709 
of para bromine phenyldimethyl allyl ammonium bromide, besides 
from the study of the equilibria between the keto- and enol forms 
of the acetyl acetic ester made by Kurt Mrwer’). In spite of various 
attempts the explanation of this phenomenon has not yet been found. 
Yet it seems to me that the solution might be given in the follow- 
ing way. 
For this purpose we start from the equation: 
Fi BORER egg, et re, aay 
When with constant P and 7’ we now differentiate with respect 
to n,, we get: 
dZ dE dH dV 
A EE teen | ee EGR i Nea erie 
dn, / P-T dn, /P.1 dn, pr dn, /P.r 
dZ Er 4 
Fa i ama ayy Sone te 
It should further be noticed that as we consider solutions here, 
dV 
=| is very small. 
dn, )pr 
With regard to P it may be said that when the solvent has a 
slight vapour tension and the experiment is made in vacuum, this 
quantity is very small too. But also when an open vessel is 
r 
Now 
. : | 
used, and P is 1 -atm., the term P bey is so small, that we 
NJ P.T 
may safely neglect it by the side of the others. 
Just as in general the entropy may be split up into a concen- 
tration entropy and a concentration term, we can write here for 
the entropy increase when 1 gr. mol. is added reversibly : 
dH LH 
ea (5) NN 
dn, /P.T dn. JP.r 
Gl 
so that we get: 
LE lH 
= Gel rn ee + RT ln C, ig eM a (5) 
dn, )P.T dn, )P.T 
Ci 
Now on summation over all reacting components, we get: 
LE dll 
= PE == Sv (a) — Tp a + RT ZrinC, . (6) 
PT dn, ) PT 
1 
dn, : 
If we now put: 
LE LH 
(=) == KE and ee) =H, 
dn, / P.v dn,/P.T ga. 
1) Ber. 47, 832 (1914), 
