1109 
Chemistry. — “On velocities of reaction and equilibria.” By Dr. F. 
E. C. Scnerrer. (Communicated by Prof. A. F. HorrLrMAN). 
(Communicated in the meeting of January 25, 1913) 
1. In a previous paper in conjunction with Prof. Konnstamm’). 
I discussed the relation between the velocity of reaction and the 
thermodynamic potentials of the substances participating in the 
reaction. It then appeared that the velocity of a reversible reaction 
may be given by the expression: | 
de in. RE 
a ay ) AAE ae (1) 
in which u, represents the sum of the molecular thermodynamic 
potentials of the substances of the tirst member, «,, the sum of 
the potentials of the substances of the second member of the reaction 
equation. The constant C accounts for the choice of the unities of 
concentration and time, and has therefore the same value for all 
reactions when the same unities are used. We have shown that the 
function JF” possesses the same value for both partial velocities, that 
it is independent of time and volume, and that it is equally in 
relation with both systems before and after the reaction. As further, 
quantities of energy and entropy must occur in the quantity /’, we 
have tried to make clear that in general in case of chemical reac- 
tions “intermediate states” mnst be assumed, and we have pronounced 
the possibility that the energy and entropy of these transitional states 
are the only quantities dependent on the nature of the substances, 
which occur in the function /. By entropy we mean here the 
entropy “free from concentration”; we have namely shown in our 
cited paper that # is independent of the concentrations in case of 
gas reactions and reactions in dilute solutions; hence it can contain 
no terms originating from GiBBs’s paradox. The value of the two 
partial velocities would therefore be determined according to this 
by the difference in energy and entropy (free from concentration) 
of the reacting substances and the transitional state. This in my 
opinion obvious assumption comes to this that both the difference 
of energy and the difference of entropy between the first and the 
second system must be split up into two parts; the first part then 
gives the differences of energy and entropy of the first system with 
1) These Proc. Jan. 1911. p. 789. 
