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Analytical Electrochemistry (Third Edition)电子书
Preface xi
Abbreviations and Symbols xiii
1 Fundamental Concepts 1
1.1 Why Electroanalysis?, 1
1.2 Faradaic Processes, 3
1.2.1 Mass-Transport-Controlled Reactions, 4
1.2.1.1 Potential-Step Experiment, 7
1.2.1.2 Potential-Sweep Experiments, 9
1.2.2 Reactions Controlled by the Rate of Electron Transfer, 12
1.2.2.1 Activated Complex Theory, 16
1.3 Electrical Double Layer, 19
1.4 Electrocapillary Effect, 23
1.5 Supplementary Reading, 25
Problems, 27
References, 28
2 Study of Electrode Reactions and Interfacial Properties 29
2.1 Cyclic Voltammetry, 29
2.1.1 Data Interpretation, 32
2.1.1.1 Reversible Systems, 32
2.1.1.2 Irreversible and Quasi-reversible Systems, 34
2.1.2 Study of Reaction Mechanisms, 35
2.1.3 Study of Adsorption Processes, 37
2.1.4 Quantitative Applications, 41
2.2 Spectroelectrochemistry, 42
2.2.1 Experimental Arrangement, 43
2.2.2 Principles and Applications, 44
2.2.3 Electrochemiluminescence, 47
2.2.4 Optical Probing of Electrode–Solution Interfaces, 48
2.3 Scanning Probe Microscopy, 49
2.3.1 Scanning Tunneling Microscopy, 50
2.3.2 Atomic Force Microscopy, 51
2.3.3 Scanning Electrochemical Microscopy, 53
2.4 Electrochemical Quartz Crystal Microbalance, 57
2.5 Impedance Spectroscopy, 58
Examples, 61
Problems, 63
References, 64
3 Controlled-Potential Techniques 67
3.1 Chronoamperometry, 67
3.2 Polarography, 69
3.3 Pulse Voltammetry, 76
3.3.1 Normal-Pulse Voltammetry, 76
3.3.2 Differential-Pulse Voltammetry, 77
3.3.3 Square-Wave Voltammetry, 80
3.3.4 Staircase Voltammetry, 82
3.4 AC Voltammetry, 84
3.5 Stripping Analysis, 85
3.5.1 Anodic Stripping Voltammetry, 86
3.5.2 Potentiometric Stripping Analysis, 89
3.5.3 Adsorptive Stripping Voltammetry and Potentiometry, 91
3.5.4 Cathodic Stripping Voltammetry, 94
3.5.5 Abrasive Stripping Voltammetry, 94
3.5.6 Applications, 94
3.6 Flow Analysis, 98
3.6.1 Principles, 98
3.6.2 Cell Design, 100
3.6.3 Mass Transport and Current Response, 103
3.6.4 Detection Modes, 105
Examples, 108
Problems, 111
References, 112
4 Practical Considerations 115
4.1 Electrochemical Cells, 115
4.2 Solvents and Supporting Electrolytes, 117
viii CONTENTS
4.3 Oxygen Removal, 118
4.4 Instrumentation, 119
4.5 Working Electrodes, 123
4.5.1 Mercury Electrodes, 123
4.5.2 Solid Electrodes, 127
4.5.2.1 Rotating Disk and Rotating Ring Disk Electrodes, 128
4.5.2.2 Carbon Electrodes, 130
4.5.2.2.1 Glassy Carbon Electrodes, 131
4.5.2.2.2 Carbon Paste Electrodes, 131
4.5.2.2.3 Carbon Fiber Electrodes, 133
4.5.2.2.4 Diamond Electrodes, 133
4.5.2.3 Metal Electrodes, 134
4.5.3 Chemically Modified Electrodes, 136
4.5.3.1 Self-Assembled Monolayers, 136
4.5.3.2 Carbon-Nanotube-Modified Electrodes, 139
4.5.3.3 Sol-gel Encapsulation of Reactive Species, 139
4.5.3.4 Electrocatalytically Modified Electrodes, 140
4.5.3.5 Preconcentrating Electrodes, 141
4.5.3.6 Permselective Coatings, 143
4.5.3.7 Conducting Polymers, 146
4.5.4 Microelectrodes, 149
4.5.4.1 Diffusion at Microelectrodes, 151
4.5.4.2 Microelectrode Configurations, 152
4.5.4.3 Composite Electrodes, 154
Examples, 158
Problems, 158
References, 159
5 Potentiometry 165
5.1 Principles of Potentiometric Measurements, 165
5.2 Ion-Selective Electrodes, 173
5.2.1 Glass Electrodes, 173
5.2.1.1 pH Electrodes, 173
5.2.1.2 Glass Electrodes for Other Cations, 177
5.2.2 Liquid Membrane Electrodes, 177
5.2.2.1 Ion Exchanger Electrodes, 179
5.2.2.2 Neutral Carrier Electrodes, 182
5.2.3 Solid-State Electrodes, 185
5.2.4 Coated-Wire Electrodes and Solid-State Electrodes Without an
Internal Filling Solution, 188
5.3 On-line, On-site, and In Vivo Potentiometric Measurements, 190
Examples, 194
Problems, 196
References, 197
CONTENTS ix
6 Electrochemical Sensors 201
6.1 Electrochemical Biosensors, 202
6.1.1 Enzyme-Based Electrodes, 202
6.1.1.1 Practical and Theoretical Considerations, 202
6.1.1.2 Enzyme Electrodes of Analytical Significance, 208
6.1.1.2.1 Glucose Sensors, 208
6.1.1.2.2 Ethanol Electrodes, 212
6.1.1.2.3 Urea Electrodes, 213
6.1.1.2.4 Toxin (Enzyme Inhibition) Biosensors, 215
6.1.1.3 Tissue and Bacteria Electrodes, 215
6.1.2 Affinity Biosensors, 216
6.1.2.1 Immunosensors, 216
6.1.2.2 DNA Hybridization Biosensors, 218
6.1.2.2.1 Background and Principles, 218
6.1.2.2.2 Electrical Transduction of DNA
Hybridization, 219
6.1.2.2.3 Other Electrochemical DNA
Biosensors, 221
6.1.2.3 Receptor-Based Sensors, 222
6.1.2.4 Electrochemical Sensors Based on Molecularly
Imprinted Polymers, 224
6.2 Gas Sensors, 224
6.2.1 Carbon Dioxide Sensors, 225
6.2.2 Oxygen Electrodes, 226
6.3 Solid-State Devices, 227
6.3.1 Ion-Selective Field Effect Transistors, 227
6.3.2 Microfabrication of Solid-State Sensor Assemblies, 229
6.3.3 Microfabrication Techniques, 229
6.3.4 Micromachined Analytical Microsystems, 232
6.4 Sensor Arrays, 234
Examples, 237
Problems, 238
References, 239
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