242 REPORTS ON INVESTIGATIONS AND PROJECTS. 



During the past year the studies on catalysis and the mechanism of 

 organic reactions have reached the point where it seems certain that both 

 ions and nonionized substances may be concerned in many chemical changes. 



On the mechanism of organic reactions. By S. F. Acree. Amer. Chem. Jour., 48, 352. 

 As a further contribution to our theory that in all reactions we should 

 consider the possibility of the direct transformation of both ions and non- 

 ionized substances, the writer presents in this article work by his collabo- 

 rators, Dr. H. C. Robertson, Dr. E. K. Marshall, Dr. Julia Peachy Harrison, 

 Dr. J. Chandler, Dr. Sidney Nirdlinger, Dr. F. M. Rogers, Miss B. Marion 

 Brown, and Mr. J. H. Shrader, on the reactions of alkyl halides with sodium, 

 potassium, and lithium ethylates, with sodium, potassium, and lithium phen- 

 olates, and with sodium phenylurazole. In all of these cases it has been 

 found that the alkyl halide reacts with both the nonionized salts, such as 

 nonionized sodium ethylate or sodium phenolate, and with the anion of the 

 salt, such as the ethylate anion and the phenolate anion. 



C 2 H 5 I+OC 2 H 5 w+ (C 2 H 5 ) 8 0+I 

 C 2 H 5 I+NaOC 2 H 5 m-> (C 2 H 5 ) 2 0+Nal 



When both of these reactions are taking place side by side the total reaction 

 must be expressed by the equations 

 dx 



~J7 = *^\ a \*~sM _ X J V^alkjlhalide - X / 



+ K m (i-a) (C salt -x) (C alkTlhalide -x) 



= [K,a+K m (i-«)] (C 6alt -x) (C alkylhalide -x) 



— "-v V^-salt X / V ^alkylhalide X / 



When solutions varying in concentration from N/i to N/32 are used, 

 the simultaneous equations VK v :=K n =K i a+K m (1 — a) can be used to 

 find the values of Kj and K m , which are the reaction velocities of a gram 

 ion of ethylate ions, for instance, and a gram molecule of sodium ethylate 

 molecules, in one liter. 



Although there is a wide variation in K u and in a, the values for K. and 

 K m are quite constant and give the average K;= 0.127 an d K m = 0.0594, f° r 

 the reaction of sodium ethylate and methyl iodide. But if this theory is 

 correct we should obtain the same value for K, for the ethylate ion when we 

 study the reaction of methyl iodide with sodium ethylate and with potas- 

 sium ethylate, although the values of K m may differ in the two cases on 

 account of the difference between the two molecules. Potassium ethylate 

 actually gives the same value, K.= 0.127, for the ethylate ion, that we 

 obtain from sodium ethylate and methyl iodide. This is especially strik- 

 ing in view of the fact that the molecular potassium ethylate, for which 

 K m = 0.066 for this reaction, reacts 12 per cent faster with the methyl 

 iodide than does the molecular sodium ethylate. 



Still other satisfactory evidence for the theory is the fact that sodium 

 phenolate, potassium phenolate, and lithium phenolate have different de- 



