Low-Temperature Electrochemistry II. Evaluation of Rate Constants and Activation Parameters for Homogeneous Chemical Reactions Coupled to Charge Transfer

A simple method is presented for analyzing the temperature dependence of pseudo first order chemical reaction(s) coupled to a heterogeneous charge transfer process. The temperature dependent factors associated with the mass transport and heterogeneous charge transfer processes have been specifically separated from those pertaining to the coupled chemical reactions. The following kinetic cases have been treated in some detail: EC, simple ECE, catalytic, 1/2 regeneration scheme, and the moee general ECEC decay scheme. Single and double potential step and cyclic voltammetry methods have been treated theoretically via finite difference or analytical solutions and their potential utility for analyzing the pertinent rate constants is discussed.