CHEMISTRY — ACREE. l8l 



that acetylhalogenaminobenzene derivatives rearrange in the presence of 

 hydrochloric acid into halogen acetanilide derivatives according to the 

 following reaction : 



CH3C0NClCeH, + H + CI ?^ CH3C0NHC1,C6H5 ^~^ 



(or) 



+ _ 

 CHjCONHQH.Cl + H + CI 



^-- = Ktraus Chal ^ Ch ^ Cci = Ktrans Chal ^ Ch 



in which Ktrans is the reaction velocity, Chai the concentration of the 

 acetylhalogenaminobenzene derivative, and C^ and 0^ the concentrations 

 of the hydrogen and chloride ions. This work and researches on the 

 hydrolysis of oximes prove that the three so-called laws of catalysis do not 

 apply to all catalytic reactions, and show directly that (i) not all catalytic 

 reactions have velocity constants directly proportional to the concentration 

 of the catalyzer, and that (2) in some reversible reactions the equilibrium- 

 point is changed by a change in the concentration of the catalyzer. The 

 work further makes it clear that whereas in the catalysis of esters, amides, 

 oximes, and cane-sugar in the presence of acids these substances, as weak 

 bases, unite with a small amount of hydrogen ions and form complex cations 

 which undergo transformation, yet in other catalytic reactions, such as the 

 transformation of acetylchloraminobenzene, the substance really undergoing 

 change is a neutral molecule formed by the union of the catalyzed substance 

 and an anion and cation, or neutral catalyzer. 



On the Constitution of Phenylurasole, III: A Contribution to the Study of 

 Tautomerism. (By S. F. Acree: American Chemical Journal, vol. 38, 

 p. I.) — In a lengthy article involving the application of mathematics and 

 physical chemical methods to the study of tautomerism, the following results 

 were obtained: 



(i) Experimental work and the application of the mass law show that 

 the relative amounts of two stable derivatives formed by the reaction of a 

 tautomeric compound, existing in two reacting forms in equilibrium, and 

 another reagent depend upon (a) the relative reactivity of the two tauto- 

 meric forms toward the other reagent; (&) the ratio between the amounts 

 of the two tautomeric forms when they are in constant equilibrium with 

 each other; and (c) the rapidity of the change of each of these tautomeric 

 forms into the other as the equilibrium between them is disturbed. In some 

 cases the reaction may be complicated by the rearrangement of one, or 

 each, of the tautomeric derivatives into the other, or some other products. 



(2) Various phases of the equilibrium condition existing in a solution 

 of a tautomeric acid or base, or the salts, have been studied theoretically, by 

 the application of the mass law, and experimentally. For example, it was 



