NOTES AND CORRESPONDENCE-The Carbon-Sulfur Complex and

NOTES AND CORRESPONDENCE-The Carbon-Sulfur Complex and Carbon Disulfide Formation. J Wibaut, Wilbert Huff, and John Holtz. Ind. Eng. Chem. , 1928 ...
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INDUSTRIAL AND ENGINEERLVG CHEMISTRY

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Although the direction of the Chemical Department has been Doctor Reese’s main activity, he has found time to invent a number of processes having a direct bearing on the chemical industry, and for these he has been granted several United States patents. Matters concerning the cultural side of life have always been a source of great interest t o Doctor Reese. Since the beginning of his professional career he has been interested in education and art. He has very definite ideas on educational methods,

Vol. 20, No. 2

especially as regards the training of chemists and chemical eng,ineers, and has on several occasions contributed valuable ideas and advice in this direction. He finds no end of enjoyment in collecting and studying etchings and engravings; he is a lover of books, and has a deep appreciation of the fine arts. As a scientist, thorough; as an executive, keen; as an educator, uplifting and sympathetic; he has that rare combination of traits which make a builder of character. ARTHURM . COMEY

NOTES AND CORRESPONDENCE The Carbon-Sulfur Complex and Carbon Disulfide Formation Editor of Industrial and Engineering Chemistry: In a n interesting paper Huff and Holtzl suggest that the formation of a carbon-sulfur complex plays an important part in the origin and decomposition of carbon disulfide in gas-making. They cite my investigation of 19222on the properties of carbonsulfur complexes and state that “although he (Wibaut) passed sulfur vapors over charcoal he did not detect the formation of carbon disulfide.” I wish to point out that this has been the subject of a more extensive investigation, published by me in collaboration with La Bastide in 1924,ain which we have shown that: (1) Carbon disulfide is formed when carbon-sulfur complexes of high sulfur content are decomposed by heating in vacuo. The splitting off of carbon disulfide from this carbonsulfur complex occurs intermittently when the temperature of heating is 600°, 800°, or 1000-1100” C. (2) Small quantities of carbon disulfide are formed when sulfur vapor is conducted over pure amorphous carbon a t a temperature of 600’ C. The remaining carbon in this experiment had fixed sulfur in the form of a carbon-sulfur complex.

In 19222 I suggested that the formation of a carbon-sulfur complex precedes the formation of carbon disulfide, which is formed by decomposition of the carbon-sulfur complex, and I called attention to the analogy with the behavior of amorphous carbon towards oxygen as revealed by the investigations of Rhead and Wheeler. I believe that the experiments described in my 1924 paper support the hypothesis, which has been proposed independently by Huff and Holtz. J. P.WIBAUT

these authors used no experimental conditions comparable with commercial practice, unless the treatment of the carbon-sulfur residue with hydrogen gas can be so regarded, and here apparently no attempt was made t o detect carbon disulfide in the issuing gas stream. Our investigations,‘ on the other hand, dealt in part with the formation and decomposition of carbon disulfide on carbonaceous surfaces when these surfaces are subjected to the action of gas streams containing small amounts of hydrogen sulfide. Our experiments showed, for the first time to our present knowledge, that under conditions encountered in the usual gas-making practice there may be, and often is, a definite period during which decomposition with sulfur deposition on the fresh carbon surfaces occurs without the appearance of detectable amounts of carbon disulfide, and that this is followed by the appearance of carbon disulfide in the gaseous products. This appears to us to establish for the first time the role of the carbon-sulfur complex and the mechanism in gas-making similar to that visualized by Rhead and Wheeler in combustion. Moreover, we have been able to link the experimental phenomena noted by us directly with published information upon commercial gas processes. While we are glad to cite ancillary information and suggestions such as those of Wibaut and La Bastide, and had no wish to do otherwise than accord just credit, i t appears to us that Wibaut can hardly claim priority for the suggestion that a complex may appear in the reaction between carbon and sulfur to form carbon disulfide, since this suggestion was made in 1915 by Lewis and Lacey,6 as noted in our paper. We therefore see a t present no reason for modifying the statements made in our contribution. WILBERTJ. HUFF THEDEPARTMENT OF GASENGINBERING JOHN C. HOLTZ HOPKINS UNIVERSITY BALTIMORE, MD. January 5, 1928

JOHNS

UNIVERSITY OF AMSTERDAM AXSTERDAM, HOLLAND December 20, 1927

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Editor of Industrial and Engineering Chemistry: As noted by Wibaut, our statement concerning his work was made with reference t o his investigation of 1922, and is correct. At the time our own paper was written we had not seen the later results of Wibaut and L a Bastide and are happy t o make mention of these, which are not at variance with our independent conclusions. We do not, however, regard the work of these authors as an anticipation of our own. The problem under study by us was the “Origin and Decomposition of Carbon Disulfide in GasMaking.” So far as we are aware, the long treatment of carbon with pure sulfur and decomposition i n vacuo used by Wibaut and La Bastide is not encountered in commercial gas-making, and I n d . Eng. Chem., 19, 1268.(1927). frao. chim., 41, 163 (1922). * Ibid., 4% 731 (1924). 1

1 Rcc.

I n d . Eng. Chcm., 18, 357 (1926);19, 1268 (1927). J . A m . Chcm.,Soc., S7, 1976 (1915).

Lignin Has Industrial Value Several years ago the chemists of the Department of Agriculture undertook to salvage some of the value of agricultural wastes, such as corncobs cornstalks, and straw, and in the course of time evolved processes for the manufacture of furfural which is now being used for many purposes. As soon as its commercial possibilities were assured, the Government discontinued the furfural experiments and commercial interests took over the work. Lignin constitutes from 20 t o 30 per cent of the dry material of these wastes. Chemists have already succeeded in converting lignin into varnishes, dyestuffs, and various aromatic chemicals that give promise of finding their place in the commercial chemical field. “Lignin,” says Doctor Browne, assistant chief of the Bureau of Chemistry and Soils,,,“may be called the greatest of all unutilized agricultural wastes, and he continues with the significant statement that “it occupies with respect t o industrial possibilities the position held by coal tar a century ago.”