Comprehensive introduction to the field of electrochemistry, covering the fundamentals, key experimental approaches for many current applications, and real-life examples

Fundamentals of Electrochemistry provides a profound introduction to the principles of the field in connection to key experimental approaches in the laboratory. This is complemented by a systematic coverage of the most important applications, illustrated by real-life examples presenting electrochemistry as a cross-sectional discipline.

Part I of the book presents the fundamentals focusing on key concepts at an introductory BSc level. The parts II-IV on methods, materials, and applications address advanced students from BSc research projects to PhD students.

Written by a highly qualified and prominent professor with extensive teaching and research experience in the field, Fundamentals of Electrochemistry explores topics including:

• Basics concepts of electrochemical cells, electrodes and electrolytes, energetics and kinetics of electrochemical reactions, and their coupling to transport processes
• Elucidation and application of mechanisms in electron transfer and ion transfer reactions
• Structure of the solid-electrolyte interfaces and its modification combined with the advanced characterization methods such as vibrational spectroscopy at surfaces, ellipsometry, surface plasmon resonance, spectroscopy of core shell electrons, X-ray diffraction, mass spectrometry, quartz crystal microbalance, and scanning probe techniques
• Electrodeposition by galvanic processes, underpotential deposition and electrodeposition of oxides, self-assembled monolayers, conducting polymers and organic-inorganic hybrid materials, solid electrolytes and semiconductors, corrosion
• Electroanalytical methods, electrochemical sensors and biosensors based on potentiometry, amperometry and a large variety of voltammetric methods; micro- and nanoelectrodes
• Energy conversion in batteries, fuel cells, electrolyzers, and electrochemical capacitors; electrosynthesis

The clear and modular structure supplemented by 800+ figures and worked-out examples, supporting different course concepts, makes Fundamentals of Electrochemistry the perfect companion for BSc, MSc, and PhD students in the fields of electrochemistry and related subjects.

Symbols xvii
Important Abbreviations xxxi

Is Another Textbook on Electrochemistry Really Necessary? 1
Electrochemistry - Long Established, But Still Complicated? 1
What Can You Expect from the Subject Area and This Book? 2
Historical and Current Textbooks 4
References 4
Acknowledgments 5
Sources of Figures 6

Part I Principles 7

1 The Electrode Reaction - The Core of Electrochemistry 9
1.1 Electrical Current and Chemical Conversion in Electrochemical Cells 9
1.2 Electrodes and Ions 13
1.3 What Is the Relationship Between Degree of Chemical Conversion and Flow of Charge? 16
1.4 What Is the Relationship Between Electrical Current and Electrochemical Reaction Rate? 17
1.5 Galvanic Cells and Electrolytic Cells 20
1.6 Summary 22

2 Thermodynamics of Electrochemical Reactions 25
2.1 Electrochemical Cell Voltage and Electrode Potentials 25
2.2 What Is the Link from Cell Voltage to Thermodynamic Potentials? 28
2.3 Cell Voltages Are Associated with Charge Separation at Interfaces - The Galvani Voltage 48
2.4 Applications of Cell Voltage Measurements and of Galvanic Cells 58
2.5 Summary 80

3 Electrochemical Kinetics - Homogeneous and Heterogeneous Processes 85
3.1 Coupling Between Mass Transport and Interfacial Reactions 85
3.2 Kinetics of Charge Transfer 90
3.3 Summary 110

4 Mass Transport and Boundary Layers 115
4.1 Survey and Terminology 116
4.2 Migration 117
4.3 The Electrical Double Layer 145
4.4 Diffusion 154
4.5 The Diffusion Layer 160
4.6 Combined Transport Processes During Electrophoresis 169
4.7 Combined Transport Processes in the Nernst-Planck Transport Equation 181

Part II Experimental Methods in Electrochemistry 187

5 Electroanalytical Methods and Electrochemical Sensors 189
5.1 The Family Tree of Electroanalytical Methods 189
5.2 Potentiometry 191
5.3 Dynamic Electrochemical Methods 207
5.4 Amperometric Sensors 245
5.5 Voltammetry Under Special Mass Transport Conditions - Reactants Bound to the Electrode 249
5.6 Voltammetry Under Special Mass Transport Conditions - Microelectrodes 258
5.7 Foundations of Electrochemical Instrumentation 279

6 Investigation of Electrochemical Reaction Mechanisms in Liquid Electrolytes 303
6.1 Reaction Steps of an Electrode Reaction Mechanism 304
6.2 From the Experimental Voltammogram to a Model Mechanism 306
6.3 When Is a Model Mechanism Plausible? 318
6.4 Fundamental Mechanistic Models of Molecular Electrochemistry in Liquid Phases 326
6.5 Extracting Quantitative Information from Experiments 342
6.6 Complementary Techniques 358
6.7 Summary 369

7 Electrochemical Impedance Spectroscopy 377
7.1 Ohmic Resistors and Ideal Capacitors in AC Circuits 379
7.2 Impedance Measurements with Electrochemical Cells 381
7.3 Equivalent Circuits for Electrodes and Cells 384
7.4 Developing Equivalent Circuits 391
7.5 Summary 397

8 Surface Electrochemistry 399
8.1 Overview and Systematics 399
8.2 Vibrational Spectroscopy at Surfaces 401
8.3 Ellipsometry 410
8.4 Surface Plasmon Resonance 414
8.5 Spectroscopy of Core Electrons 416
8.6 X-Ray Diffraction 434
8.7 Mass Spectrometry 435
8.8 Electrochemical Quartz Crystal Microbalance 436x Contents
8.9 Single-Crystal Electrodes 443
8.10 A Closer Look at the Electrical Double Layer 457
8.11 Electrochemical Scanning Tunneling Microscopy (ECSTM) and Electrochemical Scanning Force Microscopy
(ECSFM) 475
8.12 Scanning Electrochemical Microscopy (SECM) 492
8.13 Further Scanning Probe Microscopies 508

Part III Materials from and for Electrochemistry 533

9 Electrochemical Deposition of Materials 535