Modern Aspects of Electrochemistry

ISBN-13: 9781468486698 / Angielski / Miękka / 2012 / 414 str.

John O. Bockris; Brian E. Conway; Ralph E. White

Opis

The present volume is comprised of six chapters covering topics having both fundamental and substantial applied significance in electrochemistry: ion-exchange membrane behavior, corrosion and metal deposition, semiconductor charge injection, and the electro- catalytic properties of carbon. In the first chapter, Verbrugge and Pintauro examine transport models for ion-exchange membranes using approaches from the direction of electrochemical thermodynamics of irreversible proces- ses and others. The properties ofth models are examined quantita- tively in some mathematical detail. Drazic, in Chapter 2, gives an up-to-date account of advances in our knowledge of the "active" dissolution of iron in corrosion processes and the accompanying processes of H2 evolution and H sorption. The important process of O reduction in iron corrosion 2 is also considered, together with the more controllable aspect of anodic dissolution and cathodic deposition, as well as the influence of anions on the dissolution kinetics of iron in aqueous medium. An important aspect of metal plating technology is the use of a modulated or pulsed-current regime to provide better control over deposit morphology. In two chapters, one by Popov and Mak- simovic and the other by Pesco and Cheh, complementary aspects of this important technique are examined in detail: from the theo- retical electrode-kinetic direction, taking into account the important nonsteady diffusion situation, and from the practical direction of examining the morphologies of electrodeposits generated under various AC modulated or pulsed-current regimes.

Spis treści

1 Transport Models For Ion-Exchange Membranes.- I. Introduction.- II. Solution of Ion-Exchange Problems Using the Nernst-Planck Equation for Ion Transport.- 1. Phenomenological Equations.- 2. Literature Review of Electrokinetic Models Employing a Membrane Microstructure.- 3. Specific Adsorption.- 4. Variation of the Dielectric Constant and Viscosity and Hydration Effects.- 5. The Structure of Ion-Exchange Membranes.- 6. Macroscopic Approaches to the Modeling of Ion-Exchange Membranes Using the Nernst-Planck Equation.- III. Transport Models Based on Irreversible Thermodynamics.- 1. Development of Membrane Flux Equations.- 2. The Kedem-Katchalsky and Spiegler Transport Models.- 3. Simulation of Membrane Transport Processes.- IV. Experimental Methods for Membrane Analyses.- 1. Equilibrium Experiments.- 2. Transport Experiments.- 3. Indirect Methods for Determining the Binary-Interaction Parameters.- V. Conclusions.- Notation.- References.- 2 Iron and Its Electrochemistry in an Active State.- I. Introduction.- 1. Corrosion Potential and Corrosion Current.- 2. Methods for Measuring Corrosion Rates.- II. Hydrogen Evolution Reaction on Iron.- 1. Kinetic Parameters and Reaction Mechanisms.- 2. Hydrogen Evolution Reaction and Iron Deposition.- 3. Experimental Measurements of pH near the Electrode Surface.- 4. Absorption of Hydrogen and Hydrogen Embrittlement.- III. Electrochemical Reduction of Oxygen and Its Influence on the Anodic Dissolution of Iron.- IV. Cathodic Deposition of Iron.- V. Anodic Dissolution of Iron.- 1. Acid Solutions.- 2. Transient Phenomena.- 3. Influence of Anions on Dissolution Kinetics.- 4. Neutral Solutions.- 5. Alkaline Solutions.- VI. Anomalous Dissolution of Iron.- VII. Conclusions.- References.- 3 Theory of the Effect of Electrodeposition at a Periodically Changing Rate on the Morphology of Metal Deposits.- I. Basic Definitions.- 1. Reversing Current.- 2. Pulsating Current.- 3. Alternating Current Superimposed on Direct Current.- 4. Pulsating Overpotential.- II. Surface Concentration in the Periodic Condition.- 1. Mathematical Model.- 2. Capacitance Effects.- 3. The Validity of the Mathematical Model.- 4. The Case of Pulsating Overpotential.- 5. Reversing Current in the Second Range.- III. Current Distribution on a Microprofile.- 1. Amplification of Surface Irregularities in Electrodeposition at Constant Deposition Rate.- 2. Amplification of Surface Irregularities in EPCR in the Millisecond Range.- 3. Amplification of Surface Irregularities in Electrodeposition for Reversing Current in the Second Range.- 4. The Effect of Deposition Current Density.- IV. Maximum Deposition Rate.- 1. Maximum Deposition Rate in Electrodeposition at a Constant Rate.- 2. Maximum Deposition Rate in EPCR in the Millisecond Range.- 3. Maximum Deposition Rate in Electrodeposition by Reversing Current in the Second Range.- V. Prevention of Formation of Spongy Deposits.- VI. Current Distribution on a Macroprofile.- VII. Surface Film Formation.- VIII. Energetic Aspects.- IX. Conclusions.- Notation.- References.- 4 Theory and Applications of Periodic Electrolysis.- I. Introduction.- II. Effect on Morphology of Electrodeposited Metals.- 1. Rectangular-Pulse Electrolysis.- 2. Periodic-Reverse Electrolysis.- 3. Sinusoidal (Symmetric and Asymmetric) Electrolysis.- III. Theoretical Aspects of Periodic Electrolysis.- 1. Mass Transfer.- 2. Current Distribution.- IV. Conclusions.- Notation.- References.- 5 Electrocatalytic Properties of Carbon Materials.- I. Introduction.- II. Physicochemical Properties of Carbon Materials.- 1. Crystallochemistry and Electronic Structure.- 2. Surface Chemistry.- III. Electrochemical Reactions on Carbon Materials.- 1. The Chlorine Reaction.- 2. The Oxygen Reaction.- 3. The Hydrogen Peroxide Reactions.- 4. The Hydrogen Evolution Reaction.- 5. Electrooxidation of Sulfur Dioxide.- 6. The Reactions of Organic Compounds.- IV. Chemically Modified Electrodes.- 1. Methods of Modifying Carbon Materials.- 2. The Mechanism of Electrocatalytic Reactions.- V. Conclusions.- References.- 6 Spin-Dependent Kinetics in Dye-Sensitized Charge-Carrier Injection Into Organic Crystal Electrodes.- I. Introduction.- II. Theoretical Considerations.- III. Experimental Aspects.- IV. Main Results.- 1. Detection of the HFM on the Surface.- 2. Origin of the HF Effect on the Surface.- 3. Decrease in the Spin Correlation Time with Increasing Electric Field, E.- 4. Decrease in the Spin Correlation Time through Recombination Centers.- V. Summary.- References.