Bimolecular multistage diffusion-influenced chemical reactions proceeding from different sites in solutions. I. Rate constants.

Abstract

General matrix algebraic equations for calculating rate constants of multistage diffusion-influenced reactions (involving bimolecular exchange reactions as elementary stages) in liquid solutions that proceed from different active sites in the immediate vicinity of the contact of reactants have been obtained on the basis of the kinematic approximation developed by the authors earlier. The equations make it possible to express rate constants of any multistage multisite bimolecular reaction between non-identical reactants in terms of the defined reaction constants and stationary Green functions averaged over reaction sites and completely determined by molecular motion of reactants or their molecular groups. The asymptotic behavior of these rate constants as they attain their steady-state values on completion of the transient stage is established. It is shown that it coincides with the corresponding exact time asymptote. Calculations are made with some specific two-stage (three-channel) bimolecular reactions as an example.