Electrochemical Systems

Provides a comprehensive understanding of a wide range of systems and topics in electrochemistry

This book offers complete coverage of electrochemical theories as they pertain to the understanding of electrochemical systems. It describes the foundations of thermodynamics, chemical kinetics, and transport phenomena--including the electrical potential and charged species. It also shows how to apply electrochemical principles to systems analysis and mathematical modeling. Using these tools, the reader will be able to model mathematically any system of interest and realize quantitative descriptions of the processes involved.

This brand new edition of Electrochemical Systems updates all chapters while adding content on lithium battery electrolyte characterization and polymer electrolytes. It also includes a new chapter on impedance spectroscopy. Presented in 4 sections, the book covers: Thermodynamics of Electrochemical Cells, Electrode Kinetics and Other Interfacial Phenomena, Transport Processes in Electrolytic Solutions, and Current Distribution and Mass Transfer in Electrochemical Systems. It also features three appendixes containing information on: Partial Molar Volumes, Vectors and Tensors, and Numerical Solution of Coupled, Ordinary Differential Equations.

• Details fundamental knowledge with a thorough methodology

• Thoroughly updated throughout with new material on topics including lithium battery electrolyte characterization, impedance analysis, and polymer electrolytes

• Includes a discussion of equilibration of a charged polymer material and an electrolytic solution (the Donnan equilibrium)

• A peerless classic on electrochemical engineering

Electrochemical Systems, Fourth Edition is an excellent resource for students, scientists, and researchers involved in electrochemical engineering.

Auteur

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.

Contenu

Preface To The Fourth Edition xv

Preface To The Third Edition xvii

Preface To The Second Edition xix

Preface To The First Edition xxi

1 Introduction 1

1.1 Definitions 2

1.2 Thermodynamics and Potential 3

1.3 Kinetics and Rates of Reaction 6

1.4 Transport 8

1.5 Concentration Overpotential and the Diffusion Potential 15

1.6 Overall Cell Potential 18

Problems 20

Notation 21

Part A Thermodynamics of Electrochemical Cells 23

2 Thermodynamics In Terms of Electrochemical Potentials 25

2.1 Phase Equilibrium 25

2.2 Chemical Potential and Electrochemical Potential 27

2.3 Definition of Some Thermodynamic Functions 30

2.4 Cell with Solution of Uniform Concentration 36

2.5 Transport Processes in Junction Regions 39

2.6 Cell with a Single Electrolyte of Varying Concentration 40

2.7 Cell with Two Electrolytes, One of Nearly Uniform Concentration 44

2.8 Cell with Two Electrolytes, Both of Varying Concentration 47

2.9 LithiumLithium Cell With Two Polymer Electrolytes 49

2.10 Standard Cell Potential and Activity Coefficients 50

2.11 Pressure Dependence of Activity Coefficients 58

2.12 Temperature Dependence of Cell Potentials 59

Problems 61

Notation 68

References 70

3 The Electric Potential 71

3.1 The Electrostatic Potential 71

3.2 Intermolecular Forces 74

3.3 Outer and Inner Potentials 76

3.4 Potentials of Reference Electrodes 77

3.5 The Electric Potential in Thermodynamics 78

Notation 79

References 80

4 Activity Coefficients 81

4.1 Ionic Distributions in Dilute Solutions 81

4.2 Electrical Contribution to the Free Energy 84

4.3 Shortcomings of the DebyeHückel Model 87

4.4 Binary Solutions 89

4.5 Multicomponent Solutions 92

4.6 Measurement of Activity Coefficients 94

4.7 Weak Electrolytes 96

Problems 99

Notation 103

References 104

5 Reference Electrodes 107

5.1 Criteria for Reference Electrodes 107

5.2 Experimental Factors Affecting Selection of Reference Electrodes 109

5.3 The Hydrogen Electrode 110

5.4 The Calomel Electrode and Other MercuryMercurous Salt Electrodes 112

5.5 The MercuryMercuric Oxide Electrode 114

5.6 SilverSilver Halide Electrodes 114

5.7 Potentials Relative to a Given Reference Electrode 116

Notation 119

References 120

6 Potentials of Cells With Junctions 121

6.1 Nernst Equation 121

6.2 Types of Liquid Junctions 122

6.3 Formulas for Liquid-Junction Potentials 123

6.4 Determination of Concentration Profiles 124

6.5 Numerical Results 124

6.6 Cells with Liquid Junction 128

6.7 Error in the Nernst Equation 129

6.8 Potentials Across Membranes 131

6.9 Charged Membranes Immersed in an Electrolytic Solution 131

Problems 135

Notation 138

References 138

Part B Electrode Kinetics and Other Interfacial Phenomena 141

7 Structure of The Electric Double Layer 143

7.1 Qualitative Description of Double Layers 143

7.2 Gibbs Adsorption Isotherm 148

7.3 The Lippmann Equation 151

7.4 The Diffuse Part of the Double Layer 155

7.5 Capacity of the Double Layer in the Absence of Specific Adsorption 160

7.6 Specific Adsorption at an ElectrodeSolution Interface 161

Problems 161

Notation 164

References 165

8 Electrode Kinetics 167

8.1 Heterogeneous Electrode Reactions 167

8.2 Dependence of Current Density on Surface Overpotential 169 &l...