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 re duction of a substrate proceeds only via intramolecular electron trans fer to the substrate molecule when it is bound to reduced catalyst mol ecules present in a single monolayer on the electrode surface. The dep endences of the voltammetric responses on the equilibrium constant for the formation of the catalyst-substrate complex, the rate of its form ation and the rate of intramolecular electron transfer are discussed. Procedures are described for estimating the rate constant for the intr amolecular electron transfer reaction and for discriminating between m echanistic possibilities.