Electrochemical Methods

Fundamentals and Applications
3. Auflage 2022
ISBN: 978-1-119-33406-4
Verlag: Wiley John + Sons

Buch, Englisch, 1104 Seiten, Format (B × H): 185 mm x 255 mm, Gewicht: 2216 g

The latest edition of a classic textbook in electrochemistry

The third edition of Electrochemical Methods has been extensively revised to reflect the evolution of electrochemistry over the past two decades, highlighting significant developments in the understanding of electrochemical phenomena and emerging experimental tools, while extending the book's value as a general introduction to electrochemical methods.

This authoritative resource for new students and practitioners provides must-have information crucial to a successful career in research. The authors focus on methods that are extensively practiced and on phenomenological questions of current concern.

This latest edition of Electrochemical Methods contains numerous problems and chemical examples, with illustrations that serve to illuminate the concepts contained within in a way that will assist both student and mid-career practitioner.

Significant updates and new content in this third edition include:

- An extensively revised introductory chapter on electrode processes, designed for new readers coming into electrochemistry from diverse backgrounds
- New chapters on steady-state voltammetry at ultramicroelectrodes, inner-sphere electrode reactions and electrocatalysis, and single-particle electrochemistry
- Extensive treatment of Marcus kinetics as applied to electrode reactions, a more detailed introduction to migration, and expanded coverage of electrochemical impedance spectroscopy
- The inclusion of Lab Notes in many chapters to help newcomers with the transition from concept to practice in the laboratory

The new edition has been revised to address a broader audience of scientists and engineers, designed to be accessible to readers with a basic foundation in university chemistry, physics and mathematics. It is a self-contained volume, developing all key ideas from the fundamental principles of chemistry and physics.

Perfect for senior undergraduate and graduate students taking courses in electrochemistry, physical and analytical chemistry, this is also an indispensable resource for researchers and practitioners working in fields including electrochemistry and electrochemical engineering, energy storage and conversion, analytical chemistry and sensors.

Autoren/Hrsg.

Bard, Allen J.

Faulkner, Larry R.

White, Henry S.

Fachgebiete

• Naturwissenschaften Chemie Physikalische Chemie Elektrochemie, Magnetochemie
• Technische Wissenschaften Maschinenbau | Werkstoffkunde Technische Mechanik | Werkstoffkunde Materialwissenschaft: Elektronik, Optik

Inhaltsverzeichnis

Preface xxi

Major Symbols and Abbreviations xxv

About the Companion Website liii

1 Overview of Electrode Processes 1

1.1 Basic Ideas 2

1.1.1 Electrochemical Cells and Reactions 2

1.1.2 Interfacial Potential Differences and Cell Potential 4

1.1.3 Reference Electrodes and Control of Potential at a Working Electrode 5

1.1.4 Potential as an Expression of Electron Energy 6

1.1.5 Current as an Expression of Reaction Rate 6

1.1.6 Magnitudes in Electrochemical Systems 8

1.1.7 Current–Potential Curves 9

1.1.8 Control of Current vs. Control of Potential 16

1.1.9 Faradaic and Nonfaradaic Processes 17

1.2 Faradaic Processes and Factors Affecting Rates of Electrode Reactions 17

1.2.1 Electrochemical Cells—Types and Definitions 17

1.2.2 The Electrochemical Experiment and Variables in Electrochemical Cells 18

1.2.3 Factors Affecting Electrode Reaction Rate and Current 21

1.3 Mass-Transfer-Controlled Reactions 23

1.3.1 Modes of Mass Transfer 24

1.3.2 Semiempirical Treatment of Steady-State Mass Transfer 25

1.4 Semiempirical Treatment of Nernstian Reactions with Coupled Chemical Reactions 31

1.4.1 Coupled Reversible Reactions 31

1.4.2 Coupled Irreversible Chemical Reactions 32

1.5 Cell Resistance and the Measurement of Potential 34

1.5.1 Components of the Applied Voltage When Current Flows 35

1.5.2 Two-Electrode Cells 37

1.5.3 Three-Electrode Cells 37

1.5.4 Uncompensated Resistance 38

1.6 The Electrode/Solution Interface and Charging Current 41

1.6.1 The Ideally Polarizable Electrode 41

1.6.2 Capacitance and Charge at an Electrode 41

1.6.3 Brief Description of the Electrical Double Layer 42

1.6.4 Double-Layer Capacitance and Charging Current 44

1.7 Organization of this Book 51

1.8 The Literature of Electrochemistry 52

1.8.1 Reference Sources 52

1.8.2 Sources on Laboratory Techniques 53

1.8.3 Review Series 53

1.9 Lab Note: Potentiostats and Cell Behavior 54

1.9.1 Potentiostats 54

1.9.2 Background Processes in Actual Cells 55

1.9.3 Further Work with Simple RC Networks 56

1.10 References 57

1.11 Problems 57

2 Potentials and Thermodynamics of Cells 61

2.1 Basic Electrochemical Thermodynamics 61

2.1.1 Reversibility 61

2.1.2 Reversibility and Gibbs Free Energy 64

2.1.3 Free Energy and Cell emf 64

2.1.4 Half-Reactions and Standard Electrode Potentials 66

2.1.5 Standard States and Activity 67

2.1.6 emf and Concentration 69

2.1.7 Formal Potentials 71

2.1.8 Reference Electrodes 72

2.1.9 Potential–pH Diagrams and Thermodynamic Predictions 76

2.2 A More Detailed View of Interfacial Potential Differences 80

2.2.1 The Physics of Phase Potentials 80

2.2.2 Interactions Between Conducting Phases 82

2.2.3 Measurement of Potential Differences 84

2.2.4 Electrochemical Potentials 85

2.2.5 Fermi Energy and Absolute Potential 88

2.3 Liquid Junction Potentials 91

2.3.1 Potential Differences at an Electrolyte–Electrolyte Boundary 91

2.3.2 Types of Liquid Junctions 91

2.3.3 Conductance, Transference Numbers, and Mobility 92

2.3.4 Calculation of Liquid Junction Potentials 96

2.3.5 Minimizing Liquid Junction Potentials 100

2.3.6 Junctions of Two Immiscible Liquids 101

2.4 Ion-Selective Electrodes 101

2.4.1 Selective Interfaces 101

2.4.2 Glass Electrodes 102

2.4.3 Other Ion-Selective Electrodes 106

2.4.4 Gas-Sensing ISEs 111

2.5 Lab Note: Practical Use of Reference Electrodes 112

2.5.1 Leakage at the Reference Tip 112

2.5.2 Quasireference Electrodes 112

2.6 References 113

2.7 Problems 116

3 Basic Kinetics of Electrode Reactions 121

3.1 Review of Homogeneous Kinetics 121

3.1.1 Dynamic E

Über Autor(innen)

Allen J. Bard is Professor and Hackerman-Welch Regents Chair in Chemistry at the University of Texas at Austin in the United States. His research is focused on the application of electrochemical methods to the study of chemical problems.

Larry R. Faulkner is President Emeritus of the University of Texas at Austin in the United States. He has served on the chemistry faculties of Harvard University, the University of Illinois, and the University of Texas.
Henry S. White is Distinguished Professor and John A. Widstoe Presidential Chair in the Department of Chemistry at the University of Utah in the United States. His research is focused on experimental and theoretical aspects of electrochemistry.