Rotating disc electrodes: the theory of chronoamperometry and its use in mechanistic investigations

Abstract

A general computational strategy is presented for the calculation of the chronoamperometric responses arising from potential-step experiments at rotating disc electrodes. The method is applicable to a wide range of electrode reaction mechanisms and theoretical results are given for single- and double-potential-step experiments for ECE, DISP1, DISP2, EC' and CE reactions. For the last, the treatment is extended to cover the case where reactants have grossly unequal diffusion coefficients. Steadystate behaviour is also deduced. The extent to which the various mechanistic pathways can be distinguished is identified and the necessary experiments defined.