Journal of Physical Chemistry, Vol.99, No.4, 1311-1316, 1995
Solvent Effects in the Electroreduction of Ethylenediaminetetraacetatochromium(III) at a Mercury-Electrode
The kinetics of the one-electron reduction of ethylenediaminetetraacetatochromium(III) have been studied by convolution potential sweep voltammetry in different solvents at a mercury electrode. The observed electron transfer rate constants and transfer coefficients have been corrected for double-layer effects using experimental double-layer data. The dependence of the diffusion coefficients, standard potentials, and corrected electron transfer rates on solvent properties has been interpreted within the context of contemporary theory. It has been shown that the standard potential is a linear function of the solvent acceptor number. The variation of the logarithm of the corrected standard rate constants is correlated to the acceptor number of the solvent and the solvent longitudinal relaxation time. No evidence was found for incorporation of the solvent as a ligand for the reactant.
Keywords:MEAN SPHERICAL APPROXIMATION;CHROMIUM(III) COMPLEXES;APROTIC-SOLVENTS;EDTA;REDUCTION;IONS;CONVOLUTION;BEHAVIOR;KINETICS;LIGANDS