Electrochemical Systems

by Newman, John; Balsara, Nitash P.

• ISBN13: 9781119514602
• ISBN10: 1119514606
• Edition: 4th
• Format: Hardcover
• Copyright: 2021-01-07
• Publisher: Wiley

Summary

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.

Author Biography

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.

Table of Contents

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