Fundamentals of Electrochemistry (The ECS Series of Texts and Monographs)

Fundamentals of Electrochemistry provides the basic outline of most topics of theoretical and applied electrochemistry for students not yet familiar with this field, as well as an outline of recent and advanced developments in electrochemistry for people who are already dealing with electrochemical problems. The content of this edition is arranged so that all basic information is contained in the first part of the book, which is now rewritten and simplified in order to make it more accessible and used as a textbook for undergraduate students. More advanced topics, of interest for postgraduate levels, come in the subsequent parts. This updated second edition focuses on experimental techniques, including a comprehensive chapter on physical methods for the investigation of electrode surfaces. New chapters deal with recent trends in electrochemistry, including nano- and micro-electrochemistry, solid-state electrochemistry, and electrocatalysis. In addition, the authors take into account the worldwide renewal of interest for the problem of fuel cells and include chapters on batteries, fuel cells, and double layer capacitors.Content: Chapter 1 Electric Currents in Ionic Conductors (pages 1–18): Chapter 2 Electrode Potentials (pages 19–31): Chapter 3 Thermodynamics of Electrochemical Systems (pages 33–50): Chapter 4 Mass Transfer in Electrolytes (pages 51–67): Chapter 5 Phase Boundaries (Interfaces) between Miscible Electrolytes (pages 69–77): Chapter 6 Polarization of Electrodes (pages 79–98): Chapter 7 Aqueous Electrolyte Solutions (pages 99–126): Chapter 8 Nonaqueous Electrolytes (pages 127–137): Chapter 9 Electron Work Functions and Volta Potentials (pages 139–146): Chapter 10 Structure and Properties of Surface Layers (pages 147–180): Chapter 11 Transient Processes (pages 181–189): Chapter 12 Electrochemical Research Techniques (pages 191–215): Chapter 13 Multistep Electrode Reactions (pages 217–237): Chapter 14 Some Aspects of Electrochemical Kinetics (pages 239–260): Chapter 15 Reactions at Nonconsumable Electrodes (pages 261–295): Chapter 16 Reactions Involving Metals (pages 297–317): Chapter 17 Industrial Electrolytic Processes (pages 319–325): Chapter 18 Electrochemical Reactors (pages 327–342): Chapter 19 Batteries (Electrochemical Power Sources) (pages 343–360): Chapter 20 Fuel Cells (pages 361–368): Chapter 21 Some Electrochemical Devices (pages 369–377): Chapter 22 Corrosion of Metals (pages 379–386): Chapter 23 Electrochemical Methods of Analysis (pages 387–403): Chapter 24 Electrochemistry and the Environment (pages 405–416): Chapter 25 Solid?State Electrochemistry (pages 417–447): Chapter 26 Conductive Polymers (pages 449–465): Chapter 27 Physical Methods for Investigation of Electrode Surfaces (pages 467–519): Chapter 28 Electrocatalysis (pages 521–555): Chapter 29 Photoelectrochemistry (pages 557–571): Chapter 30 Bioelectrochemistry (pages 573–593): Chapter 31 Electrokinetic Processes (pages 595–606): Chapter 32 Interfaces Between Two Immiscible Electrolyte Solutions (pages 607–619): Chapter 33 Various Electrochemical Phenomena (pages 621–635): Chapter 34 Main Concepts of Elementary Reaction Act Theory (pages 637–660): Chapter 35 Computer Simulation in Electrochemistry (pages 661–677): Chapter 36 Nanoelectrochemistry (pages 679–691): Chapter 37 Development of Electrochemistry (pages 693–700): Cover Page 1 Title Page 2 Copyright © 2006 by John Wiley & Sons, Inc. 3 CONTENTS 4 Contributors xv 4 Preface to the Second Edition xvii 4 Preface to the First Edition xix 4 List of Photographs xxii 4 Abbreviations xxiii 4 Symbols xxv 4 PART I BASIC CONCEPTS 1 4 1. Electric Currents in Ionic Conductors 3 4 2. Electrode Potentials 19 4 3. Thermodynamics of Electrochemical Systems 33 4 4. Mass Transfer in Electrolytes 51 5 5. Phase Boundaries (Interfaces) Between Miscible Electrolytes 69 5 6. Polarization of Electrodes 79 5 7. Aqueous Electrolyte Solutions 99 5 8. Nonaqueous Electrolytes 127 5 9. Electron Work Functions and Volta Potentials 139 6 10. Structure and Properties of Surface Layers 147 6 11. Transient Processes 181 6 12. Electrochemical Research Techniques 191 6 PART II KINETICS OF ELECTROCHEMICAL REACTIONS 217 6 13. Multistep Electrode Reactions 219 6 14. Some Aspects of Electrochemical Kinetics 239 7 15. Reactions at Nonconsumable Electrodes 261 7 16. Reactions Involving Metals 297 7 PART III APPLIED ASPECTS OF ELECTROCHEMISTRY 319 7 17. Industrial Electrolytic Processes 321 7 18. Electrochemical Reactors 327 7 19. Batteries (Electrochemical Power Sources) 343 8 20. Fuel Cells 361 8 21. Some Electrochemical Devices 369 8 22. Corrosion of Metals 379 8 23. Electrochemical Methods of Analysis 387 8 24. Electrochemistry and the Environment 405 8 PART IV SELECTED TOPICS IN ELECTROCHEMISTRY 417 9 25. Solid-State Electrochemistry 419 9 26. Conductive Polymers 449 9 27. Physical Methods for Investigation of Electrode Surfaces 467 9 28. Electrocatalysis 521 9 29. Photoelectrochemistry 557 10 30. Bioelectrochemistry 573 10 31. Electrokinetic Processes 595 10 32. Interfaces Between Two Immiscible Electrolyte Solutions 607 10 33. Various Electrochemical Phenomena 621 10 34. Main Concepts of Elementary Reaction Act Theory 637 11 35. Computer Simulation in Electrochemistry 661 11 36. Nanoelectrochemistry 679 11 37. Development of Electrochemistry 693 11 Appendix A: Derivation of the Main Equation of Debye–Hückel Theory 701 12 Appendix B: Derivation of the Main Equation of Gouy–Chapman Theory 705 12 General Bibliography 709 12 Author Index 711 12 Subject Index 715 12 CONTRIBUTORS 13 PREFACE TO THE SECOND EDITION 15 PREFACE TO THE FIRST EDITION 16 LIST OF PHOTOGRAPHS 19 ABBREVIATIONS 20 SYMBOLS 22 PART I - Basic Concepts 26 1 Electric Currents in Ionic Conductors 27 1.1 VARIOUS TYPES OF CONDUCTORS 27 1.2 IONS IN ELECTROLYTE SOLUTIONS 28 1.3 CONDUCTIVITY OF ELECTROLYTE SOLUTIONS 29 1.4 CIRCUITS INVOLVING IONIC CONDUCTORS. ELECTRODES 33 1.5 PASSAGE OF CURRENT THROUGH ELECTRODES. ELECTRODE REACTIONS 34 1.6 CLASSIFICATION OF ELECTRODES AND ELECTRODE REACTIONS 36 1.7 FARADAY’S LAWS 39 1.8 EQUATIONS FOR MASS BALANCE 40 1.9 SIGN CONVENTION FOR CURRENT AND FLUXES 42 REFERENCE 42 2 Electrode Potentials 43 E 43 2.1 INTERFACIAL POTENTIAL DIFFERENCES 44 (GALVANI POTENTIALS) 44 2.1.1 Metal–Metal Contact 44 2.1.2 Metal–Electrolyte Contact 46 2.1.3 Electric Double Layers at Interfaces 46 2.1.4 Galvani Potentials Cannot Be Determined 46 2.2 EXCHANGE CURRENTS 47 2.3 OPEN-CIRCUIT VOLTAGES 48 2.3.1 Metal Circuits 48 2.3.2 Galvanic Circuits 48 2.4 ELECTRODE POTENTIALS 50 2.4.1 Defining the Concept of Electrode Potential 50 2.4.2 Nonequilibrium Electrode Potentials 51 2.5 CELL VOLTAGE AT NONZERO CURRENT 53 2.5.1 Two Directions of Current Flow 53 2.5.2 Polarization and Ohmic Losses 54 3 Thermodynamics of Electrochemical Systems 56 3.1 CONVENTIONAL AND UNDEFINED PARAMETERS 56 3.2 THERMODYNAMIC FUNCTIONS IN ELECTROCHEMISTRY 57 3.2.1 Thermodynamic Functions 57 3.2.2 Electrochemical Potentials 58 3.3 THERMODYNAMIC ACTIVITY 59 3.3.1 Definition of the Concept of Activity 59 3.3.2 Activities of Ions in Electrolyte Solutions 60 3.4 EQUATIONS FOR THE EMF OF GALVANIC CELLS 62 3.5 CONCENTRATION DEPENDENCE OF ELECTRODE POTENTIALS 64 3.5.1 Nernst Equation for Ideal Systems 64 3.5.2 Equations for Real Systems 65 3.5.3 Electrodes of the Second Kind 66 3.5.4 Nernst Equation at Very Low Concentrations 68 3.6 SPECIAL THERMODYNAMIC FEATURES OF ELECTRODE POTENTIALS 69 3.6.1 Table of Standard Potentials 69 3.6.2 pH Dependence of Potentials; Pourbaix Diagrams 69 3.6.3 Electrode Potentials in Nonaqueous Electrolytes 71 3.6.4 Temperature Coefficients of Electrode Potentials 72 REFERENCES 73 MONOGRAPHS AND REFERENCE BOOKS 73 4 Mass Transfer in Electrolytes 74 4.1 BASIC LAWS OF IONIC DIFFUSION IN SOLUTIONS 74 4.2 LIMITING DIFFUSION CURRENTS IN ELECTROLYTES 76 4.3 IONIC TRANSPORT BY MIGRATION AND DIFFUSION 78 4.3.1 Equations for the Total Flux 78 4.3.2 Total Fluxes in Binary Electrolytes 79 4.3.3 The General Case 83 4.4 CONVECTIVE TRANSPORT 83 4.4.1 Flow-by Electrodes 84 4.4.2 Rotating-Disk Electrode 87 4.4.3 Rotating Ring–Disk Electrode 88 4.4.4 Cells with Natural Convection of the Electrolyte 89 REFERENCES 90 5 Phase Boundaries (Interfaces) Between Miscible Electrolytes 91 5.1 TYPES OF INTERFACES BETWEEN ELECTROLYTES 91 5.2 POTENTIALS BETWEEN SIMILAR ELECTROLYTES (DIFFUSION POTENTIALS) 93 5.2.1 Values of Diffusion Potentials for Different Interfaces 94 5.2.2 Ways of Reducing Diffusion Potentials 94 5.3 DISTRIBUTION OF THE IONS BETWEEN DISSIMILAR BUT MISCIBLE ELECTROLYTES 95 5.4 DISTRIBUTION OF IONS IN CELLS WITH MEMBRANE 97 5.4.1 Equilibrium Systems 97 5.4.2 Quasiequilibrium Systems 97 5.5 GALVANIC CELLS WITH TRANSFERENCE 98 REFERENCES 99 6 Polarization of Electrodes 100 6.1 BASIC CONCEPTS 100 6.1.1 Electrochemical Reaction Rates 100 6.1.2 Electrode Polarization 101 6.1.3 Overall and Partial Reaction Currents 101 6.1.4 Various Types of Polarization 102 6.2 LAWS OF ACTIVATION POLARIZATION 103 6.2.1 Polarization Equations 103 6.2.2 Influence of Reactant Concentrations 105 6.2.3 General Kinetic and Polarization Equations 106 6.2.4 Relations Between the Parameters of the Forward and Reverse Process 107 6.2.5 Relation Between the Kinetic Parameters in Regions of Low and High Polarization 108 6.2.6 Concentration Dependence of the Exchange Current Density 109 6.3 DIFFUSIONAL CONCENTRATION POLARIZATION 110 6.3.1 Solutions with Excess Foreign Electrolyte 110 6.3.2 Binary Electrolyte Solutions 113 6.4 SUPERPOSITION OF CONCENTRATION AND ACTIVATION POLARIZATION 114 REFERENCES 119 7 Aqueous Electrolyte Solutions 120 7.1 ELECTROLYTIC DISSOCIATION 120 7.1.1 Early Ideas 120 7.1.2 Arrhenius’s Theory of Electrolytic Dissociation 122 7.1.3 Further Development of the Theory of Electrolytic Dissociation 126 7.2 IONIC SOLVATION (HYDRATION) IN SOLUTIONS 127 7.2.1 Solvation Energies of Electrolytes 128 7.2.2 Solvation Energies of Individual Ions 129 7.2.3 Solvation Numbers 131 7.2.4 Hydration of Protons 132 7.3 ACTIVITY OF REAL ELECTROLYTE SOLUTIONS 133 7.3.1 Ways to Determine the Activity of Electrolyte Solutions 133 7.3.2 Concentration Dependence of the Activity Coefficient 134 7.3.3 Physical Meaning of Activity Coefficients 136 7.4 PHYSICAL THEORIES OF ION–ION INTERACTIONS 137 7.4.1 Ionic Atmosphere 138 7.4.2 Debye–Hückel Limiting Law 139 7.4.3 Second and Third Approximation of the Theory 141 7.4.4 Ion–Ion Interaction and Conductivity 143 7.4.5 Further Development of Electrolyte Solution Theory 145 REFERENCES 147 MONOGRAPHS 147 8 Nonaqueous Electrolytes 148 8.1 DIFFERENT TYPES OF ELECTROLYTES AND THEIR PRACTICAL UTILIZATION 148 8.2 NONAQUEOUS ELECTROLYTE SOLUTIONS 149 8.3 IONICALLY CONDUCTING MELTS 152 8.4 INORGANIC SOLID ELECTROLYTES 155 8.4.1 Ionic Semiconductors 155 8.4.2 Ionic Conductors 157 REFERENCES 158 MONOGRAPHS AND REVIEWS 158 9 Electron Work Functions and Volta Potentials 159 9.1 SURFACE POTENTIAL OF A PHASE 159 9.2 WORK FUNCTIONS 160 9.2.1 Work Function for the Metal–Vacuum Interface 160 9.2.2 Work Function for Metals Contacting Electrolytes 161 9.3 VOLTA POTENTIALS 163 9.4 TWO PROBLEMS IN ELECTROCHEMISTRY 164 9.4.1 Volta Problem 164 9.4.2 Problem of Absolute Potential 165 REFERENCE 166 10 Structure and Properties of Surface Layers 167 10.1 ELECTRICAL STRUCTURE OF INTERPHASES 168 10.1.1 Helmholtz Model 171 10.1.2 Gouy–Chapman Model 171 10.1.3 Models of Stern and Grahame 172 10.2 ADSORPTION PHENOMENA 176 10.2.1 Types of Adsorption 176 10.2.2 Adsorption energy 177 10.2.3 Reversible and Irreversible Adsorption 177 10.2.4 Adsorption Isotherms 178 10.2.5 Adsorption in Electrochemical Systems 180 10.3 THERMODYNAMICS OF SURFACE PHENOMENA 182 10.3.1 Surface Excesses of Substances 183 10.3.2 Excess Surface Energy 184 10.3.3 Gibbs Adsorption Equation 185 10.3.4 Electrocapillary Curves 186 10.4 MERCURY ELECTRODE SURFACE 189 10.4.1 Ion Adsorption 189 10.4.2 Adsorption of Organic Substances 191 10.5 PLATINUM ELECTRODE SURFACE 192 10.5.1 Electrochemical Methods for Investigating the Surface of Platinum Electrodes 192 10.5.2 Hydrogen Adsorption on Platinum 194 10.5.3 Surface Inhomogeneity of Platinum 195 10.5.4 Adsorption of Other Substances on Platinum 196 10.5.5 Aging of Adsorbed Particles 196 10.5.6 Ideally and Perfectly Polarizable Electrodes 198 10.6 SURFACES OF OTHER ELECTRODES 198 REFERENCES 200 MONOGRAPHS 200 11 Transient Processes 201 11.1 EVIDENCE FOR TRANSIENT CONDITIONS 201 11.2 TRANSIENT DIFFUSION TO ELECTRODES OF LARGE SIZE 202 11.2.1 Galvanostatic Conditions 203 11.2.2 Potentiostatic conditions 206 11.2.3 Use of Alternating Currents 207 11.3 TRANSIENT DIFFUSION TO ELECTRODES OF FINITE SIZE 208 12 Electrochemical Research Techniques 210 12.1 REFERENCE ELECTRODES 211 12.2 VOLTAGE AND ELECTRODE POTENTIAL MEASUREMENTS (POTENTIOMETRY) 214 12.3 STEADY-STATE POLARIZATION MEASUREMENTS 214 12.3.1 Special Technical Features 214 12.3.2 Galvanostatic and Potentiostatic Circuits 216 12.3.3 Calculation of the Kinetic Parameters 216 12.4 TRANSIENT (PULSE) MEASUREMENTS 218 12.4.1 Potentiostatic Method (Chronoamperometry) 219 12.4.2 Potentiodynamic Method (Voltammetry) 220 12.4.3 Galvanostatic Method (Chronopotentiometry) 223 12.5 IMPEDANCE MEASUREMENTS 226 12.5.1 Electrode Impedance Measurements 226 12.5.2 Impedance in the Case of Irreversible Reactions 230 12.5.3 Impedance in the Case of Reversible Reactions 232 12.5.4 Impedance in the Case of More Complex Reactions 233 REFERENCES 233 REVIEWS AND MONOGRAPHS 234 PART II - Kinetics of Electrochemical Reactions 235 13 Multistep Electrode Reactions 236 13.1 INTERMEDIATE REACTION STEPS 236 13.2 RATE-DETERMINING STEP 237 13.3 TWO-STEP ELECTROCHEMICAL REACTIONS 239 13.3.1 Equilibrium Conditions 239 13.3.2 General Kinetic Equation 240 13.3.3 Region of Low Polarization 243 13.4 COMPLEX ELECTROCHEMICAL REACTIONS 244 13.5 REACTIONS WITH HOMOGENEOUS CHEMICAL STEPS 246 13.6 REACTIONS WITH MEDIATORS 250 13.7 PARALLEL ELECTRODE REACTIONS 252 14 Some Aspects of Electrochemical Kinetics 255 14.1 ENERGY OF ACTIVATION 255 14.1.1 Chemical Reactions 255 14.1.2 Electrochemical Reactions 258 14.1.3 Activationless and Barrierless Reactions 260 14.2 KINETIC INFLUENCE OF THE ELECTRIC DOUBLE LAYER 261 14.3 KINETIC INFLUENCE OF ADSORPTION 264 14.3.1 Reactant Adsorption 264 14.3.2 Adsorption of Foreign Substances 265 14.4 SPECIAL FEATURES OF REACTIONS AT SEMICONDUCTOR ELECTRODES 266 14.5 REACTIONS PRODUCING A NEW PHASE 268 14.5.1 Intermediate Stages in the Formation of New Phases 268 14.5.2 Formation of Gas Bubbles 270 14.5.3 Crystal-Phase Formation (Metal Deposition) 274 REFERENCES 276 15 Reactions at Nonconsumable Electrodes 277 15.1 SIMPLE ELECTROCHEMICAL REACTIONS 277 15.2 HYDROGEN EVOLUTION AND IONIZATION 279 15.2.1 Mechanism of the Hydrogen Evolution Reaction 282 15.2.2 Influence of Solution Composition 285 15.2.3 Ways of Influencing the Hydrogen Evolution Reaction 287 15.3 REACTIONS INVOLVING OXYGEN 288 15.3.1 Anodic Oxygen Evolution 290 15.3.2 Cathodic Oxygen Reduction 291 15.4 REACTIONS INVOLVING CHLORINE AND OTHER HALOGENS 293 15.5 REACTIONS INVOLVING ORGANIC SUBSTANCES 296 15.5.1 Reduction Reactions 297 15.5.2 Reactions of Partial Oxidation 299 15.5.3 Complete Electrochemical Oxidation of Methanol 300 15.5.4 Reactions Involving Organometallic Compounds 303 15.6 REACTIONS AT HIGH ANODIC POTENTIALS 304 15.7 REACTION OF CARBON DIOXIDE REDUCTION 307 15.8 REACTION OF NITROGEN REDUCTION 310 REFERENCES 311 MONOGRAPHS AND REVIEWS 311 16 Reactions Involving Metals 312 16.1 REACTING METAL ELECTRODES 312 16.2 ANODIC METAL DISSOLUTION 314 16.3 SURFACE-LAYER FORMATION 316 16.4 PASSIVATION OF ELECTRODES 320 16.4.1 Passivation of Metals 320 16.4.2 Various Types of Electrode Passivation 322 16.4.3 Origins and Mechanisms of Passivation 323 16.5 CATHODIC METAL DEPOSITION 325 16.5.1 Polarization in Metal Deposition 326 16.5.2 Parallel Reactions 327 16.5.3 Structure of the Metal Deposits 328 16.6 ELECTROCHEMICAL METAL TREATMENTS 330 REFERENCES 332 MONOGRAPHS 332 PART III - Applied Aspects of Electrochemistry 333 17 Industrial Electrolytic Processes 334 17.1 CHLOR–ALKALI ELECTROLYSIS 334 17.2 WATER ELECTROLYSIS 336 17.3 ELECTROMETALLURGY 336 17.4 ELECTROPLATING 337 MONOGRAPHS 338 18 Electrochemical Reactors 339 18.1 DESIGN PRINCIPLES 339 18.2 SEPARATORS 342 18.2.1 Purpose and Types 342 18.2.2 Chief Parameters 344 18.3 MACROKINETICS OF ELECTROCHEMICAL PROCESSES (SYSTEMS WITH DISTRIBUTED PARAMETERS) 346 18.4 POROUS ELECTRODES 349 18.4.1 Liquid-Diffusion Electrodes 350 18.4.2 Gas-Diffusion Electrodes 353 18.5 THREE-DIMENSIONAL ELECTRODES 354 MONOGRAPH 354 19 Batteries (Electrochemical Power Sources) 355 19.1 CHEMICAL CURRENT-PRODUCING REACTIONS IN BATTERIES 356 19.2 PERFORMANCE OF BATTERIES 357 19.2.1 Electrical characteristics 357 19.2.2 Operational Characteristics 360 19.3 ELECTROCHEMICAL SYSTEMS 361 19.4 PRIMARY BATTERIES 362 19.4.1 Leclanché (Zinc–Carbon) Batteries 362 19.4.2 Zinc Electrode in Alkaline Solutions 364 19.4.3 Alkaline Manganese Dioxide Batteries 364 19.5 STORAGE BATTERIES 365 19.5.1 Lead–Acid Batteries 365 19.5.2 Alkaline Nickel–Cadmium (Iron) Storage Batteries 366 19.5.3 Silver–Zinc Batteries 368 19.6 LITHIUM BATTERIES 369 19.6.1 Throwaway Cells with Electrolyte Solutions Prepared from Aprotic Organic Solvents 369 19.6.2 Lithium–Thionyl Chloride Throwaway Batteries 369 19.6.3 Rechargeable Lithium Batteries 370 19.6.4 Scientific Problems in the Field of Lithium Batteries 371 REFERENCES 372 REVIEWS 372 20 Fuel Cells 373 20.1 INTRODUCTION 373 20.2 DESIGN PRINCIPLES OF FUEL CELLS 375 20.3 PROTON-EXCHANGE MEMBRANE FUEL CELLS 376 20.3.1 Major Development Stages 376 20.3.2 Membranes 376 20.3.2 Platinum Catalysts 376 20.3.4 Poisoning of Platinum by CO Impurities in the Hydrogen 377 20.4 DIRECT METHANOL FUEL CELLS 378 20.4.1 Major Development Stages 378 20.4.2 Methanol Permeation Through the Membrane 379 20.4.3 Development Prospects 379 REFERENCES 380 MONOGRAPHS AND REVIEWS 380 21 Some Electrochemical Devices 381 21.1 ELECTROCHEMICAL CAPACITORS AND SUPERCAPACITORS 381 21.1.1 Ideal Electrostatic Capacitor 381 21.1.2 Electrolytic Capacitors 383 21.1.3 Double-Layer Capacitors 383 21.1.4 Pseudocapacitors 384 21.1.5 Impedance of Supercapacitors 385 21.2 ELECTROCHEMICAL TRANSDUCERS 387 MONOGRAPH 389 22 Corrosion of Metals 390 22.1 VARIOUS TYPES OF CORROSION 391 22.2 MECHANISMS OF CORROSION PROCESSES 392 22.3 CORROSION PROTECTION 395 REFERENCES 397 MONOGRAPHS 397 23 Electrochemical Methods of Analysis 398 23.1 CONDUCTOMETRY 399 23.2 COULOMETRY 399 23.3 AMPEROMETRY 400 23.4 POLAROGRAPHY 401 23.4.1 Dropping Mercury Electrode 401 23.4.2 Classsical Polarographic Technique 402 13.4.3 Possibilities and Disadvantages of the Polarographic Method 404 23.5 TRANSIENT VOLTAMMETRIC TECHNIQUES 405 23.5.1 Impressed-AC Method 406 23.5.2 Method of Consecutive Potentiostatic Pulses 406 23.5.3 Linear Potential Scan Voltammetry 408 23.5.4 AC Voltammetry 408 23.6 POTENTIOMETRY 409 23.6.1 Ion-Selective Electrodes 410 23.6.2 Glass Electrode 413 REFERENCES 414 MONOGRAPHS 414 24 Electrochemistry and the Environment 415 24.1 CHEMICAL AND ELECTROCHEMICAL PROCESSES 415 24.2 MONITORING THE ENVIRONMENT 416 24.2.1 Electrochemical Instruments for the Analysis of Gaseous Media 416 24.2.2 Electrochemical Instruments for the Analysis of Aqueous Media 417 24.3 PURIFICATION PROCEDURES (ELIMINATION OF POLLUTANTS) 418 24.4 MEDICAL APPLICATIONS OF ELECTROCHEMISTRY 421 24.4.1 Electrochemical Detoxification of the Organism 421 24.4.2 Electrochemical Life-Supporting Systems 422 24.5 ELECTROCHEMICAL ASPECTS OF BONE REMODELING AND FRACTURE REPAIR 423 REFERENCES 426 REVIEWS 426 MONOGRAPHS 426 PART IV - Selected Topics in Electrochemistry 427 25 Solid-State Electrochemistry 428 25.1 DEFECTS IN SOLIDS 428 25.1.1 Crystal Defects and Nonstoichiometry 428 25.1.2 Solid Solutions 431 25.2 SOLID ION CONDUCTORS 434 25.2.1 Ionic Conductivity in Solids 435 25.2.2 Oxide Ion Conductors 436 25.2.3 Fluoride Ion Conductors 439 25.2.4 Silver and Copper Ion Conductors 440 25.2.5 Sodium Ion Conductors 441 25.2.6 Lithium Ion Conductors 442 25.2.7 Proton Conductors 443 25.2.8 Glassy Ion Conductors 444 25.3 SOLID MIXED IONIC–ELECTRONIC CONDUCTORS 445 25.3.1 Metallic Mixed Conductors 445 25.3.2 Mixed-Conducting Oxides 446 25.3.3 pn-Junctions in Mixed Conductors 446 25.4 ELECTROCHEMICAL REACTIONS AT INTERFACES WITH SOLID ELECTROLYTES 447 25.4.1 Investigations in a Wide Temperature Range 447 25.4.2 Reactions in Solid Electrolyte Fuel Cells 448 25.5 HETEROGENEOUS SOLID-STATE REACTIONS 450 25.5.1 Reactions Via the Solution Phase 451 25.5.2 Topochemical Reactions 451 25.6 ELECTROCHEMICAL INTERCALATION 452 REFERENCES 456 MONOGRAPHS AND REVIEWS 456 26 Conductive Polymers 457 26.1 ACTIVE POLYMERS 457 26.2 POLYMERS WITH IONIC FUNCTIONS 458 26.2.1 Polyelectrolytes 458 26.2.2 Ion Exchangers 459 26.2.3 Ion-Exchange Membranes 461 26.3 POLYMERS WITH ELECTRONIC FUNCTIONS 465 26.3.1 Conventional Approaches 465 26.3.2 Intrinsically Conductive Organic Polymers 465 REFERENCES 472 REVIEWS AND MONOGRAPHS 473 27 Physical Methods for Investigation of Electrode Surfaces 474 27.1 TOPICS OF INVESTIGATION 475 27.1.1 Electrode Bulk Processes 475 27.1.2 Surfaces of Metal Single Crystals 476 27.1.3 Adsorption of Monolayers 476 27.1.4 Surface Topography and Morphology 476 27.1.5 Electrocrystallization 476 27.1.6 Anodic Films 477 27.2 X-RAY METHODS 477 27.2.1 X-Ray Diffraction 477 27.2.2 Bulk XRD of Battery Materials 478 27.2.3 Surface X-Ray Diffraction 481 27.2.4 X-Ray Reflectivity 483 27.2.5 X-Ray Absorption Spectroscopy 486 27.3 SCANNING PROBE METHODS 491 27.3.1 Scanning Tunneling Microscopy 491 27.3.2 Atomic Force Microscopy 494 27.4 ELECTROCHEMICAL QUARTZ CRYSTAL MICROBALANCE 494 27.5 OPTICAL SPECTROSCOPY 498 27.5.1 Polarized Light 498 27.5.2 Reflectance Spectroscopy 499 27.5.3 Ellipsometry 500 27.5.4 Raman Spectroscopy 504 27.5.5 Second Harmonic Generation 507 27.5.6 Sum-Frequency Generation 509 27.6 INFRARED SPECTROSCOPY 510 27.7 ELECTROCHEMICAL NMR 513 27.8 EX SITU METHODS 514 27.8.1 Low-Energy Electron Diffraction 515 27.8.2 Auger Electron Spectroscopy 516 27.8.3 X-Ray Photoelectron Spectroscopy 517 27.8.4 High-Resolution Electron Energy Loss Spectroscopy 519 27.8.5 Soft X-Ray X-Ray Absorption Spectroscopy 521 27.9 THE FUTURE OF PHYSICAL METHODS IN ELECTROCHEMISTRY 523 REFERENCES 524 MONOGRAPHS AND REVIEWS 525 28 Electrocatalysis 527 28.1 INTRODUCTION 527 28.1.1 The Field of Electrocatalysis 527 28.1.2 Special Features of Electrocatalysis 528 28.1.3 Electrocatalysis and Electrochemical Kinetics 529 28.2 ELECTROCATALYSIS AND ADSORPTION EFFECTS 529 28.3 METAL ELECTRODES: INFLUENCE OF THE NATURE OF THE METAL 530 28.3.1 Groups of Metals 530 28.3.2 Correlation Between Catalytic Activity of Metals and Their Bulk Properties 532 28.3.3 Criteria for Catalytic Activity 532 28.3.4 Correlation with the Electron Work Function 533 28.3.5 Correlation with the Bond Energy of Intermediates 535 28.4 METAL ELECTRODES: INFLUENCE OF SURFACE STATE AND STRUCTURE 536 28.4.1 Influence of Crystallographic Surface Structure 537 28.4.2 The Problem of Active Sites 539 28.4.3 Influence of Surface Impurities 540 28.5 HIGHLY DISPERSE METAL CATALYSTS 541 28.5.1 Methods for Preparing Electrodes with Disperse Catalysts 541 28.5.2 Crystallite Size and Specific Surface Area 542 28.5.3 Macrokinetic Limitations in Electrodes with Disperse Catalyst 543 28.5.4 Influence of Catalyst Crystallite Size 543 28.5.5 Influence of the Catalyst Substrate 545 28.6 BINARY AND MULTICOMPONENT METAL CATALYSTS 545 28.6.1 Metal Alloys 546 28.6.2 Adatoms 547 28.7 NONMETALLIC CATALYSTS 548 28.7.1 Carbon Materials 548 28.7.2 Oxides 550 28.7.3 Metal Complexes with Organic Ligands 553 28.7.4 Bioelectrocatalysis 555 28.8 STABILITY OF ELECTROCATALYSTS 556 28.9 OTHER ASPECTS OF ELECTROCATALYSIS 557 28.10 DISCUSSION 558 REFERENCES 560 MONOGRAPHS AND REVIEWS 560 29 Photoelectrochemistry 562 29.1 ENERGY LEVELS OF ELECTRONS 563 29.1.1 Electrochemical Potential of Electrons in Metals and Semiconductors 563 29.1.2 Electrochemical Potential of the Electrons in Solutions 565 29.1.3 Electron Transitions Between Electrode and Solution 567 29.2 ELECTRON PHOTOEMISSION INTO SOLUTIONS 567 29.3 PHOTOEXCITATION OF SEMICONDUCTOR ELECTRODES 569 29.3.1 Behavior of Illuminated Semiconductor Electrodes 569 29.3.2 Devices Based on the Photoexcitation of Semiconductor Electrodes 572 29.4 PHOTOEXCITATION OF REACTING SPECIES 575 REFERENCES 576 MONOGRAPH 576 30 Bioelectrochemistry 577 30.1 TRANSMISSION OF THE NERVOUS IMPULSE 579 30.1.1 Functions and Structure of Cell Membranes 579 30.1.2 Electrochemical Properties of Cell Membranes 580 30.1.3 Excitation of Cell Membranes 584 30.1.4 Propagation of the Excitation 586 30.2 BIOENERGETICS 588 30.2.1 Oxidizing Reactions in Cells 588 30.2.2 Photosynthesis 590 30.3 ELECTROCHEMICAL METHODS IN BIOLOGY AND MEDICINE 593 30.3.1 Biological Macropotentials 593 30.3.2 Electrochemical Sensors 594 30.3.3 Influence of Electric Currents on the Organism 595 30.3.4 Use of Electrokinetic Methods 596 REFERENCES 596 MONOGRAPH 597 31 Electrokinetic Processes 598 31.1 ELECTROKINETIC POTENTIAL 600 31.1.1 Metal–Solution Interface 600 31.1.2 Insulator–Solution Interface 601 31.1.3 Electrochemical Properties of Colloidal Solutions 602 31.2 BASIC EQUATIONS OF ELECTROKINETIC PROCESSES 603 31.3 PRACTICAL USE OF ELECTROKINETIC PROCESSES 608 REFERENCES 609 32 Interfaces Between Two Immiscible Electrolyte Solutions 610 32.1 EQUILIBRIUM GALVANI POTENTIAL DIFFERENCE 611 32.1.1 Charge-Charge-Transfer Processes at ITIES 611 32.1.2 Scale of Galvani Potential Differences 614 32.2 IDEALLY POLARIZABLE ITIES 615 32.3 POLARIZATION MEASUREMENTS 615 32.4 STRUCTURE OF ITIES 617 32.5 CHARGE-TRANSFER RATE 619 32.6 APPLICATIONS 621 REFERENCES 622 REVIEWS AND MONOGRAPHS 622 33 Various Electrochemical Phenomena 623 33.1 ELECTROCHROMISM 623 33.2 ELECTROCHEMICAL NOISE 628 33.3 ELECTROCHEMICAL PROPERTIES OF HIGH-TEMPERATURE SUPERCONDUCTORS 632 33.4 ELECTROCHEMICAL “COLD FUSION” 634 REFERENCES 637 34 Main Concepts of Elementary Reaction Act Theory 638 34.1 OUTER-SPHERE ELECTRON TRANSFER REACTIONS IN THE BULK SOLUTION 639 34.2 ADIABATIC AND NONADIABATIC REACTIONS 644 34.3 ELECTROCHEMICAL ELECTRON TRANSFER 646 34.4 ELECTROCHEMICAL ADIABATICITY PARAMETER. MEDIUM DYNAMICS VS. STATIC DISTRIBUTION 651 34.5 ADIABATIC ELECTROCHEMICAL ELECTRON TRANSFER REACTIONS 653 34.6 ELECTRIC DOUBLE-LAYER EFFECTS ON THE ELEMENTARY ACT OF ELECTRON TRANSFER 654 34.7 BOND-BREAKING ELECTRON TRANSFER 656 34.8 REORGANIZATION ENERGY OF THE MEDIUM AND THE FREQUENCY FACTOR 658 34.9 ELECTROCHEMICAL PROTON TRANSFER 659 Acknowledgments 661 REFERENCES 661 REVIEWS AND MONOGRAPHS 661 35 Computer Simulation in Electrochemistry 662 35.1 INTRODUCTION 662 35.2 MOLECULAR (ATOM) DYNAMICS 663 35.2.1 Metal–Water and Ionic Solution–Metal Interphases 664 35.2.2 Electron Transfer Reactions 666 35.2.3 Electrochemical Ion-Transfer Reactions 668 35.3 MONTE CARLO METHODS 669 35.3.1 Some Basic Ideas on Random Variables and Markov Chains 669 35.3.2 Brownian Dynamics 672 35.3.3 Off-Lattice Models 672 35.3.4 Lattice Models 674 Acknowledgments 677 REFERENCES 677 REVIEWS AND MONOGRAPHS 678 36 Nanoelectrochemistry 679 36.1 INTRODUCTION 679 36.2 PROBE-INDUCED ELECTROCHEMICAL NANOSTRUCTURING OF METALLIC SURFACES 680 36.3 DEFECT NANOSTRUCTURING 681 36.4 TIP-INDUCED LOCAL METAL DEPOSITION 684 36.5 LOCALIZED ELECTROCHEMICAL NUCLEATION AND GROWTH 686 36.6 ELECTRONIC CONTACT NANOSTRUCTURING 688 36.7 NANOSTRUCTURING BY SCANNING ELECTROCHEMICAL MICROSCOPY 689 Acknowledgments 690 REFERENCES 691 REVIEWS AND MONOGRAPHS 691 37 Development of Electrochemistry 692 37.1 FIRST ELECTROCHEMICAL POWER SOURCES 692 37.2 DEVELOPMENT OF A LARGE-SCALE ELECTROCHEMICAL INDUSTRY 695 37.3 FUEL CELLS AND LITHIUM BATTERIES 698 REFERENCES 698 APPENDIX A: Derivation of the Main Equation of Debye–Hückel Theory 700 APPENDIX B: Derivation of the Main Equation of Gouy–Chapman Theory 703 General Bibliography 706 MONOGRAPHS AND CONTRIBUTED BOOKS 706 SERIALS 706 PERIODICALS 707 AUTHOR INDEX 708 SUBJECT INDEX 712 Cover Page......Page 1 Title Page......Page 2 Copyright © 2006 by John Wiley & Sons, Inc.......Page 3 3. Thermodynamics of Electrochemical Systems 33......Page 4 8. Nonaqueous Electrolytes 127......Page 5 13. Multistep Electrode Reactions 219......Page 6 18. Electrochemical Reactors 327......Page 7 24. Electrochemistry and the Environment 405......Page 8 28. Electrocatalysis 521......Page 9 33. Various Electrochemical Phenomena 621......Page 10 37. Development of Electrochemistry 693......Page 11 Subject Index 715......Page 12 CONTRIBUTORS......Page 13 PREFACE TO THE SECOND EDITION......Page 15 PREFACE TO THE FIRST EDITION......Page 16 LIST OF PHOTOGRAPHS......Page 19 ABBREVIATIONS......Page 20 SYMBOLS......Page 22 PART I - Basic Concepts......Page 26 1.1 VARIOUS TYPES OF CONDUCTORS......Page 27 1.2 IONS IN ELECTROLYTE SOLUTIONS......Page 28 1.3 CONDUCTIVITY OF ELECTROLYTE SOLUTIONS......Page 29 1.4 CIRCUITS INVOLVING IONIC CONDUCTORS. ELECTRODES......Page 33 1.5 PASSAGE OF CURRENT THROUGH ELECTRODES. ELECTRODE REACTIONS......Page 34 1.6 CLASSIFICATION OF ELECTRODES AND ELECTRODE REACTIONS......Page 36 1.7 FARADAY’S LAWS......Page 39 1.8 EQUATIONS FOR MASS BALANCE......Page 40 REFERENCE......Page 42 E......Page 43 2.1.1 Metal–Metal Contact......Page 44 2.1.4 Galvani Potentials Cannot Be Determined......Page 46 2.2 EXCHANGE CURRENTS......Page 47 2.3.2 Galvanic Circuits......Page 48 2.4.1 Defining the Concept of Electrode Potential......Page 50 2.4.2 Nonequilibrium Electrode Potentials......Page 51 2.5.1 Two Directions of Current Flow......Page 53 2.5.2 Polarization and Ohmic Losses......Page 54 3.1 CONVENTIONAL AND UNDEFINED PARAMETERS......Page 56 3.2.1 Thermodynamic Functions......Page 57 3.2.2 Electrochemical Potentials......Page 58 3.3.1 Definition of the Concept of Activity......Page 59 3.3.2 Activities of Ions in Electrolyte Solutions......Page 60 3.4 EQUATIONS FOR THE EMF OF GALVANIC CELLS......Page 62 3.5.1 Nernst Equation for Ideal Systems......Page 64 3.5.2 Equations for Real Systems......Page 65 3.5.3 Electrodes of the Second Kind......Page 66 3.5.4 Nernst Equation at Very Low Concentrations......Page 68 3.6.2 pH Dependence of Potentials; Pourbaix Diagrams......Page 69 3.6.3 Electrode Potentials in Nonaqueous Electrolytes......Page 71 3.6.4 Temperature Coefficients of Electrode Potentials......Page 72 MONOGRAPHS AND REFERENCE BOOKS......Page 73 4.1 BASIC LAWS OF IONIC DIFFUSION IN SOLUTIONS......Page 74 4.2 LIMITING DIFFUSION CURRENTS IN ELECTROLYTES......Page 76 4.3.1 Equations for the Total Flux......Page 78 4.3.2 Total Fluxes in Binary Electrolytes......Page 79 4.4 CONVECTIVE TRANSPORT......Page 83 4.4.1 Flow-by Electrodes......Page 84 4.4.2 Rotating-Disk Electrode......Page 87 4.4.3 Rotating Ring–Disk Electrode......Page 88 4.4.4 Cells with Natural Convection of the Electrolyte......Page 89 REFERENCES......Page 90 5.1 TYPES OF INTERFACES BETWEEN ELECTROLYTES......Page 91 5.2 POTENTIALS BETWEEN SIMILAR ELECTROLYTES (DIFFUSION POTENTIALS)......Page 93 5.2.2 Ways of Reducing Diffusion Potentials......Page 94 5.3 DISTRIBUTION OF THE IONS BETWEEN DISSIMILAR BUT MISCIBLE ELECTROLYTES......Page 95 5.4.2 Quasiequilibrium Systems......Page 97 5.5 GALVANIC CELLS WITH TRANSFERENCE......Page 98 REFERENCES......Page 99 6.1.1 Electrochemical Reaction Rates......Page 100 6.1.3 Overall and Partial Reaction Currents......Page 101 6.1.4 Various Types of Polarization......Page 102 6.2.1 Polarization Equations......Page 103 6.2.2 Influence of Reactant Concentrations......Page 105 6.2.3 General Kinetic and Polarization Equations......Page 106 6.2.4 Relations Between the Parameters of the Forward and Reverse Process......Page 107 6.2.5 Relation Between the Kinetic Parameters in Regions of Low and High Polarization......Page 108 6.2.6 Concentration Dependence of the Exchange Current Density......Page 109 6.3.1 Solutions with Excess Foreign Electrolyte......Page 110 6.3.2 Binary Electrolyte Solutions......Page 113 6.4 SUPERPOSITION OF CONCENTRATION AND ACTIVATION POLARIZATION......Page 114 REFERENCES......Page 119 7.1.1 Early Ideas......Page 120 7.1.2 Arrhenius’s Theory of Electrolytic Dissociation......Page 122 7.1.3 Further Development of the Theory of Electrolytic Dissociation......Page 126 7.2 IONIC SOLVATION (HYDRATION) IN SOLUTIONS......Page 127 7.2.1 Solvation Energies of Electrolytes......Page 128 7.2.2 Solvation Energies of Individual Ions......Page 129 7.2.3 Solvation Numbers......Page 131 7.2.4 Hydration of Protons......Page 132 7.3.1 Ways to Determine the Activity of Electrolyte Solutions......Page 133 7.3.2 Concentration Dependence of the Activity Coefficient......Page 134 7.3.3 Physical Meaning of Activity Coefficients......Page 136 7.4 PHYSICAL THEORIES OF ION–ION INTERACTIONS......Page 137 7.4.1 Ionic Atmosphere......Page 138 7.4.2 Debye–Hückel Limiting Law......Page 139 7.4.3 Second and Third Approximation of the Theory......Page 141 7.4.4 Ion–Ion Interaction and Conductivity......Page 143 7.4.5 Further Development of Electrolyte Solution Theory......Page 145 MONOGRAPHS......Page 147 8.1 DIFFERENT TYPES OF ELECTROLYTES AND THEIR PRACTICAL UTILIZATION......Page 148 8.2 NONAQUEOUS ELECTROLYTE SOLUTIONS......Page 149 8.3 IONICALLY CONDUCTING MELTS......Page 152 8.4.1 Ionic Semiconductors......Page 155 8.4.2 Ionic Conductors......Page 157 MONOGRAPHS AND REVIEWS......Page 158 9.1 SURFACE POTENTIAL OF A PHASE......Page 159 9.2.1 Work Function for the Metal–Vacuum Interface......Page 160 9.2.2 Work Function for Metals Contacting Electrolytes......Page 161 9.3 VOLTA POTENTIALS......Page 163 9.4.1 Volta Problem......Page 164 9.4.2 Problem of Absolute Potential......Page 165 REFERENCE......Page 166 10 Structure and Properties of Surface Layers......Page 167 10.1 ELECTRICAL STRUCTURE OF INTERPHASES......Page 168 10.1.2 Gouy–Chapman Model......Page 171 10.1.3 Models of Stern and Grahame......Page 172 10.2.1 Types of Adsorption......Page 176 10.2.3 Reversible and Irreversible Adsorption......Page 177 10.2.4 Adsorption Isotherms......Page 178 10.2.5 Adsorption in Electrochemical Systems......Page 180 10.3 THERMODYNAMICS OF SURFACE PHENOMENA......Page 182 10.3.1 Surface Excesses of Substances......Page 183 10.3.2 Excess Surface Energy......Page 184 10.3.3 Gibbs Adsorption Equation......Page 185 10.3.4 Electrocapillary Curves......Page 186 10.4.1 Ion Adsorption......Page 189 10.4.2 Adsorption of Organic Substances......Page 191 10.5.1 Electrochemical Methods for Investigating the Surface of Platinum Electrodes......Page 192 10.5.2 Hydrogen Adsorption on Platinum......Page 194 10.5.3 Surface Inhomogeneity of Platinum......Page 195 10.5.5 Aging of Adsorbed Particles......Page 196 10.6 SURFACES OF OTHER ELECTRODES......Page 198 MONOGRAPHS......Page 200 11.1 EVIDENCE FOR TRANSIENT CONDITIONS......Page 201 11.2 TRANSIENT DIFFUSION TO ELECTRODES OF LARGE SIZE......Page 202 11.2.1 Galvanostatic Conditions......Page 203 11.2.2 Potentiostatic conditions......Page 206 11.2.3 Use of Alternating Currents......Page 207 11.3 TRANSIENT DIFFUSION TO ELECTRODES OF FINITE SIZE......Page 208 12 Electrochemical Research Techniques......Page 210 12.1 REFERENCE ELECTRODES......Page 211 12.3.1 Special Technical Features......Page 214 12.3.3 Calculation of the Kinetic Parameters......Page 216 12.4 TRANSIENT (PULSE) MEASUREMENTS......Page 218 12.4.1 Potentiostatic Method (Chronoamperometry)......Page 219 12.4.2 Potentiodynamic Method (Voltammetry)......Page 220 12.4.3 Galvanostatic Method (Chronopotentiometry)......Page 223 12.5.1 Electrode Impedance Measurements......Page 226 12.5.2 Impedance in the Case of Irreversible Reactions......Page 230 12.5.3 Impedance in the Case of Reversible Reactions......Page 232 REFERENCES......Page 233 REVIEWS AND MONOGRAPHS......Page 234 PART II - Kinetics of Electrochemical Reactions......Page 235 13.1 INTERMEDIATE REACTION STEPS......Page 236 13.2 RATE-DETERMINING STEP......Page 237 13.3.1 Equilibrium Conditions......Page 239 13.3.2 General Kinetic Equation......Page 240 13.3.3 Region of Low Polarization......Page 243 13.4 COMPLEX ELECTROCHEMICAL REACTIONS......Page 244 13.5 REACTIONS WITH HOMOGENEOUS CHEMICAL STEPS......Page 246 13.6 REACTIONS WITH MEDIATORS......Page 250 13.7 PARALLEL ELECTRODE REACTIONS......Page 252 14.1.1 Chemical Reactions......Page 255 14.1.2 Electrochemical Reactions......Page 258 14.1.3 Activationless and Barrierless Reactions......Page 260 14.2 KINETIC INFLUENCE OF THE ELECTRIC DOUBLE LAYER......Page 261 14.3.1 Reactant Adsorption......Page 264 14.3.2 Adsorption of Foreign Substances......Page 265 14.4 SPECIAL FEATURES OF REACTIONS AT SEMICONDUCTOR ELECTRODES......Page 266 14.5.1 Intermediate Stages in the Formation of New Phases......Page 268 14.5.2 Formation of Gas Bubbles......Page 270 14.5.3 Crystal-Phase Formation (Metal Deposition)......Page 274 REFERENCES......Page 276 15.1 SIMPLE ELECTROCHEMICAL REACTIONS......Page 277 15.2 HYDROGEN EVOLUTION AND IONIZATION......Page 279 15.2.1 Mechanism of the Hydrogen Evolution Reaction......Page 282 15.2.2 Influence of Solution Composition......Page 285 15.2.3 Ways of Influencing the Hydrogen Evolution Reaction......Page 287 15.3 REACTIONS INVOLVING OXYGEN......Page 288 15.3.1 Anodic Oxygen Evolution......Page 290 15.3.2 Cathodic Oxygen Reduction......Page 291 15.4 REACTIONS INVOLVING CHLORINE AND OTHER HALOGENS......Page 293 15.5 REACTIONS INVOLVING ORGANIC SUBSTANCES......Page 296 15.5.1 Reduction Reactions......Page 297 15.5.2 Reactions of Partial Oxidation......Page 299 15.5.3 Complete Electrochemical Oxidation of Methanol......Page 300 15.5.4 Reactions Involving Organometallic Compounds......Page 303 15.6 REACTIONS AT HIGH ANODIC POTENTIALS......Page 304 15.7 REACTION OF CARBON DIOXIDE REDUCTION......Page 307 15.8 REACTION OF NITROGEN REDUCTION......Page 310 MONOGRAPHS AND REVIEWS......Page 311 16.1 REACTING METAL ELECTRODES......Page 312 16.2 ANODIC METAL DISSOLUTION......Page 314 16.3 SURFACE-LAYER FORMATION......Page 316 16.4.1 Passivation of Metals......Page 320 16.4.2 Various Types of Electrode Passivation......Page 322 16.4.3 Origins and Mechanisms of Passivation......Page 323 16.5 CATHODIC METAL DEPOSITION......Page 325 16.5.1 Polarization in Metal Deposition......Page 326 16.5.2 Parallel Reactions......Page 327 16.5.3 Structure of the Metal Deposits......Page 328 16.6 ELECTROCHEMICAL METAL TREATMENTS......Page 330 MONOGRAPHS......Page 332 PART III - Applied Aspects of Electrochemistry......Page 333 17.1 CHLOR–ALKALI ELECTROLYSIS......Page 334 17.3 ELECTROMETALLURGY......Page 336 17.4 ELECTROPLATING......Page 337 MONOGRAPHS......Page 338 18.1 DESIGN PRINCIPLES......Page 339 18.2.1 Purpose and Types......Page 342 18.2.2 Chief Parameters......Page 344 18.3 MACROKINETICS OF ELECTROCHEMICAL PROCESSES (SYSTEMS WITH DISTRIBUTED PARAMETERS)......Page 346 18.4 POROUS ELECTRODES......Page 349 18.4.1 Liquid-Diffusion Electrodes......Page 350 18.4.2 Gas-Diffusion Electrodes......Page 353 MONOGRAPH......Page 354 19 Batteries (Electrochemical Power Sources)......Page 355 19.1 CHEMICAL CURRENT-PRODUCING REACTIONS IN BATTERIES......Page 356 19.2.1 Electrical characteristics......Page 357 19.2.2 Operational Characteristics......Page 360 19.3 ELECTROCHEMICAL SYSTEMS......Page 361 19.4.1 Leclanché (Zinc–Carbon) Batteries......Page 362 19.4.3 Alkaline Manganese Dioxide Batteries......Page 364 19.5.1 Lead–Acid Batteries......Page 365 19.5.2 Alkaline Nickel–Cadmium (Iron) Storage Batteries......Page 366 19.5.3 Silver–Zinc Batteries......Page 368 19.6.2 Lithium–Thionyl Chloride Throwaway Batteries......Page 369 19.6.3 Rechargeable Lithium Batteries......Page 370 19.6.4 Scientific Problems in the Field of Lithium Batteries......Page 371 REVIEWS......Page 372 20.1 INTRODUCTION......Page 373 20.2 DESIGN PRINCIPLES OF FUEL CELLS......Page 375 20.3.2 Platinum Catalysts......Page 376 20.3.4 Poisoning of Platinum by CO Impurities in the Hydrogen......Page 377 20.4.1 Major Development Stages......Page 378 20.4.3 Development Prospects......Page 379 MONOGRAPHS AND REVIEWS......Page 380 21.1.1 Ideal Electrostatic Capacitor......Page 381 21.1.3 Double-Layer Capacitors......Page 383 21.1.4 Pseudocapacitors......Page 384 21.1.5 Impedance of Supercapacitors......Page 385 21.2 ELECTROCHEMICAL TRANSDUCERS......Page 387 MONOGRAPH......Page 389 22 Corrosion of Metals......Page 390 22.1 VARIOUS TYPES OF CORROSION......Page 391 22.2 MECHANISMS OF CORROSION PROCESSES......Page 392 22.3 CORROSION PROTECTION......Page 395 MONOGRAPHS......Page 397 23 Electrochemical Methods of Analysis......Page 398 23.2 COULOMETRY......Page 399 23.3 AMPEROMETRY......Page 400 23.4.1 Dropping Mercury Electrode......Page 401 23.4.2 Classsical Polarographic Technique......Page 402 13.4.3 Possibilities and Disadvantages of the Polarographic Method......Page 404 23.5 TRANSIENT VOLTAMMETRIC TECHNIQUES......Page 405 23.5.2 Method of Consecutive Potentiostatic Pulses......Page 406 23.5.4 AC Voltammetry......Page 408 23.6 POTENTIOMETRY......Page 409 23.6.1 Ion-Selective Electrodes......Page 410 23.6.2 Glass Electrode......Page 413 MONOGRAPHS......Page 414 24.1 CHEMICAL AND ELECTROCHEMICAL PROCESSES......Page 415 24.2.1 Electrochemical Instruments for the Analysis of Gaseous Media......Page 416 24.2.2 Electrochemical Instruments for the Analysis of Aqueous Media......Page 417 24.3 PURIFICATION PROCEDURES (ELIMINATION OF POLLUTANTS)......Page 418 24.4.1 Electrochemical Detoxification of the Organism......Page 421 24.4.2 Electrochemical Life-Supporting Systems......Page 422 24.5 ELECTROCHEMICAL ASPECTS OF BONE REMODELING AND FRACTURE REPAIR......Page 423 MONOGRAPHS......Page 426 PART IV - Selected Topics in Electrochemistry......Page 427 25.1.1 Crystal Defects and Nonstoichiometry......Page 428 25.1.2 Solid Solutions......Page 431 25.2 SOLID ION CONDUCTORS......Page 434 25.2.1 Ionic Conductivity in Solids......Page 435 25.2.2 Oxide Ion Conductors......Page 436 25.2.3 Fluoride Ion Conductors......Page 439 25.2.4 Silver and Copper Ion Conductors......Page 440 25.2.5 Sodium Ion Conductors......Page 441 25.2.6 Lithium Ion Conductors......Page 442 25.2.7 Proton Conductors......Page 443 25.2.8 Glassy Ion Conductors......Page 444 25.3.1 Metallic Mixed Conductors......Page 445 25.3.3 pn-Junctions in Mixed Conductors......Page 446 25.4.1 Investigations in a Wide Temperature Range......Page 447 25.4.2 Reactions in Solid Electrolyte Fuel Cells......Page 448 25.5 HETEROGENEOUS SOLID-STATE REACTIONS......Page 450 25.5.2 Topochemical Reactions......Page 451 25.6 ELECTROCHEMICAL INTERCALATION......Page 452 MONOGRAPHS AND REVIEWS......Page 456 26.1 ACTIVE POLYMERS......Page 457 26.2.1 Polyelectrolytes......Page 458 26.2.2 Ion Exchangers......Page 459 26.2.3 Ion-Exchange Membranes......Page 461 26.3.2 Intrinsically Conductive Organic Polymers......Page 465 REFERENCES......Page 472 REVIEWS AND MONOGRAPHS......Page 473 27 Physical Methods for Investigation of Electrode Surfaces......Page 474 27.1.1 Electrode Bulk Processes......Page 475 27.1.5 Electrocrystallization......Page 476 27.2.1 X-Ray Diffraction......Page 477 27.2.2 Bulk XRD of Battery Materials......Page 478 27.2.3 Surface X-Ray Diffraction......Page 481 27.2.4 X-Ray Reflectivity......Page 483 27.2.5 X-Ray Absorption Spectroscopy......Page 486 27.3.1 Scanning Tunneling Microscopy......Page 491 27.4 ELECTROCHEMICAL QUARTZ CRYSTAL MICROBALANCE......Page 494 27.5.1 Polarized Light......Page 498 27.5.2 Reflectance Spectroscopy......Page 499 27.5.3 Ellipsometry......Page 500 27.5.4 Raman Spectroscopy......Page 504 27.5.5 Second Harmonic Generation......Page 507 27.5.6 Sum-Frequency Generation......Page 509 27.6 INFRARED SPECTROSCOPY......Page 510 27.7 ELECTROCHEMICAL NMR......Page 513 27.8 EX SITU METHODS......Page 514 27.8.1 Low-Energy Electron Diffraction......Page 515 27.8.2 Auger Electron Spectroscopy......Page 516 27.8.3 X-Ray Photoelectron Spectroscopy......Page 517 27.8.4 High-Resolution Electron Energy Loss Spectroscopy......Page 519 27.8.5 Soft X-Ray X-Ray Absorption Spectroscopy......Page 521 27.9 THE FUTURE OF PHYSICAL METHODS IN ELECTROCHEMISTRY......Page 523 REFERENCES......Page 524 MONOGRAPHS AND REVIEWS......Page 525 28.1.1 The Field of Electrocatalysis......Page 527 28.1.2 Special Features of Electrocatalysis......Page 528 28.2 ELECTROCATALYSIS AND ADSORPTION EFFECTS......Page 529 28.3.1 Groups of Metals......Page 530 28.3.3 Criteria for Catalytic Activity......Page 532 28.3.4 Correlation with the Electron Work Function......Page 533 28.3.5 Correlation with the Bond Energy of Intermediates......Page 535 28.4 METAL ELECTRODES: INFLUENCE OF SURFACE STATE AND STRUCTURE......Page 536 28.4.1 Influence of Crystallographic Surface Structure......Page 537 28.4.2 The Problem of Active Sites......Page 539 28.4.3 Influence of Surface Impurities......Page 540 28.5.1 Methods for Preparing Electrodes with Disperse Catalysts......Page 541 28.5.2 Crystallite Size and Specific Surface Area......Page 542 28.5.4 Influence of Catalyst Crystallite Size......Page 543 28.6 BINARY AND MULTICOMPONENT METAL CATALYSTS......Page 545 28.6.1 Metal Alloys......Page 546 28.6.2 Adatoms......Page 547 28.7.1 Carbon Materials......Page 548 28.7.2 Oxides......Page 550 28.7.3 Metal Complexes with Organic Ligands......Page 553 28.7.4 Bioelectrocatalysis......Page 555 28.8 STABILITY OF ELECTROCATALYSTS......Page 556 28.9 OTHER ASPECTS OF ELECTROCATALYSIS......Page 557 28.10 DISCUSSION......Page 558 MONOGRAPHS AND REVIEWS......Page 560 29 Photoelectrochemistry......Page 562 29.1.1 Electrochemical Potential of Electrons in Metals and Semiconductors......Page 563 29.1.2 Electrochemical Potential of the Electrons in Solutions......Page 565 29.2 ELECTRON PHOTOEMISSION INTO SOLUTIONS......Page 567 29.3.1 Behavior of Illuminated Semiconductor Electrodes......Page 569 29.3.2 Devices Based on the Photoexcitation of Semiconductor Electrodes......Page 572 29.4 PHOTOEXCITATION OF REACTING SPECIES......Page 575 MONOGRAPH......Page 576 30 Bioelectrochemistry......Page 577 30.1.1 Functions and Structure of Cell Membranes......Page 579 30.1.2 Electrochemical Properties of Cell Membranes......Page 580 30.1.3 Excitation of Cell Membranes......Page 584 30.1.4 Propagation of the Excitation......Page 586 30.2.1 Oxidizing Reactions in Cells......Page 588 30.2.2 Photosynthesis......Page 590 30.3.1 Biological Macropotentials......Page 593 30.3.2 Electrochemical Sensors......Page 594 30.3.3 Influence of Electric Currents on the Organism......Page 595 REFERENCES......Page 596 MONOGRAPH......Page 597 31 Electrokinetic Processes......Page 598 31.1.1 Metal–Solution Interface......Page 600 31.1.2 Insulator–Solution Interface......Page 601 31.1.3 Electrochemical Properties of Colloidal Solutions......Page 602 31.2 BASIC EQUATIONS OF ELECTROKINETIC PROCESSES......Page 603 31.3 PRACTICAL USE OF ELECTROKINETIC PROCESSES......Page 608 REFERENCES......Page 609 32 Interfaces Between Two Immiscible Electrolyte Solutions......Page 610 32.1.1 Charge-Charge-Transfer Processes at ITIES......Page 611 32.1.2 Scale of Galvani Potential Differences......Page 614 32.3 POLARIZATION MEASUREMENTS......Page 615 32.4 STRUCTURE OF ITIES......Page 617 32.5 CHARGE-TRANSFER RATE......Page 619 32.6 APPLICATIONS......Page 621 REVIEWS AND MONOGRAPHS......Page 622 33.1 ELECTROCHROMISM......Page 623 33.2 ELECTROCHEMICAL NOISE......Page 628 33.3 ELECTROCHEMICAL PROPERTIES OF HIGH-TEMPERATURE SUPERCONDUCTORS......Page 632 33.4 ELECTROCHEMICAL “COLD FUSION”......Page 634 REFERENCES......Page 637 34 Main Concepts of Elementary Reaction Act Theory......Page 638 34.1 OUTER-SPHERE ELECTRON TRANSFER REACTIONS IN THE BULK SOLUTION......Page 639 34.2 ADIABATIC AND NONADIABATIC REACTIONS......Page 644 34.3 ELECTROCHEMICAL ELECTRON TRANSFER......Page 646 34.4 ELECTROCHEMICAL ADIABATICITY PARAMETER. MEDIUM DYNAMICS VS. STATIC DISTRIBUTION......Page 651 34.5 ADIABATIC ELECTROCHEMICAL ELECTRON TRANSFER REACTIONS......Page 653 34.6 ELECTRIC DOUBLE-LAYER EFFECTS ON THE ELEMENTARY ACT OF ELECTRON TRANSFER......Page 654 34.7 BOND-BREAKING ELECTRON TRANSFER......Page 656 34.8 REORGANIZATION ENERGY OF THE MEDIUM AND THE FREQUENCY FACTOR......Page 658 34.9 ELECTROCHEMICAL PROTON TRANSFER......Page 659 REVIEWS AND MONOGRAPHS......Page 661 35.1 INTRODUCTION......Page 662 35.2 MOLECULAR (ATOM) DYNAMICS......Page 663 35.2.1 Metal–Water and Ionic Solution–Metal Interphases......Page 664 35.2.2 Electron Transfer Reactions......Page 666 35.2.3 Electrochemical Ion-Transfer Reactions......Page 668 35.3.1 Some Basic Ideas on Random Variables and Markov Chains......Page 669 35.3.3 Off-Lattice Models......Page 672 35.3.4 Lattice Models......Page 674 REFERENCES......Page 677 REVIEWS AND MONOGRAPHS......Page 678 36.1 INTRODUCTION......Page 679 36.2 PROBE-INDUCED ELECTROCHEMICAL NANOSTRUCTURING OF METALLIC SURFACES......Page 680 36.3 DEFECT NANOSTRUCTURING......Page 681 36.4 TIP-INDUCED LOCAL METAL DEPOSITION......Page 684 36.5 LOCALIZED ELECTROCHEMICAL NUCLEATION AND GROWTH......Page 686 36.6 ELECTRONIC CONTACT NANOSTRUCTURING......Page 688 36.7 NANOSTRUCTURING BY SCANNING ELECTROCHEMICAL MICROSCOPY......Page 689 Acknowledgments......Page 690 REVIEWS AND MONOGRAPHS......Page 691 37.1 FIRST ELECTROCHEMICAL POWER SOURCES......Page 692 37.2 DEVELOPMENT OF A LARGE-SCALE ELECTROCHEMICAL INDUSTRY......Page 695 REFERENCES......Page 698 APPENDIX A: Derivation of the Main Equation of Debye–Hückel Theory......Page 700 APPENDIX B: Derivation of the Main Equation of Gouy–Chapman Theory......Page 703 SERIALS......Page 706 PERIODICALS......Page 707 AUTHOR INDEX......Page 708 SUBJECT INDEX......Page 712 Fundamentals of Electrochemistry provides the basic outline of most topics of theoretical and applied electrochemistry for students not yet familiar with this field, as well as an outline of recent and advanced developments in electrochemistry for people who are already dealing with electrochemical problems.

The content of this edition is arranged so that all basic information is contained in the first part of the book, which is now rewritten and simplified in order to make it more accessible and used as a textbook for undergraduate students. More advanced topics, of interest for postgraduate levels, come in the subsequent parts.

This updated second edition focuses on experimental techniques, including a comprehensive chapter on physical methods for the investigation of electrode surfaces. New chapters deal with recent trends in electrochemistry, including nano- and micro-electrochemistry, solid-state electrochemistry, and electrocatalysis. In addition, the authors take into account the worldwide renewal of interest for the problem of fuel cells and include chapters on batteries, fuel cells, and double layer capacitors.