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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.
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.
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.
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.
Über den Autor
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.
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 Equilibrium 121
3.1.2 The Arrhenius Equation and Potential Energy Surfaces 122
3.1.3 Transition State Theory 123
3.2 Essentials of Electrode Reactions 125
3.3 Butler-Volmer Model of Electrode Kinetics 126
3.3.1 Effects of Potential on Energy Barriers 127
3.3.2 One-Step, One-Electron Process 127
3.3.3 The Standard Rate Constant 130
3.3.4 The Transfer Coefficient 131
3.4 Implications of the Butler-Volmer Model for the One-Step, One-Electron Process 132
3.4.1 Equilibrium Conditions and the Exchange Current 133
3.4.2 The Current-Overpotential Equation 133
3.4.3 Approximate Forms of the i-eta Equation 135
3.4.4 Exchange Current Plots 139
3.4.5 Very Facile Kinetics and Reversible Behavior 139
3.4.6 Effects of Mass Transfer 140
3.4.7 Limits of Basic Butler-Volmer Equations 141
3.5 Microscopic Theories of Charge Transfer 142
3.5.1 Inner-Sphere and Outer-Sphere Electrode Reactions 142
3.5.2 Extended Charge Transfer and Adiabaticity 143
3.5.3 The Marcus Microscopic Model 146
3.5.4 Implications of the Marcus Theory 152
3.5.5 A Model Based on Distributions of Energy States 162
3.6 Open-Circuit Potential and Multiple Half-Reactions at an Electrode 168
3.6.1 Open-Circuit Potential in Multicomponent Systems 169
3.6.2 Establishment or Loss of Nernstian Behavior at an Electrode 170
3.6.3 Multiple Half-Reaction Currents in i-E Curves 171
3.7 Multistep Mechanisms 171
3.7.1 The Primacy of One-Electron Transfers 172
3.7.2 Rate-Determining, Outer-Sphere Electron Transfer 173
3.7.3 Multistep Processes at Equilibrium 173
3.7.4 Nernstian Multistep Processes 174
3.7.5 Quasireversible and Irreversible Multistep Processes 174
3.8 References 177
3.9 Problems 180
4 Mass Transfer by Migration and Diffusion 183
4.1 General Mass-Transfer Equations 183
4.2 Migration in Bulk Solution 186
4.3 Mixed Migration and Diffusion Near an Active Electrode 187
4.3.1 Balance Sheets for Mass Transfer During Electrolysis 188
4.3.2 Utility of a Supporting Electrolyte 192
4.4 Diffusion 193
4.4.1 A Microscopic View 193
4.4.2 Fick's Laws of Diffusion 196
4.4.3 Flux of an Electroreactant at an Electrode Surface 199
4.5 Formulation and Solution of Mass-Transfer Problems 199
4.5.1 Initial and Boundary Conditions in Electrochemical Problems 200
4.5.2 General Formulation of a Linear Diffusion Problem 201
4.5.3 Systems Involving Migration or Convection 202
4.5.4 Practical Means for Reaching Solutions 202
4.6 References 204
4.7 Problems 205
5 Steady-State Voltammetry at Ultramicroelectrodes 207
5.1 Steady-State Voltammetry at a Spherical UME 207
5.1.1 Steady-State Diffusion 208
5.1.2 Steady-State Current 211
5.1.3 Convergence on the Steady State 211
5.1.4 Steady-State Voltammetry 212
5.2 Shapes and Properties of Ultramicroelectrodes 214
5.2.1 Spherical or Hemispherical UME 215
5.2.2 Disk UME 215
5.2.3 Cylindrical UME 221
5.2.4 Band UME 221
5.2.5 Summary of Steady-State Behavior at UMEs 222
5.3 Reversible Electrode Reactions 224
5.3.1 Shape of the Wave 224
5.3.2 Applications of Reversible i-E Curves 226
5.4 Quasireversible and Irreversible Electrode Reactions 230
5.4.1 Effect of Electrode Kinetics on Steady-State Responses 230
5.4.2 Total Irreversibility 232
5.4.3 Kinetic Regimes 234
5.4.4 Influence of Electrode Shape 234
5.4.5 Applications of Irreversible i-E Curves 235
5.4.6 Evaluation of Kinetic Parameters by Varying Mass-Transfer Rates 237
5.5 Multicomponent Systems and Multistep Charge Transfers 239
5.6 Additional Attributes of Ultramicroelectrodes 241
5.6.1 Uncompensated Resistance at a UME 241
5.6.2 Effects of Conductivity on Voltammetry at a UME 242
5.6.3 Applications Based on Spatial Resolution 243
5.7 Migration in Steady-State Voltammetry 245
5.7.1 Mathematical Approach to Problems Involving Migration 245
5.7.2 Concentration Profiles in the Diffusion-Migration Layer 246
5.7.3 Wave Shape at Low Electrolyte Concentration 248
5.7.4 Effects of Migration on Wave Height in SSV 248
5.8 Analysis at High Analyte Concentrations 251
5.9 Lab Note: Preparation of Ultramicroelectrodes 253
5.9.1 Preparation and Characterization of UMEs 254
5.9.2 Testing the Integrity of a UME 254
5.9.3 Estimating the Size of a UME 256
5.10 References 257
5.11 Problems 258
6 Transient Methods Based on Potential Steps 261
6.1 Chronoamperometry Under Diffusion Control 261
6.1.1 Linear Diffusion at a Plane 262
6.1.2 Response at a Spherical Electrode 265
6.1.3 Transients at Other Ultramicroelectrodes 267
6.1.4 Information from Chronoamperometric Results 270
6.1.5 Microscopic and Geometric Areas 271
6.2 Sampled-Transient Voltammetry for Reversible Electrode Reactions 275
6.2.1 A Step to an Arbitrary Potential 276
6.2.2 Shape of the Voltammogram 277
6.2.3 Concentration Profiles When R Is Initially Absent 278
6.2.4 Simplified Current-Concentration Relationships 279
6.2.5 Applications of Reversible i-E Curves 279
6.3 Sampled-Transient Voltammetry for Quasireversible and Irreversible Electrode Reactions 279
6.3.1 Effect of Electrode Kinetics on Transient Behavior 280
6.3.2 Sampled-Transient Voltammetry for Reduction of O 282
6.3.3 Sampled Transient Voltammetry for Oxidation of R 284
6.3.4 Totally Irreversible Reactions 285
6.3.5 Kinetic Regimes 287
6.3.6 Applications of Irreversible i-E Curves 287
6.4 Multicomponent Systems and Multistep Charge Transfers 289
6.5 Chronoamperometric Reversal Techniques 290
6.5.1 Approaches to the Problem 292
6.5.2 Current-Time Responses 293
6.6 Chronocoulometry 294
6.6.1 Large-Amplitude Potential Step 295
6.6.2 Reversal Experiments Under Diffusion Control 296
6.6.3 Effects of Heterogeneous Kinetics 299
6.7 Cell Time Constants at Microelectrodes 300
6.8 Lab Note: Practical Concerns with Potential Step Methods 303
6.8.1 Preparation of the Electrode Surface at a Microelectrode 303
6.8.2 Interference from Charging Current 305
6.9 References 306
6.10 Problems 307
7 Linear Sweep and Cyclic Voltammetry 311
7.1 Transient Responses to a Potential Sweep 311
7.2 Nernstian (Reversible) Systems 313
7.2.1 Linear Sweep Voltammetry 313
7.2.2 Cyclic Voltammetry 321
7.3 Quasireversible Systems 325
7.3.1 Linear Sweep Voltammetry 326
7.3.2 Cyclic Voltammetry 326
7.4 Totally Irreversible Systems 329
7.4.1 Linear Sweep Voltammetry 329
7.4.2 Cyclic Voltammetry 332
7.5 Multicomponent Systems and Multistep Charge Transfers 332
7.5.1...
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 Equilibrium 121
3.1.2 The Arrhenius Equation and Potential Energy Surfaces 122
3.1.3 Transition State Theory 123
3.2 Essentials of Electrode Reactions 125
3.3 Butler-Volmer Model of Electrode Kinetics 126
3.3.1 Effects of Potential on Energy Barriers 127
3.3.2 One-Step, One-Electron Process 127
3.3.3 The Standard Rate Constant 130
3.3.4 The Transfer Coefficient 131
3.4 Implications of the Butler-Volmer Model for the One-Step, One-Electron Process 132
3.4.1 Equilibrium Conditions and the Exchange Current 133
3.4.2 The Current-Overpotential Equation 133
3.4.3 Approximate Forms of the i-eta Equation 135
3.4.4 Exchange Current Plots 139
3.4.5 Very Facile Kinetics and Reversible Behavior 139
3.4.6 Effects of Mass Transfer 140
3.4.7 Limits of Basic Butler-Volmer Equations 141
3.5 Microscopic Theories of Charge Transfer 142
3.5.1 Inner-Sphere and Outer-Sphere Electrode Reactions 142
3.5.2 Extended Charge Transfer and Adiabaticity 143
3.5.3 The Marcus Microscopic Model 146
3.5.4 Implications of the Marcus Theory 152
3.5.5 A Model Based on Distributions of Energy States 162
3.6 Open-Circuit Potential and Multiple Half-Reactions at an Electrode 168
3.6.1 Open-Circuit Potential in Multicomponent Systems 169
3.6.2 Establishment or Loss of Nernstian Behavior at an Electrode 170
3.6.3 Multiple Half-Reaction Currents in i-E Curves 171
3.7 Multistep Mechanisms 171
3.7.1 The Primacy of One-Electron Transfers 172
3.7.2 Rate-Determining, Outer-Sphere Electron Transfer 173
3.7.3 Multistep Processes at Equilibrium 173
3.7.4 Nernstian Multistep Processes 174
3.7.5 Quasireversible and Irreversible Multistep Processes 174
3.8 References 177
3.9 Problems 180
4 Mass Transfer by Migration and Diffusion 183
4.1 General Mass-Transfer Equations 183
4.2 Migration in Bulk Solution 186
4.3 Mixed Migration and Diffusion Near an Active Electrode 187
4.3.1 Balance Sheets for Mass Transfer During Electrolysis 188
4.3.2 Utility of a Supporting Electrolyte 192
4.4 Diffusion 193
4.4.1 A Microscopic View 193
4.4.2 Fick's Laws of Diffusion 196
4.4.3 Flux of an Electroreactant at an Electrode Surface 199
4.5 Formulation and Solution of Mass-Transfer Problems 199
4.5.1 Initial and Boundary Conditions in Electrochemical Problems 200
4.5.2 General Formulation of a Linear Diffusion Problem 201
4.5.3 Systems Involving Migration or Convection 202
4.5.4 Practical Means for Reaching Solutions 202
4.6 References 204
4.7 Problems 205
5 Steady-State Voltammetry at Ultramicroelectrodes 207
5.1 Steady-State Voltammetry at a Spherical UME 207
5.1.1 Steady-State Diffusion 208
5.1.2 Steady-State Current 211
5.1.3 Convergence on the Steady State 211
5.1.4 Steady-State Voltammetry 212
5.2 Shapes and Properties of Ultramicroelectrodes 214
5.2.1 Spherical or Hemispherical UME 215
5.2.2 Disk UME 215
5.2.3 Cylindrical UME 221
5.2.4 Band UME 221
5.2.5 Summary of Steady-State Behavior at UMEs 222
5.3 Reversible Electrode Reactions 224
5.3.1 Shape of the Wave 224
5.3.2 Applications of Reversible i-E Curves 226
5.4 Quasireversible and Irreversible Electrode Reactions 230
5.4.1 Effect of Electrode Kinetics on Steady-State Responses 230
5.4.2 Total Irreversibility 232
5.4.3 Kinetic Regimes 234
5.4.4 Influence of Electrode Shape 234
5.4.5 Applications of Irreversible i-E Curves 235
5.4.6 Evaluation of Kinetic Parameters by Varying Mass-Transfer Rates 237
5.5 Multicomponent Systems and Multistep Charge Transfers 239
5.6 Additional Attributes of Ultramicroelectrodes 241
5.6.1 Uncompensated Resistance at a UME 241
5.6.2 Effects of Conductivity on Voltammetry at a UME 242
5.6.3 Applications Based on Spatial Resolution 243
5.7 Migration in Steady-State Voltammetry 245
5.7.1 Mathematical Approach to Problems Involving Migration 245
5.7.2 Concentration Profiles in the Diffusion-Migration Layer 246
5.7.3 Wave Shape at Low Electrolyte Concentration 248
5.7.4 Effects of Migration on Wave Height in SSV 248
5.8 Analysis at High Analyte Concentrations 251
5.9 Lab Note: Preparation of Ultramicroelectrodes 253
5.9.1 Preparation and Characterization of UMEs 254
5.9.2 Testing the Integrity of a UME 254
5.9.3 Estimating the Size of a UME 256
5.10 References 257
5.11 Problems 258
6 Transient Methods Based on Potential Steps 261
6.1 Chronoamperometry Under Diffusion Control 261
6.1.1 Linear Diffusion at a Plane 262
6.1.2 Response at a Spherical Electrode 265
6.1.3 Transients at Other Ultramicroelectrodes 267
6.1.4 Information from Chronoamperometric Results 270
6.1.5 Microscopic and Geometric Areas 271
6.2 Sampled-Transient Voltammetry for Reversible Electrode Reactions 275
6.2.1 A Step to an Arbitrary Potential 276
6.2.2 Shape of the Voltammogram 277
6.2.3 Concentration Profiles When R Is Initially Absent 278
6.2.4 Simplified Current-Concentration Relationships 279
6.2.5 Applications of Reversible i-E Curves 279
6.3 Sampled-Transient Voltammetry for Quasireversible and Irreversible Electrode Reactions 279
6.3.1 Effect of Electrode Kinetics on Transient Behavior 280
6.3.2 Sampled-Transient Voltammetry for Reduction of O 282
6.3.3 Sampled Transient Voltammetry for Oxidation of R 284
6.3.4 Totally Irreversible Reactions 285
6.3.5 Kinetic Regimes 287
6.3.6 Applications of Irreversible i-E Curves 287
6.4 Multicomponent Systems and Multistep Charge Transfers 289
6.5 Chronoamperometric Reversal Techniques 290
6.5.1 Approaches to the Problem 292
6.5.2 Current-Time Responses 293
6.6 Chronocoulometry 294
6.6.1 Large-Amplitude Potential Step 295
6.6.2 Reversal Experiments Under Diffusion Control 296
6.6.3 Effects of Heterogeneous Kinetics 299
6.7 Cell Time Constants at Microelectrodes 300
6.8 Lab Note: Practical Concerns with Potential Step Methods 303
6.8.1 Preparation of the Electrode Surface at a Microelectrode 303
6.8.2 Interference from Charging Current 305
6.9 References 306
6.10 Problems 307
7 Linear Sweep and Cyclic Voltammetry 311
7.1 Transient Responses to a Potential Sweep 311
7.2 Nernstian (Reversible) Systems 313
7.2.1 Linear Sweep Voltammetry 313
7.2.2 Cyclic Voltammetry 321
7.3 Quasireversible Systems 325
7.3.1 Linear Sweep Voltammetry 326
7.3.2 Cyclic Voltammetry 326
7.4 Totally Irreversible Systems 329
7.4.1 Linear Sweep Voltammetry 329
7.4.2 Cyclic Voltammetry 332
7.5 Multicomponent Systems and Multistep Charge Transfers 332
7.5.1...
Details
| Erscheinungsjahr: | 2022 |
|---|---|
| Fachbereich: | Physikalische Chemie |
| Genre: | Chemie |
| Rubrik: | Naturwissenschaften & Technik |
| Medium: | Buch |
| Seiten: | 1044 |
| Inhalt: | 1104 S. |
| ISBN-13: | 9781119334064 |
| ISBN-10: | 1119334063 |
| Sprache: | Englisch |
| Herstellernummer: | 1W119334060 |
| Einband: | Gebunden |
| Autor: |
Bard, Allen J.
Faulkner, Larry R. White, Henry S. |
| Auflage: | 3. Auflage |
| Hersteller: | Wiley John + Sons |
| Maße: | 255 x 185 x 64 mm |
| Von/Mit: | Allen J. Bard (u. a.) |
| Erscheinungsdatum: | 26.05.2022 |
| Gewicht: | 2,216 kg |
Über den Autor
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.
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 Equilibrium 121
3.1.2 The Arrhenius Equation and Potential Energy Surfaces 122
3.1.3 Transition State Theory 123
3.2 Essentials of Electrode Reactions 125
3.3 Butler-Volmer Model of Electrode Kinetics 126
3.3.1 Effects of Potential on Energy Barriers 127
3.3.2 One-Step, One-Electron Process 127
3.3.3 The Standard Rate Constant 130
3.3.4 The Transfer Coefficient 131
3.4 Implications of the Butler-Volmer Model for the One-Step, One-Electron Process 132
3.4.1 Equilibrium Conditions and the Exchange Current 133
3.4.2 The Current-Overpotential Equation 133
3.4.3 Approximate Forms of the i-eta Equation 135
3.4.4 Exchange Current Plots 139
3.4.5 Very Facile Kinetics and Reversible Behavior 139
3.4.6 Effects of Mass Transfer 140
3.4.7 Limits of Basic Butler-Volmer Equations 141
3.5 Microscopic Theories of Charge Transfer 142
3.5.1 Inner-Sphere and Outer-Sphere Electrode Reactions 142
3.5.2 Extended Charge Transfer and Adiabaticity 143
3.5.3 The Marcus Microscopic Model 146
3.5.4 Implications of the Marcus Theory 152
3.5.5 A Model Based on Distributions of Energy States 162
3.6 Open-Circuit Potential and Multiple Half-Reactions at an Electrode 168
3.6.1 Open-Circuit Potential in Multicomponent Systems 169
3.6.2 Establishment or Loss of Nernstian Behavior at an Electrode 170
3.6.3 Multiple Half-Reaction Currents in i-E Curves 171
3.7 Multistep Mechanisms 171
3.7.1 The Primacy of One-Electron Transfers 172
3.7.2 Rate-Determining, Outer-Sphere Electron Transfer 173
3.7.3 Multistep Processes at Equilibrium 173
3.7.4 Nernstian Multistep Processes 174
3.7.5 Quasireversible and Irreversible Multistep Processes 174
3.8 References 177
3.9 Problems 180
4 Mass Transfer by Migration and Diffusion 183
4.1 General Mass-Transfer Equations 183
4.2 Migration in Bulk Solution 186
4.3 Mixed Migration and Diffusion Near an Active Electrode 187
4.3.1 Balance Sheets for Mass Transfer During Electrolysis 188
4.3.2 Utility of a Supporting Electrolyte 192
4.4 Diffusion 193
4.4.1 A Microscopic View 193
4.4.2 Fick's Laws of Diffusion 196
4.4.3 Flux of an Electroreactant at an Electrode Surface 199
4.5 Formulation and Solution of Mass-Transfer Problems 199
4.5.1 Initial and Boundary Conditions in Electrochemical Problems 200
4.5.2 General Formulation of a Linear Diffusion Problem 201
4.5.3 Systems Involving Migration or Convection 202
4.5.4 Practical Means for Reaching Solutions 202
4.6 References 204
4.7 Problems 205
5 Steady-State Voltammetry at Ultramicroelectrodes 207
5.1 Steady-State Voltammetry at a Spherical UME 207
5.1.1 Steady-State Diffusion 208
5.1.2 Steady-State Current 211
5.1.3 Convergence on the Steady State 211
5.1.4 Steady-State Voltammetry 212
5.2 Shapes and Properties of Ultramicroelectrodes 214
5.2.1 Spherical or Hemispherical UME 215
5.2.2 Disk UME 215
5.2.3 Cylindrical UME 221
5.2.4 Band UME 221
5.2.5 Summary of Steady-State Behavior at UMEs 222
5.3 Reversible Electrode Reactions 224
5.3.1 Shape of the Wave 224
5.3.2 Applications of Reversible i-E Curves 226
5.4 Quasireversible and Irreversible Electrode Reactions 230
5.4.1 Effect of Electrode Kinetics on Steady-State Responses 230
5.4.2 Total Irreversibility 232
5.4.3 Kinetic Regimes 234
5.4.4 Influence of Electrode Shape 234
5.4.5 Applications of Irreversible i-E Curves 235
5.4.6 Evaluation of Kinetic Parameters by Varying Mass-Transfer Rates 237
5.5 Multicomponent Systems and Multistep Charge Transfers 239
5.6 Additional Attributes of Ultramicroelectrodes 241
5.6.1 Uncompensated Resistance at a UME 241
5.6.2 Effects of Conductivity on Voltammetry at a UME 242
5.6.3 Applications Based on Spatial Resolution 243
5.7 Migration in Steady-State Voltammetry 245
5.7.1 Mathematical Approach to Problems Involving Migration 245
5.7.2 Concentration Profiles in the Diffusion-Migration Layer 246
5.7.3 Wave Shape at Low Electrolyte Concentration 248
5.7.4 Effects of Migration on Wave Height in SSV 248
5.8 Analysis at High Analyte Concentrations 251
5.9 Lab Note: Preparation of Ultramicroelectrodes 253
5.9.1 Preparation and Characterization of UMEs 254
5.9.2 Testing the Integrity of a UME 254
5.9.3 Estimating the Size of a UME 256
5.10 References 257
5.11 Problems 258
6 Transient Methods Based on Potential Steps 261
6.1 Chronoamperometry Under Diffusion Control 261
6.1.1 Linear Diffusion at a Plane 262
6.1.2 Response at a Spherical Electrode 265
6.1.3 Transients at Other Ultramicroelectrodes 267
6.1.4 Information from Chronoamperometric Results 270
6.1.5 Microscopic and Geometric Areas 271
6.2 Sampled-Transient Voltammetry for Reversible Electrode Reactions 275
6.2.1 A Step to an Arbitrary Potential 276
6.2.2 Shape of the Voltammogram 277
6.2.3 Concentration Profiles When R Is Initially Absent 278
6.2.4 Simplified Current-Concentration Relationships 279
6.2.5 Applications of Reversible i-E Curves 279
6.3 Sampled-Transient Voltammetry for Quasireversible and Irreversible Electrode Reactions 279
6.3.1 Effect of Electrode Kinetics on Transient Behavior 280
6.3.2 Sampled-Transient Voltammetry for Reduction of O 282
6.3.3 Sampled Transient Voltammetry for Oxidation of R 284
6.3.4 Totally Irreversible Reactions 285
6.3.5 Kinetic Regimes 287
6.3.6 Applications of Irreversible i-E Curves 287
6.4 Multicomponent Systems and Multistep Charge Transfers 289
6.5 Chronoamperometric Reversal Techniques 290
6.5.1 Approaches to the Problem 292
6.5.2 Current-Time Responses 293
6.6 Chronocoulometry 294
6.6.1 Large-Amplitude Potential Step 295
6.6.2 Reversal Experiments Under Diffusion Control 296
6.6.3 Effects of Heterogeneous Kinetics 299
6.7 Cell Time Constants at Microelectrodes 300
6.8 Lab Note: Practical Concerns with Potential Step Methods 303
6.8.1 Preparation of the Electrode Surface at a Microelectrode 303
6.8.2 Interference from Charging Current 305
6.9 References 306
6.10 Problems 307
7 Linear Sweep and Cyclic Voltammetry 311
7.1 Transient Responses to a Potential Sweep 311
7.2 Nernstian (Reversible) Systems 313
7.2.1 Linear Sweep Voltammetry 313
7.2.2 Cyclic Voltammetry 321
7.3 Quasireversible Systems 325
7.3.1 Linear Sweep Voltammetry 326
7.3.2 Cyclic Voltammetry 326
7.4 Totally Irreversible Systems 329
7.4.1 Linear Sweep Voltammetry 329
7.4.2 Cyclic Voltammetry 332
7.5 Multicomponent Systems and Multistep Charge Transfers 332
7.5.1...
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 Equilibrium 121
3.1.2 The Arrhenius Equation and Potential Energy Surfaces 122
3.1.3 Transition State Theory 123
3.2 Essentials of Electrode Reactions 125
3.3 Butler-Volmer Model of Electrode Kinetics 126
3.3.1 Effects of Potential on Energy Barriers 127
3.3.2 One-Step, One-Electron Process 127
3.3.3 The Standard Rate Constant 130
3.3.4 The Transfer Coefficient 131
3.4 Implications of the Butler-Volmer Model for the One-Step, One-Electron Process 132
3.4.1 Equilibrium Conditions and the Exchange Current 133
3.4.2 The Current-Overpotential Equation 133
3.4.3 Approximate Forms of the i-eta Equation 135
3.4.4 Exchange Current Plots 139
3.4.5 Very Facile Kinetics and Reversible Behavior 139
3.4.6 Effects of Mass Transfer 140
3.4.7 Limits of Basic Butler-Volmer Equations 141
3.5 Microscopic Theories of Charge Transfer 142
3.5.1 Inner-Sphere and Outer-Sphere Electrode Reactions 142
3.5.2 Extended Charge Transfer and Adiabaticity 143
3.5.3 The Marcus Microscopic Model 146
3.5.4 Implications of the Marcus Theory 152
3.5.5 A Model Based on Distributions of Energy States 162
3.6 Open-Circuit Potential and Multiple Half-Reactions at an Electrode 168
3.6.1 Open-Circuit Potential in Multicomponent Systems 169
3.6.2 Establishment or Loss of Nernstian Behavior at an Electrode 170
3.6.3 Multiple Half-Reaction Currents in i-E Curves 171
3.7 Multistep Mechanisms 171
3.7.1 The Primacy of One-Electron Transfers 172
3.7.2 Rate-Determining, Outer-Sphere Electron Transfer 173
3.7.3 Multistep Processes at Equilibrium 173
3.7.4 Nernstian Multistep Processes 174
3.7.5 Quasireversible and Irreversible Multistep Processes 174
3.8 References 177
3.9 Problems 180
4 Mass Transfer by Migration and Diffusion 183
4.1 General Mass-Transfer Equations 183
4.2 Migration in Bulk Solution 186
4.3 Mixed Migration and Diffusion Near an Active Electrode 187
4.3.1 Balance Sheets for Mass Transfer During Electrolysis 188
4.3.2 Utility of a Supporting Electrolyte 192
4.4 Diffusion 193
4.4.1 A Microscopic View 193
4.4.2 Fick's Laws of Diffusion 196
4.4.3 Flux of an Electroreactant at an Electrode Surface 199
4.5 Formulation and Solution of Mass-Transfer Problems 199
4.5.1 Initial and Boundary Conditions in Electrochemical Problems 200
4.5.2 General Formulation of a Linear Diffusion Problem 201
4.5.3 Systems Involving Migration or Convection 202
4.5.4 Practical Means for Reaching Solutions 202
4.6 References 204
4.7 Problems 205
5 Steady-State Voltammetry at Ultramicroelectrodes 207
5.1 Steady-State Voltammetry at a Spherical UME 207
5.1.1 Steady-State Diffusion 208
5.1.2 Steady-State Current 211
5.1.3 Convergence on the Steady State 211
5.1.4 Steady-State Voltammetry 212
5.2 Shapes and Properties of Ultramicroelectrodes 214
5.2.1 Spherical or Hemispherical UME 215
5.2.2 Disk UME 215
5.2.3 Cylindrical UME 221
5.2.4 Band UME 221
5.2.5 Summary of Steady-State Behavior at UMEs 222
5.3 Reversible Electrode Reactions 224
5.3.1 Shape of the Wave 224
5.3.2 Applications of Reversible i-E Curves 226
5.4 Quasireversible and Irreversible Electrode Reactions 230
5.4.1 Effect of Electrode Kinetics on Steady-State Responses 230
5.4.2 Total Irreversibility 232
5.4.3 Kinetic Regimes 234
5.4.4 Influence of Electrode Shape 234
5.4.5 Applications of Irreversible i-E Curves 235
5.4.6 Evaluation of Kinetic Parameters by Varying Mass-Transfer Rates 237
5.5 Multicomponent Systems and Multistep Charge Transfers 239
5.6 Additional Attributes of Ultramicroelectrodes 241
5.6.1 Uncompensated Resistance at a UME 241
5.6.2 Effects of Conductivity on Voltammetry at a UME 242
5.6.3 Applications Based on Spatial Resolution 243
5.7 Migration in Steady-State Voltammetry 245
5.7.1 Mathematical Approach to Problems Involving Migration 245
5.7.2 Concentration Profiles in the Diffusion-Migration Layer 246
5.7.3 Wave Shape at Low Electrolyte Concentration 248
5.7.4 Effects of Migration on Wave Height in SSV 248
5.8 Analysis at High Analyte Concentrations 251
5.9 Lab Note: Preparation of Ultramicroelectrodes 253
5.9.1 Preparation and Characterization of UMEs 254
5.9.2 Testing the Integrity of a UME 254
5.9.3 Estimating the Size of a UME 256
5.10 References 257
5.11 Problems 258
6 Transient Methods Based on Potential Steps 261
6.1 Chronoamperometry Under Diffusion Control 261
6.1.1 Linear Diffusion at a Plane 262
6.1.2 Response at a Spherical Electrode 265
6.1.3 Transients at Other Ultramicroelectrodes 267
6.1.4 Information from Chronoamperometric Results 270
6.1.5 Microscopic and Geometric Areas 271
6.2 Sampled-Transient Voltammetry for Reversible Electrode Reactions 275
6.2.1 A Step to an Arbitrary Potential 276
6.2.2 Shape of the Voltammogram 277
6.2.3 Concentration Profiles When R Is Initially Absent 278
6.2.4 Simplified Current-Concentration Relationships 279
6.2.5 Applications of Reversible i-E Curves 279
6.3 Sampled-Transient Voltammetry for Quasireversible and Irreversible Electrode Reactions 279
6.3.1 Effect of Electrode Kinetics on Transient Behavior 280
6.3.2 Sampled-Transient Voltammetry for Reduction of O 282
6.3.3 Sampled Transient Voltammetry for Oxidation of R 284
6.3.4 Totally Irreversible Reactions 285
6.3.5 Kinetic Regimes 287
6.3.6 Applications of Irreversible i-E Curves 287
6.4 Multicomponent Systems and Multistep Charge Transfers 289
6.5 Chronoamperometric Reversal Techniques 290
6.5.1 Approaches to the Problem 292
6.5.2 Current-Time Responses 293
6.6 Chronocoulometry 294
6.6.1 Large-Amplitude Potential Step 295
6.6.2 Reversal Experiments Under Diffusion Control 296
6.6.3 Effects of Heterogeneous Kinetics 299
6.7 Cell Time Constants at Microelectrodes 300
6.8 Lab Note: Practical Concerns with Potential Step Methods 303
6.8.1 Preparation of the Electrode Surface at a Microelectrode 303
6.8.2 Interference from Charging Current 305
6.9 References 306
6.10 Problems 307
7 Linear Sweep and Cyclic Voltammetry 311
7.1 Transient Responses to a Potential Sweep 311
7.2 Nernstian (Reversible) Systems 313
7.2.1 Linear Sweep Voltammetry 313
7.2.2 Cyclic Voltammetry 321
7.3 Quasireversible Systems 325
7.3.1 Linear Sweep Voltammetry 326
7.3.2 Cyclic Voltammetry 326
7.4 Totally Irreversible Systems 329
7.4.1 Linear Sweep Voltammetry 329
7.4.2 Cyclic Voltammetry 332
7.5 Multicomponent Systems and Multistep Charge Transfers 332
7.5.1...
Details
| Erscheinungsjahr: | 2022 |
|---|---|
| Fachbereich: | Physikalische Chemie |
| Genre: | Chemie |
| Rubrik: | Naturwissenschaften & Technik |
| Medium: | Buch |
| Seiten: | 1044 |
| Inhalt: | 1104 S. |
| ISBN-13: | 9781119334064 |
| ISBN-10: | 1119334063 |
| Sprache: | Englisch |
| Herstellernummer: | 1W119334060 |
| Einband: | Gebunden |
| Autor: |
Bard, Allen J.
Faulkner, Larry R. White, Henry S. |
| Auflage: | 3. Auflage |
| Hersteller: | Wiley John + Sons |
| Maße: | 255 x 185 x 64 mm |
| Von/Mit: | Allen J. Bard (u. a.) |
| Erscheinungsdatum: | 26.05.2022 |
| Gewicht: | 2,216 kg |
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