Understanding voltammetry:
Gespeichert in:
| Beteiligte Personen: | , |
|---|---|
| Format: | Buch |
| Sprache: | Englisch |
| Veröffentlicht: |
London
Imperial College Press
2011
|
| Ausgabe: | 2. ed. |
| Schlagwörter: | |
| Links: | http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=021160851&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA |
| Beschreibung: | Hier auch später erschienene, unveränderte Nachdrucke Literaturangaben |
| Umfang: | XIII, 429 S. Ill., graph. Darst. |
| ISBN: | 9781848165854 1848165854 1848165862 9781848165861 |
Internformat
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| 245 | 1 | 0 | |a Understanding voltammetry |c Richard G. Compton ; Craig E. Banks |
| 250 | |a 2. ed. | ||
| 264 | 1 | |a London |b Imperial College Press |c 2011 | |
| 300 | |a XIII, 429 S. |b Ill., graph. Darst. | ||
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Datensatz im Suchindex
| _version_ | 1819310911988432896 |
|---|---|
| adam_text | Titel: Understanding voltammetry
Autor: Compton, Richard G
Jahr: 2011
Contents
Preface vii
1 Equilibrium Electrochemistry and the Nernst Equation 1
1.1 Chemical Equilibrium....................... 1
1.2 Electrochemical Equilibrium: Introduction............ 5
1.3 Electrochemical Equilibrium: Electron Transfer at the
Solution-Electrode Interface ................... 9
1.4 Electrochemical Equilibrium: The Nernst Equation....... 11
1.5 Walther Hermann Nernst..................... 17
1.6 Reference Electrodes and the Measurement of Electrode Potentials 19
1.7 The Hydrogen Electrode as a Reference Electrode ........ 26
1.8 Standard Electrode Potentials and Formal Potentials....... 27
1.9 Formal Potentials and Experimental Voltammetry........ 30
1.10 Electrode Processes: Kinetics vs. Thermodynamics........ 32
2 Electrode Kinetics 35
2.1 Currents and Reaction Fluxes................... 35
2.2 Studying Electrode Kinetics Requires Three Electrodes...... 37
2.3 Butler-Volmer Kinetics...................... 40
2.4 Standard Electrochemical Rate Constants and Formal Potentials 43
2.5 The Need for Supporting Electrolyte............... 45
2.6 The Tafel Law........................... 46
2.7 Julius Tafel............................. 47
2.8 Multistep Electron Transfer Processes............... 49
2.9 Tafel Analysis and the Hydrogen Evolution Reaction....... 52
2.10 B. Stanley Pons........................... 57
2.11 Cold Fusion ? The Musical! ................... 58
x Understanding Voltammetry
2.12 Why Are Some Standard Electrochemical Rate Constants Large
but Others Slow? The Marcus Theory of Electron Transfer: An
Introduction............................ 60
2.13 Marcus Theory: Taking it Further. Inner and Outer Sphere
Electron Transfer.......................... ^
2.14 Marcus Theory: Taking it Further. Adiabatic and Non-Adiabatic
Reactions.............................. 67
2.15 Marcus Theory: Taking it Further. Calculating the Gibbs Energy
of Activation............................ 70
2.16 Relationship between Marcus Theory and Butler-Volmer Kinetics 73
2.17 Marcus Theory and Experiment. Success!............. 74
3 Diffusion 77
3.1 Fick s Ist Law of Diffusion..................... ^
3.2 Fick s 2nd Law of Diffusion.................... 79
3.3 The Molecular Basis of Fick s Laws................ 81
3.4 How Did Fick Discover His Laws?................. 83
3.5 The Cottrell Equation: Solving Fick s 2nd Law.......... 88
3.6 The Cottrell Problem: The Case of Unequal Diffusion Coefficients 92
3.7 The Nernst Diffusion Layer.................... 94
3.8 Mass Transfer vs. Electrode Kinetics: Steady-State
Current-Voltage Waveshapes ................... 97
3.9 Mass Transport Corrected Tafel Relationships .......... lu0
4 Cyclic Voltammetry at Macroelectrodes 107
4.1 Cyclic Voltammetry: The Experiment............... 107
4.2 Cyclic Voltammetry: Solving the Transport Equations...... 1°9
4.3 Cyclic Voltammetry: Reversible and Irreversible Kinetics..... I*1
4.4 What Dictates Reversible and Irreversible Behaviour? ..... 119
4.5 Reversible and Irreversible Behaviour: The Effect of Voltage Scan
Rate................................. 120
4.6 Reversible versus Irreversible Voltammetry: A Summary..... 126
4.7 The Measurement of Cyclic Voltammograms: Three Practical
Considerations........................... 127
4.8 The Effect of Unequal Diffusion Coefficients, DA ^ B..... 129
4.9 Multiple Electron Transfer: Reversible Electrode Kinetics . . . ? 133
4.10 Multiple Electron Transfer: Irreversible Electrode Kinetics .... 142
4.11 The Influenceof pH on Cyclic Voltammetry........... 147
Contents xi
4.12 The Schemeof Squares ...................... 151
4.13 Simultaneous Two-Electron Transfer in Electrode Kinetics? ... 152
Voltammetry at Microelectrodes 157
5.1 The Cottrell Equation for a Spherical or Hemispherical Electrode 157
5.2 Potential Step Transients at Microdisc Electrodes......... 162
5.3 Microelectrodes Have Large Current Densities and Fast Response
Times................................ 163
5.4 Applications of Potential Step Chronoamperometry Using
Microdisc Electrodes........................ 165
5.5 Double Potential Step Microdisc Chronoamperometry Exploring
the Diffusion Coefficient of Electrogenerated Species ...... 168
5.6 Cyclic and Linear Sweep Voltammetry Using Microdisc Electrodes 176
5.7 Steady-State Voltammetry at the Microdisc Electrode...... 186
5.8 Microelectrodes versus Macroelectrodes............. 187
5.9 Ultrafast Cyclic Voltammetry: Megavolts per Second Scan Rates . 191
5.10 Ultrasmall Electrodes: Working at the Nanoscale......... 192
Voltammetry at Heterogeneous Surfaces 197
6.1 Partially Blocked Electrodes.................... 197
6.2 Microelectrode Arrays....................... 213
6.3 Voltammetry at Highly Ordered Pyrolytic Graphite Electrodes . . 219
6.4 Electrochemically Heterogeneous Electrodes........... 223
6.5 Electrodes Covered with Porous Films .............. 226
6.6 Voltammetric Particle Sizing.................... 229
6.7 Scanning Electrochemical Microscopy (SECM).......... 233
Cyclic Voltammetry: Coupled Homogeneous Kinetics and Adsorption 239
7.1 Homogeneous Coupled Reactions: Notation and Examples . . . 239
7.2 Modifying Fick s Second Law to Allow for Chemical Reaction . . 241
7.3 Cyclic Voltammetry and the EC Reaction............. 242
7.4 How Do the Parameters Ki and A Emerge?............ 246
7.5 Cyclic Voltammetry and the EC2 Reaction............ 249
7.6 Examples ofEC and EC2 Processes................ 252
7.7 ECE Processes........................... 260
7.8 ECE versus DISP.......................... 268
7.9 The CE Mechanism........................ 270
7.10 The EC (Catalytic) Mechanism.................. 272
xii Understanding Voltammetry
7.11 Adsorption............................. 274
7.12 Voltammetric Studies of Droplets and Solid Particles....... 283
8 Hydrodynamic Electrodes 291
8.1 Convection............................. 291
8.2 Modifying Fick s Laws to AUow for Convection.......... 293
8.3 The Rotating Disc Electrode: An Introduction.......... 294
8.4 The Rotating Disc Electrode ? Theory.............. 295
8.5 Osborne Reynolds (1842-1912).................. 299
8.6 The Rotating Disc Electrode ? Furfher Theory......... 299
8.7 Chronoamperometry at the Rotating Disc Electrode: An
Illustration of the Valueof Simulation .............. 306
8.8 The Rotating Disc and Coupled Homogeneous Kinetics..... 309
8.9 The Channel Electrode: An Introduction............. 312
8.10 The Channel Electrode: The Levich Equation Derived...... 315
8.11 Channel Flow Cells and Coupled Homogeneous Kinetics .... 316
8.12 Chronoamperometry at the Channel Electrode.......... 322
8.13 The Channel Electrode is not UniformlyAccessible ....... 324
8.14 Channel Microelectrodes..................... 325
8.15 Channel Microband Electrode Arrays for Mechanistic
Electrochemistry.......................... 327
8.16 The High Speed Channel Electrode................ 331
8.17 Hydrodynamic Electrodes Based on Impinging jets........ 333
8.18 Sonovoltammetry......................... 335
9 Voltammetry for Electroanalysis 347
9.1 Potential Step Voltammetric Techniques ............. 347
9.2 Differential Pulse Voltammetry.................. 348
9.3 Square Wave Voltammetry..................... 350
9.4 Stripping Voltammetry ...................... 351
9.5 Sono-electroanalysis........................ 358
10 Voltammetry in Weakly Supported Media: Migration and Other Effects 367
10.1 Potentials and Fields in Fully Supported Voltammetry...... 367
10.2 The Distribution of Ions Around a Charged Electrode...... 370
10.3 The Electrode-Solution Interface: Beyond the Gouy-Chapman
Theory............................... 375
10.4 Double Layer Effect on Electrode Kinetics: Frumkin Effects . ? ? 379
10.5 A.N. Frumkin........................... 381
Contents xiii
10.6 Transport by Diffusion and by Migration............. 382
10.7 Measurement of Ion Mobilities.................. 384
10.8 Liquid Junction Potentials..................... 386
10.9 Chronoamperometry and Cyclic Voltammetry in Weakly
Supported Media.......................... 389
11 Voltammetry at the Nanoscale 397
11.1 Transport to Particles Supported on an Electrode......... 397
11.2 Nanoparticle Voltammetry: The Transport Changes as the
Electrode Shrinks in Size...................... 405
11.3 Altered Chemistry at the Nanoscale................ 414
Appendix: Simulation of Electrode Processes 419
A.l Fick s First and Second Laws.................... 419
A.2 Boundary Conditions....................... 420
A.3 Finite Difference Equations.................... 420
A.4 Backward Implicit Method .................... 421
A.5 Conclusion............................. 423
Index 425
|
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| discipline | Chemie / Pharmazie |
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| id | DE-604.BV037247474 |
| illustrated | Illustrated |
| indexdate | 2024-12-20T14:47:33Z |
| institution | BVB |
| isbn | 9781848165854 1848165854 1848165862 9781848165861 |
| language | English |
| oai_aleph_id | oai:aleph.bib-bvb.de:BVB01-021160851 |
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| owner_facet | DE-11 DE-20 DE-29T DE-703 |
| physical | XIII, 429 S. Ill., graph. Darst. |
| publishDate | 2011 |
| publishDateSearch | 2011 |
| publishDateSort | 2011 |
| publisher | Imperial College Press |
| record_format | marc |
| spellingShingle | Compton, Richard G. Banks, Craig E. Understanding voltammetry Elektrochemie (DE-588)4014241-3 gnd Voltammetrie (DE-588)4188605-7 gnd |
| subject_GND | (DE-588)4014241-3 (DE-588)4188605-7 |
| title | Understanding voltammetry |
| title_auth | Understanding voltammetry |
| title_exact_search | Understanding voltammetry |
| title_full | Understanding voltammetry Richard G. Compton ; Craig E. Banks |
| title_fullStr | Understanding voltammetry Richard G. Compton ; Craig E. Banks |
| title_full_unstemmed | Understanding voltammetry Richard G. Compton ; Craig E. Banks |
| title_short | Understanding voltammetry |
| title_sort | understanding voltammetry |
| topic | Elektrochemie (DE-588)4014241-3 gnd Voltammetrie (DE-588)4188605-7 gnd |
| topic_facet | Elektrochemie Voltammetrie |
| url | http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=021160851&sequence=000002&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA |
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