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A perturbation solution of an assumed Boltzmann-type equation for bimolecular chemical reactions in a homogeneous gas phase consisting of molecules with or without internal degrees of freedom, leads to the conclusion that the law of mass action as well as the usually assumed phenomenological rate expressions for chemical reactions, is strictly valid only in lowest order of the perturbation. Higher order perturbations introduce an affinity and time dependence in the rate coefficient and the law of mass action becomes inadequate to the extent of the contribution of the effects of the perturbations. A transition state formation of rate coefficients for bimolecular gas-phase reactions is presented under less restrictive sufficient conditions than reported previously.
Ross et al. (Sat,) studied this question.