Simulation of Square Wave Voltammetry of Three Step Redox Reactions on Spherical Electrodes

The theory of three step electrode reaction is developed for square wave voltammetry on stationary spherical electrodes. It was assumed that all electroactive species are solution soluble. The dependence of the response on the thermodynamic stability of intermediates, on the electrode radius and the scan direction is investigated for the fast and reversible electrode reactions. The criterion of reversibility is postulated. Furthermore, the influence of electrode kinetics on the response was calculated for the cathodic and anodic scan directions. The difference in responses caused by the variation of scan direction is an indication of multiple electron transfers. The method for the estimation of transfer coefficient is demonstrated.