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…mehr
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 moltensalt 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.
1 Gas-Phase Ion Equilibria and Ion Solvation.- I. Introduction.- 1. Gas-Phase Hydration of Ions in Relation to Hydration in Solution.- 2. Ion-Molecule Reactions in the Gas Phase.- 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.- 1. Physical Properties of Water at High Pressures.- 2. Physical Properties of Other Solvents at High Pressures.- III. Electrical Conductivity of Electrolyte Solutions under Pressure.- 1. Experimental Methods.- 2. Results.- IV. Ionization Equilibria under Pressure.- 1. Thermodynamics of Equilibria in Solution at High Pressures.- 2. Experimental Methods for Measuring Ionization Constants under Pressure.- 3. Discussion of Results.- V. Properties of Electrolyte Solutions at High Shock Pressures.- 1. Elementary Theory of Shock Waves.- 2. Experimental Methods of Generating Strong Shock Waves.- 3. Measurements on Shock-Compressed Materials.- 4. Disadvantages and Advantages of Shock-Wave Methods.- 5. Electrical Conductivities of Weak Electrolytes in Shock Waves.- 6. Electrical Conductivities of Solutions of Strong Electrolytes in Shock Waves.- 7. Ionization Constant of Water at High Shock Pressures.- References.- 3 Models for Molten Salts.- I. Introduction.- 1. Models.- 2. Radial Distribution Functions (RDF).- II. Operational Models.- 1. Hole Models.- 2. Liquid Free-Volume Model.- 3. Relationship between Free Volume from Different Models and the Hole Volume.- 4. The Adam and Gibbs Configurational-Entropy Theory.- 5. The Significant Structures Model.- III. Models Involving Intermolecular Forces.- 1. Intermolecular Potentials in Molten Salts. Basic Theory.- 2. Statistical Mechanics of Molten Salts.- References.- 4 The Electrical Double Layer: The Current Status of Data and Models, with Particular Emphasis on the Solvent.- I. Introduction.- 1. Basic Double-Layer Model.- 2. The Diffuse Layer.- II. Some Considerations of the Properties of a Solvent in the Region Adjacent to a Surface.- 1. Introduction.- 2. General Properties of a Solvent Near Interfaces.- 3. The Aqueous-Air Interface.- 4. The Role of the Metal.- 5. The Surface and the Work Function.- III. Double-Layer Characteristics at Mercury.- 1. Introduction.- 2. Classical Double-Layer Analysis.- 3. Solvent Excesses.- 4. Surface Excesses of Entropy and Volume.- 5. Ionic Systems: General Characteristics.- 6. The Fluoride Ion-Is Its Behavior Anomalous?.- 7. Capacitances over the Entire Concentration Range.- 8. Maxima in the Capacitance-Potential Function.- 9. Anion Adsorption.- 10. Organic Systems.- IV. Models of the Double Layer.- 1. Introduction.- 2. Earlier Theories of Adsorption.- 3. Organic Systems: Classical Treatments.- 4. Summary of Basis for Recent Developments.- 5. Recent Developments.- 6. Recent Ionic Models.- 7. Intermediate Models.- 8. Organic Systems.- 9. The Gallium-Solution Interface.- 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.- 1. General.- 2. Thermal Theory.- 3. Electrostatic Theory.- 4. Improved Transition State Theories for Electrode Reactions.- III. Effect of Adsorption on the Rate of Reaction.- IV. Factors Other Than ?Hads° Affecting Reaction Rates.- 1. Nuclear Transmission Coefficient.- 2. Electron Transmission Coefficient.- 3. Effects of the Diffuse Double Layer.- 4. Effect of the Electronic Structure of the Electrode Material.- 5. Effect of ?Hads° on the Entropy of Activation.- V. Experimental Rate Correlations.- 1. General.- 2. The Hydrogen Evolution Process.- 3. Volcano Plots in the Hydrogen Evolution Reaction.- 4. Heats of Adsorption and Frequency Factors in Hydrogen Evolution.- 5. Electrocatalytic Studies in Other Systems.- VI. Electrocatalysis and the Oxygen Electrode.- 1. Introduction.- 2. The Oxygen Electrode on Platinum Oxide Surfaces.- 3. The Oxygen Electrode on Other Oxidized Metals.- 4. Electrocatalysis of the Oxygen Evolution Reaction.- 5. Discussion of the Mechanism of the Oxygen Electrode on Oxidized Metals.- VII. The Kinetics and Mechanism of Oxygen Reduction on Phase-Oxide-Free Metals.- 1. General.- 2. Oxygen Reduction in Acid Solution.- 3. Oxygen Reduction on Phase-Oxide-Free Palladium and Rhodium in Acid Solution.- 4. Ruthenium, Iridium, and Osmium Electrodes.- 5. Gold and Silver Electrodes.- 6. Reaction Products-Effect of Impurities.- 7. Electrocatalysis of the Oxygen Reduction on Phase-Oxide-Free Metals in Acid Solution.- 8. Heats of Activation and Frequency Factors in the Oxygen Reduction Reaction.- 9. Correlation between Heats of Activation and Estimated Heats of Adsorption.- 10. The Compensation Effect.- 11. Consequences of the Compensation Effect.- VIII. The Oxygen Electrode in Other Electrolytes.- 1. Alkaline Solutions.- 2. Oxygen Electrodes in Nonaqueous Media.- References.
1 Gas-Phase Ion Equilibria and Ion Solvation.- I. Introduction.- 1. Gas-Phase Hydration of Ions in Relation to Hydration in Solution.- 2. Ion-Molecule Reactions in the Gas Phase.- 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.- 1. Physical Properties of Water at High Pressures.- 2. Physical Properties of Other Solvents at High Pressures.- III. Electrical Conductivity of Electrolyte Solutions under Pressure.- 1. Experimental Methods.- 2. Results.- IV. Ionization Equilibria under Pressure.- 1. Thermodynamics of Equilibria in Solution at High Pressures.- 2. Experimental Methods for Measuring Ionization Constants under Pressure.- 3. Discussion of Results.- V. Properties of Electrolyte Solutions at High Shock Pressures.- 1. Elementary Theory of Shock Waves.- 2. Experimental Methods of Generating Strong Shock Waves.- 3. Measurements on Shock-Compressed Materials.- 4. Disadvantages and Advantages of Shock-Wave Methods.- 5. Electrical Conductivities of Weak Electrolytes in Shock Waves.- 6. Electrical Conductivities of Solutions of Strong Electrolytes in Shock Waves.- 7. Ionization Constant of Water at High Shock Pressures.- References.- 3 Models for Molten Salts.- I. Introduction.- 1. Models.- 2. Radial Distribution Functions (RDF).- II. Operational Models.- 1. Hole Models.- 2. Liquid Free-Volume Model.- 3. Relationship between Free Volume from Different Models and the Hole Volume.- 4. The Adam and Gibbs Configurational-Entropy Theory.- 5. The Significant Structures Model.- III. Models Involving Intermolecular Forces.- 1. Intermolecular Potentials in Molten Salts. Basic Theory.- 2. Statistical Mechanics of Molten Salts.- References.- 4 The Electrical Double Layer: The Current Status of Data and Models, with Particular Emphasis on the Solvent.- I. Introduction.- 1. Basic Double-Layer Model.- 2. The Diffuse Layer.- II. Some Considerations of the Properties of a Solvent in the Region Adjacent to a Surface.- 1. Introduction.- 2. General Properties of a Solvent Near Interfaces.- 3. The Aqueous-Air Interface.- 4. The Role of the Metal.- 5. The Surface and the Work Function.- III. Double-Layer Characteristics at Mercury.- 1. Introduction.- 2. Classical Double-Layer Analysis.- 3. Solvent Excesses.- 4. Surface Excesses of Entropy and Volume.- 5. Ionic Systems: General Characteristics.- 6. The Fluoride Ion-Is Its Behavior Anomalous?.- 7. Capacitances over the Entire Concentration Range.- 8. Maxima in the Capacitance-Potential Function.- 9. Anion Adsorption.- 10. Organic Systems.- IV. Models of the Double Layer.- 1. Introduction.- 2. Earlier Theories of Adsorption.- 3. Organic Systems: Classical Treatments.- 4. Summary of Basis for Recent Developments.- 5. Recent Developments.- 6. Recent Ionic Models.- 7. Intermediate Models.- 8. Organic Systems.- 9. The Gallium-Solution Interface.- 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.- 1. General.- 2. Thermal Theory.- 3. Electrostatic Theory.- 4. Improved Transition State Theories for Electrode Reactions.- III. Effect of Adsorption on the Rate of Reaction.- IV. Factors Other Than ?Hads° Affecting Reaction Rates.- 1. Nuclear Transmission Coefficient.- 2. Electron Transmission Coefficient.- 3. Effects of the Diffuse Double Layer.- 4. Effect of the Electronic Structure of the Electrode Material.- 5. Effect of ?Hads° on the Entropy of Activation.- V. Experimental Rate Correlations.- 1. General.- 2. The Hydrogen Evolution Process.- 3. Volcano Plots in the Hydrogen Evolution Reaction.- 4. Heats of Adsorption and Frequency Factors in Hydrogen Evolution.- 5. Electrocatalytic Studies in Other Systems.- VI. Electrocatalysis and the Oxygen Electrode.- 1. Introduction.- 2. The Oxygen Electrode on Platinum Oxide Surfaces.- 3. The Oxygen Electrode on Other Oxidized Metals.- 4. Electrocatalysis of the Oxygen Evolution Reaction.- 5. Discussion of the Mechanism of the Oxygen Electrode on Oxidized Metals.- VII. The Kinetics and Mechanism of Oxygen Reduction on Phase-Oxide-Free Metals.- 1. General.- 2. Oxygen Reduction in Acid Solution.- 3. Oxygen Reduction on Phase-Oxide-Free Palladium and Rhodium in Acid Solution.- 4. Ruthenium, Iridium, and Osmium Electrodes.- 5. Gold and Silver Electrodes.- 6. Reaction Products-Effect of Impurities.- 7. Electrocatalysis of the Oxygen Reduction on Phase-Oxide-Free Metals in Acid Solution.- 8. Heats of Activation and Frequency Factors in the Oxygen Reduction Reaction.- 9. Correlation between Heats of Activation and Estimated Heats of Adsorption.- 10. The Compensation Effect.- 11. Consequences of the Compensation Effect.- VIII. The Oxygen Electrode in Other Electrolytes.- 1. Alkaline Solutions.- 2. Oxygen Electrodes in Nonaqueous Media.- References.
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