Modern Aspects of Electrochemistry, Softcover reprint of the original 1st ed. 1982 No. 14

This volume contains eight chapters covering a wide range of topics: ultrasonic vibration potentials, impedance measurements, photo­ electrochemical kinetics, chlorine production, electrochemical behavior of titanium, structural properties of membranes, bioelec­ troche mistry, and small-particle effects for electrocatalysis. Chapter 1, contributed by Zana and Yeager, discusses the little used but potentially important area of ultrasonic vibration potentials. The authors review the historical literature and the associated theoretical equations. They continue by discussing various aspects of the experimental technique and close with a review of the existing studies. They conclude by noting that vibra­ tion potentials may be useful for determining the effects of various agents on colloidal suspensions found in such important industries as paper production. Chapter 2 is a review of impedance techniques, written by Macdonald and McKubre. The authors include not only derivations of various impedance functions for electrochemical systems but also particularly useful discussions of instrumental methods. The authors close with an interesting claim: "the distribution of current and potential within a porous battery or fuel-cell electrode and within 'flow-through' electrodes is best analyzed in terms of the frequency dispersion of the impedance." Chapter 3, by Khan and Bockris, is a timely review of photo­ electrochemical kinetics and related devices. Their work begins by reviewing critically important papers on photoelectrochemical kinetics. They continue by presenting detailed discussions concern­ ing the conceptual ideas of the semiconductor-solution interface.

1 Ultrasonic Vibration Potentials.- I. Introduction.- II. Theory of Ionic Vibration Potentials (IVP).- 1. Derivation of the Expression for the IVP.- 2. Physical Meaning of the Apparent Molar Masses W+ and W? and Their Relationship to the Partial Molar Volumes at Infinite Dilution of the Ions, $$\bar V_ + ^0$$ and $$\bar{V}_{-}^{0}$$.- 3. IVP of Mixtures of Electrolytes.- 4. Case of Solutions in which Fast Physical or Chemical Processes Occur.- 5. Solutions of Electrolytes in Organic Solvents.- III. Quantitative Measurements of Ultrasonic Vibration Potentials.- 1. Generation of the Electrical Impulse Driving the Transducer.- 2. The Transducer.- 3. The Propagation System.- 4. Double-Electrode Probe and Cell Assembly.- 5. Detection Electronics.- 6. Determination of Velocity Amplitudes.- 7. False Effects.- IV. Review of IVP Studies.- 1. Aqueous Solutions.- 2. Solutions in Organic Solvents.- 3. Factors which Determine the Partial Molar Volume of Ions.- 4. IVPs and Solvation Numbers.- V. Miscellaneous Studies.- 1. Colloidal Vibration Potentials.- 2. Polyelectrolyte Vibration Potentials.- VI. Conclusion.- References.- 2 Impedance Measurements in Electrochemical Systems.- I. Introduction.- II. Interfacial Impedance.- 1. Definitions and General Concepts.- 2. Electrochemical Systems.- III. Derivation of Impedance Functions for Electrochemical Systems.- 1. Quasireversible Reaction.- 2. Coupled Chemical-Electrochemical Reactions.- 3. Surface-Controlled Processes.- 4. Edge Effects and Porous Electrodes.- IV. Instrumental Methods.- 1. Frequency Domain Measurements—Small-Amplitude Sinusoidal Perturbation.- 2. Time Domain Measurements.- V. The Future.- References.- 3 Photoelectrochemical Kinetics and Related Devices.- I. Introduction.- II. Some Important Papers in Photoelectrochemical Kinetics.- 1. Green: The Basic Dependence on Surface States.- 2. Green, McBreen and Jendrassic: Determination of Surface States.- 3. Bockris and Reddy: n/p Junctions and e/i Junctions.- 4. Fujishima and Honda: Hydrogen Production?.- 5. Ellis, Keizer, and Wrighton: Stabilizing by Adding S2? to the Solution.- 6. Bockris and Uosaki: Photoelectrochemical Kinetics, Taking into Account the Effect of Surface States.- 7. Wilson: Recombination Kinetics.- 8. Schoijet: Empiricistic Evaluation of Photovoltaics.- 9. Hodes: Surface Etching.- 10. Reichmann: No Schottky Barrier and Rate-Determining Charge Transfer in the Double Layer.- 11. Bard: Tungstic Selenide.- 12. Grätzel et al.: Colloidal Bielectrodes.- 13. Guruswamy and Bockris: The Shift in Onset Potential.- 14. Bard et al.: Fermi Level Pinning.- III. Theory.- 1. The Structure of the Double Layer.- 2. The Concept of a Schottky Barrier.- 3. The Theory of the Onset Potential.- 4. The Cutting Edge of Models in Semiconductor-Solution Interfaces.- 5. Questionable Aspects of the Theories of Semiconductor Photoelectrochemistry.- 6. The Rate-Determining Step.- 7. The Nernst-Planck Equation.- 8. The Photoelectrochemical Cell.- IV. Analysis of the Surface.- V. Practical Devices.- VI. Electricity Generation with Redox Couples.- VII. Carbon Dioxide Reduction.- VIII. Chlorine Production.- IX. Applications.- 1. Redox Systems.- 2. Hydrogen-Oxygen Production.- 3. Hydrogen and Oxygen Production by Bioelectrochemical Methods.- 4. Ammonia.- 5. Universal Photoelectrochemical Reactor.- X. Summary.- References.- 4 Fundamental and Applied Aspects of Anodic Chlorine Production.- I. Introduction.- 1. General Aspects of the Reaction.- 2. Scope of the Review.- II. Anode Materials for Chlorine Evolution.- 1. Electrode Preparation.- 2. Other Anode Materials and Some Future Materials Trends.- 3. Physical and Morphological Characteristics of (RuO2 + TiO2)-Based Electrodes.- 4. Materials Requirements for Chlorine Anodes.- III. Fundamental Aspects of the Anodic Chlorine Evolution Reaction.- 1. Thermodynamic Aspects of the Cl2-Cl? Reaction.- 2. Coulombic Efficiency of the Cl2 Evolution Reaction.- IV. Kinetic Aspects of the Chlorine Evolution Reaction.- 1. The State of Anode Surfaces.- 2. Surface Oxidation of Pt Anodes in the Absence of Adsorbed Cl?.- 3. State of Oxidation of Surfaces of RuO2 and Oxidized Ru and Ir Anodes.- 4. State of Oxidation of Surfaces of Carbon Anodes.- 5. Chloride Ion Adsorption and its Effects on Oxide Film Formation at Noble Metal Anodes.- 6. Mechanisms of Anodic Chlorine Evolution.- 7. Chlorine Reduction in Aqueous Solutions.- V. Industrial Aspects of Chlorine Evolution.- 1. Wofld Production of Chlorine.- 2. Commercial Electrolytic Methods for Chlorine Production.- References.- 5 Electrochemical Behavior of Titanium.- I. Introduction.- II. Active State Dissolution and Passivation.- 1. Experimental Background.- 2. Mechanisms.- III. Effects of Ti(III) and Ti(IV) Ions.- 1. Oxidation of Ti(III) Ions.- 2. Reduction of Ti(IV) Ions.- 3. Autopassivation of Electrolyte-Coupled Active-Passive Systems.- IV. Noble Metal Alloys and the Hydrogen Evolution Reaction.- 1. Noble Metal Alloys of Titanium.- 2. Hydrogen Evolution Reaction.- References.- 6 Structural Properties of Membrane Ionomers.- I. Introduction.- II. General Aspects of Ionomeric Membranes.- 1. Overall Structure and Swelling.- 2. Donnan Exclusion.- III. Theoretical Models of Crosslinked Polyelectrolytes.- 1. Gregor’s Mechanical Model.- 2. The Model of Katchalsky et al..- 3. The Model of Harris and Rice.- IV. Ion Pairing in Ionomeric Membranes.- 1. Dissociation Equilibrium of Counterions in Ionomers.- 2. A Theory of Membrane Internal Water Activity.- V. Supermolecular Structure of Ionomeric Materials.- 1. Introduction.- 2. Polymer-Polymer Interfaces and Interphases.- 3. Formation of Spherical Domains in Block Copolymers.- 4. Application of Spherical Domain Block Copolymer Theory to Ionomeric Structure.- 5. Experimental Investigations of the Structure of Ionomers.- 6. Theories of Cluster Formation and lonomer Structure.- VI. Conclusion.- References.- 7 Bioelectrochemistry-Electrophysiology-Electrobiology.- I. Introduction.- II. Ions, Membranes, and Fields.- 1. Fields and Ion Transport.- 2. Transmembrane Potentials.- III. Bioelectrokinetics.- 1. Cardiovascular System.- 2. Bone and Cartilage.- IV. Medical and Biological Applications of Fields.- 1. Bone, Limb, and Cartilage Regeneration.- 2. Electroanalgesia.- 3. Biomaterials and Surface Charge.- 4. Miscellaneous Applications.- References.- 8 Small-Particle Effects and Structural Considerations for Electrocatalysis.- I. Introduction.- II. Surface Structure of Small Particles.- III. Dependence of Metal Properties on Particle Size.- 1. Melting Point.- 2. Lattice Parameter.- 3. Low-Temperature Specific Heat.- 4. Magnetic Properties.- 5. Electrical Properties.- 6. Optical Properties.- 7. Properties of Specific Metals.- IV. Electrocatalysis on Solid Metal Electrodes.- 1. Pretreatment of Noble Metal Electrodes.- 2. Potential Cycling of Metal Electrodes.- 3. Single-Crystal Electrodes.- 4. Effects of Applied Mechanical Stress.- V. Particle Size Effects in Electrocatalysis.- 1. Oxygen Reactions on Platinum.- 2. Hydrogen Reactions.- 3. Oxidation of Hydrocarbons.- VI. Concluding Remarks.- References.