Effect of brownian diffusion on chemical kinetics

Abstract

Abstract A new method of theoretical prediction of the kinetic rate constants of fast chemical reactions in solutions is presented. It takes into account the effect of finite diffusive displacements of the reacting molecules. The approach is based on the solution of the steady‐state Fokker–Planck equation by the moments method of Grad developed in the theory of coagulation of aerosol particles. A comparison of the predicted rate constants with the experimental data provided by Schuh and Fischer for the self‐reaction of tert ‐butyl radicals in n ‐alkanes shows a good correspondence.