Modern Aspects of Electrochemistry

ISBN-13: 9781461574484 / Angielski / Miękka / 2012 / 451 str.

J. O'm Bockris;B. E. Conway

Opis

The present collection of articles follows the arrangement used in previous volumes. Solutions are discussed first, surfaces and double- layers second, electrode kinetics third, and then the applied subjects. The introduction of spectroscopic methods to electrochemistry is well exemplified by NMR studies of ionic solutions, as represented here in the detailed article by E. von Goldammer. Correspondingly, the spectroscopic approach can be applied to surfaces, and B. G. Baker has written an introduction to this topic for electrochemists from the point of view of gas phase measurements. One of the topics which begins to reach a degree of sophistica- tion in electrode process chemistry is the adsorption of organic species on electrodes, and this topic is described in our volume by the well-known electrochemist M. W. Breiter. The work has much rele- vance to the corresponding electrode kinetics and oxidation of organic materials. Much less sophisticated is the position in the electrochemistry of sulfide minerals, but it has seemed worthwhile to have the present record described by D. F. A. Koch; his chapter demonstrates the value of qualitative electrochemical studies in this field. The Hydrogen Economy is perhaps an example of straw fire in electrochemistry, for its great popularity beginning in 1973 reflects an interest which can hardly grow larger. However, much discussion of the Hydrogen Economy is concerned with its nonelectrochemical v vi Preface aspects and D. P. Gregory gives here the latest from the hydrogen front, with emphasis on the electrochemistry.

Spis treści

1 NMR Studies of Electrolyte Solutions.- I. Introduction.- II. Theoretical and Experimental Background of a Nuclear Magnetic Resonance Experiment in Liquid Systems.- 1. Chemical Shift.- 2. Relaxation Times.- 3. Frequency Distribution of the Molecular Motions.- 4. Analytical Expressions for the Time Autocorrelation Function K(?).- 5. Relaxation Mechanisms.- 6. Experimental Methods.- III. Nuclear Magnetic Resonance Studies of Liquid Water.- 1. Chemical Shift.- 2. Relaxation-Time Measurements.- IV. Electrolyte Solutions.- 1. Chemical Shift.- 2. Magnetic Relaxation Behavior of Diamagnetic Electrolyte Solutions.- 3. Paramagnetic Electrolyte Solutions.- V. Relation between NMR and Thermodynamic Behavior.- References.- 2 Surface Analysis by Electron Spectroscopy.- I. Introduction.- II. Surface Analysis.- III. Principles of Electron Spectroscopy.- 1. Electron Emission Processes.- 2. XPS and Auger Energies.- 3. Ultraviolet Photoelectron Spectroscopy (UPS).- 4. Appearance Potential Spectroscopy (APS).- 5. Ion-Neutralization Spectroscopy (INS).- IV. Electron Energy Analysis.- 1. Requirements of the Analyzer.- 2. Retarding-Field Analyzers.- 3. Improved Retarding-Field Analyzers.- 4. Deflection Analyzers.- V. The Interpretation of Spectra.- 1. Identification of Elements.- 2. Escape Depth of Electrons.- 3. Quantitative Surface Analysis.- 4. Chemical Shifts.- 5. Comparison of XPS and AES Chemical Shifts.- VI. Experimental Conditions for Surface Analysis.- 1. Vacuum Requirements and Sample Preparation.- 2. Effects of the Incident Beam.- VII. Applications.- 1. Comments on Experimental Standards.- 2. Electronic Structure of Solid Surfaces.- 3. Surface Analysis of Metals and Alloys.- 4. Surface Analysis of Semiconductors.- 5. Catalysts.- 6. Miscellaneous Materials.- 7. Trace Analysis.- VIII. Conclusions.- References.- 3 Adsorption of Organic Species on Platinum Metal Electrodes.- I. Introduction.- II. Comparison of Techniques for Coverage Determination.- 1. Coverage from Anodic Pulses.- 2. Hydrogen Codeposition.- 3. Radiometric Measurements.- 4. Optical Techniques.- III. Nature of O-Type Species Formed from Simple Fuels.- 1. Coulometric Studies.- 2. Simultaneous Determination of Anodic Charge and Amount of Carbon Dioxide.- 3. Simultaneous Measurement of Anodic Charge and Radiometric Intensity.- 4. Usefulness of Kinetic Parameters in the Comparison of O-Type Species.- 5. Effect of O-Type Species on Other Reactions.- 6. Comparison of Surface Properties in Different Studies.- IV. Species Formed from Fuels with Several Carbon Atoms.- 1. General Considerations.- 2. Non-Desorbable Species.- 3. Desorbable Species.- 4. Conversions between Different-Type Species.- V. Potential Dependence of Adsorbed Species.- 1. Mechanisms for the Establishment of the Coverage at a Given Potential.- 2. Adsorption Mechanism for Non-Desorbable Species.- 3. Adsorption Mechanism for Desorbable Species.- 4. Kinetics of Adsorption and Desorption.- VI. Role of Adsorbed Species in the Oxidation of Organic Fuels.- 1. Oxidation of Simple Fuels.- 2. Oxidation of Fuels with More than One Carbon Atom.- References.- 4 Electrochemistry of Sulfide Minerals.- I. Introduction.- II. Synthesis.- III. Structure.- IV. Semiconductor Properties.- V. Rest Potentials.- VI. Mechanisms of Sulfide Reactions.- 1. Copper Sulfides.- 2. Lead Sulfide.- 3. Zinc Sulfide.- 4. Iron Sulfides.- VII. Electrometallurgy of Sulfides.- VIII. Flotation.- IX. Conclusions.- References.- 5 Electrochemistry and the Hydrogen Economy.- I. Introduction.- II. A General Outline of “The Hydrogen Economy”.- III. Fossil-Fuel Crisis.- IV. Choices of Synthetic Fuels.- V. Future Patterns of Energy Production.- VI. Production of Hydrogen by Electrolysis.- VII. Design Optimization for Electrolyzers.- VIII. Criteria for Evaluating Electrolyzer Cells.- IX. Types of Electrolyzer Designs.- X. Advanced Electrolyzer Designs.- XI. Production of Hydrogen from Coal.- XII. Production of Hydrogen from Nuclear Heat.- XIII. Transmission of Hydrogen.- XIV. End Use of Hydrogen.- XV. Conclusions.- References.- 6 Electrochemical Mechanisms and the Control of Biological Growth Processes.- I. Introduction.- II. Cells and Their Electrochemical Environment.- III. Regenerative Growth and Electrochemical Mechanisms.- IV. Electrochemical Mechanisms and Bone Growth.- V. Bioelectrochemical Modeling.- VI. Electrochemical Information Transfer.- VII. The Future of Bioelectrochemistry.- References.- 7 Power Sources for Electric Vehicles.- I. Introduction.- II. Discussion of Automotive Battery Systems.- 1. Criteria for Vehicles and Power Sources.- 2. The Lead-Acid Battery.- 3. Fuel Cells (and Hybrids).- 4. What’s New with Batteries (1971–1973).- III. Efforts Outside the USA.- 1. Electric Vehicles in England.- 2. Electric Vehicles in Japan.- 3. Electric Vehicles in Germany.- 4. Electric Vehicles in France.- 5. Electric Vehicles in Other Countries.- IV. Conclusions.- 1. Outlook for Electric Vehicle R&D in the USA.- 2. The Technology to Make Such a Vehicle Exists.- References.