Characterization of follow-up chemical reactions by reverse pulse voltammetry. An analytical solution for spherical electrodes and microelectrodes

The study of the EC mechanism by reverse pulse voltammetry (RPV) is assessed in this paper. RPV is a pulse technique very well suited to the investigation of the products of an electrode process and in particular the quantitative characterization of the homogeneous chemical reaction involving the electrode product(s).A readily applicable analytical solution for the RPV response of the EC mechanism is deduced for spherical electrodes of any size. From the solution the influences of the rate constants, equilibrium constant, electrode radius and pulse times are analyzed. This facilitates the use of optimum experimental conditions for experimental studies. Further, criteria for the identification of EC processes and procedures for their quantitative analysis are given.

► An analytical solution for EC mechanism in reverse pulse voltammetry (RPV) is deduced. ► The solution is valid for (hemi)spherical electrodes of any size. ► Influence of rate and equilibrium constants, electrode size and pulse times are shown. ► Simple criteria for the detection of follow-up reactions through RPV are established. ► The chemical reaction can be characterized from oxidative limiting current of RPV curves.