Electrochemical systems:
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| Main Authors: | , |
|---|---|
| Format: | Book |
| Language: | English |
| Published: |
Hoboken, N.J.
Wiley
2004
|
| Edition: | 3. ed. |
| Series: | Electrochemical Society series
|
| Subjects: | |
| Online Access: | Inhaltsverzeichnis |
| Physical Description: | XX, 647 S. Ill., graph. Darst. |
| ISBN: | 0471477567 |
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Titel: Electrochemical systems
Autor: Newman, John S
Jahr: 2004
niversitätsbibHothek
Duisburg - Essan
Copyright © 2004 by John Wiley Sons, Inc. All rights reserved.
Published by John Wiley Sons, Inc., Hoboken, New Jersey.
Published simultaneously in Canada.
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Library of Congress Cataloging-in-Publication Data:
Newman, John S., 1938-
Electrochemical systems / John Newman and Karen E. Thomas-Alyea.- 3rd ed.
p. cm.
Includes bibliographical references and index.
ISBN 0471-47756-7 (cloth)
1. Electrochemistry, Industrial. I. Thomas-Alyea, Karen E. II. Title.
TP255.N48 2004
660\297-dc22
2004005207
18
CONTENTS
PREFACE TO THE THIRD EDITION xv
PREFACE TO THE SECOND EDITION xvii
PREFACE TO THE FIRST EDITION xix
1 INTRODUCTION 1
1.1 Definitions / 2
1.2 Thermodynamics and Potential / 4
1.3 Kinetics and Rates of Reaction / 7
1.4 Transport / 8
1.5 Concentration Overpotential and the Diffusion Potential / 18
1.6 Overall Cell Potential / 21
Problems / 25
Notation / 25
Vi CONTENTS
PART A THERMODYNAMICS OF
ELECTROCHEMICAL CELLS 27
2 THERMODYNAMICS IN TERMS OF ELECTROCHEMICAL
POTENTIALS 29
2.1 Phase Equilibrium / 29
2.2 Chemical Potential and Electrochemical Potential / 31
2.3 Definition of Some Thermodynamic Functions / 35
2.4 Cell with Solution of Uniform Concentration / 43
2.5 Transport Processes in Junction Regions / 47
2.6 Cell with a Single Electrolyte of Varying
Concentration / 49
2.7 Cell with Two Electrolytes, One of Nearly Uniform Concentration / 53
2.8 Cell with Two Electrolytes, Both of Varying
Concentration / 58
2.9 Standard Cell Potential and Activity Coefficients / 59
2.10 Pressure Dependence of Activity Coefficients / 69
2.11 Temperature Dependence of Cell Potentials / 70
Problems / 72
Notation / 82
References / 83
3 THE ELECTRIC POTENTIAL 85
3.1 The Electrostatic Potential / 85
3.2 Intermolecular Forces / 88
3.3 Outer and Inner Potentials / 91
3.4 Potentials of Reference Electrodes / 92
3.5 The Electric Potential in Thermodynamics / 94
Notation / 96
References / 97
4 ACTIVITY COEFFICIENTS 99
4.1 Ionic Distributions in Dilute Solutions / 99
4.2 Electrical Contribution to the Free Energy / 102
4.3 Shortcomings of the Debye-Hückel Model / 107
4.4 Binary Solutions / 110
4.5 Multicomponent Solutions / 112
4.6 Measurement of Activity Coefficients / 116
CONTENTS VII
4.7 Weak Electrolytes / 119
Problems / 122
Notation / 127
References / 128
5 REFERENCE ELECTRODES 131
5.1 Criteria for Reference Electrodes / 131
5.2 Experimental Factors Affecting The Selection of
Reference Electrodes / 133
5.3 The Hydrogen Electrode / 134
5.4 The Calomel Electrode and Other Mercury-Mercurous
Salt Electrodes / 137
5.5 The Mercury-Mercuric Oxide Electrode / 140
5.6 Silver-Silver Halide Electrodes / 140
5.7 Potentials Relative to a Given Reference Electrode / 142
Notation / 147
References / 148
6 POTENTIALS OF CELLS WITH JUNCTIONS 149
6.1 Nernst Equation / 149
6.2 Types of Liquid Junctions / 150
6.3 Formulas for Liquid-Junction Potentials / 151
6.4 Determination of Concentration Profiles / 153
6.5 Numerical Results / 153
6.6 Cells with Liquid Junction / 154
6.7 Error in the Nernst Equation / 160
6.8 Potentials Across Membranes / 162
Problems / 163
Notation / 167
References / 167
PART B ELECTRODE KINETICS AND OTHER
INTERFACIAL PHENOMENA 169
7 STRUCTURE OF THE ELECTRIC DOUBLE LAYER 171
7.1 Qualitative Description of Double Layers / 172
7.2 Gibbs Adsorption Isotherm / 177
VÜi CONTENTS
7.3 The Lippmann Equation / 181
7.4 The Diffuse Part of the Double Layer / 185
7.5 Capacity of the Double Layer in the Absence of Specific
Adsorption / 193
7.6 Specific Adsorption at an Electrode-Solution Interface / 195
Problems / 195
Notation / 199
References / 200
ELECTRODE KINETICS 203
8.1 Heterogeneous Electrode Reactions / 203
8.2 Dependence of Current Density on Surface
Overpotential / 205
8.3 Models for Electrode Kinetics / 207
8.4 Effect of Double-Layer Structure / 225
8.5 The Oxygen Electrode / 227
8.6 Methods of Measurement / 229
8.7 Simultaneous Reactions / 230
Problems / 233
Notation / 236
References / 237
9 ELECTROKINETIC PHENOMENA 241
9.1 Discontinuous Velocity at an Interface / 241
9.2 Electro-Osmosis and the Streaming Potential / 244
9.3 Electrophoresis / 254
9.4 Sedimentation Potential / 256
Problems / 257
Notation / 260
References / 261
10 ELECTROCAPILLARY PHENOMENA 263
10.1 Dynamics of Interfaces / 263
10.2 Electrocapillary Motion of Mercury Drops / 264
10.3 Sedimentation Potentials for Falling Mercury Drops / 266
Notation / 267
References / 268
CONTENTS IX
PART C TRANSPORT PROCESSES IN
ELECTROLYTIC SOLUTIONS 269
11 INFINITELY DILUTE SOLUTIONS 271
11.1 Transport Laws / 271
11.2 Conductivity, Diffusion Potentials, and Transference
Numbers / 274
11.3 Conservation of Charge / 276
11.4 The Binary Electrolyte / 277
11.5 Supporting Electrolyte / 280
11.6 Multicomponent Diffusion by Elimination of the
Electric Field / 282
11.7 Mobilities and Diffusion Coefficients / 283
11.8 Electroneutrality and Laplace's Equation / 286
11.9 Moderately Dilute Solutions / 289
Problems / 291
Notation / 294
References / 295
12 CONCENTRATED SOLUTIONS 297
12.1 Transport Laws / 297
12.2 The Binary Electrolyte / 299
12.3 Reference Velocities / 300
12.4 The Potential / 302
12.5 Connection with Dilute-Solution Theory / 305
12.6 Multicomponent Transport / 307
12.7 Liquid-Junction Potentials / 310
Problems / 311
Notation / 313
References / 314
13 THERMAL EFFECTS 317
13.1 Thermal Diffusion / 318
13.2 Heat Generation, Conservation, and Transfer / 320
13.3 Heat Generation at an Interface / 323
13.4 Thermogalvanic Cells / 326
Problems / 330
X CONTENTS
Notation / 332
References / 334
14 TRANSPORT PROPERTIES 335
14.1 Infinitely Dilute Solutions / 335
14.2 Solutions of a Single Salt / 335
14.3 Multicomponent Solutions / 338
14.4 Integral Diffusion Coefficients for Mass Transfer / 340
Problem / 343
Notation / 343
References / 344
15 FLUID MECHANICS 347
15.1 Mass and Momentum Balances / 347
15.2 Stress in a Newtonian Fluid / 349
15.3 Boundary Conditions / 349
15.4 Fluid Flow to a Rotating Disk / 351
15.5 Magnitude of Electrical Forces / 355
15.6 Turbulent Flow / 358
15.7 Mass Transfer in Turbulent Flow / 363
Problem / 366
Notation / 366
References / 368
PART D CURRENT DISTRIBUTION AND MASS
TRANSFER IN ELECTROCHEMICAL
SYSTEMS 369
16 FUNDAMENTAL EQUATIONS 373
16.1 Transport in Dilute Solutions / 373
16.2 Electrode Kinetics / 374
Notation / 375
17 CONVECTIVE-TRANSPORT PROBLEMS 377
17.1 Simplifications for Convective Transport / 377
17.2 The Rotating Disk / 378
17.3 The Graetz Problem / 382
CONTENTS XI
17.4 TheAnnulus / 389
17.5 Two-Dimensional Diffusion Layers in Laminar Forced
Convection / 393
17.6 Axisymmetric Diffusion Layers in Laminar Forced
Convection / 395
17.7 A Flat Plate in a Free Stream / 396
17.8 Rotating Cylinders / 397
17.9 Growing Mercury Drops / 399
17.10 Free Convection / 400
17.11 Combined Free and Forced Convection / 403
17.12 Limitations of Surface Reactions / 403
17.13 Binary and Concentrated Solutions / 404
Problems / 406
Notation / 413
References / 415
18 APPLICATIONS OF POTENTIAL THEORY 419
18.1 Simplifications for Potential-Theory Problems / 420
18.2 Primary Current Distribution / 421
18.3 Secondary Current Distribution / 424
18.4 Numerical Solution by Finite Differences / 430
18.5 Principles of Cathodic Protection / 430
Problems / 449
Notation / 456
References / 456
19 EFFECT OF MIGRATION ON LIMITING CURRENTS 459
19.1 Analysis / 460
19.2 Correction Factor for Limiting Currents / 463
19.3 Concentration Variation of Supporting Electrolyte / 465
19.4 Role of Bisulfate Ions / 471
19.5 Paradoxes with Supporting Electrolyte / 476
19.6 Limiting Currents for Free Convection / 480
Problems / 486
Notation / 488
References / 489
Xil CONTENTS
20 CONCENTRATION OVERPOTENTIAL 491
20.1 Definition / 491
20.2 Binary Electrolyte / 493
20.3 Supporting Electrolyte / 495
20.4 Calculated Values / 495
Problems / 496
Notation / 497
References / 498
21 CURRENTS BELOW THE LIMITING CURRENT 499
21.1 The Bulk Medium / 500
21.2 The Diffusion Layers / 502
21.3 Boundary Conditions and Method of Solution / 503
21.4 Results for the Rotating Disk / 506
Problems / 510
Notation / 512
References / 514
22 POROUS ELECTRODES 517
22.1 Macroscopic Description of Porous Electrodes / 518
22.2 Nonuniform Reaction Rates / 527
22.3 Mass Transfer / 532
22.4 Battery Simulation / 535
22.5 Double-Layer Charging and Adsorption / 551
22.6 Flow-Through Electrochemical Reactors / 553
Problems 558
Notation 561
References 562
23 SEMICONDUCTOR ELECTRODES 567
23.1 Nature of Semiconductors / 568
23.2 Electric Capacitance at the Semiconductor-Solution
Interface / 580
23.3 Liquid-Junction Solar Cell / 583
23.4 Generalized Interfacial Kinetics / 588
23.5 Additional Aspects / 592
CONTENTS XIII
Problems / 596
Notation / 599
References / 600
APPENDIX A PARTIAL MOLAR VOLUMES 603
APPENDIX B VECTORS AND TENSORS 605
APPENDIX C NUMERICAL SOLUTION OF COUPLED,
ORDINARY DIFFERENTIAL EQUATIONS 611
INDEX 635 |
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| genre | Matériel didactique |
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| id | DE-604.BV019635105 |
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| indexdate | 2025-04-14T16:00:27Z |
| institution | BVB |
| isbn | 0471477567 |
| language | English |
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| spelling | Newman, John 1938- Verfasser (DE-588)1145484824 aut Electrochemical systems John Newman and Karen E. Thomas-Alyea 3. ed. Hoboken, N.J. Wiley 2004 XX, 647 S. Ill., graph. Darst. txt rdacontent n rdamedia nc rdacarrier Electrochemical Society series Électrochimie industrielle Électrochimie industrielle ram Electrochemistry, Industrial Elektrochemisches System (DE-588)4151771-4 gnd rswk-swf Matériel didactique Elektrochemisches System (DE-588)4151771-4 s DE-604 Thomas-Alyea, Karen E. 1974- Verfasser (DE-588)116794240X aut HBZ Datenaustausch application/pdf http://bvbr.bib-bvb.de:8991/F?func=service&doc_library=BVB01&local_base=BVB01&doc_number=012964109&sequence=000001&line_number=0001&func_code=DB_RECORDS&service_type=MEDIA Inhaltsverzeichnis |
| spellingShingle | Newman, John 1938- Thomas-Alyea, Karen E. 1974- Electrochemical systems Électrochimie industrielle Électrochimie industrielle ram Electrochemistry, Industrial Elektrochemisches System (DE-588)4151771-4 gnd |
| subject_GND | (DE-588)4151771-4 |
| title | Electrochemical systems |
| title_auth | Electrochemical systems |
| title_exact_search | Electrochemical systems |
| title_full | Electrochemical systems John Newman and Karen E. Thomas-Alyea |
| title_fullStr | Electrochemical systems John Newman and Karen E. Thomas-Alyea |
| title_full_unstemmed | Electrochemical systems John Newman and Karen E. Thomas-Alyea |
| title_short | Electrochemical systems |
| title_sort | electrochemical systems |
| topic | Électrochimie industrielle Électrochimie industrielle ram Electrochemistry, Industrial Elektrochemisches System (DE-588)4151771-4 gnd |
| topic_facet | Électrochimie industrielle Electrochemistry, Industrial Elektrochemisches System Matériel didactique |
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