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In the last decade, the evolution of electrochemistry away from concern with the physical chemistry of solutions to its more fruitful goal in the study of the widespread consequences of the transfer of electric charges across interphases has come to fruition. The turning of technology away from an onward rush, regardless, to progress which takes into account repercussions of techno logical activity on the environment, and the consequent need for a reduction and then termination of the injection of CO into 2 the atmosphere (greenhouse effect), together with a reckoning with air and water pollution in general, ensures a long-term need for advances in a basic knowledge of electrochemical systems, an increased technological use of which seems to arise from the environmental necessities. But a mighty change in attitude needs to spread among electro chemists (indeed, among all surface chemists) concerning the terms and level in which their field is discussed. The treatment of charge transfer reactions has often been made too vaguely, in terms, it seemed, of atom transfer, with the electron-transfer step, the essence of electrochemistry, an implied accompaniment to the transfer of ions across electrical double layers. The treatment has been in terms of classical mechanics, only tenable while inadequate questions were asked concerning the behavior of the electron in the interfacial transfer. No process demands a more exclusively quantal discussion than does electron transfer.
Contents
1 Computed Thermodynamic Properties and Distribution Functions for Simple Models of Ionic Solutions.- I. Introduction.- II. Theoretical Background.- III. Some Results from Statistical Mechanics.- IV. Approximation Techniques.- V. MacMillan-Mayer Theory.- VI. Thermodynamics.- VII. Results Which Are Independent of the Model.- VIII. Properties of the Primitive Model.- IX. Some Other Models with Discontinuous Potentials.- X. Models with Continuous Potential Functions.- XI. Model Calculations in Some Related Areas.- XII. Supplement.- Acknowledgment.- References.- 2 Surface Potential at Liquid Interfaces.- I. Definitions.- II. Experimental Methods for Measuring Surface Potentials at Liquid Interfaces.- III. Surface Potential of Aqueous Solutions of Inorganic Electrolytes.- IV. Ionized Monolayers.- V. Incompletely and Un-ionized Monolayers.- Notation.- References.- 3 Transport Phenomena in Electrochemical Kinetics.- I. Introduction.- II. Flows Controlled by Motion of the Working Electrode.- III. Convective Diffusion at Electrodes with Flowing Solutions.- IV. Electrodes under Free Convection.- V. Applications to Electrochemical Kinetics.- VI. Conclusion.- References.- 4 The Mechanism of Charge Transfer from Metal Electrodes to Ions in Solution.- I. Introduction.- II. Gurney's Quantum Mechanical Theory of Charge Transfer.- III. Developments of the Quantum Mechanical Theory.- IV. Absolute Reaction Rate Approach to Charge-Transfer Reactions.- V. Electrostatic Treatment of the Rate of Redox Reactions Hush's Theory for Redox Reactions.- VI. Ion Tunneling.- VII. Concluding Remarks.- Acknowledgments.- Appendix I. The Transfer Coefficient.- Appendix II. The Adiabatic Principle and Related Approximations.- References.- 5 Electrochemical Processes in Glow Discharge at theGas-Solution Interface.- I. Introduction.- II. History.- III. Experimental Technique.- IV. Physical Features of GDE.- V. Glow-Discharge Phenomena in Conventional Electrolysis.- VI. Chemical Results of Glow-Discharge Electrolysis.- VII. Mechanism of Glow-Discharge Electrolysis.- VIII. Glow-Discharge Electrolysis and Radiation Chemistry.- IX. Applications of Glow-Discharge Electrolysis.- References.
