Electrochemical Systems

John Newman, PhD, has been a Professor of Chemical Engineering at the University of California, Berkeley, since 1963, is a member of the National Academy of Engineering, and the recipient of several awards from The Electrochemical Society.Nitash P. Balsara, PhD, holds the Charles W. Tobias Chair in Electrochemistry at the Department of Chemical and Biomolecular Engineering, University of California, Berkeley, where he has been a professor since 2000.

• Preface To The Fourth Edition xvPreface To The Third Edition xviiPreface To The Second Edition xixPreface To The First Edition xxi1 Introduction 11.1 Definitions 21.2 Thermodynamics and Potential 31.3 Kinetics and Rates of Reaction 61.4 Transport 81.5 Concentration Overpotential and the Diffusion Potential 151.6 Overall Cell Potential 18Problems 20Notation 21Part A Thermodynamics of Electrochemical Cells 232 Thermodynamics In Terms of Electrochemical Potentials 252.1 Phase Equilibrium 252.2 Chemical Potential and Electrochemical Potential 272.3 Definition of Some Thermodynamic Functions 302.4 Cell with Solution of Uniform Concentration 362.5 Transport Processes in Junction Regions 392.6 Cell with a Single Electrolyte of Varying Concentration 402.7 Cell with Two Electrolytes, One of Nearly Uniform Concentration 442.8 Cell with Two Electrolytes, Both of Varying Concentration 472.9 Lithium–Lithium Cell With Two Polymer Electrolytes 492.10 Standard Cell Potential and Activity Coefficients 502.11 Pressure Dependence of Activity Coefficients 582.12 Temperature Dependence of Cell Potentials 59Problems 61Notation 68References 703 The Electric Potential 713.1 The Electrostatic Potential 713.2 Intermolecular Forces 743.3 Outer and Inner Potentials 763.4 Potentials of Reference Electrodes 773.5 The Electric Potential in Thermodynamics 78Notation 79References 804 Activity Coefficients 814.1 Ionic Distributions in Dilute Solutions 814.2 Electrical Contribution to the Free Energy 844.3 Shortcomings of the Debye–Hückel Model 874.4 Binary Solutions 894.5 Multicomponent Solutions 924.6 Measurement of Activity Coefficients 944.7 Weak Electrolytes 96Problems 99Notation 103References 1045 Reference Electrodes 1075.1 Criteria for Reference Electrodes 1075.2 Experimental Factors Affecting Selection of Reference Electrodes 1095.3 The Hydrogen Electrode 1105.4 The Calomel Electrode and Other Mercury–Mercurous Salt Electrodes 1125.5 The Mercury–Mercuric Oxide Electrode 1145.6 Silver–Silver Halide Electrodes 1145.7 Potentials Relative to a Given Reference Electrode 116Notation 119References 1206 Potentials of Cells With Junctions 1216.1 Nernst Equation 1216.2 Types of Liquid Junctions 1226.3 Formulas for Liquid-Junction Potentials 1236.4 Determination of Concentration Profiles 1246.5 Numerical Results 1246.6 Cells with Liquid Junction 1286.7 Error in the Nernst Equation 1296.8 Potentials Across Membranes 1316.9 Charged Membranes Immersed in an Electrolytic Solution 131Problems 135Notation 138References 138Part B Electrode Kinetics and Other Interfacial Phenomena 1417 Structure of The Electric Double Layer 1437.1 Qualitative Description of Double Layers 1437.2 Gibbs Adsorption Isotherm 1487.3 The Lippmann Equation 1517.4 The Diffuse Part of the Double Layer 1557.5 Capacity of the Double Layer in the Absence of Specific Adsorption 1607.6 Specific Adsorption at an Electrode–Solution Interface 161Problems 161Notation 164References 1658 Electrode Kinetics 1678.1 Heterogeneous Electrode Reactions 1678.2 Dependence of Current Density on Surface Overpotential 1698.3 Models for Electrode Kinetics 1708.4 Effect of Double-Layer Structure 1858.5 The Oxygen Electrode 1878.6 Methods of Measurement 1928.7 Simultaneous Reactions 193Problems 195Notation 199References 2009 Electrokinetic Phenomena 2039.1 Discontinuous Velocity at an Interface 2039.2 Electro-Osmosis and the Streaming Potential 2059.3 Electrophoresis 2139.4 Sedimentation Potential 215Problems 216Notation 218References 21910 Electrocapillary Phenomena 22110.1 Dynamics of Interfaces 22110.2 Electrocapillary Motion of Mercury Drops 22210.3 Sedimentation Potentials for Falling Mercury Drops 224Notation 224References 225Part C Transport Processes In Electrolytic Solutions 22711 Infinitely Dilute Solutions 22911.1 Transport Laws 22911.2 Conductivity, Diffusion Potentials, and Transference Numbers 23211.3 Conservation of Charge 23311.4 The Binary Electrolyte 23311.5 Supporting Electrolyte 23611.6 Multicomponent Diffusion by Elimination of the Electric Field 23711.7 Mobilities and Diffusion Coefficients 23811.8 Electroneutrality and Laplace’S Equation 24011.9 Moderately Dilute Solutions 242Problems 244Notation 247References 24712 Concentrated Solutions 24912.1 Transport Laws 24912.2 The Binary Electrolyte 25112.3 Reference Velocities 25212.4 The Potential 25312.5 Connection with Dilute-Solution Theory 25612.6 Example Calculation Using Concentrated Solution Theory 25712.7 Multicomponent Transport 25912.8 Liquid-Junction Potentials 262Problems 263Notation 264References 26613 Thermal Effects 26713.1 Thermal Diffusion 26813.2 Heat Generation, Conservation, and Transfer 27013.3 Heat Generation at an Interface 27213.4 Thermogalvanic Cells 27413.5 Concluding Statements 276Problems 277Notation 279References 28014 Transport Properties 28314.1 Infinitely Dilute Solutions 28314.2 Solutions of a Single Salt 28314.3 Mixtures of Polymers and Salts 28614.4 Types of Transport Properties and Their Number 29514.5 Integral Diffusion Coefficients for Mass Transfer 296Problem 298Notation 298References 29915 Fluid Mechanics 30115.1 Mass and Momentum Balances 30115.2 Stress in a Newtonian Fluid 30215.3 Boundary Conditions 30315.4 Fluid Flow to a Rotating Disk 30415.5 Magnitude of Electrical Forces 30715.6 Turbulent Flow 31015.7 Mass Transfer in Turbulent Flow 31415.8 Dissipation Theorem for Turbulent Pipe Flow 316Problem 318Notation 319References 321Part D Current Distribution and Mass Transfer In Electrochemical Systems 32316 Fundamental Equations 32716.1 Transport in Dilute Solutions 32716.2 Electrode Kinetics 328Notation 32917 Convective-Transport Problems 33117.1 Simplifications for Convective Transport 33117.2 The Rotating Disk 33217.3 The Graetz Problem 33517.4 The Annulus 34017.5 Two-Dimensional Diffusion Layers in Laminar Forced Convection 34417.6 Axisymmetric Diffusion Layers in Laminar Forced Convection 34517.7 A Flat Plate in a Free Stream 34617.8 Rotating Cylinders 34717.9 Growing Mercury Drops 34917.10 Free Convection 34917.11 Combined Free and Forced Convection 35117.12 Limitations of Surface Reactions 35217.13 Binary and Concentrated Solutions 353Problems 354Notation 359References 36018 Applications of Potential Theory 36518.1 Simplifications For Potential-Theory Problems 36618.2 Primary Current Distribution 36718.3 Secondary Current Distribution 37018.4 Numerical Solution by Finite Differences 37418.5 Principles of Cathodic Protection 375Problems 389Notation 396References 39719 Effect of Migration On Limiting Currents 39919.1 Analysis 40019.2 Correction Factor for Limiting Currents 40219.3 Concentration Variation of Supporting Electrolyte 40419.4 Role of Bisulfate Ions 40919.5 Paradoxes with Supporting Electrolyte 41319.6 Limiting Currents for Free Convection 417Problems 423Notation 424References 42620 Concentration Overpotential 42720.1 Definition 42720.2 Binary Electrolyte 42920.3 Supporting Electrolyte 43020.4 Calculated Values 430Problems 431Notation 432References 43321 Currents Below The Limiting Current 43521.1 The Bulk Medium 43621.2 The Diffusion Layers 43721.3 Boundary Conditions and Method of Solution 43821.4 Results for the Rotating Disk 440Problems 444Notation 446References 44722 Porous Electrodes 44922.1 Macroscopic Description of Porous Electrodes 45022.2 Nonuniform Reaction Rates 45722.3 Mass Transfer 46222.4 Battery Simulation 46322.5 Double-Layer Charging and Adsorption 47722.6 Flow-Through Electrochemical Reactors 478Problems 482Notation 484References 48623 Semiconductor Electrodes 48923.1 Nature of Semiconductors 49023.2 Electric Capacitance at the Semiconductor–Solution Interface 49923.3 Liquid-Junction Solar Cell 50223.4 Generalized Interfacial Kinetics 50623.5 Additional Aspects 509Problems 513Notation 514References 51624 Impedance 51724.1 Frequency Dispersion at a Disk Electrode 51924.2 Modulated Flow With a Disk Electrode 52224.3 Porous Electrodes for Batteries 52624.4 Kramers–Kronig Relation 528Problems 530Notation 531References 532Appendix A Partial Molar Volumes 535Appendix B Vectors and Tensors 537Appendix C Numerical Solution of Coupled, Ordinary Differential Equations 543Index 567