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plex phosphoric acid-choline radical replaces one hydroxyl, and alcohols. In certain sebaceous glands cetyl and octodecyl alcohols have been reported. Unfortunately our knowledge of the skin fats is still very limited, and other bodies may also be present in the fat cells. Much yet remains to be done before the chemistry of skin can be considered to be thoroughly understood, but though progress has been slow in the past, each forward step materially widens the path for those who follow. I n any case, it is only through a sounder knowledge of the basic raw material that the art and science of leather manufacture can hope to make progress.
BIBLIOGRAPHY I-“The Chemistry of Skin,” Collegium (London), 1915, 288. 2-“Hide Substance,” J. A m , Leathev Chem. Assoc., 15 (l920), 608. 3-H. R . Procter, “uber die Einwirkung verdunnter Sauren and Salzlosungen auf Gelatine,” Koll. Chem. Beihefte, 2 (1911), 203;“Equilibrium of
Vol. 14, No. 2
Dilute Hydrochloric Acid and Gelatin,” J . Chem. Soc., 105 (1914), 313; “The Combination of Acids and Hide Substance,” Collegium (London), 1915, 3; H. R. Procter and D. Burton, “The Swelling of Gelatinous Tissues,” J . Soc Chem. I n d , 35 (19161, 404; H R. Procter and J. A. Wilson, “The AcidGelatin Equilibrium,” J . Chem. Soc., 109 (1916), 307; “The Swelling of Colloid Jellies,” J . A m . Leathev Chem. Assoc., 11 (1916), 399; “Theoryof Vegetable Tanning,” J. Chem. Soc., 109 (19161, 1328; J. A. Wilqon, “Theory of Colloids,” J . A m . Chem. Soc., 38 (19161, 1982; H. R. Procter, “The Swelling of Gelatin,” J . Soc. Leather Trades’ Chem., 2 (1918), 73. See also articles in “Colloid Chemistry Reports,” I and 111, by H. R. Prorter and J. A. Wilson, and bibliographies there given. 4-See Loeb, J . Gen. Physiol., from commencement to present date. 5-Hofmeister, Dinglers fiolytech. J., 205 (1872), 164. 6-Procter, “Principles of Leather Manufacture,” 58. 7--Shorter, J . Soc. Dyers Colour, 36 (1920). 8-Thuau, Collegium, 1908, 362; Nihoul, Bourse aux Cuirs de Lidge, 1908; Marriott, J . Soc. Leather Trades’ Chem., 5 (1921), 2. 9--“Colloid Chemistry Reports,” 1917, 10. 1&Z. physiol. Chem., 6 1 (1909), 117; Collegium, 1909. 11-Gerbcv, 1860, 111, el se4.
Influence of Sodium Chloride, Sodium Sulfate, and Sucrose on the Combination of Chromic Ion with Hide Substance”* By Arthur W. Thomas8 and Stuart B. Foster COLUMBIA UNIVERSITY, N E W YORK, N. Y.
nonelectrolyte since H. C. Jones9 has shown that it hydrates considerably in aqueous solution. Inasmuch as Thomas and Kelly’O had shown that in a period of 48 hrs.’ contact the maximum combination of chrome with hide substance was effected by a chrome liquor containing 15.5 g. Crz03per liter, The significance of the Presence of neutral salts in chrome three sets of liquors were selected, one containing 15.5 g. and ~ ~ v e r a lCrzOjper liter, and two others 3 g. and 100 g. Crz03 per liter, liquors was first shown by Wilson and studies of their effects have been published from this laboMATERIALS AND TECHNIC ratory.5 Recently Wilson and Kern6 made a further. investi1920 and 1921 American Standard Hide Powder served as gation of the question and suggested as an hypothesis that the Source of hide substance. The chrome liquors were the retarding action on the chrome tanning might be due to hydration by the added salt, resulting in an actual increase prepared by dilution of pure concentrated liquors made by in the concentration of chromic ion. Since Miss Baldwin’ reduction of chemically pure sodium dichromate with SUIhad found that increase in concentration of a chrome liquor furous acid, as described by Thomas and Kelly.” Portions of hide powder equal to 5 g. of absolutely dry subover 16 g. Cr203per liter resulted in a diminution of the amount of chromium fixed by hide substance, this hypothesis stance were covered with 50 CC. of distilled water in bottles, and allowed to stand over night, when the salts or sugar to give appeared reasonable. If llydration did take place, the concentration of hydrogen tbe desii-ed concentrations were added. Finally 150 CC. of ion should be increased as well as that of the chrome, That chrome liquor were added, of such a concentration that if i t this was actually the case with chlorides was shown by were diluted to 200 CC., it would contain 3, 15.5 or 100 g. Thomas and Baldwin,g but a t the same time they demon- Crz03 Per liter. The mixtures were rotated in a tumbling strated that sulfates lower the hydrogen-ion concentration: machine for 48 hrs., filtered through muslin bags, and washed of acid solutions, as measured by the hydrogen eleetrode. well with tap water and three times with 200-cc. portions of Since Wilson and Kern found that sodium sulfate decreased distilled water. The powder was air-dried a t 30” c., then the fixation of chrome, just as sodium chloride and other a t 100’ c., and finally allowed to come to equilibrium with chlorides did, they were obliged to admit another possible atmospheric humidity. Moisture, nitrogen, and chromium factor, namely, the formation of addition compounds between were determined. Multiplication of the per cent nitrogen the chromium salt and added sulfate as well as between the by 5.614 gave Per cent hide substance. All figures in the tables are on the moisture-free basis. acid present and added sulfate. With the view of approaching a solution of this question TABLE I (LIQUORCONTAINED 3 G. CrzOa PER LITER) Concentration of Salt Mp.CnOa the following experiments were carried out. In addition M Protein CrrOs per G. to sodiumchloride and sulfate, the former raising the CH+ and (NaC1) Per cent Per cent Hide Substance the latter lowering it, sucrose was selected as a hydrating 0 83.75 4 44 53 Continuation of the authors’ work offers evidence that the retarding action of neutral salts in chrome tanning is due to the formation of addition compounds, with hydration as a secondary cause. ................
Presented before the Section of Leather Chemistry a t the 62nd Meeting of the American Chemical Society, New York, N. Y., September 6 to 10, 1921. 1 Published as Contribution No. 381 from the Chemical Laboratories of Columbia University. 8 Assistant Professor. 4 J . A m . Leather Chem. Assoc., 12 (1917), 445. & Ibrd., 13 (1918), 248; 14 (1919), 10, J. A m Chem. Soc., 4 1 (1919), 1981. 0 J. A m . Leather Chem. Assoc., 15 (1920), 273. 7 Ibid., 14 (1919), 433. 8 J. A m . Chem. SOC.,41 (1919), 1981.
0.5 1 2 3 4 (NazSOa) 0 5 1 2 3
1
0
10 11
88 01 90.03 90 37 SS 05 87.58
3 62 3.16 3 45 3.75 4.19
41 35 38 43 48
90.71 91.27 93.12 91.82
4 35 3.19 2.13 2.11
35 23 23
Carnegre Inst Publ., 60 (1907). THISJOURNAL, 13 (1921), 31. J . A m . Leather Chem. Assoc., 16 (1920), 665.
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T H E JOURNAL OF INDUSTRIAL A N D ENGINEERING CHEMISTRY
Feb., 1922
Measurements of the hydrogen-ion concentration of the liquors belonging to Table I1 verified the contrasting effects of sodium chloride and of sodium sulfate previously reported from this laboratory. /Io
,
I
I
-Liter
0
%
PM
M
3M
4M
CONCENTRATION OF ADn,-D
-$ M
0
2M
3M
4M
SUBSVNCF
FIG. 1 TABLEI1 Concentration of Salt
M
(NaCI) 0 0.5 1 2 3 4 (NarSOd 0.5 1 2 3
(15.5 G. CrrOs
PER
LITER)
Protein Per cent 77.92 79.18 81.27 82.86 84.38 83.93
CrrOs Per cent 9.01 7.59 5.93 5.26 5.90 5.85
81.07 84.32 83.48 85.44
6.58 5.29 5.76 4.36
Mg. Crz08 per G. Hide Substance 116 96 73 63 70 70 81 63 69 51
TABLEI11 (100 G. CnOs PER LITER) Concentration of Salt Mg. CrrOa Protein M per G. CrzOs Per cent Per cent (NaC1) Hide Substance 0 75.57 7.70 101 80.78 6.17 0.6 76 1 82.13 6.15 75 2 82.42 6.35 77 81.23 6.35 3 79 4 79.10 86 6.77 (NarSOa) 0.5 80.17 6.62 83 1 81.07 6.01 74 2 77.42 6.11 79 3 78.08 6.87 88
The results are plotted in Fig. 1. The curves representing the effect of sodium chloride all proceed to a minimum and show an upward trend similar to the results Wilson and Kern found with magnesium chloride. In all cases sodium sulfate shows greater inhibiting action than sodium chloride, and a minimum with upward slope is obtained only where the liquor is very concentrated. Contrasted to the effect of the electrolytes, we find that sucrose apparently has no effect except a t 4 M concentration.
'
TABLE I V (15.5 G. CrzO3 PER LITER) Concentration of Mg. CrrOa Sucrose Protein CrrOs per G. M Per cent Per cent Hide Substance 0 77.47 8.92 115 1 74.76 8.59 115 2 74.72 8.59 115 3 74.83 8.60 115 4 76.74' 8.13 106 1 This sample appeared to be scorched in spots after drying a t l o o o C. TABLEV (LIQUORS CONTAINGD 15.5 G. Cr20r PER LITER) Concentration of Salt Log C, + of Log c ,+ of 1M Original Liquor Filtrate -2.7s -2.90 -2.54 -2.67 2 -2.39 -2.43 3 -2.20 -2.33 4 -2.10 -2.20 (NaaSOS 0 -2.80 -2.85 1 -2.91 -2.92 2 -2.91 -3.07 3 -2.67 -3.01
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INTERPRETATION OF RESULTS Since sucrose hydrates in aqueous solution, the inhibition of the fixation of chrome by the lower concentrations of sodium chloride and of sodium sulfate does not appear to be due to hydration. The writers believe that, as Wilson and Kern suggested for sulfates, sodium chloride, as well as the sulfate, forms addition compounds with the constituents of chrome liquor. rendering them less dissociated and consequently less active in combining with the proteins of hide substance. This is like the influence of sodium chloride in inhibiting the adsorption of mercuric chloride by charcoal, which Rona and Michaelis12point out is similar to the decrease in toxicity of mercuric chloride in the presence of sodium chloride. They ascribe such effect to the formation of the complex ions HgC13- and HgC14 = . Upon increasing the concentration of salt the hydration effects a virtual concentration of the chrome to such an extent that the retarding action of the addition compound formation is counterbalanced somewhat by the activity of the high chrome concentration, and the curves slope upward. Sodium sulfate does not show the upward slope because, first, owing to mass action it can drive back the ionization of chromic sulfate which represses the activity, as well RS causing addition-compound formation, and, second, according to the results of H. C. Jones, it does not hydrate to a large extent. The upward trend with sodium sulfate is shown only where the liquor is very concentrated a t the beginning. That the effect of hydration is secondary to addition compound formation is illustrated by sucrose. While it hydrates in aqueous solution, it has no retarding effect on the fixation of chrome. It would seem that since it does not retard the action of the chrome, it must not form the addition compounds, except a t concentrations over 3 AI. The 4 M value shows a retardation which we ascribe to a different chemical mechanism. The effect of compounds with several hydroxy groups in forming soluble un-ionizable complexes with the metals, such as tartrate with copper, mannite and glycerol with iron, etc., is well known. The 4 M sucrose chrome solution was thick and sirupy in consistency and it seems plausible that a similar compound of chromium and sucrose was formed. ACKNOWLEDGMENT
We take pleasure in expressing our indebtedness to Messrs. A. F. Gallun and Sons Co., of Milwaukee, for their generous support of this investigation. * 1%
Biochem. Z.,9 1 (1919), 85.
Industrial Alcohol During the past few months the securing of alcohol for legitimate manufacturing purposes has been made more difficult and new regulations or modifications of existing ones have placed hardships upon those entitled t o tax-free use of this necessary chemical raw material. Many protests have been made and the time has now come when manufacturers must be heard and their claims recognized. The American Chemical Society a t the Rochester Meeting appointed a Committee on Industrial Alcohol with the following personnel: R . F.Bacon, Charles Baskerville, F. R. Eldred, Edward Mallinckrodt, Jr., G. D. Rosengarten, M. H. Ittner, Chairman, B. R. Tunison, Secretary. This Committee is anxious to know of any and all cases where legitimate manufacturers have had difficulty in obtaining alcohol needed for industrial purposes, and urges that all details available be sent to it. The Committee is ready to cooperate in every way possible and proposes to place the facts before the authorities in Washington in an effort to have them distinguish between beverage and industrial alcohol and to have them carry out the mandatory provisions of the Prohibition Act, which provides not only for national prohibition, but for the extension and development of the use of alcohol in fuels, dyes, medicinal and pharmaceutical preparations, and other lawful industries. Correspondence should be addressed to any member of the Committee, b u t preferably to the Secretary, B. R. Tunison, U. S. Industrial Alcohol Co., 27 William St., New York.
