Electrode reactions of metal complexes in solution at high pressures

High pressure electrochemical studies are potentially dangerous and less immediately implemented than conventional investigations. Technical obstacles related to properties of the working electrode material, preparation of its surface, availability of suitable reference electrodes, and the need for specially designed high pressure equipment and cells may account for the relative lack of experimental data on electrochemistry at high pressures. However, despite the stringent requirements for system and equipment stability, significant developments have been made in recent years and the combination of electrochemical methods with high hydrostatic pressure has provided useful insights into the thermodynamics, kinetics, and other physico-chemical characteristics of a wide range of redox reactions. In addition to fundamental information, high pressure electrochemistry has also lead to a better understanding of a variety of processes under non-classical conditions with potential applications in today's industrial environment from extraction and electrosynthesis in supercritical fluids to measurement of the pH at the bottom of the ocean. The purpose of this article is to detail the experimental pressurizing apparatus for electroanalytical measurements at high pressures and to review the relevant literature on the effect of pressure on electrode processes and on the properties of aqueous electrolyte solutions.

Electrochemistry at High Pressures: A Review

The measurement of molar volume changes of redox reactions using high-pressure voltammetry

The effect of hydrostatic pressure on the 1-e- reductions of acetophenone (AP) and nitrobenzene (NB) in the absence of an inert solvent is reported. Steady-state voltammetric responses for these re...

Electrochemistry of Organic Redox Liquids at Elevated Pressures

Analytical electrochemistry: theory and instrumentation of dynamic techniques

The effects of high hydraulic pressures on electrode reactions are complex because of (i) the variation of reference electrode potentials with pressure so that only an apparent volume of activation can be directly measured experimentally, and (ii) dependence of coverage by adsorbed intermediates, such as H, with pressure. Methods of dealing with these problems are treated and the significance of measured apparent volumes of activation for the hydrogen evolution reaction is discussed in terms of the nature of the transition state for proton transfer and neutralization. The negative true volumes of activation found for the cathodic evolution reaction under some conditions are attributed to increasing electrostriction of the proton in the complex as the transition state is formed. The significance of applications to ionic redox reactions is pointed out where pressure effects may be able to distinguish activation associated with long‐range Born polarization from that associated more specifically with reorganization of the primary solvation shell or inner coordination sphere of ions.

Significance of Effects of High Pressure on Kinetics of Electrode Reactions I . Applications to Transition States in Hydrogen Evolution Reaction Mechanisms

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Significance of Effects of High Pressure on Kinetics of Electrode Reactions I . Applications to Transition States in Hydrogen Evolution Reaction Mechanisms