311 - A new model of membrane transport: electrolysis at the interface of two immiscible electrolyte solutions

Abstract

A simple membrane model is the interface between water and an organic liquid immiscible with water, with a strongly hydrophilic electrolyte dissolved in the aqueous phase and a strongly hydrophobic electrolyte in the organic phase. This interface can be electrochemically polarized in the same way as the interface electrode |electrolyte solution using various modes of voltammetry or the galvanostatic method. A four-electrode potentiostatic system is required for such studies. An electrolyte dropping electrode, analogous to Heyrovsky's DME, was also constructed. The voltammograms fully resemble those obtained with metallic electrodes. The faradaic proceses studied so far are mainly connected with the transfer of hydrophobic ions across the interface. These processes are quite rapid and the half-wave potential of a particular ion is related to its standard Gibbs transfer energy. Observed electron-transfer effects model redox processes at membranes. Macrocyclic ionophores facilitate transfer of alkali metal ions across this interface. Very fast ion transfer as well as complex formation was observed in the systems under investigation so that, generally, the diffusion of the ionophore toward the interface and of the complex into the organic phase is the rate-controlling step, no surface reaction retarding the overall process. Apart from the investigation of membrane processes, this approach can be used for elucidation of processes in ion-selective electrodes and in phase-transfer catalysis.