Mod ASP Electchem 07

Mod ASP Electchem 07

by B. E. Conway, J. O'M. Bockris


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Product Details

ISBN-13: 9780306376474
Publisher: Springer US
Publication date: 02/28/1972
Pages: 412
Product dimensions: 0.00(w) x 0.00(h) x (d)

Table of Contents

1 Ionic Solvation in Nonaqueous and Mixed Solvents.- I. Introduction.- II. Thermodynamics of Solvation.- III. Determination of Thermodynamics of Solvation.- 1. Heats of Solvation.- 2. Free Energies of Solvation.- 3. Entropies of Solvation.- IV. Theoretical Aspects of Solvation.- 1. Real Free Energy of Solvation.- 2. Electrostatic Theory of Solvation.- 3. Thermodynamics of a Dielectric Continuum.- 4. Structural Approaches.- V. Solvation Numbers.- VI. Mixed Solvents.- 1. Structural Changes in Mixed Solvents.- 2. Solvation Approach to Mixed Solvents.- 3. Thermodynamic Approach to Selective Solvation in Mixed Solvents.- 4. NMR Aspects of Solvation.- VII. Transport Processes.- 1. Viscosity.- 2. Conductance.- 3. Stokes’ Law and Walden’s Rule.- 4. Association.- References.- 2 Solvated Electrons in Field- and Photo-Assisted Processes at Electrodes.- I. Introduction.- II. Energetic Factors.- 1. Effective Work Function for Production of Solvated Electrons.- 2. Comparison of Energetics of Ion/Electrode and Electron Injection Processes.- 3. Standard Electrode Potentials for e-s: Liquid Ammonia and Water.- 4. Energy Conditions for Production of Electrons in Water.- 5. State of Solvated Electrons in Polar Media.- III. Photoassisted Electron Injection from Cathodes.- 1. Introduction.- 2. Energetic Conditions for Photoelectrochemical Emission.- 3. Experimental Characterization of the Electrochemical Photoeffect.- 4. Effects of Double-Layer Structure.- IV. Scavenger Behavior in the Electrochemical Photoeffect.- V. Chemical Evidence for Direct Cathodic Injection of Electrons into Solvents.- VI. Hydrated Electrons in Aqueous Electrochemical Reactions.- 1. Some General Problems.- 2. Standard Potential for e-aq and the Nonequilibrium Situation Arising from Annihilation Processes.- 3. Illumination Effects and Reflectance.- 4. Solvated Electrons and Organic Electrochemical Reactions.- Acknowledgment.- References.- 3 Critical Observations on the Measurement of Adsorption at Electrodes.- I. Introduction.- 1. Nature and Scope of the Discussion.- 2. Definition of “Adsorption”.- 3. Inferences about Adsorption from Observable Phenomena.- 4. Adsorption of Inorganic Species.- 5. Chemisorbed Films.- 6. Electrochemical Transformations Involving Adsorbed Reactants.- II. Direct Methods of Measuring Adsorption.- 1. Depletion of the Solution.- 2. Accumulation on the Electrode: Measurements Made after Removal from Solution.- 3. Accumulation on the Electrode: Measurements in situ.- 4. Optical Observation of the Surface Layer in situ.- III. Measurement of Surface Tension, Charge, and Capacity.- 1. Thermodynamic Theory.- 2. Measurement of Surface Tension.- 3. Measurement of Charge on the Electrode.- 4. Measurement of Double-Layer Capacity.- 5. Measurement of Tensammetric Processes.- IV. Adsorption Indicated by Effects Exerted on Faradaic Processes.- V. Summary.- Acknowledgment.- References.- 4 Transport-Controlled Deposition and Dissolution of Metals.- I. Phenomena Involved.- II. Amplification of Surface Irregularities.- III. Appearance and Growth of Dendritic Deposits.- 1. Conditions of Appearance and Factors Determining Frequency of Incidence and Rate of Growth of Dendrites.- 2. General Theory of the Appearance and Growth of Dendrites.- 3. Comparison with Results of Experiments.- 4. The Effect of the Crystal Structure of the Depositing Metal on the Direction of Growth and Shape of Dendrites.- IV. Growth of Whiskers.- 1. Introduction.- 2. Theory of Whisker Growth.- V. Formation of Powdered Deposits.- 1. Common Features.- 2. Critical Current Density of Powder Formation and Limiting Current Density of Metal Deposition.- 3. Interpretation of the Role of Transport Control in Powder Formation.- VI. Leveling.- 1. Basic Facts.- 2. Model of Leveling.- 3. Quantitative Treatment.- VII. Electropolishing.- 1. Summary of Experimental Facts.- 2. Proposed Models of Electropolishing.- 3. Quantitative Treatment of Diffusion-Controlled Smoothing.- VIII. Deposition of Metals at a Periodically Changing Rate.- 1. Reversing Currents.- 2. DC with Superimposed AC.- 3. Pulsating Currents.- 4. Theory of the Effect of Pulsating Electrolysis on the Morphology of the Deposit.- IX. Generalized Model of Transport-Controlled Processes and Approaches to Quantitative Analysis of Its Consequences.- 1. Qualitative Consideration of the Development of the Diffusion Layer.- 2. Quantitative Aspects.- 3. Some Approaches to Quantitative Solutions.- References.- 5 Mechanisms of Stepwise Electrode Processes on Amalgams.- I. Introduction.- II. Brief Historical Survey.- III. Processes with a Single Limiting Step.- 1. Rate Equations with Allowance for the ?1 Potential.- 2. Rate Equations in the Case of an Excess of Supporting Electrolyte.- 3. Principal Features of Stepwise Mechanisms.- 4. Conditions for the Accumulation of Ionic Intermediates in Solution.- 5. Combined Use of Electrochemical and Radiotracer Measurements.- 6. Experimental Data for Zinc and Indium Amalgams.- 7. Experimental Data for Other Systems.- 8. Causes of the Relative Slowness of the Last Charge-Transfer Step.- IV. Processes with Comparable Rate Constants for Successive Steps.- 1. Rate Equations for the Process with One-Electron Steps.- 2. Equations for the Partial Anodic Current.- 3. Conditions for the Applicability of the “Break” Criterion.- 4. Process Involving Higher-Order Reactions.- 5. Summary of Various Criteria for Stepwise Mechanisms.- 6. Experimental Results for Bismuth and Copper Amalgams.- 7. Experimental Results for Other Systems.- V. Application of the Criteria for Stepwise Mechanisms in Some Electrode Redox Reactions.- References.

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