engleski

Square-wave voltammetry of quasi-reversible CE reactions at spherical microelectrodes

A mathematical model for the CE mechanism in which the chemical together with electrochemical reactions are quasi-reversible at the surface of spherical macro and micro-electrodes is presented for the case of square-wave voltammetry. The analysis of voltammometric responses consideres the influence of rate and equlibrium constants, together with the electrode radius, and their dependence on the square-wave frequency (f). Both kinetics and the sphericity effects act synergistically on the electrochemical response. Also, the apparent electrode sphericity and the reversibility of the chemical as well as the electrochemical reactions are jointly affected by the variation of f. The model allows the analysis of the more realistic and complex electrochemical system that requires not only the dependence of experimental responses on f, but also their fit with theoreticla voltammograms, in order to provide some useful mechanistic information.

square-wave voltammetry; simulations; coupled chemical machanistic studies; spherical microelectrodes

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