Calculation of cyclic voltammetric responses for the catalytic reduction of substrates via intramolecular electron transfer within a catalyst-substrate complex formed on electrode surfaces

Cyclic voltammetric responses are calculated for the case where the reduction of a substrate proceeds only via intramolecular electron transfer to the substrate molecule when it is bound to reduced catalyst molecules present in a single monolayer on the electrode surface. The dependences of the voltammetric responses on the equilibrium constant for the formation of the catalyst-substrate complex, the rate of its formation and the rate of intramolecular electron transfer are discussed. Procedures are described for estimating the rate constant for the intramolecular electron transfer reaction and for discriminating between mechanistic possibilities.