384 PROCEEDINGS OF THE INDIANA ACADEMY OF SCIENCE. 



The Ethyl-Sulphuric Acid Reaction. 



P. N. Evans. 



Since the time of Williamson's classical work on etherification published 

 in 1850, the reactions between ethyl alcohol and sulphuric acid have been 

 familiar to chemists although not thoroughly understood. There are three 

 important reactions, leading respectively to ethyl-sulphuric acid, ethyl ether, 

 and ethylene, and represented bj^ the equations: 



C2H0OH + H2SO4 = ^ C.H5HSO4 + H2O (A) 



2G2H5OH = -> C2H5OC2H5 + H2O (B) 



C2H5OH = ^ C2H4 + H2O (C) 



In the last two reactions the sulphuric acid acts as a dehydrating agent. 

 Other reactions of less importance are known, leading to ethyl sulphate, 

 isethionic acid, and ethionic acid, respectively, in accordance with the 

 equations : 



2C2H,,011 + 1I,S04 = ^ (C,H5)2S04 + H2O (D) 



C2H0OII + II.SO4 = ^ CH2OH.CH2SO2OH + H2O (E) 



C2H5OH + 2H2SO4 = -> CH2HSO4.CH2SO2OH + 2H2O (F) 



No attempt is made to show the intermediate steps in the formation of 



the products mentioned. 



The reactions depend on temperature and on the proportions of sub- 

 stances present. That leading to ethyl-sul])huric acid occurs at ordinary 

 as well as higher temi)eratures, the others only inai)preciably at ordinary 

 temperatures. 



In the writer's laboratory the first tlu*ee reactions have been the subject 

 of investigation. The formation of ether was examined as to its complete- 

 ness and limitations by Miss Lena M. Sutton and the results were presented 

 in outline to this Academy (Proceedings 1910), and published in full in the 

 Journal of the American Chemical Society (1918, 3,5, 794). The same reac- 

 tion is J)eing made the subject of further study at present as to the nature 

 and quantities of the by-products. The formation of ethylene is also at 

 present under investigation as to its temperature limitations, speed, and side- 

 reactions. The ethyl-sulphuric acid reaction was last year made the subject 

 of e.xamination by Mr. J. M. Albertson, Assistant in Chemistry, as a thesis 

 for the Master of Science degree, and the results are here presented in oultine. 



Plan of the Work. 



It \v\\\ be seen from equation (A) that in the formation of ethyl-sulphuric 

 acid one of the two acid hydrogens of the sulphiiric acid is rei)laced by the 

 eth^'l group and neutralized, so that just half of the original acidity disappears 



