Abstract
AbstractThis article outlines the electrochemical methodology at the interface between two immiscible electrolyte solutions (ITIES). The fundamental concepts of the thermodynamics in biphasic systems are presented in order to show how ions are distributed between the two adjacent phases and hence, how a Galvani potential difference is established at an ITIES. Polarizable and nonpolarizable ITIES are then characterized, and it is further evidenced that the classical electroanalytical methodology at a solid electrode can be directly transposed to the ITIES, thereby allowing reversible charge‐transfer reactions to be easily monitored and interpreted.This theoretical approach is completed by a review of the analytical methods used at ITIES, namely cyclic voltammetry (CV), hydrodynamic methods, spectroscopic techniques, and micro‐ and nanointerfaces (which are the biphasic analogs of micro‐ and nanoelectrodes). The last part deals with the practical applications that electrochemistry at ITIES has attracted during the past decades in the development of amperometric and coulometric ion sensors and detectors, detection of macromolecules, extraction of metal ions by interfacial formation of a complex, and assessment of the properties and lipophilicity of ionizable drugs.
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