Modern Aspects of Electrochemistry

1 Perspectives in Electrochemical Physics.- I. Introduction.- II. Importance of Electrochemical Physics.- 1. Scope.- 2. Origins and Evolution.- 3. Current Scientific Importance.- III. Electrocatalysis by Metals and Alloys.- 1. Electrocatalysis of the h.e.r. and the Electronic Structure of Metals.- 2. Volcano Plots.- 3. The Current Experimental Situation of the Catalysis of Various Electrode Reactions.- IV. Electrode Reactions on Semiconductors.- 1. General.- 2. Simple Ion Transfer.- 3. Redox Reactions.- 4. Photoelectrochemical Reactions and Cells.- 5. Some Materials Problems in Photoelectrochemical Cells.- V. Solid-State Properties and Electrochemical Behavior: Corrosion, Anodic Dissolution, and Oxide Growth.- 1. General.- 2. The M?Mz+ + ze Reaction.- 3. Anodic Dissolution of Some Film-Covered Electrodes.- 4. The Fretting Corrosion of Metals.- 5. The Pitting Potentials of Metals.- 6. The Passivation of Metals in an Aggressive Electrolyte.- 7. Open-Circuit Corrosion and “Chemical” Dissolution.- 8. Anodic Oxide Growth and Metal/Oxide Electrodes.- VI. Electrochemical Physics of Metal/ Dielectric Interfaces.- 1. The Open-Circuit Voltages in Metal-Polymer-Metal Systems.- 2. The Nature of Metal/SF6 Reactions Accompanying the Passage of Direct Current across the Interface.- 3. The Electrical Signals at Metal Electrodes in Nitromethane During Detonation: Electrochemical Basis.- 4. Solid-State Electrochemistry of Dielectric Breakdown in Alkali Halides.- 5. Some Other Electrochemical Problems at Metal/Media Interfaces.- VII. Metal-Plasma (“Gaseous Electrolyte”) Interfaces.- 1. Electrochemical Physics of the Metal-Plasma Interface.- 2. Electrode Potentials Appropriate to the Cathode Fall Region.- 3. Estimation of the Surface Plasmon Energies of Metals.- VIII. Synopses of Work on Other Themes and Subjects.- 1. Quantum Electrochemistry.- 2. Electrochemical Physics in Biology.- 3. Solid Electrolytes.- 4. Electrochemical Materials Science.- 5. Miscellaneous Other Work.- References.- 2 Modern State of Double Layer Study of Solid Metals.- I. Introduction.- II. Double Layer Structure at Liquid Metals and Alloys.- III. The Gouy-Chapman-Stern-Grahame (GCSG) Theory for “Uniform” Solid Electrodes.- IV. Capacitance Characteristics of Solid Polycrystalline (PC) Electrodes.- 1. Preliminary Notes.- 2. Lead.- 3. Bismuth.- 4. Thallium.- 5. Antimony.- 6. Cadmium.- 7. Tin.- 8. Solid Gallium.- 9. Indium.- 10. Zinc.- 11. Copper.- 12. Silver.- 13. Gold.- V. Capacitance Characteristics of Individual Single-Crystal Faces.- 1. Introduction.- 2. Metals with a Small Difference of PZC of the Faces.- 3. Metal Faces with a Considerable Difference of their PZC.- VI. Crystallographic Inhomogeneity Effects.- VII. Conclusion.- References.- 3 Interfacial Infrared Vibrational Spectroscopy.- I. Introduction.- II. Theoretical Considerations and Experimental Techniques.- 1. Surface Selection Rule.- 2. The Spectroelectrochemical Cell.- 3. SNIFTIRS Technique.- 4. EMIRS Technique.- 5. Form of the Spectra.- 6. Polarization Modulated IRRAS Technique.- III. Applications.- 1. Electrocatalytic Reactions.- 2. Molecular Adsorption.- 3. Ion Radical Intermediates.- 4. Adsorption of Ions.- IV. Future Directions.- References.- 4 Photoelectrolysis and Photoelectrochemical Catalysis.- I. Introduction.- 1. Thermodynamics of Photoelectrolysis.- 2. Kinetic Considerations.- 3. Evaluation of Research in Photoelectrolysis.- II. Photoelectrochemistry of d-Band Sulfides.- 1. Photoelectrocatalytic Properties of TS2 Compounds.- 2. Surface States in d-Band Sulfides.- 3. Catalytic Limitations of Transition Metal Disulfides.- III. Tailoring Reactive Surface States for Photoelectrocatalysis.- 1. Theoretical Concepts of Pools for Electrons and Holes.- 2. Analogy with Hydrodesulfurization Catalysis.- 3. Towards a Photoelectrochemistry of Semiconducting Cluster Compounds.- 4. Advantages of Cooperative Mechanisms Involving Transition Metal Clusters.- IV. Experiments Using Semiconductor Electrodes with Paired and Clustered Transition Metals.- 1. Materials with Clustered Metals.- 2. Photoelectrochemistry of RuP3 with Ru Pairs.- 3. Photoelectrodes with Clustered Transition Metals.- V. Discussion.- References.- 5 Electron Transfer Reactions on Oxide-Covered Metal Electrodes.- I. Introduction.- II. Experimental Problems.- 1. Preparation of Oxide Films.- 2. Structure of the Films.- 3. Nonstoichiometry and Impurities.- 4. Films on Alloys.- 5. The Oxide-Electrolyte Interface.- III. The Metal-Passive Film-Redox Electrolyte Interface.- 1. Band Structure of a Passive Film.- 2. Electronic Equilibrium Condition for the Interface.- 3. Potential Variation and Band Bending.- 4. Band Structure of Some Oxide Films.- IV. Mechanisms of Electron Transfer at Film-Covered Electrodes.- 1. Electron Exchange with the Metal.- 2. Electron Exchange with the Film.- 3. Experimental Mechanism Criteria.- V. Discussion of Some Particular Systems.- 1. Passive Titanium Electrodes.- 2. Passive Tin.- 3. Passive Niobium Electrodes.- 4. Oxygen Evolution on Passive Platinum.- 5. Passive Gold.- 6. Passive Iron.- 7. Sandwich Oxides.- VI. Exchange Current Densities and Electronic Properties.- References.- 6 Interfacial Electrostatics and Electrodynamics in Disperse Systems.- I. Introduction.- II. Interfacial Electrostatics.- 1. Origin of Charges and Potentials.- 2. Determination of the Surface Charge.- 3. Thermodynamics.- 4. Information from the Colloidal Side.- 5. Points of Zero Charge and Isoelectric Points.- 6. Examples of Double Layer Studies: Silver Iodide.- 7. Examples of Double Layer Studies: Oxides.- III. Interfacial Electrodynamics.- 1. Types of Approach.- 2. Theory of Double Layer Relaxation.- 3. Assessment of Kinetic Double Layer Parameters.- 4. Relaxation and Colloid Stability.- IV. Conclusion and Summary.- References.