An extension of the theory of chronoamperometry for the catalytic ErevC & PRIME;rev reaction mechanism at a electrode

An extension is presented, of the theory of a chronoamperometric experiment for an ErevC & PRIME; rev catalytic reaction mechanism with a reversible charge transfer and a pseudo-first order reversible homogeneous reaction at a planar electrode. Diffusion transport is assumed. The extension refers to the case when (simultaneously) diffusion coefficients of the members of a redox couple are unequal, and the homogeneous reaction is reversible. For such a case no analytical nor semi-analytical solutions were available thus far. Non-trivial expressions, involving doubly nested complex square roots, are derived for the Laplace transform of the nonlimiting Faradaic current. They are inverted numerically. The results obtained should be of interest in the studies of homogeneous redox catalysis for electrochemical energy sources.

Automated summary

This study presents an extension of the theory of a chronoamperometric experiment for a reversible charge transfer and a pseudo-first order reversible homogeneous reaction in a catalytic mechanism. Diffusion transport is assumed on a planar electrode. The study focuses on the case when the diffusion coefficients of the redox couple members are unequal and the homogeneous reaction is reversible. The derived non-trivial expressions for the Laplace transform of the non-limiting Faradaic current involve doubly nested complex square roots and are inverted numerically. The results obtained are of interest in the studies of homogeneous redox catalysis for electrochemical energy sources.