Abstract
The cyclic voltammetric behavior of metalloporphyrin species containing different substituents was investigated by thin-layer electrochemistry. In this paper, the two-step electron transfer between zinc porphyrin species containing different substituents in nitrobenzene and Fe(CN)(6)(4-) in the aqueous phase was studied. The bimolecular rate constants for the two-step electron transfer reactions were obtained simultaneously by thin-layer theory. When we use the thin-layer theory to calculate the kinetics constants, the process of consecutive electron transfer is considered to be complete. However, this was not the case; by comparing the data that are calculated by Faraday's law of electrolysis and the theory based on thin-layer cyclic voltammetry for consecutive electron transfer across the interface between two immiscible electrolyte solutions, the correction coefficient was obtained. The kinetics constants of multistep interfacial bimolecular reactions can be further calculated with more precision.