Cyclic voltammetry is widely used to investigate redox systems and is especially useful for determining electrode kinetic data. Experiments to obtain this data typically involve measuring the peak-to-peak separation as a function of voltage scan rate and applying appropriate theory. Experimental data are almost invariably measured using a digital potentiostat and as such the applied potential will have been varied in a series of discrete steps separated by a value Delta E-step. In this work, we calculate the error introduced by approximating a potential ramp as a staircase and consider how this insight may be used to ensure that electrode kinetic parameters extracted from experimental voltammetry so measured are accurate. (C) 2008 Elsevier B.V. All rights reserved.