Introduction to electrochemistry

368 Pages·1993·26.499 MB·English

by  D. Brynn Hibbert (auth.)

Introduction to
electrochemistry
MACMILLAN PHYSICAL SCIENCE
Series advisers
Physics titles: Dr R L Havill, Universify of Sheffield
Dr A K Walton, University of Sheffield
Chemistry titles: Dr 0 M Adams, University of Leicester
Dr M Green, University of York
Published and forthcoming titles in the series
Group Theory for Chemists, G Davidson
Thermal Physics, M Sprackling
Lanthanides and Actinides, SCotton
Experimental Low-temperature Physics, A Kent
Essentials of Electromagnetism, D Dugdale
MACMILLAN PHYSICAL SCIENCE SERIES
Introduction to
electrochemistry
D. Brynn Hibbert
University of New South Wales, Australia
150th YEAR
M
MACMILLAN
©D. Brynn Hibbert 1993
All rights reserved. No reproduction, copy or transmission of
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Any person who does any unauthorised act in relation to
this publication may be liable to criminal prosecution and
civil claims for damages.
First published 1993 by
THE MACMILLAN PRESS LTD
Houndmills, Basingstoke, Hampshire RG21 2XS
and London
Companies and representatives
throughout the world
ISBN 978-0-333-56303-8 ISBN 978-1-349-22721-1 (eBook)
DOI 10.1007/978-1-349-22721-1
A catalogue record for this book is available
from the British Library
FOR MARIAN, HANNAH and EDWARD
Contents
Preface xii
Glossary of symbols xiv
Glossary of acronyms xvii
Chapter 1 Introduction to electrochemistry 1
1.1 The scope of electrochemistry 1
1.2 History 3
PANEL 1: Cold fusion: or illusion? 3
1.3 A quick tour of electrochemistry 6
Chapter 2 Theory of electrolytes 11
2.1 Introduction 11
2.2 The structure of water 11
PANEL 2: Polywater: The water that never was 13
2.3 Electrolyte solutions 15
2.4 Interactions in an electrolyte 19
2.5 Activities of ions 19
2.6 Debye-Hiickel limiting law 22
2.7 Solid electrolytes 32
2.8 Problems 34
2.9 Answers 35
Chapter 3 The electrified interface 38
3.1 Introduction 38
3.2 An electrode as giant ion 38
PANEL 3: Electric fish 39
3.3 The structure of the double layer 40
vii
viii Contents
3.4 What can be measured at a double layer 41
3.5 Theories of the double layer 44
3.6 Electrochemical potentials 50
3.7 Electrokinetic effects 51
3.8 Problems 56
3.9 Answers 57
Chapter 4 Electrodes and electrochemical
cells 59
4.1 Introduction 59
4.2 Definitions 61
4.3 Electrode potential 63
4.4 Writing electrochemical cells and potentials 69
4.5 Types of electrodes 70
4.6 Electrode potentials and activities 73
4.7 Concentration cells and membrane equilibria 75
PANEL 4: Prehistoric battery 77
4.8 Thermodynamics of cells 79
4.9 Some applications of equilibrium
electrochemical cells 81
4.10 Problems 83
4.11 Answers 85
Chapter 5 Ion transport, diffusion and
hydrodynamics 90
5.1 Introduction 90
5.2 Forces and movement 90
PANEL 5: Electrodeposited fractals 91
5.3 Fick's Laws of Diffusion 93
5.4 Conductivity of electrolytes 97
5.5 Theories of the conductivity of electrolytes 101
5.6 More about ion transport 106
5.7 Mobility and diffusion 112
5.8 Hydrodynamics 113
5.9 Problems 117
5.10 Answers 118
Chapter 6 Electrochemical kinetics 121
6.1 Introduction 121
6.2 Faraday's Laws 122
6.3 The course of an electrochemical reaction 122
6.4 The Butler-Volmer equation 124
Contents ix
6.5 Other sources of overpotential 133
6.6 Multistep reactions 135
6.7 More about electrode kinetics 135
6.8 Photoelectrochemistry 137
6.9 Problems 138
6.10 Answers 139
Chapter 7 Techniques of electrochemistry 143
7.1 Introduction 143
7.2 Electrochemical cells 144
7.3 Electronics 155
7.4 Techniques 155
7.5 Spectroelectrochemistry 166
7.6 Problems 169
7.7 Answers 170
Chapter 8 Mechanisms of electrochemical
reactions 172
8.1 Introduction 172
8.2 Deposition of copper 172
PANEL 8: Electrochemistry in crime 173
8.3 Hydrogen electrode reaction 175
8.4 Oxygen electrode reaction 180
8.5 The reduction of azobenzene 183
8.6 Techniques for determining mechanism 186
8.7 Problems 187
8.8 Answers 188
Chapter 9 Electroanalytical chemistry:
potentiometric methods 190
9.1 Introduction 190
9.2 Potentiometric methods of analysis 191
9.3 Conductiometric analysis 210
9.4 Problems 212
9.5 Answers 215
Chapter 10 Electroanalytical chemistry:
voltammetry and coulometry 221
10.1 Introduction 221
10.2 Polarography 221
PANEL 10: Electrochemistry in the dentist's chair 222
x Contents
10.3 Voltammetry 237
10.4 Amperometric titrations 243
10.5 Coulometry and electro gravimetry 245
10.6 Problems 249
10.7 Answers 250
Chapter 11 Electrochemical synthesis 254
11.1 Introduction 254
PANEL 11: Victor Frankenstein: An early
bioelectrochemist 255
11.2 Experimental methods 255
11.3 Mechanistic aspects 260
11.4 Types of electrosynthetic reaction 261
11.5 Examples of organic electrochemical synthesis 266
11.6 Examples of inorganic electrochemical synthesis 270
11.7 Problems 271
11.8 Answers 272
Chapter 12 Industrial electrochemistry 274
12.1 Introduction 274
12.2 Electrochemical engineering 274
PANEL 12: The story of electrolysis 275
12.3 The chi or-alkali industry 282
12.4 Metal winning, refining and finishing 285
12.5 Electrolysis of water 289
12.6 Electrochemical preparation of organic compounds 290
12.7 Problems 291
12.8 Answers 292
Chapter 13 Batteries and fuel cells 294
13.1 Introduction 294
13.2 Definitions 294
13.3 Energetics of batteries 295
PANEL 13: Battery research in the 1830s:
J. F. Daniell (1791-1845) 297
13.4 Economics of batteries 300
13.5 Battery design 302
13.6 Types of battery 302
13.7 Fuel cells 308
13.8 Problems 314
13.9 Answers 314