DETERMINATION OF KINETIC-PARAMETERS FROM CHRONOAMPEROMETRIC DATA

An iterative method for evaluating the chronoamperometric curves of va rious electrochemical mechanisms (ECE, irreversible, quasi-reversible and CE mechanisms) is proposed. This procedure is able to extract the corresponding kinetic parameters even when the values of the diffusion coefficient and the effective area of the electrode are not known. Te sting of this procedure by means of simulated ideal data (free of any extraneous ''noise'') showed that the method is generally applicable. Application of this technique to Monte Carlo simulated data revealed t hat the proposed method is also able to extract kinetic parameters eve n when the faradaic data are considerably obscured by ''noise''. Final ly, the method was applied to experimental chronoamperometric data of the reduction of 4-nitropyridine-N-oxide at Pt/Bi(upd) (ECE mechanism) and tetrahydroxy-1,4-benzoquinone at Pt (irreversible mechanism) in a queous acid solutions and the corresponding kinetic parameters were de termined.