The kinetics of the oxidation of Fe(bpy)2+3 by S2O2−8 have been studied in water and different water‐cosolvent mixtures. The cosolvents used were methanol t‐butyl alcohol, ethane 1,2‐diol and glycerol. The results are explained assuming an additional component of the reorganization free energy of the solvent in the mixtures, caused by dynamics of the changes in the composition of the (at least) innermost solvation shells of the reactants produced by the electron transfer. A quantitative estimation of this component is attempted.
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