Analytical solution for Reverse Pulse Voltammetry at spherical electrodes: A remarkably sensitive method for the characterization of electrochemical reversibility and electrode kinetics

Reverse Pulse Voltammetry (RPV) is a powerful double pulse technique for kinetic studies. The theory of this technique for slow charge transfer processes at spherical electrodes is developed. An explicit analytical solution is deduced applicable to electrodes of any size, whatever the reversibility of the system and the length of the two potential pulses. From this solution we examine the influence on the RPV response of the electrode sphericity and the kinetics of the electrode process. It is shown that visual inspection of the curves provides immediate valuable information on electrochemical kinetics. Moreover, simple diagnosis criteria are established and general working curves derived for the quantitative extraction of the kinetic parameters and the formal potential. Some particularities in the morphology of the anodic branch of RPV curves for slow charge transfer processes when the second potential pulse is sufficiently large are also described. The merits of RPV as an exquisitely sensitive measure of electrochemical reversibility and electrode kinetics are advocated.