Theoretical study of a surface electrode reaction preceded by a homogeneous chemical reaction under conditions of square-wave voltammetry

A theoretical model of a surface electrode reaction coupled with a preceding chemical reaction (surface CE electrode mechanism) is theoretically studied under conditions of square-wave voltammetry. The position and the shape of the theoretical voltammograms are function of the redox kinetic parameter lambda = k(s)/f where k(s) is the standard electron exchange rate constant and f is the frequency of the potential modulation, chemical kinetic parameter z = k(f)+k(b)/f, where k(f) and k(b) are the forward and backward rate constants of the preceding chemical reaction, respectively, and the equilibrium constant of the chemical reaction K. The influence of all these parameters to the theoretical square-wave voltammograms is investigated in detail. A theoretical methodology for estimation of the kinetic and thermodynamic parameters of the electrode mechanism is proposed. (c) 2005 Elsevier B.V. All rights reserved.