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Vol.
27 No. 2
March-April 2005
Electrochemistry at the Interface between Two Immiscible Electrolyte Solutions
(IUPAC Technical Report)
Z. Samec
Pure and Applied Chemistry
Vol. 76, No. 12, pp. 2147–2180 (2004)
An interface between two immiscible electrolyte solutions (ITIES) is formed between two liquid solvents of a low (ideally zero) mutual miscibility, each containing an electrolyte. One of these solvents is usually water, and the other one is a polar organic solvent of a moderate or high dielectric permittivity, such as nitrobenzene or 1,2-dichloroethane, which allows for at least partial dissociation of dissolved electrolyte(s) into ions. Electrochemical processes at ITIES have attracted a great deal of interest for two reasons. First, the biomimetic features of these processes have been a concern for over a century. Second, the electrochemical reaction at ITIES represents an essential aspect of various practical applications in chemistry, including electroanalysis, phase-transfer catalysis, ion extraction, and electrocatalysis.
This document provides an inventory of theoretical and methodological concepts in electrochemistry at the interface between two ITIES. Definitions of basic relationships are given, together with recommendations for the preferred symbols, terminology, and nomenclature. Methods of study of ITIES are briefly described, current experimental problems are indicated, and representative experimental data are shown. The practical applications of electrochemistry at ITIES are summarized.
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