Electrochemistry at liquid/liquid interfaces: methodology and potential applications
Introduction
Electrochemistry at the interface between two immiscible electrolyte solutions is a rather new topic of electrochemistry, which has been present at every meeting of the International Society of Electrochemistry (ISE) for the last decade.
The first experiments in the field were reported at the end of the last century, but it was only in the 1970s that the subject enjoyed a new era of growth. The pioneer of this renewed interest in the field was Claude Gavach in France who started to apply electrochemical methods to study ion transfer reactions [1], [2], [3], [4].
Then, the relay was taken by the Heyrovsky Institute in Prague under the influence of Professor Koryta [5], [6], [7], [8], [9], [10], [11] former president of the ISE (1985–1986). It was around this time that the acronym ITIES (interface between two immiscible electrolyte solutions) was coined and has remained ever since. When the ISE meeting was held in Prague in 1990, a plenary lecture entitled: ‘Electrochemical Processes at the Interface between Two Immiscible Solutions of Electrolytes’ was given by Professor Senda who has been the pioneer of the field in Japan. This plenary lecture was followed by the first ISE micro symposium on Immiscible Electrolytes with Professor T. Kakiuchi as Chairman.
In this review article, we shall first recall the fundamental aspects of charge transfer reactions at the ITIES and we shall present our views on some potential applications.
Section snippets
Interfacial structure
The interface between two solvents is by nature a molecular interface with its own dynamics. It is characterised by the fact that it is difficult to define an interfacial structure or thickness as the time scale becomes a parameter of the definition. Is the interface sharp or diffuse? The answer to this question is timescale dependent.
From an experimental viewpoint, capillary wave measurements by X-ray or neutron scattering [12], [13], [14], [15], [16], [17] did not provide yet a proper
Amperometric sensors and ionodes
Ion selective electrodes rely on ion or facilitated ion transfer reactions to establish a potential difference that depends on the concentration of the target ions. Potentiometric sensors depend on thermodynamic equilibria and can therefore be used to measure activities. Amperometric sensors on the other hand depend on diffusion controlled mass transfer and are therefore proportional to the concentrations. Considering that both ion transfer and assisted ion transfer reactions are reversible,
Conclusion
If the field of electrochemistry of liquid/liquid interfaces has progressed rapidly over the last couple of decades, many issues are still a matter of debate.
From a theoretical viewpoint, the key aspects of potential distribution remain the major challenge. Without a good modelling of the potential distribution, in the absence or in the presence of specific adsorption, it will be difficult to progress in the kinetics analysis of charge transfer reactions. However, considering that most transfer
Acknowledgements
The authors want to express their gratitude to Professor Z. Samec from the Academy of Sciences of the Czech Republic and to Professor T. Kakiuchi from the Kyoto University of Japan for fruitful discussions and helpful comments on this paper.
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