Electrochemical Studies at Elevated Pressures : Reaction Volumes of Some Fe(III/II), Co(III/II), and Ni(III/II) Couples in Aqueous Solution and in Acetonitrile
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Pressure dependence of the electrode potentials for various M<SUP>3+/2+</SUP> couples (M=Fe, Co, and Ni) was measured in aqueous solution and in acetonitrile with Ag/AgCl and Ag<SUP>+</SUP>/Ag reference electrodes. The reaction volumes of reference electrodes were estimated from the change in the partial molar volumes of Fe<SUB>ap</SUB><SUP>3+/2+</SUP> and Co (terpyridine) <SUB>2</SUB><SUP>3+/2+</SUP> couples, and the reaction volumes corresponding to the formation of M (II) from M (III), ΔV°<SUB>M</SUB>, were isolated. The applicability of the MSA model to the electrostrictive contribution to the reaction volumes was examined. It was shown that the MSA model explains the experimantally obtained reaction volumes well for the redox couples in solution, although the predicted interaction distances between the solute ion and solvent molecules are rather small.
- The Review of High Pressure Science and Technology
The Review of High Pressure Science and Technology 7, 1262-1264, 1998
The Japan Society of High Pressure Science and Technology