An improved algorithm for the numerical simulation of cyclic voltammetric curves affected by the ohmic potential drops and its application to the kinetics of bis(biphenyl)chromium(I) electroreduction

摘要

Previously published algorithms for the modeling of cyclic voltammetric curves affected by ohmic potential drops, in terms of the classical explicit finite differences method, are discussed briefly. A fast and efficient numerical procedure suitable for such simulations is described. This approach exhibits high numerical stability for both high scan rates and large uncompensated ohmic resistances. The procedure is based on the calculation of the faradaic current as a root of the non-linear equation, with a simultaneous calculation of the capacitive current. Comparison of the cyclic voltammograms obtained using this method with those calculated using alternative published procedures proves its validity. For comparison with the experimental data, the cyclic voltammetric response for the reduction of bis(biphenyl)chromium(l) tetraphenylborate in N,N-dimethylformamide is shown and the kinetic parameters of this process are fitted. Compared to earlier modelings, they show better concordance with the results of studies at microelectrodes. In conjunction with earlier successful applications of the analogous numerical procedure to the realistic modeling of electrochemical oscillations and multistability at a constant external voltage, the algorithm presented appears to be one of the most applicable methods of calculation of the electrochemical responses affected by the ohmic potential drops. (C) 2004 Elsevier B.V. All rights reserved.