A fallacy in some interpretations of the quasi-thermodynamics of reaction kinetics

Abstract

The fact that experimentally determined 'volumes of activation' and 'entropies of activation' obey a relationship that is formally similar to one of Maxwell's thermodynamic relations is a mathematicalconsequence of the definitions of those quantities. Contrary to suggestions in the literature, it provides no evidence in support of the quasi-thermodynamic and equilibrium assumptions of the transition state theory.