From the bulk electrolyte solution to the electrochemical interface

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Abstract

This paper is aiming at presenting some relevant contributions of Jean-Pierre Badiali during the first ten years of his growing scientific activity. This presentation does not contain new materials but is based on a number of selected papers published in the seventies, a part of them written in French. The presentation is organized around three points. The first point, corresponding to his PhD thesis, is concerned with the study of ion-solvent and ion-ion interactions in a solution using complex dielectric permittivity measurements in the Hertzian and microwave frequency range. The second one is concerned with an analysis of the ion pair absorption band observed in the far infrared region in terms of an interionic potential energy. The third one is concerned with the metal-solution interface and his significant advances on (i) the Lippmann equation linking electrocapillary and electrical measurements and (ii) the contribution of the metal to the differential interfacial capacity.

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Interactions and dynamics in electrolyte solutions by dielectric spectroscopy.

Richard Buchner, Glenn Hefter (2009)

Despite its immense abilities to quantify many aspects of ion-ion and ion-solvent interactions, dielectric relaxation spectroscopy (DRS) has long been neglected as a tool for the investigation of the structure and dynamics of electrolyte solutions. The reasons for this are briefly discussed and it is shown that many of the difficulties associated with this technique have been overcome in recent years by technological developments. Representative applications of DRS to the investigation of ion solvation and ion association in electrolyte solutions of chemical, industrial, geochemical and biological interest, including room temperature ionic liquids and polyelectrolyte systems, are discussed. The advantages of linking DRS measurements to information obtained from other experimental techniques and from computer simulations are highlighted.