Digital simulation with the fast implicit finite difference (FIFD) algorithm - Part 5: Digital simulations of square wave voltammetry for any user defined electrochemical mechanism comprising first- and second-order chemicalreactions

This paper describes a general simulator for square wave voltammetry (SWV) based on the procedures developed for the DigiSim simulation program. The r esults of test simulations for a simple charge transfer mechanism, two firs t-order and one second-order mechanism are presented. The accuracy of the s imulations is checked by comparison with available analytical solutions. Th e effect of noise (and/or the effect of inaccuracies produced by the simula tion algorithm) on kinetic parameters determined by fitting experimental vo ltammograms to simulated ones is discussed for each mechanism. The treatmen t of IR-drop and double layer effects on SWV by means of digital simulation is demonstrated for a quasi-reversible charge transfer mechanism and verif ied by measuring the square wave response of a reference system in the pres ence of different levels of uncompensated ohmic resistance. (C) 2001 Elsevi er Science B.V. All rights reserved.