Buch, Englisch, 222 Seiten, Paperback, Format (B × H): 152 mm x 229 mm, Gewicht: 354 g
Buch, Englisch, 222 Seiten, Paperback, Format (B × H): 152 mm x 229 mm, Gewicht: 354 g
ISBN: 978-1-4684-1733-3
Verlag: Springer US
Zielgruppe
Research
Autoren/Hrsg.
Weitere Infos & Material
I Adsorption in Electrochemistry.- 1. Introduction.- 1.1. Special Aspects of Adsorption from Solution.- 2. Equations of State and Isotherms.- 2.1. Definitions and Use.- 2.2. Conversion of Equation of State to Isotherms.- 3. The Langmuir Isotherm.- 3.1. Value and Deficiency.- 3.2. Methods of Derivation.- 3.3. Langmuir-like Adsorption.- 3.3.1. Adsorption of Large Molecules.- 3.3.2. Adsorption from a Second Layer.- 3.4. Langmuir Adsorption from Solution.- 4. The Temkin Isotherm.- 4.1. Assumptions, General Form, and Limiting Cases.- 5. The Frumkin Isotherm.- 5.1. Free Energy of Adsorption Decreasing with Coverage.- 5.2. Free Energy of Adsorption Increasing with Coverage.- 5.3. Frumkin-Type Adsorption from Solution.- 6. Experimental Tests of the Isotherms.- 7. Conclusions.- References.- 2 Organic Adsorption at Electrodes.- 1. Introduction.- 2. Comparison of Methods for Adsorption Studies in the Gas Phase and at Electrodes in Solution.- 3. Energetics of Adsorption.- 4. Trends in Electrosorption.- 5. Modes of Adsorption and Structure of Adsorbed Species.- 6. The Adsorption Characteristics of Some Selected Compounds.- 6.1. Carbon Monoxide.- 6.2. Formic Acid.- 6.3. Alcohols.- 6.4. Hydrocarbons.- 7. Open-Circuit Adsorption Behavior.- 8. Summary.- References.- 3 Kinetics of Diffusion-Controlled Electrosorption of Neutral Molecules.- 1 Introduction.- 2. The Adsorption Isotherm and the Mass Transfer Process.- 3. Analysis of the Diffusion Problem.- 4. The Time Variation of the Surface Concentration of Adsorbed Species.- 5. Mass Transport-Controlled Electrosorption Under Stirred Conditions.- References.- 4 Oxygen Adsorption and Oxide Formation on Electrodes.- 1. Introduction.- 2. Thermodynamics of Oxidation.- 3. Characteristics of Physically Adsorbed Oxygen.- 4. Characteristics of Chemisorbed Oxygen.- 5. The Occurrence of Physical Adsorption.- 6. The Occurrence of Chemisorption.- 7. Mechanism of Oxide Growth.- 7.1. Growth of Nonconducting Oxides.- 7.2. Growth of Semiconducting Oxides.- 7.3. Growth of Conducting Oxides.- 7.4. Growth of Oxides by Diffusion.- 8. Why is Adsorbed Oxygen Important ?.- References.- 5 The Potential of Zero Charge.- 1. Introduction.- 1.1. What is the Potential of Zero Charge ?.- 1.2. The Rational Scale of Potential.- 1.3. Electrode Kinetics and the Potential of Zero Charge.- 1.3.1. Primary Effects.- 1.3.2. Secondary Effects.- 1.4. Dependence of Adsorption on the Potential of Zero Charge.- 2. Aspects of the Potential of Zero Charge Dependent on the Metal.- 2.1. The Relation Between Potential of Zero Charge, Contact Potential Difference, and Work Function.- 2.2. Physicochemical Properties of the Metal.- 3. Aspects of the Potential of Zero Charge Related to the System.- 3.1. Specific Adsorption of Ions.- 3.2. Organic Adsorption.- 3.3. Surface Coverage with Atomic Hydrogen or Oxygen.- 3.4. pH Variation.- 4. Methods of Determination of the Potential of Zero Charge.- 4.1. Surface Tension Methods.- 4.1.1. Electrocapillary Curves.- 4.1.2. Contact Angle Method.- 4.2. Change of Surface Area.- 4.3. Capacity Measurements.- 4.4. Adsorption Methods.- 4.4.1. Ionic Adsorption.- 4.4.2. Dependence of Organic Adsorption on Electrolyte Concentration.- 4.5. Friction Methods.- 4.5.1. The Pendulum Method.- 4.5.2. The Angle of Inclination Method.- 4.6. Ultrasonic Method.- 4.7. Repulsion of Double Layers on Two Wires.- 5. Conclusions.- References.- 6 The Role of Solvents at Electrodes.- 1. Introduction.- 2. Field-Dependent Orientation of the Solvent at the Metal—Solution Interface.- 3. Dielectric Properties of the Solvent at the Electrode.- 3.1. The Double Layer as Parallel Plate Capacitor.- 3.2. Dielectric Properties of Dipolar Substances.- 3.3. Dielectric Relaxation and Rate Theory; Distribution of Relaxation Times.- 3.4. Experimental Determination of the Dielectric Properties of Water in the Electric Double Layer.- 3.5. Theoretical Considerations and Discussions.- 3.5.1. Artifacts.- 3.5.2. The Value of the Mean Relaxation Time.- 3.5.3. Dipole Relaxation and Double-Layer Structure.- 3.5.4. The Value of ?x and the Mechanism of Conduction.- 3.6. Conclusions.- 4. Adsorptive Properties of the Solvent at the Electrode.- 4.1. Gibbs Surface Excess and Adsorption of Neutral Molecules.- 4.2. Model of the Adsorption Process.- 4.2.1. Exchange Equilibrium.- 4.2.2. The Mechanism of Adsorption.- 4.2.3. Model of Adsorbed Molecules.- 4.2.4. Molecular Interactions at the Interface.- 4.3. The Electric Variable.- 4.4. Adsorption Equations.- 4.5. Conclusions.- 5. Final Remarks.- References.- 7 Theoretical Consideration of the Double Layer.- 1. An Electrostatic Model of the Electrochemical Double Layer.- 1.1. General Features of the Model.- 1.2. Distinction Between the Electrostatic Interactions in the Double Layer.- 1.3. A Closed Solution for the Coulomb Potential of an Isolated Charge.- 1.4. Determination of the Average Electrostatic Potential in the Double Layer.- 2. The Local Thermodynamic Formulation for Inhomogeneous Electrochemical Systems.- 2.1. The Local Balance Theory of Prigogine, Mazur, and Defay.- 2.2. The Definition of Pressure at the Interphase.- 2.3. The Definition of the Electrochemical Potential.- 2.4. The Distribution Function at Equilibrium.- 3. Theories of the Ionic Double Layer.- 3.1. General Evolution of the Theoretical Concepts of the Diffuse Layer.- 3.2. Preliminaries on the Statistical Mechanical Formulation in Fluids.- 3.2.1. The Set Notation.- 3.2.2. Definition of Probability Density in the Canonical Ensemble.- 3.2.3. The Correlation and Radial Distribution Function.- 3.2.4. Kirkwood’s Superposition Approximation.- 3.2.5. Distribution in the Grand Ensemble.- 3.2.6. Average Electrostatic Potential and Free Energy.- 3.3. The Differential Equation Method of Debye and Hückel.- 3.4. The Gouy Potential in the Diffuse Layer.- 3.4.1. The Integrability Condition in the Case of an Inhomogeneous System.- 3.4.2. The Solution of Gouy and Chapman.- 3.4.3. Determination of the Self-Atmosphere Effect by Means of the Cluster Expansion Method.- 3.4.4. The Diffuse Layer Version of the Expansion Method in Terms of a Charging Parameter.- 3.4.5. The Evaluation of the Electrostatic Potentials in the Diffuse Layer by Means of Stillinger and Kirkwood’s Method.- 3.4.6. Application of the Local Thermodynamic Method.- 3.5. General Evolution of Ideas on Specific Adsorption in the Inner Layer.- 3.6. General Expression of the Adsorption Isotherm.- 3.7. The Mobile Monolayer Adsorption.- 3.7.1. Description of the Model of Mobile Adsorption.- 3.7.2. The Cavity Field.- 3.7.3. The Coordination Field.- 3.7.4. The Radial Redistribution Work.- 3.7.5. The Final Form of the Adsorption Isotherm and Its Application.- 3.8. The Discreteness of Charge Model and Lattice Adsorption.- References.