J . Am. Chem. SOC.1990, 112,1952-1951
7952
Diffusion and Disequilibrium for Rapid Bimolecular Reactions in Solution: Influence of the Back-Reaction Joel Keizer Contribution from the Institute of Theoretical Dynamics and Department of Chemistry, University of California, Davis, California 9561 6 . Received February 20, 1990
Abstract: The influence of reversibility and diffusion on the rate constant of rapid bimolecular reactions in solution is explored with statistical nonequilibrium thermodynamics. For reactions with stoichiometry A + B c C, we find that in dilute solution the Smoluchowski-Collins-Kimball steady-state expression for the rate constant is valid only when the steady state is sufficiently far from equilibrium (as determined by the criterion AG
