Electrochemical electron transfer: a diffusion-reaction equation approach

Abstract

We consider electrochemical electron transfer reactions, where the rate is limited by the electron transfer process. We suggest a diffusion-reaction equation approach to the problem. The electron transfer from an ion in solution to the metal would occur as soon as the energy of the orbital on the ion crosses the Fermi energy of the metal. The electron transfer is assumed to occur at a constant rate, if this is satisfied. We suggest a new steady-state approach to the evaluation of the rate constant from the diffusion-reaction equation. The approach is able to take into account the deviation of the reactant population from the equilibrium one and thus goes beyond the results due to Morgan and Wolynes.