Supplement to the Theory of Normal Pulse Voltammetry and Its Application to the Kinetic Study of Methanol Oxidation on a Polycrystalline Platinum Electrode

Abstract

The theory of normal pulse voltammetry (NPV) for complex multistep multielectron transfer processes on a plane electrode was advanced and applied to the completely irreversible process of methanol oxidation to formic acid in the potential range from 0.3 to 0.8 V versus Ag/AgCl. The kinetic parameters for this process, such as the standard rate constant (k0) and anodic transfer coefficient (alpha) for this irreversible heterogeneous electron transfer process at the electrode/solution interface and apparent diffusion coefficient (D(app)) for the homogeneous charge transfer process within liquid film near the electrode surface, were obtained with NPV theory from analyzing the dependence of current-potential curves upon the sampling times. The results showed that this process is truly a very slow, completely irreversible kinetic process, as k0 is in the order of 10(-9) cm/s for the rate-determining step. The values of k0 and D(app) decreased with the increase of methanol concentration, while alpha was independent of the concentration of methanol and its value was 0.35 +/- 0.05. Theoretical fitting is very consistent with the experimental data.