Comprehensive Treatise of Electrochemistry
Volume 7 Kinetics and Mechanisms of Electrode Processes
Herausgegeben: Horsman, Peter; Conway, Brian E.; Yeager, E.
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1. Quantum Electrochemical Kinetics: Continuum Theory.- 1. Introduction.- 2. The Model.- 3. General Expressions for the Transition Probability.- 4. Transition Probability for Fixed Coordinates of the Ions and Reactants.- 5. Proton Transfer Reactions.- 5.1. Proton Transfer in the Case of Strong Coupling with the Medium.- 5.2. Proton Transfer in the Case of Weak Coupling with the Medium.- 6. Effect of the Discrete Structure of the Electrical Double Layer on the Kinetics.- 7. The Step of Electrochemical Desorption of Hydrogen Atoms.- 8. The Role Played by the Electronic Structure of the Electrode...
1. Quantum Electrochemical Kinetics: Continuum Theory.- 1. Introduction.- 2. The Model.- 3. General Expressions for the Transition Probability.- 4. Transition Probability for Fixed Coordinates of the Ions and Reactants.- 5. Proton Transfer Reactions.- 5.1. Proton Transfer in the Case of Strong Coupling with the Medium.- 5.2. Proton Transfer in the Case of Weak Coupling with the Medium.- 6. Effect of the Discrete Structure of the Electrical Double Layer on the Kinetics.- 7. The Step of Electrochemical Desorption of Hydrogen Atoms.- 8. The Role Played by the Electronic Structure of the Electrode.- 9. Experimental Verification of the Theory.- References.- 2. Molecular Aspects of Quantum Electrode Kinetics.- 1. Introduction.- 2. Correlation between Electrochemical Electron and Spectroscopic Photon Transfer Process.- 3. Applicability of Time-Dependent Perturbation Theory for Electron Transfer Processes at Electrodes.- 4. Proton Transfer at Interfaces.- 4.1. Gurney's Quantum Mechanical Model of Proton Transfer.- 4.2. Butler's Modification of Gurney's Model.- 4.3. The Quantum Character of Proton Transfer.- 4.4. Degree of Validity of the WKB Tunneling Probability Expression for Proton Transfer.- 4.5. A Model of Electrochemical Hydrogen Evolution Reaction.- 5. Quantal Aspects of Photoelectrochemical Kinetics.- 5.1. Photoeffect at Metal-Solution Interface.- 5.2. Non-Tafel Behavior of Photocurrent at Metal-Solution Interface.- 5.3. Photoeffect at Semiconductor-Solution Interface.- 6. Tunneling at the Oxide-Covered Electrode.- 7. Fermi Energy in Solution.- 8. Distribution of Electron States in Ions in Solution.- 9. The Adiabaticity and Nonadiabaticity in Electron Transfer Reactions.- 9.1. Landau-Zener Formulation.- 9.2. Transmission Coefficient, K, for Homogeneous RedoxReactions.- 10. Transition Probability of the Electron at the Electrode-Solution Interface.- 11. Concluding Remarks.- References.- 3. Kinetics of Electrochemical Reactions at Metal-Solution Interfaces.- 1. Introduction: Steps of Electrode Processes.- 2. Phenomenological Theory of the Elementary Act of an Electrode Reaction.- 2.1. Brønsted-Polanyi Relation and Electrode Reaction Activation Energy.- 2.2. Electronic Work Function and Related Values in Electrochemical Kinetics.- 2.3. Activity Coefficient of an Activated Complex.- 2.4. Temperature Dependence of Electrode Reaction Rates.- 2.5. Activationless and Barrierless Electrode Processes.- 3. Formal Kinetics of Electrode Reactions.- 3.1. Kinetic Equations.- 3.2. Stoichiometric Numbers.- 4. Electrode Double-Layer Structure and Electrode Reaction Rate..- 4.1. Basic Relations.- 4.2. Hydrogen Evolution.- 4.3. Reduction of Anions.- 4.4. Electrode Reactions of Organic Compounds.- References.- 4. Electrocatalysis.- 1. Introduction.- 2. Electrocatalysis and Catalysis.- 2.1. General.- 2.2. Effect of Potential on Rate.- 3. The Rates of Complex Processes.- 4. Potential Energy Diagrams and Electrocatalysis.- 4.1. General.- 4.2. Some Correlations.- 5. Some Quantum Mechanical Aspects.- 5.1. General.- 5.2. Radiationless Transfer Theories.- 6. Some Electrocatalytic Reactions.- 6.1. General.- 6.2. Hydrogen Electrode Reaction.- 6.3. Oxygen Electrode Reactions.- 6.4. Organic Oxidations.- 6.5. Chlorine Evolution.- 6.6. General Remarks on Practical Electrocatalysts.- References.- 5. Hydrogen Electrode Reaction on Electrocatalytically Active Metals.- 1. Introduction.- 2. Adsorption of Hydrogen on Metal Electrodes.- 2.1. Hydrogen Wave by a Potential Sweep Technique.- 2.2. Adsorption Isotherm for Atomic Hydrogen.- 2.3. Structure of theHydrogen Wave and Experiments on Single-Crystal Planes.- 3. Basic Kinetic Equations.- 4. Experimental Behavior and Possible Mechanisms-Existence of a Unique Rate-Determining Step.- 4.1. Possible Reaction Routes and Mechanisms.- 4.2. The Stoichiometric Number.- 4.3. The Tafel Slope.- 4.4. Magnitude of the Tafel Slope.- 4.5. The Reaction Orders.- 5. Mechanism with No Unique Rate-Determining Step.- 5.1. Tracer
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