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Full Description
As the subject of electrochemistry moves into the final quarter of the century, a number of developed areas can be assessed in depth while some new areas provide quantitatively and qualitatively novel data and results. The first chapter, by Kebarle, deals with an example of the latter type of field in which new information of the energetics and equilibria of reactions between ions and solvent molecules is studied in the gas phase and provides interesting basic information for treatments of ions in solution, i.e., ionic solvation. Chapter 2, by Hamann, discusses the behavior of electrolyte solutions under high pressures, a matter of intrinsic interest in relation to ion-solvent interaction and the structural aspects of the properties of ionic solutions, especially in water. This topic is also of current interest with regard to the physical chemistry of the marine environment, especially at great depths. In the article by Bloom and Snook (Chapter 3), models for treatments of molten salt systems are examined quantitatively in relation to the structure of molten ionic liquids and to the statistical mechanical approaches that can be meaningfully made to interpret their properties and electrochemical behavior.
Contents
1 Gas-Phase Ion Equilibria and Ion Solvation.- I. Introduction.- II. Principles of Gas—Phase Ion Equilibrium Methods.- III. Gas—Phase Studies of Acids and Bases. Proton Transfer Equilibria.- IV. Enthalpies and Free Energies of Formation of Ions in the Gas Phase and Total Energies of Solvation of Single Ions.- V. Hydration of Spherically Symmetric Ions. The Positive Alkali and Negative Halide Ions.- VI. The Hydrogen Ion and the Hydroxyl Ion Hydrates in the Gas Phase.- VII. Hydrogen Bonding to Negative Ions.- VIII. Ion Solvation by Protic and Aprotic Solvents.- References.- 2 Electrolyte Solutions at High Pressure.- I. Introduction.- II. Physical Properties of Water and Other Solvents at High Pressures.- III. Electrical Conductivity of Electrolyte Solutions under Pressure.- IV. Ionization Equilibria under Pressure.- V. Properties of Electrolyte Solutions at High Shock Pressures.- References.- 3 Models for Molten Salts.- I. Introduction.- II. Operational Models.- III. Models Involving Intermolecular Forces.- References.- 4 The Electrical Double Layer: The Current Status of Data and Models, with Particular Emphasis on the Solvent.- I. Introduction.- II. Some Considerations of the Properties of a Solvent in the Region Adjacent to a Surface.- III. Double-Layer Characteristics at Mercury.- IV. Models of the Double Layer.- V. Discussion and Conclusions.- VI. Recent Advances Not Directly Applicable to Metal—Solution Interfaces.- References.- 5 Electrocatalysis.- I. Introduction.- II. Electron Transfer at the Metal-Solution Interface.- III. Effect of Adsorption on the Rate of Reaction.- IV. Factors Other Than ?Hadso Affecting Reaction Rates.- V. Experimental Rate Correlations.- VI. Electrocatalysis and the Oxygen Electrode.- VII. The Kinetics and Mechanism of OxygenReduction on Phase-Oxide-Free Metals.- VIII. The Oxygen Electrode in Other Electrolytes.- References.
