Modern Aspects of Electrochemistry No. 7

423 Pages·1972·8.912 MB·English

by  J. I. Padova (auth.), B. E. Conway, J. O’M. Bockris (eds.)

MODERN ASPECTS OF
ELECTROCHEMISTRY
No.7
CONTRIBUTORS TO THIS VOLUME
H.H.BAUER P.J.HERMAN
Department of Chemistry Department of Chemistry
University of Kentucky University of Michigan
Lexington, Kentucky Ann Arbor, Michigan
B.E.CONWAY
V. V.LOSEV
Commonwealth Visiting Professor
(1969-1970) Karpov Institute of
Physical Chemistry
Universities of Southampton and
Moscow, USSR
N ewcastle-on-Tyne
Southampton, England
J. I. PAD OVA
A. R.DESPIC
Israel A tomic Energy
University of Belgrade
Commission
Belgrade, Yugoslavia
Soreq, Israel
P. ELVING
Department of Chemistry K. I. POPOV
University of Michigan University of Belgrade
Ann Arbor, Michigan Belgrade, Yugoslavia
MODERN ASPECTS OF
ELECTROCHEMISTRY
No.7
Edited by
B. E. CONWAY
Department of Chemistry
University of Ottawa
Ottawa, Ontario
and
J. O'M. BOCKRIS
Electrochemistry Laboratory
John Harrison Laboratory of Chemistry
University of Pennsylvania, Philadelphia, Pennsylvania
g?PLENUM PRESS· NEW YORK· 1972
Library of Congress Catalog Card Number 54-12732
ISBN-13: 978-1-4684-3005-9 e-ISBN-13: 978-1-4684-3003-5
DOl: 10.1007/978-1-4684-3003-5
© 1972 Plenum Press, New York
Softcover reprint of the hardcover 1st edition 1972
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United Kingdom edition published by Plenum Press, London
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No part of this publication may be reproduced in any
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Preface
Despite reductions in the level of research activity in most fields
which, for reasons of economic decline, have taken place in the U.S.
during the last year or two, world progress in the fundamental aspects
has continued actively. An important aspect of such recent work has
been the use of nonaqueous solvents in studies on the constitution
of the double-layer and electrochemical reactions. Interpretation of
the behavior of electrode interfaces in such solvents demands more
knowledge of the solvation properties of ions in nonaqueous media.
Chapter 1 by Pad ova on "Ionic Solvation in Nonaqueous and Mixed
Solvents" gives an up to date review of the present state of knowledge
in this field, together with tabulations of data that are likely to be of
quantitative value in further investigations of both homogeneous
and heterogeneous electrochemistry in such media.
Electrochemical studies of cathodic processes in nonaqueous
solvents have, in recent years, revealed the role of solvated electrons.
These are of interest in new approaches to reductive electro-organic
synthesis. Similarly, the generation of hydrated electrons in photo
cathodic processes is of great interest. In Chapter 2, by Conway, the
conditions under which solvated electrons can arise in electrode
processes are critically examined and the electro-organic reactions
that hwe been investigated are reviewed. The supposed electro
generation of hydrated electrons in the water solvent and as inter
mediates in cathodic hydrogen evolution is shown to be unlikely.
Returning to questions concerned with the double-layer itself,
a useful critical appraisal of the significance of measurements and
v
vi Preface
measured quantities concerned with adsorption and the structure
of electrode solution interphases is given by Bauer, Herman, and
Elving in Chapter 3.
The subject of electrocrystallization and metal dissolution has
for many years been a topic of central interest both in fundamental
and applied electrochemistry. The possibility of controlling phase
growth or dissolution by electric potential control is little appreciated
outside the subject of electrochemistry yet it enters into many
processes of technological interest not least of which, in a "negative"
way, is corrosion. Chapter 4 presents a thorough analysis of various
aspects of this topic under the title "Transport Controlled Deposition
and Dissolution of Metals" by Despic and Popov. Special attention
is given to problems of leveling and dendritic growth. The large
number of diagrams and photographs will enhance the value of this
chapter both to metallurgists and electro chemists.
Finally, a contribution from the important Russian school of
electrochemistry (at the Karpov Institute) is given in Chapter 5 by
Losev, who examines the "Mechanisms of Stepwise Electrode
Processes on Amalgams." Such studies, which to a large extent are
specially his own, allow idealized· examination of corrosion-type
processes under conditions where various steps in complex reaction
schemes can be characterized and their role in the kinetics elucidated.
Simultaneous anodic and cathodic processes are involved, the latter
naturally involving H.
B. E. Conway
J. O'M. Bockris
Breakers Club
Bermuda
January 1971
Contents
Chapter 1
IONIC SOLVATION IN NONAQUEOUS
AND MIXED SOLVENTS
J. I. Pad ova
I. Introduction.................................... 1
II. Thermodynamics of Solvation. . . . . . . . . . . . . . . . . . . . . 2
III. Determination of Thermodynamics of Solvation. . . . . . 3
1. Heats of Solvation. . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2. Free Energies of Solvation. . . . . . . . . . . . . . . . . . . . . . 9
3. Entropies of Solvation. . . . . . . . . . . . . . . . . . . . . . . . . 16
IV. Theoretical Aspects of Solvation. . . . . . . . . . . . . . . . . . . 20
1. Real Free Energy of Solvation. . . . . . . . . . . . . . . . . . 20
2. Electrostatic Theory of Solvation. . . . . . . . . . . . . . . . 20
3. Thermodynamics of a Dielectric Continuum. . . . . . 24
4. Structural Approaches. . . . . . . . . . . . . . . . . . . . . . . . . 29
V. Solvation Numbers. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
VI. Mixed Solvents. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
1. Structural Changes in Mixed Solvents. . . . . . . . . . . . 38
2. Solvation Approach to Mixed Solvents. . . . . . . . . . . 43
3. Thermodynamic Approach to Selective Solvation in
Mixed Solvents. . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
4. NMR Aspects of Solvation. . . . . . . . . . . . . . . . . . . . . 47
VII. Transport Processes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
1. Viscosity ................. _. . . . . . . . . . . . . . . . . . . . 52
2. Conductance....................... . . . . . . . . . . 56
3. Stokes' Law and Walden's Rule. . . . . . . . . . . . . . . . . 63
4. Association. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
vii
viii Contents
Chapter 2
SOLVATED ELECTRONS IN FIELD- AND
PHOTO-ASSISTED PROCESSES AT
ELECTRODES
B. E. Conway
I. Introduction........................ ............ 83
II. Energetic Factors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
1. Effective Work Function for Production of Solvated
Electrons. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 85
2. Comparison of Energetics of Ion/Electrode and
Electron Injection Processes. . . . . . . . . . . . . . . . . . 87
3. Standard Electrode Potentials for e Liquid
s-:
Ammonia and Water. . . . . . . . . . . . . . . . . . . . . . . . 91
4. Energy Conditions for Production of Electrons in
Water.............. .. ..................... 95
5. State of Solvated Electrons in Polar Media. . . . . . . . 99
III. Photoassisted Electron Injection from Cathodes. . . . . . 101
1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
2. Energetic Conditions for Photo electrochemical
Emission.... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
3. Experimental Characterization of the Electro
chemical Photoeffect. . . . . . . . . . . . . . . . . . . . . . . . . 103
4. Effects of Double-Layer Structure. . . . . . . . . . . . . . . 107
IV. Scavenger Behavior in the Electrochemical Photoeffect 108
V. Chemical Evidence for Direct Cathodic Injection of
Electrons into Solvents. . . . . . . . . . . . . . . . . . . . . . . . .. 117
VI. Hydrated Electrons in Aqueous Electrochemical
Reactions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 122
1. Some General Problems. . . . . . . . . . . . . . . . . . . . . . . . 122
2. Standard Potential for e~ and the Nonequilibrium
Situation Arising from Annihilation Processes. . . 134
3. Illumination Effects and Reflectance ......... " .. 136
4. Solvated Electrons and Organic Electrochemical
Reactions. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 138
Acknowledgment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 139
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
Contents ix
Chapter 3
CRITICAL OBSERVATIONS ON THE
MEASUREMENT OF ADSORPTION AT
ELECTRODES
H. H. Bauer, P. J. Herman, and P. J. Elving
I. Introduction.... .. ..... ... ... . .. . . . . . . . . .. . . . . .. 143
1. Nature and Scope of the Discussion. ........... 143
2. Definition of "Adsorption". . . . . . . . . . . . . . . . . . . .. 147
3. Inferences about Adsorption from Observable
Phenomena. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 152
4. Adsorption of Inorganic Species.... . . . . . . . . . . . .. 154
5. Chemisorbed Films.... . . . . . . . . . . . . . . . . . . . . . . .. 154
6. Electrochemical Transformations Involving
Adsorbed Reactants. . . . . . . . . . . . . . . . . . . . . . . .. 155
II. Direct Methods of Measuring Adsorption.. . . . . . . . . . 157
1. Depletion of the Solution. . . . . . . . . . . . . . . . . . . . .. 157
2. Accumulation on the Electrode: Measurements
Made after Removal from Solution. . . . . . . . . . .. 157
3. Accumulation on the Electrode: Measurements in
situ. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 158
4. Optical Observation of the Surface Layer in situ. .. 159
III. Measurement of Surface Tension, Charge, and Capacity 160
1. Thermodynamic Theory. . . . . . . . . . . . . . . . . . . . . .. 160
2. Measurement of Surface Tension. . . . . . . . . . . . . . .. 171
3. Measurement of Charge on the Electrode.. . . . . . . . 174
4. Measurement of Double-Layer Capacity. . . . . . . . . 176
5. Measurement of Tensammetric Processes. . . .. . ... 181
IV. Adsorption Indicated by Effects Exerted on Faradaic
Processes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185
V. Summary................. ... .......... . . . . . . . . . 187
Acknowledgment. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
x Contents
Chapter 4
TRANSPORT-CONTROLLED DEPOSITION
AND DISSOLUTION OF METALS
A. R. Despic and K. I. Popov
I. Phenomena Involved. . . . . . . . . . . . . . . . . . . . . . . . . . . .. 199
II. Amplification of Surface Irregularities. . . . . . . . . . . . .. 203
III. Appearance and Growth of Dendritic Deposits. . . . .. 220
1. Conditions of Appearance and Factors Determining
Frequency of Incidence and Rate of Growth of
Dendrites. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 221
2. General Theory of the Appearance and Growth of
Dendrites. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 222
3. Comparison with Results of Experiments. . . . . . . . .. 231
4. The Effect of the Crystal Structure of the Depositing
Metal on the Direction of Growth and Shape of
Dendrites. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 238
IV. Growth of Whiskers. . . . . . . . . . . . . . . . . . . . . . . . . . . .. 242
1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 242
2. Theory of Whisker Growth. . . . . . . . . . . . . . . . . . . .. 245
V. Formation of Powdered Deposits..... . . . . . . . . . . . . .. 250
1. Common Features. . . . . . . . . . . . . . . . . . . . . . . . . . .. 250
2. Critical Current Density of Powder Formation and
Limiting Current Density of Metal Deposition.. 251
3. Interpretation of the Role of Transport Control in
Powder Formation. . . . . . . . . . . . . . . . . . . . . . . . .. 254
VI. Leveling... . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 256
1. Basic Facts. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 256
2. Model of Leveling.... . . . . . . . . . . . . . . . . . . . . . . . .. 261
3. Quantitative Treatment. . . . . . . . . . . . . . . . . . . . . . .. 263
VII. Electropolishing................................. 268
1. Summary of Experimental Facts. . . . . . . . . . . . . . .. 268
2. Proposed Models of Electropolishing. . . . . . . . . . .. 273
3. Quantitative Treatment of Diffusion-Controlled
Smoothing. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 277