The role of diffusion in bimolecular solution kinetics

Abstract

An appropriate boundary condition is derived which permits both the bimolecular association and dissociation steps to be simultaneously treated within the framework of the theory of Smoluchowski, Debye, and Collins, and Kimball. Kinetic theory expressions are derived for the intrinsic rate constants. The transient case of the suddenly switched-on reaction is considered as well as the suddenly perturbed equilibrium, but only the time dependence of the rate constants is obtained. The frequency response spectrum for a diffusion-controlled reaction is obtained in the linear approximation and compared with the corresponding Debye relaxation spectrum.