Electrochemical methods

PREFACE......Page 3
CONTENTS......Page 5
MAJOR SYMBOLS......Page 6
1.1 Introduction......Page 19
1.2 Nonfaradaic Processes And The Nature Of The Electrode-Solution Interface......Page 29
1.5 Semiempirical Treatment Of Nernstian Reactions With Coupled Chemical Reactions......Page 36
1.6 The Literature Of Electrochemistry......Page 57
1.8 Problems......Page 60
2.1 Basic Electrochemical Thermodynamics......Page 62
2.2 A More Detailed View Of Interfacial Potential Differences......Page 72
2.3 Liquid Junction Potentials......Page 81
2.4 Selective Electrodes......Page 92
2.5 References......Page 100
2.6 Problems......Page 102
3.1 Review Of Homogeneous Kinetics......Page 105
3.2 Essentials Of Electrode Reactions......Page 109
3.3 Butler-Volmer Model Of Electrode Kinetics......Page 110
3.4 Implications Of The Butler-Volmer Model For The One-Step, One-Electron Process......Page 116
3.5 Multistep Mechanisms......Page 125
3.6 Microscopic Theories Of Charge Transfer......Page 133
3.7 References......Page 150
3.8 Problems......Page 152
4.1 Derivation Of A General Mass Transfer Equation......Page 155
4.2 Migration......Page 157
4.3 Mixed Migration And Diffusion Near An Active Electrode......Page 158
4.4 Diffusion......Page 164
4.5 References......Page 171
4.6 Problems......Page 172
5.1 Overview Of Step Experiments......Page 174
5.2 Potential Step Under Diffusion Control......Page 179
5.3 Diffusion-Controlled Currents At Ultramicroelectrodes......Page 186
5.4 Sampled-Current Voltammetry For Reversible Electrode Reactions......Page 194
5.5 Sampled-Current Voltammetry For Quasireversible And Irreversible Electrode Reactions......Page 209
5.6 Multicomponent Systems And Multistep Charge Transfers......Page 222
5.7 Chronoamperometric Reversal Techniques......Page 225
5.8 Chronocoulometry......Page 228
5.9 Special Applications Of Ultramicroelectrodes......Page 234
5.10 References......Page 239
5.11 Problems......Page 240
6.1 Introduction......Page 244
6.2 Nernstian (Reversible) Systems......Page 246
6.3 Totally Irreversible Systems......Page 252
6.4 Quasireversible Systems......Page 254
6.5 Cyclic Voltammetry......Page 257
6.6 Multicomponent Systems And Multistep Charge Transfers......Page 261
6.7 Convolutive Or Semi-Integral Techniques......Page 265
6.8 Cyclic Voltammetry Of The Liquid-Liquid Interface......Page 270
6.9 REFERENCES......Page 273
6.10 Problems......Page 274
7.1 Behavior At Polarographic Electrodes......Page 279
7.2 Polarographic Waves......Page 290
7.3.1 Tast Polarography and Staircase Voltammetry......Page 293
7.3.2 Normal Pulse Voltammetry......Page 296
7.3.3 Reverse Pulse Voltammetry......Page 301
7.3.4 Differential Pulse Voltammetry......Page 304
7.3.5 Square Wave Voltammetry......Page 311
7.3.6 Analysis by Pulse Voltammetry......Page 317
7.4 References......Page 320
7.5 Problems......Page 321
8.1 Introduction......Page 323
8.2 General Theory Of Controlledcurrent Methods......Page 325
8.3 Potential-Time Curves In Constantcurrent Electrolysis......Page 329
8.4 Reversal Techniques......Page 334
8.5 Multicomponent Systems And Multistep Reactions......Page 336
8.6 The Galvanostatic Double Pulse Method......Page 338
8.7 Charge Step (Coulostatic) Methods......Page 340
8.9 Problems......Page 346
9.1 Introduction......Page 349
9.2 Theoretical Treatment Of Convective Systems......Page 350
9.3 Rotating Disk Electrode......Page 353
9.4 Rotating Ring And Ring-Disk Electrodes......Page 366
9.5 Transients At The RDE And RRDE......Page 371
9.6 Modulated Rde......Page 375
9.7 Convection At UMEs......Page 378
9.8 Electrohydrodynamics And Related Phenomena......Page 380
9.9 References......Page 382
9.10 Problems......Page 383
10.1 Introduction......Page 386
10.2 Interpretation Of The Faradaic Impedance......Page 395
10.3 Kinetic Parameters From Impedance Measurements......Page 398
10.4 Electrochemical Impedance Spectroscopy......Page 401
10.5 Ac Voltammetry......Page 406
10.6 Higher Harmonics......Page 419
10.7 Chemical Analysis By Ac Voltammetry......Page 423
10.8 Instrumentation For Electrochemical Impedance Spectroscopy......Page 424
10.9 Analysis Of Data In The Laplace Plane......Page 428
10.10 References......Page 432
10.11 Problems......Page 433
11.1 Classification Of Techniques......Page 435
11.2 General Considerations In Bulk Electrolysis......Page 436
11.3 Controlled-Potential Methods......Page 441
11.4 Controlled-Current Methods......Page 448
11.5 Electrometric End-Point Detectio......Page 453
11.6 Flow Electrolysis......Page 459
11.7 Thin-Layer Electrochemistry......Page 470
11.8 Stripping Analysis......Page 476
11.9 References......Page 482
11.10 Problems......Page 484
12.1 Classification Of Reactions......Page 489
12.2 Fundamentals Of Theory For Voltammetric And Chronopotentiometric Methods......Page 498
12.3 Theory For Transient Voltammetry And Chronopotentiometry......Page 505
12.4 Rotating Disk And Ring-Disk Methods......Page 534
12.6 Sine Wave Methods......Page 540
12.7 Controlled-Potential Coulometric Methods......Page 541
12.8 References......Page 547
12.9 Problems......Page 549
13.1 Thermodynamics Of The Double Layer......Page 552
13.2 Experimental Evaluation Of Surface Excesses And Electrical Parameters......Page 557
13.3 Models For Double-Layer Structure......Page 562
13.4 Studies At Solid Electrodes......Page 575
13.5 Extent And Rate Of Specific Adsorption......Page 581
13.6 Effect Of Adsorption Of Electroinactive Species......Page 587
13.7 Double-Layer Effects On Electrode Reaction Rates......Page 589
13.8 References......Page 593
13.9 Problems......Page 595
14.1 Introduction-Intellectual And Technological Motivations......Page 598
14.2 Types, Preparation, And Properties Of Films And Modified Electrodes......Page 599
14.3 Electrochemical Responses Of Adsorbed Monolayers......Page 607
14.4 Overview Of Processes At Modified Electrodes......Page 626
14.5 Blocking Layers......Page 637
14.6 Other Methods Of Characterization......Page 645
14.7 References......Page 646
14.8 Problems......Page 648
15.1 Operational Amplifiers......Page 650
15.2 Current Feedback......Page 653
15.3 Voltage Feedback......Page 657
15.4 Potentiostats......Page 658
15.5 Galvanostats......Page 662
15.6 Difficulties With Potential Control......Page 663
15.7 Measurement Of Low Currents......Page 668
15.8 Computer-Controlled Instrumentation......Page 670
15.9 Troubleshooting Electrochemical Systems......Page 672
15.10 References......Page 674
15.11 Problems......Page 675
16.2 Scanning Tunneling Microscopy......Page 677
16.3 Atomic Force Microscopy......Page 684
16.4 Scanning Electrochemical Microscopy......Page 687
16.6 Problems......Page 696
17.1 Ultraviolet And Visible Spectroscopy......Page 698
17.2 Vibrational Spectroscopy......Page 718
17.3 Electron And Ion Spectrometry......Page 727
17.4 Magnetic Resonance Methods......Page 740
17.5 Quartz Crystal Microbalance......Page 743
17.6 X-Ray Methods......Page 746
17.7 References......Page 749
17.8 Problems......Page 752
18.1 Electrogenerated Chemiluminescence......Page 754
18.2 Photoelectrochemistry At Semiconductors......Page 763
18.3 Electrochemical Detection Of Photolytic And Radiolytic Products......Page 778
18.4 References......Page 782
18.5 Problems......Page 784
А. 1 Solving Differential Equations By The Laplace Transform Technique......Page 787
A. 2 Taylor Expansions......Page 795
A. 3 The Error Function And The Gaussian Distribution......Page 796
A.5 Complex Notation......Page 798
A. 6 Fourier Series And Fourier Transformation......Page 800
A. 8 Problems......Page 801
B. 1 Setting Up The Model......Page 803
B. 2 An Example......Page 811
B. 3 Incorporating Homogeneous Kinetics......Page 814
B. 4 Boundary Conditions For Various Techniques......Page 816
B. 5 Simulations In Convective Systems......Page 820
B. 6 Miscellaneous Digital Simulations......Page 821
B. 8 Problems......Page 824
Appendix C Reference Tables......Page 826
A - E......Page 832
F - P......Page 839
Q - Z......Page 845