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Bulletin 278 May, 1926 
 
 (Eatuwrtirut Agrtntltitral iExpmmrtti -8>tatum 1 , 
 
 •Dfatii 3Bau?tt, (Hannutxmt 
 
 A Chemical Investigation of Some 
 Standard Spray Mixtures 
 
 R. E. ANDREW AND PHILIP GARMAN 
 
 The Bulletins of this Station are mailed free to citizens of Connecticut 
 who apply for them, and to other applicants as far as the editions permit. 
 
CONNECTICUT AGRICULTURAL EXPERIMENT STATION 
 
 OFFICERS AND STAFF 
 
 as of 
 May, 1926 
 
 BOARD OF CONTROL 
 His Excellency, John H. Trumbull, ex-officio, President. 
 
 Charles R. Treat, Vice President Orange 
 
 George A. Hopson, Secretary Mount Carmel 
 
 Wm. L. Slate, Jr., Treasurer '. Xew Haven 
 
 Joseph W. Alsop ' , Avon 
 
 Elijah Rogers Southington 
 
 Edward C. Schneider Middletown 
 
 Francis F. Lincoln Cheshire 
 
 STAFF. 
 E. H. Jenkins, Ph.D., Director Emeritus. 
 
 Administration. Wm. L. Slate, Jr., B.Sc, Director and Treasurer. 
 
 Miss L. M. Brautlecht, Bookkeeper and Librarian. 
 Miss J. V. Berger, Stenographer and Bookkeeper. 
 Miss Mary E. Bradley, Secretary. 
 G. E. Graham, In charge of Buildings and Grounds. 
 
 Chemistry: E. M. Bailey, Ph.D., Chemist in Charge. 
 
 Analytical C. E. Shepard ~| 
 
 Laboratory. Owen L. Nolan I Assistant Chemists 
 
 Harry J. Fisher, A.B. {Assistant Liicmists. 
 
 W. T. Mathis J 
 
 Frank C. Sheldon, Laboratory Assistant. 
 V. L. Churchill, Sampling Agent. 
 Miss Mabel Bacon, Stenographer. 
 
 Biochemical T. B. Osborne, Ph.D., Chemist in Charge. 
 
 Laboratory. H. B. Vickery, Ph.D., Biochemist. 
 
 Miss Helen C. Cannon, B.S., Dietitian. 
 
 Botany. G. P. Clinton, Sc.D., Botanist in Charge. 
 
 E. M. Stoddard, B.S., Pomologist. 
 Miss Florence A. McCormick, Ph.D., Pathologist. 
 Willis R. Hunt, Ph.D., Assistant in Botany. 
 
 A. D. McDonnell, General Assistant. 
 Mrs. W. W. Kelsey, Secretary. 
 
 Entomology. W. E. Britton, Ph.D., Entomologist in Charge; State 
 
 Entomologist. 
 
 B. H. Walden, B.Agr. \ 
 
 M. P. Zappe, B.S. > Assistant Entomologists. 
 
 Philip Garman, Ph.D. ) 
 
 Roger B. Friend, B.Sc, Graduate Assistant. 
 
 John T. Ashworth, Deputy in Charge of Gipsy Moth Work. 
 
 R. C. Botsford, Deputy in Charge of Mosquito Elimination. 
 
 Miss Grace A. Foote, B.A., Secretary. 
 
 Forestry. Walter O. Filley, Forester in Charge. 
 
 H. W. Hicock, M.F., Assistant Forester. 
 J. E. Riley, Jr., M.F., In charge of Blister Rust Control. 
 Miss Pauline A. Merchant, Stenographer. 
 
 Plant Breeding. Donald F. Jones, S.D., Geneticist in Charge. 
 
 P. C. Mangelsdorf, S.D., Assistant Geneticist. 
 H. R. Murray, B.S., Graduate Assistant. 
 
 Soil Research. M. F. Morgan, M.S., Investigator. 
 
 George D. Scarsetii, B.S., Assistant. 
 
 Tobacco Sub-station Paul J. Anderson, Ph.D., Pathologist in Charge. 
 
 at Windsor. N. T. Nelson, Ph.D., Plant Physiologist. 
 
 THE TUTTLE, MOREHOUSE & TAYLOR COMPANY 
 
A Chemical Investigation of Some 
 Standard Spray Mixtures 
 
 R. E. Andrew* and Philip Garman 
 
 Modern spray practices have become complicated procedures. 
 The necessity of attaining' maximum efficiency with a minimum 
 of labor has led in the case of fruit growing to the use of high 
 powered outfits which apply spray mixtures at a rapid rate and to 
 the combination of sprays in order to avoid separate applications. 
 In the combination of sprays there has been much uncertainty 
 of results and failure to explain certain phenomena which have 
 not been well understood, at least from a chemical standpoint. 
 For instance, we know that the ingredients of a certain spray 
 formula mixed in a certain order give a definitely colored mixture, 
 whereas an entirely different order of combination may give a 
 different appearance. What goes on under these conditions as 
 regards the ingredients themselves has only been conjectured by 
 the entomologist, and it is in an attempt to throw some further 
 light on what happens when various insecticides and fungicides 
 are put together that the present work was undertaken. 
 
 Historical Summary 
 
 Probably the earliest studies of spray mixtures from a chemical 
 standpoint were made by Bradley 2 and Bradley and Tartar 3 , 
 who found that there was a distinct chemical reaction between 
 lime-sulphur and lead arsenate resulting in the formation of 
 soluble arsenic. The latter undesirable condition was found to 
 be greatly helped by the addition of lime to the mixture. 
 Robinson 15 , following this clue, described the beneficial action of 
 lime upon the standard spray mixture and came to the conclusion 
 that lime prevents the reaction between lime-sulphur and lead 
 arsenate and does not lower the polysulphide sulphur in the 
 lime-sulphur to a harmful extent. Ruth 17 made an extensive 
 investigation of spray mixtures from a chemical standpoint, reach- 
 ing the general conclusion that when these two components are 
 mixed, a thioarsenate of some kind is formed which holds it 
 insoluble in lime-sulphur solution, and that thiosulphates and 
 sulphites are increased, possibly accounting for the improved 
 fungicidal properties of the mixture. More recently Thatcher 
 and Streeter 22 have investigated the addition of casein, gelatin, 
 
 * Until March, 1926, Assistant Chemist in the Analytical Laboratory. 
 
49 2 CONNECTICUT EXPERIMENT STATION BULLETIN 278 
 
 nicotine and other preparations to the combined lead arsenate, 
 lime-sulphur sprays, finding that casein-lime and nicotine exert 
 a beneficial action upon the spray mixture. Still more recently, 
 with the use of somewhat different methods, Goodwin and 
 Martin 10 reached somewhat different conclusions, stating- that 
 casein and gelatin do not always protect lead arsenate from harm- 
 ful reactions with lime-sulphur and in fact give an increased 
 amount of soluble arsenic, contrary to the conclusions of Thatcher 
 and Streeter. They found furthermore that lime decreased the 
 amount of sulphur in solution in the spray mixture, thereby reduc- 
 ing its fungicidal value, but that lime, if carbonated, exerted little 
 or no effect upon the mixture. 
 
 Plan of Study and Methods Employed 
 
 All of the work thus far described was done with double or 
 triple combinations of spray materials but the possible effect upon 
 the composition of the mixture due to the sequence in which the 
 separate ingredients were added was not considered. The work 
 herein reported began with a study of the effect of different orders 
 of mixing upon the composition of a mixture containing four ingre- 
 dients, but as the work progressed it seemed advisable to extend 
 its scope to include all possible double and triple combinations 
 as well. 
 
 In preparing the experimental mixtures the conditions obtain- 
 ing in practical spraying operations were followed as closely as 
 possible. Thus, the materials used were market products of 
 standard grades, and the proportions in which they were mixed, 
 and the method of mixing, are fairly representative of field 
 practice. It will be seen that the period of agitation was one 
 hour, which is about the maximum time required to apply a two 
 hundred gallon tank of spray mixture, using one gun or two rods. 
 With many outfits much less time than this would be required so 
 that this agitation period is probably nearer the maximum than 
 the minimum for the average spray rig. 
 
 FORMULA 
 
 The complete formula used and its equivalent in actual spraying 
 practice are as follows : 
 
 Experimental Corresponding 
 
 Mixture Field Practice 
 
 (1) Arsenate of lead (acid) 
 
 2.4 grams 
 
 4.0 pounds 
 
 (2) Nicotine sulphate 
 
 0.6 cc 
 
 0.96 pint 
 
 (3) Casein-lime 
 
 0.55 grams 
 
 0.917 pounds 
 
 (4) Lime-sulphur 
 
 145 cc 
 
 2.6 gallons 
 
 (5) Water (distilled), to make 
 
 500.0 cc 
 
 100.0 gallons 
 
CHEMICAL INVESTIGATION OF SPRAY MIXTURES 493 
 
 PREPARATION OF EXPERIMENTAL MIXTURES 
 
 In mixing the ingredients, whatever the number chosen, the 
 final volume was brought to 500 cc and the manipulation was 
 uniformly as follows : 
 
 Place about 485 cc of water in a 500 cc graduated shaking flask. Add the 
 ingredients separately, in the amounts indicated by the formula, shaking 
 by hand for two minutes after each addition. Stopper the flask securely, 
 place in a shaking machine of the revolving type and agitate the mixture 
 for one hour. Remove the flask from the shaking device and allow the 
 mixture to stand for one hour. Filter on a 9 cm filter paper using a 
 Buchner funnel with gentle suction, transferring as much of the insoluble 
 material as possible to the filter. Do not rinse the flask or wash the 
 residue upon the filter. Transfer the yellow filtrate (A), to a suitable 
 flask, stopper, and hold for analysis. 
 
 Return the filter ■ with the insoluble residue to the original graduated 
 shaking flask and wash into the flask also any of the insoluble residue 
 which may have adhered to the funnel. Fill the flask to the 500 cc mark, 
 stopper securely, place in the shaking machine and agitate the contents 
 for one hour. Remove the flask from the shaking device and allow to 
 stand for one hour, after which filter through a large filter. Do not wash 
 the residue. Reserve the filtrate, solution (B), for analysis. 
 
 EXAMINATION OF MIXTURES 
 
 ■ The various experimental mixtures were examined with refer- 
 ence to certain physical characteristics and to chemical composi- 
 tion, the latter being confined to determinations of total sulphur 
 in the lime-sulphur solution (filtrate A), and of total arsenic, as 
 arsenic pentoxide (As 2 O s ), both in filtrate A and filtrate B. 
 The results obtained for total sulphur are of interest as an index 
 to the extent of chemical change which has taken place in the 
 mixture so far, at least, as the sulphur originally present has been 
 converted into insoluble forms. Foliage injury, in part, results 
 from excessive amounts of soluble arsenic in the lime-sulphur 
 solution ; and it seems not improbable that the insoluble arsenic- 
 containing residue which is deposited upon foliage in the process 
 of spraying might become, upon exposure to weather conditions, 
 a potential source of further injury. For this reason the water- 
 soluble arsenic in the insoluble residue was determined. 
 
 METHODS OF ANALYSIS 
 
 The determination of the small amounts of soluble arsenic 
 involved in preparations made on the scale of these laboratory 
 mixtures presented some difficulty. After some preliminary 
 trials, the method used by Bradley 2 and by others whereby sulphur 
 is oxidized by means of hydrogen peroxide and arsenic finally 
 titrated with dilute iodine solution appeared to be promising. The 
 results, however, were not satisfactory and the method is objec- 
 
494 CONNECTICUT EXPERIMENT STATION BULLETIN 2/8 
 
 tionable chiefly for the following reasons : it requires large 
 quantities of a relatively expensive reagent (hydrogen peroxide) ; 
 the evaporation of a large volume of liquid is time consuming; 
 the filtration of the large amount of sediment which forms during 
 the evaporation, and the necessary washing, introduce potential 
 errors ; and finally, the iodine titration does not give a sharply 
 defined end point. 
 
 About this time Cox 5 published a critical review of certain 
 methods for the determination of small quantities of arsenic, 
 citing particularly the methods of Bang and Ramberg, his expe- 
 rience favoring the last named. As pointed out by Cox, neither 
 method involves any new principle, but, on trial, the Ramberg 
 method was found to be adaptable to our problem. Briefly, the 
 procedure consists in oxidizing the sulphur and destroying organic 
 matter by digestion with nitric and sulphuric acids, removing the 
 excess of nitric acid by means of ammonium oxalate, distilling 
 with hydrochloric acid and titrating the arsenic with potassium 
 bromate solution, using methyl orange (i : 5000) as as indicator. 
 
 The digestion was conducted in a long-neck Kjeldahl flask made 
 to fit a condensing tube with a ground glass joint; thus the diges- 
 tion and distillation were both made without a transfer of mate- 
 rial. Arsenic-free reagents, tested by means of suitable blanks, 
 were used throughout. The standard potassium bromate solution 
 was prepared of such strength that I cc was equivalent to 0.0005 
 gm. of arsenic pentoxide (As 2 O s ). 
 
 The procedure in detail as used by us is as follows : 
 
 Arsenic in lime-sulphur solution (Solution A). Transfer 100 cc of the 
 solution to the digestion-distillation flask, add a few glass beads, 50 cc of 
 concentrated nitric acid and evaporate over a low flame until the volume 
 is reduced to about 25 cc. Cool, add 25 cc of concentrated sulphuric acid 
 and heat until fumes of sulphuric acid appear. From a suitable dropping 
 device add 50 cc of concentrated nitric acid dropwise, meanwhile boiling 
 the solution very gently. Continue the boiling until sulphuric acid fumes 
 appear. Cool, add 25 cc of saturated ammonium oxalate solution and again 
 boil until fumes of sulphuric acid are noticed. Cool, rinse the neck of the 
 flask with 20 cc of water and then add 2 grams of ferrous sulphate, 50 cc 
 of concentrated hydrochloric acid and 0.1 gram of potassium bromide. 
 (If any yellow or brown color appears at this point nitrogen acids are 
 present and the experiment must be rejected.) Connect the flask with the 
 condensing tube, adjust a receiving flask containing 150 cc of water, and 
 allow the condenser to dip about 1 cm. below the surface of the liquid 
 therein. Distill at such a rate that 20 to 25 cc of distillate are obtained 
 in about 10 minutes. Heat the distillate to 50 C, add three drops of 
 methyl orange and titrate at once with standard potassium bromate solu- 
 tion, adding this reagent very slowly as the end point is approached. The 
 end point is reached when the red color of the indicator is discharged. 
 Each cc of potassium bromate used corresponds to 0.0005 gram of As^Oo. 
 
 Arsenic in Solution B. Transfer 50 cc of the solution to the digestion- 
 distillation flask, add 50 cc of concentrated nitric acid and evaporate over 
 a low flame until the volume is reduced to about 25 cc. Cool, add 25 cc of 
 concentrated sulphuric acid and boil until sulphuric acid fumes appear. 
 
. CHEMICAL INVESTIGATION OF SPRAY MIXTURES 495 
 
 Cool, add 10 cc of concentrated nitric acid and again heat until fumes of 
 sulphuric acid are noted. Cool, add 25 cc of saturated ammonium oxalate 
 solution and from this point proceed as directed in the previous paragraph. 
 
 Total sulphur in Solution A. Total sulphur was determined substan- 
 tially according to the official procedure 1 except that oxidation of sulphur 
 was effected by means of hydrogen peroxide in alkaline solution as allowed 
 by a former optional method. 13 
 
 Transfer 10 cc of solution A to a 250 cc beaker containing 10 cc of a 
 10 per cent solution of sodium hydroxide, 50 cc of water and 50 cc of 
 hydrogen peroxide. Cover the beaker with a watch glass and heat for 
 one hour on a steam bath. Cool, acidify with dilute hydrochloric acid 
 (1 to 1), and precipitate the sulphur as barium sulphate. Calculate the 
 percentage of sulphur from the weight of barium sulphate, using the factor 
 0.1374. 
 
 PRELIMINARY EXPERIMENTS 
 
 The adaptability of the method for the determination of arsenic 
 as described may be illustrated by the following experiments. 
 Blanks on the reagents, in the amounts used in the method, 
 showed titerable substances equivalent to 0.3 cc of standard 
 potassium bromate and this correction was uniformly made in all 
 determinations. 
 
 , Arsenic, as As 2 5 ^ 
 
 Present Added Total Recovered 
 
 Material gm. gm. gm. gm. 
 
 100 cc water -\-i gm. sugar 0.01160 0.01160 0.01160 
 
 100 cc water -j- 1 gm. sugar 0.01160 0.01160 0.01160 
 
 Lime-sulphur-Lead arsenate 0.00613 0.01160 0.01773 0.01775 
 
 0.01160 O.01773 0.01773 
 
 INTERPRETATION OF RESULTS 
 
 In the analytical data herein reported total sulphur is expressed 
 in terms of grams per 100 cc of the lime-sulphur solution. 
 x\rsenic is expressed in percentages of As 2 O s based on the amount 
 of lead arsenate, 2.4 grams, present in the mixture. 
 
 In the tables also abbreviations are necessary and the following 
 are used: L.A. = Lead arsenate; L.S. — Lime-sulphur; N. S. = 
 Nicotine sulphate ; C.L. = Casein-Lime ; L. = Lime ; Blk. = 
 Black ; G. = Grey ; G.B. = Greyish-black. 
 
496 
 
 CONNECTICUT EXPERIMENT STATION 
 
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498 connecticut experiment station bulletin 2/8 
 
 Discussion 
 
 Effect of Adding Lime-Sulphur to Different Ingredients 
 Separately and Combined (Tables i to 3) 
 
 It will be seen that addition of lime-sulphur to lead arsenate 
 brings about a tremendous increase in soluble arsenic, — nearly 136 
 times the original content of the lead arsenate alone. When 
 lime-sulphur is added to nicotine sulphate and lead arsenate in 
 combination there is likewise a great increase, — 34 to 140 times, 
 while in the complete quadruple combination the increase is not 
 so great, due probably to addition of casein-lime in the mixture. 
 It is thus evident that there is an important reaction between lime- 
 sulphur and lead arsenate, but that this is not increased by nicotine 
 sulphate, and is lessened when casein-lime is added. 
 
CHEMICAL INVESTIGATION OF SPRAY MIXTURES 
 
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chemical investigation of spray mixtures 50i 
 
 Effect of Adding Nicotine Sulphate to Different 
 Ingredients Separately and Combined 
 
 (Tables 4 to 8) 
 
 A study of Tables 4 to 8 shows that there is a negligible action 
 when nicotine sulphate and lime-sulphur are mixed together as 
 regards total sulphur in solution. There is likewise little or no 
 action when nicotine sulphate and lead arsenate are mixed 
 together. When nicotine sulphate is added to lime-sulphur and 
 casein-lime in combination, not so much sulphur is precipitated 
 from the solution although the difference is small and of doubtful 
 importance. When added to lead arsenate and casein-lime there 
 is a distinct increase in soluble arsenic and when nicotine sulphate 
 is added to lead arsenate and lime-sulphur in combination there is 
 a decrease in soluble arsenic, and also a decrease in the amount of 
 sulphur in solution. Added to triple combinations as in Table 8, 
 there are variable results. The sulphur content of the filtrate is 
 only slightly altered and the soluble arsenic is decreased in 8 cases 
 but increased in 4. 
 
5°2 
 
 CONNECTICUT EXPERIMENT STATION 
 
 BULLETIN 278 
 
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504 connecticut experiment station bulletin 278 
 
 Effect of Adding Casein-Lime to Different 
 Ingredients Separately and Combined 
 
 (Tables 9 to 13) 
 
 It will be seen from Table 9 that the addition of casein-lime 
 increased the soluble arsenic and reduced the sulphur when mixed 
 with lead arsenate and lime-sulphur alone. When added to lead 
 arsenate and lime-sulphur in combination, the amount of soluble 
 arsenic is greatly reduced and the sulphur in solution is increased. 
 
 When added to nicotine sulphate and lead arsenate in combina- 
 tion the soluble arsenic is distinctly increased, but when added 
 to lime-sulphur and nicotine sulphate the sulphur content of the 
 solution is not greatly altered. In quadruple mixtures, Table 13, 
 there seems to be, in general, an increase of sulphur in solution 
 where casein-lime is used over mixtures where this material is 
 omitted; and, in general, the soluble arsenic is reduced, but it 
 may sometimes be increased. 
 
 Effect of Replacing Casein-Lime with ■ 
 Pure Lime (Table 14) 
 
 In order to find out whether the casein or lime of the casein- 
 lime mixture was responsible for the results noted in Tables 9 to 
 13, a quantity of pure lime (CaO), equivalent to the amount used 
 in the casein-lime, was substituted (Di). This amount was then 
 doubled (D2). It will be seen that the amount of soluble arsenic 
 is decreased as much or more by lime alone as by casein-lime 
 (Exp. No. 2) ; also that the amount of sulphur in solution is 
 not greatly reduced by the additional lime. 
 
 Effect of Different Orders of Mixing on 
 Quadruple Mixtures (Table 15) 
 
 It is easily demonstrated that different orders of mixing pro- 
 duce differently colored mixtures, but to determine if possible the 
 value of this criterion for judging spray mixtures Table 15 was 
 prepared. It will be seen that some of the mixtures are dark in 
 color while others are light. It was noted in the course of the 
 work that some of the blackness of the resulting spray was due 
 to the mixture of lime-sulphur and nicotine sulphate as well as 
 the formation of lead sulphide as noted by others. The actual 
 color of the sediment does not vary greatly, but there is a con- 
 siderable variation in the turbidity of the filtrate, certain ones 
 remaining clear, while others produce a decided murkiness. The 
 turbid filtrates were tested by chemical means and found to be 
 due to a very finely divided sulphur and not to lead, calcium or 
 
CHEMICAL INVESTIGATION OF SPRAY MIXTURES 
 
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506 CONNECTICUT EXPERIMENT STATION BULLETIN 2"/8 
 
 nicotine. This fact is of some significance in spraying" practices 
 since it has been demonstrated that colloidal sulphurs are impor- 
 tant fungicides. 28 Whether such combinations as these, however,, 
 contain enough colloidal sulphur to affect the efficiency of the 
 spray has not been determined. 
 
 It will be noted that combinations showing' the lowest arsenic 
 in solution (Nos. 5 and 12) are both extremely low in soluble 
 sulphur and that both filtrates are clear. It would probably not be 
 wise to select merely on the basis of soluble arsenic and sulphur 
 content alone, although Ave know from the work of Saffro 19 that 
 spray injury may be caused by calcium poly sulphides and to a less 
 extent by calcium thiosulphate (p. 32). An attempt to avoid spray 
 injury would, therefore, include selection of mixtures low in 
 sulphur and arsenic in solution, but these would probably be 
 reduced in fungicidal action since the filtrates are clear and the 
 total sulphur, supposedly the active forms, is reduced 25% or 
 more (Nos. 5 and 12). It is important to note that in all cases 
 the greater part of the soluble arsenic is found in the residue 
 which emphasizes the necessity of cleaning the spray tank fre- 
 quently, in order to avoid accumulation of sludge from previous 
 tanks, and the importance of ample agitation to avoid this 
 difficulty. 
 
 General Conclusions 
 
 (1) The Bramberg method of determining small amounts of 
 
 arsenic has been found adaptable to the determination of 
 soluble arsenic in spray mixtures. 
 
 (2) Lime-sulphur reacts strongly with lead arsenate* giving in- 
 
 creased soluble arsenic and decreased sulphur in solution. 
 It reacts similarly with lead arsenate and nicotine sulphate 
 in combination and with lead arsenate and casein-lime but 
 the reaction is not as great in the latter case. 
 
 (3) Nicotine sulphate does not react with lead arsenate or with 
 
 lime-sulphur so far as indicated by the chemical data ; a 
 color change is noted, the significance of which is not 
 explained. When added to lead arsenate and casein-lime 
 together the soluble arsenic is increased ; added to lead 
 arsenate and lime-sulphur together there is a marked 
 decrease in soluble arsenic and also a decrease in the 
 amount of sulphur in solution. When added to triple 
 combinations of lead arsenate, casein-lime and lime-sul- 
 phur, variable results are noted. 
 
 (4) Casein-lime increases the soluble arsenic content of lead 
 
 arsenate when mixed with it alone. When mixed with 
 
 * Acid lead arsenate is implied wherever lead arsenate is mentioned. 
 
CHEMICAL INVESTIGATION OF SPRAY MIXTURES 507 
 
 lime-sulphur alone the amount of sulphur in solution is 
 somewhat reduced. When added to nicotine sulphate and 
 lead arsenate the soluble arsenic is distinctly increased, but 
 when added to lime-sulphur and nicotine sulphate the sul- 
 phur content of the solution is not greatly altered. In 
 quadruple mixtures there is, in general, an increase of sul- 
 phur in solution due to the casein-lime and there is in 
 general a decrease in soluble arsenic. The latter, however, 
 may sometimes be increased. 
 
 (5) The lime in casein-lime is largely responsible for the decrease 
 
 in soluble arsenic where this material is used. 
 
 (6) Different orders of mixing quadruple mixtures give different 
 
 results, but so many factors are involved and the varia- 
 tions are so small that the selection of improved mixtures 
 seems an impossibility. 
 
 (7) Colloidal sulphur is sometimes formed in the spray mixtures. 
 
 (8) The color of the resulting mixture is not a satisfactory means 
 
 of judging a spray solution. 
 
 Bibliography 
 
 1. Association of Official Agricultural Chemists, Methods of Analysis, 
 
 1924. 
 
 2. Bradley, C. E. Soluble arsenic in mixtures of lead arsenate and lime- 
 
 sulphur solution. In Journal of Industrial Engineering Chemistry 
 1 : 606-607 : 1009. 
 
 3. Bradley, C. E., and Tartar, H. V. Further studies of the reaction of 
 
 lime-sulphur solution and alkali waters on lead arsenates. In 
 Journal of Industrial Engineering Chemistry 2: 328-329: 1910. 
 
 4. Cook, F. C, and Mclndoo, N. E. Chemical, physical and insecticidal 
 
 properties of arsenicals. U. S. Department of Agriculture, Depart- 
 ment Bulletin No. 1147, 1923. 
 
 5. Cox, H. E. In the Analyst, 50: 586: 3, 1924. 
 
 6. De Ong, E. R. California University Agricultural Experiment Sta- 
 
 tion Bulletin 338: 1921. Survey of waters made in 1919 and 
 found that many had a high chlorine content. Concluded that 
 basic lead arsenate should be used. 
 
 7. Ellett, W. B., and Grisson, J. T. The amount of arsenic in solution 
 
 when lead arsenate is added to different spray solutions. Virginia 
 Experiment Station Technical Bulletin 8: 160-164: 1915. 
 
 8. Fulmer, H. L., and Caesar, Lawson. Lime-sulphur wash, Ontario 
 
 Agricultural College, Bulletin 177: 1909. 
 
 9. Fields, W. S., and Elliott, J. A. Making bordeaux mixture and some 
 
 other spraying problems. Arkansas Agricultural Experiment 
 Station, Bulletin 172: 33: 1020. 
 
 10. Goodwin, W., and Martin, H. In Journal of Agricultural Science 15: 
 
 307, 476-490: 1925- 
 
 11. Haywood, J. K. U. S. Department of Agriculture, Bureau of Chem- 
 
 istry, Bulletin 101. States that increase in fungicidal action of 
 mixture is due to formation of thiosulphate which later changes 
 to sulphites. 
 
 12. Harcourt, R. Lime-sulphur wash. In annual report, Ontario Agri- 
 
 cultural College and Experiment Farm 36: 100-102: 1910. 
 
 13. Journal Association of Official Agricultural Chemists, 1 : 75,: 1915. 
 
508 CONNECTICUT EXPERIMENT STATION BULLETIN 2/8 
 
 14. McDonnell, C. C, and Graham, J. J. T. The decomposition of dilead 
 
 arsenate in water. In Journal American Chemical Society 29: 
 1912-1918: 1917. 
 
 15. Robinson, R. H. Beneficial action of lime in lime-sulphur and lead 
 
 arsenate combination spray. In Journal Economic Entomology 
 12: 420-433: I9I9- 
 
 16. Robinson, R. H. The valuation of commercial arsenate of lead. In 
 
 Journal Industrial Engineering 7: 409-502: 1915. 
 
 17. Ruth, W. E. In Illinois Horticultural Transactions, new series 49; 
 
 393: I9I5- 
 
 18. Ruth, \Y. E. Chemical studies of the lime-sulphur lead arsenate 
 
 spray mixture, Iowa Agricultural Experiment Station Research 
 Bulletin 12: 409-419: 1913. 
 
 19. Saffro, V. I. An investigation of lime-sulphur injury; its causes and 
 
 prevention. Oregon Agricultural College Experiment Station, 
 Research Bulletin No. 2, 1913. Page 32. Lime-sulphur injury is 
 caused by the calcium polysulphides and to a less extent by 
 calcium thiosulphate. Advised increased dilution. Increased boil- 
 ing of the lime-sulphur affects burn. Density or specific gravity 
 not a good index of its value. 
 
 20. Sanders, G. E., and Brittain, W. H. The toxic value of some poisons 
 
 alone and in combination with fungicides on a few species of 
 
 biting insects. In Proceedings of the Entomological Society of 
 Nova Scotia for 1916, No. 2 : 55-64. 
 
 21. Smith, C. R. The determination of •arsenic. U. S. Department of 
 
 Agriculture, Bureau of Chemistry, Circular 102: 1912. 
 
 22. Thatcher, R. W., and Streeter, Leon R. Chemical studies of the 
 
 combined lead arsenate and lime-sulphur spray. New York State 
 (Geneva) Agricultural Experiment Station Bulletin 521 : 1924. 
 
 23. Van Slyke, L. L, Hedges, C. G, Bosworth, A. W. A chemical study 
 
 of the lime-sulphur wash. New York State (Geneva) Agricul- 
 tural Experiment Station Bulletin 319: 410-411: 1909. Page 
 384, Effect of addition of lime-sulphur in sulphide sulphur form 
 decreased, thiosulphate increased. 
 
 24. Vermorel, V., and Dantony, E. Composition chimique des Bouillies 
 
 sulfo-calciques employees contre les Insectes et les Maladies des 
 
 Plantes. Villefranche (Rhone) Librairie Agricole du ''Progres 
 agricole et viticole" 1919. 
 
 25. Wallace, Errett. Spray injury induced by lime-sulphur preparations. 
 
 Cornell Agricultural Experiment Station, Bulletin 288; 1910. 
 Page 107, "The active agent in causing lime sulphur injury is 
 doubtless the soluble sulphur in the form of a calcium sulfid and 
 is applied as such." 
 
 26. Wilson, H. F. Combination sprays and recent insecticide investiga- 
 
 tions. In Proceedings Entomological Society British Columbia 
 No. 3, n.s. 9-16: 1913. 
 
 27. Wilson, H. F. Insecticide Investigations of 1914, in Biennial Crop 
 
 Pest and Horticultural Report for 1913 and 1914- Oregon Agri- 
 cultural Experiment Station, page 137. 
 
 28. Young, H. C. Crop Protection Digest No. 3. 403-435 ) 1923- 
 
 Grateful acknowledgment is made to Dr. E. M. Bailey who has given 
 much aid both in the preparation of the manuscript and by criticism and 
 suggestions as the work progressed. The authors also wish to thank 
 Dr. W. E. Britton for advice and criticism during the course of the 
 investigation. 
 
University of 
 Connecticut 
 
 Libraries 
 
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