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 9.1 Which Methods Can Be Used for Electrodeposition of Materials? 536 9.2 Growth Modes During Metal Deposition 539 9.

3 How Does the Current Density Influence the Deposition Process? 549 9.4 Composition of Galvanic Baths 554 9.5 Deposition of Complex Materials 560 9.6 Electrochemistry of Bipolar Electrodes 563 10 Semiconductor Electrochemistry 571 10.1 Structure and Binding in Semiconductors 571 10.2 Semiconductor Electrodes 587 10.3 Application of Semiconductor Electrodes 601 11 Solid-State Electrolytes and Other Unconventional Electrolyte Systems 613 11.1 Why Do Crystalline Solids Contain Defects? 613 11.

2 Ionic Conductivity in Solids 623 11.3 Boundary Layers in Solid Electrolytes 629 11.4 Electrochemistry in Molten Salts and Ionic Liquids 632 11.5 Conductivity in Glasses 637 11.6 Conductivity in Polymers 638 12 Electrocatalysis 647 12.1 Concepts and Definitions 648 12.2 Theoretical Treatment of Electron Transfer Reactions 652 12.3 The Role of Intermediates for Electrocatalysis 659 12.

4 Experimental Investigation of Electrocatalytic Reactions 667 12.5 Important Electrocatalytic Reactions 678 13 Modified Electrodes 689 13.1 Monolayer Systems 689 13.2 Polymer Layers on Electrodes 707 13.3 Films of Organic-Inorganic Hybrid Materials 716 13.4 Voltammetry at Modified Electrodes 717 Part IV Applications 737 14 Corrosion and Corrosion Protection 739 14.1 What Is Corrosion? 740 14.2 The Pourbaix Diagram - The Thermodynamics of Corrosion 744 14.

3 Kinetics of Corrosion Processes and Passivity 750 14.4 Principal Approaches for Corrosion Protection 758 14.5 Important and Typical Corrosion Phenomena 760 14.6 Deliberate Metal Dissolution 776 15 Electrochemical Energy Storage 789 15.1 Overview of Electrochemical Energy Conversion Systems 790 15.2 Figures of Merit for Batteries and Battery Materials 792 15.3 Battery Classification 801 15.4 Zinc-Manganese Batteries as Examples of Primary Cells 812 15.

5 Lead-Acid Accumulator as Rechargeable Battery with Aqueous Electrolyte 814 15.6 Lithium-Ion Batteries 820 15.7 Metal-Air Batteries 837 15.8 Vanadium Redox Flow Battery 839 15.9 Electrochemical Capacitors 840 16 Fuel Cells 857 16.1 Overview 857 16.2 Polymer Electrolyte Membrane Fuel Cell (PEMFC) 859 16.3 Types of Polymer Electrolyte Membrane Fuel Cells 866 16.

4 Solid Oxide Fuel Cell (SOFC) 868 16.5 Molten Carbonate Fuel Cell 873 16.6 Phosphoric Acid Fuel Cell (PAFC) 875 16.7 Alkaline Fuel Cell (AFC) 875 16.8 Water Electrolysis 879 17 Electrosyntheses in the Laboratory and Industry 887 17.1 Special Features of Electrosynthetic Reactions 887 17.2 Organic Electrosyntheses - An Overview 903 17.3 Direct Transformations 905 17.

4 Indirect Transformations 911 17.5 Examples of Electroorganic Syntheses with Reaction Control 916xvi Contents 18 Bioelectrochemistry 927 18.1 Coupling of Ion Transfer and Electron Transfer Processes in Photosynthesis and in Cellular Respiration 928 18.2 The Electrochemical Characterization of Biomolecules 935 18.3 Electrochemical Bioanalytics 946 18.4 Investigation of Ionic Currents Across Membranes 964 18.5 Review and Outlook 970 Test your knowledge 971 References 972 Appendix 979 Index 1003.