Modern Aspects of Electrochemistry

333 Pages·1993·19.671 MB·English

by  H. H. Girault (auth.), J. O’M. Bockris, B. E. Conway, Ralph E. White (eds.)

MODERN ASPECTS OF
ELECTROCHEMISTRY
No. 25
LIST OF CONTRIBUTORS
H. H. GIRAULT BRUCE G. POUND
Laboratoire d'Electrochimie Materials Research Laboratory
E.P.F.L. SRI International
CH-1015 Lausanne Menlo Park, California 94025
Switzerland
MAREKSZKLARCZYK
ZOLTANNAGY Department of Chemistry
Argonne National Laboratory Warsaw University
Divisions of Materials Science and 02-089 Warsaw
Chemical Technology Poland
Argonne, Illinois 60439-4837
WOON-KIE PAIK
Department of Chemistry
Sogang University
Seoul 121-742
Korea
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MODERN ASPECTS OF
ELECTROCHEMISTRY
No.25
Edited by
J. O'M. BOCKRIS
Department of Chemistry
Texas A&M University
College Station, Texas
B. E.CONWAY
Department of Chemistry
University of Ottawa
Ottawa, Ontario, Canada
and
RALPH E. WHITE
Department of Chemical Engineering
University of South Carolina
Columbia, South Carolina
SPRINGER SCIENCE+BUSINESS MEDIA, LLC
The Library of Congress cataloged the first volume of this title as follows:
Modern aspects of electrochemistry. no. [1]
Washington, Butterworths, 1954-
v. illus., 23 cm.
No. 1-2 issued as Modern aspects series of chemistry.
Editors: no. 1- J. Bockris (with B. E. Conway, No. 3-
Imprint varies: no. 1, New York, Academic Press. - No. 2, London, Butterworths.
1. Electrochemistry-Collected works. I. Bockris, John O'M. ed. II. Conway, B. E.
ed. (Series: Modern aspects series of chemistry)
QD552.M6 54-12732 rev
ISBN 978-1-4613-6247-0 ISBN 978-1-4615-2876-0 (eBook)
DOI 10.1007/978-1-4615-2876-0
© 1993 Springer Science+Business Media New York
Originally published by Plenum Press New York in 1993
Softcover reprint of the hardcover 1s t edition 1993
AlI rights reserved
No part of this book may be reproduced, stored in a retrieval system, or transmitted
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Preface
In the Modern Aspects of Electrochemistry series there is a sincere
effort to choose topics relevant to very current interests. This is
particularly visible in the first two chapters in Volume 25. Girault's
chapter on liquid-liquid interfaces concerns a vibrant new sub
field. Bruce Pound's chapter is relevant to the surprising field of
cold fusion. Marek Szklarzcyck's chapter on the breakdown of
liquids in terms of electrochemistry is certainly novel.
The other two chapters arrive from our desire to present basic
subjects in modern guise. There is much movement, even now, in
techniques for measuring corrosion. The use of ellipsometry not
only in measuring thin films but also in adsorption puts it, along
with FTIR, as one of the in situ methods of this time.
John O'M. Bockris
Texas A&M University
Brian E. Conway
University of Ottawa
Ralph E. White
University of South Carolina
v
Contents
Chapter 1
CHARGE TRANSFER ACROSS LIQUID-LIQUID
INTERFACES
H. H. Girault
I. The Interface .................................... 2
II. Ion Transfer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
1. Experimental Results ........................... 11
2. Discussion .................................... 22
III. Facilitated Ion Transfer. . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
IV. Electron Transfer. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
V. Photoinduced Charge Transfer Reactions ............ 50
VI. Micro-ITIES .................................... 55
VII. Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 57
References ........................................... 58
vii
viii Contents
Chapter 2
ELECTROCHEMICAL TECHNIQUES TO STUDY
HYDROGEN INGRESS IN METALS
Bruce G. Pound
I. Introduction .................................... 63
II. Hydrogen Ingress. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
1. Absorption Mechanism ........................ 65
2. Hydrogen Entry Promoters. . . . . . . . . . . . . . . . . . . . . 68
3. Surface Films . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
4. Hydrogen Trapping ........................... 69
III. Permeation Techniques without Trapping ........... 70
1. Potentiostatic Charging ........................ 72
2. Galvanostatic Charging. . . . . . . . . . . . . . . . . . . . . . . . 80
3. Charging with Time-Dependent Surface Condition 83
IV. Pulse Techniques without Trapping ................ 85
1. Potentiostatic Pulse ........................... 85
2. Galvanostatic Pulse ........................... 87
3. Triangular Pulse .............................. 88
V. Potentiometric Techniques without Trapping ........ 89
1. Step Method ................................. 89
2. Pulse Method ................................ 92
3. Sinusoidal Method ............................ 92
VI. Permeation Techniques with Trapping . . . . . . . . . . . . . . 94
1. Reversible Trapping ........................... 94
2. Reversible and Irreversible Trapping ............. 97
VII. Potentiostatic Pulse Technique with Trapping ....... 98
1. Pure Diffusion Control. . . . . . . . . . . . . . . . . . . . . . . . . 99
2. Diffusion Control with Finite Surface Kinetics . . . .. 101
VIII. Alternating Current Technique .................... 104
IX. Application of Hydrogen Ingress Techniques. . . . . . . .. 104
1. Corrosion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 105
2. Films........................................ 106
3. Trapping..................................... 109
4. Charging Conditions .......................... 111
5. Diffusion Control ............................. 113
Contents ix
X. Selected Metals of Interest ........................ 117
1. Palladium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 117
2. Iron and Steel ................................ 120
3. Nickel....................................... 124
XI. Summary....................................... 126
Notation ............................................ 128
References ........................................... 130
Chapter 3
DC ELECTROCHEMICAL TECHNIQUES FOR THE
MEASUREMENT OF CORROSION RATES
Zoltan Nagy
I. Introduction ..................................... 135
II. Electrochemical Corrosion-Rate Determination
Techniques. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 136
1. General Theory ................................ 136
2. Tafel-Plot Technique. . . . . . . . . . . . . . . . . . . . . . . . . . .. 138
3. Polarization-Resistance Technique . . . . . . . . . . . . . . .. 138
4. Three-Point Technique. . . . . . . . . . . . . . . . . . . . . . . . .. 139
5. Curve-Fitting Technique. . . . . . . . . . . . . . . . . . . . . . . .. 140
6. Miscellaneous Techniques. . . . . . . . . . . . . . . . . . . . . . .. 141
7. Experimental Classification ...................... 141
III. Error Sources and Calculational Methods ............ 143
1. Mass Transport ............................... 144
2. Double-Layer Effect ........................... 147
3. Uncompensated Solution Resistance. . . . . . . . . . . . .. 153
4. Reverse Reactions ............................. 154
5. Tafel-Slope Estimates .......................... 156
6. Linearization of Polarization Equation. . . . . . . . . . .. 156
7. Multiple Reactions. . . . . . . . . . . . . . . . . . . . . . . . . . . .. 158
8. Unequal Anode-Cathode Area Ratio. . . . . . . . . . . .. 158
9. Nonuniform Current Distribution. . . . . . . . . . . . . . .. 158
10. Time-Dependent Effects ........................ 158
x Contents
IV. Error Representations ............................. 159
1. Mass Transport ................................ 159
2. Double-Layer Effect ............................ 168
3. Uncompensated Solution Resistance. . . . . . . . . . . . . .. 174
4. Reverse Reactions .............................. 178
5. Tafel-Slope Estimates ........................... 179
6. Linearization of Polarization Equation. . . . . . . . . . . .. 180
V. Comparison of Techniques ......................... 183
Notation ............................................ 185
References ........................................... 186
Chapter 4
ELLIPSOMETRY IN ELECTROCHEMISTRY
Woon-kie Paik
I. Introduction ..................................... 191
II. Theoretical Background. . . . . . . . . . . . . . . . . . . . . . . . . . .. 193
1. Optics of Polarized Light ........................ 193
2. Ellipsometry for Film-Substrate Systems:
Three-Phase Model. . . . . . . . . . . . . . . . . . . . . . . . . . . .. 197
III. Measurement and Analysis. . . . . . . . . . . . . . . . . . . . . . . .. 199
1. Basics of Measurement and Analysis. . . . . . . . . . . . . .. 199
2. Combined Reflectance-Ellipsometry
(Three-Parameter Ellipsometry) Method . . . . . . . . . .. 206
3. Other Experimental Approaches .................. 211
4. Spectroscopic Ellipsometry. . . . . . . . . . . . . . . . . . . . . .. 213
5. Instrumentation ........................... . . . .. 214
6. Errors and Sensitivity Analysis ................... 218
IV. Applications to Electrochemical Systems. . . . . . . . . . . . .. 222
1. Anodic Films on Electrodes ...................... 223
2. Electrodeposition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 227
3. Adsorption Layers . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 228
4. Conducting Polymers ........................... 233
5. Surface Roughness . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 236
6. Double (Multiple) Films. . . . . . . . . . . . . . . . . . . . . . . .. 238
Contents xi
V. Summary ........................................ 238
VI. Appendix ........................................ 239
AI. Derivation of Ellipsometry Equations for
Film-Covered Surfaces ......................... 239
A2. Poincare Sphere Representation of Polarization
of Light . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 244
References ........................................... 249
Chapter 5
ELECTRICAL BREAKDOWN OF LIQUIDS
Marek Szklarczyk
I. Introduction ..................................... 253
II. Conduction in Liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 255
1. Interfacial Mechanisms .......................... 257
2. Bulk Mechanisms. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 270
III. Mechanisms of Electrical Breakdown ................ 278
1. Cavitation-Bubble Models ....................... 279
2. Electronic Models of Electrical Breakdown ......... 285
IV. Concluding Remarks .............................. 293
References ........................................... 293
Cumulative Author Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 297
Cumulative Title Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 307
Index ............................................... 315