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. (C) 2012 Elsevier Ltd. All rights reserved.