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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.
Electrochemical Systems, Fourth Edition is an excellent resource for students, scientists, and researchers involved in electrochemical engineering.
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 Fourth Edition
Preface to Third Edition
Preface to Second Edition
Preface to 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–Hückel 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
24 Impedance
24.1 Frequency dispersion At A Disk Electrode
24.2 Modulated Flow With A Disk Electrode
24.3 Porous Electrodes For Batteries
24.4 Kramers-Kronig Relation
Problems
References
Appendix A Partial Molar Volumes
Appendix B Vectors and Tensors
Appendix C Numerical Solution of Coupled, Ordinary Differential Equations
Index
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