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 chemical reactions

This paper describes a general simulator for square wave voltammetry (SWV) based on the procedures developed for the DigiSim simulation program. The results of test simulations for a simple charge transfer mechanism, two first-order and one second-order mechanism are presented. The accuracy of the simulations is checked by comparison with available analytical solutions. The effect of noise (and/or the effect of inaccuracies produced by the simulation algorithm) on kinetic parameters determined by fitting experimental voltammograms to simulated ones is discussed for each mechanism. The treatment of IR-drop and double layer effects on SWV by means of digital simulation is demonstrated for a quasi-reversible charge transfer mechanism and verified by measuring the square wave response of a reference system in the presence of different levels of uncompensated ohmic resistance.