/ 
 
EXCHANGE 
 
I. 
 
 The Detection of Mannite in Alkaline 
 Solutions of Copper Sulphate 
 
 Combustion of Mannite by Alkaline 
 
 Solutions of Potassium Permanganate in the 
 
 Presence of Copper Sulphate 
 
 |L 
 
 A Determination of the Volumes of Weight 
 
 Normal Solutions of Cane Sugar 
 
 at 15, 20, 25, and 30 
 
 DISSERTATION 
 
 SUBMITTED TO THE BOARD OF UNIVERSITY STUDIES OF THE 
 
 JOHNS HOPKINS UNIVERSITY IN CONFORMITY WITH 
 
 THE REQUIREMENTS FOR THE DEGREE OF 
 
 DOCTOR OF PHILOSOPHY, 
 
 BY 
 
 HENRY OTTO EYSSELL, 
 
 BALTIMORE, 
 
 1912. 
 
 GEO. W. KING PRINTING Co., 
 BALTIMORE, Mo. 
 
. 
 
 The Detection of Mannite in Alkaline 
 Solutions of Copper Sulphate 
 
 Combustion of Mannite by Alkaline 
 
 Solutions of Potassium Permanganate in the 
 
 Presence of Copper Sulphate 
 
 II. 
 
 A Determination of the Volumes of Weight 
 
 Normal Solutions of Cane Sugar 
 
 at 15, 20, 25, and 30 
 
 DISSERTATION 
 
 SUBMITTED TO THE BOARD OF UNIVERSITY STUDIES OF THI 
 
 JOHNS HOPKINS UNIVERSITY IN CONFORMITY WITH 
 
 THE REQUIREMENTS FOR THE DEGREE OF 
 
 DOCTOR OF PHILOSOPHY. 
 
 r>v 
 
 HENRY OTTO .] YSSKF.L 
 BALTIMORE. 
 
 GEO. W. KING PRINTING Co.. 
 BALTIMORE, MD. 
 

CONTENTS. 
 
 Acknowledgment 5 
 
 I. Detection of Maimite. 
 
 Introduction 7 
 
 Method 7 
 
 Strength of Solutions Used 8 
 
 Results . 9 
 
 Structure of Compound Formed 15 
 
 Conclusion 1(1 
 
 Combustion of Ma unite 
 
 Introduction 17 
 
 Results 17 
 
 Method 18 
 
 Check Experiments 19 
 
 II. Volume Determinations. 
 
 Introduction 20 
 
 Apparatus 20 
 
 Constant Temperature Bath 22 
 
 Calculations 2:; 
 
 Rotations of Solutions 24 
 
 Results 24 
 
 Summary and Conclusions 29 
 
 Biography .31 
 
 253952 
 
ACKNOWLEDGMENT. 
 
 The author wishes to express his sincere gratitude to Presi- 
 dent Remsen, Professors Morse, Jones, Acree, Lovelace and 
 Whitehead for instruction received in the lecture room and in 
 the laboratory. 
 
 To Professor Morse, the writer wishes to express especial 
 thanks for his personal direction of these investigations and 
 also to Drs. Frazer and Holland for many valuable sugges- 
 tions. 
 
PART 1. 
 
 Tin- Detection of Mannite in All-aline Solutions of Copper 
 
 Sulphate. 
 
 The measurement of the osmotic pressure of solutions, which 
 has been in progress in this laboratory for the last ten or 
 twelve years, for the purpose of determining whether this force 
 obeys the laws of gas pressure or not, has thus far been con- 
 fined mainly to solutions of cane sugar and glucose. As soon 
 as practicable, other substances will be dealt with, and mannite 
 will probably be one of the first. of these. 
 
 In the work with cane sugar and glucose, changes in the con- 
 centration of their solutions can be detected by means of the 
 polarimeter. This method can not be employed in the case of 
 mannite, which made it desirable to work out another for this 
 substance just as delicate, or even more so, than the one based 
 upon the rotatory power of cane sugar and glucose. 
 
 When the cells containing the solutions whose osmotic pres- 
 sure is to be measured, are set up, they are immersed in a vessel 
 containing an 0.01th ion X, solution of copper sulphate, while 
 the cells themselves always contain a quantity of an 0.01 ion X. 
 solution of potassium ferrocyanide besides the solutions in 
 question. These quantities are believed to be osmotically 
 equivalent, and they are used in this manner for the 
 purpose of repairing ruptures which may develop in the mem- 
 brane while the cells are giving a measurement. 
 
 It was found that when a solution of mannite is made alka- 
 line with potassium hydroxide and there is then added to it a 
 small quantity of copper sulphate, <i fine blur color is dcreloped 
 without precipitation of copper hydroxide. If more copper 
 sulphate is added, a /trecipitate of copper hi/dro.ri<]< 
 and if still wore of the copper sulphate is added, the fine 
 
8 
 
 color referred to eventually disappears, leaving the mannite un- 
 combined witli the copper, but still in solution. 
 
 At temperatures between and 60, all solutions are made 
 up with 0.001 N. thymol water to prevent the growth of the 
 mould penicillium glaucum, which it seems, thrives upon the 
 nitrogen of the ferrocyanogen anion of the membranes and de- 
 stroys them. It was possible that the thymol might affect this 
 color reaction, or give a similar one under the same conditions, 
 but such was found not to be the case. When solutions of 
 copper sulphate containing thymol in quantities sufficient to 
 make them 0.001 N. with respect to the latter substance, are 
 treated with a solution of potassium hydroxide and filtered 
 through asbestos the filtrates are clear and colorless. 
 
 This, then, seemed to be a practicable method for detecting 
 the presence of mannite in solution when other substances which 
 act similarly are known to be absent. Several other poly-acid 
 alcohols (glycerol, erythrite and arabite) were found to con- 
 duct themselves in an analogous manner. 
 
 The solutions of copper sulphate and of mannite used in the 
 subsequent work, were made up with .001 N. thymol water, 
 while the solution of potassium hydroxide was made up with 
 pure water. The solutions of copper sulphate were 0.1 and 0.01 
 volume normal, that of potassium hydroxide was approximately 
 0.5 N., each cubic centimeter containing .02805 grams. The 
 solution of mannite contained one milligram of the alcohol per 
 cubic centimeter. 
 
 Table 1 contains the quantities of mannite and the maximum 
 quantities of copper sulphate, which in 100 cubic centimeters 
 of solution, were found to give a blue colored filtrate after the 
 addition of 5 cubic centimeters of the potassium hydroxide 
 solution. When the copper sulphate exceeded the quantities 
 tabulated by one-tenth of a milligram, the filtrates became 
 practically colorless. 
 
TABLE 1. 
 
 Maximum iian- 
 
 Manuite. of Topper Sulphate. 
 
 1 mg. 37 ing. 
 
 2 mg. 88 mg. 
 
 3 nig. 107.S mg. 
 
 4 mg. 144.0 mg. 
 
 5 mg. 180.0 mg. 
 I ing. 1^7.1 mg. 
 
 7 nig. 198.3 ing. 
 
 8 mg. 236 mg. 
 !> mg. 24.~i.4 mg. 
 
 10 nig. 261 mg. 
 
 Table :! contains The results which were obtained when an 
 attempts was made to duplicate those given in Table 1. The 
 <-anse for whatever discrepancies there are between the results 
 in the two tables was found to be due to the fact that the 
 asbestos filter absorbs and retains some of the coloring: matter. 
 
 TABLE 2. 
 
 Ma unite. Maximum Quantities 
 
 of Copper Sulphate. 
 1 mg. 36.3 mg. 
 
 1 mg. 32.2 mg. 
 
 2 mg. 88.0 mg. 
 
 2 mg. 97.9 mg. 
 
 3 mg. 121.4 mg. 
 
 3 mg. 131.4 mg. 
 
 4 mg. 144.0 mg. 
 
 4 mg. 153.9 mg. 
 
 5 mg. 179 9. mg. 
 5 mg. 177.7 nig. 
 mg. ir.vs mg. 
 
 Table 3 contains ihe Quantities of copper sulphate and the 
 minimum quantities of mannite which, in 100 cubic centimeters 
 of solution, were found to give a characteristically colored fil- 
 trate after adding ."> cc. <>f the alkali solution. 
 
 TABLE 3. 
 
 Minimum Quantity 
 Sulphate. of Mauuite. 
 
 10 nig. 0.3 mg. 
 
 20 nig. 0.5 mg. 
 
 30 mg. O.G mg. 
 
 40 mg. 1.1 mir. 
 
 ~<> in-. 1.4 mg. 
 
10 
 
 Table 4 contains the quantities of inannite and the maximum 
 quantities of copper sulphate, which were found to give the col- 
 ored filtrate in 200 cc. of solution after adding 5 cc. of the alkali 
 solution, 
 
 TABLE 4. 
 
 Maximum Quantity 
 
 Mannite. of Copper Sulphate. 
 
 1 mg. 34 mg. 
 
 2 mg. 64 mg. 
 
 3 mg. 92 mg. 
 
 4 mg. 122 mg. 
 
 5 mg. 154 mg. 
 
 Table 5 contains the quantities of copper sulphate and the 
 minimum quantities of mannite, which were found to give a 
 colored filtrate in 200 cc. of solution, after making alkaline 
 with 5 cc. of the potassium hydroxide solution . 
 
 TABLE 5. 
 
 Minimum Quantity 
 Copper Sulphate. of Mannite. 
 
 10 mg. 0.4 mg. 
 
 20 mg. 0.7 nig. 
 
 30 mg. . 0.9 mg. 
 
 40 mg. 1.3 mg. 
 
 50 mg. 1.6 mg. 
 
 Tables f> and 7 contain the results obtained in 100 cc. of 
 solution when the ratio of mannite to copper sulphate was kept 
 constant. The mode of proceedure here and in the following 
 cases was the same as stated above. 
 
 TABLE 6. 
 
 Mannite. Copper Sulphate. Filtrate. 
 
 1 mg. 25 mg. Colored. 
 
 2 mg. 50 mg. Colored. 
 
 3 mg. 75 mg. Colored. 
 
 4 mg. 100 mg. Colored. 
 
 5 mg 125 mg. Colored. 
 
 6 mg. 100 mg. Colored. 
 
 7 mg. 175 mg. Colored. 
 
 8 mg. 200 mg. Colored. 
 
 9 mg. 225 mg. Colored. 
 10 mg. 250 mg. Colorless. 
 
11 
 
 The last filtrate was colored, when 10 instead of 5 cc. of 
 alkali were used. 
 
 Ma unite. 
 
 1 ing. 
 
 2 mg. 
 
 3 mg. 
 
 4 mg. 
 
 5 mg. 
 
 6 mg. 
 
 7 mg. 
 
 8 mg. 
 
 9 mg. 
 10 mg. 
 
 TABLE 7. 
 
 Copper Sulphate. 
 
 30 mg. 
 
 60 mg. 
 
 90 mg. 
 120 mg. 
 150 mg. 
 180 mg. 
 210 mg. 
 240 mg. 
 270 mg. 
 300 mg. 
 
 TABLE 8. 
 
 
 Copper. 
 
 
 Mamiite. 
 
 Sulphate. 
 
 Alkali. 
 
 1 mg. 
 
 60 mg. 
 
 140.3 mg. 
 
 1 mg. 
 
 00 mg. 
 
 500.0 mg. 
 
 1 mg. 
 
 70 mg. 
 
 ."00.0 mg. 
 
 1 mg. 
 
 SO mg. 
 
 500.0 mg. 
 
 1 mg. 
 
 90 mg. 
 
 500.0 nig. 
 
 Filtrate. 
 Colored. 
 Colored. 
 Colored. 
 Colored. 
 Colored. 
 Colored. 
 Colored. 
 Colorless. 
 Colorless. 
 Colorless. 
 
 Filtrate. 
 Colorless. 
 Colorless. 
 Colorless. 
 Colorless. 
 Colorless. 
 
 The filters were washed with 10 cc. of the alkali solution. 
 The washings were all colored. 
 
 Asbestos filters were used throughout. A new batch of asbes- 
 tos was prepared at this st;ij>e of the work. It was considerably 
 finer than that previously used, and with it colorless filtrates 
 were obtained with ratios which had given colored ones before, 
 ns may be seen from the results given in table 9. 
 
 TABLE 9. 
 
 Mannir<>. 
 1 m::. 
 1 mp. 
 1 mg. 
 1 mir. 
 
 Copper 
 Sulphate 
 i>.- nig. 
 1.5 ni.tr. 
 25 nig. 
 25 mg. 
 
 Alkali. 
 
 500 mg. 
 
 750 mg. 
 1000 mg. 
 1250 mg. 
 
 Filtrate. 
 Colorless. 
 Colorless. 
 Colorless. 
 Colorless. 
 
 When the filters were washed with 10 cc. of the alkali the 
 washings were 'not colored. They were deeply colored, how- 
 ever, when alkali of Fehling's solution strength was used. 
 Blank experiments gave colored washings with the strong alk- 
 ali, but not with 0.." X. 
 
12 
 TABLE 10. 
 
 The solutions were made alkaline with 5 cc. of the potassium 
 hydroxide solution. 
 
 Mannite. Copper Sulphate Filtrate. 
 
 1 mg. 25 mg. Colorless. 
 
 2 mg. 50 mg. Colorless. 
 
 3 mg. 75 mg. Colored. 
 
 4 mg. 100 mg. Colored. 
 
 5 nig. 125 mg. Colored. 
 
 6 mg. 150 mg. Colored. 
 
 The filters were allowed to stand for about 15 minutes with 
 10 cc. of 0.5 N. alkali. The washings were all colored. 
 
 TABLE 11. 
 
 Mannite. Copper Sulphate. Filtrate. 
 
 1 mg. 50 mg. Colored. 
 
 2 mg. 100 mg. Colored. 
 
 3 mg. 150 mg. Colorless. 
 
 4 mg. 200 mg. Colorless. 
 
 5 mg. 250 nig. Colorless. 
 
 6 mg. 300 mg. Colorless. 
 
 The filters were allowed to stand for about 15 minutes with 
 10 cc. of the 0.5 N. alkali. The washings were all colored. 
 
 TABLE 12. 
 
 Mannite. Copper Sulphate. Filtrate. 
 
 1 mg. 75 mg. Colorless. 
 
 2 mg. 150 mg. Colorless. 
 
 3 mg. 225 mg. Colorless. 
 
 4 mg. 300 mg. Colorless. 
 
 5 mg. 375 mg. Colorless. 
 
 6 mg. 450 mg. Colored. 
 
 7 mg. 525 mg. Colored. 
 
 The filters were allowed to stand with 0.5 N. alkali as stated. 
 The washings were all colored, excepting those obtained from 
 the 5 and 7 mg. experiments. Duplicate experiments gave the 
 same results. 
 
13 
 TABLE 13. 
 
 The solutions were made alkaline with 5 cc. of the potassium 
 hydroxide solution. 
 
 Maimite. Copper Sulphate. Filtrate. 
 
 1 jng. 100 mg. Colorless. 
 
 '2 ing. 200 mg. Colorless. 
 
 3 mg. 300 mg. Colorless. 
 
 4 mg. 400 mg. Colored. 
 
 5 mg. 500 mg. Colored. 
 
 6 mg. 600 mg. Colored. 
 
 The filters were treated with 0.5 X. alkali as stated. Where 
 colorless filtrates were obtained the washings were colored, 
 and vice versa. 
 
 TABLE 14. 
 
 The solutions were made alkaline with 5 cc. of the potassium 
 hvdroxide solution. 
 
 Mannite. Copper Sulphate. Filtrate. 
 
 1 mg. 10 mg. Colored. 
 
 2 mg. 20 mg. Colored. 
 
 3 ing. 30 mg. Colored. 
 
 4 mg. 40 mg. Colored. 
 
 5 mg. 50 mg. Colored. 
 
 6 mg. 60 mg. Colored. 
 
 The filters were treated as in previous cases; the washings 
 were all colored. 
 
 The results tabulated in tables 6 to 14. inclusive, were ob- 
 tained in 100 cc. of solution. Those given in table 15 were ob- 
 tained in 100 cc. of .01 N. copper sulphate solution. 
 
* 
 
 14 
 
 
 
 
 TABLE 
 
 15. 
 
 
 Mannite. 
 1 mg. 
 
 Copper 
 Sulphate. 
 
 123.92 mg. 
 
 Alkali. 
 5 cc. 
 140.3 mg. 
 
 Filtrate. 
 Colorless. 
 
 1 mg. 
 
 123.92 mg. 
 
 10 cc. 
 2S0.5 mg. 
 
 Colorless. 
 
 1 mg. 
 
 123.92 mg. 
 
 15 cc. 
 420.8 mg. 
 
 Colorless. 
 
 1 mg. 
 
 123.92 mg. 
 
 20 cc. 
 tiGl.Omg. 
 
 Colorless. 
 
 1 nig. 
 
 123.92 mg. 
 
 25 cc. 
 701.3 mg 
 
 Colorless. 
 
 1 mg. 
 
 123.92 mg. 
 
 30 cc. 
 841 .5 mg. 
 
 Colorless. 
 
 1 mg. 
 
 123.92 mg. 
 
 40 cc. 
 1122.0 mg. 
 
 Slightly 
 Colored. 
 
 1 mg. 
 
 3 23.92 mg. 
 
 45 cc. 
 1162.5 mg. 
 
 Slightly 
 Colored. 
 
 1 mg. 
 
 123.92 mg. 
 
 50 cc. 
 1402.5 mg. 
 
 Slightly 
 Colored. 
 
 2 mg. 
 
 123.92 mg. 
 
 5 cc. 
 140.3 mg. 
 
 Colorless. 
 
 2 mg. 
 
 ] 23.92 mg. 
 
 30 cc. 
 841.5 ing. 
 
 Colored. 
 
 2 mg. 
 
 123.92 mg. 
 
 50 cc. 
 1420.5 mg. 
 
 Colored. 
 
 3 mg. 
 
 ] 23.92 mg. 
 
 30 cc. 
 841.5 mg. 
 
 Colored. 
 
 r > mg. 
 
 123.92 mg. 
 
 30 cc. 
 841.5 mg. 
 
 Deep 
 Color. 
 
 None. 
 
 1 23.92 mg. 
 
 30 cc. 
 841.5 mg. 
 
 Colorless. 
 
 None. 
 
 1 23.92 mg. 
 
 50 cc. 
 1 420.5 mg. 
 
 Colorless. 
 
15 
 
 The color of the filtered solutions is probably due to 1he for- 
 mation of one of the following compounds : 
 
 (1) CH*OH 
 
 CHOH 
 
 CHOH+GCu(OH) 2 
 
 CHOH 
 
 CHOH 
 
 CHzOH 
 i i> t CHsOH 
 
 CHOH 
 2CHOH+CU (OH) 2 
 
 CHOH 
 
 CHOH 
 
 CHzOH 
 i :; > CH 2 OH 
 
 CHOH 
 
 CHOH+3Cu(OH) 2 
 
 CHOH 
 
 rilOH 
 
 CH 2 OII 
 
 CHtOCaOH 
 
 CHOCuOH 
 
 CHOCuOII+GHaO 
 
 CHOCuOH 
 
 CHOCuOH 
 
 CHsOCuOH 
 
 CeHs(OH).-,OCuO(OH)5CoHs+2 H= O. 
 
 CHip] 
 
 CHO 
 C 
 
 1 Cll 
 
 HO ] 
 }. 
 CHO J 
 
 CHO ] 
 
 j^ 
 
 CHsO I 
 
 Working with molecular ratios in 100 cc. of solution, it was 
 found that, at proportions lower than 1 of mannite to 3 of cop- 
 per sulphate, no precipitate was formed, and the color of the 
 solutions increased in intensity upon the addition of 5 cc. of 
 0.5 X. potassium hydroxide solution. The color of the solution 
 in which mannite and copper sulphate were present in the pro- 
 portion of 1 to 3.5, was no deeper than that of the 1 to 3 solu- 
 tion, and a slight precipitate could be detected in it. These 
 facts would seem to indicate that the color in the case of 
 mannite is due to the formation of compound Xo. 3. 
 
16 
 
 Some experiments were made to determine whether nickel 
 salts as well as those of copper could be employed for the de 
 tection of mannite, but with negative results. 
 
 Conclusions. 
 
 (1) The colored compound, whatever it may be, which is 
 formed when a little copper sulphate is added to an alkaline 
 solution of mannite, is decomposed by an excess (which is prob- 
 ably a definite one) of copper sulphate for every quantity of 
 maimite. The alcohol is left in solution, but uncombined with 
 copper. 
 
 (2) Although the colored compound is absorbed, more or 
 less, by the asbestos of the filters, it can be removed from them 
 by washing with alkali. In nearly every case where colorless 
 filtrates were obtained while working with proportions, which 
 had in previous experiments given colored ones, the alkaline 
 washings from the filters were colored. 
 
 (3) Alkali of the strength used in Fehling's solution can 
 not be employed for, the washing of filters, because it dissolves 
 copper hydroxide, giving a blue solution, while hot water has 
 no effect whatever when used for washing purposes. 
 
 Although mannite cannot be determined quantitatively by 
 the method described, it will serve very well for the detection 
 of mannite in the liquid exterior to the osmotic cell when leak- 
 age through the membrane is suspected. By means of it two 
 milligrammes can easily be detected in the presence of 
 123.92 milligrammes of copper sulphate in 100 cc. of liquid. 
 Since the osmotic pressure of a 0.5 N. solution of mannite is 
 about 12.5 atmospheres, a change of two milligrammes in its 
 concentration would make a difference of .00028 of an atmos- 
 phere in the osmotic pressure developed. 
 
17 
 
 of Mannitc by Alkaline Solutions of Potassium 
 Permanganate in the Presence of Copper Sulphate. 
 
 The next question to come under consideration in this con- 
 nection, was that of finding some method for the quantitative 
 determination of mannite, and its oxidation by means of potas- 
 sium permanganate seemed an appropriate one. 
 
 Theoretically, thirteen atoms of oxygen are necessary for the 
 complete combustion of every molecule of pure mannite. 
 
 This was verified, experimentally, as may be seen from the 
 
 results given in the following tables : 
 
 \. 
 
 TABLE 1. 
 
 2 
 
 - 
 
 e 
 
 i 
 
 
 
 I 
 
 6 
 
 
 
 d 
 
 Z C 
 
 SI 
 
 si 
 
 II 
 
 -1 s 
 
 ~. 
 
 j 
 
 X 
 
 5 
 
 
 
 S3 
 
 
 
 -y .' 
 
 <0 
 
 1 ing. 
 
 r. < ( . 
 
 o::.27 ing. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 4.3 mg. 
 
 12.38 
 
 1 mg. 
 
 occ. 
 
 '.:: 27 mg. 
 
 li':;. ( .tL' 
 
 mg. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 4.4 mg. 
 
 12.67 
 
 1 mg. 
 
 r, <-. 
 
 03.27 mg. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 4> mg. 
 
 13.82 
 
 1 mg. 
 
 - cc. 
 
 03.27 mg. 
 
 123.92 
 
 nig. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 4.r, mg. 
 
 12.96 
 
 1 in jr. 
 
 .- CC. 
 
 o:;.2~ ing. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 4.4 mg. 
 
 12.67 
 
 Nont' 
 
 .- ( ( 
 
 93.27 mg. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 None 
 
 None 
 
 i* mg. 
 
 r> cc. 
 
 93.27 mg. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 .-it 
 
 50 
 
 9.2 mg. 
 
 13.24 
 
 2 nig. 
 
 r. cc. 
 
 o:;.2~ mg. 
 
 11':;. '.12 
 
 mg. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 9.1 nig. 
 
 13.10 
 
 2mg. 
 
 5cc. 
 
 !>::.2-mg. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 9.0 mg. 
 
 12.96 
 
 2 mg:. 
 
 5 cc. 
 
 93.27 mg. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 8.8 mg. 
 
 12.67 
 
 2mg. 
 
 5 cc. 
 
 93.27 mg. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 o.l mg. 
 
 13.10 
 
 None 
 
 5cc. 
 
 93.27 m-. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 None 
 
 None 
 
 3 mg. 
 
 5cc. 
 
 93.27 mg. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 MI 
 
 .-,< 
 
 13.31 mg. 
 
 12.78 
 
 3mg. 
 
 5cc. 
 
 93.27 mir. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 13.18 mg. 
 
 12.64 
 
 3mg. 
 
 5cc. 
 
 '.::. 27 mi:. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 13.18 mg. 
 
 12.64 
 
 3 mg. 
 
 5 cc. 
 
 93^7 mg. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 13.U2 mg. 
 
 13.07 
 
 " in jr. 
 
 
 93.27 mg. 
 
 123.92 
 
 nig. 
 
 10 
 
 hours 
 
 at 
 
 50 
 
 13.18 mg. 
 
 12.64 
 
 None 
 
 r. cc. 
 
 93.27 mg. 
 
 123.M2 
 
 nig. 
 
 10 
 
 hours 
 
 at 
 
 .-(. 
 
 None 
 
 None 
 
 4 in-. 
 
 r, cc. 
 
 93.27 mg. 
 
 12.-l.02 
 
 mg. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 1 7.s.", mg. 
 
 12.84 
 
 4 mg. 
 
 5cc. 
 
 93.27 mg. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 ar 
 
 50 
 
 18.16 mg. 
 
 13.07 
 
 4 mg. 
 
 occ. 
 
 93.27 mg. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 17.78 mg. 
 
 12.M 
 
 4 mg. 
 
 5cc. 
 
 93.27 mg. 
 
 123.92 
 
 nig. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 17.72 mg. 
 
 12.67 
 
 4 me. 
 
 
 93.27 mg. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 ar 
 
 50 
 
 20.09 mg. 
 
 14.47 
 
 XoiU' 
 
 occ. 
 
 93.27 mg. 
 
 123.92 
 
 ing. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 None 
 
 None 
 
 ~> mg. 
 
 
 93.27 mir. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 ar 
 
 50 
 
 22.7omg. 
 
 13.10 
 
 ~ i HIT. 
 
 .- < -i 
 
 93.27 me. 
 
 12:;.! 12 
 
 mg. 
 
 19 
 
 hours 
 
 ar 
 
 50 
 
 22.51 nig. 
 
 12.96 
 
 " mg. 
 
 ~ , ., . 
 
 '.'::. 27 mg. 
 
 123.H2 mg. 
 
 19 
 
 hours 
 
 ar 
 
 50 
 
 22.rr, mg. 
 
 13.10 
 
 "> mg. 
 
 r, <<-. 
 
 '.::. 27 mp. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 22.76 mg. 
 
 13.10 
 
 -" mg. 
 
 ."i i < 
 
 '.:;.L>7 mg. 
 
 12:;.92 
 
 mg. 
 
 19 
 
 hours 
 
 ai 
 
 50 
 
 22.70 mg. 
 
 13.10 
 
 N'olH" 
 
 ~ , .,-. 
 
 93.27 mg. 
 
 12:1.02 
 
 mg. 
 
 10 
 
 hours 
 
 ar 
 
 50 
 
 None 
 
 None 
 
18 
 TABLE 2. 
 
 c5 
 
 "3 
 s 
 
 
 g 
 
 4 
 O 
 d 
 
 o 
 
 3 
 
 
 
 il 
 
 
 
 
 4 
 
 If 
 
 I| 
 
 ^ 
 
 M 
 
 t4 
 
 y 
 
 
 
 r*iH 
 
 
 
 
 
 **<o 
 
 10 mg. 
 
 occ. 
 
 1 87.05 mg. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 45.70 mg. 
 
 13.15 
 
 10 mg. 
 
 Sec. 
 
 187.05 mg. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 nt 
 
 50 
 
 45.45 mg. 
 
 13.09 
 
 10 mg. 
 
 5 cc. 
 
 1 87.05 mg. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 45.20 mg. 
 
 13.02 
 
 10 mg. 
 
 5 cc. 
 
 1 87.05 mg. 
 
 123.92 
 
 nig. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 45.33 mg. 
 
 13.05 
 
 10 mg. 
 
 5 cc. 
 
 1 87.05 mg. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 45.39 mg. 
 
 13.07 
 
 None 
 
 5cc. 
 
 1 87.05 mg. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 None 
 
 None 
 
 20 mg. 
 
 5 cc. 
 
 187.05 mg. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 90.28 mg. 
 
 12.99 
 
 20 mg. 
 
 5 ce. 
 
 1 87.05 mg. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 nt 
 
 50 
 
 90.53 mg. 
 
 13.04 
 
 20 ing. 
 
 5 co. 
 
 1 87.05 mg. 
 
 128.92 
 
 mg. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 90.07 mg. 
 
 12.96 
 
 20 mg. 
 
 5cc. 
 
 187.05 mg. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 90.07 mg. 
 
 12.96 
 
 20 mg. 
 
 5 cc. 
 
 187.05 mg. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 90.22 mg. 
 
 12.99 
 
 None 
 
 5 cc. 
 
 187.05 mg. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 nt: 
 
 no 
 
 None 
 
 None 
 
 30 nig. 
 
 5cc. 
 
 187.05 mg. 
 
 123.92 
 
 nig. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 135.1 mg. 
 
 12.97 
 
 30 mg. 
 
 5cc. 
 
 1 87.05 mg. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 135.2 nig. 
 
 12.99 
 
 30 mg. 
 
 5cc. 
 
 187.05 mg. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 135.1 mg. 
 
 12.97 
 
 30 mg. 
 
 5 cc. 
 
 187.05 mg. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 1 35.05 mg. 
 
 12.97 
 
 80 mg. 
 
 5cc. 
 
 187.05 mg. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 135.1 mg. 
 
 12.97 
 
 Non 
 
 5cc. 
 
 187.05 mg. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 None 
 
 None 
 
 40 mg. 
 
 10 cc. 
 
 361.01 mg. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 1 80.95 mg. 
 
 13.02 
 
 40 mg. 
 
 10 co. 
 
 361.01 mg. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 181.59ms. 
 
 13.08 
 
 40 mg. 
 
 lOcc. 
 
 361. Olms". 
 
 128.92 
 
 mg. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 182.24 mg. 
 
 13.11 
 
 40 mg. 
 
 10 cc. 
 
 361.01 mg. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 181.21 mg. 
 
 13.05 
 
 40 mg. 
 
 lOcc. 
 
 361.01 mg. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 181.46 mg. 
 
 13.08 
 
 None 
 
 10 cc. 
 
 301.01ms. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 at 
 
 no 
 
 None 
 
 None 
 
 50 mg. 
 
 lOcc. 
 
 432 mg. 
 
 1 23.92 
 
 mg. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 224.56 mg. 
 
 12.93 
 
 50 mg. 
 
 10 cc. 
 
 432 mg. 
 
 128.92 
 
 mg. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 224.09 mg. 
 
 12.90 
 
 50 mg. 
 
 10 oc. 
 
 432 mg. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 nt 
 
 50 
 
 224.56 mg. 
 
 12.93 
 
 50 mg. 
 
 10 oc. 
 
 432 mg. 
 
 123.92 mg. 
 
 19 
 
 hours 
 
 at 
 
 50 
 
 223.58 mg. 
 
 12.89 
 
 50 mg. 
 
 10 cc. 
 
 432 mg. 
 
 123.92 
 
 mg. 
 
 19 
 
 hours 
 
 nt 
 
 no 
 
 223.96 mg. 
 
 12.90 
 
 None 
 
 10 cc. 
 
 432 mg. 
 
 128.92 
 
 mg. 
 
 19 
 
 hours 
 
 nt 
 
 no 
 
 None 
 
 None 
 
 The solutions used were made up with water containing no 
 thymol. 
 
 It was found that the combustion is not complete until the 
 reacting substances have been allowed to stand for a period of 
 19 hours at 50. A quantity of potassium tetroxalate equiva- 
 lent to the permanganate used was then added, and the excess 
 of tetroxalate titrated back with the standard permanganate 
 solution ; the difference between the two quantities of perman- 
 ganate added being the amount of permanganate reduced dur- 
 ing the'combustion. 
 
10 
 
 The mamiite used in this work was analyzed by the electrical 
 method I'm- I he combustion of organic compounds, as devised by 
 I'rnfVssnr Morse, and round to be practically pure. 
 
 Analysis No. 1 Manuite used. .0909 gms. 
 
 Per cent, hydrogen found, 7. in;. 
 Per cent, hydrogen theoretical. 7.75. 
 Per cent, carbon theoretical, 39.54. 
 Per cent, carbon found, 39.47. 
 Per cent, purity, 100.2. 
 
 Atoms of oxygen necessary for complete combustion 13.03. 
 
 Analysis No. L' Maimite used, .0918 gins. 
 
 Per cent, hydrogen found, 7.55. 
 Per cent, hydrogen theoretical. 7.75. 
 Per cent, carbon theoretical. oD.54. 
 Per cent, carbon found, 39.27. 
 Percent, purity, 99.01. 
 
 Atoms of oxygen necessary for complete combustion 12.87 
 
 This method can be used for the quantitative determination 
 of mannite in solutions of copper sulphate. The reducing 
 action of thymol upon alkaline solutions of potassium per- 
 manganate is, however, considerably greater than that of man- 
 nite, which will probably necessitate the finding of some other 
 means for coping with penicillium. 
 
PAKT 2. 
 
 A Determination .of tlie Volumes of Weight-Normal Solutions 
 of Cane Sugar at 15, 20, 25 and 30 01 . 
 
 It is a well known fact that a contraction in volume takes 
 place W:lien sugar is dissolved in water at ordinary tempera- 
 tures, that is, the volume of the solution is not the sum of the 
 volumes of the water and sugar it contains. Determinations 
 of the volumes of sugar solutions at 0, made in this laboratory 
 a few years ago, indicated that when a gram-molecular weight 
 of sugar is dissolved in 1000 grams of water at that tempera- 
 ture, the volume of the solution is about 12 cc. less than the 
 total volume of the water and sugar composing it. 
 
 This investigation was undertaken for the purpose of throw- 
 ing some light on the amount of contraction occurring at 15 , 
 20, 25 and 30 in solutions of cane sugar of the concentra- 
 tions thus far used in the measurement of osmotic pressure, for 
 it is hoped that a careful study of their behavior will be of 
 value in explaining in a satisfactory manner the irregularities 
 in the pressures developed by them at lower temperatures. 
 
 Figure 1 represents the apparatus used in making the meas- 
 urements. It consists of a bulb having a capacity of about 
 100 cc., and a graduated stem of an inner diameter of about 4 
 mm. To this, at (c), is fused a calibrated tube about 400 mm. 
 in length, having an interior diameter of about 2 mm. The 
 exact volume of the apparatus up to the mark on the gradu- 
 ated stem, was determined by weighing the bulb with water of 
 a known temperature. In a similar manner the capacity of the 
 stem between the and 100 marks was also determined. The 
 tube was calibrated between the scratches (a) and (b), and 
 
 1. This investigation was carried out in collaboration with Mr. F. S 1 . 
 Dengler, in whose dissertation the results obtained for the even concen- 
 trations may be found. 
 
s 
 
 100 
 
 cc 
 
 FlGURK I 
 
22 ' 
 
 after it had been fused onto the bulb, the volume of the space be- 
 tween the 100 mark on the stem and the lower scratch (a) of 
 the tube was determined by means of a mercury thread. 
 
 Eleven such pieces of apparatus were prepared in the manner 
 described, and weighed. Ten of the pieces were then filled 
 with the sugar solutions and the remaining one with air-free 
 water to some point a little above the lower scratch (a) on the 
 calibrated tube. 
 
 A day or so after the apparatuses had been filled and placed 
 in the constant temperature bath, all of them were found to 
 leak around the stop-cocks to a greater or less extent. They 
 were taken down, and after the stop-cocks had been carefully 
 reground with very fine emory until they were tight, the appa- 
 ratuses were filled again as before. 
 
 The first measurements were made at 15, and in order to 
 avoid the sticking of the liquid to the walls of the tubes, the 
 solutions and water were cooled below this temperature before 
 filling the dilatometers. 
 
 To secure reliable determinations of this nature, it is of the 
 utmost importance that the apparatus be kept at a uniform 
 temperature during the experiments, and that any slight 
 changes in temperature which may occur shall be very gradual. 
 In order to secure this uniformity of temperature, a constant 
 temperature bath, originally devised by Morse and Frazer and, 
 described as at present employed in volume 44 of the American 
 Chemical Journal, was used in these experiments. 
 
 A slight change was necessary in the construction of the 
 bath. The galvanized iron cans used to hold the cells during 
 the measurement of osmotic pressure were replaced by a copper 
 trough large enough to contain all of the apparatuses at the 
 same time. In a bath of this kind temperature fluctuations 
 hardly exceed .01 of a degree. 
 
 After allowing the dilatometers to stand in the bath at the 
 temperature in question for a period of twenty-four hours or 
 more, the volumes of the solutions contained in them were read 
 by means of a cathetometer. Readings were then taken from 
 
day to day until the last three or four consecutive readings re- 
 mained constant. 
 
 When the necessary readings had been made over the desired 
 range of temperature, the apparatuses and the solutions con- 
 tained in them were weighed. From the weights of the solu- 
 tions in the dilatometers and the measured volumes at the dif- 
 ferent temperatures, the volumes of weight-normal solutions at 
 these temperatures were calculated by simple proportion in 
 this way: Weight of solution : weight of the weight-normal 
 solution : : volume found : volume required. 
 
 In making these calculations, a correction had to be intro- 
 duced for the solution contained in the hole of the stop-cock. 
 Its volume was determined by means of mercury, and was then 
 added to the measured volume of the solution. The sum of the 
 two volumes is the actual volume of the weight of solution con- 
 tained in the apparatus for the given temperature. Having 
 thus obtained the volume of the weighed amount of solution, 
 its specific gravity was calculated. Knowing the volume of the 
 hole in the stop-cock and the specific gravity of the solution, 
 it was an easy matter to determine the weight of the solution 
 contained in the opening of the stop-cock. This weight was 
 then deducted from the total weight of the solution and the 
 value thus obtained was the weight of solution whose volume 
 had been measured at the temperature in question. This cor- 
 rected weight was the one used for calculating the actual vol- 
 umes of the weight-normal solutions. 
 
 For the calculations of the sum of the volumes of water and 
 sugar contained in the various solutions, that is, for the deter- 
 mination of the volumes the solutions should have provided 
 there was no contraction, the values 1.5813, as given by Ger- 
 lach and Kopp, and 1.5800 as given by Rchroeder for the specific 
 gravity of sugar in a vacuum at 15 were used, and the value 
 .0001110 as given by Joule and Playfair for the coefficient of 
 expansion of sugar. * 
 
24 
 
 The rotations given by the solutions before and after the ex- 
 periments were as follows: 
 
 TABLE 1. 
 
 Weight Normality 
 of solutions. 
 0.1 
 0.3 
 0.5 
 0.7 
 0.9 
 
 -Rotations- 
 
 Before. 
 12.60 
 36.55 
 
 58.80 
 79.20 
 98.30 
 
 After. 
 12.60 
 36.55 
 
 08.70 
 77.50 
 75.00 
 
 Tables 2 and 3 contain the results obtained at 15. In Table 
 2, 1.5813 was taken as the specific gravity of sugar, and 1.5860 
 in table 3. 
 
 TABLE 2 (15' 
 
 01. 
 0.3 
 0.5 
 0.7 
 0.9 
 
 1000.857 
 1000.857 
 1000.857 
 1000.857 
 1000.857 
 
 !! 
 
 21.462 
 
 64.386 
 
 107.310 
 
 150.234 
 
 193.158 
 
 ZC o OS 
 
 1022.319 
 1065.243 
 1108.167 
 1151.091 
 1194.015 
 
 1022.417 
 1063.952 
 1106.576 
 1147.462 
 1190.359 
 
 Js 
 
 1 
 II 
 
 0.172 
 1.291 
 1.591 
 3.629 
 3.656 
 
 TABLE 3 (15). 
 
 
 0.1 
 0.3 
 0.5 
 0.7 
 0.9 
 
 5-2 
 
 O OS 
 
 ;> ss 
 
 1000.857 
 1000.857 
 1000.857 
 1000.857 
 1000.857 
 
 o 
 o> 
 
 Is 
 
 c^ 
 
 21.394 
 
 64.182 
 
 106.970 
 
 149.758 
 
 192.546 
 
 1022.251 
 1065.039 
 1107.827 
 1150.615 
 1193.403 
 
 tf3 
 
 1022.417 
 1063.952 
 1106.576 
 1147.462 
 1190.359 
 
 fcfi 
 
 sl 
 
 0.104 
 1.087 
 1.251 
 3.153 
 3.044 
 
25 
 
 Tables 4 and 5 contain the results obtained at 20. In Table 
 4. 1.5813 was taken as the specific gravity of sugar and 1.5860 
 in Table 5. 
 
 TABLE 4 (20) 
 i 
 
 c ^ = b 
 
 ill 
 
 I*: 
 
 r - 
 
 "5 - 
 
 -- 
 II 
 
 ?! 
 
 II 
 
 11 
 
 ^ - 
 
 ~ z 
 
 ^" /. ~ 
 
 -^ ^ 
 
 > y 
 
 VI c ~ 
 
 --. - 
 
 
 0.1 
 
 1001. 7." 1 
 
 21.474 
 
 1023.225 
 
 1023.111 
 
 0.114 
 
 0.3 
 
 1001.751 
 
 64.422 
 
 1066.173 
 
 1065.299 
 
 0.874 
 
 0.5 
 
 1001.751 
 
 1< iT.370 
 
 1109.121 
 
 1107.870 
 
 1.251 
 
 0.7 
 
 1001.751 
 
 150.318 
 
 1152.069 
 
 1148.909 
 
 3.160 
 
 0.9 
 
 1001.751 
 
 193.266 
 
 1105.017 
 
 1191.827 
 
 3.190 
 
 TABLE 
 
 20 
 
 1 
 
 '. 
 
 S 
 
 : :_- 
 
 _; 
 
 .s 
 
 . 
 
 . 
 
 
 "" "/ 
 
 5- 71* 
 
 r 7 
 
 ii!-= 
 
 _ 
 
 = *: 
 
 1^ ^ 
 
 ie 
 
 Is 
 
 ~ ? ~ f - 
 
 ~= ~ 
 
 z ^ 
 
 = =- 
 
 || 
 
 E^ 
 
 0.1 
 
 1001.751 
 
 1' 1.406 
 
 1023.157 
 
 1023.111 
 
 0.046 
 
 0.3 
 
 1001.751 
 
 64.218 
 
 1065.969 
 
 1065.299 
 
 0.670 
 
 0.5 
 
 1001.751 
 
 107.030 
 
 1108.781 
 
 1107.870 
 
 0.911 
 
 0.7 
 
 1001.751 
 
 149.842 
 
 1151.593 
 
 1148.909 
 
 2.684 
 
 0.9 
 
 1001.751 
 
 192.654 
 
 1194.405 
 
 1191.827 
 
 2.578 
 
 Tables 6 and 7 contain the results obtained at 25. In Table 
 6, 1.5813 was taken as the specific gravity of sugar and 1.5860 
 in Table 7. 
 
 TABLE 6 (25). 
 
 TtE- 
 
 r t- 
 
 11 
 
 '..-'- 
 E^- 
 
 s| 
 
 || 
 
 
 
 
 % Z 
 
 
 
 -^ s 
 
 -*" ^ 
 
 -" y 
 
 VI c r: 
 
 -< > 
 
 > 
 
 0.1 
 
 1002.911 
 
 l' 1.486 
 
 1024.397 
 
 1024.343 
 
 0.054 
 
 0.3 
 
 1002.011 
 
 64.468 
 
 1067.369 
 
 1066.464 
 
 0.905 
 
 0.5 
 
 1002.911 
 
 107.430 
 
 1110.341 
 
 1109.404 
 
 0.037 
 
 0.7 
 
 HX>2.911 
 
 150.402 
 
 1153.313 
 
 1150.565 
 
 2.748 
 
 0.9 
 
 1002.911 
 
 193.374 
 
 1195.285 
 
 110.-J.707 
 
 3.578 
 
2G 
 TABLE 7 (25). 
 
 o 
 
 > ., 
 .4.1 3 fee 
 
 1*~ 
 
 -' 
 
 t^ 
 
 C-3 
 
 |i 
 
 t 
 
 ^0^ 
 
 "3 si 
 
 3 cd 
 
 -v- C 
 
 || 
 
 1 
 
 ^"55 o 
 
 > if 
 
 i*- X 
 
 X * 
 
 
 > 
 
 0.1 
 
 1002.911 
 
 21.418 
 
 1024.329 
 
 1024.343(7) 
 
 +0.044(7) 
 
 0.3 
 
 1002.911 
 
 64.254 
 
 1067.165 
 
 1066.464 
 
 0.701 
 
 0.5 
 
 1002.911 
 
 107.090 
 
 1110.000 
 
 1109.404(7) 
 
 0.596(7) 
 
 0.7 
 
 1002.911 
 
 149.926 
 
 1152.837 
 
 1150.565 
 
 2.272 
 
 0.9 
 
 1002.911 
 
 192.762 
 
 1195.673 
 
 1193.707 
 
 1.966(7) 
 
 Instead of a contraction, an expansion appeared to have 
 taken place in the case of the 0.1 weight-normal solution, which 
 is probably due to some experimental error not yet detected, 
 or possibly to the fact that an incorrect value for the specific 
 gravity of sugar has been taken. The irregularity in con- 
 traction exhibited by the 0.5 weight-normal solution must be 
 attributed to experimental error. In the case of the 0.9 weight 
 normal solution it may have been caused by decomposition of 
 the solution which was indicated bv the loss in rotation. 
 
 Tables 8 and 9 contain the results obtained at 30. In Table 
 8, 1.5813 was taken as the specific gravity of sugar and 1.5860 
 in Table 9. 
 
 TABLE 8 (30). 
 
 Sal 
 
 lei 
 
 gjj 
 
 * 
 
 i| 
 
 Ssfj 
 
 S o^ 
 
 [3 cs 
 
 3SP 
 
 S_ e 
 
 s~ 
 
 g^s 
 
 2o 
 
 
 ^1 
 
 ^ i 
 
 ^ > 
 
 - -3 
 
 0.1 
 
 1004.314 
 
 21.497 
 
 1025.811 
 
 1025.777 
 
 0.034 
 
 0.3 
 
 1004.314 
 
 64.491 
 
 1068.805 
 
 1068.038 
 
 0.767 
 
 0.5 
 
 1004.314 
 
 107.485 
 
 1111.799 
 
 1111.106 
 
 0.693 
 
 0.7 
 
 1004.314 
 
 150.479 
 
 1154.793 
 
 1152.405 
 
 2.388 
 
 0.9 
 
 1004.314 
 
 193.473 
 
 1197.787 
 
 1195.631 
 
 2.156 
 
TABLE 9 (30). 
 
 i i Li ij -If 
 
 It ij SSs 5= 5'S 
 
 5! t m if ^ 
 
 0.1 1004.314 21.430 1025.744 1025.777 +0.033(7) 
 
 0.3 1004.314 64.290 1068.604 1068.038 0.566 
 
 0.5 1004.314 107.150 1111.464 1111.106 0.358(?) 
 
 0.7 1004.314 150.010 1154.324 1152.405 1.919 
 
 0.9 1004.314 192.870 1197.184 1195.631 1.553 (?) 
 
 The same irregularities appear here as in Table 7. The 0.1 
 weight-normal solution seemed to have expanded instead of 
 contracted. The 0.5 weight-normal solution showed a con- 
 traction, but it was not as large as might be expected. This is 
 also true for the 0.9 weight-normal solution. The various ir- 
 regularities here may be attributed to the same causes given 
 under Table 7. 
 
 In Tables 10, 11 and 12 are given the expansion coefficients 
 of the various solutions and of air-free water, as calculated 
 from the experimental data. 
 
 TABLE 10. 
 
 m fi I i I 
 
 zy~ > - . > ' ~ s-3 
 
 o.l 100.3734 100.4680 .0947 .000189 
 
 ".:\ 100.3952 100.5024 .1071 .000213 
 
 O.o 100.5770 lOO.OOr,.; .1176 .000234 
 
 0.7 100.3743 100.5008 .1265 .000252 
 
 0.9 100.4533 100.5872 .1340 .000267 
 Air-free 
 
 \vater. 100.407'; 100.407H .ossn .000175 
 
 The mean expansion coefficient of air-free water between 1.1" 
 and 20, as calculated from the values given in Landolt-Born- 
 stein, is .000178. 
 
28 
 TABLE 11. 
 
 3!! ig 
 
 0.1 
 
 100.4680 
 
 100.5890 
 
 .1210 
 
 .000241 
 
 0.3 
 
 100.5024 
 
 100.6323 
 
 .1299 
 
 .000259 
 
 0.5 
 
 100.6956 
 
 100.8350 
 
 .1394 
 
 .000277 
 
 0.7 
 
 100.5008 
 
 100.6457 
 
 .1449 
 
 .000288 
 
 0.9 
 
 100.5872 
 
 100.7369 
 
 .1497 
 
 .000298 
 
 Air-free 
 
 
 
 
 
 water. 
 
 100.6132 
 
 100.6132 
 
 .1156 
 
 .000230 
 
 The mean expansion coefficient of air-free water between 20 
 and 25, as calculated from the values given in Landolt-Born- 
 stein, is .000232. 
 
 TABLE 12. 
 
 
 111 
 
 32 
 
 > Cj 
 
 o2 
 
 Q 
 
 Kg 
 
 0.1 
 
 100.5890 
 
 100.7298 
 
 .1408 
 
 .000280 
 
 0.3 
 
 100.6323 
 
 100.7808 
 
 .1485 
 
 .000295 
 
 0.5 
 
 100.8350 
 
 100.9896 
 
 .1546 
 
 .000307 
 
 0.7 
 
 100.6457 
 
 100.8066 
 
 .1606 
 
 .000320 
 
 0.9 
 
 100.7369 
 
 100.8983 
 
 .1614 
 
 .000320 
 
 Air-free 
 
 
 
 
 
 water 
 
 100.6132 
 
 100.7507 
 
 .1375 
 
 .000274 
 
 The mean expansion coefficient of air-free water between 25 
 and 30, as calculated from the values given in Landolt-Born- 
 stein, is .000280. 
 
 In Table 13 are given the expansion coefficients of the various 
 solutions as calculated from the experimental data in terms of 
 the volumes at 15. 
 
29 
 TABLE 13. 
 
 isjj 1^ s| if 
 
 S^-I fl-2 ||= ||.-, 
 
 0.1 .000189 .000.241 .000280 
 
 0.3 .000213 .000259 .000296 
 
 0.5 .000234 .000277 .000307 
 
 0.7 .000252 .000288 .000320 
 
 .09 .000267 .000298 .000321 
 
 The solutions whose rotation changed during the investi- 
 gation all contained a growth of some sort, probably penicil- 
 liuiu. The results given in the tables for the concentrations 
 greater than O.G normal are not reliable, because those were the 
 solutions which contained more or less of the growth men- 
 tioned, and whose rotation had changed, in some cases very 
 considerably. 
 
 It is possible to correct for inversion by taking the loss in 
 rotation into account, but it would be useless to do so, since it 
 can not be stated with certainty that further decomposition 
 did not take place. 
 
 In spite of the numerous valueless results obtained, it seems 
 evident from the foregoing results; (1) that, when cane sugar 
 is dissolved in water at any given temperature, the contraction 
 in volume increases with the concentration of the solutions; 
 - i that, for any given concentration, it decreases with rise in 
 temperature. 
 
BIOGRAPHY. 
 
 Henry Otto Eyssell was borin in Kansas City, Mo., February 
 23, 1885. He received his early education in the public schools 
 of his native city. In September, 1904, he entered the Univer- 
 sar of Missouri, where he received the degree of Batchelor of 
 Arts in June, 1908. In October, 1909, he entered the Johns 
 Hopkins University as a graduate student in Chemistry. 
 
UNIVERSITY OP CALIFORNIA LIBRARY 
 
 THIS BOOK IS DUE ON THE LAST DATE 
 STAMPED BELOW 
 
 OCT 18 1916 
 
 30m-l,'15 
 

 253952