Comprehensive Treatise of Electrochemistry [E-Book] : Volume 7 Kinetics and Mechanisms of Electrode Processes / edited by Brian E. Conway, John O’M. Bockris, Ernest Yeager, Shahed U. M. Khan, Ralph E. White
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Full text |
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Personal Name(s): | Bockris, John O'Mara, editor |
Conway, Brian E., editor / Khan, Shahed U. M., editor / White, Ralph E., editor / Yeager, Ernest, editor | |
Imprint: |
Boston, MA :
Springer,
1983
|
Physical Description: |
806 p. online resource. |
Note: |
englisch |
ISBN: |
9781461335849 |
DOI: |
10.1007/978-1-4613-3584-9 |
Subject (LOC): |
- 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 Redox Reactions
- 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 the Hydrogen 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 Experiments
- 5.2. Tafel Lines and Reaction Orders
- 5.3. Absence of rds and Affinity Distribution among the Constituent Steps
- 5.4. Synthesis of the Overall Kinetics
- 5.5. Transient Experiments on the Pd Hydrogen Electrode
- 6. Related Topics
- 6.1. Effect of Catalytic Poisons upon the Individual Step Rates
- 6.2. Hydrogen Pressure Equivalent to Hydrogen Overpotential
- 6.3. Electrolytic Hydrogenation of Organic Substances
- 7. Electrode Materials
- 7.1. Pure Metals
- 7.2. Composite Materials
- References
- 6. Oxygen Electrochemistry
- 1. Introduction
- 2. Thermodynamics of the Oxygen Electrode
- 3. Open-Circuit Potentials
- 4. Oxygen Adsorbed Species and Anodic Films on Platinum and Other Noble Metals
- 4.1. Electrochemical Studies
- 4.2. In Situ Optical Studies
- 4.3. In Situ Surface Conductivity Measurements
- 4.4. Ex Situ Characterizations
- 5. The Anodic Oxygen Evolution Reaction (OER)
- 5.1. General Features
- 5.2. Kinetics and Mechanisms of the Oxygen Evolution Reaction on Metal and. Oxide Electrodes
- 6. Cathodic Reactions of Oxygen (Oxygen Cathodes)
- 6.1. The General Scheme of Parallel and Series Reactions of Oxygen and Hydrogen Peroxide
- 6.2. The Kinetics of Molecular Oxygen Reduction on Different Metallic Electrodes
- 6.3. Oxygen Reduction on Nonmetallic Materials
- 7. Concluding Remarks
- References
- 7. Deposition and Dissolution of Metals and Alloys. Part A: Electrocrystallization
- 1. Introduction
- 2. Kinetics of Atom Incorporation
- 2.1. The Structure of a Crystalline Surface
- 2.2. The Propagation Rate of Steps
- 2.3. The Current Density on a Stepped Crystal Face
- 3. Metal Deposition on a Perfect Crystal Face
- 3.1. Energy and Rate of Formation of Two-Dimensional Nuclei
- 3.2. Kinetics of Step Propagation and Mechanism of Metal Deposition
- 3.3. Deposition Kinetics on Perfect Crystal Faces
- 4. Metal Deposition on Faces Intersected by Screw Dislocations
- 4.1. The Theory of Spiral Growth
- 4.2. Current Density and Morphology of Growth
- 5. Electrolytic Phase Formation
- 5.1. Equilibrium Forms and Forms of Growth of Crystals
- 5.2. The Nucleation Rate
- 5.3. The Nucleation-Rate-Overpotential Relation
- 5.4. Comparison with Experimental Data
- 6. Conclusions and Outlook
- References
- 7. Deposition and Dissolution of Metals and Alloys. Part B: Mechanisms, Kinetics, Texture, and Morphology
- 1. Introduction
- 2. Specific Features of the Thermodynamics of Metal and Alloy Phase Formation and Degradation
- 2.1. Equilibration of a Metal Surface with Electrolyte Containing Metal Ions—the Problem of the Reversible Potential
- 2.2. Reversible Potentials of Alloys
- 2.3. Underpotential Deposition of Metals on Foreign Substrates
- 2.4. Effect of Interactions of the Metal Ion in Solution on the Reversible Potential
- 2.5. Effect of pH on Electrode Potential
- 3. Likely Mechanisms of Metal Ion Discharge and Their Kinetic Consequences
- 3.1. Mechanism and Kinetics of the Electrode Process
- 3.2. Pseudocapacitance Effects and the Concentration of Intermediate Species
- 3.3. Effect of Anions on the Kinetics of Metal Deposition and Dissolution
- 3.4. Effect of Substrate on the Kinetics of Activation-Controlled Reactions
- of Metals
- 3.5. Kinetics of Codeposition of Metals and Effects on Alloy Phase Formation
- 4. Totally Irreversible Dissolution of Metals
- 4.1. The “Floating” Electrode Potential
- 4.2. Dissolution with the Formation of Insoluble Substances
- 4.3. Acceleration of Anodic Dissolution of Metals under Strain
- 5. Formation and Physical Properties of Metallic Deposits Obtained under Conditions of Slow Discharge and Incorporation
- 5.1. Effect of Substrate on the Growth of the Deposit
- 5.2. Factors Affecting Grain Size in a Compact Deposit
- 5.3. The Appearance of Texture in Metal Deposits
- 5.4.
- Development of Stress in Metal Deposits
- 6. Effect of Slow Transport of Species to the Electrode on Surface Morphology of Metal Deposits
- 6.1. Amplification of Surface Roughness
- 6.2. The Appearance and Growth of Dendrites
- 6.3. The Formation of Metal Powders
- 6.4. Effect of Periodically Changing Conditions of Deposition
- 6.5. The Phenomenon of Electropolishing
- 7. Effect of Adsorption of Foreign Substances on Surface Morphology of Metal Deposits
- 7.1. The Growth of Whiskers
- 7.2. Leveling in Metal Deposition
- 8. Conclusion
- References
- 8. Processes at Semiconductor Electrodes
- 1. Introduction
- 2. Potential and Charge Distribution at Solid-Electrolyte Interfaces
- 3. Energy Levels in Solids and Electrolytes
- 3.1. Absolute and Conventional Electrode Potentials
- 3.2. Energy Levels in Solids
- 3.3. Energy Levels in Electrolytes
- 3.4. Energy Levels at Semiconductor-Electrolyte Interfaces
- 4. Electrode Kinetics
- 4.1. Rate of Electron Transfer (Theory)
- 4.2. Electrode Reactions in Electrolytes without Redox Systems
- 4.3. Redox Processes
- 4.4. Electron Transfer Processes at Organic Insulator Electrodes
- 4.5. Evaluations of Exchange Currents and Determination of Reorientation Energies
- 5. Photoeffects
- 5.1. Photopotentials and Photocurrents
- 5.2. Applications in Electrode Kinetics
- 5.3. Photostimulated Reactions at Organic Electrodes
- 6. Reactions of Excited Molecules at Electrodes
- 6.1. Energy Levels of Excited Molecules
- 6.2. Electron Transfer Process
- 6.3. Relaxation Phenomena, Quenching, Supersensitization
- 6.4. Competitive Photochemical Reactions in the Electrolyte
- 6.5. Production of Excited Molecules by Electron Transfer
- 7. Conclusions
- References
- 9. Electrochemistry in Molten Salts
- 1. Introduction
- 1.1. General
- 1.2. Complexions
- 1.3. Acidity and Basicity
- 1.4. emf Series and Reference Electrodes
- 2. Electroanalytical Aspects
- 2.1. General Methodology
- 2.2. Ion Transport
- 2.3. Ionic Adsorption
- 2.4. Couple.