Preface To The Fourth Edition xv
Preface To The Third Edition xvii
Preface To The Second Edition xix
Preface To The First Edition xxi
1 Introduction 1
1.1 Definitions 2
1.2 Thermodynamics and Potential 3
1.3 Kinetics and Rates of Reaction 6
1.4 Transport 8
1.5 Concentration Overpotential and the Diffusion Potential 15
1.6 Overall Cell Potential 18
Problems 20
Notation 21
Part A Thermodynamics of Electrochemical Cells 23
2 Thermodynamics In Terms of Electrochemical Potentials 25
2.1 Phase Equilibrium 25
2.2 Chemical Potential and Electrochemical Potential 27
2.3 Definition of Some Thermodynamic Functions 30
2.4 Cell with Solution of Uniform Concentration 36
2.5 Transport Processes in Junction Regions 39
2.6 Cell with a Single Electrolyte of Varying Concentration 40
2.7 Cell with Two Electrolytes, One of Nearly Uniform Concentration 44
2.8 Cell with Two Electrolytes, Both of Varying Concentration 47
2.9 Lithiumâ"Lithium Cell With Two Polymer Electrolytes 49
2.10 Standard Cell Potential and Activity Coefficients 50
2.11 Pressure Dependence of Activity Coefficients 58
2.12 Temperature Dependence of Cell Potentials 59
Problems 61
Notation 68
References 70
3 The Electric Potential 71
3.1 The Electrostatic Potential 71
3.2 Intermolecular Forces 74
3.3 Outer and Inner Potentials 76
3.4 Potentials of Reference Electrodes 77
3.5 The Electric Potential in Thermodynamics 78
Notation 79
References 80
4 Activity Coefficients 81
4.1 Ionic Distributions in Dilute Solutions 81
4.2 Electrical Contribution to the Free Energy 84
4.3 Shortcomings of the Debyeâ"H¼ckel Model 87
4.4 Binary Solutions 89
4.5 Multicomponent Solutions 92
4.6 Measurement of Activity Coefficients 94
4.7 Weak Electrolytes 96
Problems 99
Notation 103
References 104
5 Reference Electrodes 107
5.1 Criteria for Reference Electrodes 107
5.2 Experimental Factors Affecting Selection of Reference Electrodes 109
5.3 The Hydrogen Electrode 110
5.4 The Calomel Electrode and Other Mercuryâ"Mercurous Salt Electrodes 112
5.5 The Mercuryâ"Mercuric Oxide Electrode 114
5.6 Silverâ"Silver Halide Electrodes 114
5.7 Potentials Relative to a Given Reference Electrode 116
Notation 119
References 120
6 Potentials of Cells With Junctions 121
6.1 Nernst Equation 121
6.2 Types of Liquid Junctions 122
6.3 Formulas for Liquid-Junction Potentials 123
6.4 Determination of Concentration Profiles 124
6.5 Numerical Results 124
6.6 Cells with Liquid Junction 128
6.7 Error in the Nernst Equation 129
6.8 Potentials Across Membranes 131
6.9 Charged Membranes Immersed in an Electrolytic Solution 131
Problems 135
Notation 138
References 138
Part B Electrode Kinetics and Other Interfacial Phenomena 141
7 Structure of The Electric Double Layer 143
7.1 Qualitative Description of Double Layers 143
7.2 Gibbs Adsorption Isotherm 148
7.3 The Lippmann Equation 151
7.4 The Diffuse Part of the Double Layer 155
7.5 Capacity of the Double Layer in the Absence of Specific Adsorption 160
7.6 Specific Adsorption at an Electrodeâ"Solution Interface 161
Problems 161
Notation 164
References 165
8 Electrode Kinetics 167
8.1 Heterogeneous Electrode Reactions 167
8.2 Dependence of Current Density on Surface Overpotential 169
8.3 Models for Electrode Kinetics 170
8.4 Effect of Double-Layer Structure 185
8.5 The Oxygen Electrode 187
8.6 Methods of Measurement 192
8.7 Simultaneous Reactions 193
Problems 195
Notation 199
References 200
9 Electrokinetic Phenomena 203
9.1 Discontinuous Velocity at an Interface 203
9.2 Electro-Osmosis and the Streaming Potential 205
9.3 Electrophoresis 213
9.4 Sedimentation Potential 215
Problems 216
Notation 218
References 219
10 Electrocapillary Phenomena 221
10.1 Dynamics of Interfaces 221
10.2 Electrocapillary Motion of Mercury Drops 222
10.3 Sedimentation Potentials for Falling Mercury Drops 224
Notation 224
References 225
Part C Transport Processes In Electrolytic Solutions 227
11 Infinitely Dilute Solutions 229
11.1 Transport Laws 229
11.2 Conductivity, Diffusion Potentials, and Transference Numbers 232
11.3 Conservation of Charge 233
11.4 The Binary Electrolyte 233
11.5 Supporting Electrolyte 236
11.6 Multicomponent Diffusion by Elimination of the Electric Field 237
11.7 Mobilities and Diffusion Coefficients 238
11.8 Electroneutrality and LaplaceâS Equation 240
11.9 Moderately Dilute Solutions 242
Problems 244
Notation 247
References 247
12 Concentrated Solutions 249
12.1 Transport Laws 249
12.2 The Binary Electrolyte 251
12.3 Reference Velocities 252
12.4 The Potential 253
12.5 Connection with Dilute-Solution Theory 256
12.6 Example Calculation Using Concentrated Solution Theory 257
12.7 Multicomponent Transport 259
12.8 Liquid-Junction Potentials 262
Problems 263
Notation 264
References 266
13 Thermal Effects 267
13.1 Thermal Diffusion 268
13.2 Heat Generation, Conservation, and Transfer 270
13.3 Heat Generation at an Interface 272
13.4 Thermogalvanic Cells 274
13.5 Concluding Statements 276
Problems 277
Notation 279
References 280
14 Transport Properties 283
14.1 Infinitely Dilute Solutions 283
14.2 Solutions of a Single Salt 283
14.3 Mixtures of Polymers and Salts 286
14.4 Types of Transport Properties and Their Number 295
14.5 Integral Diffusion Coefficients for Mass Transfer 296
Problem 298
Notation 298
References 299
15 Fluid Mechanics 301
15.1 Mass and Momentum Balances 301
15.2 Stress in a Newtonian Fluid 302
15.3 Boundary Conditions 303
15.4 Fluid Flow to a Rotating Disk 304
15.5 Magnitude of Electrical Forces 307
15.6 Turbulent Flow 310
15.7 Mass Transfer in Turbulent Flow 314
15.8 Dissipation Theorem for Turbulent Pipe Flow 316
Problem 318
Notation 319
References 321
Part D Current Distribution and Mass Transfer In Electrochemical Systems 323
16 Fundamental Equations 327
16.1 Transport in Dilute Solutions 327
16.2 Electrode Kinetics 328
Notation 329
17 Convective-Transport Problems 331
17.1 Simplifications for Convective Transport 331
17.2 The Rotating Disk 332
17.3 The Graetz Problem 335
17.4 The Annulus 340
17.5 Two-Dimensional Diffusion Layers in Laminar Forced Convection 344
17.6 Axisymmetric Diffusion Layers in Laminar Forced Convection 345
17.7 A Flat Plate in a Free Stream 346
17.8 Rotating Cylinders 347
17.9 Growing Mercury Drops 349
17.10 Free Convection 349
17.11 Combined Free and Forced Convection 351
17.12 Limitations of Surface Reactions 352
17.13 Binary and Concentrated Solutions 353
Problems 354
Notation 359
References 360
18 Applications of Potential Theory 365
18.1 Simplifications For Potential-Theory Problems 366
18.2 Primary Current Distribution 367
18.3 Secondary Current Distribution 370
18.4 Numerical Solution by Finite Differences 374
18.5 Principles of Cathodic Protection 375
Problems 389
Notation 396
References 397
19 Effect of Migration On Limiting Currents 399
19.1 Analysis 400
19.2 Correction Factor for Limiting Currents 402
19.3 Concentration Variation of Supporting Electrolyte 404
19.4 Role of Bisulfate Ions 409
19.5 Paradoxes with Supporting Electrolyte 413
19.6 Limiting Currents for Free Convection 417
Problems 423
Notation 424
References 426
20 Concentration Overpotential 427
20.1 Definition 427
20.2 Binary Electrolyte 429
20.3 Supporting Electrolyte 430
20.4 Calculated Values 430
Problems 431
Notation 432
References 433
21 Currents Below The Limiting Current 435
21.1 The Bulk Medium 436
21.2 The Diffusion Layers 437
21.3 Boundary Conditions and Method of Solution 438
21.4 Results for the Rotating Disk 440
Problems 444
Notation 446
References 447
22 Porous Electrodes 449
22.1 Macroscopic Description of Porous Electrodes 450
22.2 Nonuniform Reaction Rates 457
22.3 Mass Transfer 462
22.4 Battery Simulation 463
22.5 Double-Layer Charging and Adsorption 477
22.6 Flow-Through Electrochemical Reactors 478
Problems 482
Notation 484
References 486
23 Semiconductor Electrodes 489
23.1 Nature of Semiconductors 490
23.2 Electric Capacitance at the Semiconductorâ"Solution Interface 499
23.3 Liquid-Junction Solar Cell 502
23.4 Generalized Interfacial Kinetics 506
23.5 Additional Aspects 509
Problems 513
Notation 514
References 516
24 Impedance 517
24.1 Frequency Dispersion at a Disk Electrode 519
24.2 Modulated Flow With a Disk Electrode 522
24.3 Porous Electrodes for Batteries 526
24.4 Kramersâ"Kronig Relation 528
Problems 530
Notation 531
References 532
Appendix A Partial Molar Volumes 535
Appendix B Vectors and Tensors 537
Appendix C Numerical Solution of Coupled, Ordinary Differential Equations 543
Index 567
