Electrochemistry at Very High Potentials: Oxidation of the Rare Gases and other Gases in Non-Aqueous Solvents at Ultramicroelectrodes

The accessible potential region in a conventional electrochemical experiment is limited by the oxidation or reduction of the solvent or supporting electrolyte. It is impossible to study the redox reactions of species with very low electron affinities or high ionization potentials by ordinary electrochemical methods. It has been demonstrated recently, however, that by reducing the electrode dimensions to very small values, however, the quantity of supporting electrolyte necessary to develop the electrical double layer can be reduced to low levels. It has thus been possible to study electrode reactions in highly resistive media; these include the oxidation of ferrocene in acetonitrile without purposely added supporting electrolyte, oxidation of chromium hexacarbonyl in pure dichloromethane, oxidation of aromatic hydrocarbons in pure benzene, oxidation ferrocene in pure acetone down to 95 C.