Physical Electrochemistry

This bestselling textbook on physical electrochemistry caters to the needs of advanced undergraduate and postgraduate students of chemistry, materials engineering, mechanical engineering, and chemical engineering. It is unique in covering both the more fundamental, physical aspects as well as the application-oriented practical aspects in a balanced manner. In addition it serves as a self-study text for scientists in industry and research institutions working in related fields. The book can be divided into three parts: (i) the fundamentals of electrochemistry; (ii) the most important electrochemical measurement techniques; and (iii) applications of electrochemistry in materials science and engineering, nanoscience and nanotechnology, and industry. The second edition has been thoroughly revised, extended and updated to reflect the state-of-the-art in the field, for example, electrochemical printing, batteries, fuels cells, supercapacitors, and hydrogen storage.

Auteur
Professor Noam Eliaz is a full professor, Director of the Biomaterials and Corrosion Laboratory, and the founder of the Department of Materials Science and Engineering at TAU. He earned a BSc degree in Materials Engineering, an MBA degree, and a PhD degree (direct track) in Materials Engineering, all cum laude from Ben-Gurion University of the Negev. Prior to joining TAU, he was a Fulbright and Rothschild Fellow at MIT. His research is interdisciplinary and includes electrodeposition of calcium phosphate coatings for implants, electrodeposition of special alloys for high-temperature applications, corrosion, and failure analysis. From 2005 to 2017 he was the Editor-in-Chief of the journal Corrosion Reviews, and currently he is an editorial board member of this journal as well as of Current Topics in Electrochemistry, Corrosion, and Materials Degradation, and Bioceramics Development and Applications. He is an elected member of The Israel Young Academy and was appointed to the Governing Board of The German-Israeli Foundation for Scientific Research and Development (GIF). He has won numerous awards, including NACE International's Herbert H. Uhlig Award (2010), Fellow Award (2012), and Technical Achievement Award (2014), as well as Fellow of The Japanese Society for the Promotion of Science (2005?2007) and the T.P. Hoar Award (2003).
Eliezer Gileadi has been a Professor of Chemistry at Tel-Aviv University (TAU) since 1966 (Emeritus since 2000). He obtained his M.Sc. at the Hebrew University in Jerusalem and his Ph.D. at the University of Ottawa, Canada. He has been a visiting professor and a lecturer at many institutes worldwide, including the University of Virginia, The University of Pennsylvania, Case Western Reserve University, The Johns Hopkins University, University of Ottawa, etc. He is a Fellow of the Royal Society of Canada, the Electrochemical Society, the American Association for the Advancement of Science, and the International Society for Electrochemistry. He received from the Electrochemical Society the prestigious Olin-Palladium Award and the Henry B. Linford Award for Distinguished Teaching. He taught this subject for 40 years and consulted to industry.

Contenu

Preface xvii

Symbols and Abbreviations xix

1 Introduction 1

1.1 General Considerations 1

1.1.1 The Transition from Electronic to Ionic Conduction 1

1.1.2 The Resistance of the Interface can be Infinite 2

1.1.3 Mass-Transport Limitation 2

1.1.4 The Capacitance at the Metal/Solution Interphase 4

1.2 Polarizable and Nonpolarizable Interfaces 4

1.2.1 Phenomenology 4

1.2.2 The Equivalent Circuit Representation 5

Further Reading 7

2 The Potentials of Phases 9

2.1 The Driving Force 9

2.1.1 Definition of the Electrochemical Potential 9

2.1.2 Separability of the Chemical and the Electrical Terms 10

2.2 Two Cases of Special Interest 11

2.2.1 Equilibrium of a Species Between two Phases in Contact 11

2.2.2 Two Identical Phases not at Equilibrium 12

2.3 The Meaning of the Standard Hydrogen Electrode (SHE) Scale 13

Further Reading 15

3 Fundamental Measurements in Electrochemistry 17

3.1 Measurement of Current and Potential 17

3.1.1 The Cell Voltage is the Sum of Several Potential Differences 17

3.1.2 Use of a Nonpolarizable Counter Electrode 17

3.1.3 The Three-Electrode Setup 18

3.1.4 Residual jRS Potential Drop in aThree-Electrode Cell 18

3.2 Cell Geometry and the Choice of the Reference Electrode 19

3.2.1 Types of Reference Electrodes 19

3.2.2 Use of an Auxiliary Reference Electrode for the Study of Fast Transients 20

3.2.3 Calculating the Uncompensated Solution Resistance for a few Simple Geometries 21

3.2.3.1 Planar Configuration 21

3.2.3.2 Cylindrical Configuration 21

3.2.3.3 Spherical Symmetry 22

3.2.4 Positioning the Reference Electrode 22

3.2.5 Edge Effects 24

Further Reading 26

4 Electrode Kinetics: Some Basic Concepts 27

4.1 Relating Electrode Kinetics to Chemical Kinetics 27

4.1.1 The Relation of Current Density to Reaction Rate 27

4.1.2 The Relation of Potential to Energy of Activation 28

4.1.3 Mass-Transport Limitation Versus Charge-Transfer Limitation 30

4.1.4 The Thickness of the Nernst Diffusion Layer 31

4.2 Methods of Measurement 33

4.2.1 Potential Control Versus Current Control 33

4.2.2 The Need to Measure Fast Transients 35

4.2.3 Polarography and the Dropping Mercury Electrode (DME) 37

4.3 Rotating Electrodes 40

4.3.1 The Rotating Disk Electrode (RDE) 40

4.3.2 The Rotating Cone Electrode (RConeE) 44

4.3.3 The Rotating Ring Disk Electrode (RRDE) 45

Further Reading 47

5 Single-Step Electrode Reactions 49

5.1 The Overpotential, 𝜂 49

5.1.1 Definition and Physical Meaning of Overpotential 49

5.1.2 Types of Overpotential 51

5.2 Fundamental Equations of Electrode Kinetics 52

5.2.1 The Empirical Tafel Equation 52

5.2.2 The Transition-State Theory 53

5.2.3 The Equation for a Single-Step Electrode Reaction 54

5.2.4 Limiting Cases of the General Equation 56

5.3 The Symmetry Factor, 𝛽, in Electrode Kinetics 59

5.3.1 The Definition of 𝛽 59

5.3.2 The Numerical Value of 𝛽 60

5.4 The Marcus Theory of Charge Transfer 61

5.4.1 Outer-Sphere Electron Transfer 61

5.4.2 The BornOppenheimer Approximation 62

5.4.3 The Calculated Energy of Activation 63

5.4.4 The Value of 𝛽 and its Potential Dependence 64

5.5 Inner-Sphere Charge Transfer 65

5.5.1 Metal Deposition 65

Further Reading 66

6 Multistep Electrode Reactions 67

6.1 Mechanistic Criteria 67

6.1.1 The Transfer Coefficient, 𝛼, and its Relation to the Symmetry Factor, 𝛽 67

6.1.2 Steady State and Quasi-Equilibrium 69 6.1.3 Calculation of the Tafel Slope 71&...