Diffusion-influenced reactions and normal solutions of the Boltzmann equation

Abstract

The influence of the boundary layer in the vicinity of a reactive sink on the chemical rate coefficients of diffusion-influenced reactions is studied using kinetic theory. It is argued that normal solutions to the Boltzmann equation break down at first order in P−1e, where Pe is the thermal Peclet number, for the reaction problem. When the effects of the kinetic boundary layer are consistently treated to first order in P−1e the rate coefficient which follows from the diffusion equation with the radiation boundary condition is obtained. The importance of properly treating terms of order P−1e is discussed and parallels with Stokes’ law calculations are described.