Applications of Kinetic Modelling (eBook)

Cover 1
Contents 16
Preface 12
Dedication 15
Chapter 1. Interaction of Theory and Experiment in Reaction Kinetics 24
1.1 Introduction 24
1.2 Examples of interaction of theory and experiment 25
References 52
Chapter 2. The application of approximate analytical models in the development of modified electrodes for NADH oxidation 58
2.1 Why bother with approximate analytical models? 58
2.2 NADH oxidation 61
2.3 Poly(aniline) 78
2.4 Analysis of experimental data 96
2.5 Conclusions 107
Appendix: Notation 109
References 110
Chapter 3. Electrochemistry of DNA 114
3.1 Introduction 114
3.2 The double helix DNA 115
3.3 The triple helix DNA 117
3.4 DNA electrochemistry 119
3.5 DNA biosensors 131
3.6 Electrochemistry for probing DNA interactions 133
3.7 Conclusions 137
References 138
Chapter 4. Kinetic modelling and the skin 144
4.1 Introduction 144
4.2 The route of penetration 144
4.3 Fick's first law 146
4.4 Fick's second law 148
4.5 Penetration enhancement 150
4.6 In vitro-in vivo modelling 153
4.7 Conclusions 154
References 154
Chapter 5. Electron transport and two-dimensional organization of metalloprotein adsorbates investigated by cyclic voltammetry and in situ scanning tunnelling and atomic force microscopy 156
5.1 Introduction 156
5.2 Some observations on the behaviour of proteins at solid-liquid interfaces 158
5.3 Approaches to electrochemical ET mechanisms of multi-centre metalloproteins 160
5.4 In situ STM and AFM of single-metal metalloproteins horse heart cytochrome c and pseudomonas aeruginosa azurin
5.5 conclusions 179
References 180
Chapter 6. The kinetics of the partitioning of compounds between octanol and water, and its relationship to the movement of molecules in biological systems 184
6.1 Introduction 184
6.2 Rotating diffusion cell theory 190
6.3 Experimental use of the RDC 197
6.4 Results 203
6.5 Discussion 210
6.6 Conclusions 216
References 217
Chapter 7. Redox mediated whole cell biosensors for toxicity assessment and environmental protection 218
7.1. Introduction 218
7.2 Whole cell biosensors for estimation of biochemical oxygen demand 221
7.3 Toxicity assessment for environmental protection 222
7.4 Toxicity assessment for environmental protection 225
7.5 Redox mediated biosensors 225
7.6 Time dependence of measured toxic effect 226
7.7 Kinetic models of whole cell biosensors 227
7.8 Notation 229
7.9 Physical model 230
7.10 Sensor response 234
7.11 Perturbations 236
7.12 Conclusion 238
Appendix 7.1 239
Appendix 7.2 241
References 243
Chapter 8. Photoelectrochemical kinetics at semiconductor electrodes 246
8.1 Introduction 246
8.2 The semiconductor/electrolyte junction 247
8.3 Electron transfer at semiconductor electrodes in the dark 250
8.4 Electron transfer at illuminated semiconductor electrodes 252
8.5 Multistep photoelectrochemical reactions 256
8.6 Surface recombination 257
8.7 Competition between recombination and electron transfer (the steady state case) 259
8.8 Separating the rate constants for recombination and charge transfer (the non-steady-state case) 262
8.9 Intensity modulated photocurrent spectroscopy 264
8.10 The influence of the RC time constant, Tcell 269
8.11 IMPS analysis of multistep photoelectrochemical reactions with adsorbed intermediates 273
8.12 Studies of photocurrent multiplication by IMPS 276
8.13 Photoelectrochemical impedance spectroscopy 282
8.14 Light modulated microwave measurements 284
8.15 Photoelectrochemical kinetics in nanocrystalline systems 288
References 301
Chapter 9. Kinetic modeling of electron transfer processes in colloidal semiconductor photocatalysis 304
9.0. Preface 304
9.1. Introduction 304
9.2 Primary processes on colloidal semiconductors 308
9.3 Photogenerated charge transfer in colloidal semiconductors 314
9.4 Some electrochemical techniques for characterizing colloidal semiconductors 348
9.5 Concluding remarks 381
Dedication 381
Appendices 382
References 385
Chapter 10. Hydrodynamic modulation methods in electrochemistry 392
10.1 Introduction 395
10.2 Classification of methods 396
10.3 Theoretical background 397
10.4 Application to electroanalysis 417
10.5 Electrohydrodynamic impedance studies 438
10.6 Summary 457
References 457
Chapter 11. AC impedance spectroscopy of polymer films–An Overview 462
11.1 Introduction 462
11.2 AC impedance theory–the transmission line 463
11.3 Indole-5-carboxylic acid films 470
11.4 Experimental 472
11.5 Results and analysis 473
11.6 Interpretation of transmission line results for ICA 479
11.7 Conclusions 481
References 482
Chapter 12. Kinetic applications of the electrochemical quartz crystal microbalance 484
12.1 Introduction 484
12.2 The quartz crystal microbalance 484
12.3 The electrochemical quartz crystal microbalance 486
12.4 Transient studies with the EQCM 487
12.5 Kinetic applications 488
12.6 Viscoelastic effects 496
References 508
Chapter 13. Visualizing ion and solvent transfer processes in electroactive polymer films 512
13.1 Introduction 513
13.2 Visualizing redox switching processes 516
13.3 polythionine (PTH) 521
13.4 Polyvinylferrocene (PVF) 525
13.5 Conclusions 540
References 543
Chapter 14. Ab initio prediction of the performance of membrane separation processes 546
14.1 Introduction 546
14.2 Prediction of ultrafiltration rates 549
14.3 Prediction of rejection in microfiltration and ultrafiltration 552
14.4 Prediction of rejection at nanofiltration membranes 557
14.5 Solute adhesion–membrane fouling 560
14.6 Conclusions 563
References 563
Chapter 15. A new approach to the prediction of diffusion coefficients 566
15.1 Introduction 566
15.2 Theory 567
15.3 Method 569
15.4 Analaysis and results 578
15.5 Discussion and conclusions 593
References 594
Chapter 16. Electrode reactions in microvolumes 596
16.1 Introduction 596
16.2 Electrochemistry in electrochemical cells of sub-microlitre volume 597
16.3 Microvolumes and separation techniques 599
16.4 Injection of microyolumes 601
16.5 Local probes–scanning electrochemical microscopy 609
16.6 Conclusion 612
References 612
Chapter 17. Some kinetic considerations of chemical vapour deposition processes 616
17.1 Introduction 616
17.2 Chemical vapour deposition 618
17.3 CVD at low pressure 624
17.4 In situ monitoring of CVD processes 641
17.5 Conclusions 650
References 653
Chapter 18. The mechanism of methanol electro-oxidation 658
18.1 Introduction 658
18.2 The adsorption of methanol and the nature of the adsorbate 658
18.3 The kinetics of oxidation of methanol to CO2 on platinum 693
18.4 Conclusions 701
References 702
Chapter 19. Spontaneous formation and breakdown of vesicles in aqueous media 706
19.1 Introduction 706
19.2 Results 710
19.3 Discussion 725
References 726
Subject Index 728