Electrochemical Systems

Electrochemical Systems, Third Edition......Page 5
CONTENTS......Page 7
PREFACE TO THE THIRD EDITION......Page 17
PREFACE TO THE SECOND EDITION......Page 19
PREFACE TO THE FIRST EDITION......Page 21
1 INTRODUCTION......Page 23
1.1 Definitions......Page 24
1.2 Thermodynamics and Potential......Page 26
1.3 Kinetics and Rates of Reaction......Page 29
1.4 Transport......Page 30
1.5 Concentration Overpotential and the Diffusion Potential......Page 40
1.6 Overall Cell Potential......Page 43
Notation......Page 47
PART A THERMODYNAMICS OF ELECTROCHEMICAL CELLS......Page 49
2.1 Phase Equilibrium......Page 51
2.2 Chemical Potential and Electrochemical Potential......Page 53
2.3 Definition of Some Thermodynamic Functions......Page 57
2.4 Cell with Solution of Uniform Concentration......Page 65
2.5 Transport Processes in Junction Regions......Page 69
2.6 Cell with a Single Electrolyte of Varying Concentration......Page 71
2.7 Cell with Two Electrolytes, One of Nearly Uniform Concentration......Page 75
2.8 Cell with Two Electrolytes, Both of Varying Concentration......Page 80
2.9 Standard Cell Potential and Activity Coefficients......Page 81
2.10 Pressure Dependence of Activity Coefficients......Page 91
2.11 Temperature Dependence of Cell Potentials......Page 92
Problems......Page 94
Notation......Page 104
References......Page 105
3.1 The Electrostatic Potential......Page 107
3.2 Intermolecular Forces......Page 110
3.3 Outer and Inner Potentials......Page 113
3.4 Potentials of Reference Electrodes......Page 114
3.5 The Electric Potential in Thermodynamics......Page 116
Notation......Page 118
References......Page 119
4.1 Ionic Distributions in Dilute Solutions......Page 121
4.2 Electrical Contribution to the Free Energy......Page 124
4.3 Shortcomings of the Debye-Hiickel Model......Page 129
4.4 Binary Solutions......Page 132
4.5 Multicomponent Solutions......Page 134
4.6 Measurement of Activity Coefficients......Page 138
4.7 Weak Electrolytes......Page 141
Problems......Page 144
Notation......Page 149
References......Page 150
5.1 Criteria for Reference Electrodes......Page 153
5.2 Experimental Factors Affecting The Selection of Reference Electrodes......Page 155
5.3 The Hydrogen Electrode......Page 156
5.4 The Calomel Electrode and Other Mercury-Mercurous Salt Electrodes......Page 159
5.6 Silver-Silver Halide Electrodes......Page 162
5.7 Potentials Relative to a Given Reference Electrode......Page 164
Notation......Page 169
References......Page 170
6.1 Nernst Equation......Page 171
6.2 Types of Liquid Junctions......Page 172
6.3 Formulas for Liquid-Junction Potentials......Page 173
6.5 Numerical Results......Page 175
6.6 Cells with Liquid Junction......Page 176
6.7 Error in the Nernst Equation......Page 182
6.8 Potentials Across Membranes......Page 184
Problems......Page 185
References......Page 189
PART B ELECTRODE KINETICS AND OTHER INTERFACIAL PHENOMENA......Page 191
7 STRUCTURE OF THE ELECTRIC DOUBLE LAYER......Page 193
7.1 Qualitative Description of Double Layers......Page 194
7.2 Gibbs Adsorption Isotherm......Page 199
7.3 The Lippmann Equation......Page 203
7.4 The Diffuse Part of the Double Layer......Page 207
7.5 Capacity of the Double Layer in the Absence of Specific Adsorption......Page 215
Problems......Page 217
Notation......Page 221
References......Page 222
8.1 Heterogeneous Electrode Reactions......Page 225
8.2 Dependence of Current Density on Surface Overpotential......Page 227
8.3 Models for Electrode Kinetics......Page 229
8.4 Effect of Double-Layer Structure......Page 247
8.5 The Oxygen Electrode......Page 249
8.6 Methods of Measurement......Page 251
8.7 Simultaneous Reactions......Page 252
Problems......Page 255
Notation......Page 258
References......Page 259
9.1 Discontinuous Velocity at an Interface......Page 263
9.2 Electro-Osmosis and the Streaming Potential......Page 266
9.3 Electrophoresis......Page 276
9.4 Sedimentation Potential......Page 278
Problems......Page 279
Notation......Page 282
References......Page 283
10.1 Dynamics of Interfaces......Page 285
10.2 Electrocapillary Motion of Mercury Drops......Page 286
10.3 Sedimentation Potentials for Falling Mercury Drops......Page 288
Notation......Page 289
References......Page 290
PART C TRANSPORT PROCESSES IN ELECTROLYTIC SOLUTIONS......Page 291
11.1 Transport Laws......Page 293
11.2 Conductivity, Diffusion Potentials, and Transference Numbers......Page 296
11.3 Conservation of Charge......Page 298
11.4 The Binary Electrolyte......Page 299
11.5 Supporting Electrolyte......Page 302
11.6 Multicomponent Diffusion by Elimination of the Electric Field......Page 304
11.7 Mobilities and Diffusion Coefficients......Page 305
11.8 Electroneutrality and Laplace's Equation......Page 308
11.9 Moderately Dilute Solutions......Page 311
Problems......Page 313
Notation......Page 316
References......Page 317
12.1 Transport Laws......Page 319
12.2 The Binary Electrolyte......Page 321
12.3 Reference Velocities......Page 322
12.4 The Potential......Page 324
12.5 Connection with Dilute-Solution Theory......Page 327
12.6 Multicomponent Transport......Page 329
12.7 Liquid-Junction Potentials......Page 332
Problems......Page 333
Notation......Page 335
References......Page 336
13 THERMAL EFFECTS......Page 339
13.1 Thermal Diffusion......Page 340
13.2 Heat Generation, Conservation, and Transfer......Page 342
13.3 Heat Generation at an Interface......Page 345
13.4 Thermogalvanic Cells......Page 348
Problems......Page 352
Notation......Page 354
References......Page 356
14.2 Solutions of a Single Salt......Page 357
14.3 Multicomponent Solutions......Page 360
14.4 Integral Diffusion Coefficients for Mass Transfer......Page 362
Notation......Page 365
References......Page 366
15.1 Mass and Momentum Balances......Page 369
15.3 Boundary Conditions......Page 371
15.4 Fluid Flow to a Rotating Disk......Page 373
15.5 Magnitude of Electrical Forces......Page 377
15.6 Turbulent Flow......Page 380
15.7 Mass Transfer in Turbulent Flow......Page 385
Notation......Page 388
References......Page 390
PART D CURRENT DISTRIBUTION AND MASS TRANSFER IN ELECTROCHEMICAL SYSTEMS......Page 391
16.1 Transport in Dilute Solutions......Page 395
16.2 Electrode Kinetics......Page 396
Notation......Page 397
17.1 Simplifications for Convective Transport......Page 399
17.2 The Rotating Disk......Page 400
17.3 The Graetz Problem......Page 404
17.4 The Annulus......Page 411
17.5 Two-Dimensional Diffusion Layers in Laminar Forced Convection......Page 415
17.6 Axisymmetric Diffusion Layers in Laminar Forced Convection......Page 417
17.7 A Flat Plate in a Free Stream......Page 418
17.8 Rotating Cylinders......Page 419
17.9 Growing Mercury Drops......Page 421
17.10 Free Convection......Page 422
17.12 Limitations of Surface Reactions......Page 425
17.13 Binary and Concentrated Solutions......Page 426
Problems......Page 428
Notation......Page 435
References......Page 437
18 APPLICATIONS OF POTENTIAL THEORY......Page 441
18.1 Simplifications for Potential-Theory Problems......Page 442
18.2 Primary Current Distribution......Page 443
18.3 Secondary Current Distribution......Page 446
18.5 Principles of Cathodic Protection......Page 452
Problems......Page 471
References......Page 478
19 EFFECT OF MIGRATION ON LIMITING CURRENTS......Page 481
19.1 Analysis......Page 482
19.2 Correction Factor for Limiting Currents......Page 485
19.3 Concentration Variation of Supporting Electrolyte......Page 487
19.4 Role of Bisulfate Ions......Page 493
19.5 Paradoxes with Supporting Electrolyte......Page 498
19.6 Limiting Currents for Free Convection......Page 502
Problems......Page 508
Notation......Page 510
References......Page 511
20.1 Definition......Page 513
20.2 Binary Electrolyte......Page 515
20.4 Calculated Values......Page 517
Problems......Page 518
Notation......Page 519
References......Page 520
21 CURRENTS BELOW THE LIMITING CURRENT......Page 521
21.1 The Bulk Medium......Page 522
21.2 The Diffusion Layers......Page 524
21.3 Boundary Conditions and Method of Solution......Page 525
21.4 Results for the Rotating Disk......Page 528
Problems......Page 532
Notation......Page 534
References......Page 536
22 POROUS ELECTRODES......Page 539
22.1 Macroscopic Description of Porous Electrodes......Page 540
22.2 Nonuniform Reaction Rates......Page 549
22.3 Mass Transfer......Page 554
22.4 Battery Simulation......Page 557
22.5 Double-Layer Charging and Adsorption......Page 573
22.6 Flow-Through Electrochemical Reactors......Page 575
Problems......Page 580
Notation......Page 583
References......Page 584
23 SEMICONDUCTOR ELECTRODES......Page 589
23.1 Nature of Semiconductors......Page 590
23.2 Electric Capacitance at the Semiconductor-Solution Interface......Page 602
23.3 Liquid-Junction Solar Cell......Page 605
23.4 Generalized Interfacial Kinetics......Page 610
23.5 Additional Aspects......Page 614
Problems......Page 618
Notation......Page 621
References......Page 622
APPENDIX A PARTIAL MOLAR VOLUMES......Page 625
APPENDIX B VECTORS AND TENSORS......Page 627
APPENDIX C NUMERICAL SOLUTION OF COUPLED, ORDINARY DIFFERENTIAL EQUATIONS......Page 633
INDEX......Page 657