... : . : . p . : ...-' : Analyse des Matieres Alimentaires et Recherche de Leur- Falsifications. V/ . ;;/ jCh. r Girar4 et A r ,Dupre. Vve. Ch. Dunod &;P... Vicq. ; : Paris. , .... 1 894. . Animal and Vegetable Oils, Fats, Butters and Waxes. C. R. Alder Wright. ; Jf •Griffin-& Co;- \ London. 1894. . rv ■ •...;: '.,.:... Chemistry of Wheat, Flour, and Bread. Wm. Jago. Simpkin Marshall. ,/j . I.ondon. ; . ^895, ■ ( - ! - ; millMi &;{ .;,:.. Commercial Organic Analysis. A. H. Allen. Third Ed. Rev.-- by H. Leff- man. Blakiston, Son" >&i Co. Phila. ^1^98;: '*■■ ■■■'■- ■■.:■/;:•■-■ Die Untersuchung ' ■ landwirtschaftlich und ge'werbiich wichtiger Stoffe. J. Konig. Paul Parey; Berlin.- i.i 1898U-: I ■ ■-''■ Food Materials ahd^their Adulterations. 1 Ellfeni H,' Richards: Borne Science Pub. Co; Boston. (i908; : •-. = >ttv-? ^■■^ -.- Plain Words about Food; -The .Rumford Kitchen .Leaflets. Ellen H Richards,: Ed. Home Science Pub. Co. Boston. 1899. Muscle, Brain, and Diet: A Plea for Simpler Foods. E. 1 H. Miles. Sonnen- schien. London.' ^1900. :■ '' V - ■■^vzcqf-r/. ri AV- Handbook of Industrial Organic Chemistry. ; .'. SJ-> • Pi-vSadtler. J. B. Lippincott Co. Phila. 1900. Flesh Foods with Methods for their Chemical, Microscopical, and Bacte- riological Examination. C. A. Mitchell. Griffin & Co. London. 1900. 268 BIBLIOGRAPHY. Food and the Principles of Dietetics. R. Hutchinson. Wood. New York. iooi. The Cost of Food: A Study in Dietaries. E. H. Richards. J. Wiley & Sons. New York. iooi. Select Methods in Food Analysis. H. Leffman and W. Beam. P. Blakis- ton's Son & Co. Phila. 1905. Suggested Standards for Food and Drugs. C. G. Moor. Bailliere, Tindall & Cox. London. 1902. Enzymes ?,nd their Applications. J. Effront. Trans. S. C. Prescott. J. Wiley & Sons. New York. 1902. Foods: their Composition and Analysis. A. W. Blyth and M. W. Blyth, Griffin & Co. London. 1903. Food Inspection and Analysis. Albert E. Leach. Wiley & Sons. New York. 1904. Organic Analysis. Henry C. Sherman. Macmillan Co. New York. 1905. Foods and their Adulteration. H. W. Wiley. P. Blackiston's Son & Co. Phila. 1907. The following bulletins of the United States Depart- ment of Agriculture will also be found useful for study or reference on the general question of food: Office of Experiment Stations, Bulletins. Ko. 9. Fermentations of Milk. 1892. 11. Analyses of American Feeding Stuffs. 1892. ai. Chemistry and Economy of Food. 1895. No. 25. Dairy Bacteriology. 1895. 28. (Rev. Ed.) Chemical Composition of American Food Materials 1895. 29. Dietary Studies at the University of Tennessee. 1896. 31. " " " " " " Missouri. 1896. 32. " " " Purdue University. 1896. 34. Carbohydrates of Wheat, Maize, Flour, and Bread. 1896. 35. Food and Nutrition Investigations in New Jersey. 1896. 37. Dietary Studies at the Maine State College. 1897. 38. " " — Food of the Negro in Alabama. 1897. 40. " " in New Mexico. 1897. 43, Composition and Digestibility of Potatoes and Eggs. 1897. 44. Metabolism of Nitrogen and Carbon in the Human Organism. 1897. BIBLIOGRAPHY. 26 9 45> A Digest of Metabolism Experiments. 1897. 46. Dietary Studies in New York City. 1898. 52. Nutrition Investigations in Pittsburgh, Pa. 189&. 53. " " at the University of Tennessee. 1898. 54. " " in New Mexico, 1898. 55. Dietary Studies in Chicago. 1898. 63. Experiments on the Conservation of Energy in the Human Body. 1899. 66. Creatin and Creatinin. 1899. 67. Bread and Bread Making. 1899. 69. Experiments on the Metabolism of Matter and Energy in the Human Body. 1899. 71. Dietary Studies of Negroes. 1899. 75. " " " University Boat Crews. 1900. 84. Nutrition Investigations at the California Agr. Expt. Station. 1900. 85. Investigations on the Digestibility and Nutritive Value of Bread. 1900. 89. Effect of Muscular Work on Digestion of Food and Metabolism of Nitrogen. 1901. 91. Nutrition Investigations at the University of Illinois, etc. 1901. 98. Effect of Severe and Prolonged Muscular Work on Food Consump- tion, Digestibility, and Metabolism. 1901. 101. Studies on Bread and Bread Making. 1901. 102. Losses in Cooking Meat. 1901. 107. Nutrition Investigations among Fruitarians and Chinese. 1901. 109. Metabolism of Matter and Energy in the Human Body. 1902. 116. Dietary Studies in New York City. 1902. 117. Effect of Muscular Work upon Digestibility of Food and Metab- olism of Nitrogen. 1902. 121. Metabolism of Nitrogen, Sulphur, and Phosphorus in the Human Organism. 1902. 126. Digestibility and Nutritive Value of Bread. 1903. 129. Dietary Studies: Boston and other Places. 1903. 132. Further Investigations among Fruitarians. 1903. Division of Chemistry, Bulletins. No. 13. Foods and Food Adulteration — (Ten Parts). 1887-1902. 45. Analyses of Cereals. 1895. 46. Official Methods of Analysis. 1895. 50. Composition of Maize. 1898. 59. Composition of American Wines. 1900. 61. Pure Food Laws of Foreign Countries. 1901. 65. Provisional Methods for Analysis of Foods. 1902. 66. Fruits and Fruit Products. 1902. 69. Foods and Food Control. 1902. 72. American Wines at Paris Exposition of 1900. 1903, %70 bibliography; . Farmers' Bulletins. ... . -..'i.\ . .-.'...•■=: . :■•>.;•?•! •::•.;.-: r ';-b. No. 23. Foods : Nutritive Value and Cost, i 894, : : 29; -Souring of Milk. ! • tSg 5 . * • ■ ■■ ! 34. Meats: Composition and Cooking. 1896. .;•:*' 74. Milk as Food. 1898. .,,>. .!:i-: . ■•,-•. •Yi 85. FiSh: a ! S Food.' 1898.;- : ; "J : • ■:^:'i '. .; ,.:;:, .. :■;.: i ... > 03. Sugar as Food. 1899, Analyses, interpretation of g 2 Aqueous vapor, tension of 236 Ash, determination in cereals 206 , in wine 218 , of milk 1 73 Babcock method for fat determination 1 76- Barium hydroxide, reagent for air analysis 255 Beer, analysis of , 224 Benzoic acid, detection of 223 Bibliography 263 Biological examination of water 135 Boric acid, detection in milk 188 Breakfast foods 161 Brook water 86 Butter, analysis of 193 , complete analysis of 204. , composition of 191 Calcium chloride, standard solution of 259 Calorie, definition of 148 Cane-sugar, detection in milk 185 Caramel, detection in vanilla 230 Carbohydrates, function of 146 , separation in cereals 209 Carbon dioxide, amount expired 15 , determination of, in air 27 , "popular tests" for 40 as a disturbing factor 12 , properties of 21 table of weight of cubic centimeter of 237 in water, determination of 1 29 , a test of ventilation 23 Carbonaceous matter in water, determination of 112 Carbonic acid in water, determination of free 129 Carbon monoxide, detection of, in air 49 , estimation of, in air 50 , effect on blood 16 Change on ignition 117 INDEX. 27^ PAGE Chlorine in ground water go- water, determination 113 ' ' , source of 71 Casein, determination of j#4 Citral, determination of 233 Clark's method for hardness 117 Classification of waters &$ Cocoanut oil, detection in butter 195 Cohen method for carbon dioxide 48. Collection of water samples 94 Color of water, determination of 130 standards for water 1 3°~ 1 3$- Colors, detection of 221 , " in milk 186- in food 163 Condensed milk, analysis of 189 , composition of 189. Cooking, changes caused by 148 Coumarin, determination of ,.. 227 , Leach's test for 228. Cream, determination of 171 " Crowd poison " 18-24 Crude fibre, determination of 214 Cycle of nitrogen 65 Dextrin, estimation in cereals 21a Diastase, estimation of starch by 212 Dietaries 152 Dissolved oxygen, reagents for, preparation of 260 in water, determination of 1 23 Distilled water 73. Dust and soot 54, 55, 56 , estimation of, in air 54 Ether, anhydrous, preparation of 261 extract of cereals 206 Extract in beer-wort, table for 249 ... , determination in beer 224 , "wine 217 in wine, table of 247 Fat, determination of, in milk 175 Fats, value of 145 Fatty acids, determination of, in butter 196 274 /INDEX. PAGE Fehling's solution, preparation of . , * 261 Filters r , r 87 Fitz and Wolpert 43 method for. carbon dioxide 45 shaker 45~47 Fluorides, detection of ,. -. 226 Food, composition of . . . .143 , definition and uses 143 , principles — ........... 143 , materials, table of composition of . . . . . 150 , predigested .. .... 162 .Formaldehyde, detection in milk 187 Glass pipe . 94 Glycerine, determination in wine 219 Gottlieb method for fat estimation 178 Ground water, history of 62 Gunning method for nitrogen 209 Hanus' iodine solution, preparation of 260 Hardness in water, determination of 117 , table of 242 Heat of combustion, values for 148 Humidity in air, effect of 14 Ice, rules for use of 72 Interpretation of water analysis 82 Iodine value, determination of 197 Iron in water, determination of — 127 , standard solution of 259 Kjeldahl method for nitrogen 206 Lactose, estimation of 181 Lake water -. . ■ 84 Lead acetate, basic, preparation of 261 in water, determination of 139 , standard solution of 260 Lemon extract 23 1 oil, determination of 23 2 Lime water, reagent for air analysis 255 .Loss on ignition in water, determination of 115 INDEX. 275 ;. >T PAGE Malt extract, preparation of ... ..... ,..„. 213 Melting point of butter 2or Meteoric water . . 59 Micro-organisms, estimation of in air 51 , role of, in water 65 Milk, acidity of . . 172 , adulterations of 184 , composition of ■, .■ 168 , fermentations of 169 , reaction of 172 , relation of constituents . 179 , United States standard 169 sugar, estimation of 181 Mineral salts, value in food 147 substances in water 91 Misbranding, defined 157 Mountain " sickness " 13 Nutritive ratio 149 Nitrates in ground water ^. 91 in water, determination of no Nitrate standard solution, preparation of 258 Nitrogen, cycle of 65 , determination of, by Kjeldahl method 106 essential to living matter 75 , total organic, determination of, in water 106 Nitrogenous substances, function of 144 Nitrites in water, determination of 108 estimation of , in air 51 Nitrite standard solution, preparation of 257 Naphthylamine acetate reagent for nitrite test 257 Nessler's reagent, preparation of 256 Odor of water, detection of 133 , analytical value of 88 Oleomargarine 192 Opacity of milk 171 Organic matter in the air 52 nitrogen in water, determination of . 106 *' Oxygen consumed," determination of 112 Oxygen dissolved in water, determination of 123-129 table for 242 Pentosans, determination of 213 Pettenkofer method for carbon dioxide 28 276 INDEX. PAGK Petterson and Palmquist apparatus 40 Phosphates in water, determination of 1 20 Purified vs. clarified water 69 " Popular tests " for carbon dioxide 70 Potassium chromate, reagent, preparation of 259 ferrocyanide 61 hydroxide 258 iodide reagent, 261 sulphide reagent 262 sulphocyanide reagent 259 Pressure, influence on respiratory exchange 13 Preservatives in food 163 Proteids of milk, determination of 183 , Kjeldahl method for 206 Residue on evaporation, determination of 115 Reducing sugar, determination in beer 225 Reducing sugar, Munson and Walker's table for 248 Refractive index of butter 201 Refractometer, Abbe 202 Reichert-Meissl number 194 Renovated butter 192 , detection of 200 Resins, detection in vanilla 229 Respiratory exchange 15 quotient 14 River water 85 " Safe " water 75-79 Salicylic acid, detection of 223 Salt, determination in butter 204 Samples, collection of water 96 Sanitary chemistry, scope of 1 science, importance of 2 Sediment of water, estimation of 136 " Sewer-air " 1 7-24 Shallow wells 90 Silver nitrate, chlorine reagent 259 Soap, standard solution of 259 Sodium carbonate, detection in milk 188 chloride, standard solution 258 Solids of milk 173 Soot, estimation of, in air 54 Specific gravity of butter 201 milk 170 INDEX. 277 PAGB Specific gravity of milk, table for 243 wine 216 Spoon test 199 Springs 88 Starch, detection in milk 186 , determination of 211 Steam vacuum 50, 51 Storage of water 71, 87 Sugars, determination in cereals 210 Sulphites, detection of 225 Surface water 85, 89 , character of 72 Turbidity of water, estimation of 136 Turmeric, detection of 233 Vanilla extract 226 Vanillin, determination of 227 Ventilation, apparatus to illustrate r 24 , natural vs. artificial 23 a necessity 19 , principle of 22 , requirements of 26 , to test efficiency of 24 Vital capacity 10 Walker method for carbon dioxide 34 Water, acceptable 82 Water analysis, blank form for 141 , points to determine in 80 , statement of results 140 , value of 94 Water, classification of 85 , circulation of 61 , determination in butter 204 , illustration of contamination of 62 , its relation to health 66 , legal restrictions upon use of 57 , need of 6 , passage through the ground 64 , preliminary inspection of source of 80 , presence of organisms in 66 , solvent power of 65 , storage of 71 j the ideal drinking-water 59 78 INDEX. PAGE- Water-rvapor in air ...... .. . . . ■ 16 Water siphon — 48, 49 <. j daily quantity needed ....... 6 Water-pipes ... 94 Waters, table of average composition of .... 238 normal . 239 ,. polluted, table of . . 240, 241 Water free from ammonia, preparation of 255: , determination in cereals • 2p|i "- ."milk. ' :c/,.j&f Well-water . — .-,=....:.■ , &w. arw&bcjd Wine, analysis of ................. .. . r 216 , composition of 215 Wolpert shaker ....... .----. • - - - uftrv? 47' Wooden pipe n?sf*~ 94-' HOV 5 19 09 /COPY. DEL. TO CAT. OiV. NOV 6.IU33 m ess \7WJp. H ■ s 'V ■ ■ ■ ■ - KM Ti ^H MB ■