Journal of Electroanalytical Chemistry, Vol.370, No.1-2, 259-267, 1994
Activation Enthalpy for Ligand-Bridged Electroreduction of Cobalt(III) Complexes in Mixtures of Water with Acetone
The activation enthalpy for the reduction of two pentaamminecobalt(III) complexes attached to a mercury electrode by thiophenecarboxylate ligands was evaluated from the temperature dependence of the unimolecular rate constants measured in a nonisothermal cell arrangement. The data obtained for the reactant with a bridge featuring uninterrupted conjugation support our previous opinion that the decrease of the rate constant on addition of acetone to the mixtures results from a decrease in the nuclear frequency factor owing to the overdamped solvent friction. The unimolecular frequency factors and the adiabaticity of the processes are discussed.
Keywords:ELECTRON-TRANSFER REACTIONS;SURFACE-ATTACHED REACTANTS;BINARY SOLVENT MIXTURES;METAL REDOX COUPLES;HETEROGENEOUS ELECTRON;POLAR-SOLVENTS;REACTION ENTROPIES;EMPIRICAL PARAMETERS;REDUCTION KINETICS;MERCURY-ELECTRODE