TRANSFORMATION OF AROMATIC NlTROAMlNES, ETC. 



91 



Experiment A. — p-chloroacetylchloroaminobenzene = - 025 gm. mol. 

 per litre. HCl = 0-025 gm. mol. Medium, 65 per cent, acetic acid. 



Table III. 



Experiment B. — As in experiment A, but in addition 1 gm. mol. 

 proportion of 2 : 4-dichloroaeetanilide. 



Table IV. 



In order to understand more fully the influence of the anilide which 

 is produced on the conversion of the chloroamine, the effect of the 

 presence of a second anilide on the equilibrium between chlorine and 

 anilide must be considered. 



Equilibrium between Chlorine and Anilide in Systems containing more than 



one Anilide. 



If one gram molecular proportion of an anilide, B, is added to a 

 system prepared from one molecular proportion of chloroamine of 

 anilide A, and one molecular proportion of hydrochloric acid, a rapid 

 readjustment occurs to a final equilibrium which is in accord with the 

 two equations : — 



[Chloroamine A] [HC1] 2 / [Anilide A] [Cl 2 ] = K A . 



[Chloroamine B] [HCl] 2 /[Anilide B] [C'„] = K D . 



Since [C1J and [HC1] - are identical in the two equations, we have: — 



Chloroamine A Chloroamine B _ ^ ,' K 



Anilide A 



Anilide B 



In 65 per cent, acetic acid, the [CLJ is generally negligible, and hence 

 the relative amounts of each anilide and chloroamine can be easily 

 calculated. When the [C1J has an appreciable value, the calculations 

 of the composition of the system involves the solution of a quintic 

 equation. 



In 90 per cent, acetic acid and above the equilibrium equation 

 contains the first instead of the second power of the concentration of 

 the hydrochloric acid, and the calculation of the composition is by 

 means of a cubic equation which has been solved. Thus in a system 

 made up from molecular proportions (0-025 gm. mol. per litre) of 

 s-tribromoacetanilide, hydrochloric acid and acetylchloroamino-p-nitro- 

 benzene (or, from p-nitroacetanilide, hydrochloric acid and acetyl- 



