Excluded Volume Effects on the Kinetics of Diffusion‐influenced Reversible Bimolecular Reactions: A + B ⇄ C + B

Abstract

We propose a new approach to treat the kinetics of diffusion‐influenced reversible bimolecular reactions and apply it first to the reactions of the type A + B ⇄ C + B. For this type of reactions with some provisions, Gopich et al. showed that the relaxation kinetics can be described exactly in the same way as the reactant decay in an “equivalent” irreversible A + B → C + B reaction. In this article, we will show that the same relationship can be derived in a very elementary way by using a new approach based on the hierarchical kinetic equations governing the reduced distribution functions of reactant molecules. Because our analysis does not require the assumption that the reactants are interaction‐free point particles, the effect of excluded volumes among the reactants can also be evaluated by utilizing the result derived for an irreversible reaction.