Modern Aspects of Electrochemistry No. 6

ISBN-13: 9781468430028 / Angielski / Miękka / 2012 / 381 str.

J. O. Bockris; B. E. Conway

Opis

In the last decade, the evolution of electrochemistry away from concern with the physical chemistry of solutions to its more fruitful goal in the study of the widespread consequences of the transfer of electric charges across interphases has come to fruition. The turning of technology away from an onward rush, regardless, to progress which takes into account repercussions of techno logical activity on the environment, and the consequent need for a reduction and then termination of the injection of CO into 2 the atmosphere (greenhouse effect), together with a reckoning with air and water pollution in general, ensures a long-term need for advances in a basic knowledge of electrochemical systems, an increased technological use of which seems to arise from the environmental necessities. But a mighty change in attitude needs to spread among electro chemists (indeed, among all surface chemists) concerning the terms and level in which their field is discussed. The treatment of charge transfer reactions has often been made too vaguely, in terms, it seemed, of atom transfer, with the electron-transfer step, the essence of electrochemistry, an implied accompaniment to the transfer of ions across electrical double layers. The treatment has been in terms of classical mechanics, only tenable while inadequate questions were asked concerning the behavior of the electron in the interfacial transfer. No process demands a more exclusively quantal discussion than does electron transfer."

Spis treści

1 Computed Thermodynamic Properties and Distribution Functions for Simple Models of Ionic Solutions.- I. Introduction.- II. Theoretical Background.- III. Some Results from Statistical Mechanics.- IV. Approximation Techniques.- 1. Monte Carlo and Molecular Dynamic Methods.- 2. Other Approximation Methods.- V. MacMillan-Mayer Theory.- VI. Thermodynamics.- VII. Results Which Are Independent of the Model.- VIII. Properties of the Primitive Model.- IX. Some Other Models with Discontinuous Potentials.- X. Models with Continuous Potential Functions.- XI. Model Calculations in Some Related Areas.- XII. Supplement.- Acknowledgment.- References.- 2 Surface Potential at Liquid Interfaces.- I. Definitions.- II. Experimental Methods for Measuring Surface Potentials at Liquid Interfaces.- 1. Vibrating Plate Method.- 2. Ionizing Electrode Method.- 3. Liquid Jet Method.- III. Surface Potential of Aqueous Solutions of Inorganic Electrolytes.- 1. Surface Tension and Adsorption of Ions at Air/Water Interfaces.- 2. Experimental Results on Surface Potential.- 3. Values of the Surface Potential XH2O.- 4. Surface Structure of Water.- IV. Ionized Monolayers.- 1. Surface Potential of Charged Monolayers.- 2. Equation of State for Charged Monolayers.- 3. Study of Charged Insoluble Monolayers by Using the Donnan Equations.- V. Incompletely and Un-ionized Monolayers.- 1. Monolayers of Un-ionized Compounds.- 2. Monolayers of Weak Acids and Bases.- Notation.- References.- 3 Transport Phenomena in Electrochemical Kinetics.- I. Introduction.- 1. Basic Equations Related to Mass Transport.- 2. Systematic Resolution of the Steady-State Mass Transfer Problem.- II. Flows Controlled by Motion of the Working Electrode.- 1. The Rotating Disk Electrode.- 2. Modified Diffusional Fluxes at a Rotating Disk Electrode.- 3. The Rotating Ring Electrode.- 4. The Rotating Ring-Disk Electrode.- 5. The Translating Electrode in Stagnation-Point Flow.- III. Convective Diffusion at Electrodes with Flowing Solutions.- 1. The Fixed Disk Electrode in Stagnation-Point Flow.- 2. Conical Electrodes in an Axial Laminar Flow.- 3. Application of Fixed Disk Electrodes in Stagnation-Point Flow and of Conical Electrodes to Convective Diffusion Controlled Processes.- 4. Tubular and Canal-Shaped Electrodes.- 5. Electrodes Consisting of Solids of Revolution.- IV. Electrodes under Free Convection.- 1. Theory of the Thermal Convective Electrode.- 2. Verification of the Theory.- 3. Comparison between the Mass Transport Rate Due to Nonisothermal Free Convection and That Due to Forced Convection in Laminar Flow.- V. Applications to Electrochemical Kinetics.- 1. General Expressions for Current-Potential Curves.- 2. Applications for Intermediate Kinetics.- 3. Stationary Current-Potential Relations Derived from the Generalized Treatment of Hydrodynamic Voltammetry.- 4. Collection Efficiency at Neighboring Electrodes.- 5. Steady Current-Potential Characteristics for Simple Electrode Processes under Laminar Isothermal Free Convection.- 6. Steady Current-Potential Characteristics for Simple Electrode Processes under Nonisothermal Free Convection.- 7. The Influence of Electrode Height on the Rate Equation.- VI. Conclusion.- References.- 4 The Mechanism of Charge Transfer from Metal Electrodes to Ions in Solution.- I. Introduction.- II. Gurney’s Quantum Mechanical Theory of Charge Transfer.- 1. Neutralization of Gaseous Ions.- 2. Neutralization of Ions in Solution, 0°K Approximation.- 3. Neutralization of Ions in Solution at Temperatures above 0°K.- 4. Solvent-Atom Interactions.- 5. Summary.- III. Developments of the Quantum Mechanical Theory.- 1. Butler’s Theory.- 2. Gerischer’s Theory.- 3. Theory Due to Bockris and Matthews.- IV. Absolute Reaction Rate Approach to Charge-Transfer Reactions.- 1. Theory Due to Horiuti and Polaryi.- 2. Calculations of Parsons and Bockris.- 3. Calculations of Conway and Bockris.- 4. Calculations of Despic and Bockris.- V. Electrostatic Treatment of the Rate of Redox Reactions Hush’s Theory for Redox Reactions.- 2. Marcus’ Theory for Redox Reactions.- 3. Theory due to Levich, Dogonadze, and Chizmadzhev.- VI. Ion Tunneling.- 1. Christov’s Work.- 2. Conway’s Work.- 3. Work of Bockris and Matthews.- VII. Concluding Remarks.- Acknowledgments.- Appendix I. The Transfer Coefficient.- Appendix II. The Adiabatic Principle and Related Approximations.- References.- 5 Electrochemical Processes in Glow Discharge at the Gas-Solution Interface.- I. Introduction.- II. History.- III. Experimental Technique.- IV. Physical Features of GDE.- V. Glow-Discharge Phenomena in Conventional Electrolysis.- VI. Chemical Results of Glow-Discharge Electrolysis.- 1. Water.- 2. Aqueous Solutions of Oxidizable Substrates.- 3. Other Inorganic Reactions in Water.- 4. Reactions of Organic Substances.- 5. Nonaqueous Reactions.- 6. Chemical Effects of Other Discharges.- VII. Mechanism of Glow-Discharge Electrolysis.- VIII. Glow-Discharge Electrolysis and Radiation Chemistry.- IX. Applications of Glow-Discharge Electrolysis.- References.