Modern Aspects of Electrochemistry №31

365 Pages·1998·6.185 MB·English

by  John O'M. Bockris, Ralph E. White, Brian E. Conway

MODERN ASPECTS OF
ELECTROCHEMISTRY
No. 31
LIST OF CONTRIBUTORS
JENS E. T. ANDERSEN MARIA JURKIEWICZ-HERBICH
Department ofChemistry Department of Chemistry
The Technical University of Denmark University of Warsaw
DK-2800 Lyngby, Denmark 02-089 Warsaw, Poland
SHAHED U. M. KHAN
AKIKO ARAMATA
Department of Chemistry and
Catalysis Research Center
Biochemistry
Hokkaido University
Duquesne University
Sapporo 060, Japan
Pittsburgh, Pennsylvania 15282-1503
GREGERS BECH-NIELSEN JOHN C. REEVE
Department of Chemistry Department of Chemistry
The Technical University of Denmark The Technical University of Denmark
DK-2800 Lyngby, Denmark DK-2800 Lyngby, Denmark
ILAN BENJAMIN JERZY SOBKOWSKI
Department of Chemistry Department of Chemistry
University of California University of Warsaw
Santa Cruz, California 95064 02-089 Warsaw, Poland
ANNE DORTHE BISGÅRD
Department of Manufacturing
Engineering
The Technical University of Denmark
DK-2800 Lyngby, Denmark
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MODERN ASPECTS OF
ELECTROCHEMISTRY
No. 31
Edited by
J. O’M. BOCKRIS
Texas A&M University
College Station, Texas
RALPH E. WHITE
University of South Carolina
Columbia, South Carolina
and
B. E. CONWAY
University of Ottawa
Ottawa, Ontario, Canada
KLUWER ACADEMIC PUBLISHERS
NEW YORK, BOSTON, DORDRECHT, LONDON, MOSCOW
eBookISBN: 0-306-46910-3
Print ISBN: 0-306-45650-8
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Print '1999 Kluwer Academic / Plenum Publishers
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Preface
Prof. Jerzy Sobkowski starts off this 31st volume of Modern Aspects of
Electrochemistry with a far-ranging discussion of experimental results
from the past 10 years of interfacial studies. It forms a good background
for the two succeeding chapters.
The second chapter is by S. U. M. Khan on quantum mechanical
treatment of electrode processes. Dr. Khan’s experience in this area is a
good basis for this chapter, the contents ofwhich will surprise some, but
which as been well refereed.
Molecular dynamic simulation is now a much-used technique in
physical electrochemistry and in the third chapter Ilan Benjamin has
written an account that brings together information from many recent
publications, sometimes confirming earlier modeling approaches and
sometimes breaking new territory.
In Chapter 4, Akiko Aramata’s experience in researching single
crystals is put to good advantage in her authoritative article on underpo-
tential deposition.
Finally, in Chapter 5, theappliedside of electrochemistry is served
by Bech-Neilsen et al. in the review of recent techniques for automated
measurement of corrosion.
J. O’M. Bockris, Texas A&M University
B. E. Conway, University of Ottawa
R. E. White, University ofSouth Carolina
This Page Intentionally Left Blank
Contents
Chapter 1
METAL/SOLUTION INTERFACE: AN EXPERIMENTAL
APPROACH
Jerzy Sobkowski and Maria Jurkiewicz-Herbich
I. Introduction.............................................. 1
II. MolecularApproachtotheMetal/Solution Interface............. 3
1. Double-Layer Structure: General Considerations .......... 3
2. Solid Metal/Electrolyte Interface.......................... 8
3. Methods Usedto StudyProperties oftheMetal/Solution
Interface: Role of the Solvent and the Metal.............15
III. The Thermodynamic Approach to the Metal/Solution Interface 35
1. The Standard Gibbs Energy of Adsorption, .......... 35
2. Effect ofSupporting Electrolyte on Electrosorption......... 54
References............................................... 63
Chapter 2
QUANTUM MECHANICAL TREATMENTS IN ELECTRODE
KINETICS
Shahed U.M. Khan
I. Introduction......................................... 71
II. Continuum Theory of Electron Transfer Reactions .......... 72
1. Born Equation and the Free Energy of Activation,
(continuum).................................. 74
vii
viii Contents
2. ReorganizationEnergy (Continuum)andtheFree
Energy of Activation ............................ 76
III. (Continuum) and theInverted Region ................ 79
1. General ......................................... 79
2. ET Reactions at Electrodes and the Inverted Region ...... 83
IV. Molecular Models of Electron Transfer Reactions at
Electrodes.......................................... 85
1.Free Energy ofActivation, andtheMolecularModels 86
V. Molecular Models of Bond-Breaking Ion and Electron
Transfer Reactions....................................... 94
1. Classical and Semiclassical Treatments ................ 95
2. Quantal Treatments................................ 99
VI. Electronic Transmission Coefficient k .................102
VII. Proton Transfer Reactions ............................ 104
VIII. Solvent Dynamic Effects on ETReactions at Electrodes .... 107
References............................................. 110
Chapter 3
MOLECULAR DYNAMIC SIMULATIONS IN INTERFACIAL
ELECTROCHEMISTRY
Ilan Benjamin
I. Introduction ....................................... 115
II. The Water/Metal Interface............................ 116
1. Preliminary Notes ................................ 116
2. Potential Energy Functions ......................... 117
3. Structure ofWater at Metal Surfaces ................. 127
4. Dynamics........................................ 135
5. Effect of External Electric Field..................... 138
III. Ionic Adsorption and Solvation at the Water/Metal Interface 143
1. Overview....................................... 143
2. Potential Energy Functions......................... 145
3. SingleIonAdsorption attheWater/MetalInterface......... 146
4. SimulationsofElectrolyte SolutionsattheWater/Metal
Interface ....................................... 153
Contents ix
IV. Interfacial Electron Transfer Reactions .................. 154
1. Preliminaries .................................... 154
2. Two-State Models ................................ 156
3. Multistate Models ................................ 168
V. Processes at the Liquid/Liquid Interface ................. 170
VI. Conclusions and Outlook ............................. 172
References.............................................. 173
Chapter 4
UNDERPOTENTIAL DEPOSITION ON SINGLE-CRYSTAL
METALS
Akiko Aramata
I. Introduction........................................ 181
1. Scope ofthis Chapter.................................. 181
2. Preparation and Qualification ofSingle Crystals........... 183
3. Well-Defined Surface Structure and Reconstruction of
Single-Crystal Surfaces ............................ 191
4. Anion Adsorption Behavior......................... 196
II. Underpotential Deposition on Single-Crystal Electrodes .... 200
1. Underpotential Deposition onAuSingleCrystals...........201
2. Underpotential Deposition on Single-Crystal Pt
Group Metals...................................... 212
3. Underpotential Deposition onAgSingleCrystals........... 219
4. Underpotential DepositionandAnionAdsorption ....... 224
III. Mechanism of Underpotential Deposition ................231
1. Kinetics and Dynamics ............................ 231
IV. Electrocatalysis on ElectrodesModified by
Underpotential Deposition............................ 240
V.Miscellaneous...................................... 241
1. Bimetallic Underpotential Deposition..................... 241
2. Effect ofUnderpotential Deposition on Overpotential
Deposition ...................................... 241
3. Effect ofOrganic Additives on Underpotential Deposition 242
4. Underpotential Deposition in Nonaqueous Solvents. ..... 243
VI. Conclusion ........................................ 243
References.............................................. 245