A study of electrode kinetics by global analysis of a single electrochemical experiment

An efficient method is presented for analyzing electrochemical processes controlled by diffusion and by the kinetics of heterogeneous electron-transfer. The method is based on a three-dimensional concept and has the advantage of utilizing all the data available from a voltammetric experiment. The three-dimensional method provides a useful diagnosis of whether Butler-Volmer kinetics is appropriate and, if so, for calculating the standard heterogeneous charge transfer rate constant, reversible halfwave potential, diffusion coefficient and charge transfer coefficient. Experiments on the [Cr(CN)₆]^3-+e^-[Cr(CN)₆]^4- reaction using cyclic voltammetry are reported and the parameters so determined are shown to agree with literature values.