ITIES

Abstract: The kinetics of the electron transfer and ion transfer at the interface between two immiscible electrolyte solutions (ITIES) were probed directly by scanning electrochemical microscopy (SECM). The liquid/liquid (Le., waterhitrobenzene) interface appeared to be sharp and wave-free on the submicrometer scale. The use of SECM allowed the electron transfer between ferrocene species in nitrobenzene and other redox species in the aqueous phase to be quantitatively separated from the ion transfer processes. The rate constants were extracted from the dependence of the steady-state current at a micrometer-sized tip electrode on the distance between the tip and the phase boundary by comparison to theoretical working curves. In some experiments, the ultramicroelectrode tip penetrating the ITIES trapped a micrometer-thick layer of water inside the nitrobenzene, forming a thin-layer cell.

Abstract: This document provides an inventory of theoretical and methodological concepts in electrochemistry at the interface between two immiscible electrolyte solutions (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

Abstract: Equilibrium Electric Potential Between Two Immiscible Electrolyte Solutions, T. Kakiuchi Distribution Potential Polarizability of the Liquid-Liquid Interface Nonpolarized ITIES and Reference Potentials in Organic Phases Free Energy of Coupling of Ion Transfer and Electron Transfer Conclusions References Volta and Surface Potentials at Liquid/Liquid Interfaces, Z. Koczorowski Introduction Electrified Liquid-Liquid Interfaces and Their Electrical Potentials Volta Potential and Voltaic Cells Voltaic Cells with Water/Nonpolar Liquid Interfaces Voltaic Cells with Immiscible Electrolyte Solution Interface Experimental Methods of Investigation of Voltaic Cells Final Remarks References Ion Solvation, Y. Marcus Introduction The Relevant Properties of Ions The Relevant Properties of Solvents Quantities Describing Ionic Hydration Transfer of Ions into Non-Aqueous Solvents Preferential Ion Solvation in Mixed Solvents References Adsorption Isotherms and the Structure of Oil/Water Interface, V.S. Markin and A.G. Volkov Introduction Surface Solution Model Analysis of the Generalized Frumkin Isotherm Classical Isotherms as a Special Case of the Generalized Adsorption Isotherm Adsorption Isotherm and the Structure of Interphase Conclusion References The Electrical Double Layer at Liquid-Liquid Interfaces, A. Watts and T.J. VanderNoot Introduction Models of Electrolytes and Double Layers Simulations of Solvents and Interfaces Experimental Methods Conclusions References Second Harmonic Generation at Liquid-Liquid Interfaces, P.F. Brevet and H.H. Girault Introduction Historical Overview Theory Experimental Apparatus Surface SH Origin from Neat Liquid-Liquid Interfaces Molecular Orientation at Liquid-Liquid Interfaces Interfacial Chemical Equilibrium Dynamics at Liquid-Liquid Interfaces Surface Sum-Frequency Generation Conclusion References Quantum Theory of Charge Transfer, Y.I. Kharkats and A.M. Kuznetsov Physical Mechanism of Charge Transfer and the Role of Polar Medium Outer-Sphere Solvent Reorganization Energy Electron Transfer at the Interface and Specific Forms of the Solvent Reorganization Energy Ion Transfer Across the Interface of Two Phases References Kinetics of Charge Transfer, Z. Samec Introduction Ion Transfer Electron Transfer References Molecular Dynamics of Charge Transfer at the Liquid-Liquid Interface, I. Benjamin Introduction The Neat Interface Electron Transfer Ion Transfer Conclusions and Outlook References Photoelectrochemical Effect at Interface Between Two Immiscible Electrolytic Solutions, N.A. Kotov and M.G. Kuzmin Introduction Reactions of Charge Transfer at Liquid-Liquid Interfaces in Microheterogeneous Systems Photoelectrochemical Effect at the Interface of Immiscible Electrolyte Solutions Conclusion References Excited State Electron Transfer at the Interface of Two Immiscible Electrolyte Solutions, M.K. De Armond and A.H. De Armond Introduction Electrochemical Probing of the ITIES Electron Transfer Kinetics Theory of Electron Transfer Rates Across Liquid-Liquid Interfaces (from Marcus and Benjamin) The Photochemical Redox Process Photoeffects at the Polarized Liquid-Liquid Interface Anomalous Photoeffects Kinetics of Charge Transfer The Instrumental System Chemicals The Future of ITIES Photoeffects References Amperometric Ion-Selective Electrode Sensors, M. Senda and Y. Yamamoto Introduction Electrochemical Principle of Ion-Selective Electrode (ISE) Amperometric ISE Sensors Amperometric ISE Biosensors Electroanalytical Chemistry at Liquid-Liquid Interfaces References Immiscible Liquid Interface and Self-Organized Assemblies of Lecithin, Y.A. Shchipunov Introduction Lecithin Self-Assembly and Self-Organization at the Interface Interfacial Structures and Ternary Phase Diagrams Electrointerfacial Phenomena Methods Prospects for Applications and Further Studies References Phospholipid Monolayers and Phospholipases, T. Kakiuchi Properties of Phospholipid Monolayers at ITIES Charge Transfer Across the Phospholipid Monolayer at ITIES Interfacial Enzymatic Reactions at ITIES References Electrodialysis Through Liquid Ion-Exchange Membranes and Oil/Water Interface, A.N. Popov Introduction Regularities of Electrodialysis Through Liquid Membranes Application of Electrodialysis of Liquid Membranes Experimental Apparatus Conclusion References Oil/Water Interfaces and the Origin of Life, D.W. Deamer and A.G. Volkov Liquid-Liquid Interfaces and Chemical Evolution on the Early Earth Environmental Conditions of the Prebiotic Earth Sources of Prebiotic Organic Compounds Membranes and Liquid-Liquid Interfaces Photochemistry in the Prebiotic Environment: Synthesis of Amphiphiles Proton Production by PAH in Hydrocarbon Carbon Dioxide Reactivity in PAH-Alkane Systems Conclusions References Electrochemical Behavior of Drugs at the Oil/Water Interface, K. Arai, F. Kusu, and K. Takamura Introduction Ion-Transfer Voltammetry at the Oil/Water Interface Electrical Potential Oscillation Across a Liquid Membrane Conclusion References Electrocatalysis and Electrolysis, V.J. Cunnane and L. Murtomaki Introduction Theory of Two Phase Electron Transfer Reactions Model Systems Electrocatalysis and Electrodeposition Summary and Future Developments References Subject Index