140 REPORTS ON THE STATE OF SCIENCE.—1913: 
identical; the production of chloroanilide and the reduction remain in 
the same proportion. 
These results illuminate some recent observations of Rivett® on the 
‘transformation ’ of acetylchloroaminobenzene in aqueous solution. In 
one series of experiments he used hydrogen chloride, but never below a 
concentration of 0:1351. Although the values for 
k,/[HCI}? (= 0-0413-0-0419) 
between the limits of 0:2702-0-4797 for [HCl], are very close, he 
seeks for an explanation of the slightly divergent values outside these 
limits of concentration only in the degree of ionisation of the hydrogen 
chloride, and in the secondary influences of the ions on one another or on 
the unionised molecules on the ions. Our demonstration of the existence 
of a subsidiary side reaction would indicate another cause for the diver- 
gence from strict constancy of the expression kr/ [HCl]?. We have pre- 
viously attempted (Reports 1910) to show how this relation, k1/ [HCl]? 
= const., is accounted for on our view of the transformation. 
The speed of the formation of chloroanilides is given by the equation : 
d [chloroanilide] / dt = ku [Cl,] [anilide] = ku K [chloroamine][HCl]?, 
since 
K [chloroamine] [HCl]? = [Cl,] [anilide], 
from the equilibrium : 
Ar.NCl. Ac+ H’+ Cl = Cl,+ Ar.NH. Ac; 
Hence as chloroamine is the only variable, 
d [chloroanilide] / dt = (kn. K [HCI]’) [chloroamine]= hk: [chloroamine]. 
Apart from the completeness of the ionisation of the hydrogen chloride, 
and apart from the slight increase in the concentration of the hydrogen 
chloride during the reaction, the quantity of chloroamine in the equation 
is supposed to be sensibly identical with that used in the preparation of the 
system, the reaction with hydrogen chloride being disregarded. These 
approximations would undeniably cause variation in the expression, 
kx / (HCI). 
The final form of the equation is not changed if the hydrolysis of the 
chloroamine is taken, as seems necessary in an aqueous medium, as the 
first step. 
Ar. NC]. Ac+ H,O ~Ar. NH. Ac+HCl0 and HCIO+H’+Cl +Cl,+H,0. 
F , 
K, [chloroamine] [H,O] = [anilide] [HClO], 
K, [Cl,] [H,0] =[HCI0] (HCI), 
K, [chloroamine] / K, [Cl,] = [anilide] / [HC1]?, 
K [chloroamine] [HCI]’ = [Cl,] [anilide]. 
In Rivett’s experiments with a pure aqueous medium, and also with 
other acids, he fails to recognise that the transformation of the chloroamine 
to the chloroanilides is merely a side-reaction, and that hydrolysis and 
reduction are the primary changes. His measurement of the rate of dis- 
5 Zeit. f. Physik. Chem., 1913, 82, 201. 
or 
