Kinetic study of the electron transfer process between Ru(NH 3) 5pz 2+ and S 2O 82− in water–cosolvent mixtures: a new component of reorganization energy

Abstract

The electron transfer process between Ru(NH 3) 5pz 2+ and S 2O 8 2− has been studied in different water–cosolvent mixtures. The results are explained assuming an additional component of the reorganization free energy of the solvent in the mixtures. This new component is caused by a translation of the solvent molecules and it is a consequence of the changes in the composition of the (at least) innermost solvation shell of the reactants produced by the electron transfer. An attempt to quantify this additional reorganization energy is made.