Modern Aspects of Electrochemistry

This volume of Modern Aspects of Electrochemistry contains six chapters. The first four chapters are about phenomena of interest at the microscopic level and the last two are on phenomena at the macroscopic level. In the first chapter, Uosaki and Kita review various theoretical models that have been presented to describe the phenomena that occur at an electrolyte/ semiconductor interface under illumination. In the second chapter, Orazem and Newman discuss the same phenomena from a different point of view. In Chapter 3, Bogus­ lavsky presents state-of-the-art considerations of transmembrane potentials and other aspects of active transport in biological systems. Next, Burke and Lyons present a survey of both the theoretical and the experimental work that has been done on hydrous oxide films on several metals. The last two chapters cover the topics of the production of chlorine and caustic and the phenomena of electrolytic gas evol­ ution. In Chapter 5, Hine et al. describe the engineering aspects of the three processes used in the chi or-alkali industry, and in Chapter 6, Sides reviews the macroscopic phenomena of nucleation, growth, and detachment of bubbles, and the effect of bubbles on the conduc­ tivity of and mass transfer in electrolytes.

Contenu

1 Theoretical Aspects of Semiconductor Electrochemistry.- I. Introduction.- II. Electronic Energy Levels of Semiconductor and Electrolyte.- 1. Junctions between Two Electronic Conductors.- 2. Semiconductor/Electrolyte Interface.- III. Potential Distribution at Semiconductor/Electrolyte Interface.- 1. Schottky Barrier.- 2. Effect of the Redox Potential on the PotentiaDrop in the Semiconductor at the Semiconductor/Electrolyte Interfaces.- 3. Distribution of Externally Applied Potential at the Semiconductor/Electrolyte Interfaces.- IV. Distribution of Energy States for Ions of Redox System in Solution.- 1. Importance of the Energy Levels of Redox Couples.- 2. Gurney's Model.- 3. Gerischer's Model.- 4. Continuum Solvent Polarization Fluctuation Model.- 5. Validity of the Models.- V. Rate Expressions for Electron Transfer at Illuminated Semiconductor/ Electrolyte Interfaces.- 1. Phenomenological Description.- 2. The Model of Bockris and Uosaki.- 3. Butler's Model-Semiconductor/Electrolyte Interface as a Schottky Barrier.- 4. Competition between Surface Recombination and Charge Transfer.- 5. Effects of Recombination in Space Charge Region.- 6. Effects of Grain Boundary Recombination.- VI. Concluding Remarks.- References.- 2 Photoelectrochemical Devices for Solar Energy Conversion.- I. Semiconductor Electrodes.- 1. Physical Description.- 2. The Mechanism of Cell Operation.- II. Mathematical Description.- 1. Semiconductor.- 2. Electrolyte.- 3. Semiconductor-Electrolyte Interface.- 4. Boundary Conditions.- 5. Counterelectrode.- III. Photoelectrochemical Cell Design.- 1. Choice of Materials.- 2. Solution of the Governing Equations.- 3. The Influence of Cell Design.- IV. Conclusions.- Notation.- References.- 3 Electron Transfer Effects and the Mechanism of the Membrane Potential.- I. Introduction.- II. Modeling Nonenzymatic Systems of Electron Transfer in the Initial Part of the Respiratory Chain of Mitochondria.- 1. Respiratory Chain.- 2. Potentials of the Respiratory Chain Elements.- 3. Ubiquinones in the Respiratory Chain.- 4. Participation of Membrane Lipids in the Functioning of the Respiratory Chain.- 5. Transmembrane Potentials in the Chain NADH-Coenzyme Q-O2.- 6. Participation of FMN in the Oxidation of Membrane Lipids.- 7. Participation of FMN in the Transmembrane Transport of Protons.- 8. Participation of FMN in the Transmembrane Transport of Electrons.- 9. Interaction of FMN with Other Chain Components.- III. Potential Generation on Bilayer Membranes Containing Chlorophyll.- 1. Chlorophyll at the Membrane/Electrolyte Interface.- 2. Redox Potentials of Chlorophyll.- 3. Reactions of Chlorophyll Inserted in the Membrane with the Redox Components in an Aqueous Solution under Illumination.- 4. Transmembrane Potentials in the Chain OX-CHLRED.- IV. Possible Mechanisms of the Motion of Electrons and Protons in the Membrane.- 1. Hypotheses on the Mechanism of Electron Motion in Biological Membranes.- 2. Ion Permeability of Bilayer Membranes in the Iodine/Iodide System Controlled by Redox Reactions at the Interface.- 3. Electron and Proton Transport in Bilayers Containing Chlorophyll and Quinones under Illumination.- 4. Possible Conductance Mechanisms in Bilayers Containing Ubiquinone.- 5. Hypothesis on the Mechanism of Proton Transport in Biological Membranes.- 6. Potentials of Coupling Membranes.- V. Conclusions.- References.- 4 Electrochemistry of Hydrous Oxide Films.- I. Introduction.- II. Formation of Hydrous Oxides.- III. Acid-Base Properties of Oxides.- IV. Structural Aspects of Hydrous Oxides.- V. Transport Processes in Hydrous Oxide Films.- VI. Theoretical Models of the Oxide-Solution Interphase Region.- 1. Classical Models.- 2. Nonclassical Models.- VII. Platinum.- 1. Monolayer Oxidation.- 2. Hydrous Oxide Growth on Platinum.- VIII. Palladium.- IX. Gold.- 1. Monolayer Behavior.- 2. Hydrous Oxide Growth.- X. Iridium.- 1. Monolayer Growth.- 2. Hydrous Oxide Films.- XI. Rhodium.- 1. Hydrous Oxide Growth.- 2. Behavior of Rh/Pt Alloys.- XII. Ruthenium.- XIII. Some Nonnoble Metals.- 1. Iron and Cobalt.- 2. Nickel and Manganese.- 3. Tungsten.- XIV. Conclusion.- Addendum.- References.- 5 Chemistry and Chemical Engineering in the Chlor-Alkali Industry.- I. Introduction.- II. Chemical and Electrochemical Principles Involved in Chlor-Alkali Production.- III. Manufacturing Processes.- 1. Importance of Brine Purification.- 2. Diaphragm Cell Process.- 3. Membrane Cell Process.- 4. Mercury Cell Process.- IV. Electrode Materials and Electrode Processes.- 1. Anodes.- 2. Cathodes.- V. Engineering Aspects in Chlor-Alkali Operations.- 1. Chemical Engineering Aspects of Amalgam Decomposition.- 2. Chemical Engineering Aspects of Porous Diaphragms.- VI. Ion-Exchange Membranes and Membrane Technology.- 1. General Requirements of Membranes for Chlor-Alkali Production.- 2. Properties of Membranes and Their Performance Characteristics.- 3. Engineering Design Aspects of Ion-Exchange Membrane Cell Technology.- 4. Advantages Afforded by Membrane Technology.- 5. State of the Art of Membrane Cell Technology.- Notation.- References.- 6 Phenomena and Effects of Electrolytic Gas Evolution.- I. Introduction.- II. Nucleation, Growth, and Detachment of Bubbles.- 1. Nucleation.- 2. Growth.- 3. Detachment.- 4. Effect of Additives and Operating Parameters.- III. Electrical Effects of Gas Evolution.- 1. Conductivity of Bulk Dispersions.- 2. Electrical Effects of Bubbles on Electrodes.- IV. Mass Transfer at Gas-Evolving Electrodes.- 1. Penetration Theory.- 2. The Hydrodynamic Model.- 3. The Microconvection Model.- 4. Microscopic Investigation.- V. Summary.- Notation.- References.