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Electrochemical Systems

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Table of Contents

PREFACE TO THE THIRD EDITION. PREFACE TO THE SECOND EDITION. PREFACE TO THE FIRST EDITION. 1 INTRODUCTION. 1.1 Definitions. 1.2 Thermodynamics and Potential. 1.3 Kinetics and Rates of Reaction. 1.4 Transport. 1.5 Concentration Overpotential and the Diffusion Potential. 1.6 Overall Cell Potential. Problems. Notation. PART A: THERMODYNAMICS OF ELECTROCHEMICAL CELLS. 2 THERMODYNAMICS IN TERMS OF ELECTROCHEMICAL POTENTIALS. 2.1 Phase Equilibrium. 2.2 Chemical Potential and Electrochemical Potential. 2.3 Definition of Some Thermodynamic Functions. 2.4 Cell with Solution of Uniform Concentration. 2.5 Transport Processes in Junction Regions. 2.6 Cell with a Single Electrolyte of Varying Concentration. 2.7 Cell with Two Electrolytes, One of Nearly Uniform Concentration. 2.8 Cell with Two Electrolytes, Both of Varying Concentration. 2.9 Standard Cell Potential and Activity Coefficients. 2.10 Pressure Dependence of Activity Coefficients. 2.11 Temperature Dependence of Cell Potentials. Problems. Notation. References. 3 THE ELECTRIC POTENTIAL. 3.1 The Electrostatic Potential. 3.2 Intermolecular Forces. 3.3 Outer and Inner Potentials. 3.4 Potentials of Reference Electrodes. 3.5 The Electric Potential in Thermodynamics. Notation. References. 4 ACTIVITY COEFFICIENTS. 4.1 Ionic Distributions in Dilute Solutions. 4.2 Electrical Contribution to the Free Energy. 4.3 Shortcomings of the Debye?Huckel Model. 4.4 Binary Solutions. 4.5 Multicomponent Solutions. 4.6 Measurement of Activity Coefficients. 4.7 Weak Electrolytes. Problems. Notation. References. 5 REFERENCE ELECTRODES. 5.1 Criteria for Reference Electrodes. 5.2 Experimental Factors Affecting The Selection of Reference Electrodes. 5.3 The Hydrogen Electrode. 5.4 The Calomel Electrode and Other Mercury?Mercurous Salt Electrodes. 5.5 The Mercury?Mercuric Oxide Electrode. 5.6 Silver?Silver Halide Electrodes. 5.7 Potentials Relative to a Given Reference Electrode. Notation. References. 6 POTENTIALS OF CELLS WITH JUNCTIONS. 6.1 Nernst Equation. 6.2 Types of Liquid Junctions. 6.3 Formulas for Liquid-Junction Potentials. 6.4 Determination of Concentration Profiles. 6.5 Numerical Results. 6.6 Cells with Liquid Junction. 6.7 Error in the Nernst Equation. 6.8 Potentials Across Membranes. Problems. Notation. References. PART B: ELECTRODE KINETICS AND OTHER INTERFACIAL PHENOMENA. 7 STRUCTURE OF THE ELECTRIC DOUBLE LAYER. 7.1 Qualitative Description of Double Layers. 7.2 Gibbs Adsorption Isotherm. 7.3 The Lippmann Equation. 7.4 The Diffuse Part of the Double Layer. 7.5 Capacity of the Double Layer in the Absence of Specific Adsorption. 7.6 Specific Adsorption at an Electrode?Solution Interface. Problems. Notation. References. 8 ELECTRODE KINETICS. 8.1 Heterogeneous Electrode Reactions. 8.2 Dependence of Current Density on Surface Overpotential. 8.3 Models for Electrode Kinetics. 8.4 Effect of Double-Layer Structure. 8.5 The Oxygen Electrode. 8.6 Methods of Measurement. 8.7 Simultaneous Reactions. Problems. Notation. References. 9 ELECTROKINETIC PHENOMENA. 9.1 Discontinuous Velocity at an Interface. 9.2 Electro-Osmosis and the Streaming Potential. 9.3 Electrophoresis. 9.4 Sedimentation Potential. Problems. Notation. References. 10 ELECTROCAPILLARY PHENOMENA. 10.1 Dynamics of Interfaces. 10.2 Electrocapillary Motion of Mercury Drops. 10.3 Sedimentation Potentials for Falling Mercury Drops. Notation. References. PART C: TRANSPORT PROCESSES IN ELECTROLYTIC SOLUTIONS. 11 INFINITELY DILUTE SOLUTIONS. 11.1 Transport Laws. 11.2 Conductivity, Diffusion Potentials, and Transference Numbers. 11.3 Conservation of Charge. 11.4 The Binary Electrolyte. 11.5 Supporting Electrolyte. 11.6 Multicomponent Diffusion by Elimination of the Electric Field. 11.7 Mobilities and Diffusion Coefficients. 11.8 Electroneutrality and Laplace?s Equation. 11.9 Moderately Dilute Solutions. Problems. Notation. References. 12 CONCENTRATED SOLUTIONS. 12.1 Transport Laws. 12.2 The Binary Electrolyte. 12.3 Reference Velocities. 12.4 The Potential. 12.5 Connection with Dilute-Solution Theory. 12.6 Multicomponent Transport. 12.7 Liquid-Junction Potentials. Problems. Notation. References. 13 THERMAL EFFECTS. 13.1 Thermal Diffusion. 13.2 Heat Generation, Conservation, and Transfer. 13.3 Heat Generation at an Interface. 13.4 Thermogalvanic Cells. Problems. Notation. References. 14 TRANSPORT PROPERTIES. 14.1 Infinitely Dilute Solutions. 14.2 Solutions of a Single Salt. 14.3 Multicomponent Solutions. 14.4 Integral Diffusion Coefficients for Mass Transfer. Problem. Notation. References. 15 FLUID MECHANICS. 15.1 Mass and Momentum Balances. 15.2 Stress in a Newtonian Fluid. 15.3 Boundary Conditions. 15.4 Fluid Flow to a Rotating Disk. 15.5 Magnitude of Electrical Forces. 15.6 Turbulent Flow. 15.7 Mass Transfer in Turbulent Flow. Problem . Notation. References. PART D: CURRENT DISTRIBUTION AND MASS TRANSFER IN ELECTROCHEMICAL SYSTEMS. 16 FUNDAMENTAL EQUATIONS. 16.1 Transport in Dilute Solutions. 16.2 Electrode Kinetics. Notation. 17 CONVECTIVE-TRANSPORT PROBLEMS. 17.1 Simplifications for Convective Transport. 17.2 The Rotating Disk. 17.3 The Graetz Problem. 17.4 The Annulus. 17.5 Two-Dimensional Diffusion Layers in Laminar Forced Convection. 17.6 Axisymmetric Diffusion Layers in Laminar Forced Convection. 17.7 A Flat Plate in a Free Stream. 17.8 Rotating Cylinders. 17.9 Growing Mercury Drops. 17.10 Free Convection. 17.11 Combined Free and Forced Convection. 17.12 Limitations of Surface Reactions. 17.13 Binary and Concentrated Solutions. Problems. Notation. References. 18 APPLICATIONS OF POTENTIAL THEORY. 18.1 Simplifications for Potential-Theory Problems. 18.2 Primary Current Distribution. 18.3 Secondary Current Distribution. 18.4 Numerical Solution by Finite Differences. 18.5 Principles of Cathodic Protection. Problems. Notation. References. 19 EFFECT OF MIGRATION ON LIMITING CURRENTS. 19.1 Analysis. 19.2 Correction Factor for Limiting Currents. 19.3 Concentration Variation of Supporting Electrolyte. 19.4 Role of Bisulfate Ions. 19.5 Paradoxes with Supporting Electrolyte. 19.6 Limiting Currents for Free Convection. Problems. Notation. References. 20 CONCENTRATION OVERPOTENTIAL. 20.1 Definition. 20.2 Binary Electrolyte. 20.3 Supporting Electrolyte. 20.4 Calculated Values. Problems. Notation. References. 21 CURRENTS BELOW THE LIMITING CURRENT. 21.1 The Bulk Medium. 21.2 The Diffusion Layers. 21.3 Boundary Conditions and Method of Solution. 21.4 Results for the Rotating Disk. Problems. Notation. References. 22 POROUS ELECTRODES. 22.1 Macroscopic Description of Porous Electrodes. 22.2 Nonuniform Reaction Rates. 22.3 Mass Transfer. 22.4 Battery Simulation. 22.5 Double-Layer Charging and Adsorption. 22.6 Flow-Through Electrochemical Reactors. Problems. Notation. References. 23 SEMICONDUCTOR ELECTRODES. 23.1 Nature of Semiconductors. 23.2 Electric Capacitance at the Semiconductor?Solution Interface. 23.3 Liquid-Junction Solar Cell. 23.4 Generalized Interfacial Kinetics. 23.5 Additional Aspects. Problems. Notation. References. APPENDIX A: PARTIAL MOLAR VOLUMES. APPENDIX B: VECTORS AND TENSORS. APPENDIX C: NUMERICAL SOLUTION OF COUPLED, ORDINARY DIFFERENTIAL EQUATIONS. INDEX.

About the Author

JOHN NEWMAN, PhD, has been a professor of chemical engineering at the University of California, Berkeley, since 1963. Known worldwide for his seminal papers in the mathematical analysis of electrochemical problems, both analytic and numerical, he is a member of the National Academy of Engineering and the recipient of several awards from the Electrochemical Society. He is the former associate editor for the Journal of the Electrochemical Society and current Director of the U. S. Department of Energy's Batteries for Advanced Transportation Technologies program. KAREN E. THOMAS-ALYEA received her PhD in chemical engineering from the University of California, Berkeley, in 2002. Her work has involved modeling of batteries and fuel cells.


"...a solid, well-rounded discussion of the principal aspects of electrochemistry and is well suited for use as a graduate-level textbook. Also, it will make a valuable personal library addition for the corrosion professional..." (Corrosion, December 2005) "Newman obviously has extensive experience in electrochemistry, as evidenced by his sophisticated treatment of the subject in this volume." (Journal of Metals Online, March 8, 2005) "?it will be a useful to anyone involved in the practice of electrochemistry?highly recommended." (CHOICE, November 2004)

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